IE44001B1 - Phosphoramidate pesticides - Google Patents

Phosphoramidate pesticides

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Publication number
IE44001B1
IE44001B1 IE2722/76A IE272276A IE44001B1 IE 44001 B1 IE44001 B1 IE 44001B1 IE 2722/76 A IE2722/76 A IE 2722/76A IE 272276 A IE272276 A IE 272276A IE 44001 B1 IE44001 B1 IE 44001B1
Authority
IE
Ireland
Prior art keywords
alkyl
compound according
substituted
phenyl
methyl
Prior art date
Application number
IE2722/76A
Other versions
IE44001L (en
Original Assignee
Rohm & Haas
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from US05/745,900 external-priority patent/US4154825A/en
Application filed by Rohm & Haas filed Critical Rohm & Haas
Publication of IE44001L publication Critical patent/IE44001L/en
Publication of IE44001B1 publication Critical patent/IE44001B1/en

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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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
    • 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
    • C07F9/2458—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aliphatic amines
    • 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
    • C07F9/5532—Seven-(or more) 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
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6509—Six-membered rings
    • C07F9/650952—Six-membered rings having the nitrogen atoms in the positions 1 and 4

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

PURPOSE: To provide an emery saw which effects running of a cut disc throughout a wide range, to performs cutting of a material to be cut in a plurality of spots through a single emery saw, reduces fear of distortion occurring owing to heat radiated from the material to be cut or vibration thereof, and facilitates maintenance. CONSTITUTION: A gantry type frame 5 is erected such that a horizontal member 6 is caused to span above a material 2 to be cut. A running body 9 runnable approximately horizontally along the horizontal member 6 is supported in a suspending state. A cutting disc 21 rotated in a surface paralleling to the horizontal member 6 is elevatably arranged to the running body 9[JPS5293752A]

Description

This invention concerns novel phosphoramidates, compositions containing them, methods of making the novel compounds and compositions and methods of using them to control a variety of harmful pests.
One class of novel compound concerned in this invention are of the formula: wherein A is phenyl or naphthyl each optionally substit10 uted with 1, 2 or 3 of the same or different substituents selected from cyano, nitro, halogen, (C^-Cg)alkyl (preferably C-^-C^ or C^), (C^-Cg)alkoxy (preferably Cl-C3 or C43, (cic6^alkylthio (preferably C^-Cj or Cj), /3i-(Cj_-Cg)alkyl/ aminocarbonyl preferably containing up to 3 or 4 carbon atoms in each alkyl group, (C^-Cg)alkyl (preferably C-^-C^ or ΟΛ) substituted with one or more halogen atoms, phenyl, phenoxy, naphthoxy or - 3 phenylthio; R is hydrogen or (C^-C^)alkyl, preferably (Cp^lalkyl; R1 is (a) (Cj-Cg)alkyl ( preferably (C^-Cj) or (C-^-C^)alkyl) optionally substituted with one substituent selected from cyano, nitro, (C-^-Cg) alkoxy, (Ci-Gg)alkylthio, (C^-Cgjalkylsulfinyl, (ci"cg)" alky lsulf onyl, /(C^-Cg)alkyl/carbonyl, alkoxy7carbonyl, /(C^-Cg) alky l/carbony loxy, /mono- or di-(C^-Cg)alkyl/aminocarbonyl (the last 8 groups preferably containing from 1 to 3 carbon atoms in each alkyl or alkoxy moiety as the case may be), phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylcarbonyl, phenoxycarbonyl, phenylcarbonyloxy and phenylaminocarbonyl, each of the last 8 groups being optionally substituted as defined above for A=phenyl or naphthyl; (b) phenylalkyl of up to 11 carbon atoms (e.g. benzyl, phenethyl or 3-phenylmethylpropyl) or naphthylalkyi of up to 11 carbon atoms, each of these groups being optionally ring-substituted with 1, 2 or 3 of the same or different substituents selected from the group of substituents specified above for the A group phenyl or naphthyl; (c) (Cg-Cg)alkenyl (preferably (Cj-C^)alkenyl) optionally substituted with one or two of the same or different substituents selected from cyano, halogen, /(C^-Cg)alkoxy7carbonyl, phenyl and naphthyl, each of the last two groups being optionally substituted as defined above for A= phenyl ,· (d) (C^-Cg)alkynyl (preferably (C3~C4)alkynyl); or ZigOGl - 4 (e) (Cg-Cg)cycloalkyl (preferably (Cg-C^)cycloalkyl); 2 R is (Cjj-Cg)alkyl, preferably (C-^-Cg) or (C^-C^) alkyl; is (C^-Cg)alkyl, preferably (Cg-C^)alkyl and particularly (Cg-C4)alkyl; and X Is oxygen or sulfur, preferably oxygen. Preferred compounds of Formula I are of the formula; (II) wherein Λ R is hydrogen or (C^-C^) alkyl (preferably methyl)? r5 is (Cg-C^)alkyl (preferably (Cg-Cg)alkyl) or (Cg-C4)alkenyl (preferably allyl); g R is (C^-C^)alkyl (preferably ethyl,; R is (Cg-C^)alkyl (preferably n-propyl, isobutyl or sec-butyl); and Υ, Y', Y1', which may be the same or different, are selected from hydrogen, (C^-Cg)alkyl, nitro and halogen and preferably selected from hydrogen, methyl and chlorine.
Another class of novel compounds provided by this invention are Formula X compounds as defined above but modified in that at least one of A, R and R^ is as follows: - 5 A is substituted phenyl or naphtyl wherein at least one of the substituents specified for A above is replaced by a substituent selected from /(C^~Cg)alky1/carbonyloxy, ‘(C^-Cg)alkylsulfonyl, (Cg-Cg)alkylsulfinyl, /(Cg-Cg)alkoxy/carbonyl, /di-(Cg-Cg)alkyl/amino and /"(Cg-Cg) alky 1/carbonyl, the alkyl or alkoxy moieties in these groups preferably having up to 3 or 4 carbon atoms; R is (Cg-Cg)alkoxy (preferably (Cg-C^)alkoxy), (Cg-Cg)alkylthio (preferably (Cj-C^)alkylthio), cyano, /di-(Cg-Cg)alkyl/amino (preferably /di-(Cg-C^)alkyl/amino, particularly diethylamino) or a saturated or unsaturated heterocyclic group having four to six carbon atoms and which contains one or two hetero nitrogen atoms optionally plus a hetero oxygen or sulfur atom; R1 is (a) (C|~Cg)alkyl (preferably Cg-Cg or C4 alkyl) substituted with one furyl, /di-(Cg-Cg)alkyl/amino, (C3_Cg)alkenyloxy or /(Cg-Cg) alkenyloxy/carbonyl group, each of the last three groups preferably having up to 3 or 4 carbon atoms in each alkenyl or alkyl moiety; or (b) substituted phenylalkyl of up to 11 carbon atoms (e.g. benzyl, phenethyl or 3-phenylmethylpropyl) or naphthylalkyl of up to ll carbon atoms, each of these groups being substituted as specified above (in connection with the second class of novel compounds) for the R group substituted phenyl or naphthyl; or (c) substituted (Cg-Cg)alkenyl (preferably (Cg-C^)alkenyl) wherein at least one of the substituents specified above for R^substituted (Cg-Cg) alkenyl is replaced by (Cg-Cg)alkoxy; or 4 0 0 1 - 6 (d) (C^-Cg)cycloalkenyl optionally substituted with 1, 2 or 3 of the same or different substituents listed above(in connection with both the first and second classes of novel compounds) for R^= substituted alkenyl; or (e) (Cg-Cg)cycloalkyl substituted with 1, 2 or 3 of the same or different substituents listed above (in connection with both the first and second classes of novel compounds) for R3'=substituted alkyl.
The terms used in this specification to indicate aliphatic hydrocarbon groups, eg. alkyl, alkenyl, alkynyl, alk- in alkoxy, are meant to include branched as well as straight chain groups. Examples of such groups are: methyl, ethyl, propyl, isopropyl, secbutyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, allyl, 2-butenyl, 3-methyl-l-pentenyl, 3-hexenyl, propynyl, 1-pentynyl, 4-methyl-l-pentynyl, hexynyl, and methoxy.
The preferred substituents in the phenyl or naphthyl group A are nitro; halogen, especially chlorine; (C^-Cg) or (Cl-C4) alkyl, particularly methyl; (C^-Cg) or (C^-C^) alkoxy, particularly methoxy, and (C^-Cg) or (C^-C^)alkylthio, particularly methylthio.
When R is a heterocyclic group it may, for example, be pyrrolidinyl, piperidyl, N-morpholinyl, piperazinyl, hexahydroazepinyl, hexahydrodiazeplnyl or hexahydrooxazeplnyl.
When R3- is substituted alkyl, preferred substituents are alkoxycarbonyl, alkylcarbonyl, mono- or di-alkylaminocarbony1, alkoxy, alkylthio, alkylsulfonyl, phenylthio and cyano.
When R1 is optionally substituted cycloalkyl, the cycloalkyl group may be cyclopentyl, cyclohexyl, or cycloheptyl. 4400 1 - 7 When R1 is substituted alkenyl, preferred substituents are cyano, halogen (preferably chlorine), alkoxy (preferably methoxy) and alkoxycarbonyl, wherein the alkyl moiety contains from 1 to 6, preferably from 1 to 3 carbon atoms; and aryl or substituted aryl as specified above for the group A in formula I.
When is optionally substituted cycloalkenyl, the latter preferably has 5 to 7 or 8 cyclic carbon atoms as in cyclopentenyl, cyclohexenyl, cycloheptenyl and cyclooctenyl.
In the preferred compounds the A substituent is of the formula: wherein Y, Y' and Y'' are the same or different and each represents hydrogen, (Cj-Cg), preferably (C^-C^), alkyl, particularly methyl; halogen, preferably chlorine; (C^-Cg) , preferably (C-L-C4), alkoxy,' particularly methoxy; (C^-Cg) , preferably (C-L~C4), alkythio, particularly methylthio; nitro; cyano; /Tc^-Cg), preferably (C^-Cj),. alkoxy7carbonyl; di(C1~C4), preferably (C^-C^), alkylamino, particularly dimethylamino; /(C^-Cg) alkyl7carbonyl; di (C^-C4) alkylaminocarbonyl; arylthio, preferably phenylyhio; or aryloxy, preferably phenoxy.
The most preferred compounds concerned in this invention are of the formula: (IV) wherein R4 is hydrogen or (C^-C^)alkyl; r5 is (C^-C^)alkyl, preferably methyl or ethyl; cyolohexyl; (C3-C4)alkenyl; propargyl; phenylthio(C^C^)alkyl; preferably phenylthioethyl; cyano(C^-C^)alkyl, preferably cyanoethyl; /TiC-^-C^Jalkoxy/carbonyl(C1-C4)alkyl, preferably ethoxycarbonylethyl; furfuryl or benzyl; R6 is a (C-^-C^)alkyl, preferably ethyl; γ R is a (C3-C4)alkyl, preferably n-propyl, isobutyl, or sec-butyl; and Υ, Υ', Y'1, which may be the same or different, each represents hydrogen; (C^-C3)alkyl, preferably methyl; nitro; alkylthio, preferably methylthio; or halogen, preferably chlorine, it being most preferred that the Ys represent hydrogen, methyl or chlorine.
Representative compounds within the scope of Formula (IV) have shown nematocidal, fungicidal or arthropdicidal, particularly acaricidal and insecticidal, activity.
Typical examples of compounds concerned in this invention are listed below. In the two lists, the alkyl substituents are n-alkyl unless otherwise indicated.
LIST A N - /Ν' - (4 - chlorophenyl)formimidoyl7 N - methyl S - propyl phosphoramidothioate or phosphorami dodithioate - 9 Ο - ethyl Ν - methyl Ν - /Ν' - (2,4 - dimethylphenyl)acetimidoyl/ Ξ - (1 - methylpropyl) phosphoramidothioate or phosphoramidodithioate - methyl S - (2 - methylpropyl) N - 7®' -(4nitrophenyl) formimidoyl/ N - propyl phosphoramidothioate or phosphoramidodithioate - ethyl S - (1 - methylpropyl) N - (2 - phenoxyethyl) N - /Ν' - (3,5 - ditrifluoromethylphenyl)formimidoyl/ phosphoramidothioate or phosphoramidodithioate N - /Ν'-(4 - chloro - 2 - methylphenyl)formimidoy3/ - ethyl N - propyl S - (1 - methylpropyl) phosphoramidothioate or phosphoramidodithioate N - /Ν' - (4 - cyanophenyl)formimidoyl/ N - ethyIthiomethyl 0 - methyl S - (2 - methylpropyl) phosphoramidothioate or phosphoramidodithioate N - /Ν' - (2,4,6 - trichlorophenyl)acetimidoyl/ 0 methyl N - (2 - methoxyethyl) S - (1 - methylpropyl) phosphoramidothioate or phosphoramidodithioate N - ethyl 0 - ethyl N - /Ν' - (3 - methylphenyl)formimidoyl/ S - propyl phosphoramidothioate or phosphoramidodithioate - ethyl N - methyl N/N' - (4 - methylthiophenyl)formimidoyl/ S - propyl phosphoramidothioate or phosphoramidodithioate N - /jj' - (2 - chlorophenyl)formimidoyl7 N - (2 - cyanoethyl) 0 - methyl S - (2 - methylpropyl) phosphoramidothioate or phosphoramidodithioate.
S - butyl N - methyl 0 - methyl N - /Ν' - (2 - methyl 4 - nitrophenyl)formimidoyl/ phosphoramidothioate or phosphoramidodithioate - 10 0 - ethyl Ν - /Ν' - (2 - ethylphenyl)formimidoyl7 S (1 - methylpropyl) N - propyl phosphoramldothioate or phosphoramidodithioate N - /Ν' - (3,4- dichlorophenyl) formimidoyV 0 - methyl N - (2 - nitropropyl) S - propyl phosphoramidothioate or phosphoramidodithioate N - ethyl N - /ft' -(4- diethylaminocarbonylphenyl)formimidoyl/ 0 - methyl S - propyl phosphoramidothioate or phosphoramidodithioate - ethyl S - hexyl N - (3 - methylsulfonylpropyl) N /Ν' - (4 - methylphenyl)formimidoyl7 phosphoramidothioate or phosphoramidodithioate N - /Ν' -(4- chlorophenyl)formimidoyl7 0 - ethyl N (2 - methylsulfinylethyl) S - propyl phosphoramidothioate or phosphoramidodithioate - ethyl N - /S' -(4- methoxy - 2 - methylphenyl)formimidoyl/ N - methyl S - propyl phosphoramidothioate or phosphoramidodithioate - methyl S - (1 - methylpropyl) N - (Ν' - phenyIbutanimidoyl) N - phenylthiomethyl phosphoramidothioate or phosphoramidodithioate - methyl N - /2 - (2 - methyl - 4 - methylthiophenoxy)ethyl7 N - (Ν' - phenyIformimidoyl) S - propyl phosphoramidothioate or phosphoramidodithioate N - benzyl 0 - ethyl S - (2 - methylpropyl) N - (Ν' phenylformimidoyl) phosphoramidothioate or phosphoramidodithioate N - (3,5 - dichlorobenzyl) N - /S' - (4 - chloromethylphenyl) formimidoyl7 0 - ethyl S - propyl phosphoramidothioate or phosphoramidodithioate 11-(2- butenyl) 0 - ethyl N - (Ν' - phenylformimidoyl) S - propyl phosphoramidothioate or phosphoramidodithioate - 11 Ν - phenyl sulfonylmethyl Ο - ethyl Ν - (Ν* - phenylformimidoyl) S - propyl phosphoramidothioate or phosphoramidodithioate - ethyl N - methyl N - /5' - (4 - phenylthiophenyl)acetimidoyl7 S - propyl phosphoramidothioate or phosphoramidodithioate O - ethyl N - ethylcarbonylmethyl N - /Ν' - (2 - phenoxyphenyl)formimidoyl/ S - propyl phosphoramidothioate or phosphoramidodithioate - butyl N - methyl N-ZN1 -(4-(2- naphthoxy)phenyl)formimidoyl7 S - propyl phosphoramidothioate or phosphoramidodithioate - ethyl N - methyl N - (Ν’ - phenylpentanimidoyl) S propyl phosphoramidothioate or phosphoramidodithioate N - /N' - (4 - chloro - 2 - methylphenyl)acetimidoyl7 - ethyl N - methyl S - propyl phosphoramidothioate or phosphoramidodithioate O - ethyl N - methoxycarbonylmethyl N - /Ν' - (4- methylphenyl) acetimidoyl/ S - propyl phosphoramidothioate or phosphoramidodithioate N - /S' - (4 - chlorophenyl)acetimidoyl7 0 - ethyl N - ’ methylaminocarbonylmethyl S - propyl phosphoramidothioate or phosphoramidodithioate N - /JJ1 " (4 - biphenylyl)formimidoyl/ S - methyl N propyl 0-(1- methylpropyl) phosphoramidothioate or phosphoramidodithioate - ethyl N - dimethylaminocarbonylmethyl S - propyl N - (Ν' - 1 - naphthylformimidoyl) phosphoramidothioate or phosphoramidodithioate - ethyl N - /Ν' -2- (4,6- dichloronaphthyl)formimidoyV N - /2 - (4 - chloro)butenyl7 S - propyl phosphoramidothioate or phosphoramidodithioate - 12 LIST Β Ο - ethyl Ν - (2 - ethylsulfinylethyl) Ν - /Imethoxy)(phenyliminoJmethy17 S - propyl phosphoramidothioate or phosphoramidodithioate N - /(4 - methoxycarbonylphenylimino) (hexy loxy) methy X7 N - methyl 0 - methyl S - (1 - methylpropyl)phosphoramidothioate or phosphoramidodithioate N - (2 - cyanoethyl) N - /(ethoxy) (4 - dimethylaminocarbonylphenylimino)methyl/ O - ethyl S - (2 methylpropyl) phosphoramidothioate or phosphoramidodithioate N - (2 -butenyl) N - /(methoxy) (2 - nitrophenylimo)methy17 0 - propyl S - propyl phosphoramidothioate or phosphoramidodithioate S - butyl 0 - ethyl N - /(4 - methylthiophenylimino)(propyloxy Jmethy 17 N - (2 - propenyl)phosphoramidothioate or phosphoramidodithioate N - /(4 - chloro - 2 - methylphenylimino)(pentyloxy)methy!7 N - hexyl 0 - methyl S - (2 - methylpropyl) phosphoramidothioate or phosphoramidodithioate - ethyl N - /(ethoxy)(3,5 - dimethylphenylimino)methyl/ N - (2 - phenoxyethyl) S - propyl phosphoramidothioate or phosphoramidodithioate N - ethylthiomethyl N - /4 - cyanophenylimino) (methoxy)methyl] 0 - methyl S - (2 - methylpropyl) phosphoramiuothioate or phosphoramidodithioate N - /(2 - chlorophenylimino)(hexylthio)methyl/ M " methyl 0 - methyl S - (1 - methylpropyl)phosphoramidothioate or phosphoramidodithioate - ethyl N - hexyl N - /(methylthio) (4-methylthiophenylimino)methyl/ S - propyl phosphoramidothioate or phosphoramidodithioate N - /(4 - cyanophenylimino)(ethylthio)methyl/ 0 - methyl S - (2 - methylpropyl) N - propyl phosphoramido44001 - 13 thioate or phosphoramidodithioate N - (2 - cyanoethyl) N - /(2 - methyl - 4 - methylsulfonylphenylimino)(propylthio)methyl/ 0 - propyl S -- propyl phosphoramidothioate or phosphoramidodithioate N - /12,4 - dichlorophenylimino)(methylthio)methyl/ 0 methyl S - pentyl N - propyl phosphoramidothioate or phosphoramidodithioate N - (2 - butnyl) N - /"(2 - chloro - 4 - methylphenylimino)(pentylthio)methyl/ 0 - ethyl S - hexyl phosphoramidothioate or phosphoramidodithioate - ethyl N - /(2 - methoxyphenyl imino) (methylthio)methyl/ N - (2 - methylcarbonylethyl) S - (2 methylpropyl) phosphoramidothioate or phosphoramidodithioate N - /(ethylthio) (4 - phenoxyphenylimino)methyl/ 0 methyl N - (2 - phenyIthioethyl) S - propyl phosphoramidothioate or phosphoramidodithioate N - (2 -butenyl)N - /(2 - methyl - 4 - nitrophenylimino)(propylthio)methyl/ 0 - propyl S - propyl phosphoramidothioate or phosphoramidodithioate N - /Tcyano)(4 - methylphenylimino)methyl/ N - ethyl 0 ethyl S - (1 - methylpropyl) phosphoramidothioate or phosphoramidodithioate N - /(cyano) (1 - napthylimino)methyl/ N methyl 0 - propyl S - propyl phosphoramidothioate or phosphoramidodithioate N - /'(4 - bromo - 2 - methylphenylimino) (cyano)methyl/ - ethyl N - (2 - propenyl) S - propyl phosphoramidothioate or phosphoramidodithioate N - /(cyano) (phenylimino)methyl/ N - hexyl 0 - methyl S - (methylethyl) phosphoramidothioate or phosphoramidodithioate - 14 Ο - butyl Ν - /1cyano)(4 - methylcarbonylphenylimino)methyl/ N - (2 - cyanobutyl) S - (2-methylpropyl) phosphoramidothioate or phosphoramidodithioate N -(2 - butenyl) N - /(3 - chlorophenylimino) (cyano) 5 methyl/ 0 - ethyl S - propyl phosphoramidothioate or phosphoramidodithioate N - /(dimethylamino) (4 - nitrophenylimino)methyl/ N hexyl 0 - propyl S - propyl phosphoramidothioate or phosphoramidodithioate 0 - ethyl N - /(dihexylamino) (phenylimino)methyl/ N (2 - propenyl) S - propyl phosphoramidothioate or phosphoramidodithioate N - (cyanomethyl) 0 - ethyl N - /12 - methoxyphenylimino)(methylpropylamino)methyl/ S - (1 15 methylpropyl) phosphoramidothioate or phosphoramidodithioate N - /(dibuty lamino) (phenylimino)methyl/ 0 - ethyl N methyl S - (propyl) phosphoramidothioate or phosphoramidodithioate N - ethyl O-ethyl N - /(4 - methylthiophenylimino) (piperidino)methyl/ S - (2 - methylpropyl) phosphoramidothioate or phosphoramidodithioate - ethyl N - /12,6 - dipropylphenylimino)(pyrrolidino)· methyl/ N - propyl S - propyl phosphoramidothi25 oate or phosphoramidodithioate N - /2 - bromo - 4 - chlorophenylimino)(dimethylamino)methyl7 0 - ethyl S - hexyl N - pentyl phosphoramidothioate or phosphoramidodithioate N - £(4 - butylcarbonylphenylimino)(piperidino)methyl/ 30 N - (2 - cyanoethyl) 0 - methyl S - (2 - methylpropyl) phosphoramidothioate or phosphoramidodithioate N - /12,4,6 - triohlorophenylimino)(morpholino)methyl/ - ethyl S - hexyl N - (2 - phenylthioethyl) - 15 phosphoramidothioate or phosphoramidodithioate N - /Ν' - (4 - fluorophenylformimidoyl7 0 - hexyl N methyl S - propyl phosphoramidothioate or phosphoramidodithioate N - /Ν' - (4 - bromo - 2 - chlorophenyl) formimidoy 3/ N - (1 - ethylcarbonyloxyethyl) 0 - ethyl S (1 - methylpropyl) phosphoramidothioate or phosphoramidodithioate - ethyl N - hexyl N - (Ν' - phenylformimidoyl) S propyl phosphoramidothioate or phosphoramidodithioate N - butyl N - /7cyano)(2 - phenoxyphenylimino)methy 3/ - ethyl S - (1 - methylpropyl) phosphoramidothioate or phosphoramidodithioate N - /(cyano) (1 - naphthylimino)methyl/ N - methyl 0 propyl S - propyl phosphoramidothioate or phosphoramidodithioate N - ethyl 0 - ethyl N - /(diethylamino) (4 - dimethylaminophenyl) methyl/ S - propyl phosphoramidothioate or phosphoramidodithioate N - butyl 0 - ethyl N - /72 - methylaminocarbonylphenylimino)(pyrroiidino)methyl? S - (1 - methylpropyl) phosphoramidothioate or phosphoramidodithioate N - /ν' - (2 - bromophenyl)formimidoyl/ 0 - ethyl S ethyl S - ethyl N-2 - (4 - chlorophenoxycarbonyl)ethyl phosphoramidothioate or phosphoramidodithioate - ethyl N - (2 - diethylamino)ethyl Ν - (Ν' - phenylformimidoyl) S - propyl phosphoramidothioate or phosphoramidodithioate - methyl S - methyl N-2 - (4 - methylphenylcarbonyloxy)propyl N - /Ν'-(2 - methylthiophenyl)acetimidoyl/ phosphoramidothioate or phosphoramidodithioate 44001 - butyl Ν - /1dimethylamino)(2 - methoxycarbonylphenylimino)methy1/ S - propyl N - 2 - (2 - propylphenylsulfinyl)ethyl phosphoramidothioate or phosphoramidodithioate 0 - ethyl N - //diethylamino)(phenylimino)methyl/ N phenylaminocarbonylmethyl S - propyl phosphoramidothioate or phosphoramidodithioate - ethyl N - furfuryl N -/S’ -(4- nitrophenyl)acetimidoyl/ S - propyl phosphoramidothioate or phosphoramidodithioate N - (3 - cyano - 2 - propenyl) 0 - ethyl N - /S' -(2• methylphenyl)acetimidoyl/ S - (2 - methylpropyl) phosphoramidothioate or phosphoramidodithioate W - /S’ -(2- bromophenyl)formimidoy/ N - (2 - methyl . - 3 - methoxycarbonyl - 2 - propenyl) 0 - pentyl S - propyl phosphoramidothioate or phosphoramidodithioate - ethyl N - /N* - (2 - ethylphenyl)acetimidoy/ S (1 - methylpropyl) N-2 - (2 - propenyloxycar20 bonyl)propyl phosphoramidothioate or phosphoramidodithioate - methyl S - (propyl) N - /3 - (4 - methylphenyl) - 2 - propenyl/ N - /S’ - (4 - methylthiophenyl)formimidoyl/ phosphoramidothioate or phosphoramidodi25 thioate O - butyl N - /3 - (2 - naphthyl) - 2 -propenyl/ N - /S’ - (4 - nitrophenyl)formimidoyl/ S propyl phosphoramidothioate or phosphoramidodithioate N - /Ν' - (3 - bromophenyl)formimidoyi/ 0 - ethyl N /2-(4- nitrophenyl)ethyl/ - S - propyl phosphoramidothioate or phosphoramidodithioate Ν - (3 - cyanopentyl) Ο - methyl S - methyl N - (Ν' phenylformimidoyl) phosphoramidothioate or phosphoramidodithioate N - cycloheptyl N - /S' - (4 - ethoxycarbonyIpheny1)acetimidoyl/ 0 - ethyl S - propyl phosphoramidothioate or phosphoramidodithioate N - (4 - cyano - 2 - cyclohexenyl) 0 - methyl S (propyl) N - /(phenylimino) (propoxy)methyl/ phosphoramidothioate or phosphoramidodithioate N - (4 - chloro - 3 - cycloheptenyl) 0 - ethyl S (propyl) N - /(2 - methyIphenylimino)(pentyloxy)methyl/ phosphoramidothioate or phosphoramidodithioate N - butyl 0 - ethyl N - /(4 - methoxycarbonylphenylimino)(piperazinyl)methyl·/ S - propyl phosphoramidothioate or phosphoramidodithioate N - /(hexahydroazepinyl)(phenylimino)methyl/ N - methyl 0 - propyl S - propyl phosphoramidothioate or phosphoramidodithioate N - ethyl 0 - ethyl N - /Jhexahydrooxazepinyl)(4 propyIphenylimino)methyl/ S - (1 - methylpropyl) phosphoramidothioate or phosphoramidodithioate N - butyl - 0 - ethyl S - (1 - methylpropyl) N - (Ν’ phenylformimidoyl) phosphoramidothioate or phosphoramidodithioate N - /Ν' - (4 - bromophenyl)formimidoyl·/ N - (3 - chloro 2 - propenyl) 0 -ethyl S - propyl phosphoramidothioate or phosphoramidodithioate N - cyclopentyl 0 - ethyl N - (Ν' - phenylformimidoyl) S - propyl phosphoramidothioate or phosphoramidodithioate N - /N' - (2 - ethoxycarbonyIpheny1) formimidoyl·/ 0 ethyl S - (2 - methylpropyl) N - propyl phosphoramidothioate or phosphoramidodithioate - 18 Ν - /S' - (4 - acetoxyphenyl) formimidoyl/ 0 -ethyl N methyl S - propyl phosphoramidothioate or phosphoramidodithioate - ethyl N - /Ν' (4 - methoxycarbonylphenyl) formi5 midoyl7 S - propyl N - (2 - naphthoxyethyl) phosphoramidothioate or phosphoramidodithioate - ethyl N - (2 - methy lpropyl) S - propyl N - /jj' (4 - propylsulfinylphenyl) formimidoyl/ phosphoramidothioate or phosphoramidodithioate N - Ν' - (2 - chloro - 4 - methylsulfonylphenyl) formimidoyl 0, S - diethyl N - methyl phosphoramidothioate or phosphoramidodithioate N - (2 - butynyl) 0 - ethyl N - /Ν' -(4- methylcarbonylphenyl) formimidoyi/'s - propyl phosphoramido15 thioate or phosphoramidodithioate The compounds concerned in the present invention can be prepared by any method of the type described in the literature for analogous compounds.
One preparative method involves reacting an 20 amidine with an O,S-dialkyl phosphorochloridothioate or phosphorochloridodithioate in the presence of an acid binding agent. The general reaction can be represented by the following equations R R X acid R R IV 2 3 II binding | V _ A-N=C-N + (Rz0)(R S)-P-Cl-► A-N=C-N OR + HCI \ agent / H X SR 3 wherein A, R, R , R , R , and X are as defined for Formula X. - 19 Representative acid binding agents include tertiary amines such as trialkylamines and dialkylamines, and inorganic bases such as hydrides, hydroxides, carbonates and bicarbonates of alkali and alkaline earth metals.
Generally, a substantially equimolar ratio of reactants is preferred but an excess of either of the reactants can be employed. While not required, the reaction is advantageously carried out in the presence of an inert organic solvent such as an ether, aromatic hydrocarbon, halogenated aromatic hydrocarbon, aliphatic hydrocarbon, aliphatic ketone, aliphatic nitrile or mixtures thereof. Suitable solvents include, for example, diethyl ether, dioxane, tetrahydrofuran, benzene, toluene, chlorobenzene, heptane, methylethyl ketone, acetone and acetonitrile. The reaction is generally conducted in a temperature range of -10° to l00°C. or more, and preferably in the range of 0° to 60°C.
All of the starting materials used in the preparation of the compounds concerned in this invention are known compounds or are readily prepared by adaptations of known routes. For example, the formamidine starting materials can be prepared by condensation of an aniline with an N-alkyl formamide (see U.S. Patent No. 3,502, 720, Belgian Patent No. 771,792 and South African Patent No. 732,129.) The 0,S-dialkylphosphorochloridothioates are prepared for example by reacting an alkylsulfenyl chloride with a dialkylchlorophosphite (A.F.
Lippman, J. Org. Chem. 30, 3217 (1965)).
Numerous compounds of Formula I have been prepared and these are chemically identified, and characterizing data given, in Table I presented later. Illustrative preparations of compounds according to Formula I are now presented as Examples 1-6. The other compounds listed in Table I can be prepared in an analogous manner. - 20 Example 1.
Preparation of 0 - ethyl N - methyl N - /5l* - (2,4 dimethylphenyl)formimidoy^7 S - propyl phosphoramidothioate (Cpd. 1, Table I) A solution of O-ethyl S-n-propyl phosphorochloxidothioate, 2.5 g. (0.0124 mole), in 10 ml. of tetrahydrofuran (THF) is added dropwise to a solution of N-methyl-N'-(2,4-dimethylphenyl)formamidine, 2.0 g. (0.0124 mole) and triethylamine, 1.25 g. (0.0124 mole), in 25 ml. of THF at room temperature. The reaction is stirred for one hour at room temperature, diluted with 70 ml. of ether, filtered to remove triethylamine hydrochloride and evaporated by vacuum stripping to give 4.2 g. of orange oil which is chromatographed on 65 g. of 60-200 mesh silica gel. Elution with 900 ml. of 7% ether in benzene (discarding the first two 50 ml. fractions) and concentration under vacuum gives 2.6 g. (64% theory) of purified product as an orange oil.
Example 2.
Preparation of K - cyclohexyl 0 - ethyl N - /5’ phenyIformimidoyl/ S - n - propyl phosphoramidothioate (Cpd. 26, Table I) A solution of O-ethyl S-n-propyl phosphorochloridothioate, 2.02 g. (O,oo99 mole), in 5 ml. of THF is added dropwise to an ice-cooled solution of N-oyolohexyl-N'-phenyl formamidine, 2.0 g. (0.0099 mole), and triethylamine, 1.01 g. ((.Ol mole), in 25 ml. of THF. The reaction is stirred one hour at room temperature, diluted with 60 ml. of ether, filtered to remove triethylamine hydrochloride, and evaporated by vacuum stripping to give 3.8 g. of yellow oil which is chromatographed on 40 g. of 60-200 mesh silica gel. Elution with 350 ml. of 10% ether in benzene (discarding the first 200 ml. fraction) gives 0.44 g. (12% of 4 0 01 -21-. theory) of purified product as an oil.
Example 3.
Preparation of 0 - ethyl N - /Ν' - phenylformimidoyl7 N - (2 - propenyl) S - n - propyl phosphoramidothioate (Cpd. 25, Table I) A solution of 0-ethyl S-n-propyl phosphorochloridothioate, 3.16 g. (0.016 mole), in 10 ml. of THF is added dropwise to an ice-cooled solution of triethylamine, 1.58 g. (0.016 mole), and N-allyl-N'-phenyl formamidine, 2.5 g. (0.016 mole) in 30 ml. of THF. The reaction is stirred one and one-half hours at room temperature, diluted with 100 ml. of ether, filtered to remove the triethylamine hydrochloride, and evaporated by vacuum stripping to give 5.6 g. of yellow oil which is chromatographed on 60 g. of 60-200 mesh siJica gel. Elution with 510 ml. of 10% ether in benzene (discarding the first 210 ml.) gives 1.7 g. (33% of theory) of purified product as an oil.
Example 4.
Preparation of H - /S' - (4 - chlorophenylformimidoyl)_7 N - (2 - cyanoethyl) 0 - ethyl S - (1 - methylpropyl) phosphoramidothioate (Cpd. 72, Table I) A solution of 0-ethyl S-(l-methyl) phosphorochloridothioate, 1.78 g. (0.008 mole), in 10 ml. of THF is added dropwise to an ice-cooled solution of N-(2cyanoethyl)-N'~(4-chlorophenyl) formamidine, 1.7 g. (0.008 mole), and triethylamine, 0.82 g. (0.008 mole), in 25 ml. of THF. The reaction is stirred one hour at room temperature, diluted with 100 ml. of ether, filtered to remove the triethylamine hydrochloride and evaporated by vacuum stripping to give 3.4 g. of yellow oil which is chromatographed on 60 g. of Biosil A. Elution with 350 ml. of 10% ether in benzene - 22 (discarding the first 300 mis.) gives 0.6 g. (19% of theory) of purified product.
Example 5.
Preparation of 0 - ethyl N - /(diethylamino) (phenylimino) methyl/’ N - (2 - propenyl) S - n - propyl phosphoramidothioate (Cpd. 80, Table I) A solution of 0-ethyl S-n-propyl phosphorochloridothioate, 6.07 g. (0.03 mole), in 15 ml. of THP is added dropwise to an ice-cooled solution of N-allyl2-diethylamino-N'-phenyl formamidine, 6.8 g. (0.029 mole) and triethylamine, 4.55 g. (0.045 mole), in 35 ml. of THF. The reaction is stirred 2 hr. at room temperature and filtered to remove the triethylamine hydrochloride. The filtrate was evaporated by vacuum stripping, and 20 ml. of ether and 1 ml. of triethylamine are added. This mixture is stirred one and one-half hour, filtered to remove the triethylamine hydrochloride and evaporated by vacuum stripping to give 10.2 g. of orange oil, 6 g. of which is chromatographed on Biosil A. Elution with ether gives 2.99 g. (44% of theory) of purified product.
Example 6.
Preparation of N - ethyl 0 - ethyl N - //methoxy)(phenylimino)methyl/ S - n - propyl phosphoramidothioate (Cpd. 83, Table I) Ο-Ethyl S-n-propyl phosphorochlorldothioate, 4.1 g. (0.02 mole), is added dropwise to an ice-cooled solution of N-ethyl-2-methoxy-N'-phenyl formamidine, 3.6 g. (0.02 mole), and triethylamine 2.1 g. (0.02 mole), in 130 ml. of THF. The reaction is stirred overnight at room temperature, filtered to remove the triethylamine hydrochloride, and evaporated by vacuum stripping to give an oil which is chromatographed on 90 g. of Biosil A. Elution with 450 ml. of 10% ether in hexane (discarding the first 350 ml. Fraction) and 350 ml. of 20% ether in hexane gives 0.5 g. (7% of theory)of purified product. w H cn in TABLE fil £ § s M fil W Γ* tf in tf τί Pl u co CN to 00 cn in Ol co ι-1 tr OJ «—ί ro o in n co • tr tr • • • • • • « O « « cn CO co σι 00 co P" r-i r* r* «*»· >_-· w—- '«-* ·—' »—· «—* ro tT tP tr O' OJ CO OJ Ol Ol m O O ro ro cn m cn r- ι-» oo co co cn CO co r- co Γ P- O oo OJ co Ol a\ P- cn O m co o tP o O Γ0 Ol Γ* H CO • • • • • « • • • • ID kD Γ- ID r- in Γ Γ*· kD •w ·«—» ’—r «*-» *—* %-» «—* OJ Ol Ol o 00 ro tn ro Ol OJ kD CO co o cn ro ι—1 ro kO kD P- M3 kO P- in p- in kO kDΛ O 00 tj* r- o cn ro Ol co in p- CO r> kD ro t—1 co r4 o in tr tr m tP. in tr tn m in «—· s-* M»·’ ·—· *-»· 'M-' co OJ Ol cn in tn ro m m in tr oo 00 «—i CD ro Ol ro cn cn in «3* tr in tr m tr m •m* tr o o o O o o o o o o 5JtfWWtftfWtfWW ro co tf tf rH Γ0 tf H r-4 rH UUUWOOUtfOO II I I Tf tr co rH ro H ro ro co tfOtftftftfUtfffiffi υ υ υ υ o o| of W φ ai I at I fil fil ai I fil V ai f I ω| | 1 P 1 p- r*· 1 (*· Γ*» r*· Γ- σι cn tf tf tf tf a tf tf W tf tf CO ro ro co n ro ro ro tr tr U O υ U υ U U U υ U ro ro ro ro M ro ro ro ro ro tf K tf tf M W w tf tf w υ a U U U a υ O υ υ tf tf tf tf a tf tf W χ tf Hoirotrinkor-oocnO 4 0 0 2. - 24 TABLE I (continued) r* >1 r8 rp cd CM O in CM r4 KO rp • * • • r-i 00 KO r- r-i »«» *—* rp r-i rp r- o r- rp « β • t-i 00 r- r-i σι in CM rp r-i 53« r* • a • • KO KO KO KO CM H σι CM co KO cO r—1 • • • a KO KO KO KO Us z—» z—» z«s. r- σι ro in a a a a Γ*· CO r-) KO n« rp in rp CM KO O CO • a a a CO σι r-l KO rp rp in rp o O o o u S3 as χ t CM CM r-l rH O WOOS I i I rp rp ^p co co co co 8 8 8 υ υ υ o GE A| Al w| A| I I I I r- r- o r* m 8 8 a co co rp ro U O O O in in ro 8 8 co S3 cm CM 8 U O □ U Ό · Ο* Ο H cm co rp U2 «-i t-1 r-i H S3 « rCd Ά A A O ft g u Ό ft u in cd Ά · ft o O 52 z—. z—% z—» Z—» z-s z—s z—s Γ- ro KO σι in in co ΙΟ rp Γ co CO ι—l co a • a a • a a Γ- Ps co CO Γ*- CO CO K_Z »-* SkH* W S~z- <-» *-* CM r-i CM rP CM r-1 CM Γ ro σι m O σ σι a a a a a • • Γ- r- co CO 00 co co KO rp r*· KO r—1 rp CO Γ» r* in co in rp in a a a a a • KO in r* KO r* r* 'w' ** ’S-U *—» ·>_* CM co CM CM r-i CM CM KO rp ro KO ro ro CO KO in c- Γ- KO r* Γ* KO CM KO P* Γ- m o σι ’Φ co rp Γ- co rp rr rp in m rp in in -w s«< -w» •s-z- z s«- in σι in co CM in tn σι co co rp CO CO CO rp rp in in rp in in o o o o o o o ro co Ο Ο Κ X ffi 8 33 I I KO KO ro r-i u rp •—J a 1 rp a a u 1 •tp I—1 u i rp a 8 CO S3 r-i a a S3 a 8 O o A| A| Al A| Al h| Al 11(1111 r* p- γ- r* p* σι r* S3 8 8 8 8 8 8 co co co ro co rp co O U O O U U U co co co co ro ro S3 S3 8 8 8 8 8 (M u o u o o o u ro co co Μη-« «τ< *τ* Τ< Μ M H-l Uh Uh Uh Uh Uh u a u in «η t»· co σι Ο M r—I fi ι—1 rd r-i CM CM TABLE I (continued) ΪΗ f— tf LT) ri Tp ri tj · ft o u a co co VD CM [— ,53(7.25) ,53(8.25) ,60(9.06) .60(7.90) ,08 (8.10) .53(8.50) .19 (7.99) .13(8.08) .53(8.65) .58(7.68) .54(8.91) .34(9.31) ,53(8.69) .91(9.37) .91(9.19) .58(7.81) Γ- CO 00 CO r· CO CO 00 CO co Γ- 00 ch CO 00 CO F- Γ rd ro o cn rd Γ- VD VD Γ- rd τρ ch F- CM cn co VD CO Tp ro rd co 00 ch VD o [- CM rd VD CO 00 ID r- Γ— r- co r- Γ r-- [- in Γ- Γ- OO F- f- Tp »— K—· «—» ·*_» ·—> K—» «_> — — «— — ·—* — CO CM CM in co Tp r- ch O r- co CM Ω Γ- F- Γ— 00 VO VO VO O co VD VO 00 cn vo r-d VO O VD ro ro rd VO t- Γ- r- VD r- Γ- Γ- r- in Γ- Γ* Γ* r- r— in __Λ rd m co VO co CM TP ro σ» ch rd o CM r* OO co tP in cn r> in VD VD in CM TP rd in co CO CM Tp in in in in in in in in in τρ in in in in in TP «—* >— 0—' »-# ·— *—' «— *—’ »—· *—* — — *—* «— VD co 00 CM r- 00 cn CM co 00 ro co O ch m in ro σι Tp tP in co VD %P VO in τρ CM TP CM tp ro co CM Tp in in in in τρ in in in tn Tp in in in in in Tp o o o o o o o o O o o o o O o o o rd u ϊπ ririwriwririririiwwriffiaw ro rd ro co rd rd υ 1 w ri EJ ri υ M a a a o K M CJ W | a ri ri ri I TP w 1 Tp TP in TP rd ro ro ro CJ ri ri a a a ri M ri ri ri ri a ri ri ri ri I U CJ CJ ro Cl I SI f1 SI | si 1 II CJi si I SI 1 SI mJ I si 1 SI «I I SI 1 1 F- r- r- 1 C- F- Ch r- I— F- f- Ch m cn cn Γ- ri ri a ri ri ri ri ffi w ri ffl ri ri W ri ri ffi CO co cn co CO co TP co co CO co τρ CM tP τρ co u u υ cj υ cj o U υ U O U O U CJ CJ CJ 0| CM w ri rd ?i SI I CJ >1 M SI 1 1— 1 Γ- ll Λ Φ in 1 in in in uo in ro ri ri ri ro ►r t-K w ri ri n ι K ri ri ro ro ro K co ro w 0 ri CM TP CM CM a CM CM CM ri ri ri CJ CJ CJ cj rd CJ CJ CJ O CJ o CJ CJ CJ CJ CJ CJ CM o κ CJ CM CM riri riffiririririririririririri Μ M* IC CM CM CN CM Γ- 00 CM CM CD CM O rd CM ro tp ro ro co ro ro in vo rro co ro ri co ro 44002- 26 - xf cn Ο r- CM CO in CM xF VO vo rd o o xF cn in cn VO CM P- Ρ*χ p- co vo m m r- O CM ζ CO Ρ- Γ- co VO CO 00 CO σι 00 P* p- CO vo r- Q +—r χ—» x—* X—» «»-» *·—’ +—r X—' Ζ cn rd CM cn in VO σι 00 XF cn 00 VO in r-4 □ ο Μ υ o in xf r- tn CM (· xf CM CM xF co ρ- Ρ-χ CO P- co p* p- co CO p- ρ» CO r* Qη X Γ* χί' m IO CM σ XF in o o co σ O VO cn ιη ρ* «3* σ VO in cn r—J in σι m tn vo 5 ΙΟ ιη VO vo in P* r· p- co γ- in vo p- vo vo p 33 +—. χ—* *—» —* ·*-*· ·—» ·—’ X—» χ—* x—· X—> X—' *—* x—* x*- υ vo CM V0 VO cn p*· CM XF CM o o o co xF in a cn ιη VO cn co vo CM σ VO XT rd XF o r· u VO ιη VO VO in p- p- vo Γ- r- VO VO P* vo vo cq H »—S. <» ^•X. X. ω cn cn co vo XF 00 σι o rH in in σ tn VO vo ω X? cn co m XF CM CM VO vo O rd vo r-l H 8 Ο ΧΓ <3· XF in m in in in in in in m in ·+—· X-* x—* χ—· +—. x—' x—' Χ—' χ—. 8 CM σ> ρ* CM cn σ cn o co XF σι cn r- in cn « * • • • • a * a a a a a • 00 cn σ 00 in χρ rd o xp VO σι r-l vo CM r—I ή X? xf χρ «3» χρ tn m in in in xF in in in m QJ α •Η X ο ο Ο o O O o o o o O o o o o +» β 0 ϋ Η >< a χ 33 a a a a a a a a a a a a W 9 cn cn &4 cn 33 X Η rd rd 33 CJ c i"l H rd r-1 υ υ υ □ ϋ U CQ ω CJ CJ CJ o X I 1 1 1 1 1 I 1 a a 1 1 a I I xF XF xF XF XF xp xp xp XF xF xF cn cn cn >ί 33 υ a a u a a a X a a a a a a L> CJ o οι °ι Ο Ol O| oi °l oi °l °l GJ Φ ο,Ι <1)1 Φ QJ Φ φ ω <11 01 ω| ω fi! tn ci oil Cl I0| raj fi! w| -h| oil ci Ρ"· 1 1 I , 1 I I I 1 1 I J I 1 oi σ <Τι ΓΡ\ p"x Cj\ b- σ\ c— σ\ γ- σι σ\ σ» px· a a a a 33 a a X a a a a a X a XF χ* cn XF cn xp cn XF XF cn xF XF xF cn CJ Ο υ u u cj u υ o u U O CJ G υ CM CM CM CM CM CM X X a a X X U CJ u u CJ u ιη in in in in in II II II II II II ιη m μ a a 33 33 33 a cn 03 33 33 CM CM CM CM CM ν a X a a X a X υ υ □ o U U u u Q υ o o u CJ CJ CM CM CM CM CM CM X X X X X a υ υ υ u u υ 03 a 33 a a a a a X a a a a a a X rj * Ch Ο σ ο rd CM cn xp in vo P- CO σ o H CM cn □ Ζ cn XF χρ XF χρ xF xp XF xp xF XF in in in m - 27 Q □ o Cm TABLE I (continued) >t >1 oX ιΛ ffi xT X τι · a o u x ,-R, »-> z-% R λ ,-r x-Rr x—» X*R« R X—R »—R »—R στ στ CM xr or VD VD CO in o r—I xr r—1 CO o r-i CM co m O CM xr in 04 co vo VD o Ci CO • VD CO CM O' Γ GO 00 00 r-~ CO στ co O' ι- O' VD i—i ο» VD O' R_» «»_» •R—' R_» R_» R—» Rx» *—» Rx» R—» R—» Rx» •S»» Rx» R—» VD CM CO r-] στ xr OO in CO o VD xr in xr xr oj in 04 CM στ in r- vo OJ CM VD (> VD • OJ xr xr o- r- O' 00 o- ο» O' co 00 O' VD r- VD rd O' VD VDΛd__ _i_l vo in στ CM CM i—) 1—) xr co στ CM co O xr στ στ ¢) co O στ στ στ O' Ο» in OJ CM r-1 in in in OJ xT in o- r- VD r- o· in in VD O' O' VD O' VD vo O' VD VD xr VO xr VD xr H 00 00 H xr xr o co co xr στ στ O r- r- CO VD στ 00 xr 00 o xr co CM in O xr xr O' VD VD O' I-- tn in vo VD O' VD O' VD VD Or VD VD _ __ _(_w co VD στ xT 04 CM in VD στ in r- r-1 in VD m O' xr co H xi* in VD i—i o in VD co VD xr 00 i—i co CO n in in in in in in m in in m in in xr in m xT in *—· •r-» ·—· *χ» Rr-> ·—· Rx» R—» R—» Rx» R—» R—» R—» Rx» Rx» ·—» •r-» 00 VD in xr VD in r—i VD 00 CO στ o m Ή 00 O' O' 04 ι—I CM VD O' r4 o in vo CM VD xr co CO CM στ στ in in in in in tn in in in in m in xr in in xr xr O o O O O o o o O o o o o O O Ό o WWWWWWffiffiffiffiffiffiffiffiffiffi X L) ω I xr co X U 1-f ω u 1 I XT r-! u I xT r—I u xr i—| o X X I ’T «—I o X X I xr ffi I—i υ I xr ffi κ ffi o a ffi ffi ffi ffi κ ffi ffi ffi ffi ffi ffi υ| ol 0| ol °l or Q)l UH ol 0)( a> cl •H| Cl I w| I tn| I fr ?’ Cl 1 fl ci I U)( I ?’ f1 ci 1 V1 Ul| 1 1 στ o* στ 1 O' στ στ O' O' στ O' O' στ «—1 Γ- O' in στ ffi ffi ffi ffi ffi ffi ffi ffi ffi ffi ffi ffi ffi ffi ffi ffi ffi xr co xr co xr xr co co xr co CO xr co co CO xr xr O u u o u U O U U u O ϋ U u U o U OJ ffi CM υ ffi OJ CM CM U in in in m in in ffi ffi ffi II ffi ffi ffi ffi ffi ffi U u □ II ffi ffi ffi ffi CM in OJ CM ffi CM CM CM co O υ O υ O ffi U υ υ a u || ll || ffi CM vo CM CM III CM CM OJ u co ll III III III o U O o σ O O ffi ffi ffi ffi υ W u υ O υ u o U u u u O u o u u »-> xr »—R xr »-H »«R Λ oj Oi Oi Oi Rx» oi oi oi CM co ffi co co ffi CO co CO ffi ffi ffi ffi u ffi ffi ffi ffi ffi 04 ffi ffi OJ ffi ffi ffi υ u υ u CM υ u υ u O O υ O O u υ u ffi U ffi ffi ffi ffi ffi ffi υ u U o υ a ffi ffi w ffi ffi ffi ffi m ffi ffi ffi ffi ffi ffi ffi ffi κ l/l m in ID rin in co στ m lc O h VD VO xr in VD VD oo στ VO VD O O' VO I’ve» vo CM CO VD Vp *0 · CU Ο υ ζ ιη ρ* ρ* in vo S in cn vo CM cn vo G\ m m p* • in in O W a X p* » cn υ rH p* «3* rf in vo cn vo rf GO rH CM cn o • ri· Γ* cn in P- CM • a a rH a a a a a • o rH CM σι rH p·» Γ» co P* p* cn rH rH rH »** Χ—» «—» ««—* *-* x—» ·»-* co CM CM CO p- CM vo VO CQ σι • « r- rH cn p* m GO a a a O ι—I o rH rH r—ι rf p- CO co l> I> CO rH rH rH σ» rf o rf O σι σ» oo in cn I—1 σι c- rH σι in tn rH CM o vo tn vo CO in vo in t>- 00 P- P- «%-* «Μ' N—« *—* *—» ·«-* ««—* *-* χ·—* X—* m CM VO in CM r- CM rf cn cn *3· rH vo vo cn o vo in VO rH 00 00 « • • a a a a • • • • m in vo r· VO VO in 10 00 r* 10 o co <«» rH rH ρ» o cn O p- cn cn σι 00 V a a a a a a « a a a CO σν VO Ό o cn n r* cn rp rf rf M‘ in rf in rf in in «? m ·>—<· •s-» «—f *—» »«-z * VO CM P- rH vo σι rp rf p- rf r a a a a a • » • a a σι CO σ\ VO VO tn σ» P* cn rf rf rf rf m rf rp r? 55» in tn tn Ο o o o o O o ω o o o a a a a a a a a a a a cn rH rH a rH H H a u a o u a a I I I I I 1 a a a a rp rf rr rf rf rf rf a a a a a a a a a a a ol oi oi oi oi fl) fl) fl>| in fl)| ra| V yl ra! Ή j | ?' cl ci rtl WI | p- σ» cn «η σι P* Γ* P· r-* Ρ» a a a a a a a a a a a rf rf SP CM rf cn cn cn rf o a u υ υ a a u u u O CM CM a r> u co z z a IN IN 11 υ a a a cn cn cn cn co co *·«* III rp rp a a a a a a a z u a a a u a a a u a CM rf CM CM CM a a U u a o CM u CM a a u O CM CO rH CO CM Ρ» tn W O J •n· p* r£ a m co cn cn a a cn m cn co m u cn a awaaaaaa cm a a a cm α α α α a a aa α o a z z fMfnrpLniop-cootOc-HcMcnrp The compounds concerned in the invention may be used in controlling the ravages of harmful and annoying pests, particularly in commercial production fields such as industry, agriculture, horticulture (e.g. olericulture),, pomology, arboriculture, silviculture, floriculture and greenhouse rearing of plants. The compounds are particularly useful against arthropods (in varying stages of development), especially members of the Class Arachnoides, which includes the Order iO Acarina, as represented by mites and ticks, and the Class Insecta, the insects. Among the arthropods which are controlled by the compounds concerned in the present invention are the chewing insects, e.g. the southern armyworm (Spodoptera eridania), the sucking insects, e.g. the green peach aphid (Myzus persicae), soil-dwelling insects, e.g. the southern corn rootworm (Diabrotica undecimpunctata howardi), houseflies and mites, e.g. the two-spotted spider mite (Tetranychus urticae).
Representative compounds concerned in this invention are also active as fungicides, e.g. as phytopathogenic fungicides. Some of the plant fungicidal diseases controlled include, for example, rice blast (Piricularia oryzae), bean powderymildew (Erysiphe polygoni) and grape downy mildew (Plasmopara viticola).
Furthermore, representative compounds concerned in this invention, particularly compounds wherein R in Formula I is a hydrogen atom, possess nematocidal activity. Among the nematodes which are controlled are soil nematodes, typified by the southern root knot nematode (Meloidogyne incognita).
Thus, in accordance with the invention, pests in the form of fungi, arthropods and/or nematodes are controlled by applying directly to the pests or to the locus to be freed of, or protected from, attack by the Oi - 30 pests, a pesticidally effective amount of one or more compounds of Formula I. A plant protection locus is usually the aerial or subterranean portion of a plant, or a propagative sub-unit thereof, and its immediate or future surround.
One example of the above pesticidal method comprises enhancing the value of a commercial product infested, or liable to infestation, with one or more of said pests, wherein the pests are controlled by applying to said product a pesticidally effective amount of at least one compound of Formula X. The commercial products to which the pesticidal compounds may be applied include, in particular, (a) vegetable matter (in a state of growth or otherwise ) such as vegetable foodstuffs for humans or domestic animals; trees grown for timber, fruit or nuts; ornamental crops; or harvested or stored forms of any of these kinds of vegetable matter, (b) fibrous material and (c) soil or another medium prepared for the growth of said vegetable matter, e.g. growth in greenhouses and tilled fields.
Another example of a pesticidal method is directed to increasing the yield of a vendible vegetable crop by controlling infestation (with one or more of said pests) of the plants yielding the crop. In such method, a yield increase may be effected by treating with one or more compounds of Formula I the plants, seeds thereof or soil which contains the plants or seeds in which the plants or seeds are to be planted.
The term control as employed in the specification and claims of this application is to be construed as any means which adversely affects the existence or growth of a living organism. Such means can comprise a complete killing action, eradication, arresting in growth, inhibition, reduction in number - 31 440θ or any combination thereof.
The novel phosphoramidates of Formula I possess general utility as arthropodicides, particularly against members of the class Arachnoidea, which includes the order Acarina as represented by mites and ticks, and Insecta the insects. Certain compounds are also active as nematocides and fungicides, particularly phytopathogenic fungicides.
Initial evaluations are made on the following 10 mite, insects, and nematode: Code Symbol Commom Name Latin Name TSM Two-spotted spider mite Tetranychus urticae GPA Green peach aphis Myzus persicae MBB Mexican bean beetle Epilachna varivestis SAW Southern armyworm Spodoptera eridania CRW Southern corn rootworm, ova and larvae Diabrotica undecimpunctata howardi nema Southern root-knot nematode Meloidogyne incognita HF House fly Musca domestica RB Rice blast Piricularia oryzae A test solution containing 600 ppm of test compound can be made by dissolving the test compound in a solvent (acetone:methanol, 1:1 by volume), adding surfactant and then water to give an acetone:methanol: water system of 10:10:80 by volume. A 1:1 by volume mixture of an alkylarylpolyetheralcohol (commercially available under the trademark Triton X-155) and a modified phthalic glycerol alkyd resin (commercially available under the trademark Triton B-1956) can be utilized at the equivalent of one ounce per 100 gallons of test solution as a surfactant.
For the mite test, infested bean (Phaseoius llmeanus) leaf discs (1.25 inches in diameter) containing about 50 mites and for green peach aphid tests; infested brocoli (Brassica oleracea italics) leaves or portions thereof containing about 50 aphids are placed in a Petri dish lid on a moistened piece of cotton. The leaves are then sprayed with the test solution using a rotating turntable. They are held for 24 hours and then the percent kill is determined.
For the bean beetle and armyworn test, detached bean leaves on pieces of moistened filter paper are sprayed as above for the mite test in similar dishes and allowed to dry. One such dish is infested with 10 third instar Mexico beetle larvae, while another is infested with 10 third instar southern armyworm larvae. The dishes are covered. After holding for 48 hours, the percent kill is obtained.
For the house fly test, half pint glass canning jars with a screened top are used. Food is supplied for the house fly (sugar water). The test insects consist of 20 adult house flies. The jars containing the insects are sprayed using the turntable. In the house fly test, a percent knockdown is determined one hour after application, the percent kill after 24 hours For the nematode test, soil is homogeneously inoculated with a macerated blend of tomato roots heavily knotted with the root knot nematode. Ten milliliters of the test solution are added to 200 milliliters of the inoculated soil in a 16 oz. jar to give a concentration by volume of about 30 ppm. The jar is then shaken to ensure thorough mixing, immediately uncapped, and allowed to air for 24 hours. The soil is then placed into a 3 inch plastic pot after which time 3 cucumber (Cucumis sativus) seeds are planted.
About 23 days thereafter the cucumber plants are - 33 removed from the soil and the root system examined for the presence of knots. A total of 25 knots or less is considered as a measure of control.
For tests involving the southern corn rootworm (Diabrotica undecimpunctata howardi) ova and larvae, two layers of 4.25 cm. filter papers are placed in small, Petri dishes, and sprayed on the turntable with a 600 ppm solution of the test compound ahd air dried. About 100 eggs in about one milliliter of water are pipetted onto the filter paper and the dishes covered. These are held for 6 days and examined under the microscope. The percent kill values for ova and larvae are determined.
Fungicidal evaluation of compounds concerned in this invention is carried out by way of a foliar screening test. The general procedure for the fungicidal test is to take potted plants in proper condition of growth for susceptibility to the plant diseases to be evaluated, to spray these on a moving belt and allow them to dry. The plants are then inoculated with the respective fungal spores which are allowed to incubate until the disease symptoms and the disease control are read or estimated. Percentage of disease control is recorded.
Compounds are tested for fungicidal activity at a concentration of 300 ppm in a solution or suspension made by dissolving a weighed amount of the candidate fungicide in a 50:50 by volume mixture of acetone and methanol and then adding an equal volume of water.
Table II gives the results of the foregoing biological evaluations on Compounds 1-82 of Table I. - 34 TABLE II Screening Results, % Controla Cpd. No. TSMb GPAb MBBb SAWb CRW E/LC Nema^ HFb RBe 1 100 100 100 100 67/100 A 100 - 2 100 100 100 100 0/89 A 100 A 3 100 100 100 100 49/90 A 100 A 4 100 100 100 100 0/87 A 100 A 5 100 100 100 100 0/83 A 100 A 6 100 100 100 100 58/95 A 100 A 7 100 100 100 100 0/70 A 100 - 8 100 100 100 100 0/96 A 100 Ξ 9 100 100 100 100 55/92 A 100 B 10 100 100 100 100 76/100 A 100 A 11 100 100 loo 100 73/95 A loo A 12 100 100 100 100 0/98 A 100 - 13 100 100 100 100 0/98 A 100 A 14 100 100 loo 100 0/93 A 100 - 15 100 100 100 100 43/100 A 100 - 16 100 100 100 100 0/100 A 100 - 17 100 100 100 100 50/100 C . 100 - 18 100 100 100 100 47/93 C 100 - 19 100 100 100 100 59/100 C 100 - 20 100 100 100 100 60/100 A 100 - 21 100 100 100 100 48/100 A 100 B 22 100 100 100 100 0/100 C 100 - 23 100 100 100 100 67/100 A loo - 24 100 100 100 100 90/100 A 100 B 25 100 100 100 100 77/100 A 100 - 26 100 100 100 100 81/100 C 100 - 27 100 100 100 100 63/86 A 100 - 28 100 100 100 100 96/100 A 100 - 29 100 100 100 100 46/100 A 100 - 30 100 100 100 100 58/100 A 100 - - 35 TABLE II (Continued) TSMb GPAb MBBb SAWb CRW E/Lc Nema^ HFb RBe loo 100 100 100 61/100 A 100 100 100 100 100 0/00 A 100 - 100 100 100 100 78/100 A 100 - 100 100 100 100 0/74 A - - 100 100 100 100 71/100 A - - 100 100 100 100 78/100 A 100 E 100 100 100 100 45/100 A 100 A 100 100 100 100 60/100 A 100 - loo 100 100 100 84/100 A - - 100 100 100 100 48/100 A - - loo loo 100 100 64/100 A - - 100 100 100 100 65/100 A - A 100 100 100 100 41/100 A - - 100 100 100 100 75/100 A - - 100 100 100 100 0/100 A 100 - 100 100 80 100 0/100 A 100 - 100 100 100 100 77/100 A 100 - 100 100 100 100 79/100 A B 100 100 100 100 57/96 A - - 100 100 100 100 59/100 A - - 100 100 100 100 58/100 A 100 A 100 100 100 100 41/100 A 100 A 100 100 100 100 58/100 A - - 100 100 100 100 0/100 A 100 A 100 100 100 100 0/100 A 100 - 100 100 100 100 o/lOO A 100 A 100 100 100 100 61/100 A 100 - 100 100 100 100 40/100 A 100 - 100 100 100 100 0/100 A 100 A 100 100 100 100 0/95 A 100 A 4001 - 36 TABLE II (Continued) TSMb CPAb MBBb SAWb CRW E/LC Nema^ HFb RB1 100 100 100 100 0/84 A 100 A 100 100 100 100 53/100 A 100 A 100 100 100 100 0/100 A - - 100 100 100 100 0/100 A 100 - 100 100 100 100 0/100 A 100 - 100 100 100 100 0/100 A 100 - 100 100 100 100 55/100 A 100 - 100 loo 100 100 60/100 A 100 B 100 100 100 100 0/100 A - - 100 100 100 100 0/100 A 100 B loo 100 100 100 0/89 A 80 - 100 100 100 100 0/100 A 100 B 100 100 100 100 55/100 A 100 - 100 100 100 100 90/100 C - - 100 100 loo 100 54/100 C - - 87 70 0 100 0/90 C - - 100 100 100 100 45/100 c - - 100 100 100 100 0/100 c 100 - 100 100 100 100 64/100 A 100 E 100 100 100 100 0/100 - - - 78 13 10 10 0/0 c 0 E a) TSM=two-spotted mite; GPA = green peach sphid; MBB = Mexican bean beetle; SAW = southern armyworm; CRW E/L = corn rootworm ova/larvae; nema = nematode; HF = housefly; RB = rice blast b) Insecticidal screening results, % control at 600 ppm c) Insecticidal screening results, % control at 150 ppm d) A = 0-9 knots on root; B = 10-25 knots on root; C = >25 knots on root (at 30 ppm in soil) e) Disease control: A = 97-100%; B = 90-96%; C = 70-89%; D = 50-69%; E = <50% (at 300 ppm) For use as pesticides, the compounds concerned in this invention can be used as solutions in organic solvents or formulations prepared by bringing together the various ingredients of the desired formulation. For example, they can be formulated as wettable powders, emulsifiable concentrates, dusts, granular formulations or flowable emulsion concentrates. In such formulations, the phosphoramidates can be extended with an agronomically acceptable liquid or solid carrier and, when desired, suitable surfactancts can likewise be incorporated. Surfactants commonly used in the art can be found in the John W. McCutcheon, Inc. publication Detergents and Emulsifers Annual. In formulations, the phosphoramidate content may range from 1 to 99, e.g. 5 to 95 percent by weight.
The phosphoramidates can be taken up or mixed with a finely particled solid carrier, as for example, clays, inorganic silicates, carbonates, and silicas. Organic carriers can also be employed. Dust concentrates can be made in which the phosphoramidate content is from about 20 to about 80% by weight. For ultimate applications, these concentrates are normally extended with additional solid to give an active ingredient content of from 1 to 20% by weight. Granular formulations can be made using a granular or pelletized form of carrier, such as granular clays, vermiculite, charcoal or corn cobs, and can contain the active ingredient in an amount from 1 to 25% by weight.
Oi - 38 Wettable powder formulations can be made by incorporating the phosphoramidates in an inert, finely divided solid carrier along with a surfactant which can be one or more emulsifying, wetting, dispersing or spreading agents or blend of these. The phosphoramidates are usually present in the range of 10 to 35% by weight and surfactants from 0.5 to 10% by weight.
One convenient method for preparing a solid formulation is to impregnate the phosphoramidate onto the solid carrier by means of a volatile solvent such as acetone. In this manner, adjuvants, such as activators, adhesives, plant nutrients, synergists and various surfactants can also be readily incorporated.
Emulsifiable concentrate formulations can be prepared by dissolving the phosphoramidates in an agronomically acceptable organic solvent and adding a solvent soluble emulsifying agent. Suitable solvents are usually water-immiscible and can be found in the hydrocarbon, ketone, ester, alcohol, and amide groups of organic solvents. Mixtures of solvents are commonly employed. The surfactants useful as emulsifying agents can constitute 0.5 to 10% by weight of emulsifiable concentrate and can be anionic, cationic or non-ionic in character. The concentration of the active ingredients can vary from 10 to 80%, preferably in the range of 25 to 50% by weight.
For use as pesticidal agents, the phosphoramidates should be applied in an effective amount sufficient to exert the desired pesticidal activity by techniques well known in the art. Usually, this will involve the application of the phosphoramidate to the loci to be protected from or freed of pests in an effective amount when incorporated in an agronomically acceptable carrier. However, in certain situations, it may be desirable and advantageous to apply the compounds 4400 1 - 39 t directly onto the loci to be protected from or freed of pests without the benefit of any substantial amount of carrier. This is a particularly effective method when the physical nature of the toxicants is such as to permit what is known as low volume application, that is, when the compounds are in liquid form or substantially soluble in higher boiling solvents .
The application rate will, of course, vary depending upon the pesticidal purpose, the phosphoramidate being utilized, the frequency of dissemination, and possible other factors as well.
By agronomically acceptable carrier is meant any substance which can be utilized to dissolve, disperse, or diffuse the chemical incorporated therein without impairing the effectiveness of the toxic agent and which does no permanent damage to such environment as soil, equipment and agronomic crops.
For use as insecticides and acaricides, dilute sprays can be applied at concentrations of 0.01 to 20 pounds of the phosphoramidate ingredient per 100 U.S. gallons of spray. The sprays are usually applied at 0.1 to 5 pounds per 100 U.S. gallons. In more concentrated sprays, the active ingredient is increased by a factor of 2 to 12. With dilute sprays, applications are usually made to the plants until run off is achieved, whereas with more concentrated low-volume sprays, the materials are applied as mists.
For use as fungicides, the compounds concerned in this invention can be applied as fungicidal sprays by methods commonly employed such as conventional highgallonage hydraulic sprays, low-gallonage sprays, airblast sprays, aerial sprays, and dusts. The dilution and rate of application will depend upon the type of equipment employed, the method of application and - 40 diseases to be controlled but the preferred effective amount is usually 0.1 lb. to 50 lbs. per acre of the active ingredient.
As a fungicidal seed protectant, the amount of toxicant coated on the seed is usually at a dosage rate of 0.1 to 20 ounces per hundred pounds of seed. As a soil fungicide the chemical can be incorporated in the soil or applied to the surface usually at a rate of 0.1 to 50 lbs. per acre. As a foliar fungicide, the toxicant is usually applied to growing plants at a rate of 0.25 to 10 lbs. per acre.
For use as a nematocide, systemic agent, or as a soil insecticide, the phosphoramidates can be applied as a solid formulation, preferably a granular formulation or as a diluted liquid preparation, by broadcasting, side-dressing, soil incorporation or seed treatment.
The phosphoramidates can also be added to transplant water or employed as dips or soaks for vegetative parts employed in propagation, such as seeds, tubers, roots and seedlings so as to disinfect and/or provide residual protection from nematodes, soil insects {and mites) and via systemic uptake, foliar pests. The application rate can be from 0.5 to 50 pounds per acre; however, higher rates can also be used. The preferred rate is from 1 to 25 pounds per acre. For soil incorporation, the phosphoramidates can be mixed with the soil at a rate of 1 to 100 p.p.m. of active ingredient.
The phosphoramidates can be utilized as the sole pesticidal agents or they can be employed in conjunction with other pesticides such as bactericides, fungicides, herbicides, Insecticides, acaricides and nematocides·Typical compounds of Formula I are those in which A is phenyl or phenyl substituted with 1, 2 or 3 4400 - 41 substituents each of which is usually in the 2, 4 or 6 position and which are selected from (C^-C^) alkyl, halogen or nitro; R is hydrogen or (C^-C 4) alkyl; R3 is (C^-C-j)alkyl or (C-j-C^)alkenyl; R2 is (C^-C^)alkyl R3 is (Cg-Cj) alkyl; and X is oxygen.

Claims (31)

1. 1. CLAIMS: 1. A compound of the formula: wherein 5 A is phenyl or naphthyl each optionally substituted with 1, 2 or 3 of the same or different substituents selected from cyano, nitro, halogen, (C-^-Cg) alkyl, (C^-Cg)alkoxy, (C^-Cg)alkylthio, /di-(Cj-Cg)alkyl7aminocarbonyl, (C^-Cg)alkyl substituted with one or more 10 halogen atoms, phenyl, phenoxy, naphthoxy and phenylthio ·, R is hydrogen or (C^-Cg)alkyl; R 1 is (a) (C^-Cg)alkyl optionally substituted with one 15 substituent selected from cyano, nitro, (C^-Cg)alkoxy, (C^-Cg)alkylthio, (C^Cg) alkylsulfinyl, (C^-Cg) alkylsulfonyl, /(C^-Cg) alkyl7carbonyl, /'(C-^-Cg) alkoxy/carbonyl, /(Cj-Cg) alkyl/carbonyloxy, /mono- or di-(C^-Cg)alky17aminocarbonyl, 20 phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylcarbonyl, phenoxycarbonyl, phenylcarbonyloxy and phenylaminocarbonyl, each of the last 8 groups being optionally substituted as defined above for A=phenyl or naphthyl; 25 (b) phenylalkyl of up to 11 carbon atoms or naphthylalkyl of up to 11 carbon atoms, each of these groups being optionally ring-substituted with 1, - 43 2 or 3 of the same or different substituents selected from the group of substituents specified above in this claim for the A group phenyl or naphthyl; (c) (C^-Cg)alkenyl optionally substituted with one or two of the same or different substituents selected from cyano, halogen, /(C^-Cg)alkoxy/* carbonyl, phenyl and naphthyl each of the last two groups being optionally substituted as defined above for A=phenyl; (d) (C 3 -Cg)alkynyl; or (e) (Cj-Cg)cycloalkyl R 2 is(C^-Cg)alkyl; R is (C^-Cg)alkyl; and X is oxygen or sulfur.
2. A compound according to Claim 1 wherein R is a hydrogen atom.
3. A compound according to Claim 1 wherein A is optionally substituted phenyl; R is hydrogen or (Cj-C^ alkyl; R 1 is (a) optionally substituted (C^-C^)alkyl; (b) (Cg-Cy)cycloalkyl; (c) optionally substituted (C 3 ~C 4 )alkenyl; (d) (C 3 “C 4 )alkynyl; or (e) optionally substituted benzy or phenethyl; R 2 is (Cj-C^) alkyl; R 3 is (C 3 ~C 4 )alkyl; and X is oxygen.
4. A compound according to Claim 3 wherein R^ is (a) (C x -C 4 )alkyl; 44 (b) (Cg-Cy)cycloalkyl; (c) (Cg-C^)alkenyl; or (d) benzyl or phenethyl.
5. A compound according to Claim 4 having the 5 formula: wherein & R' is hydrogen or (C^-C^)alkyl; R is (C^-C^)alkyl or (Cj-C^)alkenyl; 10 R 6 is (Cj-C^alkyl; R? is (C^-C^)alkyl; and Υ,Υ’,Υ' 1 , which may be the same or different, are selected from hydrogen, (C-^-Cg)alkyl, nitro and halogen
6. A compound according to Claim 5, wherein 4 15 R is hydrogen or methyl; R 5 * 7 is (C^-C 3 )alkyl or allyl; R® is ethyl; R is n-propyl, isobutyl or sec-butyl; and Υ,Υ’,Υ'' are hydrogen, methyl or chlorine. 20
7. A compound according to Claim 6 having the formula: wherein R is n-propyl or iso-butyl.
8. A compound according to Claim 6 having the formula:
9. A compound according to Claim 6 having the OC 2 H 5 SC 3 H 7 -n
10. A compound according to Claim 1 having the formula: H /CH 2 CH 2 CN wherein R is n-propyl or sec-butyl.
11. A compound according to Claim 6 having the formula: 440G& ch 2 ch=ch 2 /° C 2 H 5 SR wherein r' is n-propyl or sec-butyl.
12. A compound according to Claim 6 having the formula: 0C 2 H 5 SCjHg-sec
13. A'compound according to Claim 6 having the
14. A compound according to Claim 1 modified in 10 that at least one of A, R and R^ is as follows: A is substituted phenyl or naphthyl wherein at least one of the substituents specified for A in Claim 1 is replaced by a substituent selected from /Ic^-Cg)alk oxy/carbonyl, /3i-(C^-C 2 )alkyl7amino, /'(C^-Cg) alky 1/15 carbonyl, /(C^-Cg) alkyl7carbonyloxy, (C-^-Cg) alkylsulfinyl and (C-^-Cg) alky lsulf onyl; - 47 R is (C^-Cg)alkoxy, (Cj-C g )alkylthio, cyano, /di-(Cj-Cg)alky17amino or a saturated or unsaturated heterocylic group having four to six carbon atoms and which contains one or two hetero nitrogen atoms optionally plus a hetero oxygen or sulfur atom; R 1 is (a) (C^-Cg)alkyl substituted with one furyl, /(di(C^-Cg)alkyl/amino, (C^-Cg) alkenyloxy or /(C^-Cg) alkenyloxy/carbonyl group; (b) substituted phenylalkyl of up to 11 carbon atoms, or naphthylalkyl of up to 11 carbon atoms, or naphthylalkyl of up to 11 carbon atoms, each of these groups being substituted as specified above in this claim for the A group substituted phenyl or naphthyl; (c) substituted (C 3 ~Cg)alkenyl wherein at least one of the substituents specified in Claim 1 for R^substituted (C 3 -C g )alkenyl is replaced by (C^-Cg)alkoxy; (d) ( C 4 - Cg)cycloalkenyl optionally substituted with 1, 2 or 3 of the same or different substituents listed for R d =substituted alkenyl in Claim 1 or in this claim; or (e) (Cg-Cg)cycloalkyl substituted with 1, 2 or 3 of the same or different substituents listed for R^substituted alkyl in this claim or in Claim 1.
15. A compound according to Claim 14, wherein R is (C 3 ~C^)alkyl.
16. A compound according to Claim 1, wherein A is phenyl or phenyl substituted with 1, 2 or 3 of the same or different substituents selected from (C^-Cg)alkyl, halogen, or nitro; R is hydrogen or (C^-cpalkyl; R 1 is (Cj-C 3 )alkyl or (Cj-C^) alkenyl; R^ is (C^-C^)alkyl; - 48 3 R Is (C 3 ~C 4 )alkyl; and X is oxygen.
17. A compound according to Claim 16, wherein A is substituted'phenyl in which each substituent occupies the 2, 4 or 6 position.
18. A compound according to Claim 1, being any of Compounds 1-25 in foregoing Table I, or any of those individual compounds listed in foregoing List A but with the exclusion of any compound individually claimed in Claims 7-13.
19. A compound according to Claim 14 being any of one of those individual compounds which are identified in the foregoing descriptive portion of the specification and which are in accord with Claim 14.
20. A method for the preparation of a compound according to Claim 1 which includes the step of reacting, in the presence of an acid binding agent, a compound of the formula; A-N=C-N with a compound of the formula: X 2 3 “ (R z 0)(R 4 S)-P-C1 12 3 where A,R,R ,R ,R and X are as defined in Claim 1.
21. A method for the preparation of a compound according to Claim 14 which includes the step of reacting, in the presence of an acid binding agent, a compound of the formula: R I ι A-N=C-NHir - 49 with a compound of the formula; x 2 3 Ί (R O)(R J S)-P-C1 12 3 wherein A,R,R ,R ,R and X are in accordance with Claim 14.
22. A method according to Claim 20 as applied to the preparation of a compound according to any of Claims 2-9 and 16-18.
23. A method according to Claim 21 as applied to the preparation of a compound according to Claim 14 or 19.
24. A pesticidal composition containing, as an active ingredient, at least one compound according to any of Claims 1-9 and 16-18 and an agronomically acceptable carrier.
25. A composition according to Claim 24, (a) in the form of a dust or granules or (b) which contains a surface active agent and is in the form of a wettable powder, emulsifiable concentrate or flowable emulsion concentrate.
26. A composition according to Claim 24 or 25 modified in that it contains a compound according to any of Claims 10-14 and 19.
27. A method of controlling pests in the form of fungi, arthropods and/or nematodes which comprises applying directly to the pests or to the locus to be freed of, or protected from, attack by pests, a pesticidally effective amount of at least one compound according to any of Claims 1-9 and 16-18.
28. A method according to Claim 27, modified in that there is applied a compound according to any of Claims 10-14 and 19. - 50
29. , A compound according to claim 1 when prepared by a method according to Claim 20.
30. , A compound according to Claim 1 when prepared by a method substantially as hereinbefore described 5 with reference to foregoing Example I.
31. , A compound according to Claim 14 when prepared by a method according to Claim 21 or by a method substantially as hereinbefore described with reference to foregoing Examples 5 or 6.
IE2722/76A 1975-12-29 1976-12-13 Phosphoramidate pesticides IE44001B1 (en)

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