Method for producing 2-(triazinylcarbonyl) sulfonanilides
View Patent ↗The present application relates to a process based on the oxidative ring opening of a compound with oxindole structure for preparation of substituted 2-(triazinylcarbonyl)sulfonanilides of the formula (1-1) proceeding from N-sulfonyl-substituted 3-triazinyloxindole of the formula (2-1), and to the 2-(triazinylcarbonyl)sulfonanilides of the formula (1-1) thus prepared, and to the use thereof as intermediates for the synthesis of fine chemicals and of active ingredients in the agricultural sector. The invention also relates to a multistage process for preparation of N-alkyl-N-[2-(1,3,5-triazin-2-ylcarbonyl)phenyl]alkanesulfonamides of the formula (4-1), proceeding from a 3-(alkylsulfanyl)-1,3-dihydro-2H-indol-2-one of the formula (7-1), wherein the multistage process also comprises, as a component step, the oxidative ring opening mentioned, and to the 2-(triazinylcarbonyl)sulfonanilides of the formula (1-1) which are obtained by the oxidative ring opening and are used as intermediates in the multistage process.
1. A process for preparing a 2-(triazinylcarbonyl)sulfonanilides of formula (1-1)
in which
R 1a to R 1d are each independently selected from the group consisting of
hydrogen, fluorine, chlorine, bromine, iodine and from
(C 1 -C 6 )-alkyl where the alkyl radical is branched or unbranched and is unsubstituted or substituted by at least one substituent selected from the group consisting of fluorine, chlorine, (C 1 -C 4 )-alkoxy and (C 3 -C 7 )-cycloalkyl,
(C 3 -C 7 )-cycloalkyl where the cycloalkyl radical is unsubstituted or substituted by at least one substituent selected from the group consisting of fluorine, chlorine, (C 1 -C 4 )-alkyl and (C 3 -C 7 )-cycloalkyl and (C 1 -C 4 )-alkoxy,
(C 1 -C 6 )-alkoxy where the alkoxy radical is branched or unbranched and is unsubstituted or substituted by at least one substituent selected from the group consisting of fluorine, chlorine, (C 1 -C 4 )-alkoxy and (C 3 -C 7 )-cycloalkyl,
(C 3 -C 7 )-cycloalkoxy where the cycloalkoxy radical is unsubstituted or substituted by at least one substituent selected from the group consisting of fluorine, chlorine, (C 1 -C 4 )-alkyl and (C 1 -C 4 )-alkoxy,
(C 1 -C 6 )-alkylthio where the alkylthio radical is branched or unbranched and is unsubstituted or substituted by at least one substituent selected from the group consisting of fluorine, chlorine, (C 1 -C 4 )-alkyl and (C 1 -C 4 )-alkoxy,
(C 3 -C 7 )-cycloalkylthio where the cycloalkylthio radical is unsubstituted or substituted by at least one substituent selected from the group consisting of fluorine, chlorine, (C 1 -C 4 )-alkyl and (C 1 -C 4 )-alkoxy, and
phenyl or 1-naphthyl or 2-naphthyl or a five- or six-membered heteroaromatic ring having from 1 to 2 heteroatoms, where the heteroatoms are each selected independently from the group consisting of O and N, and where the aryl or heteroaryl radical is unsubstituted or substituted by at least one substituent selected from the group consisting of fluorine, chlorine, bromine, iodine, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy and (C 3 -C 7 )-cycloalkyl and (C 1 -C 4 )-alkylthio, and
R 2 is
(C 1 -C 6 )-alkyl where the alkyl radical is unsubstituted or fully or partly substituted by fluorine, or
(C 3 -C 7 )-cycloalkyl where the cycloalkyl radical is unsubstituted or fully or partly substituted by fluorine,
and
R 4 and R 5 are each hydrogen,
(C 1 -C 6 )-alkyl where the alkyl radical is unsubstituted or substituted by at least one substituent selected from fluorine, chlorine, (C 1 -C 4 )-alkoxy and (C 3 -C 7 )-cycloalkyl, or
(C 1 -C 6 )-alkoxy where the alkoxy radical is branched or unbranched and is unsubstituted or substituted by at least one substituent selected from the group consisting of fluorine, chlorine, (C 1 -C 4 )-alkoxy and (C 3 -C 7 )-cycloalkyl,
which comprises
using as a reactant an N-sulfonyl-substituted 3-triazinyloxindole of formula (2-1)
in which
R 1a to R 1d and R 2 , R 4 and R 5 are each as defined in formula (1-1), and
R 3 is hydrogen
and
converting the reactant of formula (2-1) initially charged in a solvent in the presence
of a base and
of an oxidizing agent.
2. The process for preparing a 2-(triazinylcarbonyl)sulfonanilide of formula (1-1) as claimed in claim 1 , where
R 1a to R 1d are each independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine and from
(C 1 -C 6 )-alkyl where the alkyl radical is branched or unbranched and is unsubstituted or substituted by at least one substituent selected from the group consisting of fluorine, chlorine, (C 1 -C 4 )-alkoxy or (C 3 -C 7 )-cycloalkyl,
(C 3 -C 7 )-cycloalkyl where the cycloalkyl radical is unsubstituted or substituted by at least one substituent selected from the group consisting of fluorine, chlorine, (C 1 -C 4 )-alkyl or (C 3 -C 7 )-cycloalkyl or (C 1 -C 4 )-alkoxy,
(C 1 -C 6 )-alkoxy where the alkoxy radical is branched or unbranched and is unsubstituted or substituted by at least one substituent selected from the group consisting of fluorine, chlorine, (C 1 -C 4 )-alkoxy or (C 3 -C 7 )-cycloalkyl,
(C 3 -C 7 )-cycloalkoxy where the cycloalkoxy radical is unsubstituted or substituted by at least one substituent selected from the group consisting of fluorine, chlorine, (C 1 -C 4 )-alkyl or (C 1 -C 4 )-alkoxy, and
R 2 is (C 1 -C 6 )-alkyl where the alkyl radical is fully or partly substituted by fluorine, and
R 4 and R 5 are each independently
(C 1 -C 6 )-alkoxy where the alkoxy radical is branched or unbranched and is unsubstituted or substituted by at least one substituent selected from the group consisting of fluorine, chlorine, (C 1 -C 4 )-alkoxy or (C 3 -C 7 )-cycloalkyl.
3. The process for preparing a 2-(triazinylcarbonyl)sulfonanilide of formula (1-1) according to claim 1 , where
R 1a to R 1d are each independently selected from the group consisting of hydrogen, fluorine, chlorine, methoxy, and
R 2 is difluoromethyl and R 3 is hydrogen, and
R 4 and R 5 are each methoxy.
4. The process for preparing a 2-(triazinylcarbonyl)sulfonanilide of formula (1-1) as claimed in claim 1 , wherein the oxidizing agent is used in combination with a catalyst which has at least one heavy metal and/or a salt of a heavy metal as a constituent.
5. The process for preparing a 2-(triazinylcarbonyl)sulfonanilide of formula (1-1) as claimed in claim 4 , wherein said oxidizing agent used is hydrogen peroxide in conjunction with a catalyst which comprises at least one heavy metal and/or a salt of a heavy metal as a constituent.
6. The process for preparing a 2-(triazinylcarbonyl)sulfonanilide of formula (1-1) as claimed in claim 4 , wherein said oxidizing agent used is potassium permanganate without or with a catalyst which comprises at least one heavy metal and/or a salt of a heavy metal as a constituent.
7. The process for preparing a 2-(triazinylcarbonyl)sulfonanilide of formula (1-1) as claimed in claim 4 , wherein the catalyst used comprises at least one of:
iron salts, iron powder, copper salts or copper powder, or
a mixture thereof.
8. The process for preparing a 2-(triazinylcarbonyl)sulfonanilide of formula (1-1) as claimed in claim 4 , wherein the catalyst used comprises:
at least one iron salt together with at least one complexing compound, or
at least one copper salt together with at least one complexing compound, or
a mixture thereof.
9. The process for preparing a 2-(triazinylcarbonyl)sulfonanilide of formula (1-1) as claimed in claim 7 , wherein
said iron salt used comprises iron(II) sulfate and/or iron chloride, and
said copper salts used comprises copper(II) sulfate and/or copper(II) chloride.
10. The process for preparing a 2-(triazinylcarbonyl)sulfonanilide of formula (1-1) as claimed in claim 8 , wherein said complexing compound used is pyridine-2-carboxylic acid.
11. The process for preparing a 2-(triazinylcarbonyl)sulfonanilide of formula (1-1) as claimed in claim 9 , wherein the catalyst used is iron(II) sulfate together with pyridine-2-carboxylic acid.
12. The process for preparing a 2-(triazinylcarbonyl)sulfonanilide of formula (1-1) as claimed in claim 1 , wherein the solvent used is a mixture comprising at least one water-miscible organic solvent and water.
13. The process for preparing a 2-(triazinylcarbonyl)sulfonanilide of formula (1-1) as claimed in claim 12 , wherein said solvent used is acetonitrile and/or 2-propanol.
14. The process for preparing a 2-(triazinylcarbonyl)sulfonanilide of formula (1-1) as claimed in claim 1 , wherein the base used is at least one of:
potassium carbonate, sodium carbonate or cesium carbonate,
potassium hydrogencarbonate or sodium hydrogencarbonate,
lithium hydroxide, sodium hydroxide, potassium hydroxide or barium hydroxide,
potassium phosphate (K 3 PO 4 ), potassium hydrogenphosphate (K 2 HPO 4 ) or sodium phosphate,
and/or
a mixture thereof.
15. The process for preparing a 2-(triazinylcarbonyl)sulfonanilide of formula (1-1) as claimed in claim 14 , wherein said base used is potassium hydrogencarbonate or potassium carbonate or a mixture thereof.