DD251135A5 - METHOD OF PREPARING N-SULFONYL-N- (PHOSPHONO-METHYL-GLYCYL-) AMINE DERIVATIVES - Google Patents

Abstract

The present invention relates to a process for the preparation of N-sulfonyl-N- (phosphono-methyl-glycyl) -amine derivatives of the general formula I. The process according to the invention is characterized in that compounds of the formula II are reacted with compounds of the formula III implements. The process according to the invention is used in the chemical industry. The compounds prepared according to the invention are used as herbicides in agriculture, or they are used as intermediates for the preparation of herbicides. Formula (I)

Description

-2- 251 135 Field of application of the invention

The present invention relates to a process for the preparation of N-sulfonyl-ISM-phosphonomethyl-glycyo-amine derivatives which are useful either as herbicides or as intermediates for the production of various phosphorus products, especially herbicides.

Characteristic of the known technical solutions

N-sulfonyl-N- (phosphonomethyl-glycyl) -amine derivatives are already known from unpublished EP-PS 135454, corresponding to DD-PS 218544 known.

Object of the invention

The aim of the invention is to provide a simpler and more economical process for the preparation of N-sulfonyl-N- (phosphonomethyl-glycyl) -amine derivatives.

Explanation of the essence of the invention

The invention has for its object to find readily available starting materials and suitable process steps for the preparation of these compounds

 According to the invention, compounds of the formula (I)

OR ² R ⁸

' 1

O = P-CH-N-CH, -CO-N-SO-R (D.

I _x I

OR ⁵ R

prepared by reaction of products of the formula (II)

OR ²

I ₈

O = P-CH ₂ -NH-R <»>

OR ³ with products of the formula (III)

X - CH ₂ - CO - N - SO ₂ - R

₂ - CO - N - SO ₂ - R _{(|| 1)}

R '.

in which mean:

R ^{1 represents} a hydrocarbon radical, especially alkyl, aryl or cycloalkyl, which radicals may optionally be substituted; as substituents, there may be specifically mentioned halogen atoms and phenyl, cyano, alkyl, alkoxy, alkyl carboxylate groups in which the alkyl groups preferably have 1 to 4 carbon atoms; R ¹ most often has 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and more preferably 3 to 7 carbon atoms, when it is a cycloalkyl group; it is preferably an alkyl radical having 1 to 4 carbon atoms which is optionally halogenated, in particular chlorinated or fluorinated, for example CF ₃ ;

R represents the hydrogen atom or has one of the meanings given for R ¹ and is preferably an alkyl group having 1 to 4 carbon atoms;

R ² and R ³ are such that OR ² and OR ^{3 are} hydrolyzable groups; R ² and R ³ may especially be an alkyl, aryl, arylalkyl radical optionally substituted, especially by substituents such as those given for R ¹ , or may together form a single divalent radical preferably having from 2 to 6 carbon atoms, such as for example, optionally substituted alkylene radicals (eg an ethylene or propylene radical); they generally have 1 to 12 carbon atoms, and preferably 1 to 8 carbon atoms;

R ⁸ is a radical of the formula Ar (R ⁵ MR ⁶ JC-, wherein Ar is an aromatic group, preferably a phenyl group which is optionally substituted and R ⁵ and R ⁶ are hydrogen atoms or an (aromatic) radical Ar or an alkyl group preferably at most 6 carbon atoms;

X represents a halogen atom such as chlorine, bromine, iodine, preferably chlorine. By hydrogenation and / or hydrolysis and / or

Salt formation, the products of formula (I) to products of formula (IV) OH

O = P-CH ₂ -NH-CH ₂ -CO-N-SO ₂ -R ¹ (IV)

I i

OH R

lead that have herbicidal properties.

The reaction according to the invention can take place in the absence or generally in the presence of a solvent. The solvent used is an organic, heat-inert solvent; it works advantageous in the presence of an acid acceptor.

The reaction temperature is generally between 30 and 150 ⁰ C, preferably between 40 and 120 ° C.

The reactants of the formula (II) and (III) are generally used in a stoichiometric ratio or

do not remove more than 40% in moles with respect to stoichiometry.

Suitable solvents which may be mentioned are the nitriles (in particular acetonitrile), the ketones (in particular acetone,

Cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone), the halogenated or nonhalogenated hydrocarbons,

especially benzene, toluene, the xylenes, chlorobenzene), esters such as alkyl alkanoates (especially ethyl acetate) and the aprotic polar solvents such as dimethylformamide and N-methylpyrrolidone.

Preferred acid acceptors are organic or mineral basic agents, in particular the alkali or

Alkaline earth hydroxides or carbonates, preferably sodium or potassium carbonate, and the tertiary amines such as the tris (alkyl) amines, in particular triethylamine, tripropylamine, tributylamine and the N, N-dialkylanilines.

The reaction product can be isolated by any means known per se.

Certain products of the formula (II) are known (Tetrahedron Letters No. 46, page 4645.1973). They are conveniently prepared by reaction of tris (aralkyl) hexahydrotriazines with diorganophosphites.

The reactants of formula (III) are also known.

embodiment

The following non-limiting examples illustrate the practice of the invention.

example 1

A solution of 2 g (7.78 mmol) of diethyl N-benzylaminomethane phosphonate of the formula (V)

⁰ * ^C 2 ^H 5

0 = P - CH ₂ - NH - CH ₂ - C ₆ H _{5 (v)}

in 10 ml of acetonitrile are heated to boiling under reflux (80 ⁰ C). A solution of 1.44 g (7,76mMol) N-methyl-N-methyl-sulfonyl-chloroacetamide of the formula are progressively within a quarter of an hour at 80 ⁰ C (Vl)

CI-CH ₂ -CO-N (CHa) -SO ₂ -CH ₃ (VI)

in 10ml acetonitrile too.

The mixture is heated for two hours and then 0.54 g (3.9 mmol) of K ₂ CO ₃ ZU and heated for 8 hours at the same temperature. It is cooled and filtered.

Chromatography shows that 1.9 g of the product of the formula (VII)

0-C ₉ H ₁ -I 0 = P-CH ₇ -N-CH ₇ -CO-N-S0 _? - CH, _(VM)

I I ""

0-C ₂ H ₅ CH ₂ -C ₆ H ₅ CH ₃

which corresponds to a yield of 60% [degree of conversion of the product of formula (V): 85%].

Example 2

A solution of 1 g (3.89 mmol) of diethyl N-benzylaminomethane phosphonate in 10 mL of methyl isobutyl ketone (MIBK) is heated to 80 ° C. A solution of 0.721 g (3.89 mmol) of N-methyl-N-methyl-sulfonyl-chloroacetamide in 10 ml of MIBK is added to the above solution progressively, then heated to 115 for two hours at ⁰ C; 0.268 g (1.94 mmol) of dry K ₂ CO ₃ are added;

heating is continued for two hours at the same temperature. It is cooled and filtered. Chromatography shows that 0.934 g (2.3 mmol) of product of formula (VII) has been obtained, which corresponds to a yield of 59%. [Degree of conversion of the product of formula (V): 91%].

Example 3

A solution of 1g (3,89mMol) of diethyl N-benzylaminomethanphosphonatin 10ml of chlorobenzene is heated to 80 ⁰ C. A solution of 0.721 g (3.89 mmol) of N-methyl-N-methylsulfonyl-chloroacetamide in 10 ml of chlorobenzene is added progressively to the above solution. The mixture is then heated for 2 hours to 11O ⁰ C and 0.268 g (1.94 mmol) of dry K ₂ CO ₃ to; heating is continued for two hours at this temperature. It is cooled and filtered.

By chromatography, it is found that 0.772 g of product of formula (VII) has been obtained, which corresponds to a yield of 48.9%. [Degree of conversion of the product of formula (V): 84.2%].

Example 4

A solution of 1 g (3,89mMol) of diethyl N-benzylaminomethanphosphat in 10 ml of acetonitrile is heated to 60 ⁰ C. A solution of 0.721 g of N-methyl-N-methylsulfonyl-chloroacetamide in 10 ml of acetonitrile is added progressively to the above solution, then heated to 80 ⁰ C for two hours; 0.195 mmol (1,945 mmol) of KHCO _{3 are added} ; Heating is continued for five hours at the same temperature. The reaction mixture is cooled and filtered. By chromatography, it is found that 0.804 g of product of formula (VII) has been obtained, which corresponds to a yield of 50.9%.

Example 5

1 g (3.89 mmol) of diethyl N-benzylaminomethane phosphonate and 0.938 g (5.05 mmol) of N-methyl-N-methylsulfonylchloroacetamide and 10 ml of ethyl acetate are mixed. The mixture is heated for three hours at reflux (78 ⁰ C), were then added 0.32 g (2,32mMol) K ₂ CO ₃ to; Heating is continued for 6 and 2 hours at this temperature. It is cooled and filtered. Chromatography shows that 1.149 g (2.8 mmol) of product of formula (VII) has been obtained, which corresponds to a yield of 72%.

Example 6

Heating a mixture of 0,738g (2.59 mmol) diisopropyl-N-benzylaminomethan-phosphonate and 0,938g (5.05 mmol) of N-methyl-N-methylsulfonyl-chloroacetamide during 5V2 hours at 85 ⁰ C; Then add 0.16 g of K ₂ CO ₃ and heat again for three hours. It is cooled and filtered.

By chromatography, it is found that 0.757 g (1.745 mmol) of product of formula (VII) has been obtained, which corresponds to a yield of 67.4%. The formula (VIII) is as follows:

(CH,) ₇ CH-0 CH

0 - P - CH ₂ - N - CH ₂ - CO - N - SO ₂ - CH ₃

(CH ₃ ) ₂ CH-O

Example 7

A mixture of 5.13 g (18 mmol) of diisopropyl N-benzylaminomethane phosphonate and 3.33 g (18 mmol) of N-methyl-N-methylsulfonyl-chloroacetamide and 45 ml of ethyl acetate are heated at 50 ^° C. for two hours; then 1.49 g (10.8 mmol) of K ₂ CO _{3 are added} . Heating is continued for a few hours at this temperature. It is cooled and filtered.

Chromatography shows that 2.03 g (4.68 mmol) of product of formula (VIII) were obtained, which corresponds to a yield of 26%.

Example 8

Heating a mixture of 1,269g (3,59mMol) of diphenyl-N-benzylaminomethan-phosphonate 0,938g (5,05mMol) N-methyl-N-methylsulfonyl-chloroacetamide and 10 ml of toluene three hours and forty-five minutes 8U ⁰ C. Man then 0.26 g (1.88 mmol) of K ₂ CO _{3 is added} . The heating is continued for four hours while adding 0.09 g (0.65 mmol) of K ₂ CO ₃ . It is cooled and filtered.

By chromatography, it is found that 0.946 g (1.88 mmol) of the product of formula (IX) has been obtained, which corresponds to a yield of 52.4% (degree of conversion of the phosphonate: 80%).

The formula (IX) is the following:

0-C.Hr

ι ^{6 5}

O = P-CH ₉ -N-CH-CO-N-SO ₀ -CH,

² I 2 2 3 (IX)

0-C ₆ H ₅ CH ₂ -C ₆ H ₅ CH ₃

Example 9

A mixture of 2.466 g (7.495 mmol) of diphenyl N-benzylaminomethane phosphonate and 1.57 g (8.46 mmol) of N-methyl-N-methylsulfonyl-chloroacetamide and 6 mL of N-methyl-2-pyrrolidone (NMP) is heated for six hours to 8O ⁰ C, then added 0.378 g (3.74 mmol) of triethylamine. The mixture is heated for 5 hours at 8O ⁰ C, while still adding 0.378 g of triethylamine. Add 10 ml of acetonitrile and filter.

Chromatography shows that 2.25 g (4.48 mmol) of product of formula (IX) were obtained, which corresponds to a yield of 60% (degree of conversion of the phosphonate: 62%).

Example 10

Add N, 932 g (2.64 mmol) of diphenyl N-benzylaminomethane phosphonate, 0.49 g (2.64 mmol) of N-methyl-N-methylsulfonylchloroacetamide (II) and 0.272 g of diisopropylamine in 2 mL of dimethylformamide (DMF). After seven hours heating to 80 ⁰ C is added again 10ml of ethyl acetate and the diisopropylamine hydrochloride formed is recovered by filtration. By chromatography, it is found that 0.670 g (1.335 mmol) of product of formula (IX) has been obtained, which corresponds to a yield of 50.5% (degree of conversion of the phosphonate: 69%).

Example 11

A mixture of 3 g (7.87 mmol) of dibenzyl-N-benzylaminomethane phosphonate and 1.45 g (7.82 mmol) of N-methyl-N-methylsulfonyl-chloroacetamide and 15 mL of acetonitrile are heated for six hours and forty-five minutes 8O ⁰ C. At the same time, progressively adding 0.792 g (7.84 mmol) of triethylamine in solution in 5 ml of acetonitrile.

Chromatography reveals that 0.95 g of product of formula (X) was obtained, which corresponds to a yield of 22.9%.

The formula (X) is the following:

C.Hr-CH-, -OCH,

⁶⁵² I! ³

0 = P - CH ₉ - N - CH ₉ - CO - N - SO ₉ - CH ₇

Il 2 3 (X)

01, .Hc-CH ₇ -OCH ₀ -C ^ H ₁ .

Dbz Z 6 5

Example 12

A batch of 5.5 g (24 mmol) of dimethyl N-benzylaminomethane phosphonate, 4.45 g (24 mmol) of N-methyl-N-methylsulfonyl-chloroacetamide and 50 ml of chlorobenzene are prepared. The mixture was heated two hours 30 min at 125 ⁰ C, 3 g (21.7 mmol) K2CO3ZU, then heated again two hours and thirty minutes, cooled and filtered; the product of the formula (XI) is obtained in a yield of 30%

0-CH ₃ O = P-CH ₉ -N-CH ₉ -CO-N-SO ₉ -CH ₇

,Δ L LD (XI)

0-CH, CH ₉ -Ch. CH,

5 L 0 5 3

Example 13

A solution of 2g (7,78mMol) of diethyl N-benzylaminomethan-phosphonate in 10 ml of acetonitrile is heated at 8O ⁰ C; A solution of 1.88 g (10.13 mmol) of N-methyl-N-methylsulfonyl-chloroacetamide in 10 ml of acetonitrile is added. The mixture is heated for one hour and then 0.64 g (4.63 mmol) of K 2 CO 3 ZU is added and the heating is continued for eight hours and thirty minutes at the same temperature. It is cooled and filtered.

Chromatography shows that 2.56 g (6.31 mmol) of product of formula (VII) were obtained, which corresponds to a yield of 81%. [Conversion process of the product of formula (V): 81%].

Claims (9)

1. Process for the preparation of compounds of the formula (I) OR ² R ⁸ Il _± O = P-CH ₀ -N-CH ₀ -CO-N-SO ₀ -R (D. OR. R characterized in that products of the formula (II) OR ² o p- ch ₂ - nh- r ⁸ (ii) Lr ³ with products of the formula (III) X - CH ₂ - CO - N - SO ₂ - R ¹ _(|||) to react, in which mean R ^{1 represents} a hydrocarbon radical, especially alkyl, aryl or cycloalkyl, these various radicals being optionally substituted, for example by halogen atoms or phenyl, cyano, alkyl, alkoxyl, alkylcarboxylate groups; R represents the hydrogen atom or has one of the meanings given for R ¹ and is preferably an alkyl group having 1 to 4 carbon atoms; R ² and R ³ are such that OR ² and OR ^{3 are} hydrolyzable groups, wherein R ² and R ^{3 are} preferably an alkyl, aryl, aralkyl radical which is optionally substituted, especially by substituents such as those given for R ¹ or R ² and R ³ may together represent an optionally substituted single bivalent radical; R ⁸ is a radical of the formula Ar (R ⁵ ) (R ⁶ ) C-, wherein Ar is an aromatic group, preferably phenyl, optionally substituted, wherein R ⁵ and R ^{6 are} hydrogen or a radical Ar or an alkyl group, preferably at most Represent 6 carbon atoms; X represents a halogen atom, such as chlorine, bromine, iodine, preferably chlorine. 2. The method according to item 1, characterized in that R and R ^{1 represent} alkyl groups having 1 to carbon atoms. 3. The method according to any one of the items 1 or 2, characterized in that R ² and R ^{3 are} alkyl, phenyl or benzyl groups. 4. The method according to any one of items 1 to 3, characterized in that one operates between 30 and 150 ° C, preferably between 40 and 120 ⁰ C. 5. The method according to any one of the items 1 to 4, characterized in that one works with a ratio of the reactants of the formula (II) with respect to the reactant of the formula (III), which deviates not more than 40% from the stoichiometry. 6. The method according to any one of items 1 to 5, characterized in that one operates in the presence of an acid acceptor. 7. The method according to any one of items 1 to 6, characterized in that the acid acceptor is a tertiary amine or an alkali or alkaline earth metal hydroxide or carbonate. 8. The method according to any one of items 1 to 7, characterized in that one operates in the presence of a solvent. 9. The method according to item 8, characterized in that the solvent is a nitrile or a ketone or an ester or an optionally halogenated hydrocarbon or an aprotic polar solvent.