US3626039A - Process for the preparation of chloroalkyl-s-alkyl-and aryl- (d1) thiol-phosphoric acid diester and ester amide chlorides - Google Patents

Process for the preparation of chloroalkyl-s-alkyl-and aryl- (d1) thiol-phosphoric acid diester and ester amide chlorides Download PDF

Info

Publication number
US3626039A
US3626039A US727738A US3626039DA US3626039A US 3626039 A US3626039 A US 3626039A US 727738 A US727738 A US 727738A US 3626039D A US3626039D A US 3626039DA US 3626039 A US3626039 A US 3626039A
Authority
US
United States
Prior art keywords
alkyl
process according
chloro
group
phenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US727738A
Inventor
Hellmut Hoffmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Application granted granted Critical
Publication of US3626039A publication Critical patent/US3626039A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/547Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6578Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and sulfur atoms with or without oxygen atoms, as ring hetero atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/06Phosphorus compounds without P—C bonds
    • C07F9/16Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165Esters of thiophosphoric acids
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/06Phosphorus compounds without P—C bonds
    • C07F9/16Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165Esters of thiophosphoric acids
    • C07F9/20Esters of thiophosphoric acids containing P-halide groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/06Phosphorus compounds without P—C bonds
    • C07F9/22Amides of acids of phosphorus
    • C07F9/24Esteramides

Definitions

  • the present invention relates to and has for its objects the provision for particular new methods of producing chloroalkyl-S-alkyland -S-aryl- (di)thiolphosphoric acid diester and ester amide chlorides, which are known insecticide, fungicide and other plant protection agent intermediates, e.g. in a simple and uniform single step reaction, using readily available starting materials whereby to attain outstanding yields, with other and further objects of the invention becoming apparent from a study of the within specification and accompanying examples.
  • R is an alkyl radical, and R is an alkyl or aryl radical.
  • R and R being the same as defined above, while R" is a, preferably lower, alkyl radical.
  • chloroalkyl-S-alkyland -S-aryl- (di)thiolphosphoric acid diester and ester amide chlorides i.e. S- and N- chloroalkyl)-S-(alkyl, oxo-alkyl, phenyl and alkyl-, haloand/or nitro-substituted phenyl)-diester chlorides and ester amide chlorides, having the general formula to 12 carbon atoms, phenyl and substituted phenyl which is substituted with one to three substitutents selected from the group consisting of lower alkyl, halo, nitro and mixtures of such substituents, X is selected from the group consisting of oxygen, sulfur, N-lower alkyl amino and N phenyl amino, and n is a whole number from 0 to l, with the proviso that R and R when taken together with the adjacently positioned carbon atom
  • the new process of the present 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 a very simple mode of performance.
  • phospholane or phosphorinane derivatives usable as starting materials in accordance with the process of the invention, there may be listed in particular 2- chlorol ,3 ,2-dioxa-, 2-chloro-4-methyl-l ,3 ,2-dioxa-, 2- chIoro-4,5-dimethyl-l ,3,2-dioxa-, 2-chloro-5 ,S-dimethyl- 1 ,3,2 -dioxa-, 2-chloro-4,4,5,5tetramethyl-l,3,2-dioxa-, 2chloro- 3-methyl-l ,3,2-oxa-aza and 2-chloro-1,3,2-oxa-thiaphospholane, and the like; and 2-chloro-l,3,2-dioxa-, 2- chloro-4-methyll ,3,2-dioxa-, 2chloro-4-propyl-5-ethyl-l ,3,2- dioxa-,
  • alkyland alkenyl-sulfenic acid chlorides such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, n-amyl, isomyl, tert.- amyl, n-hexyl, l,2,2-trimethyl-propyl, n-heptyl, n-octyl, ndodecyl, and the like, sulfenic acid chlorides.
  • the aliphatic or aromatic sulfenic acid chlorides required as starting materials are also readily accessible in known manner by reaction of the appropriate mercaptans or thiophenols with chlorine or sulfuryl chloride or by chlorinated splitting of their disulfides.
  • the process of the present invention can be carried out in the presence or absence of solvents (this term includes diluents). Practically all inert organic solvents (or diluents) and their mixtures are suitable. However, particularly good results have been obtained with aliphatic and aromatic hydrocarbons (optionally chlorinated), including lower aliphatic, especially lower alkyl, hydrocarbons, C aryl, especially benzene, hydrocarbons, chlorinated lower aliphatic, especially chlorinated lower alkyl, hydrocarbons, chlorinated C aryl, especially chlorinated benzene, hydrocarbons, such as methylene chloride, dichloroethane, ditriand tetra-chloroethylene, chlorofonn, carbon tetrachloride, benzine, benzene, chlorobenzene, toluene and xylene; ethers, including aliphatic and cycloaliphatic ethers, such as lower aliphatic, especially lower alky
  • the reaction according to the present 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 preferably carried out at a temperature substantially between about 20 to +50 C., preferably at about l0 to +30 C.
  • sulfenic acid chloride 1 mol of 2- chloro-phospholane or phosphorinane is expediently used per mol of sulfenic acid chloride, although an excess of one or the other reactant can still be used.
  • the sulfenic acid chloride will be expediently used in at least a percent excess over the molar amount of the 2chlorophospholane or phosphorinane present.
  • chloroalkyl-S-alkyl or -S-aryl (di)thiolphosphoric acid diester monochlorides or ester amide chlorides which are formed as products in accordance with the production process of the present invention, and which are known in part from the literature, are valuable intermediate products which can be used in the known way for the preparation of insecticides, fungicides and other plant protection agents of the type as disclosed in copending US. application Ser. No. 727,697, filed simultaneously herewith, corresponding to German patent application F52369 [Vb/12o, filed in Germany May 10, 1967, i.e. by reaction of the instant compounds, e.g.
  • an acid-binding agent such as sodium carbonate, methylamine, etc.
  • an appropriate alcohol, mercaptan, phenol, thiophenol or N- alkyl or N,N-dialkyl amine, or corresponding alkali metal or ammonium salt of such hydroxy or thiol compound e.g. in the presence of an inert organic solvent such as methylene chloride, benzine, benzene, diethyl ether, acetone, acetonitrile, etc., at 20-100 C., and recovering the final product, e.g. by pouring over ice, extracting with a solvent such as benzene, washing, drying and distilling.
  • Such final products contemplate chloroalkyl-thiolphosphoric acid esters and/or -ester amides of the general structure in which R,, R R R R R,, X and n are the same as defined above, and Y-R is the corresponding alcohol, mercaptan, phenol, thiophenol or amino group resulting from the splitting ofi of HCl (to achieve the condensed product), using a compound of the type H-YR
  • the following examples illustrate the new production process for the present invention:
  • the O-(Z-chloroethyl)-S-methy1-thio1phosphoric acid diester monochloride 138.6 g. (lmol) of 2-chlorosulfenyl-isobutyraldehyde are added dropwise at 10 to 20 C. to a solution of 126.5 g. (1 mol) of 2-chloro-1,3,2-dioxa-phospholane, i.e. 2-ch
  • the mixture is then left to stand for 1 hour at room temperature, the solvent is drawn off and the residue is subjected to fractional distillation, the O-(2-chloro-ethyl)-S-( 2-oxo-1,1- dimethyl-eth-l-yl)-thiolphosphoric acid diester monochloride coming over at 150 C. under a pressure of 0.4 mm. Hg.
  • the yield is 204 g. (77 percent of the theory).
  • EXAMPLE 4 (Dis) One hundred and seventy-nine grams (1 mol) of 4 chlorophenylsulfenic acid chloride are added at 30 C. to a solution of 154.5 g. (1 mol) of 2-chloro-4,5-dimethyl-l,3,2- dioxa-phospholane, i.e. 2-chloro-4,5--diemthyl-1,34:1ioxa-2- phospholane, in 300 ml. of dichloromethane. The mixture is then left to stand for 1 hour at room temperature, the solvent is drawn off and the residue is distilled. The yield is 268 g. (80 percent of the theory).
  • phospholane i.e. 2-chloro-3-methyl-1-oxa-3-aza-2- Three hundred and twelve grams (88 percent of the theory) of phospholane.
  • EXAMPLE 7 1 EXAMPLE 10 Y i 1 ClCH;OH -S-PCl (XIVa) Cl-H-CHz-CHz-O-If-Cl l CHa-S (XIa) G A solution of 82.5 g. (1 mol) of methylsulfenic acid chloride 33: 22 g: zggfig g gz s l l zgf g; in 100 ml. of tetrachloromethane is added dropwlse at 30 C. dichloromethane are added dropwise at 30 C.
  • EXAMPLE 8 EXAMPLE 1 1 CHz-Cl 144.5 g. (1 mol) of phenylsulfenic acid chloride are added at 20 C. to 132.5 g. (0.5 mol) of 4,9-dichloro-3,5,8,l0- tetraoxa-4,9-diphospha-spiro-[5,5 l-undecane dissolved in 200 ml. of dichloromethane. The reaction mixture is then worked Upon repeating the procedure of example 1 using equimolar amounts of the corresponding sulfenic acid chlorides and the appropriate 2-chloro-phospholanes or (XIIa) ph0s[ horinanes the following final products are obtained:
  • the preparation is carried out without isolation of the O-( 3- chlorobut-2-yl)-S-(4'-chlorophenyl)-thiol-phosphoric acid diester monochloride of the formula (3-chloro-but-2-y)-S-(4'-chlorophenyl)-thiol-phosphoric acid ester has a boiling point of between 148 and 150 C./0.05 Torr. The yieldamounts to 197 g. (60 percent of the theory).
  • Such final products possess strong fungitoxic effect and a broad range of activity. Despite this excellent effect in combating phytopathogenic fungi, they are only slightly toxic to warmblooded animals (average toxicity DL in the rat per os 100 to 1000 mg./kg. animal), and are excellently compatible with higher plants. Due to these properties, the final products are excellently suited for use as plant protecting agents in combating fungus diseases, and specifically for combating fungi of a great variety of classes, for example, Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes, Fungi impelfecti, and the like. Such final products have proven to be particularly effective, however, in combating fungus diseases on rice plants, particularly fungus disease caused by Piricularia oryzae. These final compounds exhibit excellent protective and curative activity in combating particularly this fungus.
  • such final compounds may be used also for purposes of combating other fungus pathogens on rice and other cultivated plants, and are particularly effective against the fol:
  • Corticium sasakii Corticium sasakii
  • Cochliobolus miyabeanus Mycosphaerella species
  • Corticium species Cerospora species
  • Alternaria species Botrytis species, and the like.
  • Such final compounds exhibit very good fungicidal activity with respect to fungi which attack the plant from the soil and partially those which cause tracheomycoses, such as for example: Fusan'um cubense; Fusarium diamhi; Verticillium alboatrum, and Phialophora cinerescens.
  • the quantity of the active substance necessary to obtain the desired concentration of active substance in the spray liquid is admixed with the stated amount of solvent, and the resulting concentrate is diluted with the stated amount of water which contains the stated dispersing agent and additive.
  • the spray liquid is sprayed onto 30 rice plants which are about 14 days old until they are dripping wet. Until they are dry, the plants remain in a hothouse at temperatures from 22 to 24 C. and a relative humidity of about percent. Thereafter, they are inoculated with an aqueous suspension of 100,000 to 200,000 spores/ml, of Piricularia oryzae and stored in a room at a temperature between 24-26 C. and a relative humidity of percent.
  • infection is determined on all leaves present at the time of inoculation as a percent of the untreated but also inoculated control plants. 0 percent means no infection, 100 percent means that infection is as high as in the control plants.
  • Whlch X is yg 1, 1, R5 and R, each respectively 18 in the foregoing formulae, hydrogen.
  • R,, R R R R and R each respectively represents It Will be appreciated that the instant specification and exhydrogen; amples are set forth by way of illustration and not limitation, lower alkyl such as methyl, ethyl, nand isopropyl, n-, iso-, and that various modifications and changes may be made and y and the like, especially l-l yl, and without departing from the spirit and scope of the present inparticularly methyl; or 40 vention which is to be limited only by the scope of the apchloro-lower alkyl, especially chloro---C, alkyl, and particularly chloromethyl; R-, represents straight and branched alkyl having one to 12 carbon atoms,
  • methyl to tert.-butyl inclusive as defined above such as methyl to tert.-butyl inclusive as defined above, nisoand tert.-amyl, n-hexyl, l,2,2-trimethyl-propyl, nheptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, and the like, especially lower alkyl, more especially C alkyl, en ee t s erlxmsthyla 0 such alkyl which is substituted with an oxo gro up (II),
  • phenyl which is substituted with one to three (same or mixed) substituents in ortho, meta and/or parapositions including lower alkyl such as methyl to tert-butyl inclusive as defined above, especially C, alkyl, and particularly methyl; halo such as chloro, bromo, iodo and/or fiuoro, especially 1- 3 chloro, and particularly monochloro; and/or nitro;
  • X represents oxygen; sulfur; N-lower alkyl amino such as N-monomethyl to tert.-butyl inclusive as defined above, -amino, especially N- C monoalkyl amino; or N-phenylamino; and n is a whole number from 0 to l;
  • R R, R R R, and R each respectively is selected from the group consisting of hydrogen, lower alkyl and chlorolower alkyl
  • R is selected from the group consisting of alkyl having one to 12 carbon atoms, oxo-substituted isobutyl, halogen-substituted alkyl having one to 12 carbon atoms, phenyl and substituted phenyl which is substituted with one to three substituents selected from the group consisting of lower alkyl, halo, nitro and mixtures of such substituents
  • X is selected from the group consisting of oxygen, sulfur, N-lower alkyl amino and N-phenyl amino
  • n is a whole number from 0 to 1; with the proviso that R, and R when taken together with the adjacent
  • said solvent is selected from the group consisting of lower alkyl hydrocarbon, chlorinated lower alkyl hydrocarbon, benzene hydrocarbon, chlorinated benzene hydrocarbon, lower alkyl ether, lower cycloaliphatic ether, lower alkyl ketone, lower alkanoic acid nitrile, and mixtures thereof.
  • n is l
  • R and R form with the adjacently positioned carbon atom said heterocyclic ring and wherein said sulfenyl chloride is present in substantially about a percent molar excess over the amount of the corresponding 2-chloro-l-oxy-phosphorus compound present.
  • R R R R R and R each respectively is selected from the group consisting of hydrogen, C alkyl and chloromethyl
  • R is selected from the group consisting of C alkyl, monooxo-substituted C alkyl, monohalogen-substituted C,C alkyl, phenyl, C alkylsubstituted phenyl, chloro-substituted phenyl and nitro-substituted phenyl
  • X is selected from the group consisting of oxygen, sulfur and NC, -monoalkyl-amino
  • n is a whole number from 0 to l, with the proviso that R and R when taken together with the adjacently positioned carbon atom form a corresponding heterocyclic ring having the structure in which X is oxygen and R R,, R, and R each respectively is hydrogen.
  • R R R R R and R each respectively, is selected from the group consisting of hydrogen and methyl, R is selected from the group consisting of phenyl, 4-chlorophenyl and C alkyl, X is selected from the group consisting of oxygen, sulfur and N-C, monoalkylamino, and n is a whole number from 0 to l.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)

Abstract

Reacting 2-chloro-(optionally 4-chloro lower alkyl)-1,3- (dioxa, oxa-thia or oxa-aza)-2-(phospholanes or phosphorinanes) with alkyl, oxo-alkyl (i.e. carbonyl-alkyl or aldehydo-alkyl), haloalkyl, phenyl or alkyl-, halo- and/or nitro-substituted phenyl sulfenylchlorides, for example at about -20 to +50* C., optionally in the presence of an inert organic solvent, to form the corresponding (O-, S- and N- chloro-substituted alkyl)-S(alkyl, oxo-alkyl, haloalkyl, phenyl and alkyl-, halo- and/or nitro- substituted phenyl)-diester chlorides and ester amide chlorides, which are known intermediates usable in the known way for producing known insecticides, fungicides and other plant protection agents.

Description

Q United States Patent [1113,626,039
[7 2] Inventor l'lellmut Hoffmann [50] Field of Search 260/971 Wuppertal-Elberfeld, Germany [21] Appl. No. 727,738 [56] References Cited [22] Filed May 8, 1968 UNITED STATES PATENTS Patented Dec-7,197! r 2,765,331 10/1956 Whetstone eta]. 260/971 [73] Asstgnee Farbenlabriken Bazer Aktiengesellschaft OTHER REFERENCES Leverkusen, Germany n [32] Priority Feb. 13,1967 Petrov et al., Chem. Abstracts. Vol. 51, (1951), [33] Germany 9473-9474 [31] F 51508 Primary ExaminerCharles B. Parker Continuation-impart of application Ser. No. 704,515, Feb. 12, 1968, now abandoned. This application May 8, 1968, Ser. No. 727,738
[54] PROCESS FOR THE PREPARATION OF CHLOROALKYL-S-ALKYL-AND ARYL- (D1) THIOL-PHOSPHORIC ACID DlESTER AND ESTER AMllDE CHLORIDES 12 Claims, No Drawings 52 user 260/971, 260/927 R, 260/928, 260/936, 260/937, 260/946,
511 llnt.Cl ..C07d 105/04, C07f 9/24, C07f 9/26 Assistant Examiner-Anton H. Sutto Attorney-Burgess, Dinklage & Sprung ABSTRACT: Reacting 2-chloro-(optionally 4-chloro lower alkyl)-1,3- (dioxa, oxa-thia or oxa'aza)-2-(phospholanes or phosphorinanes) with alkyl, oxo-alkyl (i.e. carbonyl-alkyl or aldehydo'alkyl), halo-alkyl, phenyl or alkyl-, haloand/or nitro-substituted phenyl sulfenylchlorides, for example at about 20 to +50C., optionally in the presence of an inert organic solvent, to form the corresponding (O-, S- and N- chloro-substituted alkyl)-S-(alkyl, oxo-alkyl, haloalkyl, phenyl and alkyl-, haloand/or nitrosubstituted phenyl)-diester chlorides and ester amide chlorides, which are known intermediates usable in the known way for producing known insecticides, fungicides and other plant protection agents.
PROCESS FOR THE PREPARATION OF CHLOROALKYL- S-ALKYL-ANDARYL- (lDl) Tl-llOL-PHOSPHORIC ACID DIESTER AND ESTER AMIDE CHLORIDES This is a continuation-in-part application of US. application, Ser. No. 704,515, filed Feb. 12, 1968, now abandoned.
The present invention relates to and has for its objects the provision for particular new methods of producing chloroalkyl-S-alkyland -S-aryl- (di)thiolphosphoric acid diester and ester amide chlorides, which are known insecticide, fungicide and other plant protection agent intermediates, e.g. in a simple and uniform single step reaction, using readily available starting materials whereby to attain outstanding yields, with other and further objects of the invention becoming apparent from a study of the within specification and accompanying examples.
It is already known that 0,0-dialkyl-phosphorous acid diester chlorides (A) react with sulfenic acid chlorides (B) in the sense of the following equation to give O,S-thio-phosphoric acid diester chlorides (C) alkyl chloride being split off (cf. K. A. Petrov, G. A. Sokolskij and B. M. Polees, Z. obsc. Chim. 26, 3381 [1956]):
in which R is an alkyl radical, and R is an alkyl or aryl radical.
(cf. K. A. Petrov, N. K. Bliznjik and V. A. Savosknok, Z. obsc. Chim. 31, 1361 [1961]), R and R being the same as defined above, while R" is a, preferably lower, alkyl radical.
In this case, too, in the preparation of thiolphosphoric acid ester amides (lb) with a 2- or 3-chloroalkyl group on the nitrogen atom, difficulty accessible starting materials are needed.
Finally, one-step processes for the obtaining of S,S-dithiolphosphoric acid diester halides (lc) with two different organic radicals have not up to now been described at all in the literature.
It has now been found, in accordance with the present invention, that chloroalkyl-S-alkyland -S-aryl- (di)thiolphosphoric acid diester and ester amide chlorides, i.e. S- and N- chloroalkyl)-S-(alkyl, oxo-alkyl, phenyl and alkyl-, haloand/or nitro-substituted phenyl)-diester chlorides and ester amide chlorides, having the general formula to 12 carbon atoms, phenyl and substituted phenyl which is substituted with one to three substitutents selected from the group consisting of lower alkyl, halo, nitro and mixtures of such substituents, X is selected from the group consisting of oxygen, sulfur, N-lower alkyl amino and N phenyl amino, and n is a whole number from 0 to l, with the proviso that R and R when taken together with the adjacently positioned carbon atom form a corresponding heterocyclic ring having the structure in which X, R,, R R and R, each respectively is the same as defined above, can be obtained much more simply and uniformly, that is in a one-step reaction, and with outstanding yields, by the process which comprises reacting 2-chloro phospholane or -phosphorinane, i.e. 2-chloro-l,3-(dioxa, oxathia or oxa-aza)-2-(phospholane or phosphorinane) having the general formula in which R,, R R R R and R each respectively, X and n are the same as defined above, with alkyl or aryl sulfenyl chloride having the formula R,-S--Cl (lllb) in which R, is the same as defined above, whereby to form such corresponding chloroalkyl-ester chloride, if desired, in the presence of an inert organic solvent or diluent.
The smooth and uniform course of the novel process of the present invention is completely surprising. It could not in any way have been foreseen that the aforementioned 2- chlorophospholanes and -phosphorinanes would react with sulfenic acid chlorides with the splitting up of the heterocyclic ring and the formation of appropriate 2- or 3-chloroalkylthiolphosphoric acid ester or ester amide chlorides.
Compared with the known methods mentioned above for the preparation of thioland dithiol-phosphoric acid ester and ester amide chlorides with chloralkyl radicals, the new process of the present 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 a very simple mode of performance.
lf, for example, 2-chlorol ,3,2-dioxa-phospholane or dioxaphosphorinane and methylsulfenic acid chloride are used as starting materials, the course of the reaction is illustrated by In the same manner, the reaction of 2-chloro-l,3,2-oxathis-phospholane with phenylsulfenic acid chloride proceeds in the sense of the equation:
CHz-O (IIab) (IIIa) Finally, the reaction of 4,9-dichloro-3,5,8,lO-tetraoxa-4,9- diphospha-spiro-[5,5]-undecane with 4-tolylsulfenic acid chloride is represented by the following equation:
The 2-chloro-dioxa-phospholanes or phosphorinanes and aliphatic or aromatic sulfenic acid chlorides usable as starting materials in accordance with the process of the invention are clearly defined by the appropriate general formulas (Ila), (lie) and (llb) stated above.
As examples of the phospholane or phosphorinane derivatives usable as starting materials in accordance with the process of the invention, there may be listed in particular 2- chlorol ,3 ,2-dioxa-, 2-chloro-4-methyl-l ,3 ,2-dioxa-, 2- chIoro-4,5-dimethyl-l ,3,2-dioxa-, 2-chloro-5 ,S-dimethyl- 1 ,3,2 -dioxa-, 2-chloro-4,4,5,5tetramethyl-l,3,2-dioxa-, 2chloro- 3-methyl-l ,3,2-oxa-aza and 2-chloro-1,3,2-oxa-thiaphospholane, and the like; and 2-chloro-l,3,2-dioxa-, 2- chloro-4-methyll ,3,2-dioxa-, 2chloro-4-propyl-5-ethyl-l ,3,2- dioxa-, 2-chloro-5 ,5 dimethyll ,3 ,2-dioxa-, 2-chloro-4- methyl-1,3,2-dioxa-phosphorina.ne, and the like; and 4,9- dichloro-3 ,5 ,8, l O-tetraoxa-4,9-diphosphaspiro-[ 5 ,5 ]-undecane, and the like.
As examples of aliphatic sulfenic acid chlorides usable as starting materials herein there may be listed alkyland alkenyl-sulfenic acid chlorides such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, n-amyl, isomyl, tert.- amyl, n-hexyl, l,2,2-trimethyl-propyl, n-heptyl, n-octyl, ndodecyl, and the like, sulfenic acid chlorides.
As examples of corresponding aromatic sulfenic acid chlorides usable herein 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-4chloro, 2chloro-4-tert.-butyl, 2-, 3- and 4-nitro, 2- and 3-chloro-4- nitro, 2,5- and 3,5-dichloro-4-nitro, 2- and 3-methyl-4-nitro, 3-nitro-4-methyl, and the like, phenyl sulfenic acid chlorides, and the like.
The starting 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 glycolenemercapto-alkanols or glycolene N-alkylor N-aryl-amino-alkanols and phosphorus-(lll)-chloride, for example:
The aliphatic or aromatic sulfenic acid chlorides required as starting materials are also readily accessible in known manner by reaction of the appropriate mercaptans or thiophenols with chlorine or sulfuryl chloride or by chlorinated splitting of their disulfides.
The process of the present invention can be carried out in the presence or absence of solvents (this term includes diluents). Practically all inert organic solvents (or diluents) and their mixtures are suitable. However, particularly good results have been obtained with aliphatic and aromatic hydrocarbons (optionally chlorinated), including lower aliphatic, especially lower alkyl, hydrocarbons, C aryl, especially benzene, hydrocarbons, chlorinated lower aliphatic, especially chlorinated lower alkyl, hydrocarbons, chlorinated C aryl, especially chlorinated benzene, hydrocarbons, such as methylene chloride, dichloroethane, ditriand tetra-chloroethylene, chlorofonn, carbon tetrachloride, benzine, benzene, chlorobenzene, toluene and xylene; ethers, including aliphatic and cycloaliphatic ethers, such as lower aliphatic, especially lower alkyl, and lower cycloaliphatic ethers, for example diethyl and di-n-butyl ether, dioxan, tetrahydrofuran; aliphatic ketones and nitriles of low molecular weight, including lower alkyl ketones and lower alkanoic acid nitriles, for example acetone, methylethyl ketone, methylisopropyl ketone and methylisobutyl ketone, acetonitrile and propionitrile; and the like.
The reaction according to the present 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 preferably carried out at a temperature substantially between about 20 to +50 C., preferably at about l0 to +30 C.
In accordance with the process of the invention, 1 mol of 2- chloro-phospholane or phosphorinane is expediently used per mol of sulfenic acid chloride, although an excess of one or the other reactant can still be used. in the case of a starting compound of the type contemplated by Formula (llc), however, the sulfenic acid chloride will be expediently used in at least a percent excess over the molar amount of the 2chlorophospholane or phosphorinane present.
It has proved expedient to add the sulfenic acid chloride (if desired, diluted with one of the above-mentioned solvents) dropwise to a solution or suspension of the phospholane derivative or phosphorinane derivative at the above stated temperature, with stirring and possibly with cooling of the reaction mixture. After completion of the addition, the mixture is left to stand for about 1 to 3 hours, the solvent is then removed and the residue is subjected to fractional distillation.
The products of the instant process are in most cases colorless to yellow oils, some of which can be distilled under greatly reduced pressure without decomposition. If this is not possi ble, the compounds obtainable according to the invention can,
for the purpose of purification, be slightly distilled, that is, freed 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 or use is possible without isolation and purification.
The chloroalkyl-S-alkyl or -S-aryl (di)thiolphosphoric acid diester monochlorides or ester amide chlorides, which are formed as products in accordance with the production process of the present invention, and which are known in part from the literature, are valuable intermediate products which can be used in the known way for the preparation of insecticides, fungicides and other plant protection agents of the type as disclosed in copending US. application Ser. No. 727,697, filed simultaneously herewith, corresponding to German patent application F52369 [Vb/12o, filed in Germany May 10, 1967, i.e. by reaction of the instant compounds, e.g. in an acid-binding agent such as sodium carbonate, methylamine, etc., with an appropriate alcohol, mercaptan, phenol, thiophenol or N- alkyl or N,N-dialkyl amine, or corresponding alkali metal or ammonium salt of such hydroxy or thiol compound, e.g. in the presence of an inert organic solvent such as methylene chloride, benzine, benzene, diethyl ether, acetone, acetonitrile, etc., at 20-100 C., and recovering the final product, e.g. by pouring over ice, extracting with a solvent such as benzene, washing, drying and distilling.
Such final products contemplate chloroalkyl-thiolphosphoric acid esters and/or -ester amides of the general structure in which R,, R R R R R R,, X and n are the same as defined above, and Y-R is the corresponding alcohol, mercaptan, phenol, thiophenol or amino group resulting from the splitting ofi of HCl (to achieve the condensed product), using a compound of the type H-YR The following examples illustrate the new production process for the present invention:
EXAMPLE 1 CHJS (VIa) 82.5 g. (1 mol) of methylsulfenic acid chloride dissolved in 200 ml. of tetrachloromethane are added dropwise at 20 to 30 C. to a solution of 126.5 g. (1 mol) of 2-ch1oro-1,3,2- dioxa-phospholane, i.e. 2-ch1oro-1,3-dioxa-2-phospholane, in 200 ml. of tetrachloromethane. After completion of the addition the mixture is left to stand for 1 hour at room temperature, the solvent is drawn off and the residue is distilled. The yield is 200 g. (96 percent of the theory). The O-(Z-chloroethyl)-S-methy1-thio1phosphoric acid diester monochloride 138.6 g. (lmol) of 2-chlorosulfenyl-isobutyraldehyde are added dropwise at 10 to 20 C. to a solution of 126.5 g. (1 mol) of 2-chloro-1,3,2-dioxa-phospholane, i.e. 2-ch|oro-l,3' dioxa-2-phospholane, in 300 ml. of dichloromethane. The mixture is then left to stand for 1 hour at room temperature, the solvent is drawn off and the residue is subjected to fractional distillation, the O-(2-chloro-ethyl)-S-( 2-oxo-1,1- dimethyl-eth-l-yl)-thiolphosphoric acid diester monochloride coming over at 150 C. under a pressure of 0.4 mm. Hg. The yield is 204 g. (77 percent of the theory). The product has the refractive index n =1 .5 185.
158.5 g. (1 mol) of 4-toly1sulfenic acid chloride are added dropwise at 20 to 30 C. to a solution of 126.5 g. (1 mol) of 2- chloro- 1 ,3,2-dioxa-phospholane, i.e. 2-chloro 1,3-dioxa-2- phospholane, in 400 ml. of dichloromethane and, after stand ing for 1 hour, the reaction mixture is worked up in the manner described in the preceding example. There is thus obtained O-(2-chloro-ethyl)-S-(4"tolyl)-thiolphosphoric acid diester monochloride in the form of a nondistillable oil,
EXAMPLE 4 (Dis) One hundred and seventy-nine grams (1 mol) of 4 chlorophenylsulfenic acid chloride are added at 30 C. to a solution of 154.5 g. (1 mol) of 2-chloro-4,5-dimethyl-l,3,2- dioxa-phospholane, i.e. 2-chloro-4,5--diemthyl-1,34:1ioxa-2- phospholane, in 300 ml. of dichloromethane. The mixture is then left to stand for 1 hour at room temperature, the solvent is drawn off and the residue is distilled. The yield is 268 g. (80 percent of the theory). The 0-(3-chlorobut-2-yl)-S-(4'- chlorophenyl)-thiolphosphoric acid diester monochloride comes over at 162 C. under a pressure of 1 mm. Hg and pos boils under a pressure of 1 mm. Hg at 106 C. Sesses the refractive index "20F! Analysis 5 Analysis S C for C,,,H =O,CI,PS (molecular weight Calculated for C,H,O,CI,SP (molecular weight 9.61% 209.0): 15.33% Found: 10.04% Found: 14.75%
EXAMPLE 2 EXAMPLE 5 I CH3 CH3 ([3 Cl--CHz-CH:|-Oi-C1 ClJIH( JHO-i-C1 CH i S O==CC--S (VIIa) NO;
H CH3 189.5 g. (1 mol) of Z-nitrophenylsulfenic acid chloride are added at 25 C. to a solution of 154.5 g. (1 mol) of 2-chloro- 4,5-dimethyl-l,3,2-dioxa-phospho1ane, i.e. 2-chloro-4,5- dimethyl-l ,3-dioxa-2-phospholane, in 100 ml. of
dichloromethane. and the reaction mixture, after standing for 5 up in the manner already described in the preceding example 1 hour, is worked up as described in the preceding example, In and the product of the above formula is obtained in the form this way, O-(3-chloro-but-2-yl)-S-(2'-nitrophenyl)- of an oil which cannot be distilled without decomposition. The thiolphosphoric acid diester monochloride is obtained as an yield is 175 g. (=59 percent of the theory). oily substance which, even under greatly reduced pressure, cannot be distilled without decomposition. The yield is 244 g. 2-.. EXAMPLE 9 (71 percent of the theory).
(JP-CH2 0| EXAMPLE 6 C1OHz CH-0-i Cl I 01- S 311 f[ Q (XIIIa) C1OHzCHzNP-Cl m r CHFS (WM) One hundred and seventy-nine grams (1 mol) of 4- chlorophenylsulfenic acid chloride are added at 50 C. to a solution of 175 g. (1 mol) of 2-chloro-4-chloromethyl-1,3,2- 82.5 g. (1 mol) of methylsulfenic acid chloride dissolved in dioxa-phospholane, i.e. 2-chloro-4-chloromethyl-1,3-dioxa-2- 200 ml. of tetrachloromethane are added dropwise at 0 C. to phospholane, in 300 ml. of dichloromethane. The solvent is 139.5 g. (1 mol) of 2-ch1oro-3-methyl-1,3,2-oxa-azadrawn off and the residue is distilled under reduced pressure. phospholane, i.e. 2-chloro-3-methyl-1-oxa-3-aza-2- Three hundred and twelve grams (88 percent of the theory) of phospholane. After the mixture has stood for 1 hour at room O-( l,3-dichloro-prop-2-yl)-S-(4'-chlorophenyl)- temperature, the solvent is drawn off and the residue is thiolphosphoric acid diester monochloride of boiling point distilledThe N,S-dimethyl-N-(2-ch1oro-ethy1)-thiolphosphor- 194 C./l mm. Hg and refractive index n,,=1.5765 are obic acid monoester monoamide monochloride boils at 128 C. tained. under a pressure of2 mm. Hg. The yield is 182.5 g. (82.0 percent of the theory). A a] V iv YBIS a y P S for C,H,O,C|4PS (molecular weight 354.0): Calculated for C H ONCIJS (molecular weight P S Cl 222.1): 13.95% 14.44% 8.75% 9.06% 40.06% Found: 13.82% 15.00% Found: 919% 9.02% 39.55%
40. EXAMPLE 7 1 EXAMPLE 10 Y i 1 ClCH;OH -S-PCl (XIVa) Cl-H-CHz-CHz-O-If-Cl l CHa-S (XIa) G A solution of 82.5 g. (1 mol) of methylsulfenic acid chloride 33: 22 g: zggfig g gz s l l zgf g; in 100 ml. of tetrachloromethane is added dropwlse at 30 C. dichloromethane are added dropwise at 30 C. to 142.5 g u (1 9 of g g g s gif g' mol) of 2-chloro-l,3,2-oxa-thia-phospholane, i.e. 2-chloro-li x 3 oxa-3-thia-2-phospholane. The solvent is then drawn off, the p onnane' e so f w o a ter Stan, residue is distilled and there are obtained 278 g. (86 percent the mixture, and the residue 15 distilled. There are obtained in of the theory) of s (z chlom ethyl) s (4, ch|ompheny|) thls manner 206 (87 Percent of theofy) of dithiolphosphoric acid diester monochloride which boils at chlorobut'l'ylygmethymhlolphosphonc acld 180185 C. under a pressure of 1 mm. Hg and has the refracmonochloride of b.p. 124 C./] mm. Hg. tive index 020:1.6254
Analysis I Cl P S Analysis Calculated for C," ogClgPS (Molecular weight 237.1 29.1% 11MB". JQQZZQ Found: 29.70% 13-52% 1 Calculated for C.H.OC|,S,P (molecular weight 321.5):
9.84% 19.10% Found: 9.70% 20.42%
EXAMPLE 8 EXAMPLE 1 1 CHz-Cl 144.5 g. (1 mol) of phenylsulfenic acid chloride are added at 20 C. to 132.5 g. (0.5 mol) of 4,9-dichloro-3,5,8,l0- tetraoxa-4,9-diphospha-spiro-[5,5 l-undecane dissolved in 200 ml. of dichloromethane. The reaction mixture is then worked Upon repeating the procedure of example 1 using equimolar amounts of the corresponding sulfenic acid chlorides and the appropriate 2-chloro-phospholanes or (XIIa) ph0s[ horinanes the following final products are obtained:
Yield Analysis (percent) (percent 7 7 oi the B1. or Calculated Found thcorefractive .t Constitution letlcal) index Molecular weight Cl Br I S (31 13 p S O O 04 (37113020123131 23 5 28.3 10.3 21.5 27.4 10.4 \ll l Cl Bl CH2--CIIQ S Cl -C112-*C11r-0 51 2/126 C ciutozciisvczzi 43.0 12.7 13.1 41.7 13.4 13.4
I Cl Cl--C11r-S 71 0.005 ()n11n()2$1(11g(271).. 20.2 11.8 26.0 12.1 ll nmr/ -s-- 1 -0 (inventor 10445 C113 114 0.01 llllll./ (1 11n() Cl-gSl(l23). 31.8 13.11 1.4.3 211.4 14.5 14.! ll 75 (1. ClIgS P-O-CH Cl CH-C1 CH; 02 CgH OQCIQSPQSlS)... 24.0 10.0 .1417 11.5
I Cl-CHz-CHO 0 \ll ICl Q O CH; 90 0.01 C10111302C17SP(2911)... 23.7 10.4 10.7 23.5 H 10.5 11.0 H l 150 S-1OCI3H(IJII' Cl-C11-rCH-z0 O .10 rid-1.5003. Cal-1110301151: 1(317) 22.4 0.8 10.2 23.8 51.8 111.0
CH3 7 S CH; .10 np 1.51l18 Cn1115()zCl- S1(313) .17 10.11 21.19 10.0
1 C1 CJHCHO (1111 P-Cl EXAMPLE 12 EXAMPLE 13 Upon repeating the procedure of example 1 using cor- C1CH-CHO-Ps Cl responding molar amounts of each of the following sulfenic acid chlorides with the appropriate 2-chloro-phospholanes and phosphorinane: a. 3-fluorophenyl sulfenic acid chloride and 2-chloro-3-phenyl-4,4-diisobutyl- ,5 -diethyll -oxa-3-aza-2-phospholane; b. 4-bromophenyl sulfenic acid chloride and 2-chloro-3,6-disec.butyl-4,5-di-methyl-4-tert.-butyll -0xa-3-aza-2- phosphorinane; and c. 2-nitro-3-methyl-6-iodo-phenyl-sulfenic acid chloride and 2-chIoro-4-ethyl-4isopropyl-5 -methyl 5-n-butyll -oxa-3-thia- Lphospholane; the corresponding final products are obtained:
a. N-phenyl-N-[(1,1-diisobutyl-2-ethyl-2-chloro)-but-l-yl]- S-(3'-fluorophenyl)-thiolphosphoric acid monoester amide monochloride; b. N-sec.-buty1-N-[ 1,2,4,-tri-methyl-l-tert.-butyl-3-chloro)- hexl -yl -S-(4-bromophenyl )-thiolphosphoric acid monoester amide monochloride; and c. S-[( l-ethyl-1-isopropyl-2-methyl-Z-chloro)-hex-l-yl]-S- (2'-nitro-3'-methyl-6-iodo-phenyl)-dithiolphosphoric acid diester monochloride.
The following examples illustrate the manner in which the instant compounds may be converted to and used as fungicidally active final products:
The preparation is carried out without isolation of the O-( 3- chlorobut-2-yl)-S-(4'-chlorophenyl)-thiol-phosphoric acid diester monochloride of the formula (3-chloro-but-2-y)-S-(4'-chlorophenyl)-thiol-phosphoric acid ester has a boiling point of between 148 and 150 C./0.05 Torr. The yieldamounts to 197 g. (60 percent of the theory).
in analogous manner, upon use of 4-methylphenyl-sulfenic acid chloride, the O-methyl--(3-chlorobut-2-yl)-S-(4'- l0 methylphenylQthiol-phosphoric acid ester of the formula "1.'.;. :31... is obtained having a boiling point of 160 C./0.0l Torr. The yield amounts to 200 g. (65 percent of the theory). Analysis: I p 5 Calculated for c H cl. 0,?8 (molecular wt. 308.5): 10.0% 10.4% Found: 99% 10.9%
Such final products possess strong fungitoxic effect and a broad range of activity. Despite this excellent effect in combating phytopathogenic fungi, they are only slightly toxic to warmblooded animals (average toxicity DL in the rat per os 100 to 1000 mg./kg. animal), and are excellently compatible with higher plants. Due to these properties, the final products are excellently suited for use as plant protecting agents in combating fungus diseases, and specifically for combating fungi of a great variety of classes, for example, Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes, Fungi impelfecti, and the like. Such final products have proven to be particularly effective, however, in combating fungus diseases on rice plants, particularly fungus disease caused by Piricularia oryzae. These final compounds exhibit excellent protective and curative activity in combating particularly this fungus.
in addition, such final compounds may be used also for purposes of combating other fungus pathogens on rice and other cultivated plants, and are particularly effective against the fol:
lowing fungus species: Corticium sasakii; Cochliobolus miyabeanus; Mycosphaerella species; Corticium species; Cerospora species; Alternaria species; Botrytis species, and the like.
Furthermore, such final compounds exhibit very good fungicidal activity with respect to fungi which attack the plant from the soil and partially those which cause tracheomycoses, such as for example: Fusan'um cubense; Fusarium diamhi; Verticillium alboatrum, and Phialophora cinerescens.
EXAMPLE l4 Piricularia Test/Preparation of liquid active substance Solvent: l part by weight acetone Dispening agent: 0.05 part by weight sodium oleate Additive: 0.2 part by weight gelatin Water: 98.75 part: by weight water.
The quantity of the active substance necessary to obtain the desired concentration of active substance in the spray liquid, is admixed with the stated amount of solvent, and the resulting concentrate is diluted with the stated amount of water which contains the stated dispersing agent and additive.
The spray liquid is sprayed onto 30 rice plants which are about 14 days old until they are dripping wet. Until they are dry, the plants remain in a hothouse at temperatures from 22 to 24 C. and a relative humidity of about percent. Thereafter, they are inoculated with an aqueous suspension of 100,000 to 200,000 spores/ml, of Piricularia oryzae and stored in a room at a temperature between 24-26 C. and a relative humidity of percent.
Five days after the inoculation, infection is determined on all leaves present at the time of inoculation as a percent of the untreated but also inoculated control plants. 0 percent means no infection, 100 percent means that infection is as high as in the control plants.
The active substances tested, their concentrations and the results obtained are shown in the following table:
Infection as a percent oi. the infection of the untreated control plant at a. concentration of active compound (in percent) of- Active Compound (constitution) 0. 05 0.025 0.01
(I Pr. 18 50 100 ozmo)zi s-Noi (Com4parison preparation known from U.S. Pat. 2,690, 50)
OH; CH; O Pr. 0 4 l Our. 38 Cl- HCH0I|S- Cl CH; O t Pr. 0 8 I 1; Our. 13 C1-CHCH0- I -0 N02 S CH CH3 CH3 0 Pl. 1 H Our. 01-- H HO1|=S -CH; 0 CH;
C H; (H) Pr. 0 8 Cl--CH2 iJH-O-1|O- -SCH3 S C H;
OCH;
C OMPOUND Qommued Infection as a percent of the infection of the untreated control plant at a. concentration of active compound (in percent) of- Active Compound (constitution) Pr. Cur.
SCH:
SCH:
OCH:
Pr. Our.
Pr. Cur.
CH; CH;
(ll-CH- 0 0 8 L n P P w n 5 l 4 m C I 0Hv 0 J 0 0 m an HP 0 0 G a c r H H H i 4 m m CHa A CH:
TABLE.PIRICULARA TEST/LIQUID PREPARATION OF ACTIVE Actlve Compound (constitution) 2 3 fi/Nw a): 4 Cli3H-bH-OP 2 CH; 01 N(CH:)2 0 42 Cl-H-H-O N o'rE.-Pr.=protective eflect; Cur.=curative eflect.
DETERMINATION OF THE CURATIVE EFFECT with the proviso that R and R when taken together with 7 ln the ZbBGJfiEhEBEEkst' including the preparation of the l f if positifmed cafbon atom form a corresponding the liquid active substance, there is determined not only the heterocychc ""8 moiety having the stfllcwl'e protective but also the curative effect of the active compounds. Determination of the curative effect deviates from the above-described test procedure (which only supplies data re- X C garding the protective effect) in that the active compounds are applied not prior to but 16 hours after the inoculation. Compounds which in this type of test procedure shown activi- 7 ty, are capable of killing the fungus after infection and thereby have a curative efiect.
Advantageously, in accordance with the present invention, Whlch X is yg 1, 1, R5 and R, each respectively 18 in the foregoing formulae, hydrogen. 1
R,, R R R R and R, each respectively represents It Will be appreciated that the instant specification and exhydrogen; amples are set forth by way of illustration and not limitation, lower alkyl such as methyl, ethyl, nand isopropyl, n-, iso-, and that various modifications and changes may be made and y and the like, especially l-l yl, and without departing from the spirit and scope of the present inparticularly methyl; or 40 vention which is to be limited only by the scope of the apchloro-lower alkyl, especially chloro---C, alkyl, and particularly chloromethyl; R-, represents straight and branched alkyl having one to 12 carbon atoms,
such as methyl to tert.-butyl inclusive as defined above, nisoand tert.-amyl, n-hexyl, l,2,2-trimethyl-propyl, nheptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, and the like, especially lower alkyl, more especially C alkyl, en ee t s erlxmsthyla 0 such alkyl which is substituted with an oxo gro up (II),
i.e. carbonyl or aldehydo-containing C alkyl as defined above, especially carbonyl substituted lower alkyl, egd sirsss ssia y.ser s iiebs i ytssiQ14 a ky halogen-substituted alkyl having one to 12 carbon atoms, including chloro, bromo, iodo and/or fluor0C,. preferablyC, alkyl, especially mono-halo-substituted C alkyl, and particularly chloro and bromo substituted C, alkyl;
ph or .7 v .t substituted phenyl which is substituted with one to three (same or mixed) substituents in ortho, meta and/or parapositions including lower alkyl such as methyl to tert-butyl inclusive as defined above, especially C, alkyl, and particularly methyl; halo such as chloro, bromo, iodo and/or fiuoro, especially 1- 3 chloro, and particularly monochloro; and/or nitro; X represents oxygen; sulfur; N-lower alkyl amino such as N-monomethyl to tert.-butyl inclusive as defined above, -amino, especially N- C monoalkyl amino; or N-phenylamino; and n is a whole number from 0 to l;
pended claims.
What is claimed is: 1. Process for the production of chloroalkyl-S-alkyl and -S- phenyl- (di)thiolphosphoric acid ester chlorides having the formula in which R R,, R R R, and R, each respectively is selected from the group consisting of hydrogen, lower alkyl and chlorolower alkyl, R, is selected from the group consisting of alkyl having one to 12 carbon atoms, oxo-substituted isobutyl, halogen-substituted alkyl having one to 12 carbon atoms, phenyl and substituted phenyl which is substituted with one to three substituents selected from the group consisting of lower alkyl, halo, nitro and mixtures of such substituents, X is selected from the group consisting of oxygen, sulfur, N-lower alkyl amino and N-phenyl amino, and n is a whole number from 0 to 1; with the proviso that R, and R when taken together with the adjacently positioned carbon atom form a corresponding heterocyclic ring having the structure /XC 7O ClP\ \C/ 5 R0 in which X is oxygen and R,, R,, R, and R, each respectively is hydrogen which comprises reacting a 2-chloro-l-oxyphosphorous compound having the formula in to R X and n are the as defined above, with a sulfenyl chloride having the formula in which R, is the same as defined above, whereby to form such corresponding chloroalkyl-ester chloride.
2. Process according to claim 1 wherein the reaction is carried out at a temperature substantially between about -20 to 0 C.
3. Process according to claim 2 wherein said reaction is carried out in the presence of an inert organic solvent.
4. Process according to claim 2 wherein said reaction is carried out in the presence of an inert organic solvent selected from the group consisting of aliphatic hydrocarbon, chlorinated aliphatic hydrocarbon, aromatic hydrocarbon, chlorinated aromatic hydrocarbon, aliphatic ether, cycloaliphatic ether, aliphatic ketone, aliphatic nitrile, and mixtures thereof.
5. Process according to claim 4 wherein said solvent is selected from the group consisting of lower alkyl hydrocarbon, chlorinated lower alkyl hydrocarbon, benzene hydrocarbon, chlorinated benzene hydrocarbon, lower alkyl ether, lower cycloaliphatic ether, lower alkyl ketone, lower alkanoic acid nitrile, and mixtures thereof.
6. Process according to claim 2 wherein the reactants are present in substantially about equimolar amounts.
7. Process according to claim 2 wherein n is l, R and R form with the adjacently positioned carbon atom said heterocyclic ring and wherein said sulfenyl chloride is present in substantially about a percent molar excess over the amount of the corresponding 2-chloro-l-oxy-phosphorus compound present.
8. Process according to claim 2 wherein R R R R R and R each respectively is selected from the group consisting of hydrogen, C alkyl and chloromethyl, R is selected from the group consisting of C alkyl, monooxo-substituted C alkyl, monohalogen-substituted C,C alkyl, phenyl, C alkylsubstituted phenyl, chloro-substituted phenyl and nitro-substituted phenyl, X is selected from the group consisting of oxygen, sulfur and NC, -monoalkyl-amino, and n is a whole number from 0 to l, with the proviso that R and R when taken together with the adjacently positioned carbon atom form a corresponding heterocyclic ring having the structure in which X is oxygen and R R,, R, and R each respectively is hydrogen.
9. Process according to claim 8 wherein n is 0.
10. Process according to claim 8 wherein n is l.
11. Process according to claim 2 wherein R R R R R and R each respectively, is selected from the group consisting of hydrogen and methyl, R is selected from the group consisting of phenyl, 4-chlorophenyl and C alkyl, X is selected from the group consisting of oxygen, sulfur and N-C, monoalkylamino, and n is a whole number from 0 to l.
12. Process according to claim 11 wherein R, is methyl, R R R R and R each respectively is hydrogen and X is oxygen.

Claims (11)

  1. 2. Process according to claim 1 wherein the reaction is carried out at a temperature substantially between about -20* to +50* C.
  2. 3. Process according to claim 2 wherein said reaction is carried out in the presence of an inert organic solvent.
  3. 4. Process according to claim 2 wherein said reaction is carried out in the presence of an inert organic solvent selected from the group consisting of aliphatic hydrocarbon, chlorinated aliphatic hydrocarbon, aromatic hydrocarbon, chlorinated aromatic hydrocarbon, aliphatic ether, cycloaliphatic ether, aliphatic ketone, aliphatic nitrile, and mixtures thereof.
  4. 5. Process according to claim 4 wherein said solvent is selected from the group consisting of lower alkyl hydrocarbon, chlorinated lower alkyl hydrocarbon, benzene hydrocarbon, chlorinated benzene hydrocarbon, lower alkyl ether, lower cycloaliphatic ether, lower alkyl ketone, lower alkanoic acid nitrile, and mixtures thereof.
  5. 6. Process according to claim 2 wherein the reactants are present in substantially about equimolar amounts.
  6. 7. Process according to claim 2 wherein n is 1, R3 and R4 form with the adjacently positioned carbon atom said heterocyclic ring and wherein said sulfenyl chloride is present in substantially about a 100 percent molar excess over the amount of the corresponding 2-chloro-1-oxy-phosphorus compound present.
  7. 8. Process according to claim 2 wherein R1, R2, R3, R4, R5 and R6, each respectively is selected from the group consisting of hydrogen, C1 4 alkyl and chloromethyl, R7 is selected from the group consisting of C1 4 alkyl, monooxo-substituted C4 alkyl, monohalogen-substituted C1-C4 alkyl, phenyl, C1 4 alkyl-substituted phenyl, chloro-substituted phenyl and nitro-substituted phenyl, X is selected from the group consisting of oxygen, sulfur and N-C1 4-monoalkyl-amino, and n is a whole number from 0 to 1, with the proviso that R3 and R4 when taken together with the adjacently positioned carbon atom form a corresponding heterocyclic ring having the structure
  8. 9. Process according to claim 8 wherein n is 0.
  9. 10. Process according to claim 8 wherein n is 1.
  10. 11. Process according to claim 2 wherein R1, R2, R3, R4, R5 and R6, each respectively, is selected from the group consisting of hydrogen and methyl, R7 is selected from the group consisting of phenyl, 4-chlorophenyl and C1 4 alkyl, X is selected from the group consisting of oxygen, sulfur and N-C1 4-monoalkylamino, and n is a whole number from 0 to 1.
  11. 12. Process according to claim 11 wherein R1 is methyl, R2, R3, R4, R5 and R6 each respectively is hydrogen and X is oxygen.
US727738A 1968-05-08 1968-05-08 Process for the preparation of chloroalkyl-s-alkyl-and aryl- (d1) thiol-phosphoric acid diester and ester amide chlorides Expired - Lifetime US3626039A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US72773868A 1968-05-08 1968-05-08

Publications (1)

Publication Number Publication Date
US3626039A true US3626039A (en) 1971-12-07

Family

ID=24923851

Family Applications (1)

Application Number Title Priority Date Filing Date
US727738A Expired - Lifetime US3626039A (en) 1968-05-08 1968-05-08 Process for the preparation of chloroalkyl-s-alkyl-and aryl- (d1) thiol-phosphoric acid diester and ester amide chlorides

Country Status (1)

Country Link
US (1) US3626039A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4041109A (en) * 1974-03-22 1977-08-09 Philagro Diphosphorous
US4315870A (en) * 1979-01-24 1982-02-16 Rohm And Haas Company Phosphorodiamidothioates

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2765331A (en) * 1952-02-29 1956-10-02 Shell Dev Esters of phosphorus acids and process for the preparation of the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2765331A (en) * 1952-02-29 1956-10-02 Shell Dev Esters of phosphorus acids and process for the preparation of the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Petrov et al., Chem. Abstracts. Vol. 51, (1951), 9473 9474 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4041109A (en) * 1974-03-22 1977-08-09 Philagro Diphosphorous
US4315870A (en) * 1979-01-24 1982-02-16 Rohm And Haas Company Phosphorodiamidothioates

Similar Documents

Publication Publication Date Title
US3232830A (en) Insecticidal (thio) phosphinic acid esters
US2992265A (en) Phenyl phosphonic acid esters
US2828241A (en) O,o-dialkyl s-arylmercapto phosphoro-dithioate compositions and method of destroyinginsects
US3053876A (en) Phosphorus compounds and process for their production
US3499951A (en) O-alkyl,s,s-diaryl dithiophosphates
US3626039A (en) Process for the preparation of chloroalkyl-s-alkyl-and aryl- (d1) thiol-phosphoric acid diester and ester amide chlorides
US3092649A (en) Thiophosphoric acid esters and process for their production
US2857305A (en) Phosphonate esters
US2910501A (en) Thiophosphoric acid esters and process for their manufacture
US3371095A (en) Thio-or dithio-phosphoric (-phosphonic or-phosphinic) acid esters and processes for the production thereof
US3260712A (en) Alkyl phosphonic and thiophosphonic aryl ester amides
US3322864A (en) Thionophosphoric acid esters
US3234305A (en) Thiophosphorus acid esters
US3202658A (en) Thionophosphonic acid esters and a process for their production
US3164623A (en) O-cyanophenyl esters of alkylphosphonic, alkylthiophosphonic, dialkylphosphinic, anddialkylthiophosphinic acids
US3694451A (en) Certain 2-phosphorylimino-4-thiazolines
US3053847A (en) Phosphorus compounds and processes for their production
US3171853A (en) S-benzylthiomethyl neutral esters of thiophosphorus pentavalent acids
US3099674A (en) Thiophosphonic acid ester amides
US2983748A (en) Thionophosphonic acid esters
US2931824A (en) Thiophosphoric acid esters and their production
US2941920A (en) Pesticidal phosphorus esters
US2910500A (en) Phenyl sulfoxy and lower alkyl sulfoxy o, o-di (lower alkyl) thiophosphate esters and process for preparation
US3291866A (en) Thiophosphoric acid esters
US2841520A (en) Pesticidal phosphorus esters