IL29326A - Process for the preparation of chloroalkyl-s-alkyl or aryl-(di)thiolphosphoric acid diesters and ester amide chlorides - Google Patents

Description

η*ηηητ naatn V »n(**t) »ni¾ IR Process for the preparation of chloroalisyl-S-alkyl or aryl-(di) thiolphosphoric acid diestere and ester amide chlorides FARBENFABRIKEN BAYER AK IENGESBLLSCHAPT C: 27755 e presen nvn e -aration of chloroalkyl-S-alkyl- and -aryl-(di)thiolphosphoric acid diester and ester amide chlorides.

It is already known that 0,0-dialkylphosphorous acid diester chlorides react with sulphenic acid chlorides in the sense of the following equation to give 0,S-thiolphosphoric acid diester chlorides, alkyl chloride being split off (cf. K.A. Petrov, G.A. Sokolskij and B.M. Polees, Z. ob&6. Chim. £6, 3381 [1956]: (R0) 2P-Cl + R'-S-Cl * R0-P,-C1 + RC1 R-8 (I) in which R is an alkyl radical, and R' is an alkyl or aryl radical.

In the case of the preparation of O-chloroalkylthiolphos-phoric acid diester chlorides, however, this process possesses the disadvantage that the 0,0-dialkylphosphorous acid diester chlorides (dialkylchlorophosphites) chlorinated in the alkyl radical which are required as starting materials are accessible only with difficulty.

Furthermore, thiolphosphoric acid S-monoester amide chlorides can be obtained by reaction of O-alkylphosphorous acid ester dichlorides with sulphenic acid amides according to the equation:- CI 0 RO-i-Cl + R'-S-N(R") 2 » (R")2N-,-C1 + RCl R»S (II) v according to K.A. Petrov. N.K. Bliznjik and V.A. Savosknok, Z. ob¾5. Chim.21, 1361 [1961], R and R' having the meaning stated above, while R" is a preferably lower alkyl radical.

In this case, too, in the preparation of thiolphosphoric acid ester amides with a 2- or 3-chloroalkyl group on the nitrogen, difficultly accessible starting materials are needed.

Finally, one-step processes for the obtaining of S, S-dithiolphosphoric acid diester halides with two different literature. fhe present invention provides a process by which chloroalkyl-S-alkyl- and -aryl-(di)thiolphosphoric acid diesters and ester amide chlorides of the formula in which ^ , g, R^, ^» and Rg are hydrogen atoms, alkyl, alkoxyalkyl or haloalkyl radicals, R^ is a straight or branched alkyl or alkenyl radical t?ith 1 to 12 carbon atoms (which may be substituted by 1 to 3 halogen atoms, a lower alkoxy, alkyl-mercapto, alkylamino, dialkylamino, formyl, car ox 1, alkoxy-carbonyl, alkylcarbonyl, aminocarbonyl, alkylaminocarbonyl or dialkylaminocarbonyl group) or an aryl radical (which may be substituted by one or several lower alkyl groups, halogen atoms, nitro, cyano, thiocyano, lower alkoxy, alk lmercapto, alk l- an sulphoxyl or alkylsulphonyl groups), X is/oxygen or sulphur atom or an H-alkyl or fi-arylamino group, T is chlorine or a group 0 n CI - P - 0 - R? - S and n is 0 or 1 ; can be obtained with very good yields and in outstanding purity. In this process a 2-chloro-phospholane or -phosphorinane derivative of the general formula is reacted with an aliphatic or aromatic sulphenic acid chloride of the formula R? - S - CI IV in which formulae R^ to ^, X and n have the same meaning as in formula A. and , if n is 1 , then the radicals ^ and R( of the starting compound of formula III together with the -carbon atom may also form a further heterocyclic ring of the structure The smooth and uniform course of the process of the invention is completely surprising. It could not in any way be foreseen that the aforementioned 2-chloro-phospholanes and -phos-phorinanes ¾ould react with sulphenic acid chlorides ¾ith the splitting up of the heterocyclic ring and the ormation o 2 -or 3-chloroalkyl-thiolphosphoric acid ester or ester amide chlorides.

Compared with the known methods mentioned above for the preparation of thiol- and dithiol-phosphoric acid ester and ester amide chlorides with chloroalkyl radicals, the process of the invention is distinguished by a number of substantial advantages. These include, above all, ready accessibility of the starting materials, uniform course of reaction, good yields and very simple mode of performance.

If, for example, 2-chloro-l,3,2-dioxaphospholane or di-oxaphosphorinane and methylsulphenic acid chloride are used as starting materials, the course of the reaction is illustrated by the following equation:- -Cl (n = 0 or 1) (VI) In the same manner, the reaction of 2-chloro-l, 3 , 2-oxa-thiaphospholane with phenylsulphenic acid chloride proceeds in the sense of the equation:- Analogously, the reaction of 2-chloro-3-methyl-l,3,2-oxa-azaphospholane with methylsulphenic acid chloride leads, according to the following equation to N,S-dimethyl-N-(2-chloro-ethyl)-thiolphosphoric acid monoester amide chloride :- (VIII) acid chloride is represented by the following equation:- The 2-chloro-dioxa-phospholanes or -phosphorinanes and aliphatic or aromatic sulphenic acid chlorides to be used as starting materials in the process of the invention are clearly defined by the general formulae (III) and (IV) stated above.

R2, R R^, cj and Rg are preferably hydrogen atoms or alkyl radicals with 1 to 4 carbon atoms (which may be substituted by halo en or lower alkoxy groups) such as methyl chloromethyl or methoxymethyl radicals. R^ is preferably a straight-chain or branched alkyl or alkenyl radical with 1 to 12 carbon atoms (which may be substituted by 1 to 3 halogen atoms, a lower alkoxy, alkylmercapto, alkylarnino, dialkylamino, oar-boiy-l, carboxyl, al-koxycarbonyl, alkylcarbonyl, aminocarbonyl, alkylarninocarbonyl or dialkylaminocarbonyl group) or an aryl, particularly phenyl, radical (which may be substituted one or more times by lower alkyl groups, halogen atoms, nitro, cyano, thiocyano, lower alkoxy, alkylmercapto, alk lsulphoxyl or alk lsulphonyl groups). X is preferably oxygen, sulphur, a lower N-alkyl or an N-phenyl radical.

As examples of the phospholane or p osphorinane derivatives used as starting materials in the process of the invention, there may be fisted η particular 2-chloro-l,3, 2-dioxa-, 2-chloro-4-methyl-l, 3, -dioxa-, 2-chloro-4-chloromethyl-l, 3» 2-dioxa-, 2-chloro-4 , 5-dimethyl-l, 3 , 2-dioxa-2-chloro-5 , 5-dimethyl-l, 3» 2-di 1,3,2-oxathia-phospholane, 2-chloro-l,3, 2-dioxa-, 2-chloro-¾-methyl-1, 3♦ 2-dioxa-, 2-chloro-4-propyl-5-ethyl-l,3, 2-dioxa-, 2-chloro- , 5-dimethy1-1, 3, 2-dioxa-, 2-chloro-4-methyl-l, 3, 2-dioxa-phosphorinane and 4,9-dichloro-3,5,8,10-tetraoxa-4,9-diphospha-8piro-[5, 5]-undecane.

As examples of aliphatic sulphenic acid chlorides used as starting materials there may be listed alkyl- and alkenyl-sul-phenic acid chlorides such as methyl-, ethyl, n-propyl, isopro-pyl, n-butyl, isobutyl, sec.-butyl, n-amyl, isoamyl, tert.-amyl, n-hexyl, 1,2,2-trimethyl-propyl, n-heptyl, n-octyl, n-dodecyl, allyl, crotonyl, 2-methoxyethyl, 2-ethoxy-ethyl, 2-n-butoxy-ethyl, 2-chloro-ethyl, 2-ethylmercaptoethylsulphenicacidchloride.

As examples of aromatic sulphenic acid chlorides there may be listed phenyl, 2-, 3- and 4-chloro-, 2-, 3- and 4-bromo-, 2, 4-, 3,4- and 2,5-dichloro-, 2,4,5- and 2,4,6-trichloro-, 2-, 3-and 4-methyl, 4-isopropyl, 2-chloro-4-methyl, 3-chloro-4-methyl, 3-methyl-4-chloro-, 2-chloro-4-tert .-butyl, 2-, 3- and 4-nitro-, 2- and 3-chloro-4-nitro-, 2,5- and 3, -dichloro-4-nitro-, 2- and 3-methyl-4-nitro-, 3-nitro-4-methyl, 4-methoxy, 2- and 3-methoxy- 4-nitro-, 4-cyano-, 2- and 3-methyl-4-cyano-phenyl sulphenic acid chloride.

The 2-chloro-phospholane and -phosphorinane derivatives have already been described in the literature; they can readily be prepared, even on an industrial scale, by known methods from 1,2- or 1,3-glycols or the appropriate glycolene-mercapto-alkanols or -alkyl- or -arylamino-alkanols and phosphorus-(III)-chloride, for example i- (n= 0 or 1) (X) with chlorine or sulphuryl chloride or by ebieginated oplit iag-of their disulphides/with chlorine.

The process of the invention can be carried out in the presence or absence of solvents (this term includes diluents).

Practically all inert organic solvents are suitable. However, particularly good results have been obtained with aliphatic and aromatic hydrocarbons (optionally chlorinated), such as methylene chloride , dichloroethane, di-, tri- and tetra-chloroethylene, chloroform, carbon tetrachloride, benzine, benzene, chlorobenzene , toluene and xylene; ethers, for example diethyl and di-n-butyl ether, dioxan, tetrahydrofuran, aliphatic ketones and nitriles of low molecular weight, for example acetone, methylethyl ketone, methylisopropyl ketone and methylisobutyl ketone, acetonitrile and propionitrile.

The reaction of the invention can be carried out within a fairly wide temperature range, which may vary according to the nature of the starting materials to be reacted. In general, the work is carried out at from -20° to + 50°C, preferably at -10° to + 30°C.

In the process of the invention, 1 mole of 2-chloro-phos-pholane or-phosphorinane is expediently used per mole of sulphen-ic acid chloride.

It has proved expedient to add the sulphenic acid chloride (if desired, diluted with one of the above-mentioned solvent dropwise to a solution or suspension of the phospholane derivative or phosphorinane derivative at the said temperatures, with stirring and possibly with cooling of the reaction mixture. After completion of the addition, the mixture is left to siand for about 1 to 3 hours, the solvent is then removed and the residue is subjected to fractional distillation.

The products of the process are in most cases colourless to yellow oils, some of which can be distilled under greatly purpose of purification, be si¾^¼-ky--<¾a^.fc3=l^, that is, fresd ^ from the last volatile impurities by longer heating to slightly to moderately elevated temperatures under reduced pressure. Since, however, the reaction usually yields the compounds in high purity, their further reaction is possible without isolation and purification.

The chloroalkyl-S-alkyl or -aryl-(di)thiolphosphoric acid diester or ester amide chlorides known in part from the literature are valuable intermediate products for the preparation of insecticides, fungicides and other plant protection agents.

The following Examples illustrate the process of the invent-ion:- Example 1 82.5 g (1 mole) of me hylsulphenic acid chloride dissolved in 200 ml of tetrachloromethane are added dropwise at 20 to 30°C to a solution of 126-5 g (1 mole) of 2-chloro-l,3»2-dioxaphospholane in 200 ml of tetrachloromethane. After completion of the addition the mixture is left to stand for one hour at room temperature, the solvent is drawn off and the residue is distilled. The yield is 200 g (96 of the theory). The 0-(2-chloroethyl)-S-methylthiol-phosphoric acid diester chloride boils under a pressure of 1 mm Hg at 106°C.

Analysis g Calculated for C^O^Cl^P (molecular weight 209.0): 15.33 Pound: 14.75# Example 2 138.6 g (1 mole) of 2-chlorosulphenylisobutyraldehyde are added dropwise at 10 to 20°C to a solution of 126.5 g (1 mole) fractional distillation, the 0-(2-chloroethyl)-S-(2-oxa-l,1-di-methyl-ethyl(l) )-thiolphosphoric acid diester chloride coming over at 150°C under a pressure of 0.4 mm Hg. The yield is 204 g (77 of the theory). The product has the refractive index n D= 1.5185. Anal yflia p g Calculated for CgH^O^PSC^ (molecular weight 265.1): 11.68 12.08# Pound: 11.52# 12.67# Example 3 Cl-CH2CH2-0-· ,P9Ρ-·Cl I 148.5 g (1 mole) of 4-tolysulphenic acid chloride are added dropwise at 20 to 30°C to a solution of 126.5 g (1 mole) of 2-chloro-l,3,2-dioxaphospholane in 400 ml of dichloromethane and, after standing for one hour, the reaction mixture is worked up in the manner described in the preceding Examples. There is, thus obtained the 0-(2-chloroethyl)-S-(4'-tolyl)-thiolphosphoric acid diester chloride in the form of a non-distillable oil.

Bxample 4 178 g 0(11 mole) o"f'4-chlorophenylsulphenic acid chloride are added at 30°C to a solution of 154.5 g (l mole) of 2-chloro-4,5-dimethyl-l,3,2-dioxaphospholane in 300 ml of dichloromethane. The mixture is then left to stand for one hour at room temperature, the solvent is drawn off and the residue is distilled. The yield is 268 g (80 of the theory). The 0-(3-chlorobutyl-(2) )-S-(4'-chlorophenyl)-thiolphosphoric acid diester chloride comes over at s ,02C15PS (molecular weight 333.6): 9.61 # .04 # Example 5 189.5 g (1 mole) of 2-nitropher.ylsulphenic acid chloride are added at 25°C to a solution of 154.5g (1 mole) of 2-chloro-4,5-dimethyl-l,3,2-dioxaphospholane in 100 ml of dichloromethane, and the reaction mixture, after standing for one hour, is worked up as described in the preceding Examples. In this way, 0-(3-chlorobutyl-(2))-S-(2,-nitrophenyl)-thiolphosphoric acid diester chloride is obtained as an oily substance which, even under greatly reduced pressure, cannot be distilled without decomposition. The yield is 244 g {71% of the theory).

Example 6 82.5 g (1 mole) of methylsulphenic acid chloride dissolved in 200 ml of tetrachloromethane are added dropwise at 0°C to 139· 5 g (1 mole) of 2-chloro-3-methyl-l,3,2-oxaazaphospholane. After "tbe mixture has stood for one hour at room temperature the solvent is drawn off and the residue is distilled. The N,S-dimethyl-N-(2-chloroethyl)-thiolphosphoric acid monoester amide chloride boils at 128°C under a pressure of 2mm Hg. The yield is 182.5 g (82.0# of the theory).

Analysis p g Calculated for C H ONCl PS (molecular weight 222.1): 13.95 14.44# CH^-S A solution of 82.5 g (1 mole) of methylsulphenic acid chloride in 100 ml of tetrachloromethane is added dropwise at 30°C to 155.5 g (1 mole) of 2-chloro-4-methyl-l,3»2-dioxaphosphorinane.

The solvent is drawn off after brief standing of the mixture, and the residue is distilled. There are obtained in this manner 206 g (87% of the theory) of 0-(3-chlorobutyl)-(l) )-S-methylthiolphos-phoric acid diester chloride of b.p. 124°C/lmm Hg.

Analysis Calculated for (Molecular weight 237.1): CI P S 29.1* 13.06% 13.52% Found: 2 .70$ 13.52 13.81% Example 8 0 CH2-C ft Gl-P-0-CH2 C- CH2— 0 — P-Cl 144.5 g (1 mole) of phenylsulphenic acid chloride are added at 20°C to 135 g (0.5 mole) of 4,9-dichloro-3,5,8,10-tetraoxa-4,9-diphospha-spiro-i.5>5]- undecane dissolved in 200 ml of dichloro-methane. The reaction mixture is then worked up in the manner already described and the product of the above formula is obtained in the form of an oil which cannot be distilled without decomposition. The yield is 175 g (=59 of the theory).

Example 9 Cl-CH2-CH-0-P-Cl are added at 50°C to a solution of 175 g (1 mole) of 2-chloro-4-chloromethyl-l,3,2-dioxaphospholane in 300 ml of dichloromethane. The solvent is drawn off and the residue is distilled under re-duced pressure. 312 g (88# of the theory) of 0-(l,3-dichloro-propyl-(2))-S-(4'-chlorophenyl)-thiolphosphoric acid diester chloride of boiling point 194°C/lmm Hg and refractive index n20> = 1.5765 are obtained.

Analysis Calculated for (molecular weight 354.0): P S CI 8.75# 9.06# 40.06# Found: 9.19# 9.02# 39.55 Example 10 154.5 g (1 mole) of 4-chlorophenylsulphenic acid chloride dissolved in 300 ml of dichloromethane are added dropwise at °C to 142.5 g (1 mole) of 2-chloro-l,3,2-oxathiaphospholane.

The solvent is then drawn off, the residue is distilled and there are obtained 278 g (86% of the theory) of S-(2-chloroethyl)-S- (4' -chlorophenyl)-dithiolphosphoric acid diester chloride which boils at 180-185°C under a pressure of 1 mm Hg and has the re-fractive index rr =1.6254.

D Analysis Calculated for (molecular weight 321.5): P S 9.84# 19.70* Pound: 9.70# 20.42$ 29526/2

Claims (1)

1. CLAIMS A process production of or hiolphosphoric acid dieeters or ester amide of the formula Rl 0 in which and are each or is a straight or branched alkyl or alkenyl radical with 1 to 12 carbon atoms may be substituted by 1 to halogen a lower or dialkylaminocarbonyl or an aryl radical may be substituted by one or several lower alkyl halogen lower an or allcylsulphonyl X or atom or an or Y is chlorine or a group and n is 0 or wherein a or derivative of general foraula chloride of the formula IV in which to X and n have the same cleaning a and if n is then the radicals and in the compound of III together with the atom may also a further heterocyclic ring of the structure Δ process according to Claim wherein and are hydrogen or 1 to 4 carbon atoms optionally substituted by halogen or lower alkoxy process according to any of 1 or wherein is a lower or an process according to any of 1 to wherein the phosphplane or phosphorinane derivative is one of those hereinbefore A process according to any of 1 to wherein the sulphenic acid chloride is one of those before A process according to any of Claims 1 to wherein the reaction is carried out in the presence of a process according to any of Claims 1 to in which the reaction is carried out at to A process according to any of Claims 1 to 7 therein the sulphenic acid chloride of formula IV is added to a solution of the or phosphorinane derivative of formula the mixture is thereafter left to stand for 1 to the solvent is removed and the residue is fractionally process for the production of or acid diesters or ester substantially as described herein in any of Examples 1 to or according to Claim 1 acid diesters or ester amide whenever prepared by process according to any of Claims 1 to insufficientOCRQuality