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US3886238A - S,S-dialkyl-N-substituted phosphoroamidodithionites - Google Patents

S,S-dialkyl-N-substituted phosphoroamidodithionites Download PDF

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US3886238A
US3886238A US466433A US46643374A US3886238A US 3886238 A US3886238 A US 3886238A US 466433 A US466433 A US 466433A US 46643374 A US46643374 A US 46643374A US 3886238 A US3886238 A US 3886238A
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phosphoroamidodithionite
carbon atoms
propyl
butyl
alkyl
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Iii Francis J Freenor
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Chevron USA Inc
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Chevron Research and Technology Co
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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
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/564—Three-membered rings
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/59—Hydrogenated pyridine rings

Definitions

  • the present invention is directed to phosphoroamidodithionites, more particularly S,S-dialkyl- N-monoand di-substituted phosphoroamidothionites and their use as insecticides and/or herbicides.
  • R and R are independently alkyl of 1 to 8 carbon atoms, preferably alkyl of l to 4 carbon atoms and more preferably alkyl of 3 to 4 carbon atoms, or alkenyl of 2 to 8 carbon atoms, preferably alkenyl of 2 to 4 carbon atoms, R, is hydrogen or alkyl of l to 4 carbon atoms, R, is hydrogen, alkyl or 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, aryl of 6 to 15 carbon atoms substituted with O to 5 halogen atoms of atomic number 9 to 35 or alkyl groups of l to 4 carbon atoms, or an acyl group of 2 to 4 carbon atoms, with the proviso that R and R may be joined to form an alkylene radical of 2 to 5 carbon atoms, preferably 4 to 5 carbon atoms.
  • the aryl groups which R, may represent are preferably benzyl or phenyl, either being substituted with to halogen atoms of atomic number 9 to 35 or alkyl groups of l to 4 carbon atoms. More preferably, R is phenyl substituted with 0 to 2 halogen atoms of atomic number 9 to I7 or alkyl of l to 2 carbon atoms, and still more preferably, phenyl substituted with 0 to I chlorine or fluorine atom.
  • R R R and R may represent include methyl, ethyl, n-propyl, isopropyl, butyl, t-butyl, etc.
  • Representative alkenyl groups which R R and R may represent include vinyl, allyl, crotyl, etc.
  • R and R may also be pentyl, hexyl, octyl, etc.
  • R, and R will be the same, or will be alkyl.
  • R is preferably alkyl or aryl optionally substituted as the case may be.
  • aryl groups which R may represent include phenyl, naphthyl, benzyl, o-chlorophenyl, ofluorophenyl, o-bromophenyl, p-fluorophenyl, mchlorophenyl, o-methylphenyl, p-butylphenyl, obutylphenyl, 0,p-dichlorophenyl, pentachlorophenyl, o-chloro-p-methylphenyl, o-fluoro-m-chlorophenyl, 2-chloronaphthyl, etc.
  • radicals which R and R joined together with nitrogen may represent include piperidyl, pyrrolidyl and morpholine.
  • acyl groups which R may represent include acetyl, propionyl and butyryl.
  • Representative compounds of the present invention include S,S-dimethyl-N-butyl phosphoroamidodithionite, S,S-dimethyI-N-phenyl phosphoroamidodithionite, S,S-diethyl-N,N-dimethyl phosphoroamidodithionite, S,S-dimethyl-N-acetyl phosphoroamidodithionite,
  • the compounds of the present invention are prepared by the reaction of an appropriate S,S-dialiphatic hydrocarbyl phosphorus halide with ammonia with a suitable amine or with an appropriate amide according to the following reaction:
  • R S R P X HN R S t R R S R P N HX R 3 R wherein R R R and R are as indicated above and X is a halogen, preferably chlorine.
  • the reaction is accomplished by adding the ammonia or amine slowly to the phosphorus chloride.
  • an excess e.g., up to twice the molar amount of ammonia, amide or the amine can be used.
  • the excess reactant acts as a base acceptor to react with the evolved HX and thereby neutralize it.
  • the reaction is preferably carried out in the presence of an inert solvent, such as methylene chloride ether, benzene, hexane, etc.
  • a molecular seive is preferably present which serves as a drying agent for the solvent amine. The amount of molecular seive should be enough to assure substantially complete removal of any H20.
  • the solvent is preferably added to the phosphorus chloride and the amine added slowly to the phosphorus chloride-solvent mixture.
  • the above reaction is preferably carried out at a temperature from 78 to 30C.
  • the product can be recovered by conventional means.
  • the reaction mixture may be stripped of solvent, the product washed with water and dried over magnesium sulfate.
  • the phosphorus chloride is known in the art and can be prepared as for example by the procedure in US. Pat. No. 3,210,244.
  • a suitable mercaptan may be EXAMPLE 1
  • Ammonia (large excess based on the amount of 8,8- dibutyl phosphorus chloride) was dissolved in methylene dichloride, cooled to dry ice temperature. A small number of molecular sieves were added.
  • S,S-dibutyl phosphorus chloride, 6.5 g. (0.03 mole) was then added slowly. A solid white precipitate resulted.
  • the reaction mixture was slowly warmed up to room temperature and left standing approximately 48 hours. The white solid was removed and the remaining solution stripped to obtain an oil having the following analysis:
  • the compounds of the present invention are, in general, herbicidal in both preand post-emergence applications. For pre-emergence control of undesirable vegetation these compounds will be applied in herbicidal quantities to the environment, cg, soil infested with seeds and/or seedlings of such vegetation. Such application will inhibit the growth of or kill the seeds, germi nating seeds and seedlings. For postemergence applications the compounds of the present invention will be applied directly to the foliage and other plant parts. Generally they are effective against wced grasses as well as broadleaved weeds. Some may be selective with respect to type of application and/or type of weed.
  • acetone solution of the test compound was prepared by mixing 750 mg. compound, 220 mg. ofa nonionic surfactant and 25 ml. of acetone. This solution was added to approximately 125 mi. of water containing 156 mg. of surfactant Seeds of the test vegetation were planted in a pot of soil and the compound solution was sprayed uniformly onto the soil surface at a dose of lOO micrograms per cm The pot was watered and placed in a greenhouse. The pot was watered intermittently and was observed for seedling emergence, health of emerging seedlings, etc. for a 3-week period. At the end of this period the herbicidal effectiveness of the compound was rated based on the physiological observations. A to 100 scale was used; 0 representing no phytotoxicity, 100 representing complete kill.
  • the test compound was formulated in the same manner as described above for the pre-emergence test.
  • the concentration of the compound in this formulation was 5000 ppm.
  • This formulation was uniformly sprayed on 2 replicate pots of 24-day-old plants (approximately 15 to 25 plants per pot) at a dose of lOO micrograms per cm After the plants had dried, they were placed in a greenhouse and then watered intermittently at their bases as needed. The plants were observed periodically for phytotoxic effects and physiological and morphological responses to the treatment. After 3 weeks the herbicidal effectiveness of the compound was rated based on these observations. A O to I00 scale was used; 0 representing no phytotoxicity. 100 representing complete kill.
  • compositions containing about 0.5 to 8 lbs. compound per 100 gal. spray will be used. Such application is equivalent to about 0.5 to 20 lbs. compound per acre.
  • the herbicidal compositions of this invention comprise a herbicidal amount of one or more of the above described compounds intimately admixed with a biologically inert carrier.
  • the carrier may be a liquid diluent such as water or acetone or a solid.
  • the solid may be in the form of dust powder or granules.
  • These compositions will also usually contain adjuvants such as a wetting or dispersing agent to facilitate their penetration into the plant growth media or plant tissue and generally enhance their effectiveness.
  • These compositions may also contain other pesticides, stabilizers, conditioners, fillers and the like.
  • the compounds of the present invention also possess Test Procedures Two-spotted Mites (Tetranychus urticae): An acetone solution of the candidate toxicant conmersed in the toxicant solution and then allowed to dry at room temperature for seven days at 85F. On the eighth day the egg mortality was rated on a scale of to l l; 0 representing no kill, 1 l representing 100% kill.
  • one or more of the compound derivatives of the invention may be applied in other liquid or solid formulations to the insects, their environment, or hosts susceptible to insect attack.
  • 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 carbamate de rivatives and a biologically inert carrier. Usually they will also contain a wetting agent. Solid carriers such as 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 concentration of the active ingredient to be used with inert carriers will be dependent upon many factors, such asthe particular carbamate compound which is used, the carrier in or upon which it is incorporated, the method and conditions of application, the insect species to be controlled, etc., the proper consideration of these factors being within the skill of these versed in the art.
  • the toxic ingredients of this invention will be effective in concentrations from about 0.000] percent by weight to as high as 90 percent by weight or higher. Economically, of course, it is desirable to use lower concentrations of this active ingredient. Thus, it is usually desirable to use less than percent by weight of the active ingredient in a particular composition.
  • 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 lnsecta 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.
  • Some of the compounds of the present invention are also useful in the control of nematodes and algae, for example Euglena.
  • R, and R are independently alkyl of l to 8 carbon atoms or alkenyl of 2 to 3 carbon atoms, R, is hydrogen or alkyl of l to 4 carbon atoms and R, is acyl of 2 to 4 carbon atoms.
  • R, and R are independently alkyl of l to 8 carbon atoms.
  • R and R are independently alkyl of 3 to 4 carbon atoms.

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Abstract

Compounds of the formula

WHEREIN R1 and R2 are independently alkyl of 1 to 8 carbon atoms, or alkenyl of 2 to 8 carbon atoms, R3 is hydrogen or alkyl of 1 to 4 carbon atoms, and R4 is hydrogen, alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, acryl of 6 to 15 carbon atoms optionally substituted with halogen atoms or alkyl groups of 1 to 4 carbon atoms or an acyl group of 2 to 4 carbon atoms, with the proviso that R3 and R4 may be joined to form an alkylene radical of 2 to 5 carbon atoms. The compounds possess insecticidal and herbicidal activity.

Description

United States Patent Freenor, III
[ S,S-DIALKYL-N-SUBSTITUTED PHOSPHOROAMIDODITHIONlTES [75] Inventor: Francis J. Freenor, Ill,
Richmond, Calif.
[73] Assignee: Chevron Research Company, San
Francisco, Calif.
[22] Filed: May 2, 1974 [21] Appl. No.: 466,433
Related US. Application Data [62] Division of Ser. No. 219,559, Jan. 20, 1972, Pat. No.
[52] US. Cl 260/959; 260/247.l R [5 l] Int. Cl C07f 9/24; AOln 9/36 [58] Field of Search 260/959 [56] References Cited UNITED STATES PATENTS 2,995,596 8/1961 Debo et al. 260/959 X Primary Examiner-Anton H. Sutto Attorney, Agent, or Firm-G. F. Magdeburger; Dix A. Newell; Raymond Owyang [4 1 May 27, 1975 [57] ABSTRACT Compounds of the formula wherein R and R are independently alkyl of l to 8 carbon atoms, or alkenyl of 2 to 8 carbon atoms, R is hydrogen or alkyl of l to 4 carbon atoms, and R is hydrogen, alkyl of l to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, acryl of 6 to 15 carbon atoms optionally substituted with halogen atoms or alkyl groups of l to 4 carbon atoms or an acyl group of 2 to 4 carbon atoms, with the proviso that R and R may be joined to form an alkylene radical of 2 to 5 carbon atoms, The compounds possess insecticidal and herbicidal activity.
9 Claims, N0 Drawings 1 S,S-DIALKYL-N-SUBSTITUTED PHOSPHOROAMIDODI'IHIONITES This is a division of application Ser. No. 219,559, filed Jan. 20, I972, now US. Pat. No. 3,832,424
BACKGROUND OF THE INVENTION Field The present invention is directed to phosphoroamidodithionites, more particularly S,S-dialkyl- N-monoand di-substituted phosphoroamidothionites and their use as insecticides and/or herbicides.
DESCRIPTION OF THE INVENTION Compounds of the present invention may be represented by the formula R S R P ll R I R wherein R and R are independently alkyl of 1 to 8 carbon atoms, preferably alkyl of l to 4 carbon atoms and more preferably alkyl of 3 to 4 carbon atoms, or alkenyl of 2 to 8 carbon atoms, preferably alkenyl of 2 to 4 carbon atoms, R, is hydrogen or alkyl of l to 4 carbon atoms, R, is hydrogen, alkyl or 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, aryl of 6 to 15 carbon atoms substituted with O to 5 halogen atoms of atomic number 9 to 35 or alkyl groups of l to 4 carbon atoms, or an acyl group of 2 to 4 carbon atoms, with the proviso that R and R may be joined to form an alkylene radical of 2 to 5 carbon atoms, preferably 4 to 5 carbon atoms.
The aryl groups which R, may represent are preferably benzyl or phenyl, either being substituted with to halogen atoms of atomic number 9 to 35 or alkyl groups of l to 4 carbon atoms. More preferably, R is phenyl substituted with 0 to 2 halogen atoms of atomic number 9 to I7 or alkyl of l to 2 carbon atoms, and still more preferably, phenyl substituted with 0 to I chlorine or fluorine atom.
Representative alkyl groups which R R R and R may represent include methyl, ethyl, n-propyl, isopropyl, butyl, t-butyl, etc. Representative alkenyl groups which R R and R may represent include vinyl, allyl, crotyl, etc. R and R may also be pentyl, hexyl, octyl, etc. Preferably R, and R will be the same, or will be alkyl. R is preferably alkyl or aryl optionally substituted as the case may be.
Representative aryl groups which R may represent include phenyl, naphthyl, benzyl, o-chlorophenyl, ofluorophenyl, o-bromophenyl, p-fluorophenyl, mchlorophenyl, o-methylphenyl, p-butylphenyl, obutylphenyl, 0,p-dichlorophenyl, pentachlorophenyl, o-chloro-p-methylphenyl, o-fluoro-m-chlorophenyl, 2-chloronaphthyl, etc.
Representative radicals which R and R joined together with nitrogen may represent include piperidyl, pyrrolidyl and morpholine.
Representative acyl groups which R may represent include acetyl, propionyl and butyryl.
Representative compounds of the present invention include S,S-dimethyl-N-butyl phosphoroamidodithionite, S,S-dimethyI-N-phenyl phosphoroamidodithionite, S,S-diethyl-N,N-dimethyl phosphoroamidodithionite, S,S-dimethyl-N-acetyl phosphoroamidodithionite,
2 S-methyl-S-ethyl-N-isopropyl phosphoroamidodithionite, S-methyl-S-ethyl-N-vinyl phosphoroamidodithio nite, S,S-diethyl-N,N-diethyl phosphoroamidodithionite, S,S-diisopropyl-N-methyl phosphoroamidodithionite, S,S-n-butyl phosphoroamidodithionite, S-methyl- S-hexyl-N-ethyl-N-propionyl phosphoroamidodithionite, S-propyl-S-allyl-N-methyl-N-phenyl phosphoroamidodithionite, S-methyl-S-vinyl-N-methyl phosphoroamidodithionite, S,S-dipropyl-N-2- chlorophenyl phosphoroamidodithionite, S,S-dibutyl- N-2,4-dichlorophenyl phosphoroamidodithionite, S,S-dibutyI-N-Z-ethylphenyl phosphoroamidodithionite, S,S-diethyl-N-ethyl-N-2-naphthyl phosphoroamidodithionite, S,S-dibutyl-N-pentachlorophosphoroamidodithionite, S,S-dibutyl-N-2,4-dichloro-3,5- dimethylphenyl phosphoroamidodithionite, S,S-dibutyl-N-piperidyl phosphoroamidodithionite, S,S dibutyl N-pyrrolidyl phosphoroamidodithionite, etc.
The compounds of the present invention are prepared by the reaction of an appropriate S,S-dialiphatic hydrocarbyl phosphorus halide with ammonia with a suitable amine or with an appropriate amide according to the following reaction:
R S R P X HN R S t R R S R P N HX R 3 R wherein R R R and R are as indicated above and X is a halogen, preferably chlorine.
Generally, the reaction is accomplished by adding the ammonia or amine slowly to the phosphorus chloride. Preferably an excess, e.g., up to twice the molar amount of ammonia, amide or the amine can be used. The excess reactant acts as a base acceptor to react with the evolved HX and thereby neutralize it. The reaction is preferably carried out in the presence of an inert solvent, such as methylene chloride ether, benzene, hexane, etc. Also a molecular seive is preferably present which serves as a drying agent for the solvent amine. The amount of molecular seive should be enough to assure substantially complete removal of any H20.
When ammonia is reacted with the phosphorus chloride it is generally preferable to dissolve the ammonia in the solvent and then add the phosphorus chloride to the ammonia-solvent mixture. When an amine is used, the solvent is preferably added to the phosphorus chloride and the amine added slowly to the phosphorus chloride-solvent mixture.
The above reaction is preferably carried out at a temperature from 78 to 30C. Following the reaction, the product can be recovered by conventional means. Thus the reaction mixture may be stripped of solvent, the product washed with water and dried over magnesium sulfate.
The phosphorus chloride is known in the art and can be prepared as for example by the procedure in US. Pat. No. 3,210,244. Thus a suitable mercaptan may be EXAMPLE 1 Preparation of S,S-di-n-buty1 phosphoroamidodithionite Ammonia (large excess based on the amount of 8,8- dibutyl phosphorus chloride) was dissolved in methylene dichloride, cooled to dry ice temperature. A small number of molecular sieves were added. S,S-dibutyl phosphorus chloride, 6.5 g. (0.03 mole), was then added slowly. A solid white precipitate resulted. The reaction mixture was slowly warmed up to room temperature and left standing approximately 48 hours. The white solid was removed and the remaining solution stripped to obtain an oil having the following analysis:
Calculated Found EXAMPLE 2 Preparation of S,S'di-n-buty1-N,N-diethyl phosphoroamidodithionite 100 ml. of methylene dichloride plus a small amount of molecular sieves were mixed with 13.05 g. of S,S-din-butyl phosphorus chloride. Diethyl amine (7.8 g.)
was added slowly. The resulting slurry was allowed to stand for approximately 24 hours. The resulting mixture was filtered and stripped to obtain a colorless oil which on chemical analysis showed:
S,S-di-n-butyl N-pyrrolidyl phosphoroamidodithionite 5.84 g. (0.024 mole) of S,S-di-n-buty1 phosphorus chloride was dissolved in approximately 150 ml. of methylene dichloride. A small number of molecular sieves were added. Piperidine, 4.06 g. (0.05 mole) was added slowly. The reaction mixture was cooled in an ice bath during the reaction. The reaction mixture was permitted to stand overnight after which it was filtered and evaporated down to obtain a yellow oil which was then dissolved in methylene dichloride, washed twice with water and dried over magnesium sulfate. After isolation, the chemical analysis showed:
Calculated Found EXAMPLE 4 Preparation of S,S-di-n-buty1-N-acety1 phosphoroamidodithionite Under a nitrogen atmosphere ml. of diethyl ether was dried over several molecular sieves. Then, 9.15 g. (0.0373 mole) of S,S-di-n-buty1 phosphorus chloride was added to the dry ether. Next, 2.21 g. (0.0373 mole) of acetamide was added and the reaction mixture turned cloudy. Triethylamine, 3.78 g. (0.0373 mole) was added dropwise. A white precipitate formed, and the reaction mixture was stirred for 1 hour at ambient temperature. After warming, the reaction mixture was stirred for 24 hours.
The white precipitate was removed by filtration. The resulting solution slowly formed two layers. After 30 days the layers were separated. The upper layer weighed 5.30 grams. Analysis:
Calculated Found TABLE 1 Elemental Analysis 1:
Ex. P Halogen No. Compound Calculated Found Calculated Found Calculated Found 5 S,S-n-butyl-N,Ndi-n-propy1 20.7 20.7 10.0 10.0
phosphoroamidodithionite 6 S.Sdi-n-buty1 N,N-dimethyl 25.3 25.1 12.2 11.8
phosphoroamidodithionite 7 S,S-di'n-buty1-N-methyl 5.8 5.3
phosphoroamidodithionite 8 S ,S-di-n-butyl N ,N-di-n-butyl 19.0 19.0 9.2 8.8
phosphoroamidodithionite 9 S,S-diisopropyl-N,N'diethyl 12.2 11.8
phosphoroamidodithionite 10 S,S diisopropyl-N.N-di-N-propyl 22.8 22.3 1 1.0 10.6
phosphoroamidodithionite 1 1 S.S-di-n-buty1-N-4-ch1oropheny1 10.6" 10.5"
phospho roamidodithionite 12 S,S-di-n-butyLN-Z-t'luorophenyl 6.0 6.2"
phosphoroamid odithionite 14 S,S-diisopropy1N-2-11uoropheny1 22.0 21.8 11.6 1 1.0
pho sphoroamidodithionite 15 S.S-diisopropyl-N.N-di-n-butyl 20.7 18 .6 10.0 9 2 phosphoroamidodithionite The compounds of the present invention are, in general, herbicidal in both preand post-emergence applications. For pre-emergence control of undesirable vegetation these compounds will be applied in herbicidal quantities to the environment, cg, soil infested with seeds and/or seedlings of such vegetation. Such application will inhibit the growth of or kill the seeds, germi nating seeds and seedlings. For postemergence applications the compounds of the present invention will be applied directly to the foliage and other plant parts. Generally they are effective against wced grasses as well as broadleaved weeds. Some may be selective with respect to type of application and/or type of weed.
Preand post-emergence herbicidal tests on representative compounds of this invention were made using the following methods:
Pre-Emergence Test An acetone solution of the test compound was prepared by mixing 750 mg. compound, 220 mg. ofa nonionic surfactant and 25 ml. of acetone. This solution was added to approximately 125 mi. of water containing 156 mg. of surfactant Seeds of the test vegetation were planted in a pot of soil and the compound solution was sprayed uniformly onto the soil surface at a dose of lOO micrograms per cm The pot was watered and placed in a greenhouse. The pot was watered intermittently and was observed for seedling emergence, health of emerging seedlings, etc. for a 3-week period. At the end of this period the herbicidal effectiveness of the compound was rated based on the physiological observations. A to 100 scale was used; 0 representing no phytotoxicity, 100 representing complete kill.
10 Post-Emergence Test The test compound was formulated in the same manner as described above for the pre-emergence test. The concentration of the compound in this formulation was 5000 ppm. This formulation was uniformly sprayed on 2 replicate pots of 24-day-old plants (approximately 15 to 25 plants per pot) at a dose of lOO micrograms per cm After the plants had dried, they were placed in a greenhouse and then watered intermittently at their bases as needed. The plants were observed periodically for phytotoxic effects and physiological and morphological responses to the treatment. After 3 weeks the herbicidal effectiveness of the compound was rated based on these observations. A O to I00 scale was used; 0 representing no phytotoxicity. 100 representing complete kill.
The results of these tests appear in Table II.
TABLE II Compound S S-dinbutyI-N.N-diethyl phosphoroarnidodithionite S S-n-butyl-N N-di-n-propyi phosphoroamidodithionite S,S-di n-butyl-N,N-dimethyl phosphoroamidodithionitc S,S-di-n-butyl phosphoroamido dithionite S,Sdin-butyl-Nmethyl phosphoroamidodithionite S S-di-n-butyl-N,N-di-n-butyl phosphoroamidodithionitc S,S-diisopropyl-N,N-diethyl phosphoroamidodithionite S,S-diisopropylN ,N-di-n-propyl phosphoroarnidodithionite S,S-di-n-butyl-N-2-fluorophenyi phosphoroamidodithionite S.S-diisopropyLMH-di'n-butyl phosphoroamidodithionite S,S-diisopropyl phosphoroamidodithionite S,S-diisopropyl-N-methyl phosphoroamidodithionite S,Sdi-nbutyl N-pyrrolidyl phosphoroamidodlthionite S ,S-diisopropyl-Ncthyl phosphoroamidodithionite S,S-diisopropyl-N-n-butyl phosphoroamidodithionite S,Sdi n'octyl-N-methyl phosphoroamidodithionite S S-di-noctylNpiperidyl phosphoroamidodithionite Herbicidal Effectiveness 0 w C M P L 93/85 loo/100 /100 100/100 100/I00 /!O0 1100 /lUO -/i00 /i00 /100 -ls5 ---/s0 -195 -rs5 -/05 /90 90% so/ioo 75 TABLE ll Continued Herbicidal Effectiveness Compound 0 S,S-diethyl-N-N-diethyl /9O phosphoroamidodithionite phosphoroam idodithionite sfi'diethyl-N N-dimethyl phosphoroamidodithionite S,S-diethyl-N-ethyl phosphoroamidodithionite phosphoroamidodithionite S,S-cli-n-propyl-N acetyl 100/- 100/- phosphoroamidodithionite S,S-di-i-propyl-N-butyryl phosphoroamidoditionite S,S-di-i-propyl N-acetyl 85/ phosphoroamidodithionite phosphoroamidodithionite phosphoroamidodithionite phosphnoroamidodithionite S,S-di-n-propyl-N-piperidyl /85 /80 phosphoroamidodithionite S,S-di-n-propyl-N-methyl 100/ 80/85 phosphoroamidodithionite phosphoroamidodithionite S.S-di-n-propyl-N-benzyl phosphoroamidodithionitc S,S di-n-propyl-N-al|yl phosphoroamidodithionite phosphoroamidodithionite S,S-di-n-butyl-N-propionyl phosphoroamidodithionite phosphoroamidodithionite The amount of compound administered will vary with the particular plant part or plant growth medium which is to be contacted, the general location of application, i.e., sheltered areas such as greenhouses as compared to exposed areas such as fields, as well as the desired type of control. For pre-emergent control of most plants dosages in the range of about 0.5 to 20 lbs. per acre will be used. Such administration will give a concentration of about 2 to ppm. compound distributed throughout 0.1 acre-foot. For post-emergence application, such as foliar spray application, compositions containing about 0.5 to 8 lbs. compound per 100 gal. spray will be used. Such application is equivalent to about 0.5 to 20 lbs. compound per acre.
The herbicidal compositions of this invention comprise a herbicidal amount of one or more of the above described compounds intimately admixed with a biologically inert carrier. The carrier may be a liquid diluent such as water or acetone or a solid. The solid may be in the form of dust powder or granules. These compositions will also usually contain adjuvants such as a wetting or dispersing agent to facilitate their penetration into the plant growth media or plant tissue and generally enhance their effectiveness. These compositions may also contain other pesticides, stabilizers, conditioners, fillers and the like.
0 The compounds of the present invention also possess Test Procedures Two-spotted Mites (Tetranychus urticae): An acetone solution of the candidate toxicant conmersed in the toxicant solution and then allowed to dry at room temperature for seven days at 85F. On the eighth day the egg mortality was rated on a scale of to l l; 0 representing no kill, 1 l representing 100% kill.
Aphids (Aphis gossypii Glover):
An acetone solution of the candidate toxicant contaming a small amount of nonionic emulsifier was diluted with water to ppm. Cucumber leaves infested with the cotton aphids were dipped in the toxicant solution. Mortality readings were then taken after 24 hours.
TABLE III Control Tw0-spotted Two-spotted Mites Compound Mites Eggs Aphids S,S-di-n-butyl-N,N-dimethyl 96 phosphoroamidodithionite $.S-n-butyLN,Ndi n-propyl IOO phosphoroamidodithionite S,S-di n-buty| 98 phosphoroamidodithionite S,S-di-n-butylN-methyl 99 99 phosphoroamidodithionite S,S-di-nbutyl-N-2-fluorophenyl 96 phosphoroamidodithionite S,Sdiisopropyl-N-methyl 98 phosphoroamidodithionite S,S-diisopropyl-N-ethyl lOO 96 phosphoroamidodithionite S,Sdiethyl-N-ethyl phosphoroamidodithionite S,S-di-n'propyl-N,N-diethyl 97* I00 phosphooamidodithionite S,S-di-n-propy]-N,N-dimethyl lOO 100 phosphoroamidodithionite S.S-di-n-pr0pyl-Nmethyl 100 phosphoroamidodithionite S,Sdi-n-propyl-N-piperidyl H30 96 phosphoroamidodithionite S,S-di-n-propyl-N N-di-n-propyl 99 99 phosphoroamidodithionite S,S-di-n-propyl-N-benzyl 100 99 phosphoroamidodithionite S,S-di-n-propy l-N-allyl v 99 phosphoroamidodithionlte S,S-di-n-propyl-N-Z-fluorophenyl 70 100 phosphoroamidodithionite S,S di-n-propyl-N-ethyl 100 90 94 phosphoroamidodithionite S,S-di-n-butyl-N-acetyl 96 96 94 phosphoroamidodithionite S,S-di-nbutyl Npropionyl 98 phosphoroamidodithionite S,Sdi-n-propyl-N-acetyl I00 [00 M0 phosphoroamidodithionite S,S-di-n-propyl-N-acetyl-Nphenyl lOO 96 phosphoroamidodilhionite In general, the preferred compounds for use as insecticides are those wherein R1 and R, are individually propyl or butyl, R is hydrogen, methyl, ethyl or propyl and R, is hydrogen, methyl, ethyl, propyl or fluorophenyl; or benzyl or allyl when R, and R are propyl.
In addition to the specific formulations and application techniques described above, one or more of the compound derivatives of the 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 carbamate de rivatives and a biologically inert carrier. Usually they will also contain a wetting agent. Solid carriers such as 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 concentration of the active ingredient to be used with inert carriers, either solid or liquid carriers, will be dependent upon many factors, such asthe particular carbamate compound which is used, the carrier in or upon which it is incorporated, the method and conditions of application, the insect species to be controlled, etc., the proper consideration of these factors being within the skill of these versed in the art. In general, the toxic ingredients of this invention will be effective in concentrations from about 0.000] percent by weight to as high as 90 percent by weight or higher. Economically, of course, it is desirable to use lower concentrations of this active ingredient. Thus, it is usually desirable to use less than percent by weight of the active ingredient in a particular composition.
The terms 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 lnsecta 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.
Some of the compounds of the present invention are also useful in the control of nematodes and algae, for example Euglena.
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.
I claim:
1. Compound of the formula wherein R, and R are independently alkyl of l to 8 carbon atoms or alkenyl of 2 to 3 carbon atoms, R, is hydrogen or alkyl of l to 4 carbon atoms and R, is acyl of 2 to 4 carbon atoms.
2. The compound of claim 1 wherein R, and R, are independently alkyl of l to 8 carbon atoms.
3. The compound of claim 1 wherein R and R are independently alkyl of 3 to 4 carbon atoms.
4. The compound of claim 1 wherein R, and R, are the same and are alkyl of l to 4 carbon atoms and R, is hydrogen.
5. S,S-di-n-butyl-N-acetyl phosphoroamidothioate, according to claim 4.
6. S,S di-n-propyl-N-acetyl phosphoroamidodithionite, according to claim 4.
7. S,S-di-i-propyl-N-butyryl phosphoroamidodithionite, according to claim 4.
8. S,S-di-i-propyl-N-acetyl phosphoroamidodithionite, according to claim 4.
9. S,S-di-n-butyl-N-propionyl phosphoroamidodithionite, according to claim 4.
t i t t l

Claims (9)

1. A COMPOUND OF THE FORMULA
2. The compound of claim 1 wherein R1 and R2 are independently alkyl of 1 to 8 carbon atoms.
3. The compound of claim 1 wherein R1 and R2 are independently alkyl of 3 to 4 carbon atoms.
4. The compound of claim 1 wherein R1 and R2 are the same and are alkyl of 1 to 4 carbon atoms and R3 is hydrogen.
5. S,S-di-n-butyl-N-acetyl phosphoroamidothioate, according to claim 4.
6. S,S-di-n-propyl-N-acetyl phosphoroamidodithionite, according to claim 4.
7. S,S-di-i-propyl-N-butyryl phosphoroamidodithionite, according to claim 4.
8. S,S-di-i-propyl-N-acetyl phosphoroamidodithionite, acCording to claim 4.
9. S,S-di-n-butyl-N-propionyl phosphoroamidodithionite, according to claim 4.
US466433A 1972-01-20 1974-05-02 S,S-dialkyl-N-substituted phosphoroamidodithionites Expired - Lifetime US3886238A (en)

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US2995596A (en) * 1956-09-01 1961-08-08 Benckiser Gmbh Joh A Production of phosphoric aciddialkylester-amines

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