N-arylsulfonamide- and pyrrolidinecarboxylic acid...

Details N-arylsulfonamide- and pyrrolidinecarboxylic acid... N-arylsulfonamide- and pyrrolidinecarboxylic acid...

1999-12-30

2002-05-07

Solola, T. A. (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C504S276000, C504S278000

Reexamination Certificate

active

06384234

ABSTRACT:

BACKGROUND OF THE INVENTION
This invention pertains to compounds and processes which are useful for preparing herbicidal sulfonamides.
WO 95/27698-A1 discloses herbicidal sulfonamides for crop protection, There is a continuing need to develop compounds and processes useful for efficiently preparing these herbicidal sulfonamides.
SUMMARY OF THE INVENTION
This invention is directed to compounds and intermediates of Formulae 6 and 3, useful in preparing herbicidal sulfonamides of Formula 1, including all geometric and stereoisomers thereof, and agricultural salts thereof.
wherein
X is H, F or Cl;
Y is F or Cl;
R
1
is C
1
-C
3
haloalkyl, C
2
-C
4
alkoxyalkyl; C
2
-C
6
haloalkoxyalkyl or C
2
-C
6
cyanoalkyl;
R
2
is H, C
1
-C
4
alkyl, C
1
-C
4
haloalkyl, C
3
-C
4
alkenyl, C
3
-C
4
alkynyl, C
2
-C
4
alkoxyalkyl, C
2
-C
4
alkylcarbonyl or C
2
-C
4
alkoxycarbonyl;
R
3
is H or OH;
R
4
is H, F or Cl; and
R
5
is F or Cl;
provided that when R
3
is H then R
4
is F or Cl and when R
3
is OH then R
4
is H.
This invention is further directed to a process for preparing a compound of Formula 1
comprising halogenation of a compound of Formula 2a
wherein the substituents are as first defined in the Summary of the Invention.
This invention is further directed to a process for preparing a compound of Formula 2
comprising cyclization of a compound of Formula 3
wherein the substituents are as first defined in the Summary of the Invention.
This invention is further directed to a process for preparing a compound of Formula 3
comprising reaction of a compound of Formula 5
with a compound of Formula 4
wherein the substituents are as first defined in the Summary of the Invention.
This invention is further directed to a process for preparing a compound of Formula 6
comprising a) reaction of a compound of Formula 8
with a compound of formula X
1
SO
2
R
1
in the presence of a base to provide a compound of Formula 7;
b) optional reaction of the compound of Formula 7 wherein R
2
is H with X
1
R
2
in the presence of a base to provide a compound of Formula 7 wherein R
2
is other than H; and c) hydrolysis of the compound of Formula 7 with an acid or base to provide a compound of Formula 6;
wherein X
1
is halogen, C
2
-C
4
alkylcarbonyloxy, C
1
-C
4
alkoxy, phenoxy, cyano or imidazolyl, and the remaining substituents are as first defined in the Summary of the Invention.
This invention is further directed to a process for preparing a compound of Formula 6a
wherein a process sequence is selected from
A) a process sequence comprising a) reduction of a compound of Formula 12
 to provide a compound of Formula 11
 and b) chlorination of the compound of Formula 11 to provide a compound of Formula 6a;
wherein the substituents are as first defined in the Summary of the Invention; and
B) a process sequence comprising a) reduction of a compound of Formula 15
 to provide a compound of Formula 14
 and b) hydrolysis of the compound of Formula 14 to provide a compound of Formula 6a;
wherein the substituents are as first defined in the Summary of the Invention.
This invention is further directed to a process for preparing a compound of Formula 1
comprising a) cyclization of a compound of Formula 3
to provide the compound of Formula 2a
and b) halogenation of the compound of Formula 2a to provide a compound of Formula 1 wherein R
3
is OH, R
4
is H, and the remaining substituents are as first defined in the Summary of the Invention.
This invention is further directed to a process for preparing a compound of Formula 2
comprising a) reaction of a compound of Formula 5
with a compound of Formula 4
to provide the compound of Formula 3
and b) cyclization of the compound of Formula 3 to a compound of Formula 2
wherein the substituents are as first defined in the Summary of the Invention.
DETAILS OF THE INVENTION
This invention relates to compounds and intermediates for preparing herbicidal sulfonamides of Formula 1, including all geometric and stereoisomers thereof, and agricultural salts thereof.
The compounds and processes of this invention are illustrated below. The compounds of Formula 1 can be prepared via the processes of Steps 1-8 when R
3
is OH. Alternatively, the compounds of Formula 1 can also be prepared via the processes of Steps 1-7 when R
4
is F or Cl (compounds of Formula 2 wherein R
4
is F or Cl are the same as compounds of Formula 1).
Further embodiments of the present invention are the alternative processes for preparing compounds of Formula 6a, which can be prepared by the processes of Steps 9-11 or by the processes of Steps 12-16.
wherein
X is H, F or Cl;
Y is F or Cl;
R
1
is C
1
-C
3
haloalkyl, C
2
-C
4
alkoxyalkyl, C
2
-C
6
haloalkoxyalkyl or C
2
-C
6
cyanoalkyl;
R
2
is H, C
1
-C
4
alkyl, C
1
-C
4
haloalkyl, C
3
-C
4
alkenyl, C
3
-C
4
alkynyl, C
2
-C
4
alkoxyalkyl, C
2
-C
4
alkylcarbonyl or C
2
-C
4
alkoxycarbonyl;
R
3
is H or OH;
R
4
is H, F or Cl;
R
5
is F or Cl; and
X
1
is halogen, C
2
-C
4
alkylcarbonyloxy, C
1
-C
4
alkoxy, phenoxy, cyano or imidazolyl;
provided that when R
3
is H then R
4
is F or Cl and when R
3
is OH then R
4
is H.
Further processes of this invention to prepare intermediates of Formula 6a are illustrated below.
wherein the definitions of X, X
1
, and R
1
are as described above.
Further processes of this invention to prepare intermediates of Formula 6a are illustrated below.
wherein X
3
is OC(═O)CH
3
, halogen or C
1
-C
4
alkoxy; and the definitions of X, X
1
, and R
1
are as described above.
In the above recitations, the term “alkyl”, used either alone or in compound words such as “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl or hexyl isomers. “Alkenyl” includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. “Alkenyl” also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. “Alkynyl” includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. “Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. “Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. “Alkoxyalkyl” denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH
3
OCH
2
, CH
3
OCH
2
CH
2
, CH
3
CH
2
OCH
2
, CH
3
CH
2
CH
2
CH
2
OCH
2
and CH
3
CH
2
OCH
2
CH
2
. “Alkylthio” includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. “Cyanoalkyl” denotes an alkyl group substituted with one cyano group. Examples of “cyanoalkyl” include NCCH
2
, NCCH
2
CH
2
and CH
3
CH(CN)CH
2
.
The term “halogen”, either alone or in compound words such as “haloalkyl”, includes 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 F
3
C, ClCH
2
, CF
3
CH
2
and CF
3
CCl
2
. The terms “haloalkoxyalkyl” and the like, are defined analogously to the term “haloalkyl”. Examples of “haloalkoxyalkyl” include CF
3
OCH
2
, CCl
3
CH
2
OCH
2
, HCF
2
CH
2
CH
2
OCH
2
and CF
3
CH
2
OCH
2
CH
2
.
The total number of carbon atoms in a substituent group is indicated by the “C
i
-C
j
” prefix where i and j are numbers from 1 to 6. For example, C
1
-C
3
alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C
2
alkoxyalkyl designates CH
3
OCH
2
; C
3
alkoxyalkyl designates, for example, CH
3
CH(OCH
3
), CH
3
OCH
2
CH
2
or CH
3
CH
2
OCH
2
; and C
4
alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH
3
CH
2
CH
2
OCH
2
and CH
3
CH
2
OCH
2
CH
2
. Examples of “alkylcarbonyl” include C(O)CH
3
, C(O)CH
2
CH
2
CH
3

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