Substituted sulfonylaminomethylbenzoic acid (derivatives) and their preparation
View Patent ↗The present invention relates to a compound of the formula (I) The compound according to the invention is suitable for the preparation of herbicidal active substances such as sulfonylureas.
1. A process for preparing a compound of the formula (XII)
R 1 is H, (C 1 –C 8 )alkyl, (C 3 –C 8 )alkenyl or (C 3 –C 8 )alkynyl, where the last 3 radicals are unsubstituted or substituted,
R 6 is H or (C 1 –C 8 )alkyl which is unsubstituted or substituted,
R 7 is (C 1 –C 8 )alkyl, (C 3 –C 8 )alkenyl, (C 3 –C 8 )alkynyl, (C 6 –C 14 )aryl or mono- or di (C 1 –C 8 )alkylamino which are unsubstituted or substituted, or
R 6 and R 7 together form a chain of the formula —(CH 2 ) m B m 1 — which is unsubstituted or substituted, and where m=2, 3 or 4, m 1 =0 or 1 and B=CO or SO 2 ,
R 8 radicals are identical or different and are (C 1 –C 4 )alkyl, (C 1 –C 4 )alkoxy, [(C 1 –C 4 )alkyl]carbonyl or [(C 1 –C 4 )alkoxy]carbonyl which are unsubstituted or substituted, or R 8 is halogen, NO 2 or CN, and
n is 0, 1, 2 or 3,
R x , R y independently of one another are a hydrogen atom, halogen, (C 1 –C 4 )alkyl, (C 1 –C 4 )alkoxy, (C 1 –C 4 )alkylthio, where each of the last-mentioned 3 radicals is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 –C 4 )alkoxy and (C 1 –C 4 )alkylthio, or are mono- or di[(C 1 –C 4 )alkyl]amino, (C 2 –C 6 )alkenyl, (C 2 –C 6 )alkynyl, (C 3 –C 6 )alkenyloxy or (C 3 –C 6 )alkynyloxy, and
X is CH or N
and wherein, unless otherwise identified, the substituents are halogen, (C 1 –C 8 )alkoxy, (C 1 –C 8 )haloalkoxy, (C 1 –C 8 )alkylthio, hydroxyl, amino, nitro, carboxyl, cyano, azido (C 1 –C 8 )alkoxycarbonyl, (C 1 –C 8 )alkylcarbonyl, formyl, carbamoyl, mono- and di-(C 1 –C 8 ) alkylaminocarbonyl, acylamino, mono- and di-(C 1 –C 8 ) alkylamino, (C 1 –C 8 )alkylsulfinyl, (C 1 –C 8 )haloalkylsulfinyl, (C 1 –C 8 )alkylsulfonyl, halo(C 1 –C 8 )alkylsulfonyl, (C 1 –C 8 )cycloalkyl, (C 1 –C 8 ) cycloalkenyl, wherein the cycloalkyl and cycloalkyl radicals are optionally substituted by (C 1 –C 8 )alkyl and halo(C 1 –C 8 )alkyl, (C 1 –C 8 )alkenyl, (C 1 –C 8 )alkynyl, (C 1 –C 8 )alkenyloxy or (C 1 –C 8 )alkynyloxy; which comprises:
reacting the compound of formula (VII):
wherein
R 1 is H, (C 1 –C 8 )alkyl, (C 3 –C 8 )alkenyl or (C 3 –C 8 )alkynyl, where the last 3 radicals are unsubstituted or substituted,
R 6 is H or (C 1 –C 8 )alkyl which is unsubstituted or substituted,
R 7 is (C 1 –C 8 )alkyl, (C 3 –C 8 )alkenyl, (C 3 –C 8 )alkynyl, (C 6 –C 14 )aryl or mono- or di (C 1 –C 8 )alkylamino which are unsubstituted or substituted, or
R 6 and R 7 together form a chain of the formula —(CH 2 ) m B m 1 — which is unsubstituted or substituted, and where m=2, 3 or 4, m 1 =0 or 1 and B=CO or SO 2 ,
R 8 radicals are identical or different and are (C 1 –C 4 )alkyl, (C 1 –C 4 )alkoxy, [(C 1 –C 4 )alkyl]carbonyl or [(C 1 –C 4 )alkoxy]carbonyl which are unsubstituted or substituted, or R 8 is halogen, NO 2 or CN,
n is 0, 1, 2 or 3, and
Y is halogen;
wherein, the substituents are halogen, (C 1 –C 8 )alkoxy, (C 1 –C 8 )haloalkoxy, (C 1 –C 8 )alkylthio, hydroxyl, amino, nitro, carboxyl, cyano, azido (C 1 –C 8 )alkoxycarbonyl, (C 1 –C 8 )alkylcarbonyl, formyl, carbamoyl, mono- and di-(C 1 –C 8 ) alkylaminocarbonyl, acylamino, mono- and di-(C 1 –C 8 ) alkylamino, (C 1 –C 8 )alkylsulfinyl, (C 1 –C 8 )haloalkylsulfinyl, (C 1 –C 8 )alkylsulfonyl, halo(C 1 –C 8 )alkylsulfonyl, (C 1 –C 8 )cycloalkyl, (C 1 –C 8 ) cycloalkenyl, wherein the cycloalkyl and cycloalkyl radicals are optionally substituted by (C 1 –C 8 )alkyl and halo(C 1 –C 8 )alkyl, (C 1 –C 8 )alkenyl, (C 1 –C 8 )alkynyl, (C 1 –C 8 )alkenyloxy or (C 1 –C 8 )alkynyloxy,
with either:
i) amine of the formula (XII) in the presence of MOCN, wherein M is an ammonium ion or an alkali metal ion,
to give a compound of the formula (XIII); or
ii) ammonia in the presence of a suitable solvent to give a compound
and subsequently preparing the compound of the formula (XIII) by
a) reacting the compound of the formula (VIII) with a compound of the formula (IX):
to give the compound of the formula (XIII); or
b) reacting the compound of the formula (VIII) with an isocyanate of the formula (X):
to give the compound of the formula (XIII); or
c) reacting the compound of the formula (VIII) with an alkyl isocyanate and phosgene to give a compound of the formula (XI)
which is subsequently reacted with an amine of the formula (XII)
to give the compound of the formula (XIII); or
d) reacting the compound of the formula (VIII) with a carbonic acid derivative R—CO—OPh, in which Ph=unsubstituted or substituted phenyl and R=halogen or unsubstituted or substituted phenoxy to give a compound of the formula (XIV)
which is subsequently reacted with an amine of the formula (XII)
to give the compound of the formula (XIII);
wherein R 1 , R 7 , R 8 , and n in formulae (XI) and (XIV) are as defined in formula (XIII) R x , R y and X in formulae (IX), (X) and (XII) are as defined in formula (XIII) and Ph in formulae (IX) and (XIV) is unsubstituted or substituted phenyl,
wherein the substituents on the phenyl ring are halogen, (C 1 –C 8 )alkoxy, (C 1 –C 8 )haloalkoxy, (C 1 –C 8 )alkylthio, hydroxyl, amino, nitro, carboxyl, cyano, azido (C 1 –C 8 )alkoxycarbonyl, (C 1 –C 8 )alkylcarbonyl, formyl, carbamoyl, mono- and di-(C 1 –C 8 ) alkylaminocarbonyl, acylamino, mono- and di-(C 1 –C 8 ) alkylamino, (C 1 –C 8 )alkylsulfinyl, (C 1 –C 8 )haloalkylsulfinyl, (C 1 –C 8 )alkylsulfonyl, halo(C 1 –C 8 )alkylsulfonyl, (C 1 –C 8 )cycloalkyl, (C 1 –C 8 ) cycloalkenyl, wherein the cycloalkyl and cycloalkyl radicals are optionally substituted by (C 1 –C 8 )alkyl and halo(C 1 –C 8 )alkyl, (C 1 –C 8 )alkenyl, (C 1 –C 8 )alkynyl, (C 1 –C 8 )alkenyloxy or (C 1 –C 8 )alkynyloxy.
2. The process of claim 1 , wherein
R 1 is H or (C 1 –C 2 )alkyl which is unsubstituted or substituted,
R 6 is H or (C 1 –C 2 )alkyl which is unsubstituted or substituted,
R 7 is (C 1 –C 4 )alkyl, phenyl or mono- or di (C 1 –C 4 )alkylamino which are unsubstituted or substituted, or
R 6 and R 7 together form a chain of the formula —(CH 2 ) m B m 1 — which is unsubstituted or substituted, and where m=3 or 4, m 1 =0,
n is 0 and
Y is fluorine, chlorine, bromine or iodine.
3. The process of claim 1 , wherein
R 1 is H or (C 1 –C 2 )alkyl which is unsubstituted,
R 6 is H or (C 1 –C 2 )alkyl which is unsubstituted,
R 7 is (C 1 –C 4 )alkyl, (C 1 –C 4 )haloalkyl, phenyl or mono- or di (C 1 –C 4 )alkylamino which are unsubstituted, or
R 6 and R 7 together form a chain of the formula —(CH 2 ) m B m 1 — which is unsubstituted and where m=3 or 4, m 1 =0,
n is 0 and
Y is fluorine, chloride or bromine.