This invention relates to ortho-heterocyclic benzene sulfonylureas which are useful as herbicides and growth regulants.

BACKGROUND OF THE INVENTION 
This invention relates to ortho-heterocyclic sulfonylureas and in 
particular, to their use as agricultural chemicals such as herbicides and 
growth regulants. 
U.S. Pat. No. 4,127,405 teaches compounds which are useful for controlling 
weeds in wheat having the formula: 
##STR1## 
wherein R.sub.1 is 
##STR2## 
R.sub.3 and R.sub.6 are independently hydrogen, fluorine, chlorine, 
bromine, iodine, alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, 
nitro, trifluoromethyl, cyano, CH.sub.3 S(O).sub.n -- or CH.sub.3 CH.sub.2 
S(O).sub.n --; 
R.sub.4 is hydrogen, fluorine, chlorine, bromine or methyl; 
R.sub.5 is hydrogen, fluorine, chlorine, bromine, methyl or methoxy; 
R.sub.7 is hydrogen, fluorine, chlorine, bromine, alkyl of 1-2 carbon atoms 
or alkoxy of 1-2 carbon atom; 
R.sub.8 is hydrogen, methyl, chlorine or bromine; 
R.sub.9 and R.sub.10 are independently hydrogen, methyl, chlorine or 
bromine; 
W and Q are independently oxygen or sulfur; 
n is 0, 1 or 2; 
X is hydrogen, chlorine, bromine, methyl, ethyl, alkoxy of 1-3 carbon 
atoms, trifluoromethyl, CH.sub.3 S-- or CH.sub.3 OCH.sub.2 --; and 
Y is methyl or methoxy; or their agriculturally suitable salts; provided 
that: 
(a) when R.sub.5 is other than hydrogen, at least one of R.sub.3, R.sub.4, 
R.sub.6 and R.sub.7 is other than hydrogen and at least two of R.sub.3, 
R.sub.4, R.sub.6 and R.sub.7 must be hydrogen; 
(b) when R.sub.5 is hydrogen and all of R.sub.3, R.sub.4, R.sub.6 and 
R.sub.7 are other than hydrogen, then all of R.sub.3, R.sub.4, R.sub.6 and 
R.sub.7 must be either chlorine or methyl; and 
(c) when R.sub.3 and R.sub.7 are both hydrogen, at least one of R.sub.4, 
R.sub.5 or R.sub.6 must be hydrogen. 
French Patent No. 1,468,747 discloses the following para-substituted 
phenylsulfonamides, useful as antidiabetic agents: 
##STR3## 
wherein R=H, halogen, CF.sub.3 or alkyl. 
Logemann et al., Chem. Ab., 53, 18052g (1959), disclose a number of 
sulfonamides, including uracil derivatives and those having the formula: 
##STR4## 
wherein R is butyl, phenyl or 
##STR5## 
and R.sub.1 is hydrogen or methyl. 
When tested for hypoglycemic effect in rats (oral doses of 25 mg/100 g), 
the compounds in which R is butyl and phenyl were most potent. The others 
were of low potency or inactive. 
Wojciechowski, J. Acta. Polon. Pharm. 19, p. 121-5 (1962) [Chem. Ab., 59 
1633 e] describes the synthesis of 
N-[(2,6-dimethoxypyrimidin-4-yl)aminocarbonyl]-4-methylbenzenesulfonamide: 
##STR6## 
Based upon similarity to a known compound, the author predicted 
hypoglycemic activity for the foregoing compound. 
Netherlands Patent 121,788, published Sept. 15, 1966, teaches the 
preparation of compounds of Formula (i), and their use as general or 
selective herbicides, 
##STR7## 
wherein R.sub.1 and R.sub.2 may independently be alkyl of 1-4 carbon 
atoms; and 
R.sub.3 and R.sub.4 may independently be hydrogen, chlorine or alkyl of 1-4 
carbon atoms. 
Compounds of Formula (ii), and their use as antidiabetic agents, are 
reported in J. Drug. Res. 6, 123 (1974), 
##STR8## 
wherein R is pyridyl. 
European Patent Application No. 7687, discloses herbicidal sulfonylureas 
which contain an o-carboalkoxybenzene moiety. 
The presence of undesired vegetation causes substantial damage to useful 
crops, especially agricultural products that satisfy man's basic food 
needs, such as soybeans, barley, wheat, and the like. The current 
population explosion and concomitant world food shortage demand 
improvements in the efficiency of producing these crops. Prevention or 
minimizing the loss of a portion of valuable crops by killing, or 
inhibiting the growth of undesired vegetation is one way of improving this 
efficiency. 
A wide variety of materials useful for killing, or inhibiting (controlling) 
the growth of undesired vegetation is available; such materials are 
commonly referred to as herbicides. The need exists, however, for still 
more effective herbicides that destroy or retard weeds without causing 
significant damage to useful crops. 
SUMMARY OF THE INVENTION 
This invention relates to compounds of Formula I, to agriculturally 
suitable compositions containing them, and to their use as general and/or 
selective pre-emergence and/or post-emergence herbicides, and as plant 
growth regulants. 
##STR9## 
where Q is 
##STR10## 
W" is O or S; W is O, S, or NR; 
R is H or C.sub.1 -C.sub.4 alkyl; 
R.sub.1 is H, F, Cl, Br, CH.sub.3, CF.sub.3 or OCH.sub.3 ; 
R.sub.2 is H, CH.sub.3, C.sub.2 H.sub.5, OCH.sub.3, OC.sub.2 H.sub.5, 
SCH.sub.3, Cl or Br; 
R.sub.3 is H, CH.sub.3, C.sub.2 H.sub.5, OCH.sub.3, OC.sub.2 H.sub.5, 
SCH.sub.3, Cl or Br; 
R.sub.5 is H, CH.sub.3, C.sub.2 H.sub.5, OCH.sub.3, OC.sub.2 H.sub.5, 
SCH.sub.3, Cl or Br; 
R.sub.6 is H, CH.sub.3 or C.sub.2 H.sub.5 ; 
R.sub.8 is H, CH.sub.3, C.sub.2 H.sub.5, OCH.sub.3, OC.sub.2 H.sub.5, 
SCH.sub.3, Cl or Br; 
R.sub.9 is H, CH.sub.3 or C.sub.2 H.sub.5 ; 
R.sub.4, R.sub.7, R.sub.10 and R.sub.11 are independently H or C.sub.1 
-C.sub.4 alkyl; 
R.sub.12 is H or CH.sub.3 ; 
R.sub.13 is H or CH.sub.3 ; 
R.sub.14 is H, CH.sub.3, C.sub.2 H.sub.5, Cl, Br, CH.sub.3 O, C.sub.2 
H.sub.5 O or CH.sub.3 S; 
R.sub.15 is H, CH.sub.3 or C.sub.2 H.sub.5 ; 
R.sub.16 is H, CH.sub.3 or C.sub.2 H.sub.5 ; 
A is 
##STR11## 
X is CH.sub.3, OCH.sub.3 or Cl; Y is CH.sub.3, C.sub.2 H.sub.5, CH.sub.2 
OCH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, CH(OCH.sub.3).sub.2, NH.sub.2, 
NHCH.sub.3, N(CH.sub.3).sub.2, OCH.sub.2 CH.sub.2 OCH.sub.3, OCH.sub.2 
CF.sub.3, CF.sub.3, SCH.sub.3 or 
##STR12## 
Z is CH or N; X.sub.1 is CH.sub.3, OCH.sub.3 or Cl; 
G is O or CH.sub.2 ; 
X.sub.2 is C.sub.1 -C.sub.3 alkyl or CH.sub.2 CF.sub.3 ; 
Y.sub.2 is CH.sub.3 O, C.sub.2 H.sub.5 O, CH.sub.3 S or C.sub.2 H.sub.5 S; 
and their agriculturally suitable salts; provided that 
(a) when R.sub.8 is other than H, CH.sub.3, C.sub.2 H.sub.5 or CH.sub.3 S, 
then W is S or O; 
(b) the total number of carbon atoms of R.sub.4, R.sub.7, R.sub.10 and 
R.sub.11 is less than or equal to 4; 
(c) when X is Cl, then Z is CH and Y is OCH.sub.3, OC.sub.2 H.sub.5, 
NH.sub.2, NHCH.sub.3 or N(CH.sub.3).sub.2 ; 
(d) when Q is 
##STR13## 
then R.sub.13 is H, R is other than H, X is Cl or OCH.sub.3 and Y is 
OCH.sub.3 or OC.sub.2 H.sub.5 ; and 
(e) when W" is S, then R.sub.13 is H; 
Q is 
##STR14## 
A is 
##STR15## 
and Y is CH.sub.3, OCH.sub.3, C.sub.2 H.sub.5, OC.sub.2 H.sub.5, CH.sub.2 
OCH.sub.3, CH(OCH.sub.3).sub.2 or 
##STR16## 
Preferred for their higher herbicidal activity and/or more favorable ease 
of synthesis are: 
(1) Compounds of Formula I where 
R is CH.sub.3 or C.sub.2 H.sub.5 ; 
R.sub.2, R.sub.3, R.sub.5, R.sub.6, R.sub.8, R.sub.9, R.sub.14, R.sub.15 
and R.sub.16 are independently H, CH.sub.3 or C.sub.2 H.sub.5 ; 
R.sub.4, R.sub.7, R.sub.10 and R.sub.11 are independently H or CH.sub.3 ; 
and 
W" is O; 
(2) Compounds of the Preferred 1 where R.sub.1 and R.sub.13 are H; 
(3) Compounds of Preferred (2) where 
Y is CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, CH.sub.2 OCH.sub.3 or 
##STR17## 
and A is 
##STR18## 
(4) Compounds of Preferred (3) where Q is 
##STR19## 
(5) Compounds of Preferred (3) where Q is 
##STR20## 
(6) Compounds of Preferred (3) where Q is 
##STR21## 
(7) Compounds of Preferred (3) where Q is 
##STR22## 
(8) Compounds of Preferred (3) where Q is 
##STR23## 
(9) Compounds of Preferred (3) where Q is 
##STR24## 
(10) Compounds of Preferred (3) where Q is 
##STR25## 
(11) Compounds of Preferred (3) where Q is 
##STR26## 
(12) Compounds of Preferred (3) where Q is 
##STR27## 
(13) Compounds of Preferred (3) where Q is 
##STR28## 
(14) Compounds of Preferred (3) where Q is 
##STR29## 
(15) Compounds of Preferred (3) where Q is 
##STR30## 
(16) Compounds of Preferred (3) where Q is 
##STR31## 
(17) Compounds of Preferred (3) where Q is 
##STR32## 
(18) Compounds of Preferred (3) where Q is 
##STR33## 
and (19) Compounds of Preferred (3) where Q is 
##STR34## 
Specifically Preferred are: 
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(1-methyl-1H-imidazol-2-yl 
)benzenesulfonamide; 
N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-(1-methyl-1H-imidazol-2-yl) 
benzenesulfonamide; 
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-(1-methyl-1H-imidazol 
-2-yl)benzenesulfonamide; 
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(oxazol-2-yl)benzenesulfon 
amide; 
N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-(oxazol-2-yl)benzenesulfona 
mide; 
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-(oxazol-2-yl)benzenes 
ulfonamide; 
N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-(oxazol-2-yl)benzenes 
ulfonamide; 
N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(oxazol-2-yl)benzenesu 
lfonamide; 
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(oxazol-2-yl)ben 
zenesulfonamide; and 
2-(4,5-dihydro-5,5-dimethyloxazol-2-yl)-N-[(4,6-dimethoxy-1,3,5-triazin-2-y 
l)aminocarbonyl]benzenesulfonamide. 
Synthesis-Oxazoles 
Compounds of Formula Ia in which Q is other than 
##STR35## 
and W" is O can be prepared by the procedure of Equation 1 in which 
sulfonamides (1) are reacted with a carbamate (2) in the presence of an 
equimolar amount of trimethylaluminum. Further details of this reaction 
and the preparation of carbamates (2) can be found in U.S. Ser. No. 
337,934. 
##STR36## 
Compounds of Formula I in which Q is other than 
##STR37## 
and W" is O are also prepared by the procedure of Equation 1a. 
##STR38## 
Details of this procedure are described in European Patent Application No. 
44809 in which a carbamate (1a) is reacted with an amine (2a) to yield the 
desired sulfonylureas Ia. 
Compounds of Formula I in which R.sub.13 is H and X is Cl or OCH.sub.3 and 
Y is OCH.sub.3 or OC.sub.2 H.sub.5 are also prepared as shown in Equations 
2, 3 and 4. Details of these reactions are described in unexamined 
European Patent No. 30-140. 
##STR39## 
Some of the compounds of Formula I where 
##STR40## 
may be prepared as described in Equation 5 in which a heterocyclicamine 
(9) is reacted with the appropriate sulfonyl isocyanate (8). 
##STR41## 
The preparation of heterocyclicamines (9) and sulfonyl isocyanates (8) can 
be found in U.S. Pat. Nos. 4,169,719, 4,127,405, EP Publication No. 
15,683, EP Publication No. 46,677 and U.S. patent application Ser. No. 
382,711, along with details of the procedures of Equation 5. 
Compounds of Formula I in which W" is S, A is 
##STR42## 
and R.sub.13 is H are prepared by the procedure of Equation 5a in which a 
sulfonamide of Formula Ia is reacted with a heterocyclicisothiocyanate of 
Formula 9a. 
##STR43## 
Details of this procedure are described in EPO Publication No. 35,893. 
Sulfonamides (1a) in which R is other than H and Q is other than 
##STR44## 
are prepared from the corresponding amines which in turn are prepared from 
the corresponding aromatic nitro compounds as described in Equations 6, 7 
and 8. 
##STR45## 
The reduction of aromatic nitro compounds to aromatic amines (Equation 6) 
is well known in the art. 
The preparation of sulfonamides from aromatic amines by the procedures of 
Equations 7 and 8 is also well known in the art. For details see U.S. Pat. 
No. 4,127,405 and references therein. 
Sulfonamides (Ia) in which Q is 
##STR46## 
are best prepared by the procedure of Equations 9 and 10. 
##STR47## 
The preparation of sulfinic acid salts (16) by the procedure of Equation 9 
is well known in the art. See U.S. Pat. No. 4,127,405 and Organic 
Reactions, Vol. 26, 1979, J. Wiley and Sons, Inc., N.Y. Sulfonamides (Ib) 
are best prepared by treatment of sulfinic acid salts with chloramine. In 
this procedure an ethereal solution or suspension of the salt (16) is 
treated at low temperature (25.degree. to -30.degree.) with a dry ethereal 
solution of chloramine. The reaction is stirred for a period of several 
minutes to several hours. After filtration, the reaction mixture is washed 
with aqueous bisulfite and then dried and the solvent removed on a rotary 
evaporator. The crude product is further purified by usual methods such as 
crystallization or chromatography. 
Ortho-heterocyclic-nitrophenyl compounds 10 are known in the art. For a 
suitable reference, see Elderfield "Heterocyclic Compounds", Vol. 5, 
Chapters 4, 5 and 8, 1957, J. Wiley and Sons, Inc., New York and R. Lakham 
and B. Ternai, Advances in Heterocyclic Chemistry, 17, 99-212 (1975). 
Nitro compounds of Formula (10a) in which Q is 
##STR48## 
and R.sub.2 and R.sub.3 are H are prepared by the procedures shown in 
Equations 11 and 12. 
##STR49## 
Details of the procedures of Equations 11 and 12 can be found in W. E. 
Cass, J. Am. Chem. Soc., 64, 785 (1942). 
Compounds of Formula (10b) in which Q is 
##STR50## 
and R.sub.2 and R.sub.3 are H, CH.sub.3 or CH.sub.3 CH.sub.2 and both 
R.sub.2 and R.sub.3 are not simultaneously H, are prepared by the 
Robinson-Gabriel synthesis of oxazoles from the corresponding 
acylaminoketones as described in Equation 13. See Elderfield, 
"Heterocyclic Compounds", Vol. 5, Chapter 5, 1957, J. Wiley & Sons, New 
York and references therein. 
##STR51## 
Compounds of Formula (10c) in which Q is 
##STR52## 
and R.sub.3 is CH.sub.3 O or CH.sub.3 CH.sub.2 O and R.sub.2 is H, 
CH.sub.3 or CH.sub.3 CH.sub.2 are prepared as shown in Equation 14. For 
further details, see Elderfield, location cited above. 
##STR53## 
Compounds of Formula (10d) in which Q is 
##STR54## 
R.sub.5 is H and R.sub.6 is CH.sub.3 or CH.sub.3 CH.sub.2 are prepared as 
shown in Equation 15. 
##STR55## 
Compounds of Formula (10e) in which Q is 
##STR56## 
R.sub.5 is CH.sub.3 or CH.sub.3 CH.sub.2 and R.sub.6 is CH.sub.3 or 
CH.sub.3 CH.sub.2 are prepared as shown in Equation 16. 
##STR57## 
For details of the procedure of Equations 15 and 16, see the cited 
reference on page 22, line 11. 
Compounds of Formula (10f) in which Q is 
##STR58## 
R.sub.5 is Cl or Br and R.sub.6 is H, CH.sub.3 or CH.sub.3 CH.sub.2 are 
prepared from the corresponding oxazolone (17) and POCl.sub.3 or 
POBr.sub.3 as shown in Equation 17. For details of this procedure, see I. 
J. Turche, M. J. S. Dewan, Chem. Rev., 75, 391 (1975) page 411 and related 
references therein. 
##STR59## 
Compounds of Formula (10g) where R.sub.6 is H, CH.sub.3 or CH.sub.3 
CH.sub.2 and R.sub.5 is CH.sub.3 O, CH.sub.3 CH.sub.2 O or CH.sub.3 S are 
prepared from (10f) by displacement with the appropriate nucleophile as 
shown in Equation 18. 
##STR60## 
For details of this reaction see the cited reference on page 25, section 
IIo, page 402 and references cited therein. 
The oxazoles in which Q is 
##STR61## 
are prepared by analogous procedures to those described in Equations 15, 
16, 17 and 18. Substituent limitations are the same. 
Compounds of Formula (10h) in which Q is 
##STR62## 
and R.sub.5 and R.sub.6 are both H are best prepared by the procedures of 
Equations 19 or 20. 
##STR63## 
For details of this procedure, see A. M. Van Leusen, B. E. Hoogenboom and 
H. Sederius, Tet. Let. 2369 (1972). 
##STR64## 
For details of this procedure, see Y. Koyama, K. Yokose and L. Dolby, 
Agric. Biol. Chem., 45, 1285 (1981). 
Alternatively, sulfonamide of Formula Ia where Q is 
##STR65## 
and R.sub.5 and R.sub.6 are both H can be prepared by the procedure of 
Equation 20a. 
##STR66## 
Compounds of Formula (10i) in which Q is 
##STR67## 
R.sub.3 is Cl or Br and R.sub.2 is H, CH.sub.3, CH.sub.3 CH.sub.2, 
OCH.sub.3 or OCH.sub.2 CH.sub.3 are prepared by the procedure of Equation 
21. 
##STR68## 
Details and references can be found in I. J. Turchi and M. J. S. Dewar, 
Chem. Rev., 75, 409 (1975). 
Compounds of Formula 10i in which Br or Cl has been replaced by CH.sub.3 O, 
CH.sub.3 CH.sub.2 O or CH.sub.3 S are prepared by a displacement reaction 
with the corresponding nucleophile, using procedures known to those 
skilled in the art. 
Thiazoles 
Compounds of Formula (10j) in which Q is 
##STR69## 
and R.sub.8 is H, CH.sub.3 or CH.sub.3 CH.sub.2 and R.sub.9 is H, CH.sub.3 
or CH.sub.3 CH.sub.2 are prepared by the procedure of Equation 22. 
##STR70## 
Similarly, compounds of Formula (10k) in which Q is 
##STR71## 
R.sub.6 is H, CH.sub.3, CH.sub.3 CH.sub.2 and R.sub.5 is H, CH.sub.3 or 
CH.sub.3 CH.sub.2 are prepared by the procedure of Equation 23. 
##STR72## 
In like fashion to the above, compounds of formula (10l) in which Q is 
##STR73## 
and R.sub.2 is CH.sub.3 or CH.sub.3 CH.sub.2, and R.sub.3 is H, CH.sub.3 
or CH.sub.3 CH.sub.2 are prepared by the procedure of Equation 24. 
##STR74## 
Routes to compounds of Formulas (10m), (10n) and (10p) are available by 
reaction of the corresponding acylaminocarbonyl compounds with P.sub.2 
S.sub.5 (Gabriel Synthesis) as shown in Equations 25, 26 and 27 
respectively. 
##STR75## 
where R.sub.5 is H, CH.sub.3, CH.sub.3 CH.sub.2, CH.sub.3 O or CH.sub.3 
CH.sub.2 O; R.sub.6 is CH.sub.3, CH.sub.3 CH.sub.2. 
##STR76## 
where R.sub.8 is H, CH.sub.3, CH.sub.3 CH.sub.2, CH.sub.3 O or CH.sub.3 
CH.sub.2 O; 
R.sub.9 is CH.sub.3 or CH.sub.3 CH.sub.2. 
##STR77## 
where R.sub.2 is H, CH.sub.3 or Et; 
R.sub.3 is CH.sub.3, CH.sub.3 CH.sub.2, CH.sub.3 O or CH.sub.3 CH.sub.2 O. 
For additional details on the procedures of Equations 22-27 see: 
(1) J. V. Metzger (ed.), Chem. Heterocyclic Compounds, 34, parts (1-3) 
(1978-1979). 
(2) J. M. Sprague and A. H. Land, "Heterocyclic Compounds", (R. C. 
Elderfield, ed.) V, 484-722. Wiley, N.Y. 
Compounds of Formula (10q) in which Q is 
##STR78## 
and R.sub.6 is H, CH.sub.3 or CH.sub.3 CH.sub.2, and R.sub.5 is Cl or Br 
are prepared via the Sandmeyer reaction on the corresponding amino 
derivative as shown in Equation 28. 
##STR79## 
The amino derivatives (20) are prepared by substitution of the thioamide 
(19) with thiourea (Equation 23). Treatment of (10q) with NaOCH.sub.3, 
NaOCH.sub.2 CH.sub.3 or NaSCH.sub.3 by procedures known to one skilled in 
the art yields the products in which R.sub.5 is OCH.sub.3, OCH.sub.2 
CH.sub.3 or SCH.sub.3 in Formula (10q). 
In like fashion to the above, compounds of Formula (10s) in which Q is 
##STR80## 
R.sub.9 is H, CH.sub.3 or CH.sub.3 CH.sub.2 and R.sub.8 is Cl, Br, 
OCH.sub.3, OCH.sub.2 CH.sub.3 or SCH.sub.3 can be prepared. 
Compounds of Formula (10t) in which Q in (10) is 
##STR81## 
and R.sub.2 is H, CH.sub.3 or CH.sub.3 CH.sub.2 and R.sub.3 is Cl or Br 
are prepared by the procedure of Equation 29. 
##STR82## 
Compounds (10t) are in turn used to prepare the corresponding analogs in 
which Br is replaced by OCH.sub.3, OCH.sub.2 CH.sub.3 or SCH.sub.3 via 
displacement. 
While OCH.sub.3, OCH.sub.2 CH.sub.3 and SCH.sub.3 are best introduced at 
the nitro stage, Cl or Br are best introduced at the sulfonamide stage in 
order to avoid possible loss of halogen during reduction. 
Imidazoles 
Compounds of Formula (10u) in which Q in (10) is 
##STR83## 
and R is H or C.sub.1 -C.sub.4 alkyl, R.sub.2 is H, CH.sub.3 or CH.sub.3 
CH.sub.2 and R.sub.3 is H, CH.sub.3 or CH.sub.3 CH.sub.2 are prepared by 
the procedure of Equation 30. 
##STR84## 
Additionally, compound (10u) may be prepared from the corresponding 
imidazoline (10v) by dehydrogenation with a suitable catalyst (Equation 
31). 
##STR85## 
For compounds in which R.sub.3 is OCH.sub.3, OCH.sub.2 CH.sub.3 or 
SCH.sub.3 in the final product, these substituents are best introduced 
into the nitro compound (10u) and are prepared by the displacement of 
compounds in which R.sub.3 is Cl or Br in (10u); halogen is introduced by 
treatment of the compounds of Formula (10u) (R.sub.3 is H) with NBS or 
NCS. To avoid loss of halogen during reduction, halogen is best introduced 
into the final product at the sulfonamide stage (Equation 32). 
##STR86## 
Compounds of Formula (10w) in which Q is 
##STR87## 
in (10), R.sub.5 is H or CH.sub.3 S and R.sub.6 is H, CH.sub.3 or CH.sub.3 
CH.sub.2 are prepared by treatment of the corresponding 
.alpha.-aminoketone with the appropriate isothiocyanate R.sub.5 NCS as 
shown in Equation 33. Similarly prepared are compounds (10x) in which 
R.sub.8 is H or SCH.sub.3 and R.sub.9 is H, CH.sub.3 or CH.sub.3 CH.sub.2. 
##STR88## 
Contacting the appropriate .alpha.-haloketone with an amidine provides 
compounds of Formula 10 in which Q is 
##STR89## 
and R.sub.5 is H, CH.sub.3 or CH.sub.3 CH.sub.2 as shown in Equation 33-A. 
##STR90## 
Alkylation of this product with a C.sub.1 -C.sub.4 alkyl iodide using 
procedures known to those skilled in the art leads to products in which 
R.sub.5 is H, CH.sub.3 or CH.sub.3 CH.sub.2 and R is C.sub.1 -C.sub.4 
alkyl. 
Also produced in the alkylation are compounds in which R is C.sub.1 
-C.sub.4 alkyl and R.sub.8 is H, CH.sub.3 or CH.sub.3 CH.sub.2 and R.sub.9 
is H, CH.sub.3 or CH.sub.3 CH.sub.2 as shown in Equation 33-B. 
##STR91## 
Oxazolines, Thiazolines and Imidazolines 
The intermediate oxazolines, thiazolines and imidazolines (14), are 
required for use in preparing compounds of Formula I in which Q is 
##STR92## 
For methods see: 
"Heterocyclic Compounds", V, R. C. Elderfield, Editor, John Wiley & Sons, 
Inc., New York, 1957. 
R. J. Fern and J. C. Riebsomer, Chem. Rev., 54, 543-613 (1954). 
R. H. Wiley and L. L. Bennett, Jr., Chem. Rev., 44, 447-476 (1944). 
Compounds of Formula (10y) in which Q is 
##STR93## 
are best prepared by displacement of halogen from the corresponding halo 
aromatic nitro compound with the imidazole salt as shown in Equation 34. 
##STR94## 
The reaction is conducted in the presence of an appropriate solvent such 
as dimethylformamide, N-methylpyrrolidone or THF at temperatures from 
ambient to reflux and for a period of one to twenty-four hours. The 
procedure is especially useful when R.sub.14 is H, CH.sub.3 or CH.sub.3 
CH.sub.2. When R.sub.14 is CH.sub.3 S, CH.sub.3 O or CH.sub.3 CH.sub.2 O 
in (10y), these substituents are best introduced by displacement of the 
corresponding iodo, bromo or chloro derivatives of 10y. 
For the preparation of 2-haloimidazoles see: 
"Heterocyclic Compounds" V, R. C. Elderfield, Editor, John Wiley & Sons, 
New York, 1957. 
K. Hofmann, "The Chemistry of Heterocyclic Compounds," (A. Weissberger, 
ed.), Vol. 6, pp. 1-420. Wiley (Interscience), New York, 1953. 
The following examples serve to more fully illustrate the preparation of 
compounds of this invention. All temperatures are in degrees centigrade 
and all parts are by weight unless otherwise indicated.