US3801680A - O(s),s-dihydrocarbyl-n-acylphosphoroamidothio,dithoates - Google Patents

O(s),s-dihydrocarbyl-n-acylphosphoroamidothio,dithoates Download PDF

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US3801680A
US3801680A US00317315A US3801680DA US3801680A US 3801680 A US3801680 A US 3801680A US 00317315 A US00317315 A US 00317315A US 3801680D A US3801680D A US 3801680DA US 3801680 A US3801680 A US 3801680A
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2479—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1)
    • C07F9/2487—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1) containing the structure P(=X)n-N-C(=X) (X = O, S, Se; n = 0, 1)

Definitions

  • R and R individually are alkyl, alkenyl or alkynyl of up to 6 carbon atoms, Y and X individually are oxygen or sulfur, n is whole number of from 1 to 6, preferably 1 or 2, R is alkyl of 1 to 6 carbon atoms, aryl of up to 10 carbon atoms substituted with up to 2 (0 to 2) fluorine, chlorine or bromine atoms, and R is hydrogen or alkyl of 1 to 6 carbon atoms.
  • Representative alkyl groups which R, R R and R may represent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, sec-pentyl and hexyl.
  • Representative alkenyl of 3 to 6 carbon atoms which R and R may represent include allyl, Z-butenyl, 2-hexanyl, etc.
  • R and R groups are alkyl of 1 to 3 carbon atoms, especially methyl.
  • the preferred R groups is hydrogen.
  • Representative hydrocarbyl aryl R groups include phenyl, naphthyl, aralkyl of 7 to 10 carbon atoms, e.g., benzyl, 2-phenylethyl, 3-tolylpropyl, 4-phenylbutyl, and alkaryl of 7 to 10 carbon atoms, e.g., Z-methylphenyl, 3- methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 3,5- diethylphenyl and 4-t-butylphenyl.
  • halo substituted aryl R group include halophenyl of 1 to 2 fluorine, chlorine or bromine atoms such as 2-fluorophenyl, 3-chlorophenyl, 4-bromophenyl, 2,4-dichlorophenyl, 3,5-dibromophenyl, etc.; and haloaralkyl and haloalkaryl of 7 to 10 carbon atoms and 1 to 2 fluorine, chlorine or bromine atoms such as 2-fluorobenzyl, 4-chlorobenzyl, 2,4-dibromobenzyl, 2-(4-chlorophenyl)ethyl, 3-(2-fluorophenyl)propyl, 2-chloro-4-methylphenyl, 3-fluoro-4-methylphenyl, 3,5-dibromo-4-ethylphenyl, etc.
  • N alkoxyalkanoylphosphoroamidothioates of Formula I are:
  • N alkylthioalkanoylphosphoroamidothioate of Formula I are:
  • N-aryloxyalkanoylphosphoroamidothioates of Formula I are:
  • N-arylthioalkanoylphosphoroamidothioates of Formula I are:
  • N-alkylthioalkanoylphosphoroamidodithioate of Formula I are:
  • N aryloxyalkanoylphosphoroamidodithioates of Formula I are:
  • the preferred compounds of Formula I are O,S-dialkyl- N-alkoxyalkanoylthiophosphorothioate (Y and X are oxygen).
  • the most preferred compounds are O,S-dialkyl-N- alkoxyalkanoylphosphoroamidothioates wherein R, R and R are alkyl of 1 to 3 carbon atoms, n is 1 or 2, and R is hydrogen.
  • the compounds of Formula I may be prepared by acylating an appropriate O-hydrocarbyl-S-hydrocarbylphosphoroamidothioate or S-hydrocarbyl-S-hydrocarbylphosphoroamidodithioate.
  • O-alkyl S-alkylphosphoroamidothioates and their preparation are disclosed in U.S. Pat. No. 3,309,266.
  • O-alkyl-S-unsaturated hydrocarbylphosphoroamidothioate and their preparation are disclosed in U.S. 3,649,723.
  • acylating agents such as acyl halides, ketenes and acid anhydrides and conventional acylating conditions may be used in this reaction.
  • Alkoxyalkanoyl and alkylthioalkanoyl chlorides are preferred acylating agents.
  • This acylation reaction (illustrated with an acyl chloride as the acylating agent) may be represented by the following equation:
  • R, R R R Y, X, and n have the same significance as previously defined.
  • This acylation will usually be carried out at about 0 to 60 C. in the presence of solvents such a methylene chloride, chloroform, tetrahydrofuran and benzene. Pressure is not critical in this reaction. For convenience, atmospheric or autogenous pressure will be used. Under normal conditions, stoichiometric proportions or a slight deficiency of acylating agent will be used. The acylation will usually take 2 to 24 hours to reach completion.
  • the reaction product may be purified by conventional extraction and recrystallization techniques.
  • N-acylated phosphoroamidothioates of this invention may also be prepared by acylating an appropriate 0,0- dialkyl phosphoroamidothioate and then isomerizing the resulting N- acylphosphoroamidothionate with an alkylating agent to produce the O-alkyl-S-alkyl-N-acylphosphoroamidothioate.
  • This reaction scheme is represented (using an acyl chloride as the acylating agent) by the following equations:
  • R represents an alkylating agent corresponding to R
  • This acylation may be carried out by the same techniques described above for the acylation reaction depicted in Equation 1.
  • the acylation reaction (2) is also described in applicants U.S. Ser. No. 148,139, filed May 28, 1971.
  • the reaction between the N-acylphosphoroamidothionate and the alkylating agent may be done according to the procedures described in U.S. 3,309,266 for reacting 0,0-dialkylphosphoroamidothionate with an alkylating agent.
  • Suitable alkylating agents represented by R include alkyl, alkenyl, and alkynyl halides, particularly iodides, e.g., methyl iodide, ethyl iodide, allyl iodide, propargyl iodide, butyl iodide, etc. and dialkyl/dialkenyl sulfates, e.g., dimethyl sulfate, diethyl sulfate, diallyl sulfate and dihexyl sulfate.
  • iodides e.g., methyl iodide, ethyl iodide, allyl iodide, propargyl iodide, butyl iodide, etc.
  • dialkyl/dialkenyl sulfates e.g., dimethyl sulfate, diethyl sulfate, dially
  • the 0,0-dihydrocarbyl-N-acylphosphoroamidothioate (VI) can be converted to the O,S-dihydrocarbylphosphoroamidothioate (VII) by treating the 0,0- compound (V1) with a sodium alkyl mercaptide (VIH) to form the S-sodium salt and alkylating the S-sodium salt to form the O,S-compound (VII).
  • This reaction scheme is represented by the following equations:
  • the metalation reaction depicted in Equation 4 is conducted by contacting substantially equimolar amounts of the reactants (VI) and (VIII) in the liquid phase in an inert solvent at a temperature of 10-100 C.
  • the reaction is complete withinlO hours, more usually in 5 hours or less.
  • the sodium salt product (IX) may be used for further reaction without separation.
  • the alkylation of the sodium salt (D0 is effected by mixing substantially equimolar amounts of sodium salt (IX) and the alkylating agent R in an inert solvent at a tempearture of in the range of 0-80 C., preferably 25- 60 C.
  • the product (VII) is isolated by conventional methods, e.g., extraction, chromatography, etc.
  • the phosphoroarnidothioate compounds may also be prepared by amidating an appropriate 0,0-dihydrocarbylphosphorothiochloridate to obtain an 0,0-dihydrocarbyl- N-acylphosphoroamidothioate and isomerizing said N-acylphosphoroamidothioate with an alkylating agent as de- 7 scribed above.
  • This reaction scheme is illustrated by the following set of equations:
  • the S-hydrocarbyl S hydrocarbylphosphoroamidodithioate can be prepared by the reaction of phosphorous oxychloride with a mercaptan followed by amidation of the resulting S-hydrocarbyl S hydrocarbylphosphoroamidodithioate.
  • the first step of the synthesis involves the addition of 2 moles of a mercaptan to 1 mole of phosphorous oxychloride (POCl according to the following equations (if R and R are the same, a single reaction can be carried out):
  • the above reactions are preferably carried out in the presence of a weak base, such as the organic amines, for example pyridine, dimethyl aniline, triethyl amine, etc.
  • the base is preferably present in an amount at least equal to the moles of mercaptan.
  • An inert organic solvent such as diethyl ether, tetrahydrofuran, dioxane, dichloromethane, etc. may be present.
  • the reaction temperatures are generally in the range of to 13 C., preferably 0 to 5 C.
  • the reaction time necessary to complete the addition of the mercaptan to the phosphorous oxychloride will range from about 1 to hours.
  • the S-hydrocarbyl- S-hydrocarbylphosphorochloridodithioate product can be purified by distillation, crystallization or chromatography, if desired.
  • the second step of the preparation i.e. amidation, is carried out by adding gaseous ammonia or an amine to a solution of the S hydrocarbyl-S-hydrocarbylphosphorochloridodithioate according to the following equation:
  • the reaction is preferably carried out in an inert organic solvent, such as benzene, toluene, xylene and the like, at temperatures in the range of 10 to 75 C., preferably 40 to 60 C. Completion of the reaction is indicated by cessation of ammonium chloride precipitation.
  • the crude product can be isolated by filtration and then separated from ammonium chloride by selective extraction with a solvent, such as acetone, methanol or similar organic materials.
  • Houseflies (Musca domestica L.).A 500' p.p.m. acetone solution of the candidate toxicant was placed in a microsprayer (atomizer). A random mixture of anesthetized male and female flies was placed in a container and 55 mg. of the above-described acetone solution was sprayed on them. A lid was placed on the container. A mortality reading was made after 24 hours.
  • Two-spotted mites (T etramuchus urticae) .An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 100 p.p.m. Pinto bean leaves which were infested with mites were dipped in the toxicant solution. Mortality readings were taken after 24 hours.
  • Aphids (Aphis gossypii glover).An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 30 p.p.m. Cucumber leaves infested with the cotton aphids were dipped in the toxicant solution. Mortality readings were then taken after 24 hours.
  • one or more of the compounds of this invention may be applied in other liquid or solid formulations to the insects, their environment or hosts susceptible to insect attack. For example, they may be sprayed or otherwise applied directly to plants or soil so as to effect control of insects coming into contact therewith.
  • Formulations of the compounds of this invention will comprise a toxic amount of one or more phosphoroamidothioate and/or phosphoroamidodithioate and a biologically inert carrier. Usually they will also contain a wetting agent. Solid carriers such as silica, clay, talc, sawdust and the like may be used in such formulations.
  • Liquid diluents which may be used with these compounds include water and aromatic solvents.
  • these formulations may contain other compatible pesticides, plant growth regulators, fillers, stabilizers, attractants and the like.
  • insecticide and insect refer to their broad and commonly understood usage rather than to those creatures which in the strict biological sense are classified as insects.
  • insect is used not only to include small invertebrate animals belonging to the class Insecta but also to other related classes of arthropods whose members are segmented invertebrates having more or fewer than six legs, such as spiders, mites, ticks, centipedes, worms and the like.
  • R and R individually are alkyl, alkenyl or alkynyl of up to 6 carbon atoms, Y and X individually are oxygen or sulfur, n is a whole number of from 1 to 6, R is alkyl of 1 to 6 carbon atoms, aryl of up to 10 carbon atoms substituted with up to 2 fluorine, chlorine or bromine atoms, and R is hydrogen or alkyl of 1 to 6 carbon atoms.
  • R is alkyl of 1 to 6 carbon atoms
  • Y is oxygen
  • X is sulfur
  • R, R and R are alkyl of 1 to 3 carbon atoms, "R is hydrogen, and n is 1, 2 or 3.
  • R is phenyl substituted with up to 2 fluorine, chlorine, or bromine atoms and n is 1.

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Abstract

O,S-DIHYDROCARBYN-N- ACYLPHOSPHOROANIDOTHIOATES AND S,S-DIHYDROCARBYL-N- ACYLPHOSPHOROAMIDODITHIOATES HAVE A HIGH DEGREE OF INSECTICIDAL ACTIVITY WITH RELATIVELY LOW MAMMALIAN TOXICITY.

Description

United States Patent O 3,801,680 (S),S-DIHYDROCARBYL-N-ACYLPHOSPHORO- AMIDOTHIO, DITHOATES Philip S. Magee, Ignatio, Calif., assignor to Chevron Research Company, San Francisco, Calif.
No Drawing. Continuation-impart of application Ser. No. 13,846, Feb. 24, 1970, now Patent No. 3,716,600, dated Feb. 13, 1973, which is a continuation-in-part of abandoned application Ser. No. 810,383, Mar. 25, 1969. This application Dec. 21, 1972, Ser. No. 317,315
Int. Cl. C01n 9/36; C07f 9/24 U.S. Cl. 260-950 9 Claims ABSTRACT OF THE DISCLOSURE O,S-dihydrocarbyl N acylphosphoroamidothioates and S,S-dihydrocarby1 N acylphosphoroamidodithioates have a high degree of insecticidal activity with relatively low mammalian toxicity.
CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of U.S. Ser. No. 13,846, filed Feb. 24, 1970 now U.S. Pat. No. 3,716,- 600, granted Feb. 13, 1973, which, in turn, is a continuation-in-part of U.S. Ser. No. 810,383, filed Mar. 25, 1969 now abandoned.
DESCRIPTION OF THE PRIOR ART U.S. 3,309,266 teaches that O-alkylS-alkyl phosphoroamidothioates are insecticidal. U.S. 3,649,723 teaches that O-alkyl S -unsaturated hydrocarbylphosphoroamidothioates are insecticidal. U.S. 3,201,446 teaches that 0,0-diethyl-N-trichloroacetylphosphoroamidothioate [N-(diethoxyphosphinothioyl)-2,2,2-trichloroacetamide] is useful as an insecticide. Russian patent 253,483, issued on Sept. 30, 1969 to G. V. Protopopova et al., dicloses the use of O,S-dialkyl N alkylthiocarbonylphosphoroamidothioates, e.g.,
CHaO 0 CHrS as insecticides. L. Almasi et al., Chem. Ber. 100 2626 1967) and Chem. Ber. 99 3293 (1966), disclose O-ethyl- S-methyl N benzoylphosphoroamidothioate, O-ethyl-S- methyl-N-p-chlorobenzoylphosphoroamidothioate and O- ethyl S methyl-N-p-methylbenzoylphosphoroamidothioate.
DESCRIPTION OF THE INVENTION The phosphoroamidothioates and phosphoroamidodithioates of this invention are represented by the Formula l:
wherein R and R individually are alkyl, alkenyl or alkynyl of up to 6 carbon atoms, Y and X individually are oxygen or sulfur, n is whole number of from 1 to 6, preferably 1 or 2, R is alkyl of 1 to 6 carbon atoms, aryl of up to 10 carbon atoms substituted with up to 2 (0 to 2) fluorine, chlorine or bromine atoms, and R is hydrogen or alkyl of 1 to 6 carbon atoms.
Representative alkyl groups which R, R R and R may represent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, sec-pentyl and hexyl. Representative alkenyl of 3 to 6 carbon atoms which R and R may represent include allyl, Z-butenyl, 2-hexanyl, etc.
ice
Representative alkynyl of 3 to 6 carbon atoms which R and R may represent include 2-pr0pynyl, Z-butynyl, 2- hexynyl, etc. Preferred R, R and R groups are alkyl of 1 to 3 carbon atoms, especially methyl. The preferred R groups is hydrogen.
Representative hydrocarbyl aryl R groups include phenyl, naphthyl, aralkyl of 7 to 10 carbon atoms, e.g., benzyl, 2-phenylethyl, 3-tolylpropyl, 4-phenylbutyl, and alkaryl of 7 to 10 carbon atoms, e.g., Z-methylphenyl, 3- methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 3,5- diethylphenyl and 4-t-butylphenyl. Representative halo substituted aryl R group include halophenyl of 1 to 2 fluorine, chlorine or bromine atoms such as 2-fluorophenyl, 3-chlorophenyl, 4-bromophenyl, 2,4-dichlorophenyl, 3,5-dibromophenyl, etc.; and haloaralkyl and haloalkaryl of 7 to 10 carbon atoms and 1 to 2 fluorine, chlorine or bromine atoms such as 2-fluorobenzyl, 4-chlorobenzyl, 2,4-dibromobenzyl, 2-(4-chlorophenyl)ethyl, 3-(2-fluorophenyl)propyl, 2-chloro-4-methylphenyl, 3-fluoro-4-methylphenyl, 3,5-dibromo-4-ethylphenyl, etc.
Representative N alkoxyalkanoylphosphoroamidothioates of Formula I are:
O-allyl-S-methyl-N-n1ethoxyacetylphosphoroamidothioate, O-propargyl-S-methyl-N-ethoxyacetylphosphoroamidothioate, O-methyl-S-ethyl-N-ethyl-N-propoxyacetylphosphoroamidothioate, O-propyl-S-allyl-N-methoxyacetylphosphoroamidothioate, O-methyl-S-methyl-N-butoxyacetylphosphoroamidothioate, O-methyl-S-methyl-N-pentoxyacetylphoshporoamidothioate, O-methyl-S-methyl-N-hexoxyacetylphosphoroamidothioate, O-isopropyl-S-isopropyl-N-3 -methoxypropionylphosphoroamidothioate, O-methyl-S-methyl-N-3-ethoxypropionylphosphoroamidothioate, 0-allyl-S-allyl-N-isopropyl-N-3-propoxypropionylphosphoroamidothioate, O-methyl-S-methyl-N-3 -isopropoxypropionylphosphoroamidothioate, O-methyl-S-methyl-N-methyl-N-4-methoxybutyrylphosphoroamidothioate, O-methyl-S-methyl-N-4-propoxybutyrylphosphoroamidothioate, O-butyl-S-methyl-N-4-ethoxybutyrylphosphoroamidothioate, O-2-bentenyl-S-butyl-N-S-methoxypentanoylphosphoroamidothioate, O-methyl-Smethyl-N-5-methoxybutanoylphosphoroamidothioate, O-methyl-S-methyl-N-5-pentoxypentoylphosphoroamidothioate, O-methyl-S-methyl-N-6-methoxyhexanoylphosphoroamidothioate, O-methyl-S-methyl-N-6-isopropoxyhexanoylphosphoroamidothioate, O-methyl-S-pentyl-N-7-methoxyheptanoylphosphoroamidothioate, and O-methyl-S-methyl-N-7-hexoxyheptanoylphosphoroamidothioate.
Representative N alkylthioalkanoylphosphoroamidothioate of Formula I are:
O-methyl-S-allyl-N-methylthioacetylphosphoroamidothioate,
O-allyl-S-methyl-N-methyl-N-ethylthioacetylphosphoroamidothioate,
O-methyl-S-methy1-N-propylthioacetylphosphoroamidothioate, O-propargyl-S-methyl-N-butylthioacetylphosphoroamidothioate, O-methyl-S-methyl-N-pentylthioacetylphosphoroamidothioate, O-methyl-S-methyl-N-hexylthioacetylphosphoroamidothioate, O-methyl-S-methyl-N-3-methylthiopropionylphosphoroamidothioate, O-al1yl-S-al1yl-N-3-ethylthiopropionylphosphoroamidothioate, O-ethyl-S-ethyl-N-3-isopropylthiopropionylphosphoroamidothioate, O-methyl-S-methyl-N-3-propylthiopropionylphosphoroamidothioate, O-4-hexenyl-S-methyl-N-3-buty1thiopropionylphosphoroamidothioate, O-methylS-methyl-N-4-sec-butylthiobutyrylphosphoroamidothioate, O-propyl-S-isopropyl-N-isopropy1-N-4-methy1thiobutyrylphosphoroamidothioate, O-methyl-S-methyl-N-4ethylthiobutyrylphosphoroamidothioate, O-allyl-S-methyl-N-S-methylthiopentanoylphosphoroamidothioate, O-allyl-S-methyl-N-S-ethylthiopentanoylphosphoroamidothioate, O-propyl-S-2-penteny1-N-6-methy1thiohexanoylphosphoroarnidothioate, and O-hexyl-S-pentyl-N-7-methylthioheptanoylphosphoroamidothioate.
Representative N-aryloxyalkanoylphosphoroamidothioates of Formula I are:
O-methyl-S-methyl-N-ethyl-N-p-bromophenoxyacetyl phosphoroamidothioate,
O-methyl-S-allyl-N- 3-methyl-phenoxy acetylpho sphoroamidothioate,
O-allyl-S-propargyl-N-3-benzyl-oxypropionylphosphoroamidothioate and O-methyl-S-methyl-N-4- (4-chlorophenoxy butyrylphosphoroamidothioate.
Representative N-arylthioalkanoylphosphoroamidothioates of Formula I are:
' S-propyl-S-methyl-N-methoxyacetylphosphoroamidodithioate, S-allyl-S-allyl-N-butoxyacetylphosphoroamidodithioate, S-methyl-S-methyl-N-pentoxyacetylphosphoroamidodithioate, S-methyl-S-methyl-N-hexoxyacetylphosphoroamidodithioate, S-isopropyl-S-isopropyI-N-isopropyl-N-S-methoxypropionylphosphoroamidodithioate, S-methyl-S-methyl-N-3 -ethoxypropionylphosphoroamidodithioate,
S-methyl-S-methyl-N-3-propoxypropionylphosphoroamdiodithioate, S-methy1-S-methy1-N-3 -isopropoxypropionylphosphcroamidodithioate, S-2-buteny1-S-methyl-N-4-methoxybutyrylphosphoroamidodithioate, S-methyl-S-methyl-N-4-methoxybutyrylphosphoroamidodithioate, S-methyl-S-methyl-N-4-propoxybutyrylphosphoroamidodithioate, S-butyl-S-methy1-N-4-ethoxybutyrylphosphoroamidodithioate, S-butyl-S-butyl-N-S-methoxypentanoylphosphoroamidodithioate, S-methyl-S-methyl-N-S-methoxypentanoylphosphoroamidodithioate, S-allyl-S-allyl-N-5-pentoxypentanoylphosphoroamidodithioate, S-methyl-S-methyl-N-6-methoxyhexanoylphosphoroamidodithioate, S-methyl-S-methyl-N-6-isopropoxyhexanoylphosphoroamidodithioate, S-methy1-S-pentyl-N-7-methoxyheptanoylphosphoroamidodithioate and S-methyl-S-methyl-N-7-hexoxyheptanoylphosphoroamidodithioate.
Representative N-alkylthioalkanoylphosphoroamidodithioate of Formula I are:
S-methyl-S-methyl-N-methylthioacetylphosphoroamidodithioate, S-methyl-S-methyl-N-ethylthioacetylphosphoroamidodithioate, S-methyl-S-methyl-N-propy1thioacetylphosphoroamidodithioate, S-allyl-S-methyl-N-buty1tl1ioacetylphosphoroamidodithioate, S-allyl-S-a1lyl-N-pentylthioacetylphosphoroamidodithioate, S-methyl-S-methyl-N-hexylthioacetylphosphoroamidodithioate, S-methy1-S-methyl-N-3-methylthiopropiony1phos phoroamidodithioate, S-methyl-S-methyl-N-3-ethylthiopropionylphosphoroamidodithioate, S-ethyl-S-ethyl-N-3-isopropylthiopropionylphosphoroamidodithioate, S-methy1-S-methyl-N-3-propylthiopropionylphosphoroamidodithioate, S-methyl-S-methyl-N-3-butylthiopropionylphosphoroamidodithioate, S-methyl-S-methyl-N-4-sec-butylthiobutyrylphosphoroamidodithioate, S-methyl-S-methyl-N-4-methy1thiobutyrylphosphoroamidodithioate, S-methyl-S-methyl-N-4-ethylthiobutyrylphosphoroamidodithioate, S-methyl-S-allyl-N-isopropyl-N-S-methylthiopentanoylphosphoroamidodithioate, S-propyl-S-propargyl-N-5-ethylthiopentanoylphosphoroamidodithioate, S-propyl-S-butyl-N-6-methylthiohexanoylphosphoroamidodithioate and S-hexyl-S-pentyl-N-7-methylthioheptanoylphosphoroamidodithioate.
Representative N aryloxyalkanoylphosphoroamidodithioates of Formula I are:
S-allyl-SFmethy1-N-methyl-N-p-bromophenoxyacetylpho sphoroamidodithioate,
S-methyl-S-methyl-N- 3-methylphenoxy) -acety1phosph0- roamidodithioate,
S-ethyl-S-ethyl-3-benzyloxypropionylphosphoroamidodithioate and S-propargyl-S-methyl-N-4- (4-chlorophen oxy butyrylphosphoroamidodithioate.
S-methyl-S-methyl-N-4-chlorophenylthioacetylphosphoroamidodithioate,
S-allyl-S-allyl-N-benzylthioacetylphosphoroamidodithioate,
S-ethyl-S-methyl-N-3- (2,4-dichlorophenylthio propionylphosphoroamidodithioate,
S-methyl-S-methyl-N-3- 4-methylphenylthio -propionylphosphoroamidodithioate and S-isopropyl-S-prop argyl-N-propyl-N-3- (p-chlorobenzylthio propionylphosphoro amidodithioate.
The preferred compounds of Formula I are O,S-dialkyl- N-alkoxyalkanoylthiophosphorothioate (Y and X are oxygen). The most preferred compounds are O,S-dialkyl-N- alkoxyalkanoylphosphoroamidothioates wherein R, R and R are alkyl of 1 to 3 carbon atoms, n is 1 or 2, and R is hydrogen.
The compounds of Formula I may be prepared by acylating an appropriate O-hydrocarbyl-S-hydrocarbylphosphoroamidothioate or S-hydrocarbyl-S-hydrocarbylphosphoroamidodithioate. O-alkyl S-alkylphosphoroamidothioates and their preparation are disclosed in U.S. Pat. No. 3,309,266. O-alkyl-S-unsaturated hydrocarbylphosphoroamidothioate and their preparation are disclosed in U.S. 3,649,723.
Conventional acylating agents, such as acyl halides, ketenes and acid anhydrides and conventional acylating conditions may be used in this reaction. Alkoxyalkanoyl and alkylthioalkanoyl chlorides are preferred acylating agents.
This acylation reaction (illustrated with an acyl chloride as the acylating agent) may be represented by the following equation:
wherein R, R R R Y, X, and n have the same significance as previously defined. This acylation will usually be carried out at about 0 to 60 C. in the presence of solvents such a methylene chloride, chloroform, tetrahydrofuran and benzene. Pressure is not critical in this reaction. For convenience, atmospheric or autogenous pressure will be used. Under normal conditions, stoichiometric proportions or a slight deficiency of acylating agent will be used. The acylation will usually take 2 to 24 hours to reach completion. The reaction product may be purified by conventional extraction and recrystallization techniques.
N-acylated phosphoroamidothioates of this invention may also be prepared by acylating an appropriate 0,0- dialkyl phosphoroamidothioate and then isomerizing the resulting N- acylphosphoroamidothionate with an alkylating agent to produce the O-alkyl-S-alkyl-N-acylphosphoroamidothioate. This reaction scheme is represented (using an acyl chloride as the acylating agent) by the following equations:
wherein R represents an alkylating agent corresponding to R This acylation may be carried out by the same techniques described above for the acylation reaction depicted in Equation 1. The acylation reaction (2) is also described in applicants U.S. Ser. No. 148,139, filed May 28, 1971. The reaction between the N-acylphosphoroamidothionate and the alkylating agent may be done according to the procedures described in U.S. 3,309,266 for reacting 0,0-dialkylphosphoroamidothionate with an alkylating agent.
Suitable alkylating agents represented by R include alkyl, alkenyl, and alkynyl halides, particularly iodides, e.g., methyl iodide, ethyl iodide, allyl iodide, propargyl iodide, butyl iodide, etc. and dialkyl/dialkenyl sulfates, e.g., dimethyl sulfate, diethyl sulfate, diallyl sulfate and dihexyl sulfate.
Alternatively, the 0,0-dihydrocarbyl-N-acylphosphoroamidothioate (VI) can be converted to the O,S-dihydrocarbylphosphoroamidothioate (VII) by treating the 0,0- compound (V1) with a sodium alkyl mercaptide (VIH) to form the S-sodium salt and alkylating the S-sodium salt to form the O,S-compound (VII). This reaction scheme is represented by the following equations:
The metalation reaction depicted in Equation 4 is conducted by contacting substantially equimolar amounts of the reactants (VI) and (VIII) in the liquid phase in an inert solvent at a temperature of 10-100 C. The reaction is complete withinlO hours, more usually in 5 hours or less. The sodium salt product (IX) may be used for further reaction without separation.
The alkylation of the sodium salt (D0 is effected by mixing substantially equimolar amounts of sodium salt (IX) and the alkylating agent R in an inert solvent at a tempearture of in the range of 0-80 C., preferably 25- 60 C. The product (VII) is isolated by conventional methods, e.g., extraction, chromatography, etc.
The phosphoroarnidothioate compounds may also be prepared by amidating an appropriate 0,0-dihydrocarbylphosphorothiochloridate to obtain an 0,0-dihydrocarbyl- N-acylphosphoroamidothioate and isomerizing said N-acylphosphoroamidothioate with an alkylating agent as de- 7 scribed above. This reaction scheme is illustrated by the following set of equations:
r (ROh-P-Cl R -X(CH2)n-C-NH The S-hydrocarbyl S hydrocarbylphosphoroamidodithioate can be prepared by the reaction of phosphorous oxychloride with a mercaptan followed by amidation of the resulting S-hydrocarbyl S hydrocarbylphosphoroamidodithioate. The first step of the synthesis involves the addition of 2 moles of a mercaptan to 1 mole of phosphorous oxychloride (POCl according to the following equations (if R and R are the same, a single reaction can be carried out):
The above reactions are preferably carried out in the presence of a weak base, such as the organic amines, for example pyridine, dimethyl aniline, triethyl amine, etc. The base is preferably present in an amount at least equal to the moles of mercaptan. An inert organic solvent, such as diethyl ether, tetrahydrofuran, dioxane, dichloromethane, etc. may be present. The reaction temperatures are generally in the range of to 13 C., preferably 0 to 5 C. The reaction time necessary to complete the addition of the mercaptan to the phosphorous oxychloride will range from about 1 to hours. The S-hydrocarbyl- S-hydrocarbylphosphorochloridodithioate product can be purified by distillation, crystallization or chromatography, if desired.
The second step of the preparation, i.e. amidation, is carried out by adding gaseous ammonia or an amine to a solution of the S hydrocarbyl-S-hydrocarbylphosphorochloridodithioate according to the following equation:
RS\(T) RS (T) P-Cl R NHz P-NHR H0! wherein -R, R and R have the same significance as previously defined.
The reaction is preferably carried out in an inert organic solvent, such as benzene, toluene, xylene and the like, at temperatures in the range of 10 to 75 C., preferably 40 to 60 C. Completion of the reaction is indicated by cessation of ammonium chloride precipitation. Following the reaction, the crude product can be isolated by filtration and then separated from ammonium chloride by selective extraction with a solvent, such as acetone, methanol or similar organic materials.
8 The 0,0 dihydrocarbylphosphoroamidothioate compounds used to prepare the compounds of the invention are prepared by the following reactions:
The above reactions 11-13 are conducted by essentially the same procedures described for reactions 8-10.
EXAMPLES The following examples describe methods which may be used to prepare the phosphoroamidothioates and phosphoroamidodithioates of this invention. Representative compounds prepared by these methods are tabulated in Table I.
EXAMPLEI Preparation of 0,S-dimethyl N methoxyacetylphosphoroamidothioate.
A mixture of 45 'g. (0.5 mole) methoxyacetic acid and g. (0.675 mole) thionyl chloride was heated at 50 C. for 30 minutes. The reaction mixture was evaporated under reduced pressure to give the crude methoxyacetyl chloride.
A 15.5 g. sample of the crude methoxyacetyl chloride was added to 20 g. (0.142 mole) O,S-dimethylphosphoroamidothioate in 80 ml. methylene dichloride. The reaction mixture was refluxed for 3 hours and then poured into 50 m1. of water. The mixture was neutralized with aqueous sodium bicarbonate solution and extracted with methylene dichloride. The methylene dichloride extracts were dried over magnesium sulfate, filtered and evaporated under reduced pressure to give the crude product. The crude was chromatographed on silica (methylene dichloride/acetone eluant) to give the product as an oil. The elemental analysis on this product is tabulated in Table I.
EXAMPLE 11 Preparation of O,S-dimethyl-N-ethylthioacetylphosphoroamidothioate A mixture of 14.1 g. (0.1 mole) O,S-dimethylphosphoroamidothioate, 13.8 g. (0.1 mole) ethylthioacetyl chloride and 40 ml. methylene dichloride was refluxed for 2 hours. The reaction mixture was worked-up and purified by chromatography on silica by a procedure similar to that of Example I. The elemental analysis on this product is tabulated in Table I.
EXAMPLE III Preparation of 0,8-dimethyl-N-phenoxyacetylphosphoroamidothioate A mixture of 5 g. 0,0-dimethyl N-phenoxyacetylphosphoroamidothioate and 1 g. dimethyl sulfate in 5 ml. chloroform was refluxed for about 3 hours (7080 C.). The reaction mixture was chromatographed on silica (methylene chloride/acetone eluants) to give the product. Elemental analysis on this product is tabulated in Table 1.
EXAMPLE IV Preparation of O,S-dimethyl-N-phenylthioacetylphosphoroamidothioate A mixture of 9 g. 0,0-dimethyl-N-phenylthioacetylphosphoroamidothioate, 1.8 g. dimethyl sulfate and 9 ml. chloroform was refluxed for about 3 hours. The crude reaction mixture was chromatographed in silica (methylene dichloride/hexane eluants) to give the product. Elemental analysis on the product is tabulated in Table 1.
EXAMPLE V Preparation of 0,S-dimethyl-N-bromoacetylphosphoroamidothioate This compound was prepared by the reaction of O,S- dimethylphosphoroamidothioate and bromoacetyl chloride in methylene chloride by a procedure similar to that of Example IV. The product was purified by chromatography or silica (methylene dichloride/acetone eluants). Elemental analysis on the product is tabulated in Table I.
EXAMPLE VI Preparation of S,S-dimethyl-N-acetylphosphoroamidodithioate A solution of 73.2 g. (0.48 mole) of phosphorous oxychloride in 300 m1. of dry diethyl ether was charged to a 1 liter flask at a temperature of C. A solution of 76.2 g. (0.96 mole) of pyridine and 49 g. (1.0 mole) of methyl mercaptan in 400 m1. of diethyl ether was added slowly to the flask containing phosphorous oxychloride over a 2-hour period of time, maintaining the temperature from 0 C. to 5 C. The mixture was then stirred for an additional 6 hours at temperatures of 0 to C. After 18 hours of standing at 0 C. the crude reaction product was separated from the solid residue, stripped of solvent and purified to give 31.7 g. of a liquid S,S dimethylphosphorochloridodithioate.
The above S,S'dimethylphosphorochloridodithioate was then charged with 500 ml. of toluene to a 1 liter flask and ammonia gas added slowly at a temperature of 50 to 55 C. When the temperature started to drop, ammonia addition was stopped. The reaction was held at 50 C. for A hour and then cooled to room temperature and filtered. The filtrate was stripped of solvent under vacuum, then purified to give 6.6 g. of S,S-dimethylphosphoroamidodithioate. The compound had a melting point of 103-105 C., and the following N, S, P analysis:
Calculated, percent: N, 8.9; S, 41.0; -P, 19.7. Found, percent: N, 9.65; S, 38.1;P, 19.2.
S,S-dimethylphosphoroamidodithioate was dissolved in 250 ml. of dichloromethane and charged to a 500 ml. flask. 39.3 g. (90.5 mole) of acetylchloride was added. The solution was refluxed for 2 hours and stored at room temperature for 18 hours. The dichloromethane and excess acetylchloride were removed by evaporation and the product dissolved in 250 ml. of dichloromethane to which was added 250 ml. water containing suflicient calcium hydroxide to give a pH of 7 after thorough mixing. The organic phase was separated from the aqueous phase and the S,S-dimethyl N aoetylphosphoroamidodithioate recovered irom the organic phase as an oil (3.7 g.). Analysis was as follows:
Calculated, percent: N, 7.03; S, 32.1; P, 15.52. Found, percent: N, 6.48; S, 31.05; P, 14.08.
10 EXAMPLE v11 Preparation of O-allyl-S-methyl-N-acetylphosphoroamido thioate A 68 g. 1.1 mole) sample of allyl alcohol was added 5 dropwise to 84 g. (0.5 mole) phosphorous thiochloride (PSC1 at 0-10 C. The resulting reaction mixture was cooled in a Dry-Ice/acetone both while g. (1 mole) a 50% sodium hydroxide solution was added. After the addition was completed, the reaction mixture was stirred at about 25 C. for 1% hours, diluted with 200 ml. water and 50 ml. chloroform. The organic phase was separate, dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was distilled to 31.3 g. of 0,0-dial1ylphosphorochloridothioate, B.P. 72-74 C. (0.15 mm. Hg).
The above 0,0-diallylphosphorochloridothioate (30 g.) and 500 m1. benzene were then charged to a flask and ammonia (10 g.) in 100 ml. benzene was slowly added. A heavy precipitate was formed in an exothermic reaction. The reaction was evaporated to give a cloudy white liquid. The liquid was diluted with 50 ml. methylene chloride and refluxed with 10 g. of ammonium hydroxide for /2 hour. The organic layer was washed with water, dried over magnesium sulfate, filtered and evaporated to give 20 g. of 0,0-diallylphosphoroarnidothioate.
A 10 g. (0.0518 mole) sample of the above 0,0-diallylphosphoroamidothioate, 6 g. (0.059 mole) acetic anhydride, 40 ml. methylene chloride and 1 ml. phosphoric acid was refluxed for 3 hours. The reaction mixture was diluted with 50 ml. water and 100 ml. aqueous saturated ammonium chloride solution. The aqueous solution was extracted with methylene chloride. The methylene chloride extracts were washed with aqueous ammonium chloride solution, dried over magnesium sulfate and evaporated to give 10.4 g. of 0,0-diallyl-N-acetylphosphoroamidothioate.
A mixture of 10 g. (0.0425 mole) of the above 0,0- diallyl-N-acetylphosphoroamidothioate, 4.3 g. (0.0425 mole) sodium n-butyl mercaptide and 40 m1. methanol was refluxed for 4 hours and then evaporated under reduced pressure to give the crude S-sodium-O-allyl-N-acetylphosphoramidothioate salt. The salt, 6 g. dimethyl sulfate and 40 ml. acetonitrile were then refluxed for 25 hours. A heavy precipitate formed. The reaction mixture was filtered and the filtrate was evaporated under reduced pressure to give 9 g. of a yellow liquid residue. The residue was chromatographed on silica (hexane/methylene chloride/ acetone eluants) to give the S-methyl-O-allyl-N- acetylphosphoroamidothioate product as an oil. Elemental analysis for C H NO PS showed:
Calculated, weight percent: P, 14.8; S, 15.4. Found, weight percent: P, 14.62; S, 15.8.
UTILITY The compounds of this invention were tested as follows to illustrate their insecticidal activity. Test results are reported in Table II.
TABLE I Elemental analysis Percent P Percent S Melting Number Compound point Cale. Found 1 0,S-dimethyl-N-rnethoxyacetylphosphoroamldothioate Oil 14.53 13.70 2 0,S-dimethyl-N-3-methoxypropionyllphosphoroanudothioate Oil 13.61 13.23 3..- O,S-dimethyl-N-3-butoxypropionylp osph0roam1dothioate.. Oil 11.5 10.5 4... 0,S-dimethyl-N-3-isopropoxypropionylphosphoroamidothloate. 011 12.1 11.93 5.- O,S-dimethyl-N-ethylthioacetylphosphoroamidothioate Oil 12.72 11.72 6.- 0,S-dimethyl-N-3-metl'1ylthiopropionylphosphoroamidoth oate. 133-135 12.7 11.0 7 O,Sdimethyl-N-4-methylthiobutyrylphosphoroamidothioate.... 76-78 12.02 12.27 8-. O,S-dlmethyl-N-phenoxyacetylphosphoroalmdothioate Oil 11.25 10.32 9.. O,S-dimethyl-N-2,4-dichlorophenoxyacetylphosphoroamidothioate. -100 7.8 9.0 10. O,S-dlmethyl-N-phenylthioacetylphosphoroamldothioato Oil 10. 6 10. 15 11 S,S-dimethyl-N-acetylphosphoroamidodlthloate Oil 15.52 14.08 12 O-allyl-S-methyl-N-acetylphosphoroamidothioate Oil 14.8 14. 62
Test Procedures Cabbage looper (Trichoplusia ni) .An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 500 p.p.m. Cabbage leaf sections were dipped in the toxicant solution and dried. The sections were then infested with cabbage looper larvie. Mortality readings were taken after 24 hours.
American cockroach (Periplaneta americana L.).A 500 p.p.m. acetone solution of the candidate toxicant was placed in a microsprayer (atomizer). A random mixture of anesthetized male and female roaches was placed in a container and 55 mg. of the above-described acetone solution was sprayed on them. A lid was placed on the container. A mortality reading was made after 24 hours.
Houseflies (Musca domestica L.).A 500' p.p.m. acetone solution of the candidate toxicant was placed in a microsprayer (atomizer). A random mixture of anesthetized male and female flies was placed in a container and 55 mg. of the above-described acetone solution was sprayed on them. A lid was placed on the container. A mortality reading was made after 24 hours.
Two-spotted mites (T etramuchus urticae) .An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 100 p.p.m. Pinto bean leaves which were infested with mites were dipped in the toxicant solution. Mortality readings were taken after 24 hours.
Aphids (Aphis gossypii glover).An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 30 p.p.m. Cucumber leaves infested with the cotton aphids were dipped in the toxicant solution. Mortality readings were then taken after 24 hours.
TABLE II Percent mortality In addition to the specific formulations and application techniques described above, one or more of the compounds of this invention may be applied in other liquid or solid formulations to the insects, their environment or hosts susceptible to insect attack. For example, they may be sprayed or otherwise applied directly to plants or soil so as to effect control of insects coming into contact therewith.
Formulations of the compounds of this invention will comprise a toxic amount of one or more phosphoroamidothioate and/or phosphoroamidodithioate and a biologically inert carrier. Usually they will also contain a wetting agent. Solid carriers such as silica, clay, talc, sawdust and the like may be used in such formulations.
Liquid diluents which may be used with these compounds include water and aromatic solvents. In addition these formulations may contain other compatible pesticides, plant growth regulators, fillers, stabilizers, attractants and the like.
The term insecticide 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 is used not only to include small invertebrate animals belonging to the class Insecta but also to other related classes of arthropods whose members are segmented invertebrates having more or fewer than six legs, such as spiders, mites, ticks, centipedes, worms and the like.
As will be evident to those skilled in the art, various modifications on this invention 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.
What is claimed is:
1. A compound of the formula wherein R and R individually are alkyl, alkenyl or alkynyl of up to 6 carbon atoms, Y and X individually are oxygen or sulfur, n is a whole number of from 1 to 6, R is alkyl of 1 to 6 carbon atoms, aryl of up to 10 carbon atoms substituted with up to 2 fluorine, chlorine or bromine atoms, and R is hydrogen or alkyl of 1 to 6 carbon atoms.
2. Compound of claim 1 wherein R is alkyl of l to 6 carbon atoms and Y and X are oxygen.
3. Compound of claim 1 wherein R, R and R are alkyl of 1 to 3 carbon atoms and n is 1 or 2.
4. O,S-dimethyl N methoxyacetylphosphoroamidothioate.
5. Compound of claim 1 wherein R is alkyl of 1 to 6 carbon atoms, Y is oxygen, and X is sulfur.
6. Compound of claim 5 wherein R, R and R are alkyl of 1 to 3 carbon atoms, "R is hydrogen, and n is 1, 2 or 3.
7. Compound of claim 6 wherein R and R are methyl, R is ethyl and n is 1.
8. Compound of claim wherein R is phenyl substituted with up to 2 fluorine, chlorine, or bromine atoms and n is 1.
9. Compound of claim 8 wherein R and R are methyl, R is phenyl, Y is oxygen and X is oxygen.
References Cited FOREIGN PATENTS 1,067,433 10/ 1959 Germany 260-948 ANTON H. SUTTO, Primary Examiner US. Cl. X.R.
' P -w UNITED STATES PATENT OFFICE 9 V V CERTIFICATEOF CORRECTION Patent I a ,a0 1",se0 Dated April 2 197 Inventor(s) Philip S. Magee It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Col. 12, line +8, "claim wherein" should read --Claim 1 wherein---.
Signed arzd sealed this 24th day of September 1974.
(SEAL) Attest:
McCOY M. GIBSON JR. c. MARSHALL DANN Attesting Officer Commissioner of Patents
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0014386A2 (en) * 1979-01-24 1980-08-20 Rohm And Haas Company Phosphoramido(di)thioate derivatives, processes for their preparation and pesticidal compositions containing them, as well as intermediates
US4299783A (en) * 1980-04-28 1981-11-10 Chevron Research Company 1-Alkylsulfonyl-3-substituted phosphinylthio- or phosphinothioylthio-propenes
US20030100604A1 (en) * 2000-03-28 2003-05-29 Reiner Fischer Active substance combinations having insecticidal and acaricidal properties
US6576661B1 (en) 1999-11-09 2003-06-10 Bayer Aktiengesellschaft Active ingredient combination having insecticidal and acaricidal characteristics
US7060692B2 (en) 2000-08-31 2006-06-13 Bayer Cropscience Ag Active ingredient combinations comprising insecticidal and acaricidal properties

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0014386A2 (en) * 1979-01-24 1980-08-20 Rohm And Haas Company Phosphoramido(di)thioate derivatives, processes for their preparation and pesticidal compositions containing them, as well as intermediates
EP0014386A3 (en) * 1979-01-24 1980-10-15 Rohm And Haas Company Phosphoramido(di)thioate derivatives, processes for their preparation and pesticidal compositions containing them, as well as intermediates
US4299783A (en) * 1980-04-28 1981-11-10 Chevron Research Company 1-Alkylsulfonyl-3-substituted phosphinylthio- or phosphinothioylthio-propenes
US6576661B1 (en) 1999-11-09 2003-06-10 Bayer Aktiengesellschaft Active ingredient combination having insecticidal and acaricidal characteristics
US6818670B2 (en) 1999-11-09 2004-11-16 Bayer Aktiengesellschaft Active ingredient combination having insecticidal and acaricidal characteristics
US20030100604A1 (en) * 2000-03-28 2003-05-29 Reiner Fischer Active substance combinations having insecticidal and acaricidal properties
US6900190B2 (en) 2000-03-28 2005-05-31 Bayer Aktiengesellschaft Active substance combinations having insecticidal and acaricidal properties
US7060692B2 (en) 2000-08-31 2006-06-13 Bayer Cropscience Ag Active ingredient combinations comprising insecticidal and acaricidal properties

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