NO855244L - PROCEDURE FOR THE PREPARATION OF PHOSPHORUS ORGANIC COMPOUNDS. - Google Patents

Abstract

1. A process for preparing compounds of formula : see diagramm : EP0189725,P9,F1 wherein products of formula see diagramm : EP0189725,P9,F2 are reacted with products of formula : see diagramm : EP0189725,P9,F3 in which formulae - R**1 denotes an alkyl, aryl or cycloalkyl radical, these various radicals optionally being able to be substituted with halogen atoms or phenyl, cyano, alkyl, alkoxyl or alkyl carboxylate groups, in which groups the alkyl groups have from 1 to 4 carbon atoms, R**1 having at most 18 carbon atoms, - R denotes a hydrogen atom or has one of the meanings given for R**1, - R**2 and R**3 are an alkyl, aryl or arylalkyl radical, which are optionally substituted with substituents such as those given for R**1 (sic), or alternatively R**2 and R**3 can constitute together a single divalent radical having 2 to 6 carbon atoms, R**2 and R**3 having at most 12 carbon atoms, - R**8 denotes a radical of formula Ar(R**5)(R**6)C- in which Ar is a phenyl group, and R**5 and R**6 are a hydrogen atom or a radical Ar or an alkyl group having at most 6 carbon atoms, - X denotes a halogen atom such as chlorine, bromine or iodine.

Description

The present invention relates to a method for the production of N-sulfonyl-\_ N-(phosphonomethyl) glycyl amine derivatives, which can either be used as herbicides or as starting material for the production of various phosphorus-containing compounds, in particular herbicides.

The present invention relates more particularly to a method for producing compounds with the general formula:

in that compounds of general formula: are reacted with compounds of general formula:

in which,

- R is a hydrocarbon radical, in particular an alkyl, aryl or cycloalkyl radical, as these radicals can optionally be substituted, the substituents particularly being halogen atoms and phenyl, cyano, alkyl, alkoxyl and alkylcarboxylated groups, in which the alkyl groups preferably have from 1 to 4 carbon atoms, and wherein R"<*>" usually has from 1 to 18 carbon atoms, preferably from 1 to 7 carbon atoms, and more particularly from 3 to 7 carbon atoms when it is a cycloalkyl group, R<1> is preferably an alkyl radical with from 1-4 carbon atoms, optionally halogenated, in particular with chlorine or fluorine, for example CF-.,1;- R is a hydrogen atom or has the same meaning as R , and is preferred in an alkyl group with 1 to 4 carbon atoms, 2 3 2 3 ;- R and R are such that OR and OR are hydrolyzing; 2 3 ; groups, R and R can in particular be an alkyl, aryl or arylalkyl radical, which is optionally substituted, and in particular with substituents such as those given for R"<*>". or they can together form a single divalent radical, which is optionally substituted and which preferably has 2 to 6 carbon atoms such as an alkylene radical, for example ethylene or propylene; generally they have from 1-12 carbon atoms, and preferably from 1-8 carbon atoms,

8 5 6

- R is a radical with the formula Ar(R )(R )C- where Ar is an aromatic group, preferably a phenyl group, optionally substituted, and R^ and R^ are a hydrogen atom or an aromatic radical Ar or an alkyl group preferably with at most 6 carbon atoms, in which Ar may be substituted with

alkyl, alkoxy, nitro groups or chlorine atoms etc.,

- X is a halogen atom such as chlorine, bromine or iodine, preferably chlorine.

By hydrogenation and/or hydrolysis and/or salt formation, the compounds of general formula (I) can lead to compounds of formula:

which have herbicidal properties.

The reaction according to the invention can be carried out in the absence or usually in the presence of a solvent. An organic solvent can be used as a solvent which is inert when heat is applied; the turnover is advantageously carried out in the presence of an acid acceptor.

The temperature is generally between 30 and 150°C, preferably between 40 and 120°C.

The compounds of formula (II) and (III) are generally used in stoichiometric conditions, or do not deviate from the stoichiometry by more than 40% with regard to the number of moles.

As solvents that can be used, one can mention nitriles (in particular acetonitrile), ketones (in particular acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone), hydrocarbons, halogenated or substituted in another way (in particular benzene, toluene, xylene, chlorobenzene) , esters such as alkyl alkanoates (in particular ethyl acetate) and aprotic polar solvents such as dimethylformamide and N-methylpyrrolidone.

As acid acceptors, organic or inorganic basic agents are preferred, in particular alkali metal or alkaline earth metal hydroxides or carbonates, preferably sodium carbonate or potassium carbonate, as well as tertiary amines such as tris(alkyl)amines, in particular triethylamine, tripropylamine, tributylamine and N,N -dialkylanilines.

The obtained compound can be isolated by means of any known method per se.

Some compounds of general formula (II) are known (Tetrahedron Letters No. 46, p. 4645, 1973). They are usually prepared by reacting tris(aralkyl)hexahydrotriazines with diorganophosphites.

The compounds of general formula (III) are also known.

The following examples illustrate the invention and also show how it can be used.

Example 1.

A solution of diethyl N-benzylaminomethylphosphonate (2 g,

7.78 mmol) with general formula:

in acetonitrile (10 cc) heated at reflux to the boiling point (80°C). A solution of N-methyl-N-(methylsulfonyl)chloroacetamide (1.44 g, 7.76 mmol) in acetonitrile (10 cc) of general formula:

is added gradually over the course of 15 min. at 80 C.

The mixture is heated for two hours and I^CO^ (0.54 g,

3.9 mmol) is then added, and the mixture is heated for a further eight hours at the same temperature. The mixture is cooled and filtered.

By means of chromatography, it has been found that a compound (1.9 g) with general formula:

is obtained, equivalent to 60% yield (the degree of conversion of the compound with general formal (V): 85

Example 2.

A solution of diethyl N-benzylamine ethyl phosphonate (1 g,

3.89 mmol) in methyl isobutyl ketone (MIBK) (10 cc) is heated to 80°C. A solution of N-methyl-N-(methylsulfonyl)chloroacetamide (0.721 g, 3.89 mmol) in MIBK (10 cc) is gradually added to the above solution, and the mixture is heated for two hours at 115°C, then dry K 2 CO 3 is added (0.268 g,

1.94 mmol) and the heating continues for two hours at the same temperature. The mixture is cooled and filtered. By chromatograph i, a compound of formula (VII) has been obtained

(0.934 g, 2.3 mmol) equivalent in 59% yield. (Degree of conversion of the compound of formula (V): 91%).

Example 3.

A solution of diethyl N-benzylaminomethylphosphonate (1 g,

3.89 mmol) in chlorobenzene (10 cc) is heated to 80°C. A solution of N-methyl-N-(methylsulfonyl)chloroacetamide (0.721 g, 3.89 mmol) in chlorobenzene (10 cc) is gradually added to the above solution, and the mixture is heated for two hours at 110°C and dry K 2 CO 3 (0.268 g, 1.94 mmol) is added,

and heating continues for two hours at the same temperature.

The mixture is cooled and filtered.

By means of chromatography it has been found that a compound of formula (VII) (0.772 g) is obtained, equivalent to 48.9% yield.

(The degree of conversion of the compound of general formula (V): 84.2%).

Example 4.

A solution of diethyl N-benzylaminomethylphosphonate (1 g,

3.89 mmol) in acetonitrile (10 cc) is heated to 60°C. A solution of N-methyl-N-(methylsulfonyl)-chloroacetamide (0.721 g) in acetonitrile (10 cc) is gradually added to the above solution and the mixture is heated for two hours at 80°C,

KHCO 3 (0.195 g, 1.945 mmol) is added and heating is continued for five hours at the same temperature. The mixture is cooled and filtered. By means of chromatography it has been found that a compound of general formula (VII) (0.804 g) is obtained, equivalent to 50.9% yield.

Example 5.

Mix diethyl N-benzylaminomethylphosphonate (1 g, 3.89 mmol), N-methyl-N-(methylsulfonyl)chloroacetamide (0.938 g, 5.05 mmol) and ethyl acetate (10 cc). The mixture is heated at reflux (78°C) for three hours and K 2 CO 3 (0.32 g, 2.32 mmol) to

is set, the heating is continued for six hours and thirty minutes at this temperature. The mixture is cooled and filtered. By means of chromatography it has been found that a compound of general formula (VII) (1.139 g, 2.8 mmol) is obtained, equivalent to 72% yield.

Example 6.

A mixture of diisopropyl N-benzylaminomethylphosphonate

(0.738 g, 2.59 mmol) and N-methyl-N-(methylsulfonyl)chloroacetamide (0.938 g, 5.05 mmol) are heated for five hours and thirty minutes

at 85°C, K2CO3 (0.16 g) is then added and mix-

the thing is heated again for three hours. The mixture is cooled and filtered.

By means of chromatography it has been found that a compound of general formula (VIII) (0.757 g, 1.745 mmol) is obtained, equivalent to 67.4% yield. The general formula (VIII) is as follows:

Example 7.

A mixture of diisopropyl N-benzylaminomethylphosphonate

(5.13 g, 18 mmol), N-methyl-N-(methylsulfonyl)chloroacetamide (3.33 g, 18 mmol) and ethyl acetate (45 cc) are heated for two hours at 50°C, K 2 CO 3 (1.49 g , 10.8 mmol) is then added. The heating continues for eight hours at the same temperature. The mixture is then cooled and filtered.

By means of chromatography it has been found that a compound of general formula (VIII) (2.03 g, 4.68 mmol) is obtained, equivalent to 26% yield.

Example 8.

A mixture of diphenyl N-benzylaminomethylphosphonate (1.269 g, 3.59 mmol), N-methyl-N-(methylsulfonyl)chloroacetamide (0.938 g, 5.05 mmol) and toluene (10 cc) is heated for three hours, 45 minutes at 80°C, K 2 CO 3 (0.26 g, 1.88 mmol) is then added. Heating is continued for four hours, with a further amount of I 2 CO 2 (0.09 g, 0.65 mmol) being added. The mixture is cooled and filtered.

By means of chromatography, it has been found that a compound of general formula (IX) (0.946 g, 1.88 mmol) is obtained, equivalent to 52.4% yield (degree of conversion of phosphonate: 80%).

The general formula (IX) is as follows:

Example 9.

A mixture of diphenyl N-benzylaminomethylphosphonate (2.646 g, 7.495 mmol), N-methyl-N-(methylsulfonyl)chloroacetamide (1.57 g, 8.46 mmol) and N-methyl-2-pyrrolidone (NMP) (6 cc ) is heated for six hours at 80°C, after which triethylamine (0.378 g, 3.74 mmol) is added. The mixture is heated again at 80°C for five hours, a further amount of triethylamine (0.378 g) being added. The mixture is cooled, acetonitrile (10 cc) is added and the mixture is then filtered.

By means of chromatography, it has been found that a compound of general formula (IX) (2.25 g, 4.48 mmol) is obtained, equivalent to 60% yield (the degree of conversion of phosphonate: 62%).

Example 10.

Diphenyl-N-benzylaminomethylphosphonate (0.932 g, 2.64 mmol), N-methyl-N-(methylsulfonyl)chloroacetamide (VI) (0.49 g, 2.64 mmol) and diisopropylamine (0.272 g) are dissolved in dimethylformamide ( DMF)

(2 cc) . After seven hours of heating at 80°C, ethyl acetate (10 cc) is added and the formed diisopropylamine hydrochloride is obtained by filtration.

By means of chromatography, it has been found that a compound of general formula (IX) (0.670 g, 1.335 mmol) is obtained, equivalent to 50.5% yield (degree of conversion of phosphonate: 69%).

Example 11.

A mixture of dibenzyl N-benzylaminomethylphosphonate (3 g,

7.87 mmol), N-methyl-N-(methylsulfonyl)chloroacetamide (1.45 g, 7.82 mmol) and acetonitrile (15 cc) are heated for six hours and 45 minutes at 80°C, while triethylamine ( 0.792 g, 7.84 mmol), dissolved in acetonitrile (5 cc), is added gradually.

By means of chromatography it has been found that a compound of general formula (X) (0.95 g) is obtained, equivalent to 22.9% yield. The general formula (X) is as follows:

Example 12.

Dimethyl N-benzylaminomethylphosphonate (5.5 g, 24 mmol), N-methyl-N-(methylsulfonyl)chloroacetamide (4.45 g, 24 mmol) and chlorobenzene (50 cc) are mixed. The mixture is heated at 125°C for two hours and thirty minutes, then I^CO^ (3 g, 21.7 mmol) is added

and the mixture is heated again for two hours and thirty minutes,

is cooled and filtered, and a compound of formula (XI) is obtained in 30% yield.

Example 13.

A solution of diethyl N-benzylaminomethylphosphonate (2 g,

7.78 mmol) in acetonitrile (10 cc) is heated to 80°C, a solution of N-methyl-N-(methylsulfonyl)chloroacetamide (1.88 g, 10.13 mmol) in acetonitrile (10 cc) is added. The mixture is heated for one hour and then K^ CO^ (0.64 g,

4.63 mmol) and the heating is continued for eight hours and thirty minutes at the same temperature. The mixture is cooled and filtered.

By means of chromatography, it has been found that a compound of general formula (VII) (2.56 g, 6.31 mmol) is obtained, equivalent to 81% yield (degree of conversion of the compound of formula (V): 81%).

Claims (9)

1. Procedure for the preparation of compounds of general formula: characterized in that compounds with general formula: reacted with compounds of general formula: in which: - R"*" is a hydrocarbon radical, in particular an alkyl, aryl or cycloalkyl radical, as these various radicals can optionally be substituted, for example with halogen atoms or phenyl, cyano, alkyl, carboxyl or alkylcarboxylate groups ( - R is a hydrogen atom or has one of the meanings given for R" <*> ", and is preferably an alkyl group with 1 to 4 carbon atoms, 2 3 2 3 - R and R are such that OR and OR are hydrolyzable groups, R<2> and R 3 are preferably an alkyl, aryl or arylalkyl radical, which is optionally substituted, in particular with substituents such as those given for R"' ", 2 3 or R and R optionally together constitute a single divalent radical which is optionally substituted, - R <8> is a radical of formula Ar(R <5> )(R <6> )C- in which Ar is an aromatic group, preferably a phenyl group, optionally substituted, and R~ <*> and R^ are a hydrogen atom or a radical Ar or an alkyl group with preferably at least 6 carbon atoms, - X is a halogen atom such as chlorine, bromine or iodine, preferably chlorine. 2. Method as stated in claim 1, characterized in that R and R"<*>" are alkyl groups with 1 to 4 carbon atoms. 3. Procedure as specified in claims 1 and 2, 2 3 characterized in that R and R are alkyl, phenyl or benzyl groups. 4. Method as stated in claims 1-3, characterized in that the reaction is carried out at a temperature between 30 and 150°C, preferably between 40 and 120°C. 5. Method as stated in claims 1-4, characterized in that the reaction is carried out with a ratio between the compounds of general formula (II) and the compound of general formula (III) which does not deviate from the stoichiometry by more than 40%. 6. Method as stated in claims 1-5, characterized in that the conversion is carried out in the presence of an acid acceptor. 7. Method as stated in claims 1-6, characterized in that the acid acceptor is a tertiary amine or an alkali metal hydroxide or carbonate or alkaline earth metal hydroxide or carbonate. 8. Method as stated in claims 1-7, characterized in that the reaction is carried out in the presence of a solvent. 9. Method as stated in claim 8, characterized in that the solvent is a nitrile, a ketone, an ester, a hydrocarbon which is optionally halogenated, or an aprotic polar solvent.