4P049

ᅛయ NMR ࡟ࡼࡿ࢜ࢡࢳࣝᒀ⣲⤖ᬗࡢᵓ㐀┦㌿⛣࡜ศᏊࢲ࢖ࢼ࣑ࢡࢫࡢ◊✲(㔠ἑ኱㝔 ⮬↛ 1, ⚄ᡞ኱㝔 ⮬↛ 2)‫ⱝۑ‬ᯘ ࿃Ᏹ 1, ኱ᶫ ❳ኴ㑻 1, ῧ⏣ ㈗ᏹ 1, ஭⏣ ᭸ᬛ 1, Ỉ㔝 ඖ༤ 1,ᶫᮏ ┾బ⏨ 2, ᒣᮧ බ᫂ 2࠙ᗎࠚ࢜ࢡࢳࣝᒀ⣲⤖ᬗ (C8-Uࠊ⼥Ⅼ:Tm = 374.6 K) ࡣ 353.2 K (Tc)࡛ప ┦(II ┦)࠿ࡽ㧗 ┦(I ┦)࡟㌿⛣
ࡍࡿࠋDSCᐃ [1]࠿ࡽࠊࡇࡢ II-I ┦㛫ࡢ┦㌿⛣ࡢ࢚ࣥࢺࣟࣆ࣮(33.4 J K-1 mol-1)ࡣ⼥ゎ࢚ࣥࢺࣟࣆ࣮(65.1 JK-1 mol-1)࡟༉ᩛࡍࡿ኱ࡁ࡞್ࢆ♧ࡋ࡚࠾ࡾࠊI ┦ࡣ࢚ࣥࢺࣟࣆ࣮ࡀᴟࡵ࡚㧗࠸≧ែ࡟࡞ࡗ࡚࠸ࡿࠋࡲࡓࠊ࢚ࣥࢺࣟࣆ࣮ࡔࡅ࡛࡞ࡃࠊ㹖⥺ᵓ㐀ゎᯒ [1] ࠿ࡽほ ࡉࢀࡿ ᗘᅉᏊࡶࠊI ┦(ᅗ 1 a)ࡢ᪉ࡀ II ┦(ᅗ 1 b)࡟ẚ࡭㧗࠸஦ࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋ≉࡟ࠊI ┦࡛ࡣࠊ࣓ࢳࣝᇶ (C8) ࡀ trans ࡜ skew ࡢ 2 ࡘࡢ㓄ᗙ࡛ disorder ࡜࡞ࡗ࡚࠸ࡿ(ᅗ 2)ࠋࡇࡢࡼ࠺࡞ࠊ࢔ࣝ࢟ࣝ㙐ࡢ disorder ࡀ C8-U ࡢ I ┦࡛ࡢ㧗࢚ࣥࢺࣟࣆ࣮≧ែࡢཎᅉ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊࡇࡢ disorder ࡀᵓ㐀ࡢ㟼ⓗ࡞୙ᆒ୍ᛶ࡟ࡼࡿࡶࡢ࠿ࠊศᏊ㐠ື࡟ࡼࡿࡶࡢ࠿ࡣࠊ᫂ࡽ࠿࡟࡞ࡗ࡚࠸࡞࠸ࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣ C8-U ࡟ࡘ࠸࡚ᅛయ㧗ศゎ⬟ 13C NMR ࢆ ᐃࡋࠊ13C ࡢ໬Ꮫࢩࣇࢺ࡜ࢫࣆࣥ-᱁Ꮚ⦆࿴᫬㛫( T1 )࠿ࡽࠊC8-U ࡢ disorder ≧ែ࡜ࢲ࢖ࢼ࣑ࢡࢫࡢ㛵ಀ࡟ࡘ࠸࡚ㄪ࡭ࡓࠋ
(b)(a)
C2C4C6C8T

C2C4C8C6C8T
HH

CU

CU
C1C3ᒀ⣲㒊ศ(U)C5C7C8S

C1C3C5H

C7H

H

C5࢔ࣝ࢟ࣝ㙐(C8)

H
H

C8S

C5 H

trans 㓄ᗙ

skew 㓄ᗙ

ᅗ 2 I ┦࡛ࡢ C8 ࡢ㓄ᗙᅗ1 X ⥺⤖ᬗᵓ㐀ゎᯒ࡟ࡼࡿC8-U ࡢศᏊᵓ㐀ࡓࡔࡋỈ⣲ࡣ┬␎ (a)I ┦ (b) II ┦࠙ᐇ㦂ࠚᅛయ 13C NMR ࡢ ᐃࡣࠊ13C 74 MHz (1H 295 MHz)ࡢ☢ሙ࡛⾜ࡗࡓࠋ13C ࢫ࣌ࢡࢺࣝࡢ ᐃࡣCP/MAS ࡛⾜࠸ࠊ1H decoupling ࡟ࡣ TPPM ἲ [2]ࢆ⏝࠸ࡓࠋT1 ࡢ ᐃ࡟ࡣ Torchia ࡢ᪉ἲࢆ⏝࠸ࡓࠋ࠙⤖ᯝ࡜⪃ᐹࠚ
C2~C6
࣭13C NMR ࢫ࣌ࢡࢺࣝC7 C8ᅗ 3 ࡟ C8-U ࡢྛ┦࡟࠾ࡅࡿ 13C NMR(a)ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋ࡞࠾ CUࠊC1ࠊ͐ࠊ
C8 ࡣᅗ 1 ࡟ᑐᛂࡍࡿࠋࡇࡢ࠺ࡕ CU, C1
C1CU࡟ࡘ࠸࡚ࡣࠊI ┦ࠊII ┦࡛኱ࡁ࡞ኚ໬ࡀぢࡽࢀ࡞࠸ࠋ୍᪉ࠊC7 ࡢࣆ࣮ࢡࡣ 2.1 ppm
C2~C6
㧗☢ሙࢩࣇࢺࠊ C8 ࡢࣆ࣮ࢡࡣ 0.7 ppm
ప☢ሙࢩࣇࢺࡋࡓࠋ
(b)
CU≧ែࡢ㛗㙐࢔ࣝ࢝ࣥࡢ࣓ࢳࣝᇶ࠿ࡽȘ఩ࡢ࣓ࢳࣞࣥᇶࡣࠊtrans ࡜ gauche ࡢ㓄ᗙ

165

160
160

C1404030
30

20201010ppm

ࡢ஺᥮ࡀࠊ▷࠸࿘ᮇ࡛㉳ࡇࡿ஦࡛ࠊ㧗☢ሙࢩࣇࢺࡍࡿ஦ࡀሗ࿌ࡉࢀ࡚࠸ࡿ [3]ࠋC8C7

 C7 ࡢ㧗☢ሙࢩࣇࢺࡢཎᅉ࡜ࡋ࡚ࠊ୰㛫ᅗ313C NMRࢫ࣌ࢡࢺࣝ(a) 359K (I ┦) (b) 343 K (II ┦)ࡲࡓࠊtrans ࡜ skew ࡢ 2 ࡘࡢ㓄ᗙࢆ࡜ࡿ࡟ࡶ࠿࠿ࢃࡽࡎࠊI ┦࡟࠾࠸࡚ࠊC8 ࡢࣆ࣮ࢡࡣࢩ࣮ࣕࣉ࡞ 1 ᮏ࡛࠶ࡗࡓࠋࡇࡢ஦࠿ࡽࠊC8 ࡣ trans ࡜ skew ࡢ㓄ᗙࡢ஺᥮࡛ࣆ࣮ࢡࡀᖹᆒ໬ࡉࢀ࡚࠸ࡿ஦ࡀ♧၀ࡉࢀࡿࠋ ࣭13C NMR T1 ࡢ ᗘ౫Ꮡᛶᅗ 4 ࡟ CU ࡢ 13C ࡢ T1 ࡢ370.4103

ᗘኚ໬ࢆ♧ࡍࠋII ┦࡛ࠊT1 ࡣTc

303.0 T (K)333.3ᗘୖ᪼࡜ඹ࡟ῶᑡࡋࡓࠋࡑࡋ࡚ࠊI ┦࡛ࠊT1 ࡣ ᗘୗ㝆࡜ඹࡾ㐜࠸ศᏊ㐠ືࢆࡋ࡚࠸ࡿ஦ࡀࢃ࠿ࡿࠋ102

T1 (s)

࡟ቑຍࡋࡓࠋT1 ࡢ ᗘኚ໬࠿ࡽࠊI ┦ࠊII ┦ඹ࡟ 74 MHz ࡼϨ

101ᅗ 5 ࡟ C1 ࡢ T1 ࡢ ᗘኚ໬ࢆ♧ࡍࠋII ┦࡛ࠊT1 ࡣ ᗘୖ᪼II ┦I┦࡜ඹ࡟ῶᑡࡋࡓࠋࡑࡋ࡚ࠊI ┦࡛ࠊT1 ࡣ ᗘୗ㝆࡜ඹ࡟ቑຍࡋ

100ࡓࠋࡼࡗ࡚ࠊI ┦ࠊII ┦ඹ࡟ 74 MHz ࡼࡾ㐜࠸ศᏊ㐠ືࢆࡋ࡚2.8

࠸ࡿ஦ࡀࢃ࠿ࡿࠋ

3.0
3.2
1000/T (K-1)

3.4

ᅗ 4 C㹓ࡢ 13C ࡢ T1ୖグࡢࡼ࠺࡟ࠊᒀ⣲㒊ศ௜㏆࡛ࡣ I ┦ࠊII ┦ඹ࡟ 74 MHz370.4103

ࡼࡾ㐜࠸ศᏊ㐠ືࢆࡋ࡚࠸ࡿ஦ࡀࢃ࠿ࡿࠋTcᗘ౫Ꮡᛶ

303.0 T (K)

333.3

ϩ

ᅗ 6 ࡟ C7 ࡢ 13C ࡢ T1 ࡢ ᗘኚ໬ࢆ♧ࡍࠋII ┦࡛ࠊT1 ࡣ࡟ᣦᩘ㛵ᩘⓗ࡟ῶᑡࡋࡓࠋࡼࡗ࡚ࠊII ┦࡛ࡣ 74 MHz ࡼࡾ㐜

102T1 (s)ᗘୖ᪼࡜ඹ࡟ῶᑡࡋࡓࠋࡑࡋ࡚ࠊI ┦࡛ࠊT1 ࡣ ᗘୗ㝆࡜ඹ

101

࠸ࠊI ┦࡛ࡣ 74 MHz ࡼࡾ㏿࠸ศᏊ㐠ືࢆࡑࢀࡒࢀࡋ࡚࠸ࡿ஦

I┦ࡀࢃ࠿ࡿࠋࡲࡓࠊI ┦࡟ᑐࡋ࡚ࠊ࢔ࣞࢽ࢘ࢫࡢάᛶ໬㐣⛬ࢆ௬Ϩ

100

ᐃࡋ࡚ࠊT1 ࡢ ᗘኚ໬ࡢഴࡁ࠿ࡽάᛶ໬࢚ࢿࣝࢠ࣮ࢆぢ✚ࡶࡿ࡜ࠊ17 kJ mol-1 ࡜࡞ࡗࡓࠋࡇࡢ್ࡣࣈࢱࣥࡢ trans-gauche

2.83.4ᗘ౫ᏑᛶϨ

370.4103࣌ࢡࢺࣝࡢ㧗☢ሙࢩࣇࢺࡢ⤖ᯝ࡜ྜࢃࡏ࡚ࠊI ┦࡛ࡢάᛶ໬࢚
ࢿࣝࢠ࣮ࡣ trans-gauche 㓄ᗙ㛫ࡢ஺᥮࡟ᑐᛂࡍࡿ࡜⪃࠼ࡽࢀTc

303.0 T (K)333.3
II ┦I┦102

T1 (s)

ᅗ 7 ࡟ C8 ࡢ 13C ࡢ T1 ࡢ ᗘኚ໬ࢆ♧ࡍࠋII ┦࡛ࠊT1 ࡣ

3.0
3.2
1000/T (K-1)

ᅗ 5 C㸯ࡢ 13C ࡢ T1㓄ᗙ㛫ࡢάᛶ໬࢚ࢿࣝࢠ࣮(15 kJ mol-1)࡟㏆࠸ࠋ13C NMR ࢫࡿࠋ

II ┦ᗘୖ᪼࡜ඹ࡟ᣦᩘ㛵ᩘⓗ࡟ቑຍࡋࡓࠋࡑࡋ࡚ࠊI ┦࡛ࠊT1 ࡣ101ᗘୗ㝆࡜ඹ࡟ᣦᩘ㛵ᩘⓗ࡟ῶᑡࡋࡓࠋࡼࡗ࡚ I ┦ࠊII ┦ඹ࡟EaϨ = 17 kJ mol -1

74 MHz ࡼࡾ㏿࠸ศᏊ㐠ືࢆࡋ࡚࠸ࡿ஦ࡀศ࠿ࡿࠋࡲࡓࠊI ┦100

࡜II┦ࡢT1 ࡢ ᗘኚ໬ࡢഴࡁ࠿ࡽάᛶ໬࢚ࢿࣝࢠ࣮ࡣࡑࢀࡒ

2.8

3.0
3.2
1000/T (K-1)

ᅗ 6 C7 ࡢ 13C ࡢ T1

ࢀࠊ13 kJ mol-1 ࠊ9.6 kJ mol-1 ࡜࡞ࡗࡓࠋࡇࡢάᛶ໬࢚ࢿࣝ
ࢠ࣮ࡣ࣓ࢳࣝᇶࡢ 3 ᅇ㍈࿘ࡾࡢᅇ㌿࡟ᑐᛂࡍࡿ࡜⪃࠼ࡽࢀࡿࠋ

370.4103ᮏ◊✲࡛ࡣࠊ໬Ꮫࢩࣇࢺ࡜ T1 ࡢ ᗘኚ໬࠿ࡽࠊI ┦࡛ࡣࠊ

Tc

3.4

ᗘ౫Ꮡᛶ
303.0 T (K)333.3࡞࡝ࡢศᏊ㐠ືࡀ⃭ࡋࡃ㉳ࡇࡗ࡚࠸ࡿ஦ࡀ♧၀ࡉࢀࡓࠋࡇࡢ஦࠿ࡽࠊX ⥺⤖ᬗᵓ㐀ゎᯒ࡟ࡼࡿ C8-U ࡢ I ┦࡛ࡢ disorder ࡣࢲT1 (s)C8-U ࡢ࢔ࣝ࢟ࣝ㙐࡟trans-gauche ࡸtrans-skew ࡢ㓄ᗙ஺᥮࢖ࢼ࣑ࢵࢡ࡞ disorder ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ

1021I┦II ┦EaI = 13 kJ mol -1
Eaϩ = 9.6 kJ mol-1

10࠙ཧ⪃ᩥ⊩ࠚ
[1] M. Hashimoto, F. Tajima, K. Eda, K. Yamamura, T.
Okazaki, J. Mol. Struct., 734 23 (2005)[2]A. E. Bennet et al, J. Chem. Phys., 103, 6951(1995)[3] S. Ishikawa, H. Kurosu and I. Ando, J. Mol. Struct., 734 23 (1991)

100

2.8

3.0
3.2
1000/T (K-1)

ᅗ 7 C8 ࡢ 13C ࡢ T1

3.4

ᗘ౫Ꮡᛶϩ