IT8419480A1 - Process for the preparation of aryloxybenzoic acids with sulfonamide group - Google Patents

Description

DOCUMENTATION

BOUND

PH 583 I , Eng. Barzan? & Zanardo

DESCRIPTION

of the industrial invention entitled:

"Process for the preparation of aryloxybenzoic acids with sulfonamide group" >

of the company? RHONE-FOULENC AGRO CHIMI What about your nationality? French, based in LYON (France)

Inventor: Alain CHEME

deposited the N? 1

7 FEL488$ 84

SUMMARY

Preparation of N-sulfonyl-aryloxybenzamide by reaction of an aryloxybenzoic acid with

C

a sulfonyl isocyanate or isothiocyanate.

DESCRIPTION

The present invention relates to an improved process for the preparation of certain sulfonamide-containing aryloxybenzoic acid derivatives having herbicidal properties.

Herbicidal derivatives of aryloxybenzoic acids

with sulfonamide group (or N-solf onyl-phenoxybenzyl aromas) are known in European patent applications 3416, 23392 and in Japanese patent application No. 82.106654?

These patent applications describe well products of this type and in particular products

of formula

OO-MH-SO2-R3

"-v' )-??-* * y- A ( I )

and their scili,

in which:

A ? hydrogen, fluorine, chlorine, bromine, iodine, a nitro-group; -N=NCF ; N* ; a dialkylamino group; an alkyl group; trialkylammonium; an al? kylthio- group, alkylsulfinyl, alkylsulfonyl, dialkylsulfonium, cyanosulfonyl, alkanoyloxyl, alkoxyl, alkoxyl substituted with an alkoxycarbonyl, nitroso, -SCN , azide, CF^ , -N=N-P-(0CH^)2-,

0

acyl;

Z ? hydrogen, fluorine, chlorine, bromine, iodine, or an alkyl, alkoxyl, alkylsulfinyl, alkylsulfonyl group, CF^ , NO^ , CN ;

Z1 ? hydrogen or a halogen or an alkyl or dialkylamino group;

D ? fluorine, chlorine, bromine, iodine; or a CF group, alkylthio, alkylsulfinyl, alkylsulfo-3

nil, haloalkyl, sulfammoyl, formyl, alkylcarbonyl, alkyl or dimethylamino;

And? hydrogen or a haloalkyl group, J - X liy or Dai zj cuw ex ^cuiui alkoxy, alkylsulfinyl, alkylsulfonyl, CN, CF3 ;

W ? a trivalent nitrogen atom or a

* group -C(G)=;

G has one of the meanings given for z; R is a phenyl, pyridyl or thio group possibly substituted with one or more halogen atoms, or alkyl groups, or nitro groups; or an alkenyl or alkynyl radical having from 2 to 4 carbon atoms or an alkyl radical having from 1 to 4 carbon atoms possibly substituted with one or more fluorine, chlorine, bromine or iodine atoms, preferably CF * or with one or more of the following substituents: alkoxycarbonyl having 2 to 5 carbon atoms, alkylcarbonyl having 2 to 5 carbon atoms, dialkylcarbamoyl in which the alkyl groups have 1 to 4 carbon atoms, alkylthio, alkylsulfinyl, alkylsulfonyl, each having 1 to 4 carbon atoms, alkylcarbonyloxyl having 2 to 5 carbon atoms, or the cyano group.

According to known processes, the products of formula (i) can be prepared by reacting at a temperature between 25? and 140?C, an intermediate acid halide of formula:

yj ,?x

D- cu;

E^y?-<3-t

- 4 - Eng. Barzan? & Zanardo

1 in which X is chlorine, bromine or iodine and A, Z, Z , D, E, W have the meanings already indicated, with a sulfonamide of formula:

R3SO2NH2 (III)

3

where R has the meaning already indicated, but generally in the presence of an acid acceptor, in particular a tertiary amine such as N,N-dimethylaniline or pyridine, or an alkali metal carbonate such as anhydrous potassium carbonate, or an alkali metal fluoride such as caesium fluoride.

The compounds of formula (i) can subsequently be alkylated in a known manner, for example by reacting a diazoalkane having from 1 to 4 carbon atoms, so as to obtain the corresponding products substituted on the nitrogen atom of the sulfonamide group with an alkyl group having from 1 to 4 carbon atoms; the hydrogen atom of this same nitrogen atom can also be replaced with atoms of alkali metals such as sodium, for example by the action of basic alkaline agents (salts of the compounds of formula (l) are thus obtained).

This condensation process of products of formula (II) and (III) presents several drawbacks, in particular low yields. It is thought that in general it is the presence of the acid acceptor that decreases the yield because it favors the diacylation reaction. Furthermore, the use of an acid acceptor makes the isolation and purification of the final products more difficult and more expensive.

Another drawback of the known process is that it requires an additional reaction step to obtain the acid halide of formula (II) starting from the acid of formula (IV) defined below.

One purpose of the invention is to overcome the drawbacks of known processes. Other advantages will become apparent in the following discussion.

It has now been found that these objects could be achieved completely or partially thanks to a process according to the invention which consists in reacting an acid of the formula:

COOH

(IV)

AND

with a sulfonyl isocyanate (or isothiocyanate) of formula:

And SO -N=C=Y (V)

- 6 - Eng. Barzan? & Zanardo in which Y is the oxygen or sulfur atom, the symbols A, Z, Z1, D, E, G, and R3 having the meanings already indicated. This process is generally carried out in the liquid phase, preferably in the presence of a catalyst, and at a temperature such that the compound COY (i.e., carbon dioxide when Y = ? or carbonyl sulfide when Y = S), which is formed during the reaction, is eliminated as it is formed and in gaseous form from the reaction medium.

A subgroup of products of formula (i) for the preparation of which the process according to the invention is particularly suitable and advantageous, is constituted by the products in whose general formula A is the hydrogen atom or an N02 group or a chlorine atom; Z is a halogen atom and more in 1

in particular a chlorine atom; Z and E are 3' atoms

hydrogen; D is the CF^ group; R is an alkyl group most often having 1 to 4 carbon atoms, in particular CH^; W is -CH=.

The preferred reagents of formula (IV) and (V) are evidently chosen in such a way that the symbols found in their formulas have a meaning similar to that indicated for the products of formula (i).

- 7 - Eng. Barzan? & Zanardo Among the catalysts that can be used, the following can be mentioned, but are not limited to:

- tertiary animines such as triethylamine, pyridine, N,N-dimethylaniline, 1,4-diazabicyclo(2,2,2)octane, or

- tin derivatives, and in particular alkyltin salts such as dibutyltin diacetate, dibutyltin dilaurate*

The molar ratio of (IV) to (v) is generally between 0.8 and 1.2, preferably between 0.9 and 1.1; more often, these reagents are in stoichiometric proportions*

the molar ratio of the catalyst to the acid of formula (IV) generally varies between 0.001 and 0.1, preferably between 0.01 and 0.05*

The reagents are preferably dissolved in an inert, aprotic organic solvent having a boiling point higher than or equal to the reaction temperature, for example, a liquid hydrocarbon, aliphatic or aromatic, chlorinated or non-chlorinated, such as benzene, toluene, xylenes, mixtures of xylene, 1,2-dichloroethane, chlorobenzene, or an ether or a nitrile; a mixture of different solvents can also be used. The use of an inert solvent has the practical advantage of allowing better heat transfer in an industrial-scale process; it thus makes it possible to avoid local overheating of the reaction medium.

As previously stated, the temperature at which the process according to the invention is carried out is advantageously such that the compound of formula COY (carbon dioxide or carbonyl sulfide) formed during the reaction is eliminated from the reaction medium in gaseous form as it is generated. This "temperature" is, however, lower than the decomposition temperature of the products of formulas (IV), (V), and (I) involved in the process. It is advantageously lower than or equal to the boiling temperature of the solvent and is therefore generally between 60 and 180°C, preferably between 70 and 150°C.

At the end of the reaction, the product of formula (I) can be isolated using any method known in itself.

The process according to the invention is distinguished by the simplicity of the method of recovery of the final product since this is generally insoluble in the hot reaction medium and separates by crystallizing in pure form in such a way that this recovery is practically reduced to filtration. This filtration can also be facilitated by adding a non-solvent.

The following examples, given for non-limiting purposes, illustrate the invention and show how it can be realized. The Anglo-Saxon nomenclature has been used to indicate the products by placing the numbers indicating the position of the substituents in front of (and not after) the name of these substituents.

Example 1

5 g (0.0138 mol) of 5-[2'-chloro-4'-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid are suspended in 10 cm of toluene. The mixture is stirred, and then at room temperature, 1.9 g (0.0138 mol) of methanesulfonyl isothiocyanate and 0.04 g (0.0004 mol) of di-triethylamine are added. The reaction mixture is heated to boiling under reflux for 10 minutes with stirring.

Carbonyl sulfide evolves from the reaction mixture as it is formed. After adding 3

of 20 cm of toluene, the precipitate formed is filtered, washed with toluene and then with dichloromethane

Thus, 5 g (0.0114 moles; yield 83%) are obtained - 10 - Ing. Barzan? & Zanardo of a white solid consisting of 5-[21-chloro-4'--(trif fluorometil)phenoxy]-2?nitro-N-methanesulfonylbenzamide which melts at 218?C. The structure of this product is confirmed by infrared spectrum and nuclear magnetic resonance spectrum. . '

Example 2

In the procedure of example 1, replacing the 1.9 g of methanesulfonyl isothiocyanate with 1.7 g of . methanesulfonyl isocyanate (CH SO^^ C^ )f the previous N-methanesulfonylbenzamide is obtained with a yield of 88/o?

1. Preparation process of formula products:

z z C0-NH-S02-R" s

D? ( ^ >-0-( (1)

in which:

A ? -hydrogen, fluorine, chlorine, bromine, iodine, a nitro-group; -N=NCF ; N* ; a dialkylamino group; an alkyl group; trialkyl ammonium; alkylthio, alkylsulfinyl, alkylsulfonyl, dialkylsulfonium, cyanosulfonyl, alkanoyloxyl, alkoxyl, alkoxyl substituted with an afkoxycarbonyl, nitroso,

y

- 11 - Ing. Bar.zan? & Zanardo -SCN p azide , CF3 , -B.=N-P-(OCH3)2 , acyl;

0

Z ? hydrogen, fluorine, chlorine, bromine, iodine, or an alkyl, alkoxy, alkylsulfinyl, alkylsulfonyl group, CF^ , ?O? , CN ;

1

Z ? hydrogen or a halogen or an alkyl or dialkylamino group

D ? fluorine, chlorine, bromine, iodine; or a CF^, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkyl, sulfammoyl, formyl, alkylcarbonyl, alkyl or dimethylamino group;

And is it hydrogen or a haloalkyl, alkoxy, alkylsulfinyl, alkylsulfonyl, CN, CF group;

W ? a trivalent nitrogen atom or a -C(G) group=;

G has one of the meanings given for Z;

R ? a phenyl, pyridyl or thio group possibly substituted with one or more halogen atoms, or with alkyl groups or with nitro-groups; or an alkenyl or alkynyl radical having from 2 to 4 carbon atoms or an alkyl radical having from 1 to 4 carbon atoms possibly substituted with one or more fluorine, chlorine, bromine or iodine atoms, preferably CF^ , or with one or more of the following substituents: alkoxy| ? J_ ny ? ID CL? L* ajiu ix licuiai uu carbonyl having from 2 to 5 carbon atoms, alkylcarbonyl having from 2 to 5 carbon atoms, dialkylcarbamoyl in which the alkyl groups have from 1 to

4 carbon atoms, alkylthium, alkylsulfinyl,

alkylsulfonyls, each having 1 to 4 atoms of

carbon, alkylcarbonyloxyl having 2 to 5 atoms

of carbon or the cyano group,

characterized by the fact that an acid is reacted with it

of formula:

GOOH

A (IV)

W

with a sulfonyl isocyanate of formula:

R3SO2-H=C=Y. (V)

in which Y is the oxygen or sulfur atom

and the symbols? A, Z, Z1' , D, E, W, R3 have the same meanings as indicated in formula (i).

2. Process according to claim 1, characterised in that the process is carried out in the liquid phase at a temperature such that the COY compound

which is formed during the reaction is eliminated

as it is formed and in gaseous form from the medium

of reaction.

3? Process according to one of claims 1 and 2, characterised in that the following is carried out:

13 Eng. Barzan? & Zanardo in the presence of a catalyst?

* 4? Process according to claim 3? characterized in that the catalyst is a tertiary amine or an alkyltin salt,

5. Process according to one of claims 3 and 4, characterised in that the molar ratio of the catalyst with respect to the acid of formula (IV) is between 0.001 and 0.1, preferably between 0.01 and 0.05?

6th Process according to one of claims 1 to 5, characterised in that the molar ratio between the acid of formula (IV) and the sulfonylsocialiate of formula (V) is between 0.8 and 1.2, preferably between 0.9 and 1.1.

7? Process according to one of claims 1 to 6, characterized in that the reaction is carried out in an inert aprotic organic solvent having a boiling point higher than or equal to the reaction temperature.

8. Process according to claim 7, characterized in that the solvent is a liquid hydrocarbon, aliphatic or aromatic, or an ether or a nitrile.

9. Process according to one of claims 1 to 8, characterised in that in the

Claims (1)

14 Ing? Barzan? & Zanardo formulas (i) and (v), A is the hydrogen or chlorine atom or an NQ^ group, Z is a halo-1 atom gene, Z , E and G are hydrogen atoms, D ? CF_ , R3 ? an alkyl group, W ? -CH=. THE MANDATORY! (signature) and for others) ?// & ?nr ? ' ss ? ''&<* 'il* ?;.???? ^ 7883/COR/vr/