DD264921A5 - METHOD FOR PRODUCING N-SULFONYL-ACETAMIDO-AMINOMETHANE PHOSPHONATES - Google Patents

Abstract

Preparation of intermediates for herbicides of formula: <IMAGE> by reaction of products of formula: <IMAGE> with products of formula: <IMAGE> in which R, R<1>, R<2>, R<3> and R<4> are organic radicals or H in some cases and X is halogen. The molar ratio II/III is greater than 1.5.

Description

Field of application of the invention The invention relates to a Vorfehron for the preparation of compounds of the formula:

OR ² R ^A

I i

0 - P - CH ₂ --N - CH ₂ - CO - N - SO ₂ - R 'II

OR ³ R

(I)

by reaction of substances of the formula:

O = P - CH ₂ -NH - R ⁴ OR ³

with substances of the formula:

(II)

X - CH, - CO - N - SO, - R ^J

(III)

R 'is a hydrocarbon radical, especially an alkyl, aryl or cycloalkyl radical, where the

Various radicals may optionally be substituted and as substituents in particular the halogen atoms and the phenyl, cyano, alkyl, alkoxy, • Alkoxycarboxylatgruppen- wherein the alkyl groups preferably contain 1 to 4 carbon atoms and P ¹ generally 1 to 18 carbon atoms preferably contains from 1 to 7 carbon atoms, and more preferably from 3 to 7 carbon atoms, when os is a cycloalkyl group; Of course, it is an alkyl group having 1 to carbon atoms, optionally halogenated, lnst / ββοη. chlorinated or fluorinated, such. B. CFj, - R is a hydrogen atom or has one of the meanings given for R, and preferably one

Alkyl group having 1 to 4 carbon atoms;

R 'and R ¹ are selected such that OR' and OR ¹ represent hydrolyzable groups, R 'and R ¹ being mainly alkyl,

Aryl, Arnlkylgruppen are optionally substituted, in particular by substituents such as those for R * or together can form a bivalent radical, preferably having 2 to β carbon atoms, ζ. B. an optionally substituted Aklylenrest (eg., An ethylene propylene propylene rest) and generally 1 to 12 carbon atoms, preferably 1 to 8 Ko 'lenstoff atoms contain;

R 'is a radical of formula Ar (R *) (R *) C-, in which Ar is an aromatic group, preferably one

Phenyl which is optionally substituted; and R ¹ and R * are each a hydrogen atom or an (aromatic) radical Ar or an alkyl group having preferably at most C carbon atoms;

-X is a halo-atom such as "in chlorine, bromine or iodine. <, preferably a chlorine atom.

As substituents for the group Ar, the alkyl, alkoxy, nitro groups, and the halogen atoms, etc. can be mentioned. Characteristic of the known state of the art

Such a reaction is known from EP-A-1 0189726. The compounds obtained are /wlschenp.c-uKve for the preparation of herbicides.

Object of the invention

It is an object of the present invention to develop an improved simplified process for the preparation of compounds of formula I for improving industrial production.

Presentation of this invention O-O compounds of the formula I are prepared by reacting compounds of the formula II

OR ² O = P-CH ₉ -NH-R ⁴ (ID

¹ T) It Compounds of the formula III

X-CH ₂ -CO-N-SO ₂ -R ¹ _{(| 11)}

The ancestor according to the invention is characterized by a molar ratio of compound II to compound III greater than The reaction according to the invention can be carried out in the absence or generally in the presence of solvent

become. Due to the presence of solvents, the temperature can be better controlled. The solvent used is an organic, heat-inert solvent.

Suitable L fertilizers are: the nitriles (in particular acetonitrile), the ketones (in particular acetone, Cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone) which halogenate or do not halogenate hydrocarbons

(in particular benzene, toluene, xylene and chlorobenzene), the esters, such as the alkylalkenoic acid esters, especially ethyl acetate, and dinpolar aromatic solvents, such as dimethylformamide and N-methylpyrrolidone.

DIb Roakt onstemperutur generally liogt to 30 to 150 ° C, preferably to 40 to 120X. The reaction product can be isolated by all known procedures. Certain products of formula II are known (Tetrahedron letters 46, p.44645, 1973). You can easily by implementing Tris (aralkyl) hexahydrotriazines are obtained with diorganophosphites. The reaction temperature of formula III are also known. The molar ratio of pre-bond II to compound III is preferably above 1.8, in particular between 1.9 and 4. It has been shown that it makes possible the molar ratios used in the process according to the invention, without Addition of an acid corrosion sensor to work. This leads to two important advantages, namely that firstly no elimination level

is necessary for the Siureeakzeptor and that the yield is improved.

The invention is thus characterized in a preferred procedure characterized in that the reaction in the absence or

almost absence of an acid acceptor. By near absence one understands that the

Reaction medium may contain traces of acidocreptor for various reasons. An important consequence of the absence or near absence of additional acid acceptor is that it is possible to

to develop an improved cycle process which also improves yield and industrial applicability.

According to another variant of the invention VnrfHnronit this is continuously by recycling the compound

performed the formula II.

This recycling is ensured by extraction of the unreacted compound of formula II at the end of the reaction

in an aqueous acidic medium and then transferring to an organic phase after neutralization.

The process is particularly suitable for compounds in which R and R ^{1 are} alkyl groups having 1 to 4 carbon atoms,

preferably methyl groups and / or R 'and R ^{1 are} alkyl! , Phenyl or benzyl groups.

The following non-limiting examples illustrate the invention and show how the process is carried out example 1

A mixture of 11.43 g (4 χ 10 'mol) of diisopropyl Nber.zylaminomethan-phoiphonat (PM 285k) and 3.71 g (2 χ 10' mol) of N-methyl-N-ethylsulfonyl-chloroacetamide for 2 h 8OX. The reaction mixture is diluted to 50 ml with toluene and treated with water and hydrochloric acid. The aqueous phase and the toluene phase are separated. The toluene phase is concentrated and found to be 8.025 g of the product by chromatography, corresponding to a yield of 92.4%, based on the N-methyl-N-methylsulfonyl-chloroacotamide used.

The Diisüpropyl-N-benz / laminomethan-phosphonate hydrochloride contained aqueous Phoae is poured into 20 ml of toluene, neutralized the Gomisch with a stocilometric amount of aqueous 2N sodium hydroxide solution. The aqueous phase and the toluene Phuse be separated. The toluene phase contains 1.82 χ 10 'mol of isopropyl-N-henzylaminomethanphosphonat in the form of the base, which can be optionally not distilled off distilling off the toluene.

Example 2

The same procedure, when carried out at 70X, leads to a chromatography-specific yield of 72.5%, based on the N-methyl-N-methylsulfonyl-chlorotetamide employed.

Example 3

The same procedure carried out at 90 ° C. leads to a yield of 60.7% determined by chromatography. boiled on the employed N-methyl-N-methyl-sulfonyl-chloroacetamide.

Example 4 (comparison

5.71 g (2 x 10 " ² mol) of diisopropyl N-benzylaminomethane phosphonate and 3.71 g (2 x 10 ² mol) of N-methyl-N-methylsulfonylchloroacetamide are heated to 30" C for 2 hours. A solution of 2.8 ml of triethylamine (2 × 10-rr.ol) in 15 ml of toluene is added gradually over 5 hours to the reaction mixture, which is kept at 80 ° C. The mixture is then cooled to 20X, poured into 15 ml of room temperature water and the aqueous phase and toluene phase are separated. The ToluoIPhiee is concentrated under vacuum. By chromatography, it is found that 6.6 g of the desired product are obtained, corresponding to a yield of 75.8%, based on the two reactants used. Examples

59.5 g (0,166mol) tribenzyl-1,3,5-hexahydrotriazine, 83g (0.5 mol) and 100 g of toluene are heated Oiisopropylphosphit 41/2 h euf 120 "C. The mixture is cooled to 20 ⁰ C.

A chromatographic determination shows that the yield of the reaction based on diisopropyl N-benzylaminomethanephosphonate is quantitative. 37.1 g (0.2 mol) of N-methyl-N-methylsulfonylchloradetemid are added. The reaction mixture is heated to 8O ⁰ C for 2 h and then cooled to room temperature. It is then eaten in 150 g of water and 12 ml of aqueous 37% hydrochloric acid are added to adjust the pH to 1. The phases are separated by Abdeknntieren. The organic phase weighs 173g. The aqueous phase (265 g) is adjusted with 30 ml of 30% sodium hydroxide solution to pH = f> after addition of 100q toluene, the phases are separated by decantation. The second organic phase weighs 195 g.

The first organic phase (173i) k) contains 44.6% of the desired product, which is 0.18 mol. The second organic phase (195 g) contains 42 g of diisopropyl N-benzylaminomethane phosphonate, which is 0.287 mol.

1. Return

The second organic phase (196 g) is azeotropically dried (67 g of toluene and water are removed). Then, 120 g of a toljol solution containing 0.25 mol of diisopropyl N-benzylaminomethane phosphonate and 37.1 g (0.2 mol) of N-methyl-N-methylsulfonylchloroacetamide are added and the mixture is heated at 80 ° C for 2 hours. The reaction mixture is treated exactly as above.

2. Return

A second recycle of diisopropyl N-benzylaminomethane phosphonate is performed exactly as above. The results are given in the following table

A - Diisopropyl N-benzylaminomethane phosphonate B * -. N-methyl-N-methylsulfonylchloroacetamide C - obtained condensation product

TABLE

used substances A recycled Rdt / B of C A- 0.6 mol B-0.2 mol 89% I.Registration A-0.26 mol B-0.2 mol 0.28 mol 100% 2. recycling A-0.26 mol B - 0.2 mol 0.18 mol 100%

Claims (9)

1. Veifahren for the preparation of compounds of the formula: OR ² R * I i O - P - CH ₂ --N - CH ₂ - CO - N - SO ₂ - R ¹ <·) _/ I i OR ³ R characterized in that substances of the formula:
OR ² - P - CH ₂ - NH - R ⁴ (ID OR ³
reacted with substances of the formula: X - CH ₂ - CO - H - SO - - R ¹ I "" - "Ί ¹ a hydrocarbon radical, especially an alkyl, aryl or cycloalkyl radical means, wherein the individual radicals may optionally be substituted, for. By halogen atoms or by phenyl, cyano, alkyl, alkoxy or alkylcarboxylate groups, - R is a hydrogen atom οJer has a meaning given for R ¹ and preferably an alkyl group having 1 to 4 carbon atoms, R ² and R ³ are selected so that OR ² and OR ^{3 are} hydrolyzable groups, wherein R ² and R ^{3 are} each preferably an alkyl, aryl, aralkyl group, optionally substituted, in particular by substituents such as those indicated for R ¹ or R ² and R ³ together may form a uniform divalent, optionally substituted group. R ⁴ denotes a group of the formula Ar (R ⁶ ) (R ^e ) C-, in which Ar is an aromatic group, preferably a phenyl group which is optionally substituted, and R ⁵ and R "are hydrogen atoms or in each case a radical Ar or an alkyl group having preferably at most 6 carbon atoms X is a halogen atom, such as a chlorine, bromine or iodine atom, preferably a chlorine atom bedoutet, and that the process is characterized in that the molar ratio of compound II to compound III is greater than 1.5. 2. The method according to claim 1, characterized gekonnzeichnet that the molar ratio of the compound II to III is greater than 1.8, preferably 1.9 to 4.0. Method according to one of claims 1 or 2, characterized in that the reaction is carried out in the absence or almost absence of an added acid acceptor. 4. The method according to claim 1, characterized gekonnzeichnet that R and R ^{1 are} alkyl groups having 1 to 4 carbon atoms, preferably methyl groups. 5. Process according to Claim 1, characterized in that R ² and R ^{3 are} alkyl, phenyl or benzyl groups. 6. The method according to claim 1, characterized in that boi 30 to 15O ⁰ C, preferably to 120 ° C, operates. 7. The method according to claim 1, characterized in that one works in the presence of a solvent. 8. The method according to claim 7, characterized in that the solvent is a nitrile or a ketone or an ester or a halogenated or a non-halogenated hydrocarbon or a polar aprotic solvent. 9. The method according to any one of the preceding claims, characterized in that the unreacted product of the formula II is recycled. 10. The method according to claim 9, characterized in that the recycling is carried out by adding an aqueous acid to the reaction medium, separation and subsequent recycling in the organic phase after neutralization.