Processes for preparing aminophenylsulfonylureas, and intermediates therefor

A process for preparing a compound 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, 1, 2 or 3,
• A is hydrogen or an acyl radical,
• R1 is hydrogen or an unsubstituted or substituted hydrocarbon or hydrocarbonoxy radical having 1 to 6 carbon atoms,
• R2 is hydrogen or an unsubstituted or substituted hydrocarbon radical having a total of 1 to. 10 carbon atoms,
• or the group
• NR1R2 is a heterocyclic ring having 3 to 8 ring atoms which is unsubstituted or substituted and contains the nitrogen atom of the group NR1R2 as ring heteroatom and may also contain one or two further ring heteroatoms from the group consisting of n. 0 and s:
• R3 is hydrogen or C1-C4-alkyl,
• X and Y independently of one another are halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, each of the three latter radicals being unsubstituted or substituted by one or more radicals from the group consisting of halogen, C1-C4-alkoxy and C1-C4-alkylthio, or are C3-C6-Cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-alkenyloxy or C3-C6-alkynyloxy, and
• Z is CH or N,
• which comprises
• 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 then
• a) subjecting the compound (III) to ammonolysis at the SO2Cl 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, C1-C4-alkyl or a metal cation, to give the compound of the formula (I) in which R3 is, in agreement with M in formula (VI), H or C1-C4-alkyl or, if M is a metal cation, is a hydrogen atom, and A=H, or
• b) subjecting the compound of the formula (III) to ammonolysis at the SO2Cl 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 R3 is, like M, analogously to formula (VI), H or C1-C4-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 (VII)
• in which R3 is as defined in formula (I) to give the sulfonylurea of the formula (VII), which by reduction at the nitro group gives the compound of the formula (I) in which A is H, and
• 3. if A in the desired 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, R1, R2F X, Y, and Z in the formulae (II) to (VIII) being as defined for the end product of the formula (I).