U. S. DEPARTMENT OF COMMERCE

BUREAU OF STANDARDS

THE OPTICAL ROTATION OF LIQUIDS

ITS VARIATION WITH WAVE LENGTH

TEMPERATURE, SOLVENT

AND CONCENTRATION

By T. MARTIN LOWRY

MISCELLANEOUS PUBLICATION No. 118

U. S. DEPARTMENT OF COMMERCE

R. P. LAMONT, Secretary BUREAU OF STANDARDS

GEORGE K. BURGESS, Director

Miscellaneous Publication No. 118

THE OPTICAL ROTATION OF LIQUIDS

ITS VARIATION WITH WAVE LENGTH

TEMPERATURE, SOLVENT

AND CONCENTRATION

BY

T. MARTIN LOWRY

MARCH 25, 1932

UNITED STATES

GOVERNMENT PRINTING OFFICE

WASHINGTON : 1932

For sale by the superintendent of Documents, Washington, d. c.
PREFACE

The compilation of the available data on this topic, as presented in

the following pages, was made in conjunction with work undertaken

for the International Critical Tables and covers, with the exceptions

noted below, the literature preceding January 1, 1923. No attempt

has been made to include fragmentary data. Data for the sodium

D-line at ordinary temperatures and in the common solvents will be

found in International Critical Tables. 1 The common sugars have

also been omitted from the present compilation, since they have been

covered in the saccharimetry section of International Critical Tables.2

i Int. Crit. Tables, 7, pp. 355-489. McGraw-Hill Book Co., New York; 1931.

» Int. Crit. Tables, 2, pp. 334-355. McGraw-Hill Book Co., New York; 1927.
CONTENTS

Page Preface n

L Arrangement 1 II. Symbols and abbreviations 2

III. Class I. Organic substances in which the asymmetric carbon

atom does not form part of a ring 2 IB. The molecule contains one carbon atom attached to four

different atoms or groups 2

IBi. The asymmetric carbon atom is attached to two other carbon atoms 3

1. Amines 3

2. Monohydroxy alcohols, their ethers and esters 4

3. Amino acids 30

IB2. The molecule contains two asymmetric carbon atoms which

are attached each to two other carbon atoms 34

4. Tartaric acid and its esters 34 IQ. The molecule contains one asymmetric carbon atom attached

to three other carbon atoms 48

5. Citronellal derivatives 48

6. Amylacetone derivatives 48

IV. Class II. Organic substances, at least one asymmetric carbon atom

of which forms part of a ring 49

IIB. The molecule contains asymmetric carbon atoms attached to two other carbon atoms 49

7. Tetrahydronaphthol and derivatives 49

8. Amines 50

IIC. The molecule contains asymmetric carbon atoms attached each to three other carbon atoms 54

9. Methylcyclohexane derivatives 54

10. Dimethyltetrahydroquinoline and derivatives.. 55

11. Myrtenol estersl 56

12. Menthone 56 IIC B. The molecule contains two or more asymmetric atoms at- tached respectively to two and three other carbon atoms 57

13. Menthol, isopulegol and derivatives 57 IID C. The molecule contains two or more asymmetric atoms at- tached respectively to three and four other carbon atoms 66

14. Camphoric and campholytic acids and derivatives 66

15. Limonene 68

16. Camphor and derivatives 69

17. Camphorcarboxylic acid and derivatives 76

18. Borneol and related compounds 79

19. Fenchyl alcohol derivatives 81

20. Teresantalic and isoteresantalic acids 82

V. Class III. Compounds containing no asymmetric carbon atom, or containing an asymmetric or dissymmetric atom of some other element 83

(a) Compounds containing asymmetric atoms of S, P,

etc 83

21. Methylethylphenacvlthetine derivatives 83

22. Bromocamphor- and camphor-sulphonates 83 in
IV CONTENTS

V. Class III—Continued. Page

(6) Compounds containing dissymmetric metallic atoms, Co, Cr, Rh, Ir, Pt, etc 84

23. Cobalt complexes 84

24. Chromium complexes 86

25. Rhodium complexes 87

26. Iridium complexes 88

27. Platinum complexes 88

28. Molybdenyl and tungstyl derivatives of malic and tartaric acids 88

VI. Class IV. Substances of unknown, doubtful or complex structure.. 92

29. Alkaloids and derivatives 92

VII. Class V. Influence of salts and other substances on rotatory power. 94

VIII. Literature references 101 IX. Index 105
THE OPTICAL ROTATION OF LIQUIDS, ITS VARIATION

WITH WAVE LENGTH, TEMPERATURE, SOLVENT,

AND CONCENTRATION 1 By T. Martin Lowry

I. ARRANGEMENT

Arrangement is by classes denned as follows:

CARBON COMPOUNDS 2

I. None of the asymmetric carbon atoms forms part of a ring.

II. At least one asymmetric carbon atom forms part of a ring.

III. The compound contains no asymmetric carbon atom or contains at least one asymmetric or dissymmetric atom other than

carbon. IV. Substances of unknown, doubtful, or complex structure. Classes I to IV are subdivided according to the number and nature

of the asymmetric atoms as follows:

An The molecule contains n asymmetric atoms which are attached

each to only one other carbon atom.

B„ The molecule contains n asymmetric atoms which are attached

each to two other carbon atoms.

Cn The molecule contains n asymmetric atoms which are attached

each to three other carbon atoms.

D„ The molecule contains n asymmetric atoms which are attached

each to four other carbon atoms.

For substances which fall within two or more of the above subdivisions the higher (in the order D, C, B, A) division receives prefer- ence in deciding the arrangement. Within a subdivision the ar- rangement is in accordance with the value of n in the order 1, 2, 3, etc.

1 This section includes data and bibliography to January 1, 1924.

1 Sugars and their derivatives are classed as open chain compounds. In general, derivatives are listed under the parent compound, even when they contain additional asymmetric atoms

1
BUREAU OF STANDARDS

II. SYMBOLS AND ABBREVIATIONS

txD

a{

Ml

[M]!

cV

Temperature in degrees centigrade (°C).

Wave length of light expressed in Angstrom units; that is, in tenths of a millimicron (Ko mm) unless otherwise indicated.

A wave length of 5893 A.

Observed rotation at the given values for t. Specific rotation at the given values for t. Molecular rotation at the given values for f( = Mx[a]x/

100).

Concentration in grams per 100 cm 3 of solution.

Concentration in grams per 100 g of solution (= Wt. per

cent). (Values in italics when column heading is "c"

or "p.")

d d{ = density at the given value for t referred to water at 4°C, unless otherwise indicated.

2 per cent NaOH (etc.) 2 per cent of solution of NaOH in water.

2 per cent NaOH MeOH 2 per cent of solution of NaOH in methyl

alcohol. M Moles.

N NaOH Normal aqueous solution of NaOH ( = 1 equivalent/liter),

s Solvent.

SYMBOLS FOR SOLVENTS AND RADICALS

A ^

Ac =

Bu =

en =

Et = Me =

The acid radical under

which it is used.

(CH3 CO) Acetyl.

(C4H9 ) Butyl.

(C?H8N2 ) a, 0-Ethylenediamine.

(C2 H5 ) Ethyl.

(CHS ) Methyl.

Ph = (C6 H5 ) Phenyl.

pn = (C3H10N2) a, jS-Propylenediamine.

Pr = (C3 H7) Propvl.

Py ^ (C5 H5 N) Pyridine,

tr = (C3 H10N2 ) a, 7-Diaminopropane (trimethylenediamine).

III. Class I.—ORGANIC SUBSTANCES IN WHICH

THE ASYMMETRIC CARBON ATOM DOES NOT

FORM PART OF A RING

IB. THE MOLECULE CONTAINS 1 CARBON ATOM ATTACHED TO 4 DIFFERENT ATOMS OR GROUPS

CHsCUKO^S, ammonium chloriodomethanesulphonate (176) [•IS

i c 5,461 5,781 5,893 HjO L 000 15.8 13.3 12.3 H3 L 674 16.0 13.4 12.4 H2 3. 402 15.7 13.2 12.2 EtOH L671 19.5 16.8 15.7 Notk.—Throughout this paper, black-face figures in parentheses refer to correspondingly numbered

citations in the bibliography, p. 101.
OPTICAL ROTATION OF ORGANIC SUBSTANCES 3

to Tin? a cv^\/^"^/1"c^TTPT^, rAPRr>M atotmt tq ATTAPHirn to o

1X3] 1 JtXE< Ao i iVlivlJi I JXlv^ L-ArCJDVw/iN AO Al 1 AUhbIJ 1 U Z CARBON ATOMS

1. AMINES

Sec-butylamine ( = Am) and derivatives (171) [ a ]x° «=H2 Sulphonyl =Su *\ 5,893 5,780 5,461

C4H11N. /-Am 1. 4. 70

3. 40

1. 00

3. 01

-5.00

.88 30.7

2. 40

-5.22

.96 32.2

2. 49 .81 -5.40

-5.75

1. 25 37.1 2.49

.81 -5. 58

CtHnClN 1-Am hydrochloride CnHuNO

CioHuNOjS

Benzoyl-d-Am

Benzene-Su-d-Am. CuHnNOjS.

CiaHuNOjS

p-Toluene-Su-d-Am

Naphthalene-a-Su-/-Am

3.03

2.73

.81 -5.40 Ci5 Hi5 NO, benzoyl-l-a-phenylethylamine (174; cf. 131)

[-R M?

8 c \ 5,893 5,780 6,461 5,461 CeH6 C.Hj

C.H.

3. 004

2.384 .795

-40.

1

-43.7 -52.5 -41.9

-45.7 -55.7

-48.3

-52.6 -64.2 -137-149 -182
BUREAU OF STANDARDS

I SB,

8

"3a3

>> X!

CO CO CO lO

SIC «D <*< <N OO

id >d id id

<x>t~-r o oi

CM tt< lO

id id o

(CflOtO

oi c*"i os

lemon

id id id id ctccoi 00 r- >o C X CM lO t^-^cd^n ^occ-;H

co co co co n w :i

ec rj< r~ t— (Occ « O)

io >c o *o i ic *r

d,ow^ <;hqo &<ooo

<* OO O OlOOf

00 lO OS OS CO 00 I "NOO) OOOOt^l

NOlrtOl ©S00COt~-

CM O

im ocsooco ooe^j lO CO t~ OS r-C i-( t- o

i-i o osododoo t>t^

SB ® «

8 e O o

jcyl. oiz; P

si

oqoo oq%%

dodo dodo do
OPTICAL ROTATION OF ORGANIC SUBSTANCES 5

Ethyl carbinols (163; cf. 136)

r 120 r 120

L a

J5,461 MS ["]2 [ m\d

rnyl-1140

CUHioO Methyl 13. 87 16. 09 10. 02 8. 73 C6 H,>0 Ethyl Optically inactive. CeHnO „ Propyl 1. 97 2. 24 2. 01 2. 12 2. o2 — CtHisO Butyl 8. 13 9. 58 9. 43 9 58 y. to 10. Oo CiHl8 Amyl ... 8. 22 9. 64 10. 69 10. 95 11. 14 11. 24 Hexyl 7. 38

6. 68

8. 63 10. 63 11. 10 11 IK 11. 10 11 C\A 11. v% C10H23O Heptyl 7. 76 10. 55 10.66 10. 64 10. 49 CuHmO Octyl 6. 25 7. 23 10. 74 10.96 11. 00 11. 10 CuHmO.... - Nonyl 5. 97 6. 92 11.09 10. 33 10. 21 1U. 00 CisHjgO Decyl 6. 23 7.21 12.44 12.28 12.13 12.11 ChHsoO Undecyl 5. 87 6. 80 12.56 12.28 12.19 12 16 C15Hj,0 Dodecyl 5. 53 6.40 12. 61 12. 26 12. 13 12. 20 CuHmO Tridecyl 5.11 5.92 12. 38 12. 34 12.11 11. 76 C,»HM Pentadecyl 4. 77 5.49 12. 87 12. 80 12. 72 12. 63

Isopropyl carbinols (126, 162) MS

C5H12O--- Methyl 4.85

15. 06 21.25

25.64

22. 84

21. 46

18. 55 16.15

4.3

15.4 24.7

33.3

32.9

33.9

34.5 34.5

3.7

12.4 21.9

29.1 28.7

29.2

29.0 29.0

CeHnO Ethyl. C»H,«0 n-Propyl CtHmO n-Butyl C9H20O n-Amyl CinHwO n-Hexyl... CuHmO n- Octyl C14H30O n-DecyL.

1 At boiling point.
BUREAU OF STANDARDS

4,

358

1 SESSSS

140.8 156.7 136.2 124.8

87.24

155.5 115.0

5,

461

-14.89 -2. 05

13. 85

26.89 37. 47

44.37 48.78 61.34 62. 86

53. 67

51.06

The

following

are

approximately

5

per

cent

solutions

at

room

temperature

(102,

1C5)

80. 0289. 97

78.03 72. 6260.58 85. 64

64. 00

5,

893 SSSSSS 8£S28

I

1

65. 37

74. 67

64. 7660. 1542. 36

71.48 64. 46

1

<*

-8.

01

-19.20 -37.

97

-65!

27

-72.

71

-77.41 -78.41 -78.

56

-78.

14

-76.

68

-159.1 -198.9 -138.5

—

168. 8

-167.2 -116.8

-9. 61

-16.

14

-26.51 —34

23

-40i 19

-43.

98

-45.

98

-46.

66

-46.

70

-46.

05

-45.

50

-89.04

-112.6 -78.

52

—94.

34

-85^29

-89.

02

-07.

04

1

•o 1

1 1 1 I 1 1 1 1 1 1

-74.

39

-93.

87

-65.

92

-78.

25

-70.

99

-74.01 -66.

11

!? t

i

-28.11 -29.28 -30.

45

-31.44 -32.

03

-32.

32

-32.28 -38.

89

-42.

79

-34.40 -62.65 -34.

18

-34.

40

«,461 2£2222 2

1 II II I I

-23.

13

-26.

45

-20.

37

-30.

78

-20.65 1

id

-14.

23

-14.

74

-15.

17

-15.61 -15.90 -15.

97

-15.83 -19.

45

-19.41 -17.20 -25.68 -17.

13

4,

358

•«

69. 03

61.22 62. 70

63. 36

62.94 61.98 60. 67

59. 07

57.41

5,

461 iiszzz MM 19.36 50. 82

46. 7289!

60

58. 02

5,893 16. 13

41.82 39. 0273!

57

47.88

i -64.

95

-60.49 -65.

16

-68.

82

-70.

84

-71.03 -70.34 -69.07 -65.06 -79.

16

-92.23 -93.

69

-122.7

5,

461

-32.

91

-36.

02

-38.

71

-40.83 -42.01 -42.

11

-41.

56

-40.

76 WW

1

>©

-25.

86

-30.

24

-32.

82

-34.46 -35.

31

-35.

51

-35.28 -34.

37 fffff

4,358 mm

5,461 49.94 57. 93

65. 18

70". 01

84.22 i 4L77 41. 51

41. 18

40

6440!

12

39.31 38.48 41.94 48.88 64. 13

68.33 70.66

4,358 10. 64

7.78 1.87

6.

32

6.02

5,461 6.

86 3.89 .79

2.70 2.74 1 7.71 6.84 6.94 6.27 4.68 4.87 8.31 .59 2.18

2.28

s jjj \ 1 1

s 1 iloc £
OPTICAL ROTATION OF ORGANIC SUHSTANCES 7

I

8gj2222«i

8SSS8§S SS8S8§§

8S8SS0S

2S232S

ss£2S£

£38

ooSo 288

£3$

S32S gas

2333 3S3

23£

sss

23££$S3

238S3£

28S;38§

sisals

2£§3gg?£

e4<NeococCTti g28£SS?

ei «i eo 10 8S£38S 2£g£g3

££££££

KS?g883

£38

S3S

3d*

S3£8S8

2S8gS8

g$28 3833S8

3S33 3S3

88©

StStt &Cfftf*4
BUEEAU OF STANDARDS

Specific rotation [a]\ of ethers of d-benzylmethyl carbinol (159)

t = 17° t = EWH CSi

Ether \ \ 5, 893 5, 461 4, 358 \ x

c \

5,893 5, 461 4,358

c \

\ \

Methyl 5.00 2.8 4.9 7.3 5.00 36.2 39.5 81.3 Ethyl 4. 95 19.7 24.4 41.1 5. 01 44.4 51.4 94.3 Propyl 5. 01 21.1 24.0 41.3 5.00 42.8 52.

1

93.2 Butyl 5.00 25.3 30.6 49.4 4. 98 42.7 53.0 95.2 Amyl 4.91 25.6 31.1 51.1 5. 01 41.5 48.1 89.1 Hexyl 5.04 25.5 30.7 50.3 4.99 41.2 49.9 90.3 Heptyl 5. 07 24.8 29.8 49.3 4. 87 38.1 47.2 82.1 Octyl 4. 95 24.2 29.8 49.0 5. 05 37.9 45.6 81.9 Nonyl 5.04 24.4 29.7 48.6 4.96 37.5 44.6 sa 6 Specific rotation of d-P-octyl ethers

d-/3-Octyl ether

Methyl. . Ethyl—

n-Propyl.

n-Butyl.. n-Amyl.

.

n-Hexyl.- n-Heptyl.

n-Octyl.. n-Nonyl..

V

I I

I 6, 438 5, 461 5, 086 4, 800 4, 678 4, 358

6. 42| 8. 14. 68120.

20.

116. 63122.

!l3. 03118.

111. 68 16.

!l3. 1818.

10. 80 15. 10. 98 15.

6310.

33 24. 51L_.

46 26. 19 22. 2918.

41 21. 33 17. 4518.

2011.

13 26. 66 12. 95 28. 13 29. 09 23. 68 21. 58 24. 59 19. 41 20.

64 31. 83 25. 05 22. 1125. 96 20. 26 21.

23 13. 79 46 32. 86

.. 32. 92

01 36. 13 42 29.06

45 25. 95

72 29. 75 84 24. 77 35 24. 60

(100)

5, 461*5, 086 4, 800 4, 678 4, 3.58

3. 02 4. 52 1 5. 80 6. 70 7. 18 8. 35

10. 79 14. 73 17. 15 19. 54 20. 32 23. 04

, 15. 7» 1 25. 65

12. 34117. 61:19. 61 21. 88 23. 19 27. 32

10. 34114. 19 16. 56 18. 92 19. 86,22. 87

: 8. 65 12. 36,14. 39 15. 68 16. 97 19. 54

10. 42,14. 62 16. 48 19. 05 19. 73 22. 85

i 7. 95.11. 29 12. 88 14. 47 14. 98 18. 11

8. 98' 12. 43 14. 52 15. 96 16. 70 19. 82

I

I I I I

I

4. 97...

4. 73..

5.47. .. 4.56-

.

3.53...

3.17... 4.26. .. 3.41. . 3.30. .

12.31,20.

'24. 27 32. 31.

24. 58l33. 119.00 25.

17. 97123. |19.15|26.

16. 14 20. .....21.

44 24. 68 41. 42'... 7939. 42 30. 96 27. 20 32. I

26

:

31 28. 10 29. 50 45. 85 47. 60 45."

5

; 4?." 62 : 34. 16 36. 51 33. 16i34. 90137. 71 39. 9S 29. 20.30.

10 35. 93 58.

56. 71 57. 61 43. 99 40. 50 45. 09 35. -1 27.

s=EtOH[a J'

95il9.60 6. 16 24. 75|13. 26 25.50...

81122. 65115. 81 24. 05 12. S3 17. 60 12. 23 24. 20 13. 52 14. 65 10. 4021.05...

37 7.52 8. 94 17. 6S 22.

.. 17.24 ... 67 19. 86 24. 37 15. 50 IS. 9113. 85 18. 22 17. 66 20. 26 14. 02 15. .. 14. 97...

92 9. 22 25. 06 26." 82 21. 59 20. 96 23. 73,17.3010.

35 26.

12 21. 01 21. 13 24. 78 IS.

07 12. 24

57 30. 00

.. 28.99

03 33.36

84 25.28

85 24.69

99 27.88

46 21. 37 ..26.35

1 <=room temperature.
OPTICAL ROTATION OF ORGANIC SUBSTANCES 9

Specific rotation [<x Jx of alkyl esters at various temperatures (164, 166)

20. _ 40..

60.

.

80..

100.

120.

140.

,160.

20

40... 60

so

100

120

140..

30.17

28. 15

26. 29

24. 79

23. 40

25. 43

23. 69 22.14

20.85

19. 66

Pelargonate Ci3 H26 2

17. 80

16.73

15. 75

14. 82

13. 96

13.11

12. 51

12. 25

15.03

14. 14 13.31

12.51

11. 76

11. 10 10.59

10.33

Acetate CtHhO,

20. 27

18. 44

17.04 15.58

14.54

13. 87

17. 16

16. 67

14. 50

13.20

12. 36

11. 85

Acetate CgHieOi

11.80

10. 30

8. 92

7. 67

6. 53 5.66

10.13

8. 85

7. 68

6. 58

5. 59 4

Pelargonate CisHsoOi

7. 77 7.24

6. 73

9. 38

8. 61

7. 87

7.19

6. 63

6. 21

5. 84

5,461 5,893

Propionate CtHuOj

28. 19

26. 47

24. 74

23. 33

23. 85

22. 37 20.91

19. 71

Undecylate

CisHaoOj

15. 81

14. 83

13. 97

13. 13

12. 40

11.81 11.26

10.69

13. 42

12. 48 11.73

11.09

10. 47

9. 98

9. 45

8. 99

Propionate CgHuOi

19. 29

17. 85

16. 44

15. 26 14.25

13. 47

16. 43 15.24 14.03 13.00

12. 15

11. 49

Propionate CsHisOj

11. 41

10. 17 9.06

8.06

7.19

9.76

8. 73

7. 80

6.91

6. 16

Undecylate Ci7H$4 02

9.75

8. 97

8. 17 7.56

7.02 6.49

5. 99

8. 35

7. 67 7.00

6. 48

6.02

5. 55

5. 15

5,461 5, 893

n-Butyrate CsHuOa

25.96

24. 19 22.61 21.50

20. 35

19. 36

21. 97 20.44

19.09

18. 18 17.18

16. 33

Laurate C«H3 aOi

15. 03

14. 11

13. 22

12. 39

11.69

11.15

10. 57

10. 07

12. 69 11.91

11. 13 10.43

9. 83

9.41

8. 92

8. 50

n-Butyrate C»HnO,

18. 42

16. 89

15. 46

14.09

13. 29 12.69

15. 77

14. 46

13. 23 12.08

11. 34

10. 86

5,461 5,893

n-Valerate C9 Hi«02

24. 53

23. 10

21. 65 20.22

18.94

17. 90

17.02

20.72

19. 50

18. 27

17. 10 16.00

15. 13

14. 40

Myristate Ci»H,6 Oa

13. 42

12. 70

11. 95

11.26 10.55

9.95

9. 44

9. 03

11.34 10.69

10.07

9. 50

8. 91

8. 41 7.95

7. 65

n-Valerate CioHjoOj

7i-Butyrate CioHaoOj

12. 66 11.47

10. 32

9. 32

8. 33

7. 65 7.02

10. 83

9. 76

8. 81 7.94

7. 13

6. 53

5,

Laurate C18H3»0,

9. 34

8. 53

7. 75

7. 11 6.52

6. 01

5. 64

7. 99

7. 27

6. 64 6.09

5. 60

5. 16

4.

18. 77 17.13

15. 98

14. 84

13. 98

13. 27

12. 62

16. 01 14.70

13. 63

12. 71

11. 95

11.32

10. 80

5,461

Caproate

C10H20O1

22.07

20. 53

19. 16

18. 02

17. 04

16.04 15.26

18. 66

17. 18

16. 15

15. 17

14. 44

13. 53

12. 90

Palmitate

CjoBUoOj

12. 12 11.44

10. 81 10.23

9. 62

9. 11

10.25

9. 65

9. 12

8. 61

8. 10

7. 68

7. 29

5,461 5,893

Enanthate

C11H22OJ

20.48

19.22

18. 00

16.99

16.03 15.03 14.30

13. 76

17. 37

16. 24

15. 19

14. 32

13.54

12. 71 12.04

11. 60

Stearate CJ3H44OJ

Caproate CnHjjOa

n-Valerate C11H22O1

13. 05

11. 97

10.92

9. 87 9.08 8.27

7.61

22. 48 20.27

18. 19 16.19

11. 14 10.47

9. 86

9.32

8. 89

8. 45

8. 01

7. 66

9. 39

8. 83

8. 32

7. 89

7.48

7. 12

6. 75

6. 48

18. 74

16. 87

15. 04! 13.48

Caproate

C12H24OJ

11. 16

10. 26

7. 74 7.08

6. 52

12. 66

11. 69

10. 69

9. 85 9.03

8. 32

7. 66

Myristate

CaoHioOj

7. 84

7. 18

6. 60

5. 66 5.29 5.03

7. 40

6. 70

6. 14

5. 62

5. 21 4.84

4.63 4,30

10. 84

9. 96

9. 16 8.41 7.74

7. 14

Palmitate CaiHuOa

8. 10

7. 44

6. 84

6.26

5. 81

6. 61 5.31

6. 87 6.31

5. 87

5. 37

4. 97

4. 70

4. 55

Enanthate CuHaeOa

12.12

11.11

10. 18 9.28

8. 56 7.94

7.43

10.36

9. 50

8. 73j

7. 96!

7. 31 6.78

6.31

5,461 5,893

Caprylate

Ci2 Ha40j

19. 04

17. 97

16. 82

15. 83

14.84

13. 99

13. 30

12. 75

Stearate Ca4H480a

7. 21 6.44

5. 88

5. 43

5. 03

4. 68

4. 40

4. 21

6. 16

5. 52

5. 02

4. 65

4. 31

4. 02

3.78

3. 58

16. 14

15. 13

14. 22

13. 33

12. 52 11.84

12. 24

10. 77
10 BUREAU OF STANDARDS

Specific rotation [aj^of alkyl esters at various temperatures (164, 166) —Continued

100.

120. 140.

1160.

20..

40.. 60..

80..

100. 120. 140.

160.

180.

20

40

60

6,461 5

Acetate CsHnOj

9. 55

8. 07

6. 88

5.89

4. 85

3. 92

8. 23

6. 91

5. 89

5. 03

4. 16

3. 35

Pelargonate Ci9H32 0»

10.15

9. 40

8. 62 7.92

7.25

6. 72 6.33

6. 10

8.70

8.04

7.36

6.77

6. 21 5.76

5. 42 5.20

5,461 5,893

Propionate

9.77

8. 67 7.64

6. 67

5. 70

4. 85

8. 37 7.40

6. 53

5. 72 4

4.14

Undecylate

Acetate C,oH2oOj

8. 01 6.85

5. 67 4.59

3. 67

2. 68

1. 82

1. 20

6. 84

5. 84

4. 85

3. 93

3. 15

2. 37 1.70

1.15 .85

Pelargonate C17H34OJ

9. 34 7. 96

8.50 7. 29

7. 83 6. 71 7.22 6. 19 6.73 5.72

6. 30 5. 36

5. 92 5.06 5.67 4.83

8. 65 7.98

7.41

6.41 6.00

6. 54

7.7.40

6. 84

6.36

5. 86

5. 46 5.11

4. 73

Propionate CuHmOj

8. 16

6. 98 6.00

5. 14 4.35

3.64 3.04

5

5. 14 4.40

3.72

3. 11 2.60

Undecylate

8.57 7.35

7.90' 6.77 7.24 6.18 6.59 5.61

6.031 5. 5.54 4.73

5.23 4.47

5,461 5,893

n-Butyrate CuHmOj

11. 86

10. 80

9. 72 8.78

7.91

7. 13

6. 47

6. 03

10.16

9. 24

8. 34

7.52

5,461 5,893

n-Valerate CijHnOi

12.02

11. 07

10. 20

9. 32

6. 78 8. 57

6. 12 7. 83

5. 44 7. 16

6. 16 6. 62

Laurate Ci.HmOj

8. 85 8.28

7. 62

6. 97

6,5.85

5. 46

5.16

7. 58

7. 08

6. 49

5. 95

5. 45 5.00 4.67

4.41

n-Butyrate

10. 46

9. 48 8.50

7.63

6. 87

6. 12 5.50

4.97

8.95

8. 12 7.29 6.54

5. 90

5.24 4.70

4. 26

Laurate C2oH<oOi

8. 21 7.53

6. 91

6. 40

5.5.44

5. 05 4.73

5,461 5,

Caproate CuHjeOj

10.26 11.63 9.97

9.48: 10.38 8 8.70 9.48i 8.12 7.99 8.76' 7.50

7. 34

6. 70

6. 13

5. 66

Myristate

C,iH,jOi

8. 10 7.50

6. 91

6. 36 5.91 5.54

6. 14 4.85

6. 91

6. 40

5. 89

5. 42 5.05 4.74

4. 38 4.15

n-Valerate CuHmOj

10.65

9. 16

8. 22

7. 46

6. 85

6.22

5. 68

5. 21

9. 16

7. 83

7. 03

6. 36

5.84

5. 31

4. 86 4.44

Myristate C2 3H«Oi

7.00

6. 47

5. 94

5. 45

5. 02

4.66

4.29

4.03

7.72

7. 05

6. 43

5.84

5. 35

5.03

4.71

6. 59

6. 02

5.48

4.99

4.59

4.31 4.04

8.121 6.95

7. 48 6

7. 07 6. 03

Palmltate CmHuOj

7.69

6. 97

6. 32 5.80

5. 43

5.08 4.74

4.401

6. 53 5.98

5. 40

4.

4. 63

4. 34 4.05

3. 77

Caproate CuHi»Oa

10.54

9. 52

8. 66 7.92 7.27

6.73

6.24

8. 96

8. 16 7.42

6.79 6.24

5,461 5,893 5,461 5,893

Enanthate CuHmOj

11. 16 10.31

9. 49 8.78

8. 07

7.43

6. 89

6. 47

9. 53 8.80

8.09

7. 49

6. 88

6. 35

5. 87

5.51

Stearate CjjHsoOj

7.10 6.06 6.38 5.42

5.79| 4.95

5.311 4.55

5. 03

4. 65

;

4.35

4.31 3.98

3. 73

Enanthate C14H3 oOj

9. 97

9. 31

8. 52 7.73 6.99

5.73! 6.40

5. 34 5. 98

5.66

Palmitate C3<H48 0»

7. 18

6. 58

6. 10

5. 62

5. 18

4. 80

4.42

8.59

7. 95

7.30

6.63

6. 01

5. 45

5.11 4.88

Stearate CjsHsjOi

6. 14

5.641

5. 21

!

4.79 4411

4.10

3.78

6. 68

6. 19

5. 69

5. 19 4.83 4.47 4.12

3. 78

5. 71

5. 28 4.45

4. 12 3.53

3.23
OPTICAL KOTATION OF ORGANIC SUBSTANCES 11

Specific rotation [a Jx of alkyl esters at various temperatures (164, 166) —Continued

5,461 5, 893 5, 461 5,893 5, 461 5, 893 5,461 5, 893 5,461 5,893 5,461 5, 893

t Acetate CuHaaOj

Propionate CuHjsOjn-Butyrate

CieHaoOi

n-Valerate Caproate

C17H34O1 Enanthate Ci8Hj«Oj

7l

esters

|

(2040

60.... 80

100

120... 140

6. 17

4. 94

3. 90 3.08

2. 36

2. 07

1. 19 .61 -. 11

5.27 4.24

3. 35

2. 62 2.02

1. 87

1. 17 .47 +.11

6.04

5.12

4. 39

3.71 3.06

2.53 2.08 :

). 15

L 40

i. 75

5. 17

I. 60

>. 15 .75

8. 67

7. 52

6. 58

5.83

5. 28

4.77

4. 32

7.31

6. 40

5. 62 4.99

4.49

4. 07 3.70

8.72

7.79

6. 95

6. 19 5.57

5.03

4. 63 4.34

7. 46

6. 67

5. 96

5. 30

4.76

4. 30

3. 97

3. 69

8. 63

7. 85

7. 10 7.46 5.94

5. 50

5.11 4.79

7.37

6. 69

6. 07

5. 52 5.09

4. 69

4.36

8.36

7.71 7.13

6. 51

5. 93

5. 36

4. 91 4.68

7.17

6. 60

6. 10

5. 57 5.07

4. 57

4. 22 160 4.08 4.01 180

5 / s

XJp

20

Pelargonate C2oE4o03 Undecylate C22H«02 Laurate Myristate

CjsHsoOj

6. 19 5.70

5. 27 4.77

4.32

4.09

3. 87

3. 67

6.68

6. 09

5. 48 4.97

4. 63 4.33

4. 11

3. 99

5.72

5. 21

7. 96

7.27

6.68

6.16

5.69

5. 20

4.79

4.46

6.81

6. 21

6. 71 5.29 4.87

4. 44

4. 10

3. 82

7.38

6.75 6.15

5.65 5.20

4.80

4.60

4.27

6. 30

5.76

5.25 4.85

4.43

4.11

3. 85

3.66

7. 21

6. 67

6. 16 5.57

6.04 4.75 4.52

4.29

40

60 - 4.71 4.25

3. 98

3. 71

3. 50

80

100 120 140

160... 3. 42

Formates Acetates

d-0-Butyl C4HioO»

d-/J-Octyl d-0-Nonyl CnHjjOj

d-/3-Decyl C12H24O1

d-0-Tridecyl OisHjo0 2

2040

GO80

10( 12(

22.48 20.27

18. 19

16. 19

18. 74

16. 87 15.04

13.48

-5.04

-6. 43 -7. 84 -9. 15 -10. 38 -11. 25

-4. 16 -5.35

-6. 45 -7. 45 -8. 36 -9.04

-9.47

7.24

5.76

4.73

3. 80 2.90

2.06

1. 28 .60

6. 21

4. 92

4.04

3. 26

2. 49

1.74

1.09 .50

6.61

5.44

4. 36

3. 36 2.56 L85

1.12 .57

5.64

4. 67

3. 73 2.88 2.19

1. 60

1. 11 -.64

5.39 4.45

3.54

2.76

2.11 1.55

1. 05

.51 ±.00

4.63

3. 83

3. 03 2.36

1.79

1. 35

.89 .40 ±. 00

).

) 14( m

18(

) -11. 85

))....

Laurates

d-0-Amyl d-/3-Nonyl CjiHuOi

d-^-Decyl C22H«Oj

d-/S-Dodecyl C24H«Oi

d-/3-Tridecyl CmHsoOj

2040

6080

10(

12.24

11.42

10.75

10.17

9. 65

9. 17 8.74

10.44 9.17

9. 16

8. 69

8. 21 7.80

7.43

7.87

7.15

6.53

5. 98

5.48 5.05 4.69

4,35

6.71 6.12

6.60

5. 14

4. 67 4.31

4.01 3.72

7.51 7.05

6. 40

5. 72

5. 18 4.81 4.60

4.45

6.41 6.02 5.47

4.88

4.42

4. 11

3. 92 3.78

6. 99

6. 42

5. 91

5. 45

5.04

4. 69 4.37

4.10

5.99

5.49

5. 07

4.67

4.31

4. 01

3. 72 3.50

6.83

6.21 5.64

5.87

5.33

4. 86

5.20! 4.47

4.81 4.13

4.46 3.82

4.22| 3.62 4.10 3.50

) 1 12( 14(

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12 BUREAU OF STANDARDS

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27.79 26. 47

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OPTICAL ROTATION OF ORGANIC SUBSTANCES 17

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OPTICAL ROTATION OF ORGANIC SUBSTANCES 19

Specific rotatory power [ajx °f ty* preceding esters in approximately 5 per cent solution

Esters S"=Ethyl alcohol Carbon disulphide

e t 5,893 5,461 4,358 e t 5,893 5,461 4,358

4.95 20 13. 14 16. 28 24. 36 4. 57 20 11.48 12. 47 18. 27 d-fl-CjjHttOi 4.99 18 13. 61 18.03 25.64 5. 01 18 9. 98 12.08 18. 47 d-/J-CisHn04 malonate 5.04 21 7.34 8. 14 13. 70 5. 06 19.5 -5.04 -7. 01 -14. 62 5.05 20 -1.29 -2. 18 -2.97 5.06 20 12. 66 16.02 31. 54 d-^-CuH2eO« 5.07 18 1.87 2. 66 4. 73 4.99 17 -13. 34 -14. 94 -3L09

4. 99 18 23. 73 27. 54 43. 66 4. 97 16 10. 37 13. 79 17. 22

5.04 18 9.63 10.52 16. 07 4.99 17 -13. 13 -15. 14 —30. 17 d-fi-CtoKuOi 5.10 18 1.77 1. 67 -.29 5.03 17 -21. 18 -24. 97 -49. 82 5.07 18 8. 39 9.48 14. 51 5. 05 17 -11.69 -13. 67 —27 33 d-^-C«H4i04 5.03 18 9.45 10. 35 16. 72 5.11 17 -10. 95 -13. 10 -26! 70 d-^-CMH«04 - —

-

5.04 18 9.43 11.03 17.98 5.09 18 -8. 85 -11. 90 -22. 81 d-0-CnH4»O4 - 5.03 19 8.95 10.74 17. 70 5. 01 18 -9. 59 -11.29 -20. 48 d-0-CMH4lO4 5.15 19 9.22 10.86 16.11 5.03 18 -7. 86 -9. 75 -20.19 d-fi-CuUuOi

d-0-CirHMO4

5.00

5.04

1818

8. 71

8. 93

10. 41

10. 12

16. 81

16. 36

4. 96

4. 97

18

18 -8. 06 -7.75

-10. 28 -9. 46 -20. 34 -20. 22 d-(8-CMHM04 5. 01 19 9.29 9. 98 16. 58 4. 97 18 -7. 65 -9. 36 -18.94 d-0-CnHttOi 4.62 19 9.41 10.06 15.15 4.71 18 -6. 26 -7. 85 -15. 50

Alkylisopropylcarbinyl hydrogen

phthalates (182)

CHClj c=5 EtOH c=5

[M]D [«]d [M]D CuHn04 d-Methyl i 37.9 -.5

-7.8

-7.8

13.9 -13.8

13.5

89.3 -1.2

20.9

41.4 97.7 -10.1

22.

1

C14H11O4 d-Ethyl 1 C1SH10O4 d-Propyl

C15HJ0O4 J-n-Propyl -4.0

8.4 -8.0

12.8 -12.9

15.1 17.0

17.2 16.8

Ci6Hm04 d-n-Butyl CuHmOi J-tt-Butyl 38.7 35.5 C17HMO4 d-n-Amyl 39.3

36.1 56.3

50.3

44.1

52.1 57.3 61.0 CuHm04 d-n-Hexyl.. CioHM04 d-n-Octyl... CmHm04 d-n-Decyl

11.8

16.9

13.9

1 Not recrystallized, being very soluble in organic media. a, p-Dichloropropionates 1 (67) C4HiC18 0i Methyl CjHgChOj Ethyl CrHijChO* Isobutyl CioHi8Cl2 2 Heptyl

t t [«]/> t [«]/> t Mo

3.5

13.5 20.0

43.5

54.5

0. 95

1.47 1.70

2. 35 2.54

12.0 20.0

39.5

56.5

-1.96

-1.79 -1.40 -.97

14.5 20.0

40.5 68.0

-3. 73 -3. 62 -3. 31 -2. 91

12.0 20.0 40.0

53.0 99.0

-1.84

-1. 73 -1. 62 -1. 54 -1.26

1 Prepared from corresponding /-glycerates, possibly partly racemized.
BUREAU OF STANDARDS

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OPTICAL ROTATION OF ORGANIC SUBSTANCES 21

Specific rotation [a]x °f d-y-nonyl esters in solution (99)

<=* Temperature oflaboratory

jiiSter Ethyl alcohol c Carbon disulphide x= 5,893 5,461 4,358 X= 5,893 5,461 4,358

Acetate - 4. 495 —8. 12 —9. 57 — 1 6. 90 5.115 —17. 89 —21. 31 —38. 62 Propionate - 5. 240 —8. 77 —20 68 — 17 97 5. 430 20. 72 25. 59 01 n-Butyrate 5. 195 -5! 69 -a 65 -1L 55 5.175 -17! 10 -24. 80 -36! 74 n-Valerate 5. 095 -4.91 -5.59 -9.61 5.050 -15. 36 -19. 42 -34. 48 Caproate 4.885 -4. 19 -4.93 -8.84 5. 255 -14. 55 -17. 51 -31. 49 Enanthate 5.170 -3. 67 -4.32 -7.61 5. 005 -13. 40 -16. 10 -28. 30 Caprylate : - - 5. 035 -3. 07 -3. 52 -6.05 5. 435 -12. 51 -15. 37 -26. 22 Pelargonate..- 5. 260 -2. 76 -3.48 -5. 42 5. 295 -11.90 -14. 73 -24. 93 Caprate 5.720 -2. 62 -3. 32 -6. 03 5. 720 -10.75 -13. 63 -24. 04 Undecylate- 5. 440 -2. 42 -2.84 -5.26 5.745 -10. 35 -12. 61 -23. 31 Laurate 5. 090 -2. 36 -2.86 -4. 47 4. 995 -10. 30 -12. 51 -22.02 -2.31 -2. 48 -3. 85 4. 925 -9. 75 -11.68 -20. 31 Palmltate 4. 735 -2. 40 -2. 69 -3. 36 5. 140 -9. 15 -10.51 -18. 78 Stearate - 4. 755 -2. 30 -2.49 -3. 33 5. 245 -8. 67 -10.49 -17.93

Specific rotation of d-y-nonyl acetate (99) Py — 4. 820 -13. 39 -16. 08 25. 72 C.H, 4.831 -12. 42 -14. 87 25. 50 CHClj 4.615 -8. 73 -9. 55 16. 25 AcOEt 4. 996 -5. 91 -7.00 12.21 MeiCO -- 4. 684 -6.08 -7. 15 12.06 CiHiBrj 4. 898 -3.74 -4. 49 8.13

1

C4 H8 03 Methyl /-lactate (148; c/., 66, 231)

(66; cf., 321) 8=PhNOi CjHjCh

t [>]h t Hi. t [-K

-75.0

-51.0

16.7 35.4

78.8 125.0

5. 48

5. 84 8.10

8. 68

9. 98

11. 13

£ 16.0

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=? 56.5

o, 104.5 141.0

9.85

9.90

10. 16

10. 63 10.95

S -7.8 3 39.7 t 94.3

o, 12a

-7.66

-2. 53

1. 96

3. 74

CsHioO* Methyl i-a-acetoiypropionate

-7.4

43.0

83.2

141.0

54.26 54.20

54.03

54. 08

3 0.3 6 19.2 T 65.0

0, 141.0

59.78

57. 20

62. 77 50.88

1 17.6 1 54.7 V 91-3

©,

I 39- 3

47.56

47. 32

47. 34

47. 80

C»HioOi Methyl /-a-methoxypropionate

-16.6

16.4

51.1

78.4 130.0

103.3

97. 16 91.81 88.28

84. 16

e, 16.6 § 41.7

o> 70.5

II 92.

8

* 119.0

88. 82

85. 27

82. 17

79. 25

76. 40

£ 16.7 8 39.8 2 77.0

II 101.

e. 119.0

73. 69

72. 52

70. 52

69. 40

68. 21
22 BUREAU OF STANDARDS

Esters of methylbenzyl carbinol in various solvents (5 per cent solution) at laboratory

temperature (101) s=EtOH CSi

Ester - 5,893 5,700 5,461 4, 358 5, 893 5, 700 5,461 4,358

Acetate 5. 805 8. 01 8. 61 9. 47 15 72 5.060 —8. 17 —8.36 —10.42 —22. 55 Propionate.. - 5. 315 124 7. 62 8.56 14. 11 5.165 -13. 78 -14. 62 —16. 85 —34. 57 Butyrate - 5. 145 12. 14 12. 74 14.48 24.01 5.405 -7. 77 -8. 42 -9. 17 -22.29

Valerate 5. 630 14.70 15. 75 17.20 29.23 3. 645 -4. 61 -4. 86 -6.11 -14. 21 Caproate 5.605 14. 55 15. 53 16. 96 28. 57 5.020 -3.26 -3.98 -4. 62 -10. 95 Enanthate 5. 240 15.09 15. 38 17. 67 29.98 5.040 -1.80 -2.25 -2.80 -8. 12

5. 360 14. 66 15.03 17. 18 29. 32 5. 540 -.90 -.98 -1.15 -5. 57 Pelargonate 5. 550 14. 34 15.24 17. 50 28. 85 5.500 -.36 -.45 -.73 -4. 45 Caprate 5. 525 14. 32 15. 13 16. 93 28. 72 6. 450 -.33 -.50 -1.00 -3.92

Undecylate 5.250 13. 61 14. 19 16.19 27. 71 5. 270 .00 -.19 -.28 -3. 51 Laurate 5.180 13.02 13.50 15. 71 26.23 5.560 .08 -.08 -. 33 -2.70

Myristate 5.455 12.28 13.20 14.48 24.75 5.255 .26 .00 -.17 -1.82 Palmitate— 5.425

6.025

11. 25 10.4511.98 10.95

13. 55

12. 74 23.23

21. 19

6. 270

5.915

.38

.54 .19.31 -.09 -1. 71 .23 -1.31
OI>TlCAL ROTATION OF ORGANIC SUBSTANCES

4,358

I

21. 1919. 5317. 70

16.42 15.29 14.16 13.11 12.56 12. 3012.44

j|

20.90 18.22 17.05 16.08 15. 38

14.71 14. 17

13. 6113. 17

5,461

12.79 11.69 10.58 9.84 9.28 a

75

8.

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5,700 oooJodod oo oo I-' ^

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10.06 9.30 8.

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8.29 7.99

5,461

5,700 11. 36

10. 53

9.81 9.25 8.

76

8.27 8.00 7.

82

7.67 7.67

5,893 SfeSSS SSgSoS

doSoiodoo r~ i-- 1-

4,358

CijHuOj

Propionate

8.69 6.

76 5.

14 3.

79

2.73

L96

1.20 .58 ±.00

-.48

i

21.26 19. 53

18.28 17.00 Ifi

90

15.11 14. 60

14. 10

13. 60

13. 14

5,461 o ^ ec c4 cn L65

1.20 .87 .66 .49

12.72 11. 80

11. 03

10. 32

o> co cd od od

5,700

5.06 4.09 3.25 2.51 1.

96

1.56 1.20 .93 .72 .67

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4,

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1

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10. 46

9.

58

8.88 8.

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8.09 7.77

7.

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OPTICAL ROTATION OF ORGANIC SUBSTANCES 25

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26 BUREAU OF STANDARDS

Specific rotation of the above esters in 5 per cent solutions at room temperature

d-a-Naphthyl-n-hexyl carbinyl

Acetate

Propionate. n-Butyrate.

n-Valerate.. Caproate... Enanthate. Caprylate—

Pelargonate Caprate

Undecylate.

*=EtOH

5,893

33. 80

36.31

32. 18

27. 21

26. 52 23.26 25.27

22.01

19. 54

17. 99

5,700

35.38

37.88

33. 66

29. 32

27. 33 24.68

26.27

22. 87 20.64

18.88

5,461

40.84

43.88

38. 77

33. 01 31.23

27. 91

30. 16

26. 32 23.00

21.46

4,358

75.88

80. 52 71.76 61.80

51.58

56.76 49.53

42.74

CSi (102)

5,893

111.5

122.8

113.1 102.7

99. 10 89.74

86.64 84.06

78.36

74. 22

5,700

117.3

129.1 119.5

108.1

102.7 94.99

91.07 88.54

82.35

78.05

5,461

137.0

150.7

139.3 126.6

119.8 110.3 106.2

104.6 96.20

90.99

4,358

268.2 293.6

273.2

247.3 240.4

217.4

207.9 203.8

199.6

183.1

C:3H2604 hydrogen phthalic

ester in various solvents

(102) C25H2i04 Na sodium phthalic

ester in EtOH (102)

<=room temperature c=5 g in 100 cc

5,893 5,461 4,358 5,893 5,461 4,358

CSj 75. 26

25. 25 17.50

90.72

29. 66 20.80

4. 74 -3. 13 -28.63

170.0 47.94 32.38

1.00 -11. 14 -61. 02

29. 35 35. 52 63.24 AcOH

CHC1,

C»He 5.00 -1.30

-22. 46 Py - — —

EtOH

Specific rotation of CuHu02 l-methyl-a-naphthyl carbinyl acetate

t 5,893 5,461 4,358

20

40.. -32.2839. 51 44.58 49.18

52.85

55.22

56.78

58. 11

59. 29

-38.90

47. 47 -73. 79 88.04

101. 51

113. 02

121. 57 126.02

129. 82

132. 62

135. 39

60. 80- -

100. 120 -

64.04

59. 39

64.21

67. 07 68.68

70.33

71.83

140 160- - -

180 -

/-methyi-a-naphthyl carbinyl hydrogen phthalate (102, 165)

Approximately 5 per cent solutions at room temperature

s x_ 5,893 5,461 4,358 CHCU

EtOH

-43. 67 -69.68 -53.47

-84. 80 -109.6

-171.7
OPTICAL ROTATION OF ORGANIC SUBSTANCES

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30 BUREAU OF STANDARDS

3. AMINO ACIDS

C10H11NO3 N-Benzoylalanine 1 [a ]? w

s c 5,893 5,780 5,461

d-Acid H2 1.022 2.4 -2.4

10.5 24.9

2.7 -2.7

10.9

26. 1

3.2 -3.2

12.7 30.2

/-Acid H2O 1 1.025 d-Acid /EtOH 1.009 \MejO 1.016

C4H1N2O3 Z-Asparagine (47; cf. IS, 210) s=HsO

I P 5,893 5,461 4,358

34 L 961 -6.7 -7.5 -14.7

40 1.961 -7.7 -8.3 -17.7

60 1.961 -10.5 -11.3 -22.4

38 7. 407 -6.4 -6.9 -13.2

52... 7. 407 -8.3 -9.3 -18.3

68.. 7. 407 -10.5 -11.7 -23.5

C4H7NO4 Z-Aspartic acid. (47; cf. 18, 50, 140, 141)

s = H,0

[ a ]l

t P 5,893 5,461 4,358

14 0. 990 5.1 7.1 15.2

35 0.990 2.5 5.1 12.7 48 0.990 1.3 3.1 9.2

48 L 961 2.3 4.0 9.3

68 L961 0.0 1.3 4.5

78 L 961 -1.5 -0.3 2.3

1 The effect of KOH on the specific rotation is also given in the article.
OPTICAL ROTATION OF ORGANIC SUBSTANCES

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OPTICAL ROTATION OF ORGANIC SUBSTANCES 33

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34 BUREAU OF STANDARDS

IB2

. THE MOLECULE CONTAINS 2 ASYMMETRIC CARBON ATOMS

WHICH ARE ATTACHED EACH TO 2 OTHER CARBON ATOMS

4. TARTARIC ACID AND ITS ESTERS

Specific rotation [a]x of d-tartaric acid in aqueous solution 1 (121)

d 1. 2987 1.2658 1.2352 1.2052 1. 1760 1. 1476 1. 1201 1. 0942 1.0692 1. 0448 1.0211 X

i 55.0 50.0 45.0 40.0 35.0 30.0 25.0 20.0 15.0 10.0 5.0

6.004

6.501

6. 734

7. 366

7. 421

8. 219

8. 078

9. 010

8. 728

9. 799

9. 336 9. 886 10. 457 11.047 11.645 12.209

14. 070

6,438 5,893 10. 500 11. 207 11.949 12.642 13.383

5,790 6. 566 7. 466 8. 331 9. 162 9. 975 10. 752 11. 481 12. 197 12. 948 13.687 14. 527

5,769 6. 577 7. 487 8. 346 9. 184 10. 014 10. 786 11. 535 12. 246 12. 980 13. 687 14. 527

5,461 - 6.613 7. 653 8. 645 8.668

9. 594 10. 532 11.417 12. 237 13.061 13. 925 14.740 15. 609

5.088 6.235 7. 479 9. 784 10. 876 11.927 12.904 13. 899 14. 855 15. 856 17.040

4,800.. 4.678

6. 348

4. 739

6. 781 6.241 8.150

7. 707

9. 430

9. 056

10. 714

10. 427

11. 859

11.660

13. 032

12. 969

14. 162

14. 051

15. 297

15. 359

16. 446

16. 558

17. 922

18. 150 4,358.— —- 1. 848 3. 631 5.421 7. 025 8.637 10. 131 11. 570 13. 023 14. 486 15. 952 17. 791

i In fused and supercooled states: (28). In various solvents: (10, 11, 83, 90, 93, 117, 184, 211, 213, 229, 230). Rotatory dispersion in aqueous solutions of d-tartaric acid at 20°; constants and

anomalies (121)

(Range X= 6,438-4,358) [M] =

ffi^hxfi

~

iq-9 (x1 -\

,i)

' tt<>-«Xi»=0.03) (10-*X3 i=0.074)

V kt HMM

(Inflection)

10-<X (Maxi- mum)

10-W

(Reversal)

55.0 17. 127 12. 093 0. 6571 0. 5527 0. 42S9

54.1 17. 188 12. 080 .6533 .5485 .4220

50.0 17. 485 12. 043 .6376 .5373 H40

45.0 17. 686 11. 877 .6197 .5232 .4050

41. 25 17. 960 11. 869 .6092 .5150 .3997 40.0 18. 053 11. 865 .6058 .5123 .S980 35.0 18. 367 11. 812 .5929 .5022 . S915

30.0 18. 709 11. 799 .5822 .4937 .S861 25.0 18. 936 11. 714 .5722 .4859 .S81S 20.0 19. 160 11. 624 .5628 .4785 .S767

15.0 19. 485 11. 605 .5543 .4720 .8726

10.0 19. 657 11. 475 .5458 .4653 .S684

5.0 19. 592 11. 108 .5341 .4562 .S628

* All values which lie outside the range of observations are in italics.
OPTICAL ROTATION OF ORGANIC SUBSTANCES 35

C6 H130« specific rotation [a]TM of dimethyl d-tartrate (130; cf., 6, 51, 167, 228)

s c *l 10-8Xji Range X X=6,708 6,438 Nil— 22. 576

24. 762

17. 145

17. 049

20. 360

27. 425

19.448

42. 828

37. 555

20. 079

21. 193

9. 979

10. 640

22. 202

24. 000

6. 683

43. 581

33. 211

0.056

.052

.065 .070

.058 .054 .082

.047

.058

6, 708-3, 741

6, 708-4, 135

6, 438-4, 358

6, 708-4, 137

6, 708-4, 236

6, 708-3, 750

6, 438-4, 800

6, 438-4, 358

6, 438-4, 800

+2.79

+5. 69 +2.65+5. 80 +16. 04 +13. 41 -9. 31 +4.67

+30. 48 -7.20

+4. 47

Nil at 100.5° C

HiO.... 25

25

25

2520

2021.5

OHONRi

CiH<Cli (CHi)jCO CsHsN Pyridine

+12.65

-8. 16 +4. 59 C7H»0 Anisole C0H7N Quinoline8 X =5,893 5,780 5,461 5,086 4,800 4,678 4,358 Nil +2.22

+6. 27 +2. 05 +6.29

+19.28

+15, 80 -13.50

+4. 50 +37. 44 -11.00

+3. 19

+1.28

+6.25

+21. 17 +16. 96 -16. 51 +4. 01 +41. 60 -13.80

+1. 73

-0.39

+5. 68 +23. 44 +18. 14 -21. 53 +2. 73 +47. 15

-2. 47 +4. 74 +25. 23 +18. 74 -27. 09 +0. 87 +52. 01 -23.68 -5.24

-8.93 +1.26

+27. 33 +17. 85 -40. 92

Nil at 100.5° C.... - .. HiO.

+4. 07 +25. 86 +18. 87 -30. 12 CHONHi

CtH^Clj

(CHj),CO

+15. 39 +4. 62 CsHaN Pyridine +36. 32 CtH$0 Anisole -37. 08 C|H7N Quinoline +3.56 -1. 35 CgHnOe Diethyl d-tartrate [ a fx

(146)

X 6, 708 6,234 5,769 5,461 4, 960 4, 358

t s = CsH»N Pyridine. p=19.263

0.0

15.7 58.6 100.0

34.74 32.26

26. 38

21. 99

39. 50

36. 63 29.90

25. 19

46. 75 43.23 35.03

29. 50

52.06

48.11

38. 70

32. 63

62. 48

57. 63 45.89

38.41

78. 63

72. 06

59. 90

46.51 s=C7H«0 Benzaldehyde. p=10.385

17.0 86.7

135.5

39. 12 26.49

22. 66

42.35 130.5

26. 52

47. 33

33. 93

29. 18

57.26

1 39.8

34. 07

1 73.3

1 49.4

41.93

X 6, 708 6,234 5,790 5,461 4,960 4, 358

t s = C7HoOj Salicylaldehyde. p=20.214

19.8

32.1 6L1

79.5 114.2

20. 34

> 20.0

19. 81

19. 13 18.23

23. 88

1 23. 54

22. 97

22. 36 21.23

27. 36

1 27.0

1 26.2

25. 55

24. 21

30. 39

1 30.0 129.1

28. 32 26.74

35. 73

1 35.3

34. 43 33.29

31. 57

43.52

1 42.6

40. 93

39. 34

37. 09 s=C9H7N Quinoline. p=4.972

19.8 60.3

82.0 99.0

38.25

1 20.0

18. 13

17. 47

30.3

l 22.4

20. 57 19.5

35.07

25.94

23. 50 22.35

38.25

27. 73

25. 15 24.08

44. 00

31.2

27. 75 27.27

49. 46 132.3

31. 26 29.20 s=C9H7 N Quinoline. p=13.601 -13.0

0.0

16.8 44.5

65. 116.0

134.4

31. 13

31. 60

19.19

18. 21

139.0

35.23

30.29

24.54

21. 55 20.36

146.0

41.20

35.26 28.00

24.48

22.92

50.93

45. 42

38. 70

30. 60

26.76

25.14

60.86

53. 77

45. 18

35. 17

30. 41

173.3

63. 63

52. 06

38. 78

32. 58

1 These values have been interpolated by the compiler from the author's data.
36 BUREAU OF STANDARDS

CiHmOo, Diethyl d-tartrate » (152) s=C2H4 Br3 +PhNOj

P

p of PhNOj MS P

p of PhNOj MS

19. 925

17. 105

19. 922

15. 022

14. 928

100.00 61.92

49. 95

35. 63

35. 03

25.9

15. 95

11. 50

7.01 6.80

19. 926

13. 391

19. 942

12.061

33. 35

15. 55 .00

.00

6.06 -1.70

-7.56

-10. 72

1 In other solvents see (149, 150, 152). CsHhOs, Diethyl tartrate (123, 124)

fa fa a

HH(X»-Xi0 '=0.030)

t Ai kt io-«x2

» Range X

i 20.0 25.005 20. 678 0.056 6, 708-3, 860

20.0 25.22 21.05 .055 6, 708-3, 879

64.3 22. 941 17. 670 .057 6, 708-3, 923 98.7 24. 091 18.284 .055 6, 708-4, 358 (C= 25) CHONHj 19. 62 9. 46 .07 6, 708-3, 960 C2H4 Bri 18.08 19. 335 .061 6, 708-4, 154

point of 18.7° C

Specific rotatory power [a]

2x

° of diethyl tartrate (123, 124)

6,708 5,893 5,780 5,461 4,358

f 6.87 7. 82 7. 88 7. 87 l 1.98

\ 6.69 7. 45 7. 52 7.50 1.62

9. 64 11.44 11.66 12.28 10. 42

11.09 13. 35 13.70 14.64 15.13 20 18.23 23. 39 24. 46 27.06 38. 18 25 18. 59 23.74 24.60 27. 19 37.89

20 .20 -1.34 -1.73 -3. 11 -17. 17 20 1.84 .83 .63 -.30

5 22. 80 29. 38 30.50 33.73 46. 75

10 22. 75 28. 99 30. 01 33.20 46. 30 20 21.87 27. 80 28. 76 31.86 43. 89

25 21.81 27. 73 28. 72 31.70 43.68

23 -6.30 -11.33 -13. 95 -35. 36

5 -10. 35 -15. 17 -16.20 -19. 55 -45. 17

10 -9.54 -14.31 -15. 26 -18.48 -43. 57

20 -8. 13 -12. 41 -13.30 -16.33 -39. 70 5 -10.90 -16.60 -17. 11 -20. 73 -48.70

10 -9. 60 -14. 26 -15.23 -18. 65 -44.76

20 -7.40 -11.52 -12. 35 -15.23 -38. 76

25 -6. 66 -10.56 -11.33 -14. 11 -36. 77

5 -1.71 -4. 63 -6.40 -23.80

10 -1. 55 -3.76 -4.24 -6. 09 -23. 11 20 -1.36 -3. 63 -4.11 -5.88 -22. 39 20 -1.50 -3.40 -4. 40 -6.40 -23.35

40 9. 38 11.09 11.30 11. 88 10.00 5 10. 73 12. 80 13.23 13.97 11. 37

10 10. 10 12.28 12. 63 13.24 10. 99

20 9.90 11.66 11.93 12. 46 9. 52

20 19. 32 24. 45 26. 02 29. 01

Nil at 20°.. Nil at 64.3° Nil at 98.7° H2 J.. ecu... CHBr8 . CHONHj.

C2H2 Br4—

CjH3 Cl4—

CjH4 Br2 .

CtEUCI). CsHsBra- C3H5OH. Me2 CO.. C«Hfi N02

1 The ester used for these determinations was specially purified by distillation and freezing and had a

setting point of 18.7° C . Specific rotations for other wave lengths are as follows:

a . =

6, 438 6, 362 5,782 5,700 5,218 5,153 5, 105 5, 086 4,810 4,800

7. 38 7. 43 7.87 7. 88 7. 61 7.48 7. 36 7.34 6.25 6.22

4, 722 4, 678 4,603 4, 475 4, 415 4,359 4,315 4,271 4,240 4,210

5. 75 5. 45 4.9 3.5 2.8 2.1 1.4 0.7 -0.7

4,148 4,119 4, 071 4,005 3, 967 3,900 3, 889 3,872 3, 868 3,860 -2.1 -2.8 -4.2 -6.2 -7.7 -10.3 -11.1 -11.5 -11.8 -12.2

1 The data for water are uncertain, on account of hydrolysis; but they serve to show the general character

of the dispersion in this solvent.
OPTICAL ROTATION OF ORGANIC SUBSTANCES 37

C6 Hu 6 Diethyl tartrate 1 [a] lD (231) s=Ha O

100 75.05 50.23 25.03 10.08 5

203040

5060

7. 67

8. 72

9. 72

10. 60

11. 31

11. 81

12. 38

12. 90

13.37

13. 65

17. 51

17. 34

17. 18 17.04

16. 90

23. 69

23. 13

22. 55

21. 97

21. 40

25. 98

25. 52

25. 00

24.41

23. 76

26. 52

26. 28 25.78

25. 17

24. 52 70

80

90

11. 94

12. 50

13. 01

13. 90

14. 14

14. 40

16. 77

16.65

16. 53

20. 81

20. 23

19. 65

23.08

22. 39 23.8923. 25 100 13. 47 14. 65 16. 42 19. 06 s=MeOH

100 75 50 25 10 5

20

3040

50

7. 67

8. 72

9. 72

10. 60

9. 13

10. 10

11. 00

11. 80

10. 45

11. 34

12. 15

12. 82

11. 20

12. 07

12. 80

13. 48

11. 45

12. 30

13. 10

13. 48

11.51

12. 37

13. 10

13. 74 s=EtOH

100 60 50 25 10 5

2030407. 67

8. 72 9.72

7. 60

8.70

9. 63

7. 90

9. 00

10. 02

8. 37

9. 52

10. 46

8.55 9.60

10. 62

8. 75

9. 75

10. 75 s=CHCls

100 79.95 60.04 39.91 19.12 9.0

20

' 30

4050

7. 67

8. 72

9. 72

10. 60

3. 84 5.23

6. 46 7.67

0. 70

2. 32

3. 83 5.26

1. 56 .32

2.05

3.61

2.80

.89 .82

2. 50

2. 80

.89

.79

2. 30

1 For dispersion (light-filter sources only) see (228, 229); (or influence of solvents, concentration, and

temperature see (6, 74, 151, 167).
BUREAU OF STANDARDS

Cs HuOi, Diethyl tartrate (231) «=CHONH2 Formamide «=CjH<Brj Ethylene bromide

P Hi? p MB

74. 67 1. 1986 16.00 69.60 1. 3867 2. 62

61. 10 1. 1806 22. 55 44. 47 1.5899 -1.94

25.69 1. 1577 27. 60 22. 49 1.8297 -6.99

8.86 1. 1425 29. 74 11.58 1. 9814 -10.79

5. 35 1. 1396 30.13 5.53 2. 0788 -14. 16 1.90 1. 1365 30.3 2.31 2. 1362 -16. 72 1.20 2. 1567 -17.3

.42 2. 1713 -18.7 C12 H22 6 Diisobutyl tartrate

[ a ][ (146)

\ - 6,716 6,234 6,790 6,461 4,960 4,358

73.0 99.0

132.0

171.7

193.0 226.3

15. 86

16. 33

16. 42

16. 02

15.64

15.28

17.94

18.51

18. 73 18.31

17. 93

17. 30

20.60

21. 17 21.43

20. 94

20. 56

19. 79

22.77

23. 34 23.64

23. 14

22. 71

21. 97

26. 14

27. 19

27. 75

27. 34

26. 86

26.03

29. 69 31.40

32. 33

32. 10 31.73 30.96

«=CjHiCl«. p= 33.362

0.0

16.4 44.0

68.0

99.4

5. 46

7. 47

10. 19 11.90

13.26

5. 82

8.23

11.39

13. 34 14.92

6. 97

8.89

12.58

14.91 16.84

6.81

9. 15

13. 43

16. 01

18. 35

4.58

8.84

14. 32

17.84

20. 78

-0.26

6.63 13.31 18.24 22.56

«=C,HiCl4. V-=48.15

24.8 42.2

67.0

99.7

9.29

10.85

12.39 13.78

10.44

12.24 14.07

15. 59

11.50

13. 58

15. 82

17. 60

12.20

14. 57

17. 21 19.28

12.74

15.83

19. 25 22.06

11.04

15. 30

20. 08 24.26 »=C9H7N Quinoline. p=20.066

0.0 39.35

69. 75 99.5

147.6

54. 49

39. 40

32. 67

28. 35 23.93

63.29

45. 63 37.69

32. 48

28. 30

73.72

62. 56 52.79

42. 99

i 37.63

83. 36

59. 45

48. 15 41.87

« 36.9

103.44 72.50

58. 62

50. 61 42.94

133.63

91. 47 73.26

62.28 152.9

» These values have been interpolated by the compiler from the author's

data.
OPTICAL ROTATION OF ORGANIC SUBSTANCES

Ci6#2608 Diisobutyl diacetyl-d-tartrate (146)

I - 6,742 6,234 5,790 5,461 4,960 4,358 -2L0

0.0

14.0

17.25 42.25 75.2

98.9 200.0

l 16.2

13. 53

12. 86

12. 83

12.21 11.92

11. 94 14.28

1 16.5 15.29

14. 69

14.54 13.94

13.61

13. 80

16. 51

18. 63 17.34

16. 58

16. 42

15. 75

15. 45

15. 69 19.00

20. 33

18. 95

18. 15

17. 96

17.09

16. 94

17. 30 21.26

23.34

21. 63 20.74

25. 92

23.86

22. 92

19. 75 19.60

20. 14

21. 93

22. 22

23. 32

31. 45 S=C2 H2 C14. p = 20.034

6,716 6,234 5,790 5,461 4,960 4,358

0.0

16.9 43.0

57.5

76.85

10. 62

9. 86

9. 49

• 9.4

9. 35

11. 75

11. 10

10. 57 10.49

10. 40

10. 80

13.06

i 12.5

11. 87

i 11.6

11. 70

14. 25

i 13.5 12.82

12. 68

12. 73

15. 87

14. 93

14.29

14.26

14. 41

15. 27

16. 51

i 15.4

14. 65

i 14.8

15.49

99. 75 9.63 12. 12 13.24 16. 78 s=C7H7NOj o-Nitrotoluene. p=58.86

0.0

46.7 99.1

147.0

3. 38

5. 18

7. 48

9. 61

2. 96 5.31

8. 15

10. 93

2. 11

5. 22

8. 80

12. 27

0.91

4. 81

9. 17

13. 19

-3. 52

2. 52

8. 97

14. 16

-18. 30 -6. 21 J9. 34

s=C7H7NOj o-Nitrotoluene. p=24.694

0.0

17.0 49.8

73.7

150.0

-3.08

»-1.4

1. 65

3. 74 7.68

-4. 60 1-2.8

0. 71 2.99

8. 31

-7.20

-4. 83 -0. 49

2. 47 8.83

-10. 19 -7. 36 -1.94

1. 62

9. 00

-19.41

1-14.9

-7. 14 -1. 93

9.11

J-42. 85 J-33. 22

s=CoH7N Quinoline. p=74.96

! - 6,742 6,234 5,790 5,461 4,960 4,358

0.0

16.6

59. 75 100.0

15.51 14.64

13.23

12. 89

17.81

16. 73

15. 15

14. 77

20. 32

19. 17

17. 26

22. 44 21.09

19.06

18. 75

26. 22

24. 55

22. 22 22.02

30.54

28. 65 25.70

s=Ct)H7N Quinoline. p =20.476

0.0

17.0 36.7

76.75

103.2

33. 53

21.37

19.49

39. 32

34. 35

29. 94

24. 37

l 22.1

46.48 140.5

i 35.2 128.5

i 25.8

62.79 146.1

i 39.8

i 32.2

i 29.2

65. 26 67.41

49. 56

39. 22

35. 35

89.54

76. 59

66. 04 51.00

i These values have been interpolated by the compiler from the author's data.

» These readings were difficult to make and are, therefore, less accurate.
40 BUREAU OF STANDARDS

Rotatory dispersion of tartrates (65)

[-: 1 »2 dm

C12H22O6, n-Dibutyl d-tartrate \

t 6,708 6,563 6,147 5,893 5,769 5,679 5,568 5,461 5,219 4,861 4,662 <\

9.0 1.1044 7.44 7.68 8. 32 8.67 8. 82 8. 92 9.04 9. 13 9.26 8.7 8.1 21.5 1. 0934 8.55 8. 80 9.63 10. 20 10. 45 10. 61 10. 81 11.00 11.25 11.23 11.0 41.5 1. 0759 9. 93 10. 22 11.27 11. 92 12. 27 12.50 13. 08 13. 61 14. 19 14.1 72.5 • 1. 0492 11.31 11. 73 13.06 13. 91 14. 36 14. 65 15. 05 15. 44 16.26 17.4 17.9 98.0 1. 0269 12. 11 12. 54 13. 99 14. 95 15.45 15. 83 16.29 16. 75 17. 87 19. 43 20.2 118.0 1. 0099 12. 39 12. 83 14. 36 15. 35 15.89 16.30 16. 82 17.26 18. 39 20. 21 20.9

128. 1.0011 12.4 12. 91 14. 51 15. 53 16. 08 16. 46 16. 97 17. 53 18. 65 20.4 140.0 .9906 12.44 13.00 14. 54 15. 65 16. 23 16. 62 17.15 17.63 18.88 20. 76 21.4 151.0 .981 12.54 12. 97 14.54 15.69 16. 19 16. 57 17.04 17. 66 18. 77 20. 51 21.6

165.0 .969 12. 52 12. 99 14.58 15.69 16. 25 16.67 17. 16 17. 67 18.97 20.60 21.9

C18H34O6, n-Diheptyl d-tartrate

44.5 0. 9952 7. 66 7.92 8. 70 9. 17 9.43 9.64 9.84 10.03 10.44 10.77 10.6 79.0 .9685 8. 87 9.20 10. 16 10.88 11.23 11.49 11.78 12.08 12.73 13.69 14.1 100.0 .9520 9.27 9. 59 10.71 11.43 11.81 12.12 12. 44 12. 79 13.60 14. 76 15.2 125.2 .9328 9.66 10.00 11. 16 11.96 12. 38 12. 71 13.09 13. 48 14. 46 15. 78 16.5 149.0 .914 9. 78 10. 17 11.35 12. 14 12.60 12.88 13. 33 13. 71 14. 77 16. 18 16.9 168.0 .8995 9.68 10.06 11. 30 12. 12 12. 59 12.88 13.29 13. 69 14.68 16.20 16.8

CjoBUsOs, n-Dioctyl d-tartrate

45.0 0. 9817 7. 14 7. 35 8. 05 8. 51 8. 73 8.88 9.08 9.29 9.71 9.98 9.9 79.0 .9551 8. 32 8. 59 9.54 10. 18 10. 51 10. 75 11.05 11.32 12.02 12. 72 13.0 89.0 .9473 8. 54 8.84 9. 86 10. 53 10. 86 11. 13 11. 44 11.76 12. 53 13.40 13.8 112.0 .9292 8. 90 9.26 10. 35 11.06 11.44 11.73 12.07 12.42 13. 32 14. 50 15.0 132.0 .9140 9.04 9. 39 10. 51 11.26 11.65 11.93 12.30 12.68 13.57 14.96 15.6 145.0 .9035 8. 06 9.41 10. 58 11.34 11. 73 12. 01 12. 40 12. 73 13. 66 15.07 15.8 165.0 .887 9. 05 9. 41 10.54 11.33 it 74 12.06 12. 45 12.80 13.74 15.04 16.0

I ! i )
OPTICAL ROTATION OF ORGANIC SUBSTANCES

d-Tartrates (128, 145; cf. 6, 167, 228, 229)

doHnOi Diallyl Mi

15.6 15.28 20.0 15. 52 33.2 16.23

71.5 17.95 106.6 18. 66 131.6 18.82

148.2 18. 75 168.0 18.44

Diisobutyl

t Ml

20.0 17.75 69.1 19.83 80.6 20.03 97.5 20.44

CioHisOe Di-n-propyl

16.5 12.22 20.0 12.54

45.5 14. 52 77.7 16.48

111.2 17. 44 123.0 17. 62 133.2 17. 72 147.2 17. 82

161.0 17. 77 173.0 17.70

CioHisO» Diisopropyl

CnH2 5 4 Ethyl octyl

16.0 7. 63 21.5 7. 83 41.5 9. 36 50.0 10. 13 62.0 10. 89

71.0 11.43 98.0 12.72

CigH3 oO» Ethyl octyl diacetyl

18.5 4.20

44.0 4. 63 61.0 5. 37 81.5 6. 43 100.0 7.23

16.4 10. 25 20.0 10. 45 41.0 11.38 74.4 12.54

107.5 13. 31 133.0 13. 58 159.0 13. 75 173.0 13.67 179.0 13.64

CjoHsjOi Di-d-/3-octyl

C38H340g Ethyl octyl dibenzoyl

10.8 49. 41 24.2 49.31 38.0 49. 16 47.5 48. 81 54.0 48.64

67.0 48.39

79.0 47. 12 88.0 46. 18 99.0 44. 88

15.3 20. 55 20.0 20.90 49.7 22. 66 73.0 23.67

118.0 24. 69

136.0 24. 82

144.5 24.79

155.0 24. 77 173.0 24.63

CmH3 80s Di-0-octyl tartrates

[ a]^ (161)

d-Tartrate i-Tartrate r-Tartrate

Di-d-/3-octyl DH-0-octyl

24.06 -1. 93

11.02

2.06 -24.20

-11.00

14. 12 -14. 03 Di-dZ-0-octyl 0.00
42 BUREAU OF STANDARDS

d- Tartrates of organic bases in water 1

Neutral salts (87) 2.5 5.0 MS

CUHgOe d-Tartaric acid C12H28N2O6 n-Butylamine CuHiaNsOs Pyridine ChH28N:0« Piperidine CieH2oN!08 Aniline Ci»H24N20« Benzylamine

C:jH2oN20e Quinoline CajH28N20e Tetrahydroquinoline

14.44 14.02 21.0

17. 40 17.86 52.9

18. 72 19.30 59.5 16.80 17. 12 54.8

16. 12 16. 58 55.7

17. 40 18.28 66.5

12.80 13.22 54.0

12.80 13. 42 55.8

Acid salts (30) -is

CiHgOs d-Tartaric acid C4H«NO« Ammonia

CsHnNOj Methylamine C1H17NO1 Diethylamine C»HnNO« Pyridine CioHuNOe Aniline C10H13NO7 p-AminophenoL

(o-Toluidine CnHijNOe] ro-Toluidine [p-Toluidine CnHisNOs Benzylamine C11H1SNO7 j)-Anisidine C12H17NO7 p-Phenetidine... C»Hi3NO« Quinoline CiiHigNOs Pseudocumidine

1.50

1. 67 1.81

2. 23 2.29 j 2.43

2.59

2.57 2.57

2. 57 2.57

2. 73

2. 87

2. 79

1. 14

15.0 22.5

25. 55 42.7

23.4 42. 35 18.98 42. 35 18.5 42. 35

17. 42 42. 35 16.2 42

16.34 42.0

16. 47 42. 35 16.60 42.7

16.60 42.7

15.4 42.0

14. 75 42.4

14. 95 41.7

14.92 42.5

Neutral salts (30)

C4H12N2O8 Ammonia

C«Hi«N2 08 Methylamine

-

Ci2H28N20e Diethylamine C14HUN2O8 Pyridine CuHjoNjOb Aniline

(o-Toluidine.- C18H24N2CW m-Toluidine.

[p-Toluidine-. CisEfoNaOs Benzylamine- CMH20N2O6 Quinoline

1.84

2. 12 2.96

3.08

3. 36 3.64 3.64

3.64

3.64 4.08

34.6

29.7

21.1 19.2

17.1 15.6

15.8

15. 85 17.4

13.5

1 For effects of different ratios of acids to amines see (135)

.
OPTICAL ROTATION OF ORGANIC SUBSTANCES

d-Tartrates of organic bases in water—Continued

s c, p, or d

(157, ISO, 181) [M]g

L«1L

J

CeHioOe Dimethyl d-tartrate

Nil L 3284

1 5. 0231

2. 14 20.04

3.8 H2 35.7 CbHhOb Diethyl d-tartrate Nil 1. 2059

f 6. S2S1

tS. 106

\ 4S. 6S8

69. 440

[ 80.990

[ 1 610

27. 278

60. SI 5

65. 578

83.960

\ 6. 6479

{ 10. 7339

I 21.0627

7. 62

8. 47

7. 46

6. 97

6. 86

7. 07

7. 10

6. 01

5. 55

5. 85 6.64

6.75 6.29

6. 12

15.7 n-BuOH (1,694)

wo-BuOH (1,694)

C«Hi._ +13.9

+13. +12.6

CioHisOs Dipropyl d-tartrate

Nil.. L 1344 12.31 28. 81 HjO 4.8206 26.67 62.4

[ 6. 6205 19. 62 45.9 C»H« \ 11. 1266 20. 34 47.6

I 22.2112 18. 31 42.8 Dimethoxysuccinates C8Hh06 Dimethyl

Nil * 1. 1317 J 82. 52 » 170.

f 19.9988 78.71 162.1 H»0. „ < 10. 0315 78. 45 161.6

I 5. 0319 78.50 161.7

f 6. 2598 81.04 166.9 MeOH { 12. 0806 76.32 157.2

{ 23.0151 78. 90 162.5

20. 0036 101. 63 209.4 CaH« \ 10. 0128 104. 66 215.6

{ 5.0060 105. 47 217.3 CioHisOs Diethyl

Nil * f « 1. 0556 * 85. 39 2 199. 8

\ h 0&61 89. 96 210.6 HjO 5. 3752 89. 11 208.5

[ 6. 0569 87. 66 205.1 MeOH \ 9. 7365 87.41 204.5

[ 19. 0407 87.27 204.2

1 5. 3130 104. 93 245.5 C4H( { 10.1117 104. 14 243.7

I 19.3137 102. 65 240.2 CttH220« Dipropyl

NiP... MeOH

CeH8 ...

J 1. 0237 2 81.06 »212.5

1. 0612 84.92 222.4

6. 6571 84.99 222.7

12. 3697 84. 50 221.4

23. 7085 85. 79 224,8

5. 6932 101.26 265.3

11. 4730 101.00 264.6

21. 5619 99.24 260.0

i The p values are in italics. » At t"GO° O.
BUREAU OF STANDARDS

d-Tartrates of organic bases in water—Continued

C, HnCla O>, Dimethyl di-o- chlorobenzoyltartrate CmHuCIjOs, Dimethyl di-m- chlorobenzoyltartrate

t or p 1 d\ (64)

t or p 1 [-]]. s=EtOH. c=1.961

13.1 20.6 46.8

69.8

83.1 87.5

99.2

1. 3793 1.3719

1. 3467 1.3246

1.3117

1. 3075 1.2962

-48.83

-49. 22 -49. 79 -48. 94 -47. 95 -47. 51 -46. 80

| 20 | 0.7975 | 86.66 CioHieCljOi, Dimethyl di-p- chlorobenzoyltartrate

11.8 23.9 30.4

35.9

64.1 98.0

L 3660

1. 3536

1. 3470

1. 3414

1.3127 1.2784

-122. 20 -118. 79 -117.03

-115.50

-10S.23

-98. 30 s=EtOH. p = 1.606

20 0. 7964 -51.99

s = EtOH. p=1.62L

CjoHi«Br20», Dimethyl di-o- bromobenzoyltartrat* 20 0. 7964 -108.1

2738

60

75

93

L 602 L 587 L 559 L 543 L 524

-34.29

-34.74

-34. 23 -33. 79 -32. 89

8 = EtOH. ( = 20° LOSS

1.3057

< l.t59t

0. 7777 .7941 .7929

-72. 19 -71.85 -71.38 s=EtOH. t=20° CjoHuBrjOt, Dimethyl di-p- bromobenzoyltartrate

1.486 .9996

0.8009

.7951 -37. 39 -36. 51 21.7

4468.5

74.6

1.5832

1.5565

1. 5290

1. 5228

-112.2

-107.2

-100.7

-99. 1 s=Py. t = "XP

1.408 t.m0. 9860

.9831 -33. 12 -33. 61 8=EtOH. ^=20°

1.829

1.766

0. 7982 .7979 -101.8

-101.5

CjoHieBrjOs, Dimethyl di-ro- bromobenzoyltartrate

C20H16I3O9 Dimethyl di-o- iodobenzoyltartrate

4162340

75

L 620 L 605

1.595

1. 573

1. 531

-83. 26 -82. 05 -81. 33 -79. 19 -73.80

14.

1

20.0

45.7 74.7 99.0

1.8104

1. 8037 L 7746

1. 7420

1. 7145

-13.23

-13. 82 -16.00

-16. 72 -16. 47 CioHieCljOi, Dimethyl di-wi- chlorobenzoyltartrate

CjoHioIjOs, Dimethyl di-m16.2 iodobenzoyltartrate

26.0

35.4

42.4

52.6

79.3 99.0

1. 3556 L 3463 L 3375 1.3307

1. 3213 1.2963

1. 2779

-92. 09 -91.00

-89. 67 -88. 61 -86.84

-81. 79 -77.58

17.8

35.

1

63.0

98.5

1. 7866

1. 7665

1. 7335

1. 6918

-80.90

-79. 18 -74.88 -67.86

t p values are in italics.
OPTICAL ROTATION OF ORGANIC SUBSTANCES 45

Rotatory dispersion of d-tartrates in aqueous solutions at 20° C. (121) KjCiHiOe-HHiO NaaC4H40e-2H2 H2C4H4O1

4.329 20.178 15.0 KjO NajO AS2O1

0.403 0.220 Sat. at B. P.

-2. 62 -14.32 34. 68 -2. 71 41.55 -2. 71 -19. 17 42. 87 -3. 71 -22.55 47. 83 -5. 52 -27. 75 54. 33 -7.24 -33. 11 60. 35 -8. 96 -35. 85 63. 02 -12. 12 -46. 14 70. 62

6,438

6,893 5,780

5,461 5,086

4,800 4,678

4,358

For further data on these and

other metallic salts of tar- taric acid see (83, 107, 113, 114, 115, 143, 144, 208, 218)

;

also the main table.

Drude's equation [jV/i]^=°

1Q_3 XiS) io-s (x2-x3 n

Solute c Moles ki kt 10-8\i2 10-SX21 Eange X

n JHiC4H<06-- 7.5 4.65

15.0 6.2

2.5

1.65

14.0 2.5

0.05

.075

.10 .10 .0167

.0167

.25 .0167

(D \HjBO» 24. 08 0. 0246 6, 708-4, 100

r2./H,C4H4 0i

(2) \H»BO,_ 25.7 1.249 ; .03 .065 6, 708-4, 046 [H|C4H40e___

(3HASl O, iKOH 20. 148 .017 6, 438-4, 259 [HiC4H40«

(4) Bi(OH)j 2. 16 1 . 0083 IKOH 14.0

37. 075

.25 37. 414

17. 117

.0645

.060

6, 438-4, 249

6, 438-3, 919

6, 438-4, 242

(5) (NRY)jC4H40« 38. 676

18. 56 .038

<„> fNaoCiHiO* 4.6 .02 .000

< w\NaOH_

-JKlClHiOl 4.7 .02 17. 298 .013 6, 438-4, 242

(/) KOH

(8) Na2C4 H40s 25. 72 41.97

41. 647

40. 255

55. 938 5.516

37.445

37. 108

41, 750

41. 108

38. 513

142. 78

18. 025

18. 348

19. 255

18. 886

18. 066

.038 .038

.038

.038

. 038

.0494

.060

.060

.060 .060

.060

6, 708-4, 005

6, 438-3, 874

6, 708-4, 046

6, 438-4, 251

6, 438-4, 055

6, 708-3, 984

(9) NaiC4H40«

(10) KsCHiO...

(11

(12) KNaC4H40..4Hj(

(13) K(SbO)C4H40t.}-

(14) {|^0)C4H40a

)... 2H2O $H2 5. 53

11.2 .0167.20 89. 48 .0627 6, 708-4, 358

Molecular rotations of the preceding solutions

6,708

(1) 55.

9

(2) 57.

8

ii ...

(6) (7)

(8) 45. 05

(9) (10) 51. 92

(11)

(12)

(13) 358.

1

(14) -229.

6,438 5,893 5,780 5,461 5,086 4,800 4,678 4,358

61.3 74.8 77.8 88.1 103.1 117.2 124.1 145.4 63.0 76.7 79.9 90.6 105.9 120.5 128. 1 150.2 51.0 63.3 72.2 83.8 95.5 99.0 114.9 -106.4 -132.2 -138.8 -159.9 -192.6 -225.5 -243. 4 -298. 4 54.24 65. 43 63. 05 76. 77 89. 10 100. 51 106. 11 122.83 43.6 55.5 62.4 71.7 80.5 84.0 98.7

42.7 53.9 61.4 70.8 79.4 84.0 97.3 49.00 58. 45 60. 55 68.23 79.65 89. 36 94.51 107. 74 47.04 56. 10 58. 35 65. 58 75.88 85.04 89. 99 103.04

56.51 67.96 70. 81 79. 61 92.39 104.06 109. 63 126. 61 55.79 67.20 69. 86 78.69 91.26 102. 81 108. 68 125.22 51.49 61. 72 64.29 72. 16 83. 72 94.41 99.44 114. 45 389.9 481.0 500. 45 573.7 682.2 789.2 842.5 1, 015. 8 -253.8 -313.

7

-330.05 -380.

4

-457.8 -534. 3 -574.

3

-702. 67316°—32 4
46 BUREAU OF STANDARDS

65

<£> W 03 OS tC CO

ttm

88S3S

n I ri r Slssf !1

-i i(C ++++

1

8918311

PHI**

8388888

ISSiliS

nisi

S 1

mm

mm

mmmm

8SS888

cJ ci - - <-<

»

++++ 1 I 118816

at- «

mm

urn*

mi**

mm

lilt

881838

mil*

torn

mi**

mm

Ml
OPTICAL ROTATION OF ORGANIC SUBSTANCES

CsHuOi Diethyl d-tartrate (153, 154, 155)

47

CiHjNS

C1H4O.. CsHsNS

CjH.O.. CaHiO..

C«H,eO.

C4H10O1S-—

C»HiOi.

C4H1NS

C»Hi»0

CjHioO! CjHiO

CjHiNOi....

C»H.N,Oj...

C«HiO

flsobutyl thiocyanate

\Isobutyl isothiocyanate.

1 Diethyl ketone \Methyl propyl ketone.. Diethyl carbonate

CeHrN.. C 6HioOj.

CeHijOj CtHtNOi...

C7H1O

Nil.__. fMethyl thiocyanate {.Methyl isothiocyanate. Acetaldehyde Ethyl thiocyanate. Acetone

n- Propyl alcohol. n-Butyl alcohol Isobutyl alcohol-

.

sec-Butyl alcohol. iert-Butyl alcohol.

Allyl alcohol. o-NitrophenoL.

(o-Nitroaniline.. •{m-Nitroaniline. [p-Nitroaniline.

Phenol.

Aniline Ethyl acetoacetate.

Paracetaldehyde...

[o-Nitroanisole jp-Nitroanisole Anisole

Benzyl alcohol. CrHiO... Jo-CresoL.

-Cresol.

C7H9N-.

CgHiNOt..

CsHioO....

fBe

Jo-C

\m-<

Lp-cCresol Methylaniline.

o-Toluldine...

Tn-Toluidine.. p-Toluiaine—

Ethyl methylacetoacetate

o-Nitrophenetole. Phenetole.

Diethyl sulphite Ethyl ethylsulphonate Methyl acetoacetate.

p t t t«Ji t Mi

100 7.58

60. 63 9. 87 61.40 7.95

49. 09

9. 98

17. 02

11.7

10.17 .37

10. 01 12.2 13 11.7 36.7 13.4 46 13.9

25. 06 11.9 11.5 11.3 32 12.8 36 13.0 25.0 6.73

12.04 +9.2

10. 00 5. 7 11.88 5.7

12. 13 3.5

9. 38

8. 66 7.9 43

10. 21 11.3 15.3 10.9 35.

1

12. 2 54 13. 2

25. 23 10.6 16.9 10.4 35.

1

11.7 57. 3 12. 8

50. 46 9. 40 15. 6 9.0 37.4 10.9 56. 2 12. 1

10. 59 6. 2

10. 67 -1.

11.79 10. 5 11.88 10.9 10.11 6.5

28. 27 11.95 8.6 11.2 35.3 13.2 55. 5 14. 2

49. 81 10.70 11.5 10.0 34. 2 11.9 53. 13.

1

23. 89 60.1 16. 2 81.4 16. 9 112. 2 17. 66

51. 12 56.8 14. 31 78. 2 15. 35 97.3 16.08 74.95 43. 4 12. 14 87. 3 14. 38 115.1 14, 21 89.3 1 12.0 14.4 » 11.6 1 38. 6

1 13. 5

89. 43 1 11 8 36 6 1 13.

1

48. 6

1 13. 8

90! 02 1 17! 8 34 8 1 18.0 41.6 1 18. 2

14.79 38. 5 30. 75 35. 47 52.3 30. 96 92.4 26. 85

23. 85 34.2 53. 5 29. 55 96. 9 25. 7 130.4 23. 65 48.2 23.94 65.2 22. 62 92. 3 21. 83 140. 6 20. 54

64. 78 17. 05 64.9 18. 38 100. 3 18. 78 126 18. 52 74 39 13. 82 53. 5 15. 60 76 5 16. 38 89.7 16. 76

79! 24 12! 37 55.5 14. 62 87.1 15. 90 117.2 16.62 7.66 37.7 34.7 36.5 59. 3 34.2 70.7 33.3

23. 98 35.2 38.

1

33. 6 55. 6 31.3 81. 8 29. 5

66. 29 21.3 43.2 21.8 75.2 20. 8 86.

1

20. 6

10. 47 8.9 14 8.0 51 11.7 71.5 13.

1

25. 08 8.

1

14 7.5 40. 5 10.0 50.5 10.8

50. 19 7.7 15.2 7.1 43.1 10.0 54. 2 10. 9

49. 99 3. 93 33.1 6.2 57 9.

1

67.5 10.0

9. 79 30.6 34.5 29.5 53.2 28. 3 62.8 27.7

21. 17 25.3 29.1 25.4 39.3 25.1 55.8 24.8

53. 84 12.5 35.1 13. 63 44.4 14.23 57.6 14. 91

9. 99 4.5 27.3 5. 34 35.2 6. 25

24. 62 6.8 33.2 8.20 52.9 10.15 "72." 8" "12.11

49. 85 8.1 30.6 9. 12 10.0 28.0 46.9 26.1 23.38 26.2 45.1 25.2 75.6 23.9 101.1 23.0

9. 61 33.2 9.64 42.6

9. 59 46.9

9. 94 23. 6 31.

7

23 1 49.8 22.8 65.0 22.5

30! 89 17! 6 19! 4 1L 5 15.7 17.3 15.3 17.3

10. 93 30.5 38.2 29.4 47.4 28.3

25. 10 27.4 45.7 25.7 58.0 25.2

50.3 21.1 34.6 20.7 60.5 20.4

11.66 48.5 29.7 46.1 43.2 42.2

24. 96 42.4 32.9 39.4 48.0 36.4 64.3 33.9

24. 92 42.3 35.7 39.4 46.8 37.7 67.8 33.6 49.98 31.4 34.7 29.8 46.3 28.6 58.2 27.5

10.23 8.5 13 7.8 30 9.5 41 10.5

25. 09 19.2 30.6 19.7 53.3 20.4 65.5 20.6 39.43 15.75 29.1 16.27 42.0 17.06

9. 99 +7. 75 27.1 8. 41 36.5 9.58

24. 96 +7. 32 31.6 8.79 43.5 10. 14 50.5 10.92 51.73 6.86 31.0 8.05 18.2 6.72

1 See footnote at end of table.
48 BUREAU OF STANDARDS

Cs HuOs Diethyl d-tartrate (153, 154, 155) —Continued

• P MS 1 [<*lb t t 1*)'d C8H8 2 CgHioO

Phenyl acetate- ^-Phenyiethyl alcohol24. 96

26. 30 15.28

1 4.48 28.2

27. 8

1 5. 33

1 4. 52 39.3

40. 7

1 5.40

1 4. 55 44.4 1 5. 37 C8 HioO

[o-Cresol methyl ether

<77i-Cresol methyl ether

Ip-Cresol methyl ether

10.06 1 8.8

10.17 10.04

/ 9.4

I 24.84

9. 02

9.38

62. 93

62. 96

\ 10.28

{ 25.17

I 50.31

24. 89

24.83

20. 78

10. 80

24. 84

4.9

7.0 4.2

5.1

10. 14.0

6. 72

4. 86

8.8 8.0

6. 83 14.68

1 3.63

1 2. 26 4.0

1 3.07

CgHuO*

C8Hi403 .

C0H10O3

Dimethylaniline - [Ethyl C-acetylacetoace1 tate .

26. 6 30.9

5. 6 6.6

43. 47.3

7. 7 8.533. 9 50.9

6. 6 9.4

J Ethyl O-acetylacetoacel tate. Ethyl ethylacetoacetate... Ethyl /8-ethoxycrotonate_ - Ethyl dimethylacetoaceBenzyl acetate

1 1 Q 11. V 13.2

12.6 31.8

28.7

13.0

8.2

7.1 6.5 14.72

35.8 38.4 32.2

43.7

10.1 9.8

8.7 M. 75

1 3. 87

1 2. 57

57.1 51.0

51.7

11.3 10.5

14. 82 C9H12O fy-Phenylpropyl alcohol. 1 3. 73

12. 18 42.0 36.3 C0H20O4

\ Benzyl ethyl ether Ethyl orthocarbonate

42.5 1 2.83 ChHhO Dibenzyl ether 16.4 3.0 32.2 13.35 40.9 13. 54

1 These are values of a L for 10-cm tubes; the specific rotations are not given by the author.

ICi. THE MOLECULE CONTAINS 1 ASYMMETRIC CARBON ATOM

ATTACHED TO 3 OTHER CARBON ATOMS

5. CITRONELLAL DERIVATIVES

Derivatives of citronellal (187; cf. 188, 196) [ a ]^

6,563 5,893 5,270 4,861

C11H20 C12H22

C13H24

C13H22 C18H28

C16H22

C16H24

C17H24

C18H26

2, 6-Dimethyl-A2

. 7 -nonadiene

2, 6-Dimethyl-A2 . 7 -decadiene -8. 12 -10. 37 -6.64 -6.68

-12.29 -16. 17

2, 6-Dimethyl-A2 s -undecadiene.-. . -5.22 -7. 98 -10. 55

2, 6-Dimethyl-A -16. 92 2 ' 8 . ^-undecatriene- . 2. fi-Dimethvl-A*. 8-octadiene-8-ovolohe,xane . _ -7. 87 -5. 03 -48.07

-10. 12 -6.40

-63.24

-7. 26 -3. 33

-12.34

-7. 65

2, 6-Dimethyl-A3 . -77. 35 7 -octadiene-8-benzene

2, 6-Dimethvl-A2-octene-8-benzene.- . -.. -108. 10

2, 6-Dimethyl-A2 . ?-nonadiene-9-benzene - - . 2, 6-Dimethyl-A2 . 8-decadiene-10-benzene -4.54 -5. 76 -6.84 -8.90

6. AMYLACETONE DERIVATIVES

Derivatives of amylacetone [a]

2x

° (204)

p=10

CgHieO I- Amylacetone. 1 C10H18O2 Acetyl-/.-amylacetone C11H20 O3 Ethyl Z-amylacetoacetate C15H20 O Benzylidene-/-amylacetone

C15H20O2 BenzoyW-amylacetone

C16H22O2 Anisylidene-^-amylacetone

T4 #

6,563 5,893 5,270 4,861 [M]z>

6.41 8.20 9. 52 12. 42 10.49 CsHe 5.4 7.34 8.5 12.5 9.4 EtOH 6.2 8.0 9.0 13.0 10.3 7.54 9.80 11.65 15. 78 16.66 CeHg 6. 12 8.0 9.5 14.0 14.1 10.62 13.66 16.23 21. 72 27.32 C«H6 10.4 14.1 16.7 23.7 28.2 C6 H« 7.8 10.8 12.2 20.0 23.3 7.28 9.41 11.34 15. 72 21.83 CsHe 5.1 6.0 8. 11 11.94 15.9 NaOH 6.4 8.93 10.6 15.05 20.7 CeHe 5.9 8.62 10. 52 16.6 21.2

1 These derivatives of i-amyl alcohol are dextrorotatory.
OPTICAL ROTATION OF ORGANIC SUBSTANCES 49

IV. Class II. ORGANIC SUBSTANCES, AT LEAST ONE

ASYMMETRIC CARBON ATOM OF WHICH FORMS

PART OF A RING

II B. THE MOLECULE CONTAINS ASYMMETRIC CARBON ATOMS

ATTACHED TO 2 OTHER CARBON ATOMS

7. TETRAHYDRONAPHTHOL AND DERIVATIVES

Specific rotation [a]

fx of d- and l-ac-tetrahydro-fi-naphthol and derivatives (103)

C10H12O d-ac-tetrahydro- C15H20O2 i-ac-tetrahydro-/3-

t 8-naphthol naphtbyl n-valerate

w.!mi M4JM

20 75.68 90. 26 162. 16 -46. 80 -56. 23 -99. 97 40 71.85 86. 72 155. 51 -45. 77 -55. 34 -98. 40 60 68. 35 82. 62 148. 98 -44. 71 -54. 43 -96. 74 80 65. 36 79. 16 142. 05 -43. 62 -53. 50 -95. 13 100 62. 56 75. 39 135. 65 -42. 48 -52. 52 -93. 40

120 59. 94 72. 33 130. 13 -41.30 -51. 54 -91. 60

140 57. 50 69. 82 125. 88 -40. 05 -50. 56 -89. 80 160 55. 26 67. 36 121.04 -38. 79 -49. 53 -87. 96

180 52. 96 64. 66 116. 10 -37. 43 -48. 45 -85. 95 200 50.86 62. 47 112. 15

s e

C10H20O d-ac-tetrahydro-0-naphthol

Py..... EtOH.. CHCU. CSi—

.

C«H«.._

5. 0815

5. 1565

4. 9840

5. 1030

4. 8265

75. 97

75. 56

67. 32 62.30

61. 50

91.54

90.88

80.71

75. 13 73.98

164.6

161.4

143.2 134.3

131.6 CisHuOiNa Sodium /-<zc-tetrahydro-/9-napthyl phthalate

HjO... EtOH..

[ 0.5117

I 1. 0332

I 1. 5280

I 1. 9660

.9423

±0°

±0°

-1.24 -2.54

-18. 05

0.87

.75 -1.02

-2.71

-21.59

5. 65

4. 84

1. 10 -2. 49 -34. 26

s e Moss

C1SH20O2 /-ac-tetrahydro-/S-napthyl rz-valerate CHCUEtOH..

CSi

4. 9355

5. 0335

4, 1395

5. 1460

-41.01

-41.21

-53. 63 -63. 86

-49. 57 -49. 45 -64. 63 -77. 36

-87. 34 -88. 49 -115.

1

-140.

CisHie04 /-etc-tetrahydro-.8-naphthyl hydrogen

phthalate Py.—

EtOH..

CHCls- C«He—

5. 2985

4. 9150

5. 1060

2. 2115

-15. 87 -9. 72 -13. 71 -27. 54

-19. 99 -11.28

-17. 27 -33. 30

-34. 23 -17. 11 -29. 40 -59. 61 CigHia04 d-o c-tetrahydro-/5-napthyl hydrogen

phthalate CHCU...

I 1. 0718 13. 57 16.03 28.84
50 BUREAU OF STANDARDS

8. AMINES

C10HmNj Nicotine (97)

t < i4i

20.0

29.5 41.5 52.0

1. 0093

1. 0017 .9924 .9840

168. 20

168. 71 169.09

169. 51 62.0 86^4

92.0

.9760

.9699

.9567

.9521

169. 74

169. 94

169. 73

169. 71 s=HjO

20.0 85.0

20.0 90.0

20.0

V

6.638

6.638

88. 338

88. 338

89. 471

76. 82 95.29

134. 16 160.34

138. 73 20.0

20.0

20.0

20.0

20.0

81.842

69. 202

60. 773

50. 134 40.237

12L48

100.47 94.02

89.03

85.09 20.0

20.0

20.0

20.0

30. 973

20.726

10. 012 2.505

82. 48 80.06

78. 66

83. 15 s= CHONHj (231)

V <» MS

100 -163.9

61. 54

38. 33

17. 80 It 32

1.0610

1. 0889

1. 1139

1. 1220

-122. 65 -102.38

-82. 77 -73. 74 s-CjHiBrj (231)

58. 12 36.29

17. 42 10.14

1. 3009

1. 5310

1. 8098

1. 9467

-172. 64 -176. 55 -179. 31 -179. 90
OPTICAL ROTATION OF ORGANIC SUBSTANCES

Specific rotation [a]x of nicotine at various temperatures (135)

51

t M4,800

t M 5,893

22.3 81.5251. 81

223. 67 22.7 -71.5

149. 97

135. 02

[a] 5, 086 —82.

1

131 7Q 101. to

22.4 81.5216. 08

191. 27 -89.0 129. 40

[ a] 5,461 M 6, 438

22.4 180.7 22.5 121. 38 5.0 -5.0

179.40

178.20 -71.2

-80.7

109. 51

106. 98 -15.0 176. 90

[<>>] 6, 708 -30.0

-45.0

-72.5

-81.5

-89.7

174.42

171.54

162. 85

159. 24

156. 61

22.5 -72.2

-81.6

110. 43

99. 23 96.98

Specific rotation [a]? of derivatives of l-tetrahydroquinaldine (177; cf. 108)

Benzoyl CnHnNO

o-Nitrobenzoyl CnHuNiOi

e 5,893 6, 780 5,461 c 5, 893 5,780 5,461

1.6890

1. 3396

1. 3285

1. 3309

326.7

246.7

318.1 364.5

342.2

258.3

333.3 382.8

397.3

299.9 389.0

445.2

1. 8332

1. 7644

2. 1108

1. 8484

17.11 -58. 5 9.60

30.

13.4 -66.8

4.5

27.5

-2. 05 -99. -12. 4 +14. 5

rn-Nitrobenzoyl CnHuNjO,p-Nitrobenzoyl CnHuNjOt

1. 7303

1. 6752

1. 7930

1. 7456

241.6 229.6

250.7 250.2

252.8

241.4

262.9 263.4

292.6

278.8 306.5

306.5

1. 3376

1. 3317

1. 3317 1.3402

369.9

320.7 353.0 379.6

388.2

337.9 371.7

401.8

459.2

396.5

440.1 473.9

p-Toluyl C18H„NOToluene- p-sulphonyl C17H19NO2S

1. 3369

1. 3333

1. 3426

1. 3472

333.2

251.5 323.6 370.7

347.2

264.4 338.9

388.6

404.5

305.5 393.7

452.0

1. 3207

1. 3029

1. 3349

1. 3179

-137.2

-134.2

-128. 8 -122.0

-143.

1

-141.9

-135.2

-127.

-163.9

-162.

7

-155.1 -145.9

Nitrobenzene-m-sulphonyl CibHuNsC^S2-Nitrotoluene-4-sulphonyl Ci7Hi$NjO*S

0. 7770

1.4096

1. 1664 1.5098

-85.2

-124.2

-100.7 -96.9

-91.7

-130.0

-107.2 -101.9

-103.3

-148.3 -123.9 -116.9

0. 6781

1. 3212

1. 2585

1. 2909

-48.7 -21.2

-53.1

-27.1

-49.8

-20.4

-54.4

-28.1

-54.0

-18.9 -60.8

-30.0

EtOH.

C.He.. MeaCO

AcOH.

EtOH.

C,H6 _. Me2 CO

AcOH.

EtOH.

C«H9 .. Me2 CO

AcOH.

EtOH. C9H6 .. MejCO

AcOH.
52 BUREAU OF STANDARDS

Specific rotation [a]TM of derivatives of l-tetrahydroquinaldine (177; cf. 108) —Con.

a-Naphthoyl

CuHhNO

EtOH.

CbHb... MejCO

AcOH.

EtOH.

C.H«... Me2 CO

AcOH.

5, 893

1. 3336

1.3192

1. 3479

1. 3342

359.9

338.5

385.8 397.2

5, 780

416.2

354.9

406.6

420.3

5, 461

490.0

421.7 478.0

491.9

Naphthalene-a-sulphonyl C20Hi»NOiS

0. 7949

1. 3465

1. 6371

1. 3596

103.8 75.0 90.9 89.0110.0 80.7 94.7

95.1

134.9 98.4

114.5 114.7

0-Napthoyl C«HiiXO

5, 893 5, 780

0. 3562

2. 0434

.3376

2. 0334

339.3 359.5

256.1 i 268.8 330.3 i 347.3 374.0 ! 393.8

5,461

415.5

311.5

405.1 457.2

Naphthalene-/3-sulphonyl CmHuNOjS

1. 2570

1. 3303 -225.0 -237.3 -231.7 -243.

1

-216.9 -227.

1

, -206.5 -216.5

-276.

1

-284.3 -264.4

-252.5

Specific rotation [a]x° °f tetrahydroquinaldinomethylene camphors,1 CnHtiNO

C21H27NO 5, 893 5, 780 5, 461 4,482 4,359

d-T-d-CK

d-T-d-C

d-T-d-C (A). ... d-T-d-C

/-T-/-C d-T-i-C

d-T-l-C

d-T-/-C (B)

J-T-d-C i-T-d-C d-T-dl-C d-T-di-C (C)._.

l-T-dl-C d/-T-d-C

dl-T-l-C

dl-T-l-C (D)-..

EtOH

EtOH

AcOH

AcOH

EtOH

EtOH

EtOH

AcOH

EtOH

EtOH

EtOH

AcOH

EtOH

EtOH

EtOH

AcOH

0. 1114 .5020

. 1052 .5009

.1108

. 1030 .5017 .1535

.1109

.5008

. 1016 .1062

. 1006

. 1066

. 1016 .1018

-133

-133

-95.5 -142 +134

-627

-734

-671 +741 +734

-440

-384 +444

+307

-307

-300

-145

-143

-105

-153 +144

-667 -780

-715 +787 +780

-475 -412

+471 +326

-326

-318

+182

-803

-945 +951

+945

-577

-504 +574

+391 -390

-598 M. P. =81. 0°

M. P. = 81. 0° M. P. =111. 5°

+1, 946 M. P. +2, 519 111.5° -1. 575 M. P. =83. 5° M. P. = 113. 0°

-975 M. P. = 113. C

1 T and C represent, respectively, the tetrahydroquinaldinomethylene, CuHuN, and the camphor, CioHhO, radicals. Note.—Tetrahydroquinaldinomethylene camphors exhibit mutarotation in acetic acid solution. All observations recorded in the above table were made after mutarotation was complete. Mutarotation of the (A), (B), (C), and (D) substances in the preceding table is given below:

Time

(in hours)

(A) (B) (C) (D)

erj,46i Vi— Vi—

2Y2— 6H—

24

-2. 54 -2.00

-1. 91

-19. 60 -18. 25 -17. 88 -17. 77

-8. 15 -7. 39 -7. 25 -7.20

-7. 13

-5.44

-5.34

-5. 26 -5. 18 48.... -1.91 Data for other smaller concentrations given in the original paper; influence of concentration is negligible.
OPTICAL ROTATION OF ORGANIC SUBSTANCES 53

Salts and derivatives of hydroxyhydrindamine (173; cf. 172) B = l-hydroxy-2-hydrindamine. A=a-bromocamphor-T-sulphonic acid. A'=camphor-/3-sulphonic acid.

Substance X W 5,461 \ 5, 893 5,780 5, 461 5,461

1. 510 -45. 2 -47.7 -56.3 -274

.413 —30.9 -32.7 -40.6 -198

1. 592 +68.3 71.9 84.5 389

.779 +76.7 81.2 95.3 439

1. 382 +31. 7 33.

1

38. 5 147

. 686 +69.2 73.2 85. 2 325

2. 271 -2.5 —2.4 —1.5 -5.9

. 801 -6.5 -6.5 -7.2 -27.3 -5.3 -5.6 -6.2 -23.7

1 103 +22.9 24.3 27.9 41. 6 L 053 +275 289 334 498

.518 +39.1 41.1 47.3 70.6 .642 +32.3 33.9 38.9 72.2

.606 -32.2 -33.8 -38.8 -72.0

.502 -26.4 -27.4 -31.9 -73.3

1. 345 +29.2 30.7 35.3 70.0

.344 +33.4 34.9 40.7 80.6

.718 -27.8 -29.2 -33.8 -71.6

.341 -52.1 -56. 5 -65.3 -138

.319 +30 7 33.

1

38. 68.4 1.200 +ie!o 17! 3 19! 4 68.6

. 432

!432 +3.5 +2.9 ±0.0 ±0.0

.432 —2. 9 —4.

1

—8.

1

-31.0

. 432 -4! 6 -5! 8 -10. 4 —39.

. 6S2 +28.2 30.1 34.5 72! 1 .690 +169 177.0 203 425! .473 -22.2 -23.2 -26.9 -73.0

.486 -122 -128 -148 -401

.455 -21.4 -22.0 -25.3 -73

.582 .582 -61. -63. 5 -73.8 -212

.582 -31.8 -34.3 -39.9 -115

.258 -58.

1

-60. 1 -68.8 -174

. 355 +90. 1 95.7 111. +262

. 386 -4.5 -4.5 -4.5 -8.7

.422 +59. 2 +61.6 +71.7 +138

d-B-l-A 1 (After 98 hours)' d-B-d-A

d-B-d-A'

/-B-d-A'

(30 minutes) *. (48 hours) d-B

(122 hours). ... (104 hours) ... d-B-HCl

f-B-HCl /-B-HBr

d-B-1/2 (HjSOi) —

(17 hours) *-.. -B-HNO3

(19 hours)*-...

d-B-1/2 (H2CO3)-

d-B-1/2 (HjPtCle). d-B picrate

(30 minutes) *. (19 hours)*...

(43 hours)*... d-B acetate

(96 hours)*...

/-B benzoate*.-.

(107 hours)*

H3 MeaCO

/H2 \Me2 CO (95 per cent). /H2 \MeaCO

HjO MeaCO

MeaCO

l-B salicylate* _. (30 minutes)*_

(378 hours)* CisHisNOa I- l-hydroxy-2-benzo- ylhydrindamine

Ci«Hi5 NO d-l-hydroxy-2-benzyl- idenehydrindamine

C10H12N2O2 d-l-hydroxy-2-carba- midohydrindene

H3 MeaCO EtOH

H2O H2 HaO HjO

MeaC O (70 per cent)

.

H3 MeaCO (98 per cent). HaO

HaO MeaCO MeaCO

MeaCO

MeaCO

HaO MeaCO H2 MeaCO

/H2 \MejCO

Me2 CO

MeaCO

MeaCO. EtOH

/AcOH

\HC1 (cone).

CaHiaNaO.

CioHiaN3 2

M-Hydroxy-2-hydrazinohydrindene (156)

.

M-Hydroxy-2-semicarbazlnohydrindene.. HaO 0. 375 EtOH 0.510

5, 893

5, 780

5, 461

5, 461

•14.0 17.6

•22.0

•14.7 Note.—Solutions marked with an asterisk (*) exhibit mutarotation, the final rotation being given for each substance. The form of the rotation-time curve is not simple and a maximum is observed in some

cases. Thus the rotations for the dextro-base (ah,m) in acetone are: 30 minutes 14.03

34 minutes 14.23

38 minutes 14.40

42 minutes 14. 51 55 minutes _ 14. 65

70 minutes 14. 71

100 minutes 14.73

190 minutes 14.69

6 hours... 14.60

23 hours 14.34

122 hours 14.07 240 hours... 14.07

II B3

(172) M?

Ci8H)tN02 Dihydroxydihydrindamine s I 5,893 5,780 5,461 5,461

/ hydrochloride. -{h2

l 0. 330

1 2. 007

1 .346 .503

83.3

81.3 -83.2

46.3

86.4

84.4 -86.1

47.2

100.0

98.1 -99.8

55.7

+28i

276 +28i

2 27,

d hydrochloride..- HaO

d-chloroplatinate EtOH—

Name s e Hi Lit. CnHajNOj. d-Hyoscyamine 50 per cent E

50 per cent E CHCls tOH 4.0

2. 165 4.0

21.0 -25.8

-23.7

(29)

(17) (29)

f =room temperature.

/-Hyoscyamine tOH

1 Concentration calculated on free base.

» Molecular rotatory power calculated on one equivalent of base.
54 BUREAU OF STANDARDS

IIC. THE MOLECULE CONTAINS ASYMMETRIC CARBON ATOMS

ATTACHED EACH TO 3 OTHER CARBON ATOMS

9. METHYLCYCLOHEXANE DERIVATIVES (158) CgHnBrClj d-4-Chloro-l-methyl-4-chlorobromomethylcyclohexane

8 c

j X. 4,359 5,780 5,893 EtOH 3.21 17.0 0.39 0.35 0.35 C»HuBr d-l-Methyl-4-bromomethylenecyclohexane 1

Ligroin - 9.01 3.05

16.0

16.0 -59. 37 -52. 34 -62.24 ! -55.38

-50.39 EtOH -5a 40

M-Methyl-4-bromomethylenecycloheiane 1

9. 17 16.0 59.11 52.17 sa is CsHuBrO: M-Methylcycloheiylidene-4-bromoacetic acid 1

EtOH { £g

19.0

16.0 -12.4 -12.1 -11.0

-10.6

-10.4

-10.3 CjHijBrChOi /-4-Chloro-l-methylcycloheiyl-4-chlorobromoacetic acid EtOH. 3. 79 17.0 -1.32 •1.05

C»Hi«BrjOj d-/3-Dibromo-l-methylcyclohexyl-4-acetic acid L 59 16.0 2.3 2.0 2.4

f 1.37 17.0 29.0 25.1 24.3 CeHi \ 1.50 17.0 29.6 25.6 -24.3

{ 2.70 17.0 28.2 24.5 23.8 CjHuBrjOi /-/5-Dibromo-l-methylcyc]ohexyl-4-acetic acid EtOAc.

C«H«...

3.29 L 49

3. 01

16.0 -2.3

16.0 -29.2

16.0 -28.2 -1.9

-25.2

-24.7 -2.3

-24.5

-23.9 CjHuBrjOj Z-a-Dibromo-l-methylcyclobexyl-4-acetic acid

\ 1.51 16.0 10.3 9.3 8.6 CeHs { 3.05 16.0 9.5 8.4 7.6

I 3.00 16.0 4.9 4.3 3.9

C9H14O3 d-l-Methylcycloheiylidene-4-acetic acid 1

EtOH. 18.0 95.8 83.7 81.1

1 These compounds are centroasymmetric.

* The rotatory powers of the a-dibromides are opposite in sign to those of the parent acids.
OPTICAL ROTATION OF ORGANIC SUBSTANCES 55

10. DIMETHYLTETRAHYDROQUINOLINE AND DERIVATIVES

CnHisN 2, 4-DIMETHYLTETRAHYDROQUINOLINE (216)

1

i ML t d

to"

*

d-..

/-d-Iso-

/-ISO20

20

15

15

1.0009

1.00078

1.0044

1.0063

60. 13 -57. 24

18. 23 -18.03

97.1 -92. 15

29. 52 -29. 05

C18H19NO Benzoyl-d-compound

00go

00

00

00000000

00000000

0. 678

1. 211 .501

1. 124 .418

1. 162 .426

.822 .392

.768

.494 .814

-312.5

-313. 7 -379. 7 -378. 9 -374. 5 -377.

-373. 6 -378.

1

-397. 7 -392. 8 -418. 2 -420. 6

-828.

-831. -1,006.0 -1,004.0

-992.

-999. -990. -1,002.0

-1, 054. -1, 041. -1, 109.0 -1, 114.0

C6H(

EtOH

MejCO

CHCls

s d- Compound

EtOH r is

1 18

1. 473

3. 675

57.0

56.7 91.8

91.3 AcOEt AeOH

/-Compound

EtOH f 18

1 18 1.270

2. 625 -56.2 -56.0

-90.6 -90.2 Benzoyl-i-compound

d-Iso- Compound CH». EtOH

AcOH

f 19

19

I 1918

19

19

0.486 .395

.809 .363

.356 .182

314. 1 314.7

313. 5 377.6

420. 401.7

832.3

833.7

830.3

1,000.6

1, 113.

1, 063. EtOH f 17

I 17

2. 102 2.76818.5

18.5

29.7 29.7 EtOAc

Mao-Compound Benzoyl-Z-iso-compound EtOH 18 0.0 0.0 EtOH r is

1 18

0. 951 2.548 -17.6 -17.9

-28.2

-28.8 C2 iH3oBrNO«S d-2, 4-Dimethyltetrahydroquinoline d-a-bromocamphor-x-sulphonate CnHuClN d-Hydrochloride H,0

f 18

J 18

1 18

I 18

0. 416

.821

1. 236

1. 640

86.2

84.9 85.0

86.5

407.0 401.0

401.0 408.0 HjO f 18

1 18

19

0. 462

.908 .422

84.4

83.1 91.4

167.0

164.5 EtOH 181.0

/-Hydrochloride d-/so-/-compound H2

f 18

1818

i 18

1. 286

1. 341 .886

.456

-55. 2 -54.8 -55.4 -55.5

-261.

-259. -262.

-262. H2 f 18

I 18

1 18

0.583

.891 .541 .146

-81.5

-80.8 -91.4

-93.2

-161. 2 -159. 8 -180. 5 -184. 5 EtOH

/-/-compound

d-7so-Hydrochloride HiO f 1818

I 18

0.450

.854

1. 913

-85.5

-86.1 -84.7

-404.0

-407. -400. H,0 18 1.085 5.1 10.1

Wso-Hydrochloride /-/so-d-compound HjO 18 1.505 -5.1 -10.1 HjO 18 1, 034 55.7 263.0
56 BUREAU OF STANDARDS

11. MYRTENOL ESTERS

(188) Esters of myrtenol [a]*

Formula Name 6,563 5,893 5,463 4,861 CioHuO Myrtenol 36.83 46. 49

40. 97

34. 13

36. 97 30.30

55.04 48.66

40.51 43.96

35.96

71.81

63. 75 53.01

57. 36

47. 13

C14H20O2 Myrtenyl crotonate . 32. 39 26.99

29.25

23. 95

C14H22O2 Mvrtenyl butyrate ... CieH2 202 C16H26O2 Myrtenyl A1 - 1 pentadiene-a-carboxylate__ Myrtenyl 7i -hexoate . C17H20O2 Myrtenyl benzoate ... .. 29. 01 20.31

20. 77

36. 67 25.68

26. 30

43.51

30. 35 31.22

56.90

39. 42 40.81 CisHjjOj Myrtenyl phenylacetate._ ....

C19H24O2 Myrtenyl /3-phenylpropionate... _. .

12. MENTHONE

Specific rotation [a]x °f menthone C^H^O at different temperatures (104)

t N.

5,863 5,780 5,461 4,358 \ 5,893 5,780 5,461 4,358

20 -26. 74 -27.84 -32. 07 -57. 15 120 -31.41 -32.88 -38.18 -71. 83

40 -27. 60 -28. 89 -33. 29 -59.92 140 -31. 63 -33. 13 -38.63 -72. 13 60 -28. 36 -29. 79 -34. 38 -62. 61 160 -31. 48 -33.06 -38. 43 -71.48

80 -29. 32 -30. 67 -35. 48 -65. 55 180 -31.77 -33.09 -38. 37 -71.52

100 -30. 43 -31. 77 -36. 82 -68.84 Anomalous rotatory dispersion of mixtures of CiqH^O I- and

d-menthone (36; cf. 13, 19, 20, 21, 69)

/-Menthone Vd-Menthone V ?

6,563 5,893 5,270 4,861

100 -22.44 -28. 84 -37. 75 -46. 47 100 19. 33 26. 83 38. 66 52. 45 46.29 53. 71 .085 1.00 3.04 6. 03 40.21 59. 79 2. 37 4. 05 7. 22 11.43 51.76

59.24

48. 24

40. 76 -1. 94 -4. 73 -1. 70 -.69 L 18 -5.41 -5. 77 -5.41
OPTICAL ROTATION OF ORGANIC SUBSTANCES 57

IICB. THE MOLECULE CONTAINS 2 OR MORE ASYMMETRIC ATOMS

ATTACHED RESPECTIVELY TO 2 AND 3 OTHER CARBON ATOMS

13. MENTHOL, ISOPULEGOL, AND DERIVATIVES

C10 H20 O I- Menthol [a]g (68) N, Phenol Eugenol \s- Pheno! Eugenol p\ C5H5OH CioHu02 CeHsOH CioHi2 3 \ \

10 -48. 96 35 -46. 51 -47. 84

15 -48. 52 40 -46. 44 -47. 73 25 -47. 16 -48. 13 45 -46. 39 -47. 63

30 -46. 74 -47. 98 50 -46. 36 -47. 56 CvH23 NOi l-Menthyl o-nitrobenzoate (49)

t d< Mi,

100 1. 050 -121. 2 p-Ester

80 1.058 -125.0

70 1.073 -124.6

65 1.078 -124.8 100 1.045 -75. 48

80 1.058 -76. 21 70 1. 070 -76.54

771-Ester 65 1. 077 -76. 94

100 1.049 -82.04

80 1.056 -82. 92

70 1. 071 -82. 54 65 1. 081 -82. 06 40 1.097 -82. 17 20 1. 118 -82. 52
58 BUREAU OF STANDARDS

Specific rotation \a\ of menthol and related compounds at different temperatures

(104)

5,893 5, 780 5,461 4,358 5, 893 5,780 5, 461 4,358 CioHmO /-Menthol CioHnN /-Menthylamine

2040

60 - 80 — -

100.

140 160

180

20

40.... 60

80

100

120

-48. 96 -49. 55 -50. 02 -49. 97 -49. 48 -48. 78 -48. 15 -47. 58 -47.09

-51. 39 -52. 10 -52. 34 -52.06 -5L53

-50. 94 -50. 34 -49. 76 -49. 09

-57. 90 -58. 80 -59. 30 -58. 95 -58. 21 -57. 48 -56. 78 -56. 14 -55. 59

-96. 61 -97.61

-98. 15 -97. 97 -97. 03 -95. 82 -94.66

-93.46 -92.04

-39. 97 -40.81

-41. 52 -42. 14 -42. 76 -43. 40 -44. 01 -44. 61 -45. 02

-41.63

-42. 51 -43.24 -43.%

-44.62

-45. 21 -45. 75 -46.20

-46. 69

-47.04

-48. 07 -48.88

-49.58

-50.27

-51. 01 -5L69

-52. 32 -52. 81

-76.40

-78.03

-79.47

-80.85 -82.22

-83.75 -85.09

-86. 52 -87. 78 CuH2jOj /-Menthyl acetate C17H23NO4 /-Menthyl o-nitroben- zoate -79.41

-79. 20 -78. 98 -78.89

-78. 57 -78. 34 -78. 11 -77. 89 -77. 62

-83. 01 -82. 73 -82. 47 -82. 31 -81. 98 -81. 74 -81. 51 -81.26

-81. 00

-94. 12 -93. 58 -93. 50 -93.28

-92. 90 -92.64

-92. 34 -92.04

-91. 70

-156.1

-155.7 -155.2

-155.1 -154.4

-153.9

-128.7

-126.1 -123.6

-121. 2 -119.0

-117.3

-136.4

-133.8 -131.0

-128.1 -125.2 -123.4

-161.3

-157.9

-154.4 -151.0

-147.6 -145.5

-143.9

-142.

1

-140. 2

-38L9

-372.7 -362.9

-352.4 -34L8

140 -153.4 -152.9

-152.4

-115.9 -114.4 -112.9

-122.1 -120.7

-119.3

160

180

20

C17HJ3NO4 /-Menthyl m-nitrobenzoate C17HS2NO4 /-Menthyl p-nitrobenzoate -82. 52 -82. 14 -81. 70

-86.30

-85. 93 -85. 43 -84. 76 -84. 00 -83.28

-82. 59 -82.27

-82. 56

-98.44

-97. 90 -173.6 -70. 99 -70. 86 -70. 73 -70.60

-70.34

-70. 18 -69. 98 -69. 98 -67. 33

-73.98

-73.91 -73.72

-73. 57 -73.40

-73. 16 -73.05

-71.86 -70.44

-83.33

-83.45 -83.28 -83.12

-82.83

-82.59

-82. 47 -81.64 -79.50

4060 -97.25

-96. 44 -95. 72 -94. 95 -94. 18 -93. 66 -93. 65

80 -81. 06 -80. 39 -79.68

-78. 93 -78. 42

100

120

140 160

180 -78. 70

20.. 40..

60..

80.. 100

120,

140, 160,

Ci$HjeOj /-Menthyl phenylacetate

-68. 06

-67. 41

-66. 65

-65. 66

-64. 74

-63. 89

-62. 95

-62. 07

-61. 55

-71. 34 -70.44

-69.56

-68. 58

-67. 54

-66. 62

-65. 67

-64. 92

-64. 40

-81. 14 -80. 09 -79. 07 -77. 87 -76. 72 -75. 80 -74. 87 -73.91

-73. 02 |

-137.4

-135.6 -133.8

-131.9 -130.0

-128.1

-126.1

-123.9 -121.9

CuH2eOj /-Menthyl p-methoxybenzoate

-86.22

-87. 42

-85. 39

-83. 52 -8L64

-79. 82

-78. 03

-76.28

-74. 87

-90. 12

-90. 38

-89. 43

-87.44

-85. 31

-83. 45

-81. 68

-79. 79 -78.00

-102.6

-103.6

-101.4 -99.04

-96. 70 -94.64

-92. 47 -90.28

-88.35

-174.7

-175.7

-170.

1

-167.2 -163.2

-159. 1 -155.4

-151.9 -148.7 C52HMO4 /-Dimenthyl oxalate 19° CirEhjIOj /-Menthyl o-iodobenzoate

2040 -93.46

-93.28

-93. 11 -92. 87 -92.64

-92. 10 -91.68

-91. 11 -90. 38

-97. 61 -97. 40 -97. 21 -96. 99 -96. 61 -96. 10 -95. 43 -94. 77 -94.04

-110.4

-110.

1

-109.9

-109.6

-109.2 -108.8

-108.1

-107.4

-106.6

-182.0

-181.9

-181.5 -181.0

-180.3

-179.6 -178.9 -178.0

-177.0

-61.35

-61. 02 -64. 30 -63. 90 -73. 57 -73. 16 -130.8-130.4

60

80

100 120 140

19° C17H33IO1 /-Menthyl miodobenzoate -61.22 -63. 90 -72. 67 -12L8

160

180 19° C17H33IOJ /-Menthyl p-iodobenzoate -63. 63 -66. 50 | -75. 30 -126.7

20° CioHjsOj /-Menthyl p-allyloxybenzoate -79.76 | -83.55 -94. 14 | 164.

6
OPTICAL ROTATION OF ORGANIC SUBSTANCES

Esters of l-Isopulegol [a\ (160)

59

6, 438 5,461 5,086 4,800 4,359

20 -18.23 -25. 90 -30. 31 -34. 51 -43. 07

40 18. 61 26. 46 31. 01 35.43 44. 30

60 18. 98 27. 05 31. 74 36. 37 45. 55 80 19. 39 27. 65 32. 47 37. 35 46. 86

100 19. 83 28. 28 33. 25 38. 37 48. 22 120 20. 26 28.95 34. 08 39. 45 49. 67 140 20. 73 29. 66 34. 95 40. 57 51. 16 160 21.22 30. 38 35. 83 41. 74 52. 71 20 -9. 58 -12. 22 -13. 61 -14. 57 -15. 65 40 —11. 61 —15. 32 —17. 18 —18. 71 —21. 24

60 -13. 65 -18. 34 -20. 74 -22. 83 -26. 38 80 -15. 82 -21. 23 -24. 16 -26. 95 -31. 56 20 -16. 66 -20. 66 -23. 95 -26. 55 -29. 44

20 —8. 19 —10. 13 —11. 06 —11. 63 —12. 20 40 -10. 17 -13. 49 -14. 80 -16. 12 -17. 98

60 -12. 22 -16. 58 -18. 51 -20. 36 -23.54

80 -14. 33 -19. 63 -22. 21 -24. 68 -29. 04

20 —15. 81 —19. 64 —22. 87 —25. 08 —27. 70 20 -5.53 -6. 46 -7. 02 -6. 93 -6. 28 40 -7.78 -9. 99 -10. 98 -11.77 -12.34

60 -9. 87 -13. 32 -14. 69 -16. 13 . -18. 10 80 -11.87 -16. 24 -18. 35 -19. 88 -23. 41 100 -14. 12 -19. 39 -22. 41 -24. 65 -29. 09 120 —16. 31 —22. 40 —26. 00 —28. 77 —34. 59 140 -18. 21 -25. 54 -29. 34 -32. 96 -39. 86

160 -20. 12 -28. 60 -32. 77 -37. 20 -45. 24 20 -14. 11 -16. 50 -19. 19 -20. 67 -23.56

20 -6. 28 -7. 57 -8. 28 -8. 57 -8. 63 40 —8. 39 —10. 87 —11. 99 —12. 87 —14. 16 60 -10. 32 -13. 78 -15. 47 -17. 12 -19. 36 80 -12. 19 -16. 51 -18. 79 -20. 95 -24. 11 20 -14. 28 -16. 79 -19. 71 -21. 62 -24. 13 20 -5. 19 -5. 95 -6. 19 -6. 30 -5. 84

40 —7. 45 —9. 04 —9. 84 — 10. 46 —11. 46

60 -9. 33 -11.93 -13.31 -14. 55 -16. 66 80 -11.06 -14. 86 -16. 77 -18. 41 -21. 47 20 -11.37 -14. 36 -17. 12 -18. 79 -21. 07 20 -4. 84 -5.48 -5.76 -5. 83 -5. 50 40 —6. 71 —8. 45 —9. 44 — 10. 07 —10. 74

60 -8. 43 -11. 27 -12. 57 -13. 82 -15. 41 80 -10. 17 -13. 88 -15.68 -17.53 -20.00

20 -10. 81 -13. 82 -15. 92 -17. 12 -19. 83

20 -4. 60 -5.23 -5. 68 -5. 86 -5. 26 40 —6. 58 —7. 92 —8. 84 —9. 68 — 10. 10 60 -8. 28 -10. 52 -11.88 -13. 23 -14. 82

80 -9. 78 -13.09 -14. 84 -16. 69 -19. 07

20 -10. 30 -13.50 -15. 10 -16. 81 -19. 21 20 -4. 36 -4. 98 -5. 38 -5. 51 -4.94

40 —6. 20 —7. 64 —8. 43 —9. 22 —9. 47 60 -7.72 -10. 24 -11.39 -12. 64 -13. 94 80 -9. 20 -12. 57 -14.06 -15. 62 -18. 12 20 -10. 21 -13. 01 -14. 81 -16. 31 -18. 72 20 -4. 15 -4. 93 -5. 20 -5. 35 -5.15

40 -5. 78 -7. 52 -8. 19 -8. 71 -9. 66 60 —7. 41 —9. 75 —11. 10 —12. 23 —13. 54 80 —9. 02 —11. 92 —13. 69 — 15. 20 —17. 38

20 —9. 77 —12. 47 —14. 16 — 15. 65 —17. 55 20 —4. 31 —4. 98 —5. 29 —5. 54 —5. 54 40 -5.94 -7. 35 -8. 21 -8. 94 -9. 41 60 —7. 31 —9. 48 —10. 83 -11.82 -13. 18 80 -8. 65 -11. 48 —13. 02 -14. 52 -16.44

20 —9. 86 —11. 87 —13. 68 —15. 39 —16. 40

on g_ §4 A AO 4 gg 4_ gg ^ g5 40 -5. 35 -6. 69 -7. 60 -8^23 -8. 57 «nDU g gg —o. Co j0 24 H_ jg 12. 27 80 -8! 32 -11. 01 -12! 47 -13! 75 -15! 93 20 -9.44 -11. 90 -13. 56 -15.04 -16. 51 20 -3. 81 -4.23 -4.68 -4.84 -4.48

40 -5.30 -6. 30 -7.05 -7. 62 -8.07

60 -6.63 -8. 32 -9.38 -10. 28 -11. 44 80 -7.82 -10.33 -11. 69 -13.00 -15.02

20 -9.24 -10. 95 -12. 76 -14. 16 -15.46

Name

Msopulegol..

Msopulegyl acetate.

(a = EtOH, c = 5) Msopulegyl propionate.

(« = EtOH, c = 5).

Msopulegyl n-butyrate.

(«=EtOH, c=5) Msopulegyl n-valerate .

.

(* = EtOH, c=5) Msopulegyl caproate...

(*=EtOH, c=5) Msopulegyl enanthate.

.

(« = EtOH, c=5) Msopulegyl caprylate..

(« = EtOH, c=5). Msopulegyl pelargonate

(«=EtOH, c=5) Msopulegyl caprate

(s=EtOH, c=5) Msopulegyl undecylate.

(* = EtOH, c=5) Msopulegyl laurate (s=EtOH, c=5) Msopulegyl myristate... (*=EtOH,c=5)
60 BUREAU OF STANDARDS

Menthol and related compounds in solution [a]l (104; cf. 12, 71, 136, 185, 191)

/= approximately 20° Formula Name 5,893 5,780 5,461

C,oHi8 0.

C,oH2oO.

CnHjaOj.

CHH24O4.

Oi7Hj3 BrC102. Cl7H2 2ClN04_. C17H23CINO4-.

C17H22CINO4-

C17H22N2O8... CnB-aNjOt...

C17H22N1O8-

C17H11CIO1-

CnHjsFOj..

C17H23IO2. C17H23IO2-

C17H23IO2.

C,7 H2iN04.

C17H23NO4-

C7H24O2... C17H25NO2

(Cl8H2304)2Mg. Cl8H2304Na...

C18H24O4

C18H26O2

C18H26O2.

C20H30O3-

C20H30O3.. C2CH38O3S

.

C22H28O3-,

C22H38O4-. C5 |H29N04

/-Menthone.

(C.He.. <EtOH.

ICS2--- /-MenthoL

/-Menthyl acetate.

(EtOH.

\CSu-.

/CS3 --- \EtOH.

/-Menthyl hydrogen suc- cinate (Cf. 12). /-Menthyl 2-chloro-6-bro- mobenzoate. /-Menthyl 4-chloro-2-nitro- benzoate. /-Menthyl 4-chloro-3-nitro- benzoate. /-Menthyl 5-chloro-2-nitro- benzoate. /-Menthyl 2, 6-dinitrobenzoate. /-Menthyl 3, 5-dinitrobenzoate. /-Menthyl 2, 4-dinitrobenzoate.

/-Menthyl m-chlorobenzoate. /-Menthyl p-fluorobenzo-

/-Ment hyl o-iodobenzoate

.

/-Menthyl 7»-iodobenzoate.

/-Menthyl p-iodobenzoate.

/-Menthyl o-nitrobenzoate.

/-Menthyl m-nitrobenzoate.

/C«H6.- \CHCI3

CSj. CSj. PyfCS2--_. C,H«... ICHCh- C«H8 ... CHCh- IP" CSj..... ICHCI3- lC«H8 ..- CSi.... Py

CHCh.

EtOH.

CSj....

CflHo..- CSj. /Py-

\CSi. /AcOEt.

IC6H«... fPy—

-

CHCh

^EtOH.

CS2--

lC«H«.. /Py- ir-

/-Menthyl benzoate. /-Menthyl phenylcarbamate. Magnesium /-menthyl

phthalate. Sodium /-menthyl phthalate. /-Menthyl hydrogen

phthalate. /-Menthyl phenylacetate.. /-Menthyl ro-toluate /-Menthyl o-propoxybenzoate. /-Menthyl p-isopropoxybenzoate.

(//-/-Menthyl sulphite

CSa -.- /C 6 H6 ... \CHCI3-

CHCh.

EtOH.. H3 0.... CHCI3-

C«H«... C9H6 CS2- CsHs- EtOH.

/-Menthyl 2-methoxynaphthoate. /-Dimenthyl oxalate. Pyridinium /-menthyl

phthalate.

/CS2--

\C6H6-

!EtOH.

CSj... C6 H6 - Py—

.

Py....

5. 01

5. 49 5.47

5. 16 5.28

5.53

5. 18

5. 79 5.08

5.09

4. 77

4. 12 4.60

4.52

4. 86

5. 46

4. 72 4.64

4. 73

4. 83

4. 94 4.80

5.67

5.31

4. 84

4.73

4. 55

4. 82

5. 17 5.28

6. 19 6.06

5.71 5.07

5. 15

4. 92

5. 57

4. 19 5.87

7.11 5.20

5. 18 4.96

3. 76 5.29

4. 97

5.07

5.03

4.89

4. 78 4.92

4.95

5.02

5.27

4. 79

4. 92

4.74

6.57

16.73

23. 19

23. 95

-49. 46 47.03 44.60

77. 01 85.23

59.43

65. 65 15.69

144. 64 72.57

151. 53 169.38

153. 71

184. 05

80. 39 116.0

133.3

135.9

138.1

85. 19

81. 45

81. 70

84. 37 90.24

86. 80

58. 59

58. 38

63. 97

57. 36

69. 69 138.91

154. 01

156. 78

162. 76

182. 40

81. 75

88. 97

90. 38

86. 61 76.91

55.23 60.74 93.74

64. 43

88. 47

59. 82

79.56

78. 81

46. 89

51. 16 97.86

82.08

98. 18

93. 69 70.92

17. 13 24.02

24.86 -51.80

49.11

46. 52 81.27

89. 02 62.24 68.50

16.74

152. 76 75.19

161. 25

180. 86

162. 40

196.83

83. 32

122.6

141.2 144.0

146. 1 89. 07

84. 94

85. 41

87. 62

93. 33 90.74

61. 76

62. 37 66.24

59.91

72. 14

146. 90

162. 01

165. 52

172. 27

193. 47

85. 67 92.83

96. 01 90.66 80.04

57.62 63.42

97. 86

67.39

92. 17 62.37

81. 75 49.32

53. 43

101. 84

85. 82

102. 55 97.43

74. 57

19. 83

27. 66

29. 07 -59. 14

55. 64 52.78 91.20

100. 93

70. 47

78. 05

19. 04

181. 74 85.41

193. 97

217. 30

195.23

237. 49 96.03

145.0

167.9

170.9 173.6

100. 13

96. 14

96. 56

99. 33

106. 72

102. 86

70.34

68. 96

74. 80

67.72

82. 13 175.00

170. 67

195. 57 208.08

230.27

97. 76

106. 48

106. 70

102. 24 91.83

65.06 72.52

113. 15 76.26

104. 99

70. 34 94.58 93.22

56.39

60. 75

115. 57

96. 68

116. 25 110 83

86. 30
OPTICAL ROTATION OF ORGANIC SUBSTANCES

Menthylamine derivatives [a}*(i©4; cf., 12, 71, 136, 185, 191)

<= approximately 20°

61

Formula

C10H52CIN

CisHssNOj. C14H25NOJ ChHjsNjO C15H29NOj

Ci8H27NOs CisH27N02 C18H28Na O CuHmNO,

CaiH27 N02 C2 iH28N2 C21 H30 NO2 r:;H«XlO

Name

/-Menthylamine hydrochloride. _ Ethyl /-menthylcarbamate

Allyl /-menthylcarbamate

7i-Propyl-/-menthylcarbamide

rc-Butyl /-menthylcarbamate

ra-Tolyl /-menthylcarbamate

3>Tolyl /-menthylcarbamate

m-Tolyl-/-menthylcarbamide

7rt-4-Xylenyl /-menthylcarbamate.

1- Naphthyl /-menthylcarbamate.-

2-Naphthyl-Z-menthylcarbamide

.

/-Menthyl /-menthylcarbamate... di-/-MenthyIcarbamide.

8 C 6,893 5,780 5,461

/HjO„_.

ICHCls. CHCI3. EtOH.. CHCI3- CHCh.

CHCh.

CHClj. PvCHCh.

EtOH..

CHCI3- CHCls.

CHCls.

5. 12

4. 98

3.94

4. 35

2. 77 4.42

2.93

1.96

2. 23

3. 85

3. 10

1. 13 4.74

4. 68

36. 29 45.72

68. 52

67. 33

66. 94

64. 18

56. 14

56. 49

80. 67

53. 91

48. 66 64.68

90.02

91. 26

37.45

49. 86

71.31 70.08

69. 47

66.74

59.20

58. 52

85. 06

55. 67

51. 86

67. 89

93. 60 95.53

42.60

54. 14 81.58

79. 86 79.20

76. 19 66.70

66.92

97.03

63. 57 59.64

76.72

106. 34

108. 02

4, 358

89. 82 137.0

135. 98

133. 17

128. 76

115. 35

112. 98

171. 32

108. 05 100.20

136. 18

178. 26

181. 25

Rotatory dispersion of some menthyl esters (197; cf., 38)

Formula Name p or e 6,563 5,893 5, 461 4, 861 C l3 H2iNOi

C,«H2«Oi.. Ci6H28 0i__ drHsoOj.. C 18H2jOj.. C,.H24 Oa _.

CjiHjoOi..

C24H30O3.-

CssHsoOk. C 27 HhOi__

Ci? H3 403 . C3oH340j.

/-Menthyl cyanoacetate... /-Menthyl acetylacetoacetate. /-Menthyl ethylacetoacetate. /-Menthyl isopropylacetoacetate. Menthyl o-toluate (38) /-Menthyl phenylpropiolate. /-Menthyl benzoylacetate. /-Menthyl benzylideneacetoacetate (cf. 82)

.

/-Menthyl /-benzylacetoacetate. /-Menthyl dZ-benzylacetoacetate. /-Menthyl benzoylphenylacetate. /-Menthyl benzoylbenzylideneacetate. /-Menthyl fl-diphenyl- methylacetoacetate. /-Menthyl /-diphenyl- methylacetoacetate

.

/-Menthyl d/-diphenyl- methylacetoacetate /-Menthyl /-benzoylcinna- mylacetate.

C«Hi....

/Nil C9H»__-. /Nil

\CeH8_... Nil CeHe—

.

C,H8 - C«H«.

C«H«. JC6H»_. [EtOH.

C,H8 ._

/-Menthyl

tate (33). triphenylaceCeH«._._ CeH«_... C«He„.. C«H6.--. fPhMe...

|jcsj MeaCO.

CHCI3-.

20

2020|

20 1/ 10+1

jldroppy

20

2020 1 26. 17 20 1 19.22 20 I 1 12. 89

20 i 1 18. 12

-64. 15 -61.49 40. 39

•50. 59

-47. 32

-66. 54

-57. 31

-50. 95 -8. 17 -94. 05

-43. 43 13.73 -43.89

-61. 75

-33. 83

-51. 13

-42. 62 -67.41 -3.04

-9. 94 -1. 58 -3. 81

-80. 92 -79. 56 -50. 77 -63. 85 -61.53

-59. 74 -84. 58 -72. 56 -64. 39 -10. 97 -121.21 -55. 10 21.10 -58. 91 -78. 62 -41. 94 -65. 15 -53. 69 -85. 08 -3.44

-13.79 -1.58

-4. 39

-95. 21 -96. 34 -59. 46 -75. 60 -72. 91 -70. 58 -108. 84 -85. 90 -76. 15 -13.66

-145. 67 -65.20

28.58 -75. 08 -93. 69 -48. 18 -78.04

-63.31

-123. 57 -131.32 -76. 50 -98. 39 -95. 05 -91. 70

-131. 72

-111. 92 -99. 89 -21.27

-196. 73 -85. 85

49. 91 -93. 57 -123.84 -60. 00

-103. 94 -82. 43 102.18 1-135.71 -3. 67 -19. 65 -1.28

-4. 83

-3.63

-25. 97 -.70

-5. 18

1 For this compound c = g/100 cc. 67316°—32 5

"
62 BUREAU OF STANDARDS

Menthol and menthyl esters [a]^

Formula

C10H20O.... CmHmNOi.

ChHmOi... OmHmOj.

CuHmOi.

Ci.HmO*.

CuHjjOi.

C17H24O5.

OitHsoOj. C«HM 2 .

Name

/-Menthol /-Menthyl cyanoacetate. /-Menthyl acetoacetate..

/-Menthyl butyrate /-Menthyl isovalerate /-Menthyl acetylacetoacetate /-Menthyl ethylacetoacetate /-Menthyl benzoate /-Menthyl isopropylaceto

acetate /-Menthyl o-toluate

I

/-Menthyl ethyl acetylsuccinate (a-ester) /-Menthyl ethyl acetylsuccinate (0-ester) CisHsaOs....

CiiBjiOs..., CigHsaOj Ci»n 26 o».... C19H34O3.

CjoHasOs. CjiH280s- ChHsoOj.

GjjHsoOs.

C22H32O3.

CssHsoOj.

CmHsoOi.

CS7H34O3. C27H34O3.

C27H34O3.

OssHsiOj. CmHmOj.

/-Menthyl diethylacetoacetate.. ) /-Menthyl phenylpropiolate. 10 /-Menthyl clnnamate 1 /-Menthyl benzoylacetate . . 10 /-Menthyl /-amylacetoace- /-Menthyl a-methylcinna- mate

/-Menthyl 0-methylcinna- mate

/-Menthyl benzylideneaeetoacetate /-Menthyl /-benzylacetoace

tate dZ-Menthyl d/-benzylacetoacetate /-Menthyl a-phenylethylacetoacetate 7-Menthyl d-benzoylphenylaeetate /-Menthyl dZ-benzoylphe-

. nylacetate /-Menthyl benzoylbenzylideneacetate /-Menthyl dibenzoylacetate /-Menthyl d-diphenylmethylacetoacetate /-Menthyl /-diphenylmethylacetoacetate /-Menthyl d/-diphenylmethylacetoacetate /-Menthyl /-benzoylcinna- mylacetate /-Menthyl dibenzoylacetoacetate

s 6,563 5,893 5,463 4,861 Lit. C»H« 37.01 46.58 .54.78 70.84 188 C 9 H6 .. -64. 15 80.92 95. 21 123. 57 197 Nil —54. 92 —69. 21 —81. 98 — 106. 35 188 C 6 H8 -55. 71 -69. 32 -82. 15 -105. 78 204 C«He -68.08 188 EtOH —70. 26 188 Nil - 55. 39 69.66 82. 13 106. 16 188 Nil 51. 88 65. 18 76. 95 99. 09 188 Nil 61. 49 -79. 56 -96.34 -13L 32 197 C«H« —51. 84 —66. 88 —80. 68 — 110. 64 Nil -50. 59 -63. 85 -75.60 -98.39 188, l»7 C6fl« 72. 41 91. 10 107. 76 139. 30 188 Nil ±V 11 —48. 69 —61. 53 —72. 91 —95. 05 188, 197 CeH» -47! 32 -59^74 -70^58 -9l! 70 /Nil. -44. 76 -56. 67 -67. 24 -87. 97 38, 197

ICfiile —45. 59 —57. 80 —67. 99 —89. 38 /Nil -38. 77 -48.80 -57. 45 -74. 02 188, 197 ICeHt -40. 94 -51.59 -60.68 -78. 29 /Nil -44. 35 -55.68 -65. 53 -84. 35 188, 197

\( an —40. 39 —50. 77 —59. 46 —76. 50 Cells -57. 31 -72. 56 -85. 90 -111.92 188, 197 Oa He- 59. 94 75. 80 89. 75 117. 42 188 C«H._ -50. 95 -64. 39 -76. 15 -99. 89 197 Nil -32.40 40.48 47.66 61.01 204 CgHe 49.99 62.26 72.95 92. 65 188 C 3 H8 ..... 53.13 66. 35 78. 01 99.61 188 OeHe -8. 17 -10. 97 -13.66 -21.27 188, 197 C( H8 -94. 05 -121.21 -145. 67 -196. 75 188, 197 C«He -43. 43 -55. 10 -65.20 -85. 85 197 C»He —84. 25 108. 2 131. 3 177. 75 204 C«Hj 13. 73 21. 10 28. 58 49. 91 197 EtOHL... -43. 89 -58. 91 -75.08 -93. 57 197 CeHj —61. 75 —78. 62 —93. 69 — 123. 84 117 C6 H, -49. 58 -64.07 -76.88 -104.1* 188, 197 C6 H, -33. 83 -41.94 -48. 18 -60.00 197 C6H» ... . -51. 13 -65. 15 -78.04 -103.94 197 C«H6 -42. 62 -53. 69 -63. 31 -82. 43 188, 197 C«H6 -67. 41 -86.08 -102. 18 -135. 71 197 C6H8 42.79 53.94 63. 30 80. 35 188

1 With one drop of piperidine.
OPTICAL ROTATION OF ORGANIC SUBSTANCES 63

Mutarotation of l-menthyl esters of keto-acids (186)

C14H24O3 /-Menthyl ! acetoacetate CuHjeOs /-Menthyl

benzoylacetate

II

C20H28O3 /-Menthyl

phenylacetoacetate

s=CeHa. p = 10.02 s=C»Hi. p=10.04 s=C6H8 . p = 10.04

Hours MS | Hours

l aiD Hours MS

1 196896

-64. -64.2

-64. 5 1 -65.5 - 5.9 !

135

7

-55. 4 -58.4

-61.7 -62.5

-63.2

80

104 144

245 319

+28. 7 -25.

1

-31.3

-38.5 -49.4

-53.5

s = EtOH. p=9.88

9

2350

-63.2

-63.9

64.0

464 628 800

1,303 1,615

-60.7

-62.1 -64.9

0.75

1.5

-71.4 -71.0

-70.8 s=EtOH. p=9.93

-66.0

1 -67. 2

2.25

3.0 -70.7 -70.2

0.75

36

-56.4

-56.6 s=EtOH. p = 10.01 -56.8

-56.9

2

5

9

i I22447

-28.3

-37.9

-49.4 -58.0

-61.5

-65.5

-67.1

; C25H30O3 /-Menthyl

phenylbenzoylacetate s=EtOH. p = 1.25

2

1725

89

-12

-16

-39

-45

-63

C20H34O4S /-Menthyl <f-/9-camphorsulphonate [ a

J 2^ (35)

t s \

\ x

c \

\

656 fip 589 mm 527 mm 486 mm 472 mm 457 mm PhMe 9. 76 7.54

9.66

-12.04

-15. 38 -17. 87

-13. 45 -17. 57 -20.63-13. 95 -19. 08 -22. 92

-12. 86 -18. 73 -23. 30-12.04

-18. 03 -22. 76 MejCO

CHCI3 -21. 46

/-Menthyl /-/3-camphorsulphonate PhMe- 9.70

11.05 -57.9

-57.3 -74.7-74.1 -98.3

-97.8

-122.0

-121.

4

-131.3 MejCO

1 In the presence of one drop of piperidine this value is reached in eight minutes.
BUREAU OF STANDARDS

Mutaroiation of l-menthyl esters of keio-acids (186) —Continued

CuHaOSj (40) Methyl /-menthyl- xanthate

(supervised) i=L 037

657 nn

589 553

527

517 508

500

492 486

473

•56.4

-64. 8 -67.7

-67.9

-67.1 -65.7

-63. 8

-61.4

-58.5

-49. 1

s = PhMe. c=5.788

673

657

622 590

560

542 528

522 517

508 500

486 473

452

•62.3

-65.

1

•70.9 76.6

-81.4

-83.9

-85. 3 -85.8 -85.8

-85.6 -85.0

-82.2 -76.5

-56. 7

CisHiiOSs (40) Ethyl /-mentbyl- xanthate Giquid)

d = 1.020

657 -52.4

589 -60.3

553 -63.0

527 -63.4

517 -62.6

508 -61.4

500 -59. 8 | 486 -55.3

473 -47.

s = PhMe. c= 9.442

657 -59.7

589 -70.4

553 -75.7

527 -78.6

517 -78.9

508 -78.9

500 -78.3

486 -75.5

478 -73.3

4,3 -70.!

CuH«OSj (42) Benzyl ^-menthyl- xanthate s=PhMe. e= 9.994

CmHssOjS* (34; c/., 33) /-Menthyl dixanthide

s = PhMe. c=9.404

656 -182 8 589 -225.1

527 -271.0

486 -293.3

478 -293.4

472 -292.

466 -288.0

461 -281.9

CmHioOjSi (42) Methylene di-J-menthyl- xanthate s=PhMe. e=10.1S

683 1. 37 657 3. 35 622 7.66 590 13.9

553 248

528 37.5

508 51.6 486 75.4

657 -32.0

590 -36.

1

5.53 -36.9

528 -36.0

508 -33.8

500 -32.0

486 -28.2

CmHjjOjSj (33) /-Menthylxanthic

thioanhydride

s = PhMe. c= 5.657

684 -48.5

657 -49.8

622 -49.6

603 -48.4

589 -46.5

548 -34.3

527 -21.3

516 -11.8

506 -2.2

498.5 -1-5.0 491 +11.8

l

Ci3 H<0 OiS4 (42; Methylene di-/-menthyl- xanthate—Contd.

s = CSi. 1 7.069

[•]?

657 -9. 70 590 -2.00

559 5.56

547 9.90

528 19.8 503 33.5

500 41.6

486 58.7

Cj4HsjNOSj (39, 41)

1. 2-Diphenyl-/-men- tnylimid o-xanthid e (/-Menthyl phenylthiobenzoylthioure- thane.Ph.CS.N Ph. CS.OCuHn) s=PhMe. c=0.138

622 -192

603 -272

590 -388

582 -449

573 -536

559 -594

547 —507

536 -260

528

508 580 492 870 478 1, 160 s=MejCO. c=0.138

657 -33

622 -105

603 -185

590 -301

582 -348

573 -507

559 -579

547 -594

536 -522

528 -261

s = PhMe. c= 0.9876

687 -a

663 -80

642 -116

622 -167
OPTICAL ROTATION OF ORGANIC SUBSTANCES 65

Mutarotation of l-menthyl esters of keto-acids (186) —Continued

Ci*HjjNOiS(39)J-Menthyl monothioure- thane (i-menthyl

phenylthiobenzoylurethane, Ph. CS. NPh. CO. OCioHn

CMH4jG:S4 (42) Ethylene di-Z-menthyl- xanthate JCHj. S.C S.OCioHujj

CojHuOsS* (42) Tri- methylene di-f- nienthylxanthate

3=PhMe. c=0.131 s = PhMe. c = 7.506 s = PhMe. c=6.49

X

L a

Jx i xL Jx

696

657

641 622 603

-31 -35

-39 —47

-57

657

622

590

553

536

-56.

1

—61.

1

-65.4

—69. 3 -70.3

675

657 622

5S9 553

— 54. 9 -57.2

-62.7

-67.1 -71.7

590

573 560 547

-78

-110 -162 -230

528 508 500

492 486

-70.4

-69.3

-67.9

-66.0

—63. 9

536

528

522

517

-72.7 -73.0

-73.2 -73.0

CnHsoOSi (4?) Diphenylcarbinyl l-men- thylxanthate

478 -58.0 508

500 486

478

-72.6

-71.7 -68.6 -65.0 CS0HMOSj(42)Triphenylcarbinyl /-men- s=EtOH thylxanthate

657 -53.4

s = PhMe. c=4.395

589 528 486

478 472 466

-65.3 -77.6

-82.4

-82.9 -83.3

-81.3

657 589

527 48G 472

-72.8

-96.9

-127.5

-159.2

-175.0

(43) [a}{

CuHjaOSt Methyl Z-menthylxanthate CmH«02 3< Methylene di-Z-menthylxanthate s=PhMe. p-10.18 s=PhMe. p=4.89

\

X\

656 ju« 589 mm 527 mm 486,41 x

656 mm 589 mm 527 mm 486 mm

-36.6

-31.8

0.0

17.4 47.5 80.6

-64.3 -64.6

-65.1 -65.3

-65.8

-66.1

-75.4

-75.7 -76.8

-76.8

-77.4

-77.5

-83.3

-83.6 -85.1

-85.3 -86.0

-86.2

-79.3 -79.8

-«1.6

-82.4 -82.8

-83.8

-22.0

0.0

22.0 50.4

80.4

17.4

10.8 2.8 -8.7

-20.3

32.4

23.4

12.0 -2.4

-17.5

63.7

51.4 36.6

16.2 -5.0

108.8 93.3

74.3

47.9

20.8

Ci£H3sOjS3 i-Menthylsanthic thioanhydrid3 s=AcOEt. p=4.83 s=PhMe. p=l.06

-78.9

-80.9

-81.9 -82.7

-87.7

-90.7

-91.5 -93.2

-86.2

-89.2

-90.2 -92.0

-47.6

0.0

20.5 49.2

-66.6

-67.7 -68.4

-69.3 -34.6

19.8 80.2

-22.6

-51.3 -76.0

1.0 -48.0

-94.7 +85.3

-20.7

-127.5

+285. +28.4
66 BUREAU OF STANDARDS

IIDC. THE MOLECULE CONTAINS 2 OR MORE ASYMMETRIC ATOMS

ATTACHED RESPECTIVELY TO 3 OR 4 OTHER CARBON ATOMS

14. CAMPHORIC AND CAMPHOLYTIC ACIDS AND DERIVATIVES

CioHizOi Camphoric acid and normal camphorates (87)

CioHieOj Nil C18H38N2O1... 71-Butylamine. C20H26N2O4 Pyridine C20H38N2O4 Piperidine C22H30N2O4 Aniline C24H34N2O4 Benzylamine

C28H30N2O4-- Quinoline - CS8H3SN2O4 Tetrahydroquinoline. CS0H34N2O4.. a-Naphthylamine

C30H34N2O4 £-Naphthylaniine

C30H42N2O4- - ac-Tetrahydro-/S-naphthylamine. C30H42N2O4- ! ar-Tetrahydro-a-naphtbylamine.

47. 72 46. 02

11. 16 10. 96

27. 12 25. 90

14. 36 14.24

31.84 32.5

17. 16 16. 92

18. 7b 19. 16 17.28 17.56

18.00 18. 12

18. 72 18. G4

14. 32 14.38

16. 76 16.92

Derivatives of camphoric acid

l«V3 01? CioHuBrN02 d-Camphorbromoimide (52)

C6H8 |

f 1.9412 12.0 2.3840 11.2

[ 3.0828 12.0 1.6644 13.6 CHCI3. 1 2. 7372 13.0

[ 2.8640 12.8

ChHitNOj d-Cainphorniethyl- imide

EtOH.

C10H14INO2 d-Camphoriodoimide

C6 H« CHCh

MejCO.

2. 4352 11.1

3. 1372 11.0

3. 5548 11.4

4. 2428 11.3

2. 8280 8.0

4. 1460 8.0

C12H19NO2 d-Camphorethylimide

EtOH.

16.0

16.0 15.2

15.3 15.7 I 15.7 I Me2 CO.

12.4

12.6 12.5

12.5 8.4

8.8 8.5

C17H20N1O4 d-Camphor p-nitro- benzyiimide

MejCO. CtH6 .

2.0284 11.8

2. 7180 12.3

3. 1392 12.3

2. 2520 2.6

3. 9712 2.8 CnHsiNOj d-Camphorbenzylimide

1. 8156 la 7 EtOH i 2.3104 12.1

3. 2128 12. 1

: 2.8268 ! 11.9 MesCO 2.9552 12.0

3. 3444 12. 2

3. 9392 i 11.9 CeH. r 2. 1904 ! i 3.8228

5.2

4.8

Derivatives of campholic and camphoric acids

s Lit. 6,563 5,893 5,463 4,861 CeHe— - 68.48 89.26 108.00 148. 65 196, 198 CeHe—

.

CsHo—

-

47.48

53. 36 59.26

67. 18

69. 36

79. 42

88.33

102. 74

1SS, 196

1SS, 198 C6H«—

.

84.29 109. 98 116. 07 185. 71 196 rxn 51.27 63. 67 74.17 93. 32 1SS, 196 LCeHe— - 53. 89 196 52.06 66. 82 79.90 107. 39 198

rNil 20. 62 1 26.73 31.57 41.24 195 iCeHe—

-

12. 99 1 16.38 18. 97 25. 41 19a

Formula

CioHisO..

CioHisO*. Cl0H2oO_. CnHisOs. CnH2oO..

C12H20O2.

C12H20OS.

Name

1, 2, 2, 3-Tetramethylcyclopentane 1-aldehyde. Campholic acid

1, 2, 2, 3-Tetramethylcyciopentane-l-carbinol.

1-Acetyl-l, 2, 2-trimethylcyclo- pentane-3-carboxylic acid.

1, 2, 2, 3-Tetramethylcyclopentane-l-metnyl ketone.

1, 2, 2, 3-Tetramethylcyclopentane-l-acrylic acid. Ethyl 1, 2, 2-trimethyl-3- methylenecyclopentane-l-carbosylate.

10

1 In (196) these figures are quoted for the methyl ester.
OPTICAL ROTATION OF ORGANIC SUBSTANCES

Derivatives of camphoiic and camphoric acids—•Continued

67

Formula Name

[alt

6,503

Lit.

CuHmOj.

CiHjsOj.

CmHmOj.

CiHuOi.

CicHaO.

C,;H240.. C13HM0.. Ci7 Hm02 . C|8H»0_.

C20H24O..

Methyl 1-acetyl-l, 2, 2-trimeth- ylcyclopentane - 3 - carbo x y 1

- ate.

1, 2, 2, 3-Tetramethylcyclopentane-l-ethyl ketone. Ethyl campholate

l f 2, 2, 3-Tetramethylcylopentane-l-proplonic acid. Ethyl 1, 2, 2, 3-tetramcthylcyclopentane-l-arrvlate. Ethyl 1, 2, 2, 3-tetramethyl- cyclopentane-l-propionate.

1, 2, 2, 3-Tetramethylcydopentane-1 phenyl ketone.

. 1, 2, 2, 3-Tetramethylcyclopentane-1 benzyl ketone.

. 1, 2, 2, 3-Tetramethyl - 1 - cyclo- pentane cinnamyl ketone.

. 1,2, 2, 3-Tetramethylcyclopentane-l-carbinyl benzoate.

1, 2, 2, 3-Tetramethylcyclopentane-1 0-phenylethyl ketone.

1, 2, 2, 3-Tetramethyleyclopentane-1 a-naphthyl ketone.

Nil...

10 C6 HS . rNU.„

rNu...

LCeHj. C6 H«.

10

Nil... CeH«. NU... C 6 Ho.

NiL... CiH6 -

EtOH.

Nil...

CeHi...

Nil.... C4 Hi„. C«H6 -

EtOH10. 53

14. 46

50. 64

38. 21

44.91 44.47

32. 32

32. 94

5. 72

2. 70

21. 74

21. 51

37. 75

18. 96

14. 32

-41.95

-12.23

14. 02

19. 17

63. 15

54. 83 40.49

39. 79

48. 38

57. 51

57. 11 40.95

41. 66 -1. 21

-11. 47

21. 68

32. 16 25.91

47. 81

23. 71

18. 15

-60. 52

-19. 97

-14. 08

-20. 18

73. 89

57. 20

-24. 99 -33. 41

94.08

75. 29

68. 80

68. 19 48.09

49. 14

91. 93

91. 60

63. 15 64.54

-12. 42

-23. 96

17. 51

-50.54

-66. 49 -3. 73

36. 40

28. 05 42.5633.34

56. 63 73. 83

27. 68

20. 86

-80. 21

-29. 45

35.43

27. 40 -132. 25 -58. 16

(112) Ci0 HmO2 doHuNOa

Caraphorquinone ; Isonitrosocamphor

p = 0.2 to 0.6

L aJ

Jx

f = laboratory temperature

= MeOH Calls EtOH

6,850

6, 680

6, 260

5, 940

5, 660

5, 430

5, 240

5, 080

5, 000

4, 930

4,860

4,800

4,740 4,690

42.7

5380

85

122.6

181 256

341 389

293. 7 144

102

38

4148

60. 8 75 100

144 227

i j2. 6 222

240. 8 291.4" 368 318

240 351.7
68 BUREAU OF STANDARDS

Derivatives of camphorquinonehydrazoxime (Q) (61) Name Q (from a-isonltrosocamphor) Q-carbamide

Isopropylidene-Q Benzylidene-Q

6is-Isonitrosocamphanazine. Q (from 0-isonitrosoepieamphor) ... Q-carbamide

Diacetyl-Q

Benzylidene-Q Benzoyl-Q. Phenylcarbaminophenyiurethane-Q

'CHCh

2 per cent NaOH

CHCi3 CHCh

CHCh

CHCh —

.

'CHCh -

K 2 per cent NaOH.

2 per cent NaOH.

rCHCh - [2 per cent NaOH

CHCh -

EtOH

CHCh

L 0388 —52. 4

0. L 0576 52. 8

1. 0184 —40. 1 L 01 G4 -73.8 L 0336 -254.2 L 0372 149.0

1. 548 103.8 L 0508 135.6 .8224 177.0

.8552 87.7

1.040 94.5 .8420 130.5 .920 137.7

15. LIMONENE

CioHie d-Limonene

(135; Cf., 26) CioHia d-Limonene 1 (135; Cf., 26) CioHie d-Limonene

(135; Cf., 26)

[ a]4,359 [ a

K.708

22.2 -.4

-22. 5 -47.0

-66.0

-80.6

-92.0

-102.0

-115.0

-123.0

232.5 241.0

249.3

259.3 266.2

274.3

277.8 282.7

289.3

292.9

20.5 -.5

-20.5

-40.8 -54.0 -67.0

-79.7

-89. 7 -116.4

-124. 5

135.7 140.2

144. 5 148.8

152.

1

155.

159. 163.0

172.0

176.0

21.0 4.0 -9.0

-24.2 -41.0

-61.0 -82.0

-102.0

-108.0

-120. 7 -123.5

85.

1

87. 1 89.2

91.2

93.6

96.5

100.4 105.6

106.5 109.4

109.5

[ a

]4,916 [ a]5,893

22.0 -12.2

-30.4 -51.0

174.6

184.3 188.4

194.5

22.2.0 -18. -64.0

115.9 120.0

124.0

132.1 -74.5

-85. -104.0

-120.8

201.1

204.1 210.7

214.6

-76.4 -89.0

-103.7 -114.0

-118.

-123. -125. 7 -128.0

135.0

137.7

141.4 143.2

143.8 145.4

146.4

146.3
OPTICAL ROTATION OF ORGANIC SUBSTANCES

16. CAMPHOR AND DERIVATIVES

Specific rotation of camphor in various solvents CioHuO camphor (231) CioHuO camphor (231) CioHuO camphor (231)

P df MS P MS P df MS

S = CeHi s=CHCl?—continued s=AcOH

34. 91 6.44

5. 36 4.12

0. 9066

.8835

.8827

.8817

44.20

39.90 ! 40.07 ; 39.75 !

4.03

2.19 L 15

1. 4452

1. 4586 L 4664

41.10

41.23 41.7

33. 26

3. 98 3.15 2.15

1. 0174

1.0458

1.0467 1.0478

45. 66

42. 33 41.81 41.3

3. 14 1 97 .8809

.8800

39.90 ! 39.2 s=CiH4 Brj L 13 1. 0488 40.7

= CHCU 36.23

3. 87 L 4929

2.0758

56. 93 58.83

35.27

5. 31 L 2476

1. 4361 45.7641.00 1

2.99

1. 86 1.C0

2. 0983

2. 1279

2. 1513

58.93

60.1 60.1

P (15?) MS

1 CioHuO camphor

s = EtOH

0. 7643 41.4

3.050 43.8

7. 538 43.5

14. 82 44.1

24. 280 45.2

37. 83 46.1

50. 72 47.4 s=MeiCO

0. 7962 50.1

3. 054 50.6

5. 037 50.2

9. 992 50.6

24. 27 51.2 37.83 51.9 50.73 52.5

66.94 53.3 s=EtOAc

1. 119 52.9

2. 671 51.5

8. 882 52.0 22.00 52.5

34. 85 52.5

51.69 53.4

P (157) MS

CioHuO camphor

s = C«Hi

0. 9796

4. 9447

23. 984

46. 148 56.654

40.1 43.7

46.2 48.2

48.9

0. 4472 38.4

.928 38. 8 2.722 40.3 4.550 41.4

9. 097 42.4

22. 470 43.4

35. 480 45.6

52. 373 47.8 S=PhCl

0. 7255 41.3

5. 509 41.2

18. 643 43.2

30. 35 44.9

59. 25 48.7 s=i*o-BuOH

P (157) [a]g CioHuBrO (c/. 226) a-Bromocamphor

s=EtOH

s=EtOAc

0. 5078 133.4

4. 973 135.9

9. 765 136.5

14. 32 137.0

18. 73 138.3 S=MeaCO

0. 7693 138.1 7.381 143.2

22. 93 144.2

34. 72 145.4 48.58 146.3

0. 4572 139.1

4. 394 141.5

20. 76 142.9 31.89 144.3 38.90 144.7 s=CeHi

0. 4665 116.2 4.512 120.4 21.21 125.1 32.50 128.3

46. 12 132.9
70 BUREAU OF STANDARDS

The interpolation formula for calculating the specific rotation applied to (C\^H\%0)

camphor in various solvents (72)

Limits of p C«He- 11.30 54.28 C«H6 11.07 64.20 MeOH 12. 34 56. 66 EtOH 12. 32 56. 79 PrOH 12. 19 56.37 HC02 H 8. 44 46.54 AcOH 9.64 49. 89 EtC03 H 10. 12 50.96

[a]2=A+Bp+Cp»

39.942+0.1627 p. 39.097+0.1583 p (*=18.5). 40.979+0.03835 p+0.0009196 p». 42.004+0.04968 p+0.001006 p>. 43.805+0.036331 p+0.0008996 pK

19.856+0.3023 p. 41.811+0.1327 p. 46.020+0.0938 p.

CioHisO Camphor in MejCO (130)

t < e Hi t < e M&

13.7 0. 87507 40. 7410 50. 549 14.3 0. 81346 3. 8695 49. 211 13.7 . 85355 27. 5673 49. 665 14.8 .81100 2. 6196 49. 511 13.7 . 83880 18. 6984 49. 133 17.0 .80887 2. 1344 49. 639 13.7 . 82864 12. 5190 48. 773 17.4 . 80708 1.7758 49. 695

14.3 . 82166 8.4604 48. 709 17.0 .80633 L 1914 49. 960

14.3 .81709 5. 7394 48. 900 25.2 . 79763 1.0684 50. 070 CioHwO Camphor (72; cf. 9, 16, 19, 54, 55, 63, 86, 91, 169, 111, 116, 182, 266, 226, 227)

s = C 6 TTl . *=20

[a]tD

11.30 40. 780

22. 34 43. 581

33. 18 44. 331

43. S2 46. 075

54.28 47. 772

* = 18.5

11.07 21.87

33.28

43. 70 54.20

40. 786

42. 548

44. 387

45. 950

47. 638

s = MeOH. t=20

12. 34

24. 14

35. 46 46.25

56. 66

41. 592

42. 495

43. 495

44. 738

46. 104

s-EtOH. <=20

12.32 42. 769

24. 10 43. 930

35. 57 45. 020

46. 25 46. 248

56. 79 48. 070

s = PrOH. <=20° (?)

;

12.19 41.381 23.90 45. 145

35. 10 46. 188

45. 93 47. 397

56. 37 48. 711 S=CHjOi. <=20

20.44 26. 03

24. 05 26. 91 34.38 29. 85

42. 32 32. 38 50.89 35.08

64.11 39.93

s = AcOH. t=20

8. 50 16.42

19.22 29.60 34.35

38.84

52. 75

43.36

43. 87

44. 24 45.93 46.60

47. 20

49. 37

s = EtC02 H. f = 20

13.60 23.06

30. 60 39.08

48. 34

48. 9*

49. 70 50.53

Simple derivatives of camphor (37)

20

Formula

CioHieO

CioHi4BrjO_„.

CioHhIjO

CioHuClO..... CioHisBrO

'"10H15IO Ci8 Hi8 BrN04S

Camphor ....|{^H-

/MeOH-LI

\dSafCSi. \C5H6- C 6H6 . rcsa .. ICeHs.

fCSs-.

1 C.H#. at-Bromocamphor {\W)H

a-Iodocamphor (cf.79) MeGH.

NH4 a-Bromo-s-camphorsul- H2O.

uhonate.

0-Camphor (epicamphor)

a, a-Dibromocamphor

a, /3-Dibromocamphor

a, a-Diiodocamphor

a-Chloroeamphor

9. 97

12. 10

9. 66

8. 47

10. 02

10. 85

9. 70

5. 25

5. 02

9. 36 9.24

9. 98

4.58

9. 40 5.25

6,563

29. 37

31. 86

-32. 84

-45. 59 28.44

27.50

61. 16 20.7

20.7

69.7 54.20

1C7.5 98.8

112, 3 63.6

5,893 I 5,270 4,861 40.56

44. 75 -45. 53 -63.23

40. 52 39.20

80.45

30.3 30.5

91.8

71. 10 141.8

129.3 147.3

85.1

58. 64

64. 99 -66. 40 -91. 57

61. 97

59. 55

109. 50 48.6 48.6

125.2 96.40

193.6

174.7 198.3

117.4

78. 94

89. 24 -90. 51 124. 33

89. 42

85. 86

140. 1 70.8 161.0

122. 30 248.2 222.0

252. 9 152,0
OPTICAL ROTATION OF ORGANIC SUBSTANCES

Mutarotation of C10H15NO3 nitrocamnhor in various solvents

(119; cf. 19, 31, 32, 56, 118, 119, 122, 127, 168)

[a]d

s c Period

Initial Final

CeHe 5 15 —124 —104 4 days PhMe 5 20 -106 -87 H day". CeEUMej 5 20 -99 -75 4 days. PhP.O.Ft 5 17 —50 —28

CSj 17 —83 —68 CHCh 5 13 —27 — 15 1 week

Et2 5 18 -37 -18 2 hours. AcOEt 5 14 -13 -2 2 hours. MejOO 5 20 -7 8 Yi hour. MeOH 5 16 -31 -12 3 hours. EtOH - 5 15 -26 -9 5 hours. PrOH 5 17 -24 -10 2 hours. HCOjH 6 15 ±0 12 3 hours. AcOH 5 13 -3 8 5 hours. EtCOjH--- - 5 14 -5 5 2 hours.

Mutarotation of CioHuBrNOj

x-Bromonitrocamphor (119) s=C8H« p=3.3

Pseudo form Time

Hours

(188. 4) 0.5 184.0 1.0 179.7 1.5 175.0 3.5 158.2

5.0 145.2

7.0 129.5 8.7 116.0 27.0 25.7 29.0 18.7

31.7 10.7 48.6 -17.5

99.3 -38.0

Limit. Normal form

(-51. 4)

1 -50.7

25 -47.2

48 -43.7

72 -42.7

118 -40.0

144 -37.5

Limit. «=13 to 15° C.
72 BUREAU OF STANDARDS

CioHi604 S d-Gampbor-0-sulphonic acid, salts, and derivatives s=H»0 (71)

Salts \vV

\N

w?

5,461 5,780 5, 893

J 1

20. 75 16. 84 15.83 100.7 ZnA|.6HjO 20. 90 16. 89 15. 79 100. 5

\ t 20. 74 16. 75 15. 80 100.5

f 2 22. 22 17.92 16.88 100. 4 MgA».6HjO

i

22. 12 18. 02 16. 92 100.7

22. 20 17. 92 16. 82 100. 1 19. 37 15. 72 14 74 100. 7 1

*819. 38

19. 37

15. 65

15. G3 14.80

14.66

101. 100. 1 19. 34 15. 60 14. 70 100. 4

f 2 22. 76 18. 47 17.22 98. 94 CaA2.4HjO 4

1 8

22. 67

22. 35

18. 32

18. 00

17. 15

16. 91 98 50

97. 15

I 16 22.06 17. 77 16. 65 95. 67

f 2 20.00 16.34 15.08 98. .58 BaAj.3H20 4

8

19. 89

19. 57

16. 11

15. 77

14. 98

14. 77 98.00

96. 64

I 16 19.23 15.49 14. 53 95.04

f 1 26.68 21. 70 20. 21 50.38

2 26. 70 21. 71 20.24 50. 45 NHjA 4 27. 01 21.79 20. 46 51.00 g 26.99 21. 81 20.46 5L 00

I 16 27.43 22. 20 20. 79 51. 85 20.83 17.04 15. 97 50.70 CjHuNA

1 '

21. 37 21.6317. 30

17. 56

16. 12 16.50

51. 18

52. 38

I 16 22.29 18. 07

Camphor-/S-sulphonyl salts s = CHClj (73: Cf. 7) •\ 5.461 5,780 5,893 [M]

CioHisClOsS 3.6 40.08 33. 91 32.17 80.62 CioHisNOjS 2.3 38.56 34. 37 33. 79 72.07 C15H25NO3S - .57 42.58 35. 91 33. 45 100. 15 (Piperidide) .97 42.46 35.88 33. 38 99.90 CSH„NA r 1.6 41.40 34.94 32 37 102.8

\ .92 40. 54 34.06 32.08 101.9
OPTICAL ROTATION OF ORGANIC SUBSTANCES 73

CioHijBj04S.3HjO d-a-Bromocamphor-0-sulphonic acid and salts s=HjO (175; Cf. 106, 133)

C Acid 3H»0... C

C BaA2 .6VsH2 C.„. D NH4A

D

D

B

C

KA.H,0(?) D.

0__ .„ D CjHsNHjA-.

D

CAgA.il/2H2O- C

C ZnAj.5i/2 Hs O D

0. 521

3. 130

.391

1. 570 .523

3. 017 0.5% (EtOH)

.503 .498 .522

3.180

.299

.504

2. 661

3.048

.686

.581

5, 461

120.8

121.6 85.7 85.2

88.4

53.7

113.0

102.1 103.1 109.0 90.2

91.3

85.4 83.2

94.4

97.3

5,780

103.6

104.1 73.5 73.0 75.0

75.4 81.7

44.8 97.0 87.2 88.0

91.9

77.3 77.9

73.0

71.3 80.2

82.2

98.3

99.1

69.7

69.3 71.2

71.5 81.1 41.8

91.4 83.4

84.1 86.0

72.9

73.6 69.0

67.7 76.5

77.9

[Mb

305.8 308.2

305.0

303.0

233.5

235.0

266

137.0 300.0

292.0

295.0

300.0

259.0

262.0 310.0

304.0

300.0

267.0 Note. The salts of this acid exist in two stereoisomer^ forms, one of low rotatory power and high

dispersion (C) and another of high rotatory power and low dispersion (B) . Both of these are converted into an equilibrium-mixture (D) in the presence of traces of ammonia.

C10H17O4S Camphor-T-sulphonic acid and its salts (87)

=2.5 5.0

24.04 24. 82 57.6

20. 44 20.36 62.1 31.72 31.42 97.7

21. 40 22. 94 72.7

23. 32 23. 28 75.7

21. 36 22.00 74.6

26. 96 27. 90 100.7

25. 36 25.98 94.8

20. 92 21. 38 80.2

20. 80 21.54 80.8

17. 36 17. 36 65.8

19. 80 19. 92 75.6

Formula Organic base (s=CHCl3) [a]^

Cl0H16 O4S

C14ET.j7NO4S.H2O C15H21NO4S CUH27NO4S

CH1H23NO4S

C17H24NO4S

Ci»H23 N04S

CigH27 N04S

C20H25NO4S C!0H25NO4S

C,oH2eN04S

CJ0H29NO4S

Nil n-Butylamine.

Pyridine

Piperidine...-

Aniline Benzylamine

Quinoline Tetrahydroquinoline a-Naphthylamine

0-Naphthylamine

ac-Tetrahydro-/3-naph thylamine

.

ar-Tetrahydro-a-naphthylamine

C11H19O2. Hydroxymethylenecamphor and derivatives (174)

Formula

CnHl8 0,_- CnHuBrOi

OkHmNOj.

Cs»Hj4NOi.

Name

d-Hydroxymethylenecamphor...

/-Hydroxymethylenecamphor..

.

d - Bromohydroxymethylenecamphor _

I - Hydroxyhydrindamino - d methylenecamphor.

d - Hydroxhydrindamino - d methylenecamphor.

Time

Hours

20H

20

4848

72

48

1854

72

EtOH* EtOHt

EtOH* EtOHt

EtOH* EtOHt—

EtOHt—.

CeH« EtOH*t—

C,H,*t—

-

AcOH't-- C6H,*t—

-

EtOH*t--

009

.188

.188

.367 .850

.497 .517

.391 .512

.618

:«]?

198 228

-195 •18573.2

71.6

73.6 145

3.1 102

163 302

5,750 5,461

207

19676.4

74.3

76.4 83.0

157

107 108

164 335

242

187

85.7

82.9 86.0

92.4

185

131 128

190 876 Notk.—Solutions marked with asterisk (*) exhibit mutarotation, the final value is given for each substance and marked with the dagger (t).
74 BUREAU OF STANDARDS

Divalent metallic salts of hydroxymethylenecamphor and of nitrocamphor

d-CnHisOj=oca d-Ci HHNOj = nica (112) [a]\

s CHCb CHCls CHC13 CHCh EtOH CHCU CHC1, V 5 5 5 5 5

Salt Co.ocaa Ni.oca2 UOj. ocas [Cu.oca2(H.Gca)2] Cu.ocaj Co.nicaj

6, 840

6, 650

6, 450

6, 250

6, 100

5, 940

5, 780

5, 650

5, 430

5, 240

5, 075

4, 940

4, 800

4, G90

178

185 200

223 233

247 268

286

333 358

412

70 140 84 119. 7 147 3 15616 128.9

101

190

167 100 37.7 87

98

106

232

200 122 18.3 276

235 280

322 355

415 465

515

145

175 221

267 320

9.4

34

56. 5 75.3

120

140

146

160 170

55.3

18.4

324 370

432 456

Tervalent metallic salts of hydroxymelhylenecamphor

Salt Cr.ocaj Al.oca3H.oca1 Salt Cr.ocai Al.ocasH.oca 1

s C6 H6 EtOH EtOH EtOH s C6 H« EtOH EtOH EtOH

P 0.1 0. 51 0. 5-1 1 V 0.1 0.51 0. 5-1 1

6,840 218.5

256.5

294.5 342

427.5

503 589 484

361

475

499

136 146

5,330... 218.5

133

11495

137.8

6,650.. 215 1 5,240 24 1,011.8 266

6,450 ! 5,150 6,250-. 311 581 170 ! 5,075 155.5 1, 138. 6 292

6,100 5,000 5,940 622

730

675.8 779.5193 213

4,940 84

59.8 180204?

1, 271 1,413

1, 566. 7 1.730

318

5,650 4,800.... 345

5,540.... • 4,690 375

5,430 407 892.8 240 4,580.... 402

1 1

1 See (174) and hydroxymethylenecamphor, p. 73
OPTICAL ROTATION OF ORGANIC SUBSTANCES \ nil sss22s n nt nnn snn nun* \$nn

§

28o? S23SS88 ssssss agssgsssssggs

Slli 8§ss|| sgigig gggggg sggsg sgsi^ggg||8i

i us i \ \SSS ! i i III !ig i« mm

m gill

S3 52

S?£^2§ ss^ggs sssssss ssss;? 88 SSSSS^SJSggSSS a^s ssaa« mmm^mm

SSo^ SSS^SS 32SSs£8£S2sSsS2£

sisg a^sga w^aa ****** iii^ ss***********
76 BUREAU OF STANDARDS

Camphor, methylcamphor, and derivatives

Formula

ChHhO....

CuH,iO.__. ChHwOj...

CuHmOi... ChHsoOj.—

Ci3H2oOi... C14H22O3— C»H29 0.

C17H22O. CiiH24 0. ChHjiO.

C20H24O2--. CmHuOi...

CsiHsiNOj. CmHmOi...

Name

Camphor

Methylcamphor

Camphorylcarbinol

Camphorylacetic acid Camphorylacetone

Camphorylcarbinyl acetate. .

.

Ethyl camphorylacetate Isoamylcamphor

Camphorylphenylmethane

o-Camphoryl-/3-phenylethane

.

a-Camphoryl-7-phenylpropane. Camphorylbenzylidene-3-acetone. Camphoryl-3-acetylacetophenone. Methylenecamphor-a-aminocamphor.

r, /S-Dicamphorylethane

10

10 2.48

6

Coii«.

fNil... ICaHe. CoHo.

Nil.,. CtHt.

Nil...

Nil... CeHo.

'Nil... CeHe.

Nil... C 6 H6- CiHe.

C*Hi.

Cell*. C.Hi.

C1H4.

563 5,893 5,463 4,861

30.94

15.82

46. 31

16. 01

27. 66 36.99

45. 91 40.46

51.01 27.07

50.19 31.29

92. 56

16. 56

39. 19

35. 41 45.38

90.51 44.99

43. 01

23. 25 62.11

23. 40

3S.06

49. 25 60.73

53. 78

67. 53

37. 18 66.78

42. 34

123. 35 22.82

52.37 47.37

62. 52 121.8 60.37

55.32

30. 76

77. 67 31.02

47.99

61.08

74.42

66. 77 83.38 46.96

82.57

53.40

153. 34 29.22

64. 75

58.54

78. 31 151.7 75.29

86. 75 50.84

113. 48

50.83

73. 33 87.60

105. 52

119. 23

70. 77 120.17

79. 14

220. 90

45. 19

93. 51 83.57

118. 59 211.4

110. 33

Lit.

188

188

188

cf. 189 203

303

203

cf. 189 lbs 203 203

194

cf. 188

188 m194 203

203

188

1 In this table " camphoryl" is used for the radical CioHuO of camphor, and not for the radical Ci»Hn02 of camphoric acid.

17. CAMPHORCARBOXYLIC ACID AND DERIVATIVES

C\\H\(,Oz Amine salts of camphorcarboxylie acid (rotation calculated on the concentration of the acid)

7.84 (133) M amine M

11u Amine HiO EtOH EtOH

CuH25NO» Propylamine

{ \

14.890. 4

90. 2 81.7

78. 5

1 91 81.7 C1JH27NO3 Butylamine. . . | 13.7 5 92.3 78.8

45 73.

1

1 92. 5 82.3 C-wHi7NOs Dietbylamine 1 ! 1.98 5 92.5 85

I 13.7 45 92.5 85.5

1 92. 5 82 CnHsiNOj Triethylamine 9.53 5 92.5 85.5

l 45 85. 6

C11H16C3 Camphorcarboxylic acid+CaH^N aniline

AfC*H7N

s

(cof acid=2.61) [a]£ (133) EtOH EtsO C4H5 PhMe C«H4Me3 MejCO PhNHj

15 45

70

63.2 62.5

57.4

34.1 27.4

55. S 55.8 33.2

33.8

39.6

39.6

44.3

44.3

57.7

57.7 27.4

1

1 1
OPTICAL ROTATION OF ORGANIC SUBSTANCES 77

Influence of bases on rotatory power of CnH^Oz camphorcarboxylic acid (27)

Base (s=C»H«Mej) Mols of base to 1 of acid

it [-K

32 44. 2 22 42. 1 23 34.5

25 61. 7 25 61.7

19 65.3

22 65.7

22 33.3

27 30. 3 22 49.'

2

30 49.4

18 42.5

21 36

22 31.8

19 32.5

19 41.2

22 65.7

25 67.2

22 36. 3

21 29! 2

22 27.5

\ 22 40. 3 17.5 30

24 25.4

22 23

19 37.5

26 36.7

20 43.0

Nil Pyridine

Piperidine- Isoainylamine --

a-Pieoline Benzylamine

771-Toluidine Collidine Dimethylaniline Diisobut ylam ine Quinoline

Tripropylamine

Quinaldine..- Dietbylbenzylamine

Triisobutylamine. .

.

0. 18 .18 .5

.5

.13 .13 .12

.12

.74 .74 .02

.02 .20

.39

.39

.18

.17 .84

.84

.84

.13 .13

1.4

1.4

1.4.o2

.41

. 17

1.2 10.4

1.4 3.0

1.0 2.0

1.0

5.1 1.5 3.0

1.9 1.02 4.5

5.5

1.2

1.04

2. 15 1.3 4.1

7.3

1.0 1.5

1.02 2.0

1.3

Dispersion data, camphorcarboxylic acid derivatives Formula Name s 5,708 6, 438 5,893 5,461

45.8 -86

5,0S6 CnHuBrNOi

CuH24BrNO»

a, a'-Bromocampborcarboxamide.

a, a'-Bromocampborpiperidide.

EtOH

EtOH

5 29.4 38.4 —54. 5 -58.5 -71.2 -102. 3

Formula Name 8 \x

\

4,800 4, 678 4, 359 Lit. CnHuBrNOj a. tt'-BromooamDhoroarboxamide EtOH

EtOH

5 82.6 CieH24BrN03 a, a'-Bromoeampborpiperidi(ie. . .. -118. -126.0 -150.9 79 67316°—32 6
BUREAU OF STANDARDS

Derivatives of camphorcarboxylic acid c = o (125)

Time [a] m«» Time [<x]»,4ai Time [a] M«

CnHi-NOi CuHnNO, CieH2 5NOi

Mutarotation of cam- Mutarotation of cam- Mutarotation of cam- phorcarboxamide phorcarboxamide phorcarboxypiperidide s=EtOH s = C4Hi « = C«Hi

Hours Hours Hours

0.

1

Q_ 2 0.

1

1 5 5 24 7 .2 . 1 .2 2^0 \l 2i. 7 .3 .2 .4 2.9 1.0 24.7

. 3 . 6 3 6 1. 24. 7

. 5 1 4

'. 8 4. 7 2 25

. 6 . 6 1. 6. 5 2. 3 25 3

! 8 l' l 2. 10! 1 2. 5 25 3 1.0 1.4 3.0 15.0 io 25. 4

1. 5 2. 5 4.0 19.9 O. 25. 6

ji. u <l 7 5.0 24.1 4. 25. 8

2. 5

o

4. a 6.0 28.7 4. 5 25.

7

3.0 6.9 7.0 32.6 5.0 25.6

o. o 7 1 8.0 36.5 5. 5 25. 6

4. 8. 2 10.0 43.4 6. 5 25 8

4. 5 9.4 12.0 49.2 8. 26. 3 5.0 10.4 13.3 52,4 9.0 26.5

8. 17. 2 23.0 67.4 10.0 26.6

9. 19. 25.0 68.0 11.0 27.0

10. 21. 28.4 69.7 12.0 27.

1

11.0 23.3 31.0 71.0 13.0 27.5

12.

4

25.8 36.0 70.9 22.0 28.0

14. 2 29. 3 48.0 72.7 28.0 29.0

22. 43. 4 61.0 73.8 30.0 29.2 26.0 50.3 96.0 74.4 33.

1

29. 6 30.0 56.4 Z6.0 30.0

33. 60. 7 Ci 8 H25NOj 46.8 30.9 34.0 62.3 Mutarotation of cam- 54.0 31.3

36. 64. 8 phorcarboxypiperidide 59. 31. 6 48.0 81.1 70.0 32.4 50.0 84.0 s=C6 H« 73.0 32.6 51.0 85.4 78.0 33.3 52 86 5 Hours 84. 33. 7 53.0 88.3

0.1 25.8 94.0 34.4

54. 5 90. 3 .4 25. 5 102.0 35.4

56. 91. 8 2.0 25.5

58. 93.8 9.0 25.3

59. 4 94. 7 12.0 25.6 61.0 96.0

99.6 24.0 27.771.0 30.0 28.7 83.0 100.4 36.0 29.9 Final 100.8 48.0 32.9 54.0 34.2

61. 36. 2 72.0 39. 1 78.0 40.6 84.0 42.2 96.0 44 2 108.0 46. 5 132.0 49.8 Days

6.0 51.2

6.5 51.2 7.0 52.9 7.5 54.3 8.0 54.7 8.5 54.8

9.0 54.8

10.0 55.6

15.0 56.3 21.0 56.9 40.0 56.7
OPTICAL ROTATION OF ORGANIC SUBSTANCES 79

Formula

18. BORNEOL AND RELATED COMPOUNDS

Borneol and isoborneol (104) Name Hi j [a]s»780 [a]5,46l

CiuKisO.

C11H22O4-

I /-Borneol

Id-Isoborneol. [d-Bornyl hydrogen phthalate.-. [Msobornyl hydrogen phthalate.

._ EtOH-.

/EtOH-.

-- \CHCh1 (CeHe—

._ CS,_.__ [EtOH.

- rcHCh.

lEtOH..

5. 51 5.16 I 4.99 : 4.78

1.65 ; 5.18

5.33

5. 19

36. 79 33.89

20. 33

42. 72

46. 06

56. 72

77. 47

81. 62

39. 10 35.38 i 20. 92 i 45. 02 I 47. 28 | 59. 71

80. 74

85. 27

44. 54 39.61

23. 33

51. 93

51. 82

68. 39

92. 76

97. 97

76. 05 65.31

37. 05

91. 70

96. 96

123. 60

163. 34

173. 71

Specific rotation [aJK of CinH^Oi l-bornyl acetate at different temperatures (104) 1- 5,893 5,780 5,461 4,358

20 -42. 43 -44. 16 -50. 18 -84. 33 40 -40. 75 -42. 49 -48. 19 -80. £8 60 -39.06 -40. 71 -46. 18 -77. 49 80 -37. 64 -39. 22 -44.52 -74.56

100 -36.44 -38.08 -43. 16 -72. 40

120 -35. 22 -36. S4 -41. SO -70.04

140 -34.00 -35.58 -40. 46 -67. 79 160 -33.04 -34. 47 -39.09 -65. 55 180 -32. 30 —33. 55 —37. 67 -63.43

[a]'x

(174; cf. 57, 58, 59, GO)

5,780 5,461

18. 5 20.7

18.6 20.8

19.8 22.3 19.5 21.9 26.8 32.0 -22.7 -26.3

-22.1 -25. 6 -39.5 -44.4

32.5 37.0 32.7 37.0

34. 5 39.4

39.9 44. 4

Formula Name

QitHaBrN.

CrHaNO.

CioHuN...

CioHwBrN CwHasNO.

!H2 0._. H»0—

EtOH. EtOH.

CHCls.

Benzoyl-d-bornylamine {It OH " " 'd-Neobornylamine 1 ; EtOH...

d-Neobornylamine *

j EtOH...

'|H2 d-Neobornylamine hydrobromide iEtOH

[CHCls"

Benzoyl-d-neobornylamine 1

j EtOH..

2. 465

1. 023 4.931

1. 644 .673

4.027

1. 005 4.413 4.0

2. 470

1. 001

1. 637

0. 671

1.8

17.6 17.6

18.9 18.6 26.0 -21.6

-20.6

-3S.0

-43.7 -31.4

-31.2 -33.0

-37.3

-44.7

1 Probably not quite pure.

'' These values were determined by Forster, and probably refer to the pure substance.
BUREAU OF STANDARDS

Derivatives of bomeol

X l«]t

CijHjoOSj (39) Methyl d-bornylxanthate s=PhMe. c=5.95

675 fifx 31.4 657 32.7

622 35.5

589 37.7

559 39.8

542 40.5

527 40.5

508 39.5 600 38.5 486 35.6 472 30.7

451 15.3

CuHssOSj (39) Ethyl d-bornylxanthate s=PhMe c=5.881

657 28.8

621 31.6

589 33.4

548 85.

1

537 35.4

527 34.9

516 34.5

506 33.5

498 32.6 486 28.9

C22H54O2S (33, 39, 40) /-Bornyldixanthide [S.CS.OBorjs (superfused)

657 -49.8

589 -58.9

553 -63.2

527 —65.3

517 -65.3

608 -65.0

500 -64.3

486 -61.0

472 -54.5 s=PHMe. c=4.154

657 -36.6

589 -42.4

548 -44.1

527 -43 8

498 -39.0

485 -33.7

478 -29.6

466 -19.5

451 2.7

446 1L3

C22H8 40 2 S (33,39,40) i-Bornyldizanthide [S.CS.OBor]j (super- fused)

e = 10.47

656

589

553 527 517

508 486

466

451

-37.3 -43.0

-44.8

-44.6

-43. 5 -42.1 -35.0

-20.5

1.3 C2»H36 2 S4 (4?) Methylene /-bornylxanthate

CHj(S.CS.OBorjj B-PhMe.

685

675

657 622

590

553 528

500 486

-1. 1 -.8

.4

3.1 5.9 12,0

18.9 31.7

39.8

C24H27NOS2 (41) 1, 2-Di- phenyl-d-bornyl imido

xanthide Ph.CS.NPh.

CS.OBor. s=PhMe. c=0.1468

622

603

590 582

578

547

536 528 492

478

242

340

399 405 408

327

129 -82

-279

-1,290

-1,500 6=MesCO. c=0.1456

603

578

573

559

647

636

309

385 412 412

275

164

X

C2 ;H29NOSj (41) l-Phenyl-2-o-tolyl-3-d-bornyl- imidoxanthide Ph.- CS.N(C7H7). CS.OBor s=PhMe. C=0.1390

657 622

590

573 559

547

119 255

417

417

331

158 s=MejCO C= 0.1424

657 622

590

573

559

547

77 190

337

351 323 182

C2iH2«OS» (41) /-Phenyl2-p-tolyl-3-d-bornyliml- doxanthide Ph. CS.N(C?H7). CS.OBor s=PhMe. c=0.1390

657 603

173 425

590 489 582

578

573 559

604 489

474

417 s=Me3 CO. c= 0.1424

657 590

578

573 559

553

547

140 380

420 450

435

365 310

C30H32OS2 (42) Triphe- nylmethyl /-bornylian- thate CPhs.S. CS.OBor s=EtOH

657

689

553 52S

508

600 486

-25.6

-34,3 -40.6

-46.4

-52.6

-56.2 -64.0
OPTICAL ROTATION OF ORGANIC SUBSTANCES

uence of temperature on dispersion of methyl l-bornylxanthate

CmHjoOSj (43) W

s=PhMe. p= 10.04 X 656 im 589 527 586

-36.6

-31.8 +20

+46.4 +80.2

-39.6 -39.3

-35.5

-32.9 -30.2

-26.4

-46.7 -46.0

-41.1

-38.1 -34.8

-30.4

-51.3 -50.0

—44.4

-40.7

-36.1 -30.2

-47.8

-46.7 -40.2

-35.6

-30.5

-23.6 s=AcOEt p ==4.86

-49.5

20.5 sa 2

-48.5

-39.2

-36.3 -31.2

-57.7

-46.0

-42.2

-36.4

-65.7

-51.1 -45.8

-38.7

-67.2

-50.4

-43.1 -34.7

19. FENCHYL ALCOHOL DERIVATIVES

Derivatives of fenchyl alcohol

CMH34O1S1 (41) Fenchylxanthic \ Tt thloanhydride L JX s=PhMe. j>=2.09. (43) \<X \

22.4 50.9 81.5

674 656

589

527 508

36.2

35.7

26.0

33.5

89.8

35.4

33.8

24.4 34.9

35.4

34.5

24.6

35.4 93.7

33.8

33.8

23.7

39.1 194.1(?)

» The query Is in the original paper.
82 BUREAU OF STANDARDS

Derivatives of fenchyl alcohol—Continued

s=PhMe. c= 6.004 Methylene fenchyl- xanthate, CHj(S.CS.O.Fen)»

L/«±ij7NUbi (35,41) 1,2-Diphenylfenchyl- imidoxanthide,

687 -36.0 Ph.CS.NPh.CS.OFen

670

657

641

631 622 612

600

589

570

559

547 536

527

-36.0

-36.1 -35.2

-34.3

-33.3 -31.6

-29.2 -25.6

-18.1 -9.6

1.9 16.7

34.1

s = PhMe. c=7.77 s = Me2 CO. c=0.1302

657 590

553 628

500 486 478

-40.8 -51.2

-57.8

-63.0

-68.0 -70.3

-70.5

657 622

603

590

582

578

573

150 430

630

799 829

876

814 CmHjtNOSi (39,41) 1,2-Diphenylfenchyl- imidoxanthide, Ph.CS.NPh.CS.OFen

566 659

553

783 630

461 246 s=Me3 CO. c=5.95 —829

547

528

701 682 -52. 6 -55. 2

s = PhMe. c = 1.416 656

631 612 588

553

527

-57.3 -57.9 -57.2

-53.8

-38.0 -6.3

696

687 663

642 634

75 109 225

338 436

517 508

504 496

42.3

57.8 73.9 87.3

s = PhMe. c=0.1304

622

603

590

582 578

573

630

900 1,050

1,040 1,000 930

C22H34O2S4 (42) Fenchvl dixanthide [.S.CS.OFenJa

s = PhMe. e=4.35

566

559

553

770

560

290

657

589

527 486

479

74.2

98.9

136.3 181.4

191.5

547 542

536 52S

508

15 -315

-640

-1,590

-2, 440 473

467 462

457

203.7 215.6

227.6 240.2

500

492

486

478

-2,940

-3, 160 -3,340

-3,530

20. TERESANTALIC AND ISOTERESANTALIC ACIDS

Dispersion data. Other acids derived from camphor (202)

Formula Name

s p or d 6,563 5,893 5,463 4,861

CnHuOj

CieHuOj.-.

CuHirClOt..

! Methyl teresantalate . iMethyl isoteresantalate fTeresantalic acid. llsoteresantalic acid.. .

/Nil.... \C6 E6-

NiL„.

CeHs.. CsHiC«H...

L 0305 10.0

1. 0269

10.0 10.0

10.0

-48. 19 -50.43

-84. 51 -60.84

-99.29

7.22

-60.79

—63. 57 -108. 75 -76.60

-127. 58 9.22

-71. 79 -75. 36 -130. 34 -91.70

-152. 41 10.45

-93.04

-97. 82 -174. 31 -117. 76 -204. 52 Methyl hydrochloroteressntalate 14.33
OPTICAL ROTATION OF ORGANIC SUBSTANCES 83

V. Class III. COMPOUNDS CONTAINING NO ASYMMETRIC CARBON ATOM, OR CONTAINING AN

ASYMMETRIC OR DISSYMMETRIC ATOM OF

SOME OTHER ELEMENT

(a) COMPOUNDS CONTAINING ASYMMETRIC ATOMS OF S, P, ETC.

21. METHYLETHYLPHENACYLTHETINE DERIVATIVES

(a) Compounds containing asymmetric atoms of S, P, etc.

Salts of methylethylphenacylthetine, CnHuOjS (=MOH)

(115) M? (?15) HI

! 4,359 5,781 5,893 4,359 5,781 | 5,893

CjiH»BrOjSj rf-M d-a-bromocamphor-x-sulphonate Ci7H::X308S t-M picrate

( 0.480 MejCO __U .948

{ 2. 289

1

-16.7

-15.8 -16.2

-14.

1

-14.0

-13.8 -13.0

-12.4 HiO. -12.6 EtOH-

| 0.603

, . 610

.945

f .807

\ 1.034

72.5

70.9

71.4

S3. 9 83.6

61.3

61.1

60.8 70.6

70.8

59.7 59.0 59.2

67.2

66.2 ! Ci:Hi:XjOiS d-M styphnate CjiHnBrOjSi i-M d-a-bromocamphor-ir-sulpho- i nate ^co .{ ;*g

11.6

11.6 10.010.2 9.2

9.1

HiO „

f 0.260

1 .484

j .760

I. 1.190

f .192

I .320

I .387

56.9 56.2 57.2

57.6

72.9

71.1 71.8

48.3

47.4 48.0 47.5

61.2

60.9

60.8

46.3

46. 4 ! 46.0

46.9

57.3 1 56.2 56.9

Ci7Hi;NjO»S /-M styphnate

EtOH.. MejCO / 0. 684

1. 1.009 -12.1 -12.3 -10.6

-10.7 -9.9

-10.0

ClT HirXiOiS d-M picrata

MejCO

f 0. 575 .713

I 1.464

15.7

15.8 15.9

13.5

13.7

13.6

12.2

11.9 12.2

22. BROMOCAMPHOR- AND CAMPHORSULPHONATES PHOSPHONIUM SALTS

s=HjO (16J)

(a) d-a-Bromocamphor-T-sulphonates 4,359 5,781 5,893 ^!iH.sBrN04S„„

<;,Hj«Br04 PS.... Ammonium salt . . 0. 4SS .886

104.0 53.9 87.9

45. 85 84.0 dZ-Phenyl-p-tolylbenzylmethylphosphonlum salt... 43. 74

(b) <f-Camphor-0-sulphonates

< :0HllNO4S Ammonium salt . .498

1.058 26.612.3 21.6

9.9

20.1

1 iHr04 PS dZ-Phenyl-p-toiylbenzylmethylphosphonium salt 9.2
84 BUREAU OF STANDARDS

(b) COMPOUNDS CONTAINING DISSYMMETRIC METALLIC ATOMS

(Co, Cr, Rh, Ir, Pt, Etc.)

en=ethylenediamine, HaN. CHj. CHj. NH».

pn=propylenediamine, HjN. CH(CHi)CHj. NH5 . tr=trimethylenediamine HjN. CHj. CHj. CHj. NHi.

23. COBALT COMPLEXES

Trialkylenediamminecobaltic salts I=[Co. pnjjBn. 2HiO. II=[Co. en3]Brj. 2HjO

s=HjO p=0.1 (212) M]x»

X I (d-pn) I (/-pn) n (d-salt) II a-salt)

6, 615 -175 +173 0(7) (?) 6,435 -120 +122 +82 -82

6,260 +232 -227

6, 075 +111 -111 +376 -374

5,893 +223 -223 +603 -603

5, 740 +459 -457 +868 -863

5,600 +836 -824 +1,237 -1,250

5,475 +1,379 -1,370 +1,841 -1,830

5, 270 +2,508 -2,479 +3, 100 -3,095

5,075 +1, 114 -1,114 +2, 477 -2, 477

5, 035

4, 990 -1,114 +1,114 +1, 452 -1, 452

4, 920 4,850 -937 +927

i The largest, value of a was 1.2°; the last figure in each number is therefore uncertain.

(94) . S=H2 0. p=60

X X X

6, 750 165 6,265 394 5, 760 828

6, 600 228 6, 100 513 5,595 J l, 069

6, 425 306 5, 910 638 »p = 1.91.
OPTICAL ROTATION OF ORGANIC SUBSTANCES

05)

X [M]x

s = HjO. p=0.5to7.3

6, 750 * ±165

6,600 ±216

6,425 ±290

6,265 ±375

6, 100 ±448

5, 910 ±599

5, 760 ±790

5, 595 ±931

5,420 ±1, 399 5,260 ±1,903

5, 085 ±2, 377 4,920 ±2, 705

[Co. em](C104)j s=Hs O. c=0.57

5, 085 ±2, 592

5, 260 =1,804

5,420 ±1, 407

5, 595 ±999

5, 760 ±743

5,910 ±513

6, 100 ±444

6, 265 ±407

6, 425 ±327

6, 600 ±212

[Mjx

Co. ens(CNS), s=HjO

d-salt, c=0.63

/-salt, c=0.81

5,420

5, 595

5, 760

5, 910 6,100

6, 265 6,425

±133

±781 ±616

±491

±401 ±267

±179

[Co. en3 ]Ij HjO s=H2 tf-salt, c=0.59

I-salt, c=0.5o

5, 085

5, 260

5, 420

5, 595

5, 760

5, 910

6, 100

6, 265

6, 425

6, 600

±2, 158 ±1,843 ±1,435

±1, 072 ±774 ±599 ±470

±357

±274

±211

[M]x

[Co(C,04)i]Ki, 3HHjO

s = HiO. c=0.41

4, 740 4,780

4,870

4,945 5,020

5, 105

5, 180

5, 260

5, 340 5,420

5, 515

5, 610

5, 700

5, 800

5,910

6, 020

6, 140

6, 260 6,380

6, 520

6, 660

6, 800

6, 940

±389 ±402

±418

±441 ±465

±492

±511 ±552

±596 ±640

±705

±786 ±869 ±974

±1,135

±1,266 ±839

=F18 =F543 +422

=F174 ^34

+19

1 Mean values for d- and /-salts.

(209, 224)

d- and /- [C4H7Oj.Co.enj] X [M]j>> Acetylacetonatodiethylenediamine salts s=HjO. c=0.1 [M]D X d- h

Clj +2, 107 +2, 102 +2,204 +2, 107 +2, 217 +2, 107 +2,040-2, 134 -2, 102 -2,204

-2, 107 -2, 217 -2, 107 -2, 261

Br2 . — -

I*- (CIOOj—

(N03 ; 2 . (SCN) 2 S20».—

d- and /- [CeH»02 .Co.en,] X

Propionyiacetonatodiethylenediamine salts

s=fi2 0. c=0.1 X d- I-

(CIO,)*. +2,476

+2.481

+2, 311

-2,436 -2,460

-2,383

(NO,),. S2 0,

1 The last figures in tiiese numbers are uncertain.
BUREAU OF STANDARDS

d- and HCeH9O2.Co.en2] I 2 Pro- pionylacetonatodiethylenediamineeobaltic iodide

i d- and i-[C«H»02.Co.eni] It Pro- pionylacetonatodiethylenediaminecobaltic iodide

s = H2 0. c=0.1 s=H20. c=0.1

X

! x

d- l- d- lr

6,440 6,260

6, 075

5, 893

5, 750

5, 600

+115

186 276

402

518 630

-135 -190

-268

-390

-535

-645

5. 540

5, 475

5, 425

5,370

5, 320

650

600

554

440 360

-672

-628

-584 -480

-388

24. CHROMIUM COMPLEXES

tCr(Cj04)s.]Kj.3H2 (85) [CrCQfO&g Ks.3HiO (95) [Cr(Cj04)»] Kj.3H,0 (95)

s = H2 s = H3 s = H2

X [M]

x

X [M]

x

X

4, 600 4,800

5,000

5, 200

5, 300

-1, 550 -1,710

-2, 100 -2, 300 -2,200

5,400

5,500

5, 600

5, 700 5,800

-2,100

-1,400 -900

+1,750

5, 950

6,200

6, 340

6, 400

6, 500

1,960

600 -100

-200

d- and f-[Cr.ena] Ij. HjO d- and HCr.enj] Is. H2 d- and HCr.em] I3 .K,0

(95; if., 96) (95; c/., 98) (95; cf., 96)

Values for d-salts are +,

for 1-salts —

Values for d-salts are +, j for 1-salts —

i

Values for d-salts are +,

for 1-salts —

s=H3 p = 1.01-0.03 t=15°-18° s=H2 p = l. 01-0.03 <=15°-18° s=HjO p= 1.01-0.03 i=15°-18°

4, 200

4, 420

4, 640

4, 860

5, 100

2, 826

2, 538

2, 205

1, 761

1, 171

5,260 5,430

0, 610 5,800

965

763

574 409

6.020 6,260

6, 520

6, 660

291 233

195 182
OPTICAL ROTATION OF ORGANIC SUBSTANCES

25. RHODIUM COMPLEXES

[M]x

d- and I- Rhodiumtriethylenediamines

[Rh.en3]Brs .2Ha O (95) s=H2 0. p=7.31

6,780 -244

6, 640 -251

6, 520 -260

6, 380 -278

6, 260 -296

6,140 -309

6,030 -328

5, 890 -346

5, 700 -372

5, 510 -400

5,340 -425

5, 180 -446

5,100 -458

4,860 -481

4,710 -495

4, 310 -508

4, 150 -509

[Rh.en3]I3 .H2 (95) s=E3 0. p=4.53

6,840 ±205

6, 660 218

6, 520 232

6, 380 247

6,260 255

6, 140 273

6, 030 293

5, 890 302

5, 800 312

5,700 326

5, 605 335

5, 510 347

5,420 359

5, 340 366

5,260 380

5, 180 387

5, 100 396

5, 020 405

4,945 411 4,860 420

4,780 428

4, 710 434

4, 650 442

4, 560 447 4,480 450

4, 420 454 4,310 455

4,260 456 4,150 457 4,060 458

4, 010 459

3, 940 460 3,880 402

3, 820 366

3, 780 340

3,740 323 3,700 322

[M]x

d- and /- Rhodiumtriethylenediamines [Rh.em](N08)3 (95) s=H2 0. p = 3.37

6, 840

6, 660

6, 520

6, 380

6,260

6,140

6, 063

5, 890

5, 800

5, 700

5,605

5, 510 5,420

5. 340

6, 260

5, 180

5, 100

4, 945

4, 780

4, 650

4, 480 4,310

-240 260

265

284 298

319

334 300

370

402

420

430

440 456

463 472

495

518

536 550

562 [Rh(C2 4 ) 3]Kj.HiO (95) s=HjO. p = 10.96-0.5

4,860

4, 950

5, 020

5, 100

5, 180

5, 260

5, 340

5, 420

5, 510

5, 605

5, 700

5, 800

5, 890

6, 900

5, 970

6, 030

6, 140

6, 260

6, 380

6, 520

6, 660

6, 800

6,946

1, 724

1, 419

1, 225

997

833

553

411 325

225

146

7930

25 -22

-56 -82

-102

-114

-121 -126

-133

d- and /- Rhodiumtriethylenediamines [Rh(C3H2 4) 3]K3 .lVSHs O

Malonate (95) s=H2 0. p=0,804 and

1.503

5, 340 ±261

5, 420 J ±263

5, 515 ±267

5,610 « ±276

6,700 ±280

5, 800 i±284

5, 910 ±271

6,020 l ±258

6, 140 ±250

6, 2C0 1 ±246

6, 380 ±241

6, 520 1 ±236

=0.511.
88 BUREAU OF STANDARDS

26. IRIDIUM COMPLEXES

d-Triethylenediamine salts (225)

d-[Ir.enj]X» [a]x X

? >~ 6,663 5,893 5,270

I 0.25 30 42 06 N03 .25 41.2 57.2 75.2 C104 . 2 34.5 48.5 64.0

d-Diniiritodiethylenediamine salts [Ir(N02) 2en2 ]X(225)

s = H2 p=0.25 [a]x

j - 6,563 6,893 5,270 Br 17.2

16.4 18.0

26.0

24.8 27.2

40.0

38.4 41.2 C104 NO»

27. PLATINUM COMPLEXES

Platinum complexes containing d- and l-propylenediamine (212) s=HjO c=0.5 [M]t,563 [M]m»s [M]5 ,,70

/-[Pt. d-pn3]CU.H2 -844 -1, 013 -1, 419

d-tPt. J-pmjCU.HjO +839 +1, 035 +1,413

/-[Pt. d-pn3]Bri -833 -1, 024 -1,422

d-[Pt. l-vm]Bn +840 +1, 031 +1,429

/-[Pt. d-pn3 ]l4. -851 -1, 054 -1,433

d-l.Pt. /-pns]L +832 +1, 036 +1,424 Complex metallic salts containing l-propylenediamine (44)

s= H 2 V [M]b

Tt. pn2]Ch 16.6 +192

'Pt. pn. 2Nn3]Cl2 17.5 +94

Pt. en. pn]Cl» 19.1 +96

.Pt. pn. tr]Cl2 13.1 +98

Pd. pn2]Cl2 17.7 +258

Ni. pn3]Cl2 .H2 11.0 +55

28. MOLYBDENYL AND TUNGSTYL DERIVATIVES OF MALIC AND TARTARIC ACIDS (Mo03)(Ci Hi05 Na2) Sodium molybdenylmalate [M]D. (77, cf. 75) '\ 11.020 6.046 3.175 1.633 0.827 0.416

15 190.2 189.0 188.2 187 185 181 30 178.7 177.5 176.8 175 173 170 45 163.6 162.4 162.0 160 158 156 60 146.0 144.8 144.0 142 140 136 75 125.9 124.6 123.2 122 120 115 90 102.8 101.2 99.7 98 96 93 p«per cent of malic acid: the solutions are N/1, 2, 4, 8, 16, 32.
OPTICAL ROTATION OF ORGANIC SUBSTANCES

(MoO^niCiHiOsNai) Sodium dimolybdenylmalate [M]D. (77 cf. 75) \ p

in.

5.748 3.094 1.608 0.821 0.414 0.208

15 358.5 951.5 945 935 920 905

30 954.7 946.8 938 922 903 881

45 947.0 937.7 928 903 876 828

60 934.

1

915.9 895 860 795 717

75 913.0 884.4 849 777 672 509 90 877.6 832.5 766 661 496 218 p=per cent of malic acid: the solutions are N/2, 4, 8, 16, 32, 64. Mo02 {CiHi OsNa) 2 Sodium molybdenyldimalate [M]D- (77; cf. 75) '\ 11.792 6.275 3.241

10 -121.4 -119.8 -114.

2

20 125.8 122.9 115.7 30 128.7 124.7 116.5 40 130.4 125.8 117.1

50 i 131. 6

i 126. 8 > 117. 6 60 131.5 125.0 114.4 70 130.9 123.3 110.6 80 129.9 120.0 105.6 90 127.6 115.1 98.6

95 125.9 111.6 93.1

1 Maximum.

p=Per cent of malic acid: the solutions are N/1, 2, 4. MoOiiCiHsOiK)^ Potassium molybdenyldimalate [M]d- (75) X 6.975 3.619 1.843

20 4-382. 2 +379. 3 +377

45 381.4 378.3 374

70 380.1 374.6 365

95 372.6 359.4 342 p=Per cent of malic acid. MoOi{CiHiOi,NHi)2 Ammonium molybdenyldimalate [M]d. (77; cf. 75) X 12. 107 6. 367 3. 270 1. 658 0.835

10 -122.0 -121.4 -120.2 -109 -103

20 125.7 125.1 123.7 112 107 30 128.7 128.0 125.2 113 109

35 i 129. 5 1 128.7 » 125. 8 1 114 i 110 40 129. 3 128.2 125.6 113 109 50 129.1 128.2 123.7 109 103 60 128.6 126.2 120.6 103 94

70 126.5 123.6 115.9 96 81 80 123.8 120.3 109.6 86 67

90 120.7 116.5 102.5 75 52

95 118.9 114.8 99.6 71 45

1 Maximum.

p=»per cent of malic acid: the solutions are N/1, 2, 4, 8, 16.
BUREAU OF STANDARDS

MoOniCiHiO eAra2 ) Sodium molybdenyltartrate [M] D . (76) \ V

( \

12. 308 A 7511 0. lOL 3 569 1 831 928 u. *0/ u. 4oi nU. :

1 1117

20 832.4 813.8 787.6 750 629 695 538 421 40 815.4 797.6 769.

1

729 602 671 509 386

70 791.8 778.6 717.0 704 561 636 443 300 90 767.7 758.6 722.5 676 502 600 363 225 p = per cent of tartaric acid: the solutions are Nil, 2, 4, 8, 16, 32, 64, 128. (MoOz)2(Ci HA OsNa2 ) Sodium dimolybdenyltartrate [M]D . (76) \

\ V t\\

6.403 3.461 1.803 0.920 0.465 0.233

15 1324.9 1223 1039 802 662 692

30 1188.7 1098 918 710 592 624

45 1037. 7 926 785 611 514 450

60 894.9 777 668 516 443 382

75 771.0 651 566 434 379 320 90 666.2 565 484 375 323 270 p=per cent of tartaric acid: the solutions are N/2, 4, 8, 16, 32, 64. MoOi(CiHiOt>K)2 Potassium molybdenylditartrate [M]D. (76) '\ 6.975 3.619 1.843 0.929 0.467 0.235

20 382.2 379.3 377 372 362 366

45 381. 4 378.3 374 368 361 353

70 380. 1 374.6 365 351 338 320

95 371.6 359. 4 342 316 283 246 p=per cent of tartaric acid: the solutions are N/2, 4, 8, 16, 32, 64. WOziCiHtOiNai) Sodium tungstylmalate [M]D . (77) X 10.202 6.792 3.107 1.601 0.822 0.416

10 28.0 +29.2 +32.2 +66 +91 +124

30 28.6 31.2 38.5 64 98 131 50 30.3 36.7 51.6 81 116 139 70 33.8 45.6 66.3 103 137 150 95 37.3 57.8 82.2 124 159 162 p=per cent of malic acid; the solutions are N/1, 2, 4, 8, 16, 32. W02(CiH4 ^Na) 2 Sodium tungstyldimalate [M]D. (77) '\ 12.268 6.134 3.211 1.640

10 -99.6 -98.5 -97.1 -91

20 104.3 102.7 100.9 93

30 107.6 105.4 102.8 94 40 110.1 107.7 103.2 95 Max.

60 112.0 109.0 104. 1 Max. 94 60 113.4 110. 1 Max. 103.8 93 70 113. 7 Max. 109. 5 101.9 91 80 113.4 108.

1

98.0 88 90 112.8 106.2 93.8 82

95 112.4 105.0 91.2 77 p=per cent of malic acid; the solutions are N/1, 2, 4, 8.
OPTICAL ROTATION OF ORGANIC SUBSTANCES

WOt(Ci Hi Oi Na2) Sodium tungstyltartrate [M]D . (76) '\ Ll.o&J 0.*O0 3.484 1.409 0.922 465

20 482.8 463.5 442.4 420 395 360 40 476.1 455.7 432.8 405 378 344

70 466.7 447.2 421.3 390 354 316

90 459.3 437.5 411.9 381 336 291 p=per cent of tartaric acid: the solutions are N/1, 2, 4, 8, 16, 32. {WO,) 2 {CiHi OiNa2) Sodium ditungstyltartrate [M]D . (76) '\ 5.833 3.283 1.751 0.906 0.461 0.232

10 220.2 208.1 197 191 183 179

20 213.6 203.0 191 186 178 171 30 208.1 198.3 186 182 174 163 40 203.2 194.

1

182 178 170 155

50 198.7 190.3 179 175 166 150

60 194.8 186.8 175 172 163 145 70 191.4 183.7 172 170 159 141 80 188.7 180.7 169 168 158 139 90 186.6 177.8 167 166 157 137 95 185.8 176.6 167 164 156 134 p =» per cent of tartaric acid: the solutions are N/2, 4, 8, 16, 32, 64. WOiiCiHiOiNa)^ Sodium tungstylditartrate [M]D . (76) \

\p

1 \

12.582 6.845 3.580 1.832 0.927

10 242.4 242.7 243.5 247 256 20 245.9 247.2 248.2 252 262

30 248.5 249.9 251.7 255 264 40 250.9 252.4 254.3 257 265

50 253.0 254.4 255.9 258 264

60 255.0 256.1 257.2 258 263 70 256.4 257.6 257.0 256 261 80 257.6 257.4 256.3 254 256 90 257.9 256.6 254.7 251 248

95 258.1 256.0 252.8 250 244 p=per cent of tartaric acid: the solutions are NA, 2, 4, 8, 16.
92 BUREAU OF STANDARDS

VI. Class IV. SUBSTANCES OF UNKNOWN, DOUBTFUL, OR COMPLEX STRUCTURE

29. ALKALOIDS AND DERIVATIVES

(^2oH2\Nz02 Quinine [ a ]£ 8 = EtOH (abs.) (138)

1 2 3 4 6

-171.4 -169. 6 -167.9 -166.

1

-164. 2 -162. 4 5 -170. 5 -168.7 -167.0 -165.2 -163.4 -161.6

10 -169. 6 -167.8 -166.

1

-104. 4 -162.7 -160. 9

15 -168. 9 -167.

1

-165.4 -163.7 -162. 1 -160.4

20 -168. 2 -166. 6 -164.8 -163.2 -161.6 -159.8

C2QH25CIN2O2 Quinine hydrochloride (83) s=H»0+EtOH s=H2 0+EtOH

c=2. f = 15° c=2. < = 15°

Per cent EtOH [«]*> Per cent EtOH [«]*

9790

8580

70

-143.86

-160. 75 -168. 25 -174. 75 -182.27

605040

20

-187. 75 -187.50

-182.82

-166.59

-138. 75 CV/22 V2 Cinchonine salts (89; cf. 84, 85)

Formula Name

c = 2.5 5.0

OioHmNjO Cinchonine EtOH.. 224.5

134.2

126.3

121.4

(c=0.5)

133.5

127.8

122.3 CjjHsoNjOi Myristate.. CHCh —

C„HMNa Os Palmitate CHCh

CVHwNjOa Stearate CHCh--

Derivatives of cinchonine and cinchonidine (87) s=CHCl3 c=2.0 Cinchonine Cinchonidine

Formula Name Mg

Ci,H34Nj03 Acetyl- 108. 5

62. 15 -27. 80

12.90

11. 43

98. 65 CsjHjsNjOsS

ChHjsNsO,

BenzenesulphonylBenzoyl-
OPTICAL KOTATION OF ORGANIC SUBSTANCES

{P*HuN&$ Brucine salts, s=CHCh (85, 86, 87, 89) 93

Formula Name

c=2.5

C»HsoNiOe.

C»H32NjO».

CrH^NiOo

CjsHseNaOe. CaH38Na O«.

Acetate

Propionate. n-Butyrate

n-Valerate . n-Caproate

260.6

252.3 251.2

251.6

252.8

f = 14.5-20° O. [M) D CtaHwN2 04

CasHsoNiOs. C»H30N2O7

Cj7H32Nj07 CjjHmNjOt

C»H!4N20o. CmH38Nj06 . CJ0H32N2O6

C31H32N2O7 C8jHmN207. CS2H34N2 07 C33H36N207 CssHmNjOs

CwH3 »N207 . CssHasNiOs. C35H3«N208 C3«H38N208 C3*H4oN2 8 C^HmNjOj

CmHssNsOs

C*iHs2N20«

Brucine.. Glyoxylate Pyruvate.

Acetoacetate Levulinate

Sorbate

0, 7-Dihydrosorbate. Benzoate

Phenylglyoxylate Phenylpyruvate

Benzoylacetate

/S-Benzoylpropionate. Benzoylpyruvate Benzylpyruvate

Piperate

a, 0-Dihydropiperate

0, y-Dihydropiperate

Piperonylbutyrate . .

.

Myristate

Palmitate

Stearate

121.0 -61.3 -86.2

-53.7

-177.9 -120.6

-214. 2 -129.0 -33.4 +18.5

-188.8 -182 4 +66.1

-55.5

-28.6

-154.3

-179.

1

-170. 5 246.7

248.4 247.7

Dibrucine salts C«H56N4 0n

CsoHjeNiOu

CmHmNiOu

C48H54N4OU

C49H5SN4O12 C&0H48N4O12 C5 iH8oN40i2 C$aH5 8N40i2 CSlH«N40i2 CS2HttN40ii CS3HMN40l2 cmh«n40i1

C45H5SN4012

C5JH70N4O1J

CJSH42N4012 CsgHe4N40u

Mesoxalate

Oxalacetate Acetonedicarboxylate

Oxalate Malonate

Succinate Glutarate Muconate

fa, 0-Dihydromuconate

\fi, 7-Dihydromuconate

Adipate

Pimelate

Suberate...

Azelate Sebacate... Cinnamylidenemalonate

(a, /3-Dihydrocinnamylidenemalonate

Ij3, 7-Dihydrocinnamylidenemalonate.

-191.9 -189.1

-357. -362.

4

-428.2 -428.2 -24.6 -26.3

-470. 6 -470. 6 -580. 9 -591.6

-464. 4 -465.

8

-90.4 -88.5

-359. -354.8

365.5 -358.

8

397.8 399.2

417.9 405.2

457.5 439.6

444.2 44a 8

479.5 477.5

98.99

439.5 -444.2

505.2 -509.2 67316°—32-
94 BUREAU OF STANDARDS

VII. Class V. INFLUENCE OF SALTS AND OTHER

SUBSTANCES ON ROTATORY POWER

Influence of salts on rotatory power (48)

(a) CiH«Oj Mactic acid (containing 8 per cent d-lactic acid) s=Ha O * = 15° C.

Salt c of salt P MM61

Nil - —

-

10.73

8.71

7. 65

6. 79

1.027

1. 162 1.293

1. 485

-2.2

-7.6 -8.0

-17.7 NaOl 23.4 41.2

59.2 NaBr BaBn ._.

(6) CiHiOj Methyl /-lactate (containing 5 per cent methyl d-lactate)

s P [a]^461

Nil —- 10010.0

10.0

10. 37 10.0 10.0

10.0

10.0 10.0

9. 81

1. 093

1. 012 1.050

1.150

1.080

1. 054

1.027 1.054

1.094

1. 456

8.4

1.4.6 -2.1

.5.6

.9 -1.0

-1.3

-9. 1

H»0 —

iVNaCl

4 iVNaCl

AT NaBr NKC1 —

WNH4CI — .- - -

iSTCaCU

4 N BaBrj - -

(c) C1H1O4 d-Glyceric acid s=H1

Salt e of salt V [ a ]5?461

Nil - - - 2.40

1.84 1.90

1.01

1. 17 1.22

0.0 19

6.9 NaCl — 23.4

20.8

(d) CsHjNOj d-Alanine

s c

[ a ]5?461 HjO 10.0 2.9 N KCL 10.0 3.0 iVNaCl 10.0 3.3 iVBaCh 10.0 3.5

A iVBaBn 10.0 4.8 1.5MHC1 5. 78 17.8

(e) CSH9 N04 d-Glutamic acid

HiO

iVNaCl...

L iVNaCL.

2VKC1.--.

iVBaOlj... /WBaBra.

MNaOHBM NaOH

liMHCl.

p d"

[ a ]5?461

1.50 1.003 13.3 1.50 1. 043 14.4

1. 51 1.152 15.8

1. 53 1. 050 14.8 1.53 1.092 14.4 1.51 1.500 18.1

12. 25 1.075 -3.6

6. 55 1. 050 11.7 8.75 37.4
OPTICAL ROTATION OF ORGANIC SUBSTANCES 95

Influence of salts on rotatory power (48) —Continued

(f) Influence of NaBr s=MeOH c=10 +N NaBr

1 ft Ik am

r i 15

1 ft U ifii C4 He05 /-Malic acid -5.9 21.8 C4H9 0» (/-Tartaric acid 2.6 -9.0 C4 H8 03 Methyl /-lactate. 5.4 -5.8 CsHsOs Dimethyl Z-malate -9.4 9.1 C6HbO« Dimethyl (/-tartrate.. 2.7 -12.6 CwHmOi Dimethyl d-diacetoxysuecinate (c=4) -18.3

3.6 -12.2 CijHuOa Diethyl d-diacetoxysuccinate (c=5) 7.6

(g) Influence of sodium halides

Formula Name s c t [a 1,461

CtHioOa d-0-Phenyllactic acid „

fHjO }NNaC\

2. 505 .665

10.0

10.0

10.0

10.0

20

20

20

20

1818

25.5

13.5 21.0 -2.0

-4.5

-22.3 OwHuOi Methyl d-0-phenyllactate

1 MeOH

|AT NaBr in MeOH

/MeOH

WNaBr in MeOH.

(ft) CsHisNOi Ethyl /-aspartate

Nil C6H«.... CHCh..

MeiCOi. H»0

4 ATNaCl

A iVBaBrj

5iVCaClj

iVHCl

MeOH

JVNaBr in MeOH.

461

-11.7

10.92 -12.6

11.02 -9.7

20.0 -8.8

21.7 4.2

12.25 4.2

10.81 6.7 14.50 11.5

13. 21 14.5

11.37 12.0 20.0 -0.5

20.0 4.3

1 Ethyl /-aspartate reacts with Me:CO; «fr = -3.50 to -56.6 (c=20) in 15 hours

(i) Effect of temperature

(1) CiHeOs /-Lactic acid in aqueous solution (containing 8 per cent d-lactic acid) p—10.73

t 15 18 36 52 62 70

d* 1.03 1.03 1.02 1. 01 1. 01 1.00

[ a]5,461 -2.2 -2.0 -0.7 ±0.0 0.4 0.7
96 BUREAU OF STANDARDS

Influence of salts on rotatory power (48) —Continued

(2) C4H8O3 Methyl /-lactate (containing 5 per cent methyl d-lactate) s=NU

t [ a ]l 893 [ a Jo, 461 Mlors

15201.097

1.093 7.267. 46 8.25

8. 39

10. 89

11.21

s = H2

V [ a ]5?893 [a]5°46i [ a E°07S

10080.0

50.9 20.0

10.0

1.093 1.086

1.063 L 026

1.012

7.46

4.1

2.

1

1.8 1.3

8. 39

4.4 2.5

1.8

1.4

11. 21 4.5

1.0 -0.2

-0.5

5. 36 l.OOo 1.3 1.4 -0.9

Effect of salts on the rotatory power of CzH7 N02 d-alanine (48)

8 c

[ a ]4?359 H2 10.0 2.9 ATKC1 10.0 3.0 iVNaCl 10.0 3.3 NB&Ch - 10.0 3.5 i\TBaBr2 - 10.0 4.8 1.5MHC1 5. 78 17.8

Influence of inorganic salts on the rotation of C4H6O5, malic acid

s«=HjO, n=number of gram equivalents of salt added to 500 g of 20 per cent malic acid solution.

8, 53, 18?, 183, 387, 214, 223) A = Change in [a]o due to the presence of the salt

(214; ci.

Salt

NH4CI

(NHO2SO4. NH<NOa.

AICI3- —

A12 (S04)3- ZnCl2 —

.

ZnS04--. Zn(N03) 2 - Cd(N03) 2 _ HgClj..—

Hg(N03 )j- MgClz.---

MgS04-.-

Mg(NOa)2 . CaClj

1. 0S6

1. 103

1. 0965

1. 1418

1. 0938

1. 131

1. 0985

1. 1547

1. 1075

1.1105

1. 1915 1.118

1. 2247

1. 119 1.2283

1. 1291

1. 267

1. 125

1. 1495

1. 3472

1. 0995

1. 1556

1. 1095

1. 1935

1. 107

1. 1817

1. 1018

1.166

Salt

1. 16 3.28

.65 198

1.11 3.00

.60 2.63

.40

.56 2.55

.00

1.06

.55

2.81

.73

3.11 .36 -3.36 -3.58

. 77 2.82

.34 L51

.81 2.65

3. 95

14. 81

Ca(NOi)j BaCU

Ba(NOs) 2 . LiCl NaCl._. Na2 S04 . NaNOsKC1.

KBr. KI_—

K2SO4- KNOs.

RbCL.

CsCl..

1. 1155 L 1917 L 1256 1.2566 L 133 1.091 L 123 1.0993 L153 L 1103 L 181 L 107

1. 180 t 0905 L 1013 L 123 L 1618 L 1215 L 2363

1. 1397

1. 3015

1. 1126

1. 1095

1. S82

1.1223

1. 2417

1. 1442

1. 3185

L67

5. 39

1. 14 3.38 L61

4.64

1.04

1. 95

3. 49

5.57

2.11 6.00

2. 39 6.79

1.48 1.88

4.51

1.95

5.08

1.94 4.66
OPTICAL ROTATION OF ORGANIC SUBSTANCES

CiHtOt Tartaric acid, effect of metallic salts on rotation (129) 97

c [a] 5,780

Salt Of salt Of acid For acid alone X—

t

1+ 5,780 5,461 4,920 4,359 NaCL 24.8 39.1 9.

1

17 -3.2 -4.4 -8.0 -17.5

CaClj. 42.7 30.2 10.2 17 -42.5 -49.0 -64.9 -95.0 SrCb 41 25.8 10.9 19 -16.3 -19.4 -27.1 -43.2

BaClj. 28 47.0 8.2 17 -11.2 -13.5 -19.0 -33.8 MgClj 25 19.1 11.9 17 7.4 7.5 6.8 3.8 ZnClj 22 24.4 11.0 18 9.6 9.9 9.9 8.0 NaNOs - 36 21.8 11.3 18 0.2 -0.6 -3.0 -10.5 Ca(NOj)j 40 21.8 11.3 20 -14.0 -17.0 -24.1 -38.9 Sr(N03)j 32 21.8 11.3 20 -5.4 -7.0 -12.0 -22.5 Ba(N03 )» 8 21.8 11.3 18 5.2 4.9 -3.7 -1.0

Influence of sodium and barium halides on the rotatory power of derivatives of

succinic acid in aqueous solution (45, 46)

Formula Name

CtHiOj.. Malic acid

.

C4 HjO».. Tartaric acid.

C,H»0«..

CjHioOs.

Methyl hydrogen tartrate.

Dimethyl malate

C»Hio04 . Dimethyl tartrate.

C$Hn06 . Diethyl tartrate.

16. 67

13. 95 11.15

16.67 15.2

14.22

13. 33 14.20

13. 36

11. 15

19. 67 20.05

19.6 50.0

43. 62

36.4

49. 77

43. 62

36. 45

50.0 43.62

36. 45

HjO

4 Mi NaCl2 M BaBrj-

.

H3 2 M NaCl...

2 M NaBr._

2 M Nal

1 M BaClj..

1 M BaBrj..

2 MBaBrj..

HjO

5 M NaCl...

2.5 M BaBrj

HjO

5 MNaCl...

2.5 M BaBrj

HjO

5 M NaCl...

2.5 MBaBrj

HjO

5 M NaCl...

2.5 MBaBrj

25 -1. 55 25 4.80

25 21.8

25 12. 98

25 7.62 25 7. 03

25 5.11 25 -1.58

25 -2.34

25 -8.83

25 14.8 25 3.7

25 -8.37

25 -8.58

25 -1.65

25 9.00

16.7 > 14. 71 16.0 .73

17.0 -12.02

19.9 »17.34

17.0 2.19

15.0 -7.93

J Moles of salt per 1000 g of water, throughout the table. * See (143). * See (143). Effect of the addition of various salts on the rotation of CgHieOs Diethyl tartrate. (147)

C=11.84i

HjO

MNEUC1... MNaCl M KC1 MNH4NO3. MNaNOj.. MKNOj... Nal MKI

M7

1.021 1.046

1.088

1. 097 1.068 1.110

1.119

1. 201

1. 211

r 126

28. 37

22. 56 20.32

19.59 22.50

19.06

19.34

16. 26

16.69

MNaBr MKBr

(NH<)jS04

MKCNS....

MNaClOi... MNaCjHjOj

MCO(NHj)j M BaClj

1. 127

1. 151

1. 129 1.091 1.132

1.087

1. 058

1. 127

[-IS

19.86

18. 41 18.73

17.28

18.78

18. 25 27.29

13.94

1 The concentrations of ester and of salt are relative to 100 g. of water.
98 BUREAU OF STANDARDS

Effect of inactive substances on the rotation of tartaric acid

1. Inorganic and organic acids (23, 110, 178, 217).

2. Organic bases (178, 179).

3. Organic halide and nitro compounds (179).

4. Alcohols (22, 110, 178).

5. Benzene and homologues (179).

6. Boric acid (24, 139).

7. Alkalies (3, 219).

8. Alkali salts (113, 208, 218). Influence of acid, alkali, and salts on the rotatory power and rotatory dispersion of aspartic acid and asparagine (47) (CiHtNOi) J-Aspartic acid

HiO. 2VHC1

0.2 2V NaOH. N NaOH- —

2 JVNaOH... JVNaOH---.

0.2 2V NaOH.

2 JVNaOH...

iVNaCl.

4 2VNaCl.__. 2VBaClj

4 2VBaCla._..

Moles of acid or | alkali per

;

mole of substance

1.5 1.0

1.0

1.0

2.0 2.0

2.0

p t [«] 5.693 [a] 5,481 [a] 4,351

0. 990 25 3.8 6.0 14.0

1. 961 48 2.3 4.0 9.3

1.961 68 ±0.0 1.3 4.6

1.961 78 -1.5 -.3 2.3

7. 984 25 25.0 29.9 63.5

2.584 25 -17.3 -19.3 -33.6

11. 30 25 -6.0 -6.9 -9.4

19. 76 25 .5 1.5 5.5 6.0 25 -2.4 -2.1 L8

1.303 25 -6.9 -4.8 -1.5

11. 02 25 -.7 -.3 4.3

1. 011 25 9.5 12.7 28.6

.944 25 18.4 21.5 47.9

1.047 25 13.7 16.7 33.7

1. 007 25 21.2 25.4 50.3

(C4H8NJO3) J-Asparagine

f 1. 961 34 -6.7 -7.5 -14.7 HiO-- — J

1. 961 40 -7.7 -8.3 -17.7

1 1. 961 60 -10.5 -11.3 -22.4

I 7. 407 52 -8.3 -9.3 -18.3 nhci 1.5 8. 942 25 27.9 33.7 70.4 ZVNaOH 1.0 12. 44 25 -8.8 -10.0 -19.9

C4H8N2O3, Asparagine, effect of dilute acids on rotation of 1 mole

asparagine+300 moles HjO (18) MHC1 [-B MH2SO4 MAcOE

1 26.4 0.5 23.1 1 -3.49

1.5 30.4 0.75 27.3 2 -3. 10 2 31.5 1 29.5 5 -1. 45

3 31.9 3 32.0 7 -0. 59

5 32.3 5 34.3 10 0.00

10 33.3 10 35.5 15 1.11 15 33.7 20 2.63

20 34.3

Influence of acid, alkali and salts on rotatory power of C5H9NO4 d-glutamic acid (48)

H2O

iVNaCL.

4 2VNaCl NKC1...

2VBaCl2 _

P [a] 4,359

1.50 13.3 1.50 14.4

1. 51 15.8

1. 53 14.8 1.63 14.4

S P [«]4,359

4 2V" BaBr2 1. 51 18.1

1 MNaOH 12.25 -3.6

2 NaOH 6. 55 11.7 1.5MHCL. 8. 75 37.4
OPTICAL ROTATION OF ORGANIC SUBSTANCES

Influence of boric acid on OHuOg mannitol

(a) with HjBOi (62) s=H2Q. c = 10 AfHsBOj

Af C*HmO«

0.8

1.5 2.0

3.1 4.3

5.2

s = HjO. =15

0.4

1.0

1.3 1.5

1.5

3.6 4.5

5.4

5.9

s = EtOH. c=6

1.8 2.0

3.0 4.0

5.0 6.0

13.9

15.6

19.7 23.9 25.4

27.2

s=EtOH. c = 10 (6) with NaOH (137) MHjBO,

[«E?

MC6HuO«

1 MCt HH0, MHjBOj

2.0

2.6

1 3.0

3.5

17.3

21.1 22.9 24.6

10

9

8

76

5

4

3

2

1

-0. 37 -.47

-.70

-. 83 -.86

-1.04 -1.30

-1. 95 -2.59

-3.43

s=EtOH. c = 12

2.2 3.0

4.0

20.2

25.2

28.7

j (c) with NaBOj (137)

1 s=Hs O. c=3.555 MCuHhOs

MCeHnOa | MNaBOj t«B MHsBOj

20

1715

13

119

7

5

3

1

-0. 078 .004

.397

.873

1. 357

1. 737

2. 193

3. 439

5. 169

19. 746

6

5

4

3

2

1.5

.333 .25

-0.73

.38

1. 69

1.83 2.03 2.25

3. 77

5. 57 6.76

Influence of boric acid on derivatives of mannitol (92) s=H20 N/2 HsBOi

Formula Name e MS HS

C«HhOj Mannitol -0.25

-7. 35 -13.02

38.54

30.61 7.54

28.3 -3.88

-6. 72 40.64

29.50

8. 25

CiHjgOj. CioHaO*

C»Hi$0«

t, f-Dimethylmannitol

h, 5, <» r-Tetramethylmannitol

y, e, r-Tetramethylmannitol N/4 N/S

2V/8 iV/4 CnH2<Oi Pentamethvlmannitol N/2 CuHaOj Mannitoldiacet one N/S 23.04 22.43 The influence of papaverine on the optical activity of narcotine in acid solution (5)

C22H23NO7

Narcotine

2.0

.0

2.0

2.0 2.0

2.0

2.0 2.0 2.0

C20H21NO4

Papaverine

0.0

.5

.5.0

. 5 1.0

2.0

3.0 4.0

Length of tube=2 dcm.

in 1 per cent H2SO4

2.61 .02

2.24 2,59

2. 19 2.00

1.69 1.49 1.45

in 1 per cent HC1

2.23

0. 02

1. 76

s=PhMe

1. 333 0.00

1.333 1.333

0.00 .50

.50

1.00

-4.83 ±0.00

-4. 82 -4.84
100 BUREAU OF STANDARDS

Specific rotation of C2JH13NO7, narcotine (5)

s PhMe 90 per cent EtOH CHCli 1 per cent H1SO4

1 per cent HC1

c 2 0.4 2.0 2.0 1.0

t 32 31 33 32 29

[«]a> -148. 75 -154.5 -182

-198.0

-206.5

-242.3

57. 25 sa

52.2

56.5

[ a ]inom -203. 75° 65.2

Rotatory power of liquid crystals

For a layer 1 mm. thick; X=5,893 (220)

(a) Esters of CrHisO cholesterol

C27H45CI Chloride -120

-200

5 U80

50 -190

480

70

100 -1, 700 +80

30 -6,200

CkH^Oj Acetate CsoHsoOj Propionate

CaiHsoOj Crotonate. Cs.HnO* 7Z-Butvrate _ C32H52O2 | Allylacetate CssHmOj _ Sorbate... Cs4 H«N04

[o-Nitrocenzoate

j to-N itrobenzoate C34HS0OJ

[p-Nitrobenzoate Benzoate . CaeH&oOa Phenylpropiolate.. C36H5 iN04 p-Nitrocinnamate C38H52OJ- Cinnamate-.- -1, 400 -900

10, 500 CMH540j C7 2H,ojNj04 Hydrocinnamate

p-Azocinnamate

1 Sign uncertain.

(6) Esters of active amyl alcohol

CjjHajNOa. C21H22N2O4 C22H22N2O2 Cinnamylideneaminocinnamate

p-Nitrobenzylideneaminocinnamate

Cyanobenzylideneaminocinnamate

9,500.

6,000. 8,000 to 13,000. 6,000 to 8,000. 4,000 to 5,000. C22H2iN03 C2JH27NO3

Anisylideneaminocinnamate

Anisylideneamino-a-methylcinnamate
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102 BUREAU OF STANDARDS

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OPTICAL ROTATION OF ORGANIC SUBSTANCES 103

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1920.

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192. Rupe and Courvoisier, Helv. Chim. Acta, 6, p. 1049; 1923.

193. Rupe and Glenz, Ann., 436, p. 184; 1924.

194. Rupe and Iselin, Ber., 49, p. 25; 1916.
104 BUREAU OF STANDARDS

195. Rupe and Jaggi, Helv. Chim. Acta, 3, p. 654; 1920. 196. Rupe and Jaggi, Ann., 428, p. 164; 1922. 197. Rupe and Kagi, Ann., 420, p. 33; 1920. 198. Rupe and Lauger, Helv. Chim. Acta, 3, p. 272; 1920. 199. Rupe and Schmid, Helv. Chim. Acta, 5, p. 437; 1922. 200. Rupe, Seiberth and Kussmaul, Helv. Chim. Acta, 3, p. 50; 1920. 201. Rupe, Seiberth and Kussmaul, Helv. Chim. Acta, 3, p. 71; 1920. 202. Rupe and Tomi, Ber., 49, p. 2563; 1916. 203. Rupe, Werder and Togaki, Helv. Chim. Acta, 1, p. 309; 1918. 204. Rupe and Wild, Ann., 414, p. Ill; 1917. 205. Schener, Z. physik. Chem., 72, p. 513; 1910. 206. Schlundt, J. Physic. Chem., 7, p. 194; 1903. 207. Schneider, Ann., 207, p. 257; 1881. 208. Schiitt, Ber., 21, p. 2586; 1888. 209. Schwyser, Thesis, Zurich; 1919; and Tables ann. internat., 5, p. 727; 1922. 210. Sherry, J. Physic. Chem., 11, p. 559; 1907. 211. Shinn, J. Phvsic. Chem., 11, p. 201; 1907. 212. Smirnov, Helv. Chim. Acta, 3, p. 177; 1920. 213. Sonnenthal, Sitzber. Akad. Wiss. Wien, 100, lib, p. 570; 1891. 214. Stubbs, J. Chem. Soc, 99, p. 2265; 1911. 215. Taylor, J. Chem. Soc, 101, p. 1124; 1912. 216. Thomas, J. Chem. Soc, 101, p. 725; 1912. 217. Thomsen, J. prakt. Chem., 32, p. 211; 1889. 218. Thomsen, J. prakt. Chem., 34, p. 74; 1886. 219. Thomsen, J. prakt. Chem., 35, p. 145; 1887. 220. Vorlander and Huth, Z. physik. Chem., 75, p. 641; 1911. 221. Walker, J. Chem. Soc, 67, p. 914; 1895. 222. Waser, Helv. Chim. Acta, 6, p. 206; 1923. 223. Wender, Biochem. Z., 30, p. 357; 1911. 224. Werner, Schwvzer and Karrer, Helv. Chim. Acta, 4, p. 113; 1921. 225. Werner and Smirnoff, Helv. Chim. Acta, 3, p. 472; 1920. 226. Wetterfors, Thesis, Upsala; 1920; and Tables ann. internat., 5, p. 727; 1925. 227. Wetterfors, Z. Physik, 8, p. 229; 1922. 228. Winther, Z. physik. Chem., 41, p. 161; 1902. 229. Winther, Z. physik. Chem., 45, p. 331; 1903. 230. Winther, Z. physik. Chem., 56, p. 719; 1906. 231. Winther, Z. physik. Chem., 60, p. 563; 1907. 232. Wood, J. Chem. Soc, 105, p. 1988; 1914.
SUBJECT INDEX

(Only the more important substances are included)

Page

Acids. See under names.

Alanine .: 94,96 Alcohols, monohydroxy 4 ethers and esters 4 naphthoates of 27 secondary, benzoates of 27 Alkaloids (see also Bases, organic) 92 Alkyl dichloropropionates 19 Alkyl esters of fatty acids 9 Alkylisopropylcarbinyl phthalates 19 Alkyl tartrates 34 Amines (see also Bases, organic) 3, 50, 61, 66, 76 camphorcarboxylates of 76 Amino acids and derivatives 30 Aminoglutaric acid and derivatives 31 Ammines 84 Ammonium crUoroiodomethanesulphonate. - 2 Amylacctone and derivatives - 48 Amyl esters ._ 4, 100 Asparagine 30, 98 Asparticacid 30,32,98 B

Bases . 77 camphorates 66 camphorcarboxylates 76 organic (see also Alkaloids and Amines) 42

tartrates 42 Benzimidazolepropylsulphonic acid .... 33 Benzoates of secondary alcohols 27 Benzoylalanine... 30 Benzoylphenylethylamine 3 Benzylraethyl carbinol ethers 7 Borneol and d-erivatives 79 Bornylamine derivatives 79 Bornylxanthic-acid derivatives. .. 80 Bromocamphorsulphonates 83 Bromocamphorsul phonic acid 73 Bromonitrocamphor 71 Brucine and salts 93 Butylamine... 3 C

Campholic acid derivatives. 66 Campholytic acid derivatives 66 Camphor 69 alkyl deri\atives of 75 alkylidene derivatives of. 75 halogen derivatives 70 Camphorates of organic bases 66 Camphorcarboxamide 78 Camphorcarboxylates of amines 76 Camphorcarboxylic acid and derivatives 76 Camphorcarboxypiperidide— 78 Camphoric acid and derivatives 66 Camphorquinone 67 Camphorquinonehydrazoxime derivatives. .. 68 Campnorsulphonates 63, 83 Camphorsulphonic acid and derivatives 72 Carbinols 4 Cholesterol esters. 100 Chromium ammines 86 Chromium potassium oxalate 86 Cinchonidine derivatives. 92 Cinchonine and salts 92 Citronellal- 48 Cobalt ammines 84 Cobalt potassium oxalate 85 Crystals, liquid 100

Dicarboxylic acids, octyl esters of.. 17 Dichloropropionates, alkyl 19 Diethyl diacetyl tartrate 46 Diethyl tartrate

35.

47, 97 Dihydroxyphenylalanine 32 Diisobutyl diacetyltartrate... 39 Diisobutyl tartrate 38 Dimethyl tartrate 35 Dimethyltetrahydroquinoline derivatives 55 Dispersion 34, 40, 45, 56, 61, 75, 77, 81, 82, 98 E

Esters and ethers of monohydroxy alcohols. . 4 Ethylalkyl carbinols 6 Ethyl aspartate 95 F

Fatty acids, alkyl esters of 9 methylbenzyl carbinol esters of 22 naphthylhexyl carbinol esters of 25 Fenchyl alcohol derivatives.. 81 Fenchylxanthic-acid derivatives. 81 G

Glutamic acid. 32,94,98 Glyceric acid 94 H

Hydroxyhydrindamine derivatives 63 Hydroxymethylenecamphor and derivatives. 73

salts of 74 Hyoscyamine. 63

I Inactive substances, effect of, on tartaric acid. 98 Iridium ammines.. 88 Isoborneol 79 Isonitrosocamphor... 67 Isopropylalkyl carbinols.. 5 Isopulegol and esters 57, 59 Isoteresantalic acid 82 K

Keto-acids, menthyl esters of 63 L

Lactates and related esters _ 21, 94, 96 Lactic acid 94, 95 Leucine 32 Limonene. — 68 Liquid crystals 100 M

Malic acid, effect of salts on.. 95 Mannitol and derivatives 99 Menthol 67,60 Menthone 56 Menthylamine derivatives 61 Menthyl esters... 61 Menthylxanthates and derivatives. 64 Metal complexes _ 84 Methylalkyl carbinols 4 Methylbenzyl carbinol esters of fatty acids.. 22 Methylcamphor and derivatives 76 105
106 SUBJECT INDEX

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Methylcyclohexane derivatives 54 Methylethylphenacylthetine salts 83 Methyl lactate. 21, 94, 96 Methyl malate 95,97 Methylnaphthyl carbinyl acetate 26 Methyl phenyllactate 95 Molybdenylmalates . 88 Molybdenyl tartrates..- 90 Mutarotation 52, 53, 63, 71, 78 Myrtenol esters 56 N

Naphthoates of secondary alcohols 27 Naphthylhexylcarbinol esters of fatty acids.. 25 Narcotine 99 Neobomylarnine derivatives 79 Nicotine .— 50 Nitrocamphor 71

salts of 74 O

Octyl alkyl ethers 8 Octyl esters of dicarboxylic acids 17 P

Papaverine 99 Phenyllactic acid. 95 Phosphonium salts.. 83 Platinum ammines 88

Q Page

Quinine 92 R

Rhodium ammines 87 Rhodium potassium oxalate.. 87 malonate.. 87 S

Salts, influence of, on rotation 94 Succinic acid 97 Sulphobutryic-acid derivatives 33 T

Tartaric acid 34,97,98 Tartaric acids, substituted, esters of 39, 44 Tartrates, alkyl 35

of organic bases 42 Teresantalic acid and derivatives. 82 Tetrahydronaphthol and derivatives. 49 Tetrahydroquinaldine derivatives 51 Thetine, methyl ethylphenacyl- 83 Tungstylmalates... 90 Tungstyl tartrates 91 Tyrosine 32 X

Xanthates 64,80,81


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