DD219197A5 - PROCESS FOR PREPARING AMIDES OF S- / DIALKOXYTHIOPHOSPHORYLENE / THIOGLYKOLIC ACID - Google Patents

Abstract

The object of the invention is a process for the preparation of amides of the S- (dialkoxythiophosphorylen) thioglycolic acid of the general formula 1, in which R and R1 are the same or different and are an alkoxyl group having 1-5 carbon atoms and R2 and R3 are the same or different and is an alkyl group having 1-6 carbon atoms, an aryl group, a pyridyl and oxydahylene group, which is that the bromide of the S- (dialkoxythiophosphorylen) thioglycolic acid having the formula 2, in which R and R1 have the above significance, the action of Amine is subjected to the formula 3, in which R2 and R3 have the meaning given above or in the presence of Trireihenamins with the formula 4, in which R4, R5 and R6 are the same or different and represent an alkyl group having 1-6 carbon atoms or an aryl group in the medium of a Aprotonenloesungsmittels at a temperature of 20 to 15 C, preferably from 3 to 5 C.

Description

/ Berlin »28, 9. 84 AP C 07 C / 262 513 63 905 18

Process for the preparation of amides of S- (dialkoxythio phosphorylene) thioqlycolic acid

Field of application of the invention

The invention relates to a process for the preparation of amides of S- (dialkoxythiophosphorylen) thioglycolic acid, the general formula of which is 1, in which R and R are identical or different and have an alkoxy group having 1-5 carbon atoms.

2 3

and R and R are the same or different and denote a hydrogen atom, an alkyl group having 1-6 carbon atoms, an aryl, pyridyl and Oxydäthylengruppe,

Characteristic of the known technical solutions

The amides according to the invention are known compounds and many of them under the commercial names, such as "Cygon", "Morphotox" ¹¹ AIf ix "," Thiocron "." Fitios B / 77, "" Fostion "and others find general Application as active pesticides and acaricides,

Numerous methods for the synthesis of these amides are known. Among the methods that are most common are the processes resulting in the condensation of sodium, potassium or calcium salt of the phosphorodithioic acid with the phenyl chloroacetate (1) or haloacetyl halides (2) and the subsequent aminolysis of the resulting ester or the anhydride, or also as a result of an alternative method which is used in the reaction of the carbamylmethylmethyl thiosuifonate with the salts of O, O-dimethylthio-phosphoryl

, -3.10. ^ - 0201

acid (2).

The process is also known from US Pat. No. 3,420,919 (USA), which consists in the reaction of the condensation of salts of phosphoribithioic acids with the 2, β, cyanalkylamides of haloacetic acid. «

All of the above known processes for the preparation of amides of thioglycolic acid are processes which take place in some stages and which require the use of difficult, accessible substrates. There are also difficulties relating to the operations associated with the product separation from the reaction mixture * The yield of these processes is between 65 and 95 % in relation to the last stage of the synthesis *

Object of the invention

The object of the invention is to provide an improved process for the preparation of amides of S- (dialkoxythiophosphorylen) thioglycolic acid, with which the desired product can be obtained in high yield and high purity,

Explanation of the essence of the invention

The invention has for its object to find suitable starting compounds and suitable reaction steps for the preparation of amides of S- (dialkoxythiophosphorylen) thioglycolic acid.

The process for the preparation of amides of S- (dialkoxythiophosphorylene) thioglycolic acid having the general formula I ₁ in which R and R are the same or different and a

' 2 alkoxyl group having 1-5 carbon atoms and R and R are the same or different and a hydrogen atom, an aryl * pyridyl and Oxydäthylengruppe »an alkyl group having 1-6 carbon atoms mean» according to the invention, is that the bromide of S- (dialkoxythiophosphorylene) thioglycolic acid of the formula 2 in which R and R have the abovementioned meaning, the effect of Arain with

is subjected to the formula 3 "in which R and R have the meaning given above or in the presence of Trireihenamin with the formula 4» in which R, R and R are the same or different and are an alkyl group having 1-6 carbon atoms or an aryl group in the medium an aprotone solvent at a temperature of -20 to. 15 ⁰ C, preferably from -3 to 5 ⁰ C, preferably benzene Aprotonenlösungsmittel as "hexane, chloroform, carbon tetrachloride, ethyl ether, or their mixtures are used in the process according to the invention"

The preparation of amides by the process of the invention is a simple and powerful process. For one mole of acid bromide S (dialkoxythiophosphoryl thioglycolic acid), 1-2 moles of amine of formula 3 are used, in which R and R are as defined above, wherein in the case of the application of 1 mole of this amine, the reaction is carried out in the presence of 1 mole of the trireihehene of formula 4, in which R ₁ R and R are as defined above »

The process of the invention utilizes readily available compounds and can be carried out in a reaction vessel "without separating the resulting substrate of formula 2 according to patent specification no. / Application Hr, P" 241491 /

The separation and purification of the product is carried out by distillation under reduced pressure or by crystallization.

The yield of amides represented by the process of the invention is 95-98 % relative to the thioxophosphate sulphenyl bromide from which the substrate of formula 2 is obtained.

The purity of the product *, which was determined by analysis of the post-reaction mixture by Rezonanztechnik P / external standard 85% H ₃ PO ₄ / and the elemental analysis of the separated Verbinduagen is 98- 99 %, whereby the amides »with the method according to the invention »can be used as pesticides in the raw state without having to undergo a cleaning operation · -

Working Example

The following examples further clarify the method of the invention without limiting its scope.

-S

Example I

In the stirred solution containing 24.7 g (0.1 mol) of bromide of S- (2,2-dimethylpropoxythiophosphorylene) thioglycolic acid , P mrj cT + 92 * 4 ppm (Et ₂ O) (H ₃ PO ₄ from / «Was received.

For the formula: C " _Q H, -. N0_PS _o

Io ου d.

Calculation: C - 53.68 % _t H - 7.5 % _t N - 3.4 %, P - 7.6 % Determination: C - 53.5 %, H - 7.4 % _t N - 3.6 %, P - 8,7 Jg.

Example II

The solution of the newly obtained bromides of S- (diispropoxylthiophosphorylen) thioglycolic acid in 200 ml of carbon tetrachloride was saturated by the mixture, at a temperature of -3 ⁰ C with gaseous ammonia until the loss of the effect of the exothermic reaction. '

Mixing was continued at a temperature of +15 ⁰ C for 15 minutes, 100 ml of water was added "The organic layer was separated, dried with MeSO _4, gefiltriert; the solvent was distilled under pressure 1.9 kN / m and the distillation residue from the benzene-petroleum ether mixture was crystallized in the ratio 1: 1 to give 11.9 (91 %) amide of S- (diispropoxythiophosphorylene) thioglycolic acid, melting point 65 ⁰ C. has been"

³¹ P mrj.o + 90 ppm (CCl ₄ ) (H ₃ PO ₄ aus./ .. For the formula: C ₀ H _-

Calculation: C - 35.4 % _t H - 6.6 %, N - 5.1 % _t P - 11.4 % Determination: C - 35.6 % _t H - 6.8 %, N -. 5 *, 0 % _t P - 11.5 %.

Example III

A solution vort 17.4 g (0.2 mol) of anhydrous Morfelin in 100 ral benzene was added with mixing at a temperature of +5 ⁰ C in neuangefertigte 27.9 g (0.1 mol) of Broraid S- (dimethoxythiophosphorylen) thioglycolic acid The solvents were distilled off under reduced pressure. To the distillation residue was added 20 ml of water and 100 ml of chloroform. The organic layer was washed separately with 2 x 15 ml of water and with MgSO 4. dried. After filtering off desiccant and distilling off solvent, 26.5 g (93 %) of morpholide of S- (dimethoxythiophosphorylen) thioglycolic acid were obtained in the form of an oily liquid which solidifies on cooling, melting point 59-63 ° C, ³¹ P mrj S + 97 , 7 ppm

For the formula! AIJ ^

Calculation: C - 33.7 %, H - 5.6 % _t N - 4.9 % _t P - 10.8 % Determination: C - 33.0 95, H - 5.6 % _t N - 4.9 %, P - 11.4 %.

Example IV

To the solution 22.5 g (0.1 mol) of bromide as in Example II in 100 ml of dichloromethane were added slowly at a temperature of -15 C with vigorous mixing 10.1 g (0.1 mol) of triethylamine

and 9.4 g (0.1 mol) of 2-aminopyridine dissolved in 50 ml of _Λ benzene. The mixing was continued for 25 minutes at a temperature of c '+ lS ⁰ C, whereupon the solvents were stirred at a temperature of + 10 ⁰ C were distilled under pressure 0.6 kN / m. The syrup-like distillation residue was dissolved in 100 raral chloroform and washed with 2 × 25 H. The organic layer was dried with Na 2 SO 4 and the solvent was distilled wherein 33 »7 g (97%) of 2-Pyridolamid of S- (diizopropoxythiophosphoryien) thioglycolic acid in the form of a yellow oily liquid ³¹ P mrj -d + 87.8 ppm was obtained (CH ₃ COCH _3). For the formula: ^C i3 ^H 21 ^N 2 ° 3 ^hp 2

Calculation: C - 44.8 % _t H *. 6.0 %, N - 8.0 % _t P - 8.8 % Determination: C - 44.7 % _t H - 6.4 %, N - 8.2 %, P - 9.0 %.

Example V

In the neuangefertigte bromide, as in Example III, 27.9 g (0.1 mole) 100 ml of benzene was dripped 20% methylamine ether solution with mixing at a temperature of ⁰ C ο 31 g.

The methylamine bromide was filtered, the solvents were removed at a temperature of + 10 ° C pressure 5 mmHg and the residue was distilled. Ss were 35.0 g (97 %) of methylamide of S- (dimethoxythiophosphorylene) thioglycolic acid, b.p. 105-107 ° C (1.3 N) ra ² , melting point 50 - 51 ⁰ C, ³¹ P mrj cT + sq, i ppm (CCl ₄ ).

For the formula: ^C 5 ^H t2 ^N0 3 ^hp 2

• - 8th -

Calculation: C - 26.2 %, Η · - 5 * 2 %, N - 6.1 %, P - 13.5%. Determination: C - 26.1 %, H -5.1 %, N - 6.6 % _t P - 13.8 % ..

Example VI

In the newly prepared solution 27.9 g (0.1 mol) of bromide, as in Example III were in 100 ml of carbon tetrachloride at a temperature of 0 - 3 ⁰ C with mixing 14.6 g (0.2 mol) of diethylamine in 15 ml Ethyl ether dripped in »The reaction mixture was left for 45 minutes at a temperature of + 20 ° C., whereby it additionally received 50 ml of water»

The organic layer was separated, with MeSO. dried ^

filtered and after removal of the solvent (20, 1 _# 33 kN / m ² ) were 28.9 g (98 %) diethylamide of S- (dimethoxythiophosphorylen) thioglycolic acid> P mrj &. ' 98.6 ppm (CCl ₄ ).

For the formula: C. _n H. _Q N0_PS _o

XU Io ύ ei

Calculation: C - 35,6 % _t H - 6,64 % _t N - 5,16 %, P - 11,4 % Determination: C - 34,7 % _t H - 6,5 %, N - 6,3 %, P - 11.6 %.

For this 1 page formulas.

ρ- Ο

R. "j.

Formula

O II PS-CH ₂ -C-Br

Formula |

H-N <Nf-R

Formula III Formula IV

on .icr -IC ¹ qi. -f i i- .. i

Claims (2)

Invention claim 1, A process for the preparation of amides of S- (dialkoxythiophosphorylen) thioglycolic acid having the general formula 1 »in which R and R are the same or different and an alkoxyl group having 1-5 carbon atoms 2 3
and R and R are the same or different and a hydrogen atom, an alkyl group having 1-6 carbon atoms ^ an aryl, pyridyl and Oxydäthylengruppe, characterized in that the bromide of S- (dialkoxythiophosphorylen) thioglycolic acid with the formula 2, in which R and R have the abovementioned meaning, subjected to the action of the amine of the formula 3 2 3
in which R and R have the abovementioned meaning or in the presence of trireihenamine of the formula 4 in which R, R and R are identical or different and denote an alkyl group having 1-6 carbon atoms or an aryl group in the medium of an apron toner, solution at a temperature of -20 to 15 ⁰ C, preferably from -3 to 5 ° C » 2 · Method according to item 1, characterized in that benzene, hexane, chloroform ¹ , carbon tetrachloride, ethyl ether or mixtures thereof are used as apron solvent.