O,O-dialkyl-{62 -phenylthiovinyl phosphates used as mollusicides
United States Patent 1 [111 3,881,001  
 Brown 5] Apr. 29, 1975 1 0,0-DlALKYL-B-PHENYLTHIOVINYL 3.584.084 6/1971 Brown 260/949 PHOSPHATES USED AS MOLLUSICIDES 3,796 799 3/1974 Brown 424/216 [75] Inventor: Melancthon S. Brown, Berkeley,  
 Calif.  
 [73] Assignee: Chevron Research Company, San  
 Francisco, Calif.  
 [22] Filed: Dec. 17, 1973 [21] App]. No.: 425,463  
 Related U.S. Application Data [62] Division of Ser. No. 128,600, Dec. 4 1970 Pat. No. 3.796.799, which is a division of Set. No. 704.557 Feb. 12, 1968. Pat. No. 3,584,084.  
 [52] U.S. Cl. 424/216 [51] Int. Cl A0ln 9/36 [58] Field of Search 424/216; 260/949 [56] References Cited UNITED STATES PATENTS 2.864.740 12/1958 Dively 260/948 X Primary ExaminerAlbert T. Meyers Assistant ExaminerLeonard Schenkman Attorney, Agent, or FirmG. F. Magdeburger; John Stoner, Jr.; Raymond Owyang [57] ABSTRACT Vinyl phosphates of the formula:  
 where R is alkyl of 1 to 4 carbon atoms and X is hydrogen, halogen of atomic number 17 to 35 or alkyl of 1 to 4 carbon atoms are useful as insecticides and molluscicides.  
 5 Claims, No Drawings 0,0-DIALKYL-B-Pl-IENYLTl-IIOVINYL PHOSPHATES USED AS MOLLUSICIDES This application is a division of application Ser. No.  
 128,600, filed Dec. 4, 1970, now U.S. Pat. No. 5 3,796,799 which in turn is a division of application Ser. EXAMPLE 1 704557, filed Feb. 12, 1968., now A benzene solution of 14.45 g. 2-chloro-2-p-chloro- 3,584.084. phenylthioacetaldehyde was put in a flask and heated H to reflux. 9 g. of triemthyl phosphite in 10 ml. benzene J I I 10 was then added dropwise to the refluxing mixture. The X Q- 3 total mixture was refluxed for 4 hrs. The benzene and c1 excess phosphite were removed at 60C. under water I vacuum to give 19.25 g. of 0,0-dimethyl-B-p-chlorophenylthiovinyl phosphate. The C1 and S anaylsis of 0 5 this oily compound were 1 Calculated: c1. 12.02%; 5. 10.85%. X-S-C=C-O-1(OR) 1101 Found: C]: 12.58%; S: 11.30%.  
  Other vinyl phosphates of this invention were made by the general method described in Example 1. They 11 are reported in Table l. i  
 TABLE I Element Analyses Cl S Compound Calc. Found Calc. Found Calc. Found 0,0-diethyl-}8-p-chlorophenylthiovinyl phosphate 1 1.0 l 1.7 9.92 10.24 0,0-dimethyLB-p-tolylthiovinyl phosphate 1 1.63 l 1.77 1 1.30 10.62 Qo-diethyl-fi-p-to1ylthioviny1 phosphate 10.57 10.61 10.25 10.10 0,0-diisopropyl-B-p-tolylthiovinyl phosphate 9.70 9.31 9.39 8.40  
 0,0-diisopropyl-B-p-chlorophenylthiovinyl phosphate 10.1 10.55 9.13 9.1 l 0.0-di-n-butyl-fi-p-chlorophenylthiovinyl phosphate 9.36 9.24 8.45 8.31 0,0-diethyl-B-phenylthiovinyl phosphate 1 1.1 l 1.05 10.75 10.60 0,0-dimethyl-B-phenylthiovinyl phosphate 12.3 12.01 11.9 12.0  
 X and R are as defined previously. This reaction will UTILITY normally be carried out at temperatures in the range of to 150C. and atmospheric or autogenous pressures. An inert solvent such as benzene, toluene, methylene chloride, chloroform, ethyl ether, etc., will normally be used. The reaction time will usually be about 5 minutes to 48 hours.  
  The aldehyde reactant 1 may be prepared by reacting a p-substituted phenylsulfenyl halide, preferably a chloride, with acetaldehyde and chlorinating the carbon atom of the resulting product which is between the sulfur and the carbonyl group with a chlorinating agent such as sulfuryl chloride or chlorine. It may also be prepared by reacting a p-substituted alkali metal phenate with chloroacetaldehyde and chlorinating the resulting product as described above. A third procedure to prepare the aldehyde reactant is to react a p-substituted phenylsulfenyl halide with an alkylvinyl ether, react the resulting alkyl-1-halo-2-phenylthio ether with water and chlorinate that reaction product as described above.  
 EXAMPLES The following examples illustrate specific vinyl phosphates of this invention and their preparation. These The phosphates of this invention have exhibited exceptional abilities for controlling insects and mollusks. In general their molluscicidal activities are unexpectedly better than those of structurally related compounds. Also, the residual miticidal activities of these phosphates, especially those wherein X in the above formulae is chlorine, are vastly superior to most structurally related compounds.  
  The terms insecticide&#34; and insect as used herein refer to their broad and commonly understood usage rather than to those creatures which in the strict biological sense are classified as insects. Thus the term insect not only includes small invertebrate animals belonging to the class Insecta, but also other classes of arthropods whose members are segmented invertebrates having more or fewer than six legs such as mites, ticks, spiders, centipedes, worms and the like.  
  The term residual&#34; as used herein refers to the longevity of the effectiveness of the phosphate. It expresses the ability of controlling organisms which are not contacted by the phosphate at the time it is applied 5 to the organisms environment.  
 residual miticidal activity of these compounds was demonstrated by testing representative phosphates as follows:  
  A 1% acetone solution of the test phosphate was diluted with water to a concentration of I000 ppm. This mixture was sprayed on 4 replicate pinto bean plants at a dosage of 1000 ppm./l gal./acre. After spraying, the bean plants were placed in a greenhouse and allowed to weather for 24 hours. The plants were then infested with two-spotted mites (Tetranychus telarius L.). After 24 hours a mortality reading was taken on 20 randomly chosen mites. The dead out of 20 are represented in Table II. Dimethyl-B-chloro-B-p-chlorophenylthiovinyl phosphate was also tested by this procedure as a comparison compound.-lts control is also reported in Table II.  
  The molluscicidal activities of representative phosphates of this invention were determined by contacting common garden snails (Helix spp.) with filter papers impregnated with 20 mgs. of the test phosphate. Two replicates were used with 5 snails per replicate. Mortality readings were made after 24 hours exposure. The effectiveness of each compound, reported as control, appears in Table II. Dimethyl-B-chloro-B-p-chlorophenylthiovinyl phosphate was tested by this procedure as a comparison compound. Its control is also reported in Table III.  
 TABLE II used in formulating these phosphates include organic compounds such as acetone, benzene, and toluene. Pesticidal formulations of these phosphates may also contain dispersing agents, emulsifying agents, stickers, stabilizers and the like. These phosphates may be applied individually or in mixtures with other phosphates of this invention, and may also be used with other active compatible toxicants in theformulation of pesticidal compositions.  
  These phosphates may be applied in insecticidal or molluscicidal quantities directly to the organism. Or, they may be applied to any environmental area which hosts insects or mollusks or are susceptible to their attack. For example, they may be sprayed or otherwise applied directly to plants or other hosts, may be applied to plant seeds, sprayed upon soil or other plant environments or used in similar ways to control insects and mollusks.  
  As will be evident to those skilled in the art, various modifications on this process can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims.  
 I claim:  
  1. A method of killing mollusks which comprises contacting the mollusks with a molluscicidally effective amount of a compound of the formula RESIDUAL MITICIDAL ACTIVITY Compound Control 0,0-dimethyl-B-p-chlorophenylthiovinyl phosphate 0.0-diethyl-B-p-chlorophenylthiovinyl phosphate COMPARISON COMPOUND 0,0-dimethyI-B-chloro-B-p-chlorophenylthiovinyl phosphate TABLE III MOLLUSCICIDAL ACTIVITY Compound Control COMPARISON COMPOUND 0,0-dimethyl-B-chIoro-B-p-chlorophenylthiovinyl phosphate It was also discovered that the vinyl phosphates of 50 this invention are significantly less toxic to mammals than corresponding phosphates having a methyl substituent on the a-carbon atom. For instance in oral applications using laboratory rats, 0,0-dimethyl-oz-methyl-flp-chlorophenylthiovinyl phosphate was about to times as toxic as 0,0-dimethyl-B-p-chlorophenylthiovinyl phosphate. In like tests, 0,0-diethyl-a-methyl-B-pchlorophenylthiovinyl phosphate was about 5 times as toxic as 0,0-diethyl-B-p-chlorophenylthiovinyl phosphate. This fact makes the compounds of this invention more desirable than their corresponding a-methyl substituted analogs for use in mammalian environment.  
  .Aside from the specific formulations of the phosphates of this invention as reported in the foregoing tests, these phosphates may be dispersed in or upon other inert liquid and solid carriers. The solid carriers, such as clay, may be in the form of dusts, granules or wettable powders. The liquid diluents which may be drogen or methyl.  
  3. The method of claim 2 wherein R is methyl or ethyl.  
  4. The method of claim 3 wherein R is methyl and X is chlorine.  
 5. The method of claim 3 wherein R is ethyl and X is chlorine.  
 UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,881,001  
 DATED April 29, 1975 INVENT 3 MELANCTHON S. BROWN It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
  Column 1, lines 7 and 8, after &#34;now U. S. Pat. No. 3 ,584 ,084. the following was omitted:  
 -FIELD OF INVENTION This invention relates to novel vinyl phosphates and their use as pesticides. More particularly, it concerns a unique group of 0,0-dialkyl-B-phenylthiovinyl phosphates and their use as insecticides and molluscicides.  
 DESCRIPTION OF INVENTION The vinyl phosphates of this invention may be represented by the formula:  
 where R is alkyl of l to 4 carbon atoms and X is hydrogen,  
 halogen of atomic number 17 to 35 or alkyl of 1 to 4 carbon atoms. The R&#39;s may be the same or different. Where R represents propyl or butyl, these radicals are preferably straight chain. X may also be methyl, ethyl, propyl or butyl. Preferably, X is chlorine and R is methyl or ethyl.  
  Specific examples of vinyl phosphates encompassed within the above genus are 0,0-dimethyl-B-p-chlorophenylthiovinyl phosphate, 0,0-dimethyl-B-p -bromophenylthiovinyl phosphate, 0,0-dimethyl-B-pbutylphenylthiovinyl phosphate, 0,0-dimethylB-g-tolylthiovinyl phosphate, O-methyl-O-ethyl-B-p-tolylthiovinyl phosphate, 0,0- diethyl-B-p-ethylphenylthiovinyl phosphate, 0,0-diethylB-pbromo phenylthiovinyl phosphate, 0,0-di-n-propyl-Bp chlorophenylthiovinyl phosphate,0,0-di-iso-propyl-B-phenylthiovinyl phosphate, 0,0di-npropyl-B-p-bromophenylthiovinyl phosphate and 0,0-di r 1 butyl-Bp chlorophenylthiovinyl phosphate.  
 UNITED STATES PATENT AND TREMARK OFFIQE CERTIFICATE OF CECTIQ PATENT NO. 3 ,881, 001 Page 2 DATED April 29, 1975 INVENTOR(S) MELANCTHON s BROWN It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
  The 0,0-dialkyl-B-substituted vinyl phosphates of this invention may be prepared by reacting an appropriate aldehyde with a trialkyl phosphite. This reaction proceeds according to the following equation:-  
 Signed an second al 0 [SEAL] Attesl:  
 RUTH C. MASON C. MARSHALL DAMN Arresting Officer Commissioner oflatents and Trademarks