This invention relates to certain phenylheterocyclic compounds, herbicidal compositions thereof and a method for their use as general and selective preemergent or postemergent herbicides or plant growth regulants.

BACKGROUND OF THE INVENTION 
This invention relates to certain substituted fused heterocyclic compounds 
which are useful as herbicides and their agriculturally suitable 
compositions as well as methods for their use as general or selective 
preemergent or postemergent herbicides or as plant growth regulants. 
New compounds effective for controlling the growth of undesired vegetation 
are in constant demand. In the most common situation, such compounds are 
sought to selectively control the growth of weeds in useful crops such as 
cotton, rice, corn, wheat and soybeans, to name a few. Unchecked weed 
growth in such crops can cause significant losses, reducing profit to the 
farmer and increasing costs to the consumer. In other situations, 
herbicides are desired which will control all plant growth. Examples of 
areas in which complete control of all vegetation is desired are areas 
around railroad tracks, storage tanks and industrial storage areas. There 
are many products commercially available for these purposes, but the 
search continues for products which are more effective, less costly and 
environmentally safe. 
U.S. Pat. No. 5,032,165 discloses herbicidal compounds of the formula 
##STR1## 
SUMMARY OF THE INVENTION 
The invention comprises novel compounds of Formula I, agriculturally 
suitable compositions containing them, and their method-of-use as 
preemergent and/or postemergent herbicides and/or plant growth regulants 
##STR2## 
G.sup.1 is CR.sup.1 or N; G.sup.2 is CR.sup.4 or N; 
A is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.2 -C.sub.4 
alkenyl, C.sub.2 -C.sub.4 alkynyl, OR.sup.10, SR.sup.10 or halogen; 
B is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.3 -C.sub.4 
alkenyl or C.sub.3 -C.sub.4 alkynyl; 
A and B can be taken together as X--Y--Z to form a fused ring such that X 
is connected to nitrogen and Z is connected to carbon; 
X is CHR.sup.2, CH.sub.2 CH.sub.2 or CR.sup.2 .dbd.CR.sup.3 ; 
Y is CHR.sup.5, CR.sup.5 .dbd.CR.sup.6, CHR.sup.5 CHR.sup.6, NR.sup.7, O or 
S(O).sub.n ; 
Z is CHR.sup.8, CH.sub.2 CH.sub.2, CR.sup.8 .dbd.CR.sup.9, NR.sup.7, O or 
S(O).sub.n ; 
n is 0, 1 or 2; 
R.sup.1 and R.sup.4 are independently halogen or CN; 
R.sup.2, R.sup.3, R.sup.5, R.sup.6, R.sup.8 and R.sup.9 are independently 
H, halogen, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 haloalkyl; 
R.sup.7 is H, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 haloalkyl; 
W is O or S; 
R.sup.10 is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 haloalkyl; 
R.sup.11 is halogen; 
R.sup.12 is H, C.sub.1 -C.sub.8 alkyl, C.sub.1 -C.sub.8 haloalkyl, halogen, 
OH, OR.sup.17, SH, S(O).sub.n R.sup.17, COR.sup.17, CO.sub.2 R.sup.17, 
C(O)SR.sup.17, C(O)NR.sup.19 R.sup.20, CHO, CR.sup.19 .dbd.NOR.sup.26, 
CH.dbd.CR.sup.27 CO.sub.2 R.sup.17, CH.sub.2 CHR.sup.27 CO.sub.2 R.sup.17, 
CO.sub.2 N.dbd.CR.sup.21 R.sup.22, NO.sub.2, CN, NHSO.sub.2 R.sup.23, 
NHSO.sub.2 NHR.sup.23, NR.sup.17 R.sup.28, NH.sub.2 or phenyl optionally 
substituted with R.sup.29 ; 
R.sup.13 is C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 haloalkyl, OCH.sub.3, 
SCH.sub.3, OCHF.sub.2, halogen, CN or NO.sub.2 ; 
R.sup.14 is H, C.sub.1 -C.sub.3 alkyl or halogen; 
R.sup.15 is H, C.sub.1 -C.sub.3 alkyl, halogen, C.sub.1 -C.sub.3 haloalkyl, 
cyclopropyl, vinyl, C.sub.2 alkynyl, CN, C(O)R.sup.28, CO.sub.2 R.sup.28, 
C(O)NR.sup.28 R.sup.30, CR.sup.24 R.sup.25 CN, CR.sup.24 R.sup.25 
C(O)R.sup.28, CR.sup.24 R.sup.25 CO.sub.2 R.sup.28, CR.sup.24 R.sup.25 
C(O)NR.sup.28 R.sup.30, CHR.sup.24 OH, CHR.sup.24 OC(O)R.sup.28 or 
OCHR.sup.24 OC(O)NR.sup.28 R.sup.30 ; 
when Q is Q-2 or Q-6, R.sup.14 and R.sup.15 together with the carbon to 
which they are attached can be C.dbd.O; 
R.sup.16 is H, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.2 
-C.sub.6 alkoxyalkyl, C.sub.3 -C.sub.6 alkenyl, C.sub.3 -C.sub.6 alkynyl 
or 
##STR3## 
R.sup.17 is C.sub.1 -C.sub.8 alkyl; C.sub.3 -C.sub.8 cycloalkyl; C.sub.3 
-C.sub.8 alkenyl; C.sub.3 -C.sub.8 alkynyl; C.sub.1 -C.sub.8 haloalkyl; 
C.sub.2 -C.sub.8 alkoxyalkyl; C.sub.2 -C.sub.8 alkylthioalkyl; C.sub.2 
-C.sub.8 alkylsulfinylalkyl; C.sub.2 -C.sub.8 alkylsulfonylalkyl, C.sub.4 
-C.sub.8 alkoxyalkoxyalkyl; C.sub.4 -C.sub.8 cycloalkylalkyl; C.sub.4 
-C.sub.8 alkenoxyalkyl; C.sub.4 -C.sub.8 alkynoxyalkyl; C.sub.6 -C.sub.8 
cycloalkoxyalkyl; C.sub.4 -C.sub.8 alkenyloxyalkyl; C.sub.4 -C.sub.8 
alkynyloxyalkyl; C.sub.3 -C.sub.8 haloalkoxyalkyl; C.sub.4 -C.sub.8 
haloalkenoxyalkyl; C.sub.4 -C.sub.8 haloalkynoxyalkyl; C.sub.6 -C.sub.8 
cycloalkylthioalkyl; C.sub.4 -C.sub.8 alkenylthioalkyl; C.sub.4 -C.sub.8 
alkynylthioalkyl; C.sub.1 -C.sub.4 alkyl substituted with phenoxy or 
benzyloxy, each ring optionally substituted with halogen, C.sub.1 -C.sub.3 
alkyl or C.sub.1 -C.sub.3 haloalkyl; C.sub.4 -C.sub.8 trialkylsilylalkyl; 
C.sub.3 -C.sub.8 cyanoalkyl; C.sub.3 -C.sub.8 halocycloalkyl; C.sub.3 
-C.sub.8 haloalkenyl; C.sub.5 -C.sub.8 alkoxyalkenyl; C.sub.5 -C.sub.8 
haloalkoxyalkenyl; C.sub.5 -C.sub.8 alkylthioalkenyl; C.sub.3 -C.sub.8 
haloalkynyl; C.sub.5 -C.sub.8 alkoxyalkynyl; C.sub.5 -C.sub.8 
haloalkoxyalkynyl; C.sub.5 -C.sub.8 alkylthioalkynyl; C.sub.2 -C.sub.8 
alkyl carbonyl; benzyl optionally substituted with halogen, C.sub.1 
-C.sub.3 alkyl or C.sub.1 -C.sub.3 haloalkyl; CHR.sup.24 COR.sup.18 ; 
CHR.sup.24 P(O)(OR.sup.18).sub.2 ; CHR.sup.24 P(S)(OR.sup.18).sub.2 ; 
CHR.sup.24 C(O)NR.sup.19 R.sup.20 ; CHR.sup.24 C(O)NH.sub.2 ; CHR.sup.24 
CO.sub.2 R.sup.18 ; 
##STR4## 
R.sup.18 is C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.3 
-C.sub.6 alkenyl or C.sub.3 -C.sub.6 alkynyl; 
R.sup.19 and R.sup.21 are independently H or C.sub.1 -C.sub.4 alkyl; 
R.sup.20 and R.sup.22 are independently C.sub.1 -C.sub.4 alkyl or phenyl 
optionally substituted with halogen, C.sub.1 -C.sub.3 alkyl or C.sub.1 
-C.sub.3 haloalkyl; 
R.sup.19 and R.sup.20 may be taken together as --(CH.sub.2).sub.5 --, 
--(CH.sub.2).sub.4 -- or --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --, each 
ring optionally substituted with C.sub.1 -C.sub.3 alkyl, phenyl or benzyl; 
R.sup.21 and R.sup.22 may be taken together with the carbon to which they 
are attached to form C.sub.3 -C.sub.8 cycloalkyl; 
R.sup.23 is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 haloalkyl; 
R.sup.24 and R.sup.25 are independently H or C.sub.1 -C.sub.4 alkyl; 
R.sup.26 is H, C.sub.1 -C.sub.6 alkyl, C.sub.3 -C.sub.6 alkenyl or C.sub.3 
-C.sub.6 alkynyl; 
R.sup.27 is H, C.sub.1 -C.sub.4 alkyl or halogen; 
R.sup.28 and R.sup.30 are independently H or C.sub.1 -C.sub.4 alkyl; and 
R.sup.29 is C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 haloalkyl, OCH.sub.3, 
SCH.sub.3, OCHF.sub.2, halogen, CN or NO.sub.2 ; 
and their corresponding N-oxides and agriculturally suitable salts provided 
that 
1) the sum of X, Y, and Z is no greater than 5 atoms in length and only one 
of Y and Z can be other than a carbon containing link; 
2) when A and B are other than taken together as X--Y--Z then G.sup.1 is N 
and G.sup.2 is CR.sup.4 ; 
3) when R.sup.12 is CO.sub.2 R.sup.17, C(O)SR.sup.17, CH.dbd.CR.sup.27 
CO.sub.2 R.sup.17 or CH.sub.2 CHR.sup.27 CO.sub.2 R.sup.17 then R.sup.17 
is other than C.sub.1 haloalkyl and when R.sup.17 is CHR.sup.24 CO.sub.2 
R.sup.18 or CO.sub.2 R.sup.18 then R.sup.18 is other than C.sub.1 
haloalkyl; and 
4) when G.sup.1 is N then G.sup.2 is CR.sup.4, and when G.sup.2 is N then 
G.sup.1 is CR.sup.1. 
In the above definitions, the term "alkyl", used either alone or in 
compound words such as "alkylthio" or "haloalkyl", includes straight chain 
or branched alkyl, e.g., methyl, ethyl, n-propyl, isopropyl or the 
different butyl isomers. Alkoxy includes methoxy, ethoxy, n-propyloxy, 
isopropyloxy, the different butoxy isomers, etc. Alkenyl and alkynyl 
include straight chain or branched alkenes and alkynes, e.g., 1-propenyl, 
2-propenyl, 3-propenyl and the different butenyl isomers. Cycloalkyl 
includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. The term 
"halogen", either alone or in compound words such as "haloalkyl", means 
fluorine, chlorine, bromine or iodine. Further, when used in compound 
words such as "haloalkyl" said alkyl may be partially or fully substituted 
with halogen atoms, which may be the same or different. Examples of 
haloalkyl include CH.sub.2 CH.sub.2 F, CF.sub.2 CF.sub.3 and CH.sub.2 
CHFCl. 
The compounds of the invention preferred for reasons including ease of 
synthesis and/or greater herbicidal efficacy are: 
1) Compounds of Formula I wherein R.sup.2, R.sup.3, R.sup.5, R.sup.6, 
R.sup.8 and R.sup.9 are independently H, F, CH.sub.3 or CF.sub.3. 
2) Compounds of Preferred 1 wherein R.sup.12 is H, OR.sup.17, SR.sup.17 or 
CO.sub.2 R.sup.17 ; R.sup.13 is halogen or CN. 
3) Compounds of Preferred 2 wherein 
Q is Q-1, Q-2, Q-4 or Q-5; 
A and B are taken together as X--Y--Z; 
X i s CHR.sup.2 ; 
Y is CHR.sup.5 or CHR.sup.5 CHR.sup.6 ; 
Z is CHR.sup.8 ; 
R.sup.2, R.sup.3, R.sup.5, R.sup.6, R.sup.8 and R.sup.9 are independently H 
or F; R.sup.17 is C.sub.1 -C.sub.4 alkyl, C.sub.3 -C.sub.4 alkenyl, 
C.sub.3 -C.sub.4 alkynyl, C.sub.2 -C.sub.4 alkoxyalkyl, C.sub.1 -C.sub.4 
haloalkyl, C.sub.3 -C.sub.4 haloalkenyl or C.sub.3 -C.sub.4 haloalkynyl. 
4) Compounds of Formula I wherein G.sup.1 is N. 
5) Compounds of Formula I wherein G.sup.2 is N. 
The compounds of the invention specifically preferred for reasons of 
greatest ease of synthesis and/or greatest herbicidal efficacy are the 
compounds of Preferred 3 which are: 
3-bromo-2-4-chloro-2-fluoro-5-(2-propynyloxy)phenyl!-4,5,6,7-tetrahydropyr 
azolo1,5-a!pyridine; 
3-chloro-2-4-chloro-2-fluoro-5-(2-propynyloxy)-5,6,7,8-tetrahydoimidazo1, 
2-a!pyridine; and 
6-(3-chloro-4,5,6,7-tetrahydropyrazolo1,5-a!pyridin-2-yl)-7-fluoro-4-(1-me 
thyl-2-propynyl)-2H-1,4-benzoxazin-3(4H)-one. 
Another embodiment of the invention is an agriculturally suitable 
composition for controlling the growth of undesired vegetation comprising 
an effective amount of a compound of Formula I with the substituents as 
defined above. 
A further embodiment of the invention is a method for controlling the 
growth of undesired vegetation which comprises applying to the locus to be 
protected an effective amount of a compound of Formula I with the 
substituents as defined above. 
Compounds of Formula I may exist as one or more stereoisomers. The various 
stereoisomers include enantiomers, diastereomers and geometric isomers. 
One skilled in the art will appreciate that one stereoisomer may be the 
more active. One skilled in the art knows how to separate said 
enantiomers, diasteriomers and geometric isomers. Accordingly, the present 
invention comprises racemic mixtures, individual stereoisomers, and 
optically active mixtures. 
DETAILED DESCRIPTION OF THE INVENTION SYNTHESIS 
By using one or more of the reactions and techniques described in Schemes 
1-18 of this section as well as by following the specific procedures given 
in Examples 1-20, compounds of General Formula I can be prepared. 
Compounds of Formula Ia, where Q, X, Y, and Z are defined as above, can be 
prepared by the method in Scheme 1. Reaction of an aminoheterocycle of 
Formula II with an alpha-bromo or chloroketone of Formula III in a solvent 
such as acetonitrile or methanol at room temperature or by heating 
followed by neutralization with a base such as saturated aqueous sodium 
bicarbonate affords compounds of Formula Ia. Aminoheterocycles of Formula 
II are known and can be commercially purchased in some cases. 
Halogenation of compounds of Formula Ia with halogenating agents such as 
N-halosuccinimides or bromine affords compounds of Formula Ib (where 
R.sup.1 is halogen). Treatment of compounds of Formula Ia with Vilsmeier 
Reagent (phosphorous oxychloride, N,N-dimethylformamide) gives aldehyde 
adducts (of Formula Ib where R.sup.1 is a formyl group) which can be 
condensed with hydroxylamine hydrochloride to give oxime intermediates (Ib 
where R.sup.1 is C.dbd.NOH) which in turn can be heated in phosphorous 
oxychloride to yield cyano substituted analogs of Formula Ic. 
##STR5## 
The alpha-bromo and chloroketones of Formula III can be made by the methods 
summarized in Scheme 2. Carboxylic acids of Formula IV can be treated with 
thionyl chloride to give an acid chloride which in turn is allowed to 
react with Grignard reagent of Formula MeMgBr or MeMgCl or with methyl 
lithium to furnish ketone intermediates of Formula V. Lithiation of 
arylhalides of Formula VI followed by treatment with reagents of formula 
MeCOL (where L represents a leaving group such as halogen, dialkylamine, 
or alkoxide) gives ketones V as well. By the method of Beech J. Chem. 
Soc. 1297 (1954)!, ketones of Formula V can also be prepared from 
arylamines of Formula VII by diazotization followed by reaction of the 
generated diazonium salt with acetaldehyde oxime (MeCH.dbd.NOH) and 
hydrolysis. The starting materials IV, VI, and VII are known and can be 
commercially obtained in some cases. 
##STR6## 
An alternative and more specific method for preparing 
tetrahydroimidazo1,2-a!pyridine intermediates of Formula Id where 
R.sup.2, R.sup.5, R.sup.6, R.sup.8, and Q are defined as above (except 
when R.sup.16 or R.sup.17 on Q is an unsaturated group) is shown in Scheme 
3. Heating 2-aminopyridines of Formula VIII with an alpha-bromo or 
chloroketone of Formula III followed by neutralization with saturated 
aqueous sodium bicarbonate gives imidazo1,2-a!pyridines of Formula IX. 
Catalytic hydrogenation of imidazopyridines IX with a transition metal 
catalyst such as platinum oxide affords the tetrahydro analogs Id. Use of 
2-aminothiazoles, 2-aminoxazoles, 2-aminopyrimidines, 2-aminopyridazines, 
and 2-aminopyrazines in place of the 2-aminopyridine starting materials in 
Scheme 3 and following this same method of synthesis also gives compounds 
of Formula Ia where X, Y, and Z are heteroatoms. 
##STR7## 
Tetrahydroimidazo1,2-a!pyridines of Formula Ib or Id where R.sup.16 or 
R.sup.17 on Q is methyl or benzyl can be deprotected with borontribromide 
to give dealkylated intermediates (where R.sup.16 and R.sup.17 are 
hydrogen) which on realkylation with alkenyl or alkynyl halides give 
compounds of Formula Ib or Id where R.sup.16 or R.sup.17 represents an 
alkenyl or alkynyl moiety. 
Intermediate imidazo1,2-a!pyridines of Formula IX can also be made by the 
route shown in Scheme 4. Condensing aminopyridines of Formula X with 
bromoacetic acid followed by heating the obtained condensation adducts 
with phosphorous oxybromide gives 2-bromoimidazo1,2-a!pyridines of 
Formula XI. Palladium-catalyzed cross-couplings using 
bis(triphenylphosphine)palladium(II) chloride or 
tetrakis(triphenylphosphine)palladium(O)! of these bromoimidazopyridines 
with boronic acids of formula QB(OH).sub.2 in a solvent such as glyme in 
the presence of base such as aqueous sodium bicarbonate yields 
imidazo1,2-a!pyridines of Formula IX. 
##STR8## 
Dihydroimidazo1,2-a!pyridines of Formula Ie and If can be synthesized by 
the chemistry shown in Scheme 5. Warming tetrahydroimidazopyridines of 
Formula Id with an excess of N-halosuccinimides (2.0-2.5 equivalents) in 
dimethylformamide at 60.degree.-100.degree. C. produces Ie and If. 
##STR9## 
Scheme 6 illustrates the preparation of imidazoles of Formula Ig where 
R.sup.1 is halogen, and Q, A, and B are as previously defined. Amidines, 
isoureas, and isothioureas of Formula XII can be heated with alpha-bromo 
and chloroketones of Formula III, or with a corresponding 
alpha-hydroxyketone, in a solvent such as ethanol or dimethylformamide to 
give, after neutralization with a base such as aqueous saturated sodium 
bicarbonate, intermediates of Formula XIII. Alkylation of intermediates of 
Formula XIII with alkylating agents of Formula BL.sup.1 (where L.sup.1 is 
a leaving group) affords imidazoles of Formula XIV which on halogenation 
gives 5-haloimidazoles of Formula Ig where R.sup.1 is halogen. 
Halogenation of compounds of Formula XIV where A is hydrogen with an 
excess of the halogenating reagent produces imidazoles of Formula Ig where 
both A and R.sup.1 is halogen. 
##STR10## 
An alternative method of preparing compounds of Formula XIV is shown in 
Scheme 7. Palladium-catalyzed cross-couplings using for example 
bis(triphenylphosphine)palladium(II) chloride or 
tetrakis(triphenylphosphine)palladium(O)! of 4-bromoimidazoles of Formula 
XV with boronic acids of Formula QB(OH).sub.2 in a solvent such as glyme 
in the presence of base such as aqueous sodium bicarbonate yields 
compounds of Formula XIV. Bromoimidazoles of Formula XV can be prepared by 
established methods. 
##STR11## 
Salts (e.g., hydrochlorides and N-oxides) of I and II can be made by 
reaction of the free bases with an appropriate acid or oxidizing agent 
such as meta-chlorperoxybenzoic acid. 
Scheme 8 describes how compounds of Formula I (where G.sup.2 .dbd.N, 
G.sup.1 .dbd.CR.sup.1 and A and B are X--Y--Z) can be made by the reaction 
of sydnones of Formula XVI with appropriately substituted alkynes XVII. 
The reaction takes place at elevated temperatures generally between 
80.degree. C. and 200.degree. C. The reaction may be performed in a 
variety of solvents with aromatic hydrocarbons such as xylenes being 
preferred. 
##STR12## 
Scheme 9 describes how compounds of Formula I can be made by the reaction 
of sydnones with appropriately substituted alkenes XVIII. The initial 
product of the reaction is a dihydro aromatic compound. Often this is 
converted directly to the desired structure (Ih) in situ. It is also 
possible to include an oxidant such as chloranil or other mild oxidizing 
agent in the reaction mixture so as to make the aromatization process more 
facile (this has been shown with simpler sydnones: Huisgen et al.; Chem. 
Ber. 1968, 101, 829). The conditions for the reaction are as described 
above. The sydnones used in the above-mentioned processes can be made 
using procedures known in the art. (see S. D. Larsen and E. Martinborough, 
Tet. Lett. 1989, 4625) The chemistry of bicyclic sydnones has been 
reviewed (see Kevin Potts in "1,3-Dipolar Cycloaddition Chemistry", Volume 
II, pages 50-57; A. Padwa editor, Wiley Interscience, New York, 1984). 
##STR13## 
Scheme 10 describes an alternative synthesis of compounds of the invention 
by the photochemical cycloaddition of alkynyl substituted tetrazoles 
(XIX). The reaction can be performed in a variety of solvents, but is 
preferably carried out in inert solvents such as benzene or toluene. The 
reaction must be carried out in a vessel that allows the passage of light 
at wavelengths between 250 and 300 nm such as those made from quartz or 
vycor. The photolysis is preferably performed with a high pressure mercury 
arc lamp or other lamp which produces light above 250 nm. The reaction is 
carried out at room temperature or above. 
##STR14## 
Scheme 11 describes how the tetrazoles XIX are made by alkylation of the 
free tetrazole XX with a halide or sulfonate in the presence of an acid 
acceptor or base. Many different bases such as alkali carbonates, 
hydroxides or hydrides are suitable. A variety of solvents can be used, 
but solvents of high polarity such as dimethylformamide or dimethyl 
acetamide are preferred. Tetrazoles XX can also be alkylated with alcohols 
XXI using the Mitsonobu reaction with a phosphine and a 
diazodicarboxylate. There are many different solvents and conditions that 
can be used. (See O. Mitsonobu, Synthesis, 1981, 1) Especially useful 
conditions for the instant invention include carrying out the reaction in 
tetrahydrofuran with diethyl azodicarboxylate and triphenylphosphine. 
Under these conditions the desired 3-alkynyl tetrazole (V) is produced 
predominantly. 
##STR15## 
Scheme 12 describes how compounds of the instant invention (Ih or Ij, 
R.sup.1 .dbd.H) can be converted to other compounds of the present 
invention (Ih or Ij, R.sup.1 .dbd.Cl or Br) by reaction with halogenating 
agents. The reaction may be carried out with elemental halogens and also 
with N-halosuccinimides. The reaction with N-halosuccinimides gives 
particularly good results when conducted in dipolar aprotic solvents such 
as dimethylformamide. 
##STR16## 
Scheme 13 shows how compounds of Formula Ih can also be prepared by 
coupling compounds of Formula Ih, Q.dbd.SnR.sup.3, with aryl halides or 
sulfonates (XXVII) in the presence of palladium catalysts such as those 
described in Scheme 7. For an example of this type of coupling with 
monocyclic pyrazoles, see Yamanaka et al., Heterocycles, 33, 813-818 
(1992). Compounds of Formula Ih, Q.dbd.SnR.sup.3, can be made by sydnone 
cycloaddition as described in Scheme 8 using stannylated acetylenes. 
##STR17## 
As shown in Scheme 14 some compounds of formula Ii where G.sup.2 .dbd.N can 
be prepared by catalytic hydrogenation of compounds of Formula XXIII. The 
conditions are those disclosed in Scheme 3. Compounds of Formula XXIII can 
be prepared by cyclization of N-aminopicoline salts (XXI) with acid 
chlorides (XXII). The reaction is best performed in the presence of a 
base, preferably an amine base. Specifically preferred conditions are to 
run the reaction at elevated temperature (50.degree.-80.degree. C.) in the 
amine base, such as pyridine, as solvent (see Potts et al., J. Org. Chem., 
33, 3767-3770 (1969). 
##STR18## 
Scheme 15 describes how other compounds of the invention (Ij) can be 
obtained by the reaction of Munchnones (reactive mesoionic intermediates) 
with acetylenes (III). The Munchnones are prepared in the presence of the 
dipolarphile by dehydrating N-acyl-aminoacids (XXIV). The cycloaddition 
reaction occurs at elevated temperatues, generally between 50.degree. C. 
and 160.degree. C. Dehydrating agents such as acetic anhydride are very 
useful in this process. Other reagents and conditions for generating 
Munchnones have been described by Huisgen et al., Chem. Ber., 1970, 103, 
2315. 
##STR19## 
Scheme 16 describes how munchnones can also be made by the reaction of 
imides of structure (XXV) and a dehydrating agent in the presence of the 
alkene or alkyne. Many dehydrating reagents can be used. If the reagent 
used is acetic anhydride, it is convenient to use it as the solvent of the 
reaction. If a reagent such as a dicyclohexylcarbodiimide (DCC) is used, 
aromatic hydrocarbons such as benzene, toluene, or xylenes are preferred 
as solvents. The reaction is generally carried out at elevated temperature 
from 50.degree. C. to 180.degree. C. The chemistry of the bicyclic 
munchnones has been reviewed by Kevin Potts in "1,3-Dipolar Cycloaddition 
Chemistry", Volume II, pages 41-49 (A. Padwa editor, Wiley Interscience, 
New York, 1984). 
##STR20## 
The alkenes and alkynes (XVII and XVIII) are often commercially available. 
Scheme 7 describes how a generally useful method of synthesis is to couple 
aryl bromides and iodides (XXVII) with alkenes and alkynes in the presence 
of palladium catalysts. Appropriate catalysts and conditions are described 
in detail by Heck in "Palladium Reagents in Organic Syntheses", Academic 
Press, New York, 1985. The aryl halides (XXVII) used for the instant 
invention are either commercially available or synthesized via 
diazotization of known arylamines (XXVI). Suitable conditions for 
diazotization of arylamines (XXVI) and their conversion to aryl halides 
(XXVII) can be found in Furniss et al, "Vogel's Textbook of Practical 
Organic Chemistry, Fifth Edition", Longman Scientific and Technical, 
Essex, England, pages 922-946. There are many other known methods to 
incorporate iodine into aromatic molecules (see, Merkushev, Synthesis, 
923-937 (1988). 
##STR21## 
Compounds of Formula Ik where R.sup.12 .dbd.OH can serve as intermediates 
for the synthesis of compounds of Formula I containing many different 
R.sup.12 substituents. Scheme 18 shows some, but not all of the more 
useful transformations. In addition to well known alkylation and acylation 
chemistry, through the intermediacy of the triflate Il (R.sup.12 
.dbd.OSO.sub.2 CF.sub.3) a wide variety of R.sup.12 substituents can be 
introduced. To form esters (Im) (R.sup.12 .dbd.CO.sub.2 R.sup.17) Il may 
be reacted with carbon monoxide and an alcohol in the presence of a 
suitable palladium catalyst (see Chem. Comm. 1987, 904-905). To form 
alkenes (In) the triflates (Il) may be reacted with an alkene in the 
presence of a palladium catalyst (see Heterocycles, 26, 355-358 (1987)). 
Ketones (Ip) may be formed by reaction of enol ethers under similar 
conditions (see J. Org. Chem., 57, 1481-1486 (1992)). Aryl groups (Iq) can 
be introduced by reaction of aryl boronic acids ArB(OH)2 with palladium 
catalysts (see Tetrahedron Lett., 32, 2273-2276 (1991) and references 
cited therein)). Alkyl groups (Ir) may be introduced by nickel or 
palladium catalyzed reaction with grignard reagents (see, J. Org. Chem., 
57, 4066-4068 (1992) and references cited therein). 
##STR22##