Processes for the preparation of aminophenylsulfonyl-ureas...

Details Processes for the preparation of aminophenylsulfonyl-ureas... Processes for the preparation of aminophenylsulfonyl-ureas...

2002-11-05

2004-09-14

Raymond, Richard L. (Department: 1624)

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

Organic compounds

Chalcogen in the nitrogen containing substituent

C544S066000, C544S067000, C544S176000, C544S242000, C544S391000, C548S131000, C548S143000, C548S215000, C548S240000, C548S261000, C548S359500, C562S832000

Reexamination Certificate

active

06790955

ABSTRACT:

The invention concerns the technical field of processes for preparing herbicides or plant growth regulators.
It is known that heterocyclically substituted phenylsulfonylureas which carry an amino group or a functionalized amino group on the phenyl ring possess herbicidal and plant growth-regulatory properties (EP-A-1515; EP-A-7687 (=U.S. Pat. No. 4,383,113); EP-A-30138 (=U.S. Pat. No. 4,394,506); U.S. Pat. No. 4,892,946; U.S. Pat. No. 4,981,509; EP-A-116518 (=U.S. Pat. No. 4,664,695, U.S. Pat. No. 4,632,695)), WO-94/10154. In addition, German Patent Application P 4415049.0 (WO 95/29899) has proposed acylaminosulfonylureas as herbicides. The cited literature includes descriptions of processes for preparing sulfonylureas. The compounds having a free amino group on the phenyl ring are themselves herbicidal active ingredients or are suitable as starting compounds for preparing compounds with a substituted amino group.
Owing to the large number of reactive functional groups in the molecule, the methods for preparing aminophenylsulfonylureas can often be carried out only with low yields or poor purities. Another disadvantage is that many processes are based on the use of protecting groups, for example the tert-butyl group in the case of sulfonamides, whose elimination requires specific and difficult-to-handle reagents, such as trifluoroacetic acid. Moreover, the majority of the known processes for preparing sulfonylurea compounds are multistage and therefore give only a moderate overall yield, as a rule.
The object of the invention is therefore the provision of a process which is suitable for preparing a relatively large group of herbicides from the aminophenylsulfonylurea series and which avoids many of the abovementioned disadvantages.
The invention provides a process for preparing compounds of the formula (I) and salts thereof,
in which
(R)
n
is n identical or different radicals from the group consisting of halogen, alkyl and alkoxy,
n is 0, 1, 2 or 3, preferably 0 or 1, especially 0,
A is hydrogen or an acyl radical,
R
1
is hydrogen or an unsubstituted or substituted hydrocarbon or hydrocarbonoxy radical having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms,
R
2
is hydrogen or an unsubstituted or substituted hydrocarbon radical having a total of 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms,
or the group
NR
1
R
2
is a heterocyclic ring having 3 to 8 ring atoms which is unsubstituted or substituted and contains the nitrogen atom of the group NR
1
R
2
as ring heteroatom and may also contain one or two further ring heteroatoms from the group consisting of N, O and S,
R
3
is hydrogen or C
1
-C
4
-alkyl,
X and Y independently of one another are halogen, C
1
-C
6
-alkyl, C
1
-C
6
-alkoxy, C
1
-C
6
-alkylthio, each of the three latter radicals being unsubstituted or substituted by one or more radicals from the group consisting of halogen, C
1
-C
4
-alkoxy and C
1
-C
4
-alkylthio, or are C
3
-C
6
-cycloalkyl, C
2
-C
6
-alkenyl, C
2
-C
6
-alkynyl, C
3
-C
6
-alkenyloxy or C
3
-C
6
-alkynyloxy, and
Z is CH or N,
which comprises
1. (Stage 1) reacting the compound of the formula (II)
or its salts in the presence of a halogenating agent, with formation of the carbonyl halide and its rearrangement to form the compound of the formula (III)
2. (Stage 2) then
a) subjecting the compound (III) to ammonolysis at the SO
2
Cl group to give the compound of the formula (IV)
then reducing the compound (IV) at the nitro group to give the compound (V)
and then reacting the compound (V) with the carbamate or carbamate salt of the formula (VI)
in which Ar is unsubstituted or substituted phenyl and M is H, C
1
-C
4
-alkyl or a metal cation, to give the compound of the formula (I) in which R
3
is, in agreement with M in formula (VI), H or C
1
-C
4
-alkyl or, if M is a metal cation, R
3
is a hydrogen atom, and A═H, or
b) subjecting the compound of the formula (III) to ammonolysis at the SO
2
Cl group to give the abovementioned compound of the formula (IV), then reacting the compound (IV) with the carbamate or carbamate salt of the abovementioned formula (VI) to give the compound of the formula (VII)
in which R
3
is, in agreement with M in formula (VI), either H or C
1
-C
4
-alkyl or, if M is a metal cation, is a hydrogen atom, and reducing the compound of the formula (VII) at the nitro group to give the compound of the formula (I) in which A is H, or
c) reacting the compound of the formula (III) with cyanates and with the heterocyclic amine of the formula (VIII)
in which R
3
is as defined in formula (I) to give the sulfonylurea of the formula (VII), which by reduction at the nitro group gives the compounds of the formula (I) in which A is H, and
3. (Stage 3) if A in the end product of the formula (I) is not hydrogen but is an acyl radical, acylating the compound of the formula (I) obtained in Stage 2, in which A is H,
the radicals (R)
n
, R
1
, R
2
, X, Y, and Z in the formulae (II) to (VII) being as defined for the end product of the formula (I).
In the formulae (I) to (VIII) and in the formulae used below, the radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and their unsaturated and/or substituted counterparts may in each case be straight-chain or branched in the carbon framework. Unless indicated specifically, preference is given in the case of these radicals to the lower carbon frameworks, e.g. those having 1 to 4 carbon atoms, or, in the case of unsaturated groups, having 2 to 4 carbon atoms. Alkyl radicals, both alone and in the composite definitions such as alkoxy, haloalkyl, etc., are for example methyl, ethyl, n-propyl, isopropyl, n-butyl isobutyl, tert-butyl or 2-butyl, pentyls, hexyls, such as n-hexyl, isohexyl and 1,3-dimethylbutyl, and heptyls, such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl; alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; alkenyl is for example allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl; alkynyl is for example propargyl, but-2-yn-1-yl; but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. Halogen is for example fluorine, chlorine, bromine or iodine, Haloalkyl, haloalkenyl and haloalkynyl are alkyl, alkenyl and, respectively, alkynyl which are partially or completely substituted by halogen, preferably by fluorine, chlorine and/or bromine, in particular by fluorine or chlorine, examples being CF
3
, CHF
2
, CH
2
F, CF
3
CF
2
, CH
2
FCHCl, CCl
3
, CHCl
2
, CH
2
CH
2
Cl; haloalkoxy is for example OCF
3
, OCHF
2
, OCH
2
F, CF
3
CF
2
O, OCH
2
CF
3
and OCH
2
CH
2
Cl; corresponding comments apply to haloalkenyl and other halogen-substituted radicals.
A hydrocarbon radical is a straight-chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic hydrocarbon radical, for example alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl, preferably alkyl, alkenyl or alkynyl having up to 12 carbon atoms or cycloalkyl having 5 or 6 ring atoms, or phenyl; corresponding comments apply to a hydrocarbonoxy radical.
A heterocyclic radical or ring can be saturated, unsaturated or heteroaromatic; it contains one or more ring heteroatoms, preferably from the group consisting of N, O and S; it preferably has 5 or 6 members and contains 1, 2 or 3 ring heteroatoms. The radical may for example be a heteroaromatic radical or ring as defined above, or is a partially hydrogenated radical such as oxiranyl, pyrrolidinyl, piperidyl, piperazinyl, dioxolanyl, morpholinyl, and tetrahydrofuryl. Suitable substituents for a substituted heterocyclic radical are those mentioned below, and also oxo. The oxo group may also be on the ring heteroatoms, which may exist in various oxidation states in the case, for example, of N and S.
Substituted radicals, such as substituted hydrocarbon radicals, e.g. substituted alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or substituted heteroaryl, a substituted bicyclic radical or ring or a substituted bicyclic radical, with or without

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