DE2657972A1 - AMIDOPHOSPHORIC ACID ESTERS, THE PROCESS FOR THEIR MANUFACTURING, AND THE PEST INSPIRATORS CONTAINING THEM - Google Patents

Description

MÜLLER-BORE DBUi ¹ SL - SCHCX H23RTIIL

PATEKTAlfWlLIE

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DR. WOLFGANG MÜLLER-BORE tPATENT ADVOCATE FROM 1927-1975) DR. PAUL DEUFEL. DIPL.-CHEM. DR. ALFRED SCHÖN. D1PL.-CHEM. WERNER HERTEL. DIPL.-PHYS.

S / R 14-134

Rohm and Haas Company Independence Mall West, Philadelphia, Pa. 19105, USA

Phosphoric acid esters, process for their preparation and pesticides containing them

The invention relates to amidophosphoric acid esters or phosphoric acid ester amides, Process for the preparation of these compounds and pesticides containing these substances as active ingredients or pesticides that are suitable for controlling a number of pests.

The invention relates in particular to the amidophosphoric acid esters of the following general formula (I)

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\ ^ OR ²

in the

A is an optionally substituted aryl group with up to 12 aromatic ring carbon atoms, preferably one optionally substituted phenyl group;

R is a hydrogen atom, a Cj-Cg-alkyl group (preferably a C ₁ -C ₄ -alkyl group), a di- (C ₁ -Cg) -alkylamino group (preferably a di (C ₁ -C ₄ ) -alkylamino group, in particular the diethylamino group ), a saturated or unsaturated heterocyclic group with 4 to 6 ring carbon atoms, which (a) contains one or two nitrogen atoms and optionally also an oxygen atom or a sulfur atom, a C ₁ -C _g alkoxy group (preferably a Cj-C ^ alkoxy group) , a Cj-Cg alkylthio group (preferably a Cj-C ^ alkylthio group) or a cyano group;

R a) an optionally monosubstituted C ₁ -Cg- (preferably C ₁ -C ₃ - or Cj-C ^ jJ alkyl group,

b) an optionally substituted C ₃ -C ₃ "(preferably Cc-C ₇ -) cycloalkyl group,

c) an optionally substituted C ₃ -C 6 (preferably C ₃ -C ₄ ) - alkenyl group,

d) an optionally substituted C ₄ - or C ₅ -C ₃ - (preferably C ₅ -C 6 -) - cycloalkenyl group, or

e) a C ₃ -C 6 (preferably C ₃ -C ₄ ) alkynyl group; 2

a C ₁ -C 6 (preferably C ₁ -C ₃ or C ₁ -C ₄ ) alkyl group;

R is a C ₁ -C 6 (preferably C ₁ -C ₄ and in particular C ₃ -C ₄ ) -alkyl group; and

X is an oxygen atom or a sulfur atom and preferably mean an oxygen atom.

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The term "aryl group" used herein stands for an aromatic hydrocarbon group, the free valence of which starts from a carbon atom which is in an aromatic nucleus. Typical aryl groups are the phenyl group, the naphthyl group or groups of this type, with C.-C ₆ -alkyl, in particular Cj-Co-alkyl groups are substituted, such as the tolyl group.

If aliphatic hydrocarbon groups are referred to here, for example alkyl groups, alkenyl groups, alkynyl groups, or the alkyl groups of alkoxy groups, so include these groups both straight chain and. also branched groups. Examples of groups of this type are the methyl group, aie ethyl group, the propyl group, the isopropyl group, the sec-butyl group, the isobutyl group, the tert-butyl group, the pentyl group, the neopentyl group, the hexyl group, the allyl group, the 2-butenyl group, the 3-methyl-1-pentenyl group, the 3-hexenyl group, the propynyl group, the 1 ^ pentynyl group, the 4-methyl-1-pentynyl group, the hexynyl group and the methoxy group.

If the group A of the general formula I stands for a substituted aryl group, this can be one or more identical or different substituents ,. preferably 1 to 3 substituents have, these substituents are preferably substituents of the following type:

(a) Halogen atoms, alkoxy groups, alkylsulfonyl groups, alkylthio groups, Nitro groups, cyano groups, alkoxycarbonyl groups, dialkylamino groups, alkylcarbonyl groups, dialkylaminocarbonyl groups, Arylthio groups and alkyl groups containing one or more halogen atoms, alkylaminocarbonyl groups, alkylcarbonyloxy groups, Aryloxy groups and alkylsulfinyl groups are substituted, the alkyl groups each having 1 to 6 carbon atoms, preferably 1 to 3 or 4 carbon atoms; and

(b) aryloxy groups and arylthio groups whose aryl group is 6 to Contains 10 ring carbon atoms and preferably one phenyl group is. The preferred substituents of the aryl group A

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are nitro groups; Halogen atoms, especially chlorine atoms; C - C -, - or Cj-C. Alkyl groups, in particular methyl groups; C ₁ -C ₃ - or C.-C a -alkoxy groups, in particular methoxy groups; and C ₁ -C ₃ or Cj -C 4 alkylthio groups, especially methylthio groups.

If the group R stands for a heterocyclic group, it can be, for example, the pyrrolidinyl group, the piperidyl group, the N-morpholinyl group, the piperazinyl group, the hexahydroazepinyl group, be the hexahydrodiazepinyl group or the hexahydrooxazepinyl group.

1
If the group R represents a substituted alkyl group, this alkyl group can be substituted by a substituent selected from the following groups:

(a) Cyano groups, nitro groups> Furyl groups, alkoxy groups, Alkylthio groups, alkylsulfinyl groups, alkylsulfonyl groups,

Alkylcarbonyl groups, alkoxycarbony groups., Alkylcarbonyloxy groups, Mono- or di-alkylaminocarbonyl groups and dialkylamino groups, the alkyl groups each containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms;

(b) Alkenyloxy groups and alkenyloxycarbonyl groups, their alkenyl radical Contains 3 to 6 carbon atoms, preferably 3 to 4 carbon atoms;

(c) aryl groups or substituted aryl groups as above for the group A of the general formula (I) are defined;

(d) aryloxy groups, arylthio groups, arylsulfinyl groups, arylsulfonyl groups, Arylcarbonyl groups, aryloxycarbonyl groups,

Arylcarbonyloxy groups and arylaminocarbonyl groups, respectively Contain 6 to 10 aromatic ring carbon atoms, preferably are in a phenyl ring; and

(e) the substituents specified under (c) in this paragraph, whose "aryl group" is substituted, in particular in the manner as described above with regard to the group A of the general formula (I) is indicated for the substituted aryl group. Preferred substituents of the alkyl groups are alkoxycarbonyl groups, alkylcarbonyl groups, Mono- or di-alkylaminocarbonyl groups, alkoxy

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AT

groups, alkylthio groups, alkylsulfonyl groups. Phenylthio groups and cyano groups. If the group R represents an aralkyl group or contains such a group, then has this group preferably has no more than 11 carbon atoms and typically represents an aralkyl group of 7, 8, 9 or 10 carbon atoms, for example a benzyl group, a phenethyl group or a 3-phenylmethylpropyl group.

When the group R is a substituted cycloalkyl group stands, the cycloalkyl group can have one or more, preferably 1 to 3, identical or different substituents have, in particular substituents of the type as described above for the group R in the meaning of a substituted alkyl group are specified. The group R can have the meaning · a cycloalkyl group, a cyclopentyl group, a cyclohexyl group or a cycloheptyl group, it being possible for these groups to be optionally substituted.

1
If the group R is a substituted alkenyl group, this group can have one or more, preferably one or two, identical or different substituents, in particular substituents from group (a), the cyano groups, halogen atoms, preferably chlorine atoms, alkoxy groups, preferably methoxy groups , and alkoxycarbonyl groups, wherein the alkyl radicals contain 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and from group (b) which includes aryl groups or substituted aryl groups as defined above for group A of general formula (I) are.

ι If the group R is a substituted Cycloalkeny! group

stands, the cycloalkenyl group can be one or more, preferably have no more than 3, identical or different substituents as described above for the substituted alkenyl group are specified. When the group R represents or contains a cycloalkenyl group, the cycloalkenyl group includes preferably 5 to 7 or 8 ring carbon atoms and represents, for example, a cyclopentenyl group, a cyclohexenyl group,

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represents a cycloheptenyl group or a cyclooctenyl group

In the preferred compounds of the general formula (I), the substituent A corresponds to the following general formula

(ID

in the .

Y, Υ ¹ and Y ", which can be identical or different, hydrogen atoms; C ₁ -C _{6 -alkyl groups, preferably C 1 -C 4} -alkyl groups and in particular methyl groups; halogen atoms, preferably chlorine atoms; Cj-Cg -alkoxy groups, preferably C.-C ₄ -alkoxy groups and in particular methoxy groups; Cj-Cg-alkylthio groups, preferably Cj-C ^ -alkylthio groups and in particular methylthio groups; nitro groups, cyano groups, (C ₁ -Cg-, preferably C 1 -Cj -alkoxy ^ carbonyl groups; Di (C ₁ -C ₄ ) -alkylamino groups, preferably di (C ₁ -Cg) -alkylamino groups and in particular dimethylamino groups; (Cj-Cg-alkyl) -carbonyl groups; di- (C ₁ -C ₄ ) -alkylamino-carbonyl groups; arythio groups , preferably phenylthio groups; or aryloxy groups, preferably phenoxy groups.

Most preferred compounds of the present invention correspond to the following general formula (III)

in the ... ι

R represents a hydrogen atom or a Cj-C alkyl group;

R is a C _{1 -C 4} -alkyl group, preferably a methyl group or an ethyl group, a cyclohexy group, a

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group, a propargyl group, a phenylthio (C - C ₄ 3-alkyl group, preferably a phenylthioethyl group, a cyano- {Cj-C ^ -alkyl group, preferably a cyanoethyl group, a C ^ -C ^ -lUJcox ^ arbonyl- CC 1 -C 4 alkyl group, preferably a ethoxycarbonylethyl group, a furfuryl group or a benzyl group;

_, 6 a C ₁ -C 4 -alkyl group, preferably a ethyl group;

R is a C ₃ -C, alkyl group, preferably an n-propyl group, an isobutyl group or a see-Buity group? country

Υ, Y ¹ and Y ", which can be identical or different, denote hydrogen atoms, e ^ -Co-alkyl groups, preferably methyl groups, nitro groups, alkylthio groups, preferably methylthio groups, halogen atoms, preferably chlorine atoms and most preferably hydrogen atoms, methyl groups or chlorine atoms .

Have representative compounds of the general formula (I) nematocidal, fungicidal or arthropodicidal, especially acaricidal and insecticidal effects

Typical examples of compounds according to the invention are as follows specified. For those listed in the following JLists Compounds, the alkyl groups are the n-alkyl groups, unless otherwise stated.

List A

Έ-βΐ * - (4-chlorophenyl) -f ormiτnidoyl7-0-ethyl-l ^ -Inethyl-S-methylethylamidothiophosphate and -amidodithiophosphate (or 19 - ^ '- 4-chlorophenyl) -formimidoylJ-O-ethyl-IT- methyl — S-methylethylphosphoramido-

thioate and phosphoramidodithioate) -

O-ethyl-N-ynethyl-lJ- ^ Kr '- (2, 4-dimethylphenyl3 acetimidoyl / S- {1 -methyl-

propyl) -amidothiophosphate and -amidodithiophosphate-

O-methyl-S- {2-methylpropyl) -Ή- / Μ * - {4-nitrophenyl) -forfflimidoyl? N ~

propyl amidothiophosphate and amidodithiophosphate.

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N-Cyclopentyl-O-ethyl-N- (N'-phenylformimidoyl) -S-propyl-amidothiophosphate and amidodithiophosphate.

O-ethyl-S- (1-methylpropyl) -N- (2-phenoxyethyl) -N- / N '- (3,5-ditrifluoromethyl-phenyl) -formimidoyl-7-amidothiophosphate and amidodithiophosphate.

N- 3 '- (4-chloro-2-methylphenyl) -formidoy ^ -O-ethyl-N-methylethyl-S- (1-methylpropyl) -amidothiophosphate and -amidodithiophosphate. N- ZN '- (4-cyanophenyl) -f omimidoylZ-N-rathylthiomethyl-O-methyl-S- (2-methy1-propyl) amidothiophosphate and amidodithiophosphate. N- / N '- (2,4,6-trichlorophenyl) acetimidoyl I-O-methyl-N- (2-methoxyethyl) -S- (1-methylpropyl) amidothiophosphate and amidodithiophosphate. N-ethyl-O-ethylr-N- / N '- (3-methylphenyl) -formimidoylJ-S-propylamidothiophosphate and -amidodithiophosphate.

O-ethyl-N-methyl-N- ^ N '- (4-methylthiophenyl) -formimidoyl7-S-propylamidothiophosphate and amidodithiophosphate.

N- ^ N '- (2-chlorophenyl) -formimidoyy.-N- (2-cyanoethyl) -O-methyl-S- (2-methyl-propyl) -amidothiophosphate and -amidodithiophosphate. S-Butyl-N-methyl-O-methyl-N-ZN ¹ - (2-methyl-4-nitrophenyl) -formimidoy! / - amidothiophosphate and -amidodithiophosphate. O-ethyl-N- / N '- (2-ethylphenyl) -formimidoylZ-S- (1-methylpropyl) -N-propyl amidothiophosphate and amidodithiophosphate. N- / N '- (3,4-dichlorophenyl) formimidoyl I-O-methyl-N- (2-nitropropyl) -S-propyl-amidothiophosphate and' -amidodithiophosphate. N- ^ N '- (2-Ethoxycarbonylphenyl) -formimidoylJ-O-ethyl-S- (2-methylpropyl) -N-propyl-amidothiophosphate and. amidodithiophosphate. N-Ethyl-N- ^ N '- (4-diethylaminocarbonylphenyl) -formidoyl7-0-methyl-S-propyl-amidothiophosphate and -amidodithiophosphate. O-ethyl-S-hexyl-N- (3-methylsulfonylpropyl) -N- / N ¹ - (4-methylphenyl) -formimidoylj-amidothiophosphate and -amidodithiophosphate. N- / N ¹ - (4-chlorophenyl) -formimidoylZ-O-ethyl-N- (2-methylsulfinylethy 1) -S-propyl-amidothiophosphate and -amidodithiophosphate. O-ethyl-N- ^ N- (4-methoxy-2-methylphenyl) -formimidoylZ-N-methyl-S-propyl amidothiophosphate and amidodithiophosphate.

O-methyl-S- (1-methylpropyl) -N- (N'-phenylbutanimidoyl) -N-phenylthiomethyl amidothiophosphate and amidodithiophosphate.

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List B

O-methyl-N -, / 2- (2-methyl-4-methylthiophenoxy) -ethyr ^ -N- (N'-phenylformimidoy1) -S-propyl-amidothiophosphate and amidodithiophosphate.

N-Benzyl-0-α-chyl-S- {2-methylpropyl) -N- (N ¹ -phenyIformimidoy1) -amidothiophosphate and -amidodithiophosphate.

N- (3,5-dichlorobenzyl) -N- / N '- (4-chloromethylphenyl) -formimidoyl ^ - O-ethyl-S-propyl amidothiophosphate and amidodithiophosphate.

N- (2-butenyl) -O-ethyl-N- (N ¹ -phenylformimidoy1) -S-propyl-amidothiophosphate and -amidodithiophosphate.

N- ^ N ¹ - (4-acetoxyphenyl) -formimidoylZ-O-ethyl-N-methyl-S-propylamidothiophosphate and -amidodithiophosphate.

O-Ethyl-N- ^ N '- (4-methoxycarbonylphenyl) -formimidoyl-S-methylethyl-N- (2-naphthoxyethy1) -amidothiophosphate and amidodithiophosphate.

N-benzenesulfonylmethyl-O-ethyl-N- (N'-pheny Iformimidoyl) -S-propylamidothiophosphate and amidodithiophosphate.

O-ethyl-N-methyl-N- / N '- (4-phenylthiophenyl) -acetimidoylZ-S-propylamidothiophosphate and amidodithiophosphate.

O-ethyl-N-ethylcarbonylmethyl-N- ^ N '- (2-phenoxyphenyl) -formimidoy XJ- S-propyl-amidothiophosphate and -amidodithiophosphate.

O-Butyl-N-methyl-N-ZlJ '- (4- (2-naphthoxy) -phenyl) -formimidoy 1 / -S-propyl-amidothiophosphate and amidodithiophosphate.

O-ethyl-N-methyl-N- (N'-phenylpentanimidoyl} -S-propyl amidothiophosphate and amidodithiophosphate.

N- / N '- (4-chloro-2-methylphenyl) -acetimidoylZ-O-ethyl-N-methyl-S-propyl-amidothiophosphate and amidodithiophosphate.

O-ethyl-N-methoxycarbonylmethyl-N- 1 N '- (4-methylphenyl) acetimidoyl 7-S-propyl amidophosphate and amidodithiophosphate.

N- / N '- (4-chlorophenyl) acetimidoylZ-O-ethyl-N-methylaminocarbonylmethyl-S-propyl amidothiophosphate and amidodithiophosphate. O-ethyl-N- (2-methylpropyl) -S-propyl ^ N- ^ N '- (4-propylsulfinylphenyl) -formimidoy17-amidothiophosphate and amidodithiophosphate.

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¹ - (2-chloro-4-methylsulfonylphenyl) -formimidoylJ-Q, S-diethyl-ϊϊ-methyl-amidothiophosphate and -amidodithiophosphate-

13- (2-Butynyl) -O-ethyl-N-ZH ¹ - {4-methylcarbony! Phenyl) -formimidoyl / -S-propyl-amidothiophosphate and -amidodithiophosphate-

N- / β ^f - (4-Biphenyly 1} -formimidoyl / -S-methyl-N-methylethyl-O- {1-methylpropyl) -amidothiophosphate and -amidodithiophosphate.

O-ethyl-U-dimethylaialnocarbonylmethyl-S-propyl-U- {E * -1 -naphthylformimidoyl) amidothiophosphate and amidodithiophosphate.

O-ethyl-N- ^ N * -2- ί 4,6-dichloronaphthyl) -forHiimidoyl7-N- / 2- {4-chloro) -butenylZ-S-propyl-amidothiophosphate and -amidodithiophosphate.

O-ethyl-N- (2-ethylsulfynylethyl) -N- £ methoxy) phenylimino) methylZ-S-propyl amidothiophosphate and amidodithiophosphate. TSi / J 4-methoxycarbonylphenylimino) - {hexyloxy) methyl I-II-methyl-O-methyl-S- (1-methylpropyl) amidothiophosphate and amidodithiophosphate.

Ή— {2— cyanoethyl) —W— ^ ethoxy) - (dimethylaminocarbonylphenylimino) -methyl (-O-ethyl-S- <2-methylpropyl) -amidothiophosphate and -amidodithiophosphate.

N- (2-butenyl) -M- (1-methoxy) - (2-nitrophenylimino) -methyiy-O-propyl-S-propyl-amidothiophosphate and -amidodithiGphosphate. S-Butyl-0-ethyl-H - / ^ 4-methylthiophenylimino) - (propyloxy) -methylj-N- (2-propenyl) -amidothiophosphate and -amidodithiophosphate-N- / 14-chloro-2-methylphenylimino) - (pentyloxy ) -methyl ^ -N-hexyl-O-methyl-S- { 2-methylpropyl) amidothiophosphate and amidodithiophosphate.

0-iithyl-N- / j [ethoxy) (3,5-dimethylphenylimino) methyl / - !! - (2-phenoxyethyl) -S-propyl amidothiophosphate and amidodithiophosphate.

^ ί-S.thylthiomethyl-l ^ - / 4-cyanophenylimino) (methoxy) -methyiy-O-methyl-S- (2-methylpropyl) -amidothiophosphate and amidodithiophosphate.

Έ- {Χ 2-chlorophenylimino) (hexylthio) -methylZ-N-methyl-O-methyl-S- { 1-methylpropyl) -amidothiophosphate and -amidodithiophosphate-

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O-ethyl-N-hexyl-N - / (methylthio) (-4-methylthiophenylimino) methyl 7-S-propyl amidothiophosphate and amidodithiophosphate.

N - / (4-Cyanophenylimino) (ethylthio) -methyl-O-ynethyl-S- (2-methylpropyl) -N-propyl-amidothiophosphate and amidodithiophosphate

N- (2-Cyanoethyl) -N-Z ^ -methyl ^ -methylsulfonylphenylimino) (propylthio) -methyiy-O-propyl-S-propyl-amidothiophosphate and amidodithiophosphate.

N - / (2,4-dichlorophenylinino) - (methylthio) -methylZ-O-methyl-S-pentyl-N-propyl-amidothiophosphate and amidodithiophosphate.

N- (2-Butynyl) -N- / f (2-chlorot-methylphenylimino) (pentylthio) -methyl / -O-ethyl-S-hexyl-amidothiophosphate and amidodithiophosphate.

0-Ethyl-N - / (2-methoxyphenylimino) (methylthio) -methyl / -N- (2-methyl-carbonylethyl) -S- (2-methylpropy1) -amidothiophosphate and amidodithiophosphate.

N - / (Ethylthio) (4-phenoxyphenylimino) methyl ^ -O-methyl-N- (2-phenylthioethyl) -S-propyl amidothiophosphate and amidodithiophosphate.

N- (2-butenyl) -N - / (2-methyl-4-nitrophenylimino) (propylthio) -methyl7 " O-propyl-S-propyl-alpha-thiophosphate and amido-dithiophosphate.

N - / (cyano) (4-methylphenylimino) methyl I-N-ethyl-O-ethyl-S- (1-methylpropyl) amidothiophosphate and amidodithiophosphate.

N - / (Cyano) (1-naphthy I imino) -methylZ-N-methyl-O-propyl-S-propylamidothiophosphate and amidodithiophosphate.

N- _l / * (4-Bromo-2-methylphenyl) (cyario) -methylimino7-0-ethyl-N- (2-propenyl) -S-propyl amidothiophosphate and amidodithiophosphate.

N / "(Cyano) (phenylimino) -methyOJ-N-hexyl-O-methyl-S- (methylethyl) amidothiophosphate and amidodithiophosphate.

O-Butyl-N - / "(cyano) (4-methylcarbonylphenylimino) -methyl7 ~ N- (2-cyanobutyl) -S- (2-methylpropyl) -amidothiophosphate and amidodithiophosphate.

N- (2-butenyl) -N - / (3-chlorophenylimino) (cyano) -methyiy-O-ethyl-S-propyl-amidothiophosphate and amidodithiophosphate.

N - / (Dimethylamine) (4-nitrophenylimino) methyl I-N-hexyl-O-propyl-S-propyl-amidothiophosphate and amidodithiophosphate.

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O-ethyl-N- ^ idihexylamino) (phenylimino) -methy ^ -N- (2-propenyl) -S-propyl-amidothiophosphate and amidodithiophosphate.

N- (Cyanomethyl) -0-ethyl-N - / "(2-methoxyphenylimino) (methylpropylaminoJmethylJ-S-'n-methylpropyl) amidothiophosphate and amidodithiophosphate.

N - / (Dibutylamino) (phenylimino) methyl / '- O-ethyl-N-methyl-S- (methylethyl) amidothiophosphate. And -amidodithiophosphate-

N-Ethyl-O-ethyl-N- / ~ (4-methylthiophenylimino) (piperidino) methyl / -S- (2-methylpropyl) amidothiophosphate and amidodithiophosphate.

O-ethyl-EK / * (2; ~ 6 ~ dipropylphenylimino) (pyrrolidino) -methyl / r-N-propyl-S-propyl-amidothiophosphate and amidodithiophosphate.

N - ^ - Bromo-4-chlorophenylimino) (dimethylamino) -methylZ-O-ethyl-S-hexyl-N-pentyl-amidothiophosphate and amidodithiophosphate.

N- / T (4-butylcarbonylphenylimino) (piperidino) methyl / -N- (2-cyanoethyl) -O-methyl-S- (2-methylpropyl) amidothiophosphate and amidodithiophosphate.

N- / ~ (2 , 4,6-trichlorophenyl imino) (morpholino) -methyiy-O-ethyl-S-hexyl-N- (2-phenylthioethyl) -amidothiophosphate and -amidodithiophosphate.

~ Ζίί '- (4-Flourophenyl) -formimidoylZ-O-hexyl-N-methyl-S-propylamidothiophosphate and amidodithiophosphate.

N- / T (N '- (4-bromo-2-chlorophenyl) -formimidoyl7-N- (1-ethylcarbonyloxyethyl) -0-ethy1-S- (1-methylpropy1) amidothiophosphate and amidodithiopho sphat.

O-ethyl-N-hexyl-N- (N'-phenylformimidoyl) -S-propyl-amidothiophosphate and amidodithiophosphate.

N-Butyl-N - / "(cyano) (2-phenoxyphenylimino) -methylI-O-ethyl-S- (1-methylpropyl) -amidothiophosphate and amidodithiophosphate. N - ^ (Cyano) (1 -naphthylimino) methyl I-N-methyl-O-propyl-S-amidothiophosphate and amidodithiophosphate.

N-Ethyl-O-ethyl-N- ^ l-diethylamino) (4-dimethylaminophenyl) -methyl7 ~ S-propyl amidothiophosphate and amidodithiophosphate.

N-butyl-0-ethyl-N - / "(2-methylaminocarbonylphenylimino) (pyrrolidino) methyl / -S- (1-methylpropyl) amidothiophosphate and amidodithiophosphate. - - -

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N- / N ¹ - (2-broraphenyl) -formimidoy 1Z-O-ethyl-S-ethyl-N ^ - (4-chlorophenoxycarbonyl) -ethyl-amidothiophosphate and -amidodithiophosphate.

O-ethyl-N- (2-diethylamino) -ethyl-N- (N'-phenylformimidoyl) -S-propyl-amidothiophosphate and amidodithiophosphate

O-methyl-S-methyl-N - ^ - (4-methylphenylcarbonyloxy) -propyl-N- / N '(2-methylthiophenyl) acetimidoy3 _> 7-ainidothiophosphate and amidodithiophosphate.

O-Butyl-N - / (dimethylamine) (2-methoxycarbonylphenylimino) -methyl7-S-propyl-N-2- (2-propylphenylsulfinyl) -ethyl-amidothiophosphate and amidodithiophosphate.

0-Fithyl-N- / ~ (diethylamino) (phenylimino) -methylZ-N-phenyl-aminocarbonylmethyl-S-propyl-amidothiophosphate and amidodithiophosphate.

O-ethyl-N-furylmethyl-N- ^ N • - (4-nitrophenyl) acetimidoylZ-S-propyl amidothiophosphate and amidodithiophosphate.

N- (3-cyano-2-propenyl) -O-ethyl-N-ZN ¹ - (2-methy! Phenyl) -acetimidoyl / -S- (2-methylpropyl) -amidothiophosphate and amidodithiophosphate.

N- / N '- (2-bromophenyl) -formimidoyl 7- N- (2-methyl-3-methoxycarbonyl-2-propenyl) -O-pentyl-S-propyl-amidothiophosphate and amidodithiophosphate.

O-ethyl-N- / β '- (2-ethylphenyl) acetimidoylJ-S- (1-methylpropyl-N-2- (2-propenyloxycarbonyl) propyl amidothiophosphate and amidodithiophosphate.

O-methyl-S- (methylethyl) -N- / 3- (4-methylphenyl) -2-propenyl7 ~ N- / N ¹ - (4-methylthiophenyl) -formimidoy! / - amidothiophosphate and -amidodithiophosphate.

O-butyl-N- / 3- (2-naphthyl) -2-propenyl7-N- ^ ίj ^l - (4-nitrophenyl) formimidoyl7 ~ S-propyl amidothiophosphate and amidodithiophosphate.

N- ^ N '- (3-bromophenyl) -formimidoyl7-0-ethyl-N- / 2- (4-nitrophenyl) -ethyl ^ -S-propyl-amidothiophosphate and amidodithiophosphate.

N- (3-Cyanopentyl) -O-methyl-S-methyl-N- (N'-phenylformimidoylamidothiophosphate and amidodithiophosphate.

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N-Cycloheptyl-N- ^ N '- (4-ethoxycarbonylphenyl) -acetimidoyl / -O-ethyl-S-propyl-araidothiophosphate and amidodithiophosphate.

N- (4-Cyano-2-cyclohexenyl) -O-methyl-S- (2-methylethyl) -N - / (phenylimino) (propoxy) -methylj-amidothiophosphate and amidodithiophosphate.

N- (4-chloro-3-cycloheptenyl) -O-ethyl-S- (methylethyl) -N- / ~ (2-methylphenylimino) (pentyloxy) -methyl / -amidothiophosphate and amidodithiophosphate.

N-butyl-O-ethyl-N - / (4-methoxycarbonylphenylimino) (piperazinyl) methylZ-S-propyl amidothiophosphate and amidodithiophosphate.

N- / ~ (Hexahydroazepinyl) (phenylimino) -methylJ-N-methyl-O-propyl-S-propyl-amidothiophosphate and amidodithiophosphate.

N-Ethyl-O-ethyl-N-Zlhexahydrooxazepinyl) (4-propylphenylimino) methyl7-S- (1-methylpropyl) amidothiophosphate and amidodithiophosphate.

N-butyl-O-ethyl-S- (1-methylpropyl) -N- (N'-phenylformimidoyl) amidothiophosphate and amidodithiophosphate.

N- / N ^r - (4-bromophenyl) formimidoyl I-N- (3-chloro-2-propenyl) -0-ethyl-S-propyl amidothiophosphate and amidodithiophosphate.

The compounds according to the invention can by a process known per se for the preparation of analogous compounds or can of course also be produced with the help of other processes. One way of preparing involves reacting an amidine with a 0, S-dialkyl chloride thiophosphate or chloride dithiophosphate in the presence of an acid-binding agent. Means. The general response can be given by the following equation will

Hf = C-

£ + (R ² O) (R ³ S) J-Cl

H- "- ■■"

a ^ J ^^ or ² + _mi shake ' _: . ... ^N p / · - _;

X ^

709827/1081

1 2 where in the above equation the substituents A, R, R, R, R and X have the meanings given for the general formula (I).

Representative acid-binding agents are tertiary amines such as trialkylamines and dialkylanilines, and inorganic bases such as hydrides / hydroxides, carbonates and bicarbonates of the alkali metals and the alkaline earth metals. In general, it is preferred to use an essentially equimolar ratio of the reactants, although one of the reactants can also be used in excess. Although not required, the reaction is advantageously carried out in the presence of an inert organic solvent such as an ether, an aromatic hydrocarbon, a halogenated aromatic hydrocarbon, an aliphatic hydrocarbon, an aliphatic ketone, an aliphatic nitrile and the like. Or a mixture of these Solvents carried out. Suitable solvents include, for example, ethyl ether, dioxane, tetrahydrofuran, benzene, toluene, chlorobenzene, heptane, methyl ethyl ketone, acetone, acetonitrile and the like. The reaction-is ^ ^ imv äilgeiaeinen at a temperature in the range of about -10 ⁰ C to about 100 ⁰ C or more, and preferably in a range from about 0 ⁰ C to about 60 ⁰ C.

All of the starting materials used for the preparation of the compounds according to the invention are known or can be used without them further to be prepared in a known way. For example, the formamidines used as starting material can be condensed to prepare an aniline with an N-alkyl-formamide (see US-PS 3,502,720, BE-PS 771 792 and ZA-PS 732 129). The 0, S-dialkylchlorothiophosphates are obtained, for example, by reacting an alkylsulfenyl chloride with a dialkyl chlorophosphite (Lippman, A. F., J. Org. Chem. 30 (1965) 3217).

The ether compounds given in Table I can be found in be prepared in an analogous manner.

709827/1081

A number of compounds of general formula (I) have been prepared and chemically identified. Your physical Characteristic data are compiled in Table I below. The following examples 1 to 6 serve to illustrate the Preparation of the compounds of the general formula I.

example 1

Preparation of O-ethyl-N-methyl-N- ^ N ¹ - (2,4-dimethy! Phenyl) - formimidoyiy-Sn-propyl-amidothiophosphate (compound 1, table I )

A solution of 2.5 g (0.0124 mol) of O-ethyl-S-n-propylchlorothiophosphate is added in 10 ml of tetrahydrofuran drop by drop Room temperature to a solution of 2.0 g (0.0124 mol) of N-methyl-N '- (2,4-dimethylphenyl) formamidine and. 1.25 g (0.0124 mol) of triethylamine in 25 ml of tetrahydrofuran. The reaction mixture is stirred for 1 hour at room temperature, diluted with 70 ml of ether, filtered to remove the triethylamine hydrochloride and evaporated in vacuo, 4.2 g of an orange-colored oil being obtained, which is obtained over 55 g of silica gel with a particle size chromatographed from 0.074 mm to 0.250 mm (60 to 200 mesh). By eluting with 900 ml. Of a 7% solution of ether in benzene (discarding the first two 50 ml fractions) and concentration in vacuo gives 2.6 g (64% of theory) of the purified product in the form of an orange-colored oil.

Example 2

Production of N-cyclohexyl-0-ethyl-N- / N'-phenyl-formimidoyl7-

Sn-propyl-amidothiophosphate (Compound. 26, Table I) ·

A solution of 2.02 g (0.0099 mol) of O-ethyl-S-propylchlorothiophosphate is added in 5 ml of tetrahydrofuran dropwise to an ice-cold solution of 2.0 g (0.0099 mol) of N-cyclohexyl-N'-phenyl-formamidine and 1.01 g (Q.01 mol) of triethylamine in 25 ml of tetrahydrofuran. The reaction mixture is stirred for 1 hour at room temperature, diluted with 60 ml of ether and filtered to remove it of the triethylamine hydrochloride and evaporated in vacuo, so that 3.8 g of a yellow oil are obtained, which is poured over 40 g of silica gel with a particle size of 0.074 mm to 0.250 mm (60 to 200

709827/1081

mesh). By eluting with 350 ml of a 10% solution of ether in benzene (the first being 200 ml fraction discarded) one obtains 0.44 g (12% of theory) of the cleaned product in the form of an oil.

Example 3

Production of O-ethyl-N- / N'-phenyl-formimidoyl / '- N- (2-propenyl) -

S-n-propyl amidothiophosphate (Compound 25, Table I)

A solution of 3.16 g (0.016 mol) of O-ethyl-Sn-propylchloridothiophosphate in 10 ml of tetrahydrofuran is added dropwise to an ice-cold solution of 1.58 g (0.016 mol) of triethylamine and 2.5 g (0.016 mol) of N- Allyl-N-phenyl-formamidine in 30 ml of tetrahydrofuran. The reaction mixture is stirred for 11/2 hours at room temperature, diluted with 100 ml of ether, filtered to remove the triethylamine hydrochloride, and evaporated in vacuo to give 5.6 g of a yellow oil which is poured over 60 g of silica gel with a particle size of 0.074 mm to 0.250 mm (60 to 200 mesh) was chromatographed. Eluting with 510 ml of a 10% solution of ether in benzene (discarding the first 210 ml) gives 1.7 g (33% of theory) of the purified product in the form of an oil.

Example 4

Preparation of N- / N '- (4-chlorophenyl) -formiinidoyl7-N- (2-cyanoethyl) -O-ethyl-S- (1-methylpropyl) -amidothiophosphate (compound 72, table I)

A solution of 1.78 g (0.008 mol) of O-ethyl S- (1-methylpropyl) chlorideothiophosphate in 10 ml of tetrahydrofuran is added dropwise to an ice-cold solution of 1.7 g (0.008 mol) of N- (2-cyanoethyl) ) -N ¹ - (4-chlorophenyl) -formamidine and 0.82 g (0.008 mol) of triethylamine in 25 ml of tetrahydrofuran. The reaction mixture is stirred for one hour at room temperature, diluted with 100 ml of ether, filtered to remove the triethylamino-hydrochloride and evaporated in vacuo to give 3.4 g of a yellow oil which is chromatographed over 60 g of Biosil A. By eluting with 350 ml of a 10% solution of

709827/1081

Ether in benzene (discarding the first 300 ml) one 0.6 g (19% of theory) of the purified product.

Example 5

Production of 0-ethyl-N- ^ diethylaraino) - (phenylimino) -methyl7-N- (2-propenyl) -Sn-propyl-amidothiophosphate (compound 80, table I) " __

A solution of 6.07 g (0.03 mol) of O-ethyl-S-n-propylchlorothiophosphate is added in 15 ml of tetrahydrofuran dropwise to an ice-cold solution of 6.8 g (.0.029 mol) of N-allyl-2-diethylamino-N-phenylformamidine and 4.55 g (0.045 mol) of triethylamine in 35 ml of tetrahydrofuran. The reaction mixture is stirred for 2 hours at room temperature and the triethyl- amine hydrochloride. The filtrate is evaporated in vacuo, whereupon 20 ml of ether and 1 ml of triethylamine are added. The mixture is stirred for 1 1/2 hours, filtered to remove of the triethylamine hydrochloride and evaporated in vacuo, 10.2 g of an orange-colored oil being obtained, of which 6 g Chromatographed on Biosil A. Elution with ether gives 2.99 g (44% of theory) of the purified product.

Example 6

Preparation of N-ethyl-0-ethyl-N - / (methoxy) - (phenylimino) - methyU-sn-propyl-amidothiophosphate (compound 83, table I)

A solution of 4.1 g (0.02 mol) of O-ethyl-Sn-propylchlorothiophosphate is added dropwise to an ice-cold solution of 3.6 g (0.02 mol) of N-ethyl-2-methoxy-N ^I -phenyl formamidine and 2.1 g (0.02 mol) of triethylamine in 130 ml of tetrahydrofuran. The reaction mixture is stirred over Naclt at room temperature, the triethylamine hydrochloride is filtered off and evaporated in vacuo, giving an oil which is chromatographed over 90 g of Biosil A. By eluting with 450 ml of a 10% solution of ether in hexane (discarding the first 350 ml fraction) and with 350 ml of a 20% solution of ether in hexane, 0.5 g (7% of theory ) of the cleaned product.

.709827 / 1081

Further examples of compounds of the. general formula (I), which are prepared in a manner analogous to the above examples are compiled in Table I below, in which the analysis data are also given-

709827/1081

Table I.

Connection no.

1
2

3 H

's

7th 8th

Rj H

HHH 11 H ■ Η H

CH.

^CH CH

CH. CH.

Υ ¹

R ¹ ' Φ

1 ■ "/.

N = C- γ /.

R'- ■.: • γ. γ ,. .. γ »· .CnH ₇ -H '
JI "~ CH ₃ H-CH ₃ - H ^C 3 ^H 7 "" .. Cl H-CH ₃ H. CH ₃ H-Cl H ' . C ₃ H ₇ -H H H H ; CH ₇ -n " H ^- H-Cl '; H C ₃ H ₇ -n H H-CH ^ H ·· C-, H ₇ -n Cl. H-Cl · ' H -· ^c 3 ^H 7-a; CH ₃ ' H H C Ij Hq-I S O CH ₃ H-Cl. H

C%

Elemental analysis
calculated (found)

H %

■ / χ: -

• 0 5 ^ .8 (55.0) 7.62 (7.80) -8.53 (9.23)

0 Ί8.2 (ίΙ7.8) 6.32 (6.03) 8.0 ^ (8.12)

0 Ιι8.2 (48.11) 6.32 (6th k2) 8.OIK8.36)

0 51.9 (50.7) ■ 7.00 (7.08). 9.3 ^ (9.08)

0. il6.5 (46.7) -; 5.98 (6.02) 8.37 (8.59)

Q 53.5 (53.0) 7.33 (7.39) 8.92 (8.35)

0 .11'2.3 ('11 .9) -.5.15 (5.27) 7.58 (7.32)

0 53.5 (53.3) 7.33 (7.79) 8.92 (10.3)

(j .119.5 (51.2) ■ 6.62 (7.10) 7.72 (7. ^ 1)

CD

cn

et »

CD
CD ■ Connect I. r5 ■ ·
^ I ft • · · r7 · · Table I (continued) U-Gl
H Y " • X 'C Elemental analysis .0)
• 7) H %' .85)
.19) ■ N% ' _t .67), CO
K> dung no- TT "" • ^CH 3
CH ₃ CijHg-sec
■ 'r C ₃ H ₇ -H. 4-Cl H
2-Cl 0
0 49
48 • 9) 6.62 (6
'.6.32 (6 .45) 7.72 (7
8.04 (8 .44)
.12) .43), -h3
*> s
*; 10
11 π
H ^C 2 ^H 5 ■■■■ ^c 3 ^H 7 ~ il 4-Cl ' H.,'. ' 0 49 .3) 6.61 (6 ' .72) 7.71 (6 .60) .76) O
OO 12th H ^C 2 ^H 5 C ^ -sec . Y * H-NCv, • H ■
i 0 5i calculated (found) .5) 6.89 (6 .44) 7.44 (7 .45) 39) - * 13th "H CH ₃ ■ ■ C ₃ H ₇ -H. L CH ₃
CH ₃ '.4-Cl . H . 0 46 % ■ ■ ■ .6) 6.12 (6 .76) 11.7 (11.2) 85) 14th ■ H CH ₃ • C ₃ H ₇ -, ^ .CH ₃ 4-Cl • 6-CH ₃ 0 49 .5 (50
.2 (47. 2) :. 6.62 (6 .74) 7.72 (7 15) H ' CH ₃ , C ₃ H ₇ -Ii . CH ₃ H ■ 6-CH 0 43 ' .6 (48 6) "; • 5.48 (5 57) 7.31 (7 88) 16 H CH ₃ :; ■■ f. ^: _'-':: -: - ° 3 '7-a ^-.-. • CH ₃ 4.-CH ₃ . H · ■, 0 ' • 53 , 0 (51 7.) ' ; .7.32 (7. 86) 8..92 (8 88) CH ₃ CH ₃ , ''',' C ₃ H ₇ -Jl ₁ ' CH ₃ 4-Cl H ■ 0
• 54. .8 (46 7) 7.62 (7. 51) '8.54 (8 2Zb 18th CHg. · ^CH 3 ^: ·. . ' •: C ₃ H ₇ -Ii ₁ Cl H ' H 0 48. .5 (49 5) " 6.31 (6. 44) 8.02 (7. CD
23 * - * 9 CiU CH ₃ ""; ■ ■■■ "-Cj ₁ H ₉ -JSO ■; H H .
• H ' 0 · ^: , 53. .9 (44. 0) 7.32 (7. 58) ' 8.91 (8. ■ -J,
06Φ 20th H . C ₂ H ₅ 'C ₃ H ₇ -U ,, H 4-Clf H , 0 53. 5 (53. .7.32 (7. 87) 8.92 (8. - »« j .. 21 H CH ^ '. C ₃ Ii ₇ -Ii H'. H H 0 49. 8 (54. 5) ":" ^: 6.63 (6. 61) 7.72 (6. ORIG 22nd
* CH ₃ C ₃ H ₇ -IsO C ₃ H ₇ -Ii. H , H H ⁰ 54. 2 (4.7. 0) 7.62 (7. 83) 8.53 (7. INAL 23
r \ ti H C ₃ H ₇ -In C _o H ₇ -n '. H " H .'· H 0 54. 5 (53. 6) '. 7.62 (7. 10) 8.53 (8. ω 24 H CH ₂ CHhCH ₂ ■ '· C ₃ H ₇ -n CH ₃ H . 0 55. V (54. 7 · 05 (7th ^ 8.60 (9. -σ 25th H H ' 6 (48. 3 H 8 (53. H 8 (54. 2 (55.

Table I.

(Port setting)

Connect ■
, manure no. R * R ⁵ ' •• R ^ "■ . ' Y 4-S _; C. • Y "" X 26 ■ H cyclohexyl H ; 'η % h; · ^ 'O ', ^; : 27 H CH _3,. - ¹ C ₃ H ₇ ^ · • Ή. ' H ' ; IH ₃ H-. 0 ! ■ V 28 •. • ■ Η. "' ^C 2 ^H 5: ', · - C) ₁ Hn-JSO. . H 4-Cl ; O 29 .. ■ · H. ' CflHj-n ■■ "■ V CoHv-n • H 4-C3 H , 0 7098 ³⁰ /:, \
31 ' ■ "■■ ^Η
: H .C ₂ H ₅ V '" .. ^CH 3
CH ₃ H . I ₃ H
"H 0
0 -J 32 ' H ^CH 3 ■:. · ■■,. 'X' ^C 3 ^H 7 "- H . H - 3-Cl 0 ο 33 · .. ·. H C ₂ H ₅ ,>; C l | Hc) -se_c H H H 0 OO 34 ^; ■ '■■ '. ' ' H C ₂ H ₅ ■ "; c ₂ h ₅ ■ H H . H 0 * r »' 35 '. H C ₂ H ₅ Cl, H _g -n H r H H 0 ) RIGIi 36; ·. . H CH ₃ ■ •, C ₁₁ H ₉ -SeC . H 3-Cl H-- 0 Γ " 37 ■ H ■ CH _3. "'· . '' C ₂₁ H ₉ -J ₁ ■ H 4-Cl H 0 INSPi 38 • H CH ₃ · '. CoH ₇ -Ji ■ H 4-G1 5-ci 0 ECTE 39 H ^GH 3 · · · "'■ Cj | HQ» -sec H 4-Cl H ' f I Il 40 H CH ₃ ; . C ii Hf. - sec Cl ' H 0 -41 -. H C ₂ H ₅ " C Ii Hq-sec H H. 0

Elementary analysis calculated (found)

% ■

'"' J /: 58Ϊ7 ( 59} 3 ·),": 7 ".88 (8.39.) ^V

4'6.; 8 (50.2);, 6. 64 (7! 11)

54.'9 (55.4) 7.67 (7.87)

56.2 (56.4) 7.69 (7.86)

'55 .8 (56.3). 7.90 (7.96)

54.8 (55.9) 7.67 (7.67)

7) 5.18 (5.09)

9) -7.62 (7.71)

52.0 (51.9), .7.00 (7.24)

54.9 (55.1) 7.67 (8.19)

53.5 (53.0) 7.37 (7.67)

53.5 (53.2) 7.37 (7.82)

42.3 (42.7) 5-15 (4.89)

3) 6.36 (6.37)

4; 3) 5.52 (5.54)

49.7 (49.8) 6.66 (6.73)

1
1.1 '".' co N Q. ^; * 'ή 7th 60 (7.90) 8th. 08 (8.10) 8th. 53 (8.50) 8th, 19 (7.99) 8th. 13 (08/08) 8th. 53 (8.65) ^ o
CD
• <l 7th 58 (7.68) CO 8th. 54 (8.91) 9. 34 (9.31) 8th. 53 (8.69) 8th, 9K9.37) 6th 91 (9.19) 7th
8th. 58 (7.81 j
03 (8.04) 7th 31 (7.73) 7th 72 (7.82)

Table I (continued)

Connects η application no. ■ '■ R

* 42 43 44 45 46 47 48. 49 50 51 52 53 54 ". 55

j · H

ΓΗ

HC ₂ H ₅

H "CH,

H CH ₂ CH = CH ₂ CK ₂

H CH ₂ CH

H CH ₂ CH

H CH ₂ CH

H CH ₂ CII

H CH ₂ CH H CH ₂ CH H H

CH ₂ CK ₂ CH ₂ CH ₂

= CM

R ⁽

C-Hj-n

C i | Hg- is O H- ■ Cj | Hg- sec CH ₃ .: - Cs »7 * n-: ·. ■ ', CIU

C / jHn- SÖC H

CgHy-n II

H H .H

4-SCH ₃ H

4-Cl
H-CH,

H ■
H.

4-Cl

4-Cl

H H H

H H

USC ¹ H ₃ II

H H

• O Ö O O O

ο ο

• Ο;

, ρ

O .0 0 0

Elemental analysis calculated (found) ι

'48 .2 (48.6)

45.3 (45.4)
.54.9 (54.8)

51.3 (52.9).
50.0 (52.0)

54.8 (56.1)
56.4 (56. 5)
49.9 (50.5)
.51.3 (51.9.)

6.36 (6.46)

.5.83 (5.92) 7.67 (7.64)

7.22 (7.59) 6.94 (7.34)

8.03 (a 25) 7.05 (6.64) 8.56 (8.16) 7.49 (8.OC) 7.78 (8.-34)

7 * 40 (7.50) .6.10 (5.90)

52.5 (51.6)
51.3 (51.6.)
'52 .8 (53.8)
51.6 (51.0) ;
52.5 (54.9)

7.08 (7.59)

6.74 (6.70) 6.413. (6.66) .7.04 (7.36) 6.76 (7.05) 6.74 (6.Ρ9)

8.23 (8.26)

■ 7.78 (7.77)

7.46 (7.87)

■ 8.25 (8.56)

7.21 (6.75) 7.47 (7-20)

• 7.26 (7.89) '

7.52 (7.59)

7.21 (8.02)

- «J CD

-J : Connect,
dark. JNr H I _R 5: r7 Tabel I (continued) γ ir X C% Eleirental Analysis
calculated (found)
H % 7.36 (7.92); I.
to
N% ' cn
'π 09827 57. i- ^H CHGC (CHg) = CH _2; CgHy-rji Y . γ «- H 0 .56.4 (55 .4) _: 7.64 (7.92) 8.23 (8.24) -j ■ <.
_ » 58 JH. CH ₂ C (CHg) = CH ₂ Ci, ¥ ₉ -se £ H H ... H 0 57.6 (56 .2) 5.91 (5.71) 7.91 (8.49) ί σ
co 59 ;H CH ₂ CHCH λ -CliHg-sec .H : H H • 0. ;., 5.1i5 (51 .2); 5.88 (5.71). 7.51 (7.56)
t 60 H CH2ÖSCH;> .. '■' '■ · ■ · CgHy-n; ■ ■ · H 4-Cl.
C. . H Ό 50.1 (50 .5) 6.48 (6.54) 7.79 (8.26) 61. H .CH ₂ C = CH CgHy-n .. H' ..-.; .4-Cl H '· 0 55.6 (55 .6) 6.81 (7.23) 8.64 (9.33) 62 ,. H.
H CHgCECH .C ₁₁ H ₉ -Ii. . ■. · Η '·.' ·. ^ H, "·: ■ H 0 ■ 56.8 (56 .9) 7.ομ (7.29). '.. 8.28 (8.65) ■■ 63 · '' ·,? "'. ^: - _: H CH (CHg) CO ₂ C ₂ H ₅ -
C ₂ Hi ₁ SC ₆ H ₅ " CgHy-n. V.
CgHy-II η. ; ' H :) H
■ H .0. ·
..0 52.8. (53
. 56.9 (56 .5); - 7.30 (7.53) 7.25 (7.60)
6.63 (7.01) ^ ⁹ 65 H CH (CHg) CO ₂ C ₂ H ₅ Ci, H ₉ -sec ■;. 'H'; ^: _ ,; ■; J
'H · VH.:. ■: '■■ "'; ··
■
H . H Ό 54.0 (54 -1) · ^? 6.23 (6.50) 7.00 (7.04) 66 H CH (CHg) CO ₂ C ₂ H ₅ CgHy-rl H " H '' ■ ' H 0 4 8.5 (4'8 • V .6.53 (6.5.4) 6.66 (6.81) 67 H C ₂ H ₂₁ C = W CgHy-n;. • H .4-Cl • H 0 53.K51 .6) 7.04 (7. 29) 12.4 (11.8) 68 H CH (CH ₃ ) COgC ₂ H ₅ CgHy-n " H H ' H 0 '52.8 (53 .5) ; 6; 49 (6.4?) / 7.25 (7.60) 69 "" · H CH (CH ₃ ) CO ₂ C ₂ H ₅ CijHg-lso; H H • H 0 ■ ''19; 7 (48 6.49 (6.51 »). 6. ^ 'U6.31) 70 H CH (CH ₃ ) CO ₂ C ₂ H ₅ . Ci ₁ H ₉ -SeC il ■ 4-Cl
t H 0 49.7 (50 .4) 6.32 (6.35). 6.4i »(7.22) 71 H CH ₂ -Ps C-.Hy-n H 'I-Cl ■ H 0 55.-7 (55 ; 9) ^; . ^; 5.13 (6.19) 7.65 (7.75) 72 \. ··. " H C ₂ IO ₁ C = N.: 0,, Hg-SCC ■ H .H . . H . Ό ' ^: 49.6 (4 & .1) ■. > ■ · 10.8 (9.04) 73 C ₂ H ₄ C = N. CgHy-n. .H 4-Cl H 0 48.2 (49. _m 11.2 (11.4) • H 4-Cl

Table I (port setting)

to

Ln

Elemental analysis

Connect. Calculated (found)

Ξ. * £ _, "Β? R ⁷ 'Y_ Y ¹ Y» · XC% ■ - H% N%

.7 ί .. CH ₃ - ', CH ₃ C ₁₁ H ₉ -SeC H 4-Cl H 0 ^ 9 - 7 C ^ 9.7) 6.66 (6.70) 7.72 (7th ft 5)

75. CH ₃ IcH ₃ - ·. '· "Cyij-sejB. H' U-CH ₃ "'η 0 56.1 (56.0) · 7.95 (8.11) 8.18 (7.76)

76 CH ₃ -CH ₃ '■ · ■ ·' ■ · 'C ₂ H ₅ ' HJ] -Cl, H '0 H6.SW. 9) 6.02 (5.90) 8.37 (8.39)

ω 77; -CH ₃ ^ CH ₃ : ·. -Ci ₁ H ₉ -ISo H | l-Cl H 0 ίΙ9. .7 (50.0) 6.67 (6.59) '7.72 (7. .56)

78 CH ₃ . :. CH ₃ ': · ■ ;;. · C ₃ H ₇ -n Cl .. ■ ZiJ-ClV- /. H. . 0 ^ 3.9 (^ 3.7) '5.52 (5.5.9). 7-31 (7.7 ¹ O ^

79 H. .. CH ₃ "". ; c »H ₇ -n ■ HH" H. S '. H $. 11 (50'. 3) ■ 6.6H (7.18) 8.86 (9.28)

80 N (CH ₂ CH ₃ ) ₂ .CH ₂ CH = CH ₂ .. C ₃ H _r n 'VHHH 0 .57. ^. (57.9) "'. 8.13 (8 * 25) '10. (5 (10.1) 81 "" H CH ₂ CH ₂ N (CH _{3) ^2;} C ₃ H ₇ -n ·. 'H II' H θ '53.7 (^ 9.98) 7.83 (7.77 ) 11.8 (11.2 . ) 82 · H. ·. C ₂ H ₂₁ CN '' Cj ₁ H ₉ -SeC, H '.H HO 5M (5'K 8) /.' Β.84 (7.09) V 11.9 (12.3) '

'83 OCH _3. ' C ₂ H ^; C ₃ H ₇ -n. H, H _r H. 0 52.3 (52.5). 7.76 (7. ⁷ U) '8.13 (8.28)

8 ^ 1 N (CH ₂ CH ₃ J ₂ C ₂ H ₅ ; C ₃ H ₇ - ^, H '. ^ - CIi ₃ HO /57.4(56.9) 8.11 (8.20), 10.6 (10.6)

The compounds according to the invention can be used, in particular, for combating harmful and disruptive pests in commercial production facilities, such as in industry, agriculture, horticulture (for example in vegetable growing), in fruit growing, in arboriculture, in silviculture, in floriculture and in growing plants in the greenhouse. The compounds are particularly effective against arthropods (arthropods) at various stages of their development, in particular against representatives of the class Arachnoidea, which includes the genus Acarina, for example mites and ticks, as well as against the class of the Insecta, like the insects. Among the arthropods that are combated with the compounds according to the invention include the chewing insects, for example the cotton caterpillar (Spodoptere eridania), the sucking insects, for example the green peach aphid (Myzus persicae), the terrestrial insects, for example the corn rootworm (Diabrotica undecimpunctata howardi), houseflies and mites, for example the two-spotted leaf spider mite (Tetranychus urticae).

Representative representatives of the compounds according to the invention are effective also as fungicides, for example as phytopathogenic fungicides. Some of the with the compounds of the invention Fungal diseases to be combated include rice blight (Piricularia oryzae), bean powdery mildew (Erysiphe polygoni) and grape powdery mildew (Plasmopara viticola).

Furthermore, the compounds according to the invention have and in particular those in which the group R of the general formula (I) represents a hydrogen atom have a nematocidal effect. The nematodes or roundworms that can be combated with the compounds according to the invention include the groundworms, for example the roundworms that cause the root knot (Meloidogyne incognita).

Thus, according to the invention, the pests are in the form of fungi, Arthropods and / or nematodes are combated by the

709827/1081

Pests directly or the area to be freed from pests or to be protected against pest infestation with a pesticidally effective amount of one or more compounds of the general formula (I) treated. The area to be protected of a plant is usually the above-ground or subterranean part of a plant or reproductive subunit of this and the current or future environment of the plant.

An example of the pest control described above exists in realizing the value of a commercial product infested by one or more of these pests is or can be infested, by controlling the pests by treating the product with a pesticide effective amount of at least one compound of the general formula (I) treated. The commercial products to which the Pesticidal compounds of the invention that can be applied include in particular

(a) Salable plant products (in a growth state or in another state) '"for example vegetable Food for humans and pets; Timber trees, fruit trees and nut trees, etc .; ornamental plants; or harvested or stored forms of these herbal products;

(b) fiber materials and

(c) Soils or other media used for growing the vegetable Materials are prepared, for example when growing the plants in greenhouses and in the field.

Another example of a pest control method is the commercial yield of a salable plant product by increasing the infestation of the plants supplying the plant product by one or more of the above Prevents pests. This method can increase the yield be achieved by the fact that the plants, their seeds or the soil containing the plants or seeds, or in which the plants or seeds are planted

709827/1081

should, treated with one or more compounds of the general formula (I).

The term "combat" as used herein means a measure that exists in some way. To be available or adversely affects the growth of a living organism. This measure can be a complete kill, a Eradication, stunted growth, inhibition, diminution, or any combination of these Have effects.

The amidophosphoric acid esters of the general formula (I) according to the invention are generally suitable as arthropodicides, in particular against representatives of the class Arachnoidea, which includes the genus Acarina, of which mites and ticks are examples are, and against representatives of the class Insetrta, the insects. Certain compounds are effective nematocides and fungicides, especially phytopathogenic fungicides.

When examining the pesticidal activity of the compounds of the present invention, the following mites, insects and roundworms were found e inge s et ζ t:

Abbreviated general name Latin name . , ^ _ drawing

TSH two-spotted leaf spider mite Tetranychus urticae

GPA green peach aphids Myzus persicae

MBB spotted ladybird Epilachna varivestis

SAW cotton grape Spodoptera eridania

CRW corn rootworm, eggs and larvae Diabrötica undecim-

punctata howardi Nema Meloidogyne incognita causing the root node

Roundworm
HF housefly Musca domestica

RB rice brandy Piricularia oryzae

709827/1081

One can make a test solution that is 600 ppm of the The compound to be investigated is obtained by placing the compound to be investigated in a solvent (acetone / methanol mixture with a volume ratio of 1: 1), a surface-active agent and then water are added so that one Acetone / methanol / water system with a volume ratio of 10:10:80. As a surface-active agent, 28.35 g (one ounce) of a mixture of an alkylaryl polyether alcohol (which is commercially available under the name Triton X-155) and a modified phthalic glycerol alkyd resin (commercially available under the name Triton B-1956) in one Add volume ratio of 1: 1 to 378.5 liters (100 gallons) to the solution to be tested.

Discs are brought in to examine the action against mites (3.18 cm (1.25 inches) in diameter of infested bean leaves (Phaseolus limeanus) - which have about 50 mites and to investigate the effect against the green peach aphid, infested broccoli leaves (Brassica oleracea italica) or broccoli parts, which have around 50 aphids, on moistened cotton pieces in Petri dish lids. the Leaves are then sprayed with the solution of interest using a rotating turntable. Afterward they are kept for 24 hours, after which the percentage destruction is determined.

Sprayed to investigate the effect of the compounds according to the invention against the spotted ladybird and the cotton caterpillar one detached bean leaves, which are present on moistened pieces of filter paper in similar Petri dishes, in the above Way on which to let them dry. Then put 10 spotted ladybugs in the third one in each of such Petri dishes Manifestation, while another petri dish is filled with 10 cotton caterpillars in the third manifestation. then the dishes are covered, whereupon the percentage destruction is determined after 48 hours.

7Ü3Ü27 / 1OS1

To investigate the effect against house flies, 240 ml (half pint) canning jars with a sieve lid are used are. The houseflies are provided with food (sugar water). The investigation uses "20 adults at a time Houseflies. The jars containing the insects are sprayed using the turntable. During the examination the activity against houseflies becomes the percentage one hour after the application of the compounds according to the invention Anesthetic effect was determined, whereupon after 24 hours the percentage Killing is determined.

When examining the effect against roundworms, soil becomes homogeneous with a crushed mixture of tomato roots, which are heavily infested by roundworms that cause root knots. Then 200 ml of the infested soil, which is in a 453 g (16 oz.) Jar, is mixed with 10 ml of the soil to be tested Solution to give a concentration by volume of about 30 ppm. The glass is then shaken to a ensure good mixing, after which you open it immediately and leave it to stand in the air for 24 hours »The earth will then placed in a 3 inch plastic pot, followed by 3 cucumber seeds (Cucumis sativus). About 23 days later, the cucumber plants are removed from the ground, and it becomes their root system examined for the presence of nodes. One Total count of 25 knots or less is considered a pest control measure viewed.

To investigate the effect against the corn rootworm (Diabrotica undecimpunctata howardi), in the form of eggs and larvae, one brings two layers of 4.25 cm long filter papers in narrow petri dishes and sprinkles them on a turntable with a solution, which contains 600 ppm of the compound to be tested and dries it in the air. Then about 100 eggs are pipetted into about 1 ml Put water on the filter paper and cover the petri dishes. They are kept for 6 days and then under the microscope examined. The percentage kill values of the eggs and larvae are then determined.

709827/1081

The evaluation of the fungicidal activity of the compounds according to the invention is carried out via a leaf examination. In general, this investigation consists of placing potted plants in a suitable growth state in which they are sensitive to the plant diseases to be assessed, on a conveyor belt to spray and dry. Then you infect them Plants with the appropriate. Fungal spores that are allowed to incubate until the symptoms of the disease appear, whereupon disease control is identified or estimated. The percentage of disease control is determined.

The compounds used to study the fungicidal effect are used in the form of a solution or a suspension with a concentration of 300 ppm, which can be obtained by dissolving a weighed amount of the fungicide to be examined in an acetone / methanol mixture with a volume ratio of 50:50 and adding an equal volume of water.

In the following Table II are the results of those described above biological investigations of the compounds 1 to 82 of Table I are given.

709827/1081

Table II

Investigation of the pesticidal effect, percentage control

Compound T ^ M ⁵ GPA ^b MBB ^b SNrP CEOT E / L ^C Neraa ^d HF * ³ RB No.

1 100 100 100 100 67/100

2 100, 100 100 100 0/89

3 · ■ - ■ ': "100 100' 100 100 119/90 H. 100 100 100 100. 0/87 5; . 100,100 100, 100 0/83

6 .. 100 100 100 100 58/95

7 10p, 100 100 100. 0/70

8 ■ '. 100 100 100 100 0/96

9. 100 100 100 ioo 55/92

10, 100 100 100. 100 76/100

11 100 100 100 100 73/95

12 iodine 100 100 100 0/98

13 ■■ · .. 10p 100 100 .100 0/98

Ik 100. 100 100 100 0/93

15 100 100 100 100 43/100

16/100 "100 100 ioo 0/100

17 100 100 100 100 50/100

18 100 ioo ioo 100 ^ 7/93

19 '■'. 100 100 _.100: ioo. 59/100

20 100 100 ioo 100 60/100

A ■ . 100 - A. 100 A ' A. 100 A. A '"' ·. ' 100 A _m A. ■. 10Q A. A. '1OQ .A A \ .100 - A. . 100 E. A. - 100 B. A. .100. .- • "a A. 100 A. A '■■■ ·. ■ 100 · .-. A ' 100 A. A ". 100 A. 100 '· ■ - A. 100 ■ - c " 100 mm ^m C. • 100 - · C. :. · 100 ■ - A. 100

709827/1081

Table II (continued)

Connection TSM * ³ GPA ^b MBB ^b SAW ¹³ CFW E / L ° Nema HF ³ EB ^G

No-

21 100 100 100 100 48/100 A 100 B '

22 100 100 100 100 0/100 G 100 - -

23 100 100 100 100 67/100 A 100 -

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 ' f 100 100 100 100 58/100 A. 100 - ".

31 '100 100 100 100. 61/100 - A 100 -

32 loo loo loo loo o / oq α loo -

33 100 100 100 100 78/100 A '--1QO "' .-

3 ¹ J / 100 100 100 100 0/74 ■ -. A- -

35 100 100 100 100/71/100 A. -

36. 100 100 100 100 78/100 A 100 E

37. . 100 100 100. 100 45/100 A lOo 'A'

38 100 100 100 100 60/100 A '100 "-

39 100 100 100 100 84/100 A -

40. 100 100 100 100 48 / ioO A ->

41 100 100 100 100 64/100 A-

42. 100 100 100 100 65/100 A - «A.

43 100 100 100 100 41/100 A

709827/1081

* ^ 9 RR 7 Q 7

Table II (continued) ^{L D D} ' "-' ^L

Connection 'TSeJ ³ GPA ^b MBB ^b SSW ⁰ CFW E / L ^C

,No. ..- ■■ -

44 V-. 100 100 100 100 75/100 A .- ■ -.'- .- '

45 "100 100 100 100 0/100 λ 100 .- ·.

46 100 100 "80 100 0/100 A ■". 100. -:

47. . 100 100 100 100 77/100 A 100 -

48 100 100. 100 100 79/100 A. - B.

49. 100 100 100 100 57/96 A

50.; 100 100 100 100 59/100 Ä -

: 51 - 100 100 100 100 58/100 A 100 A

! 52 ... 100 100 100 100 41/100 .A 100 A *

; 53 · 100 100 100 100 58/100 A .'- ■ - '

..54 100 100. 100 100 0/100 Ä. 100 A

55 100. 100 100 100- 0/100 A '"100' -

56 '... 100 loo / loo 100 O / 100' A.. 100 A

57 100 100 .100 100 61/100 .V ioo -

58 100 100 100 10Ö 40/100 A 100 -

59 100. 100 100 100 0/100 ■. A x 100 a

60 J 100 100; 100 100 .0 / 95 A 100 A

61 100 100 100 100 .0 / 84. . ■: a ": .100 ■ -. A

62 ■. ,. 100 100 ioo 100 53/100 a. 100 a

6 j 100, 100 100 100 0/100 "A. - . J-.

€ 54 100 100 100 100 0/100 A 100 -

65 ν 100 100 100 100 0/100 a 100 -

709827/1 OB 1

W ~ ^; - 2S57972

Table II (continued)

Compound! Bsi * GPi ^ MEB SHSr CEH ^f l / L ^c Nana Hr EB ^e

66 ^ 100 100 100 100 Ö / 100 A 100 -

67 100 100 100 100 55/100 A 100.- -

68 100 100 100 100 60/100 A ^ -100 B SS 100 100 100 100 0/100. A- -

70 100 100 100 100 "0/100 A -. 100 ¹ B

71 - 100 100 100 100 0/89. A .. ^: SO - 72 * 100 100 100. 100 0/100 A / ' ^: 100 B / 73 100 100 100 100 55/100. A-100 ~;

7 ³ J loo loo loo loo go / loo c.-.- r ~ '\

75 '100 100 100 100 5V100 C - --.-'- ■

76 87 70 0 100 0/90. C- - -

77 -. / 100 100 100 100 ^ 5/100 C-. "- '

78. 100 100 100 100 0/100 C - 100 -

79 ■. 100 100 100 100 6V100 A 100 E.

.80 loo loo ioo loo o / ioo _: '■' - '■ .- ■ - -

81 - .78 13 10 10. 0/0 C OE

7098271

a) TSM = two-spotted leaf spider mite, GPA = green peach aphid, MBB = spotted ladybug, SAW = cotton caterpillar,

CRW E / L = corn rootworm eggs / larvae, Nema = nematodes,

HF = housefly,

RB = rice brandy;

b) Percent control of insects at 600 ppm.

c) Percentage of insect control at 150 ppm.

d) A = 0 to 9 nodes at the root,

B = 10 to 25 knots at the root,

C = more than 25 nodes at the root (with one active ingredient concentration of 30 ppm in the earth.

e) Control of the disease: A = 97 to 100%,

B = 90 to 96%, C = 70 to 89%, D = 50 to 69%, E = <50% (with an active ingredient concentration of 300 ppm).

The compounds according to the invention can be used as pesticides in the form of solutions in organic solvents or in the form of other formulations that can be used Mixing the different ingredients of the appropriate formulation is obtained. For example, you can get them in the form of wettable Powders, emulsifiable concentrates, dust powders, granular Use formulations or flowable emulsifiable concentrates. In these formulations the amidophosphoric acid esters be stretched with an agriculturally suitable liquid or solid carrier material and can if desired can also be mixed with suitable surface-active agents. The commonly used surface active agents

709827/1081

Agents are listed in the John W. McCutcheon, Inc. publication "Detergents and Emulsifiers Annual". In the formulations the amidophosphoric acid ester content can range from 1 to 99% by weight, for example from 5 to 95% by weight.

The amidophosphoric acid esters according to the invention can be finely divided solid support materials .; for example clays, inorganic Silicites, carbonates and silica materials be absorbed or mixed. Organic carrier materials can also be used. You can make dust concentrates, which have an amidophosphoric acid ester content of about 20 to about 80% by weight. For end uses will be these concentrates are usually stretched with an additional amount of a solid carrier material so that you get a Active ingredient content of about 1 to about 20% by weight is achieved. Granular Formulations can be produced by using a carrier material in granulate form or in the form of pellets, for example granulated clays, granulated vermiculite, granulated charcoal or active charcoal or granulated corn on the cob, it being possible for these granular formulations to contain the active ingredient in an amount of about 1 to about 25% by weight.

Wettable powder formulations can be prepared by combining the amidophosphoric acid esters according to the invention with a surface active agent, the one or more emulsifying agents, wetting agents, dispersing agents or the spreading agent may include facilitating agents or a mixture of these agents, in an inert, finely divided, solid carrier material incorporated. The amidophosphoric acid esters are normally present in these preparations in an amount ranging from about 10 to contain about 35% by weight, while the surfactants constitute about 0.5 to about 10% by weight.

A suitable method for preparing a solid formulation is to use a solid carrier material with the amidophosphoric acid ester impregnate using a volatile solvent such as acetone. In this way you can do without

7098 27/1081

also auxiliary materials such as activators, adhesives, plant nutrients, synergistic agents and various surface active agents.

Emulsifiable concentrate formulations can be produced by that the amidophosphoric acid esters according to the invention in an agriculturally acceptable organic Solvent dissolves and a solvent-soluble emulsifier adds. Suitable solvents are generally immiscible with water and belong to the group of organic solvents, the hydrocarbons, ketones, Esters, alcohols and amides usually include Mixtures of solvents used. The surfactants useful as emulsifying agents can be from about 0.5 to about Make up 10% by weight of the emulsifiable concentrate and can anionic, cationic or nonionic surfactants- The concentration of the active ingredients can be approximately 10 to about 80% by weight, preferably about 25 to about 50% by weight be.

When used as pesticides, the amidophosphoric acid esters should be carried out using techniques known per se be applied in an effective amount sufficient to produce the desired pesticidal effect. Usually the amidophosphoric acid ester is carried after it has been incorporated into an agriculturally suitable carrier material in an effective amount on the area that is against the Pests should be protected or freed from the pests. In certain situations, however, it can be desired and It may be advantageous to apply the compounds directly to the area without the use of substantial amounts of a carrier material, which is to be protected against the pests or to be freed from them. This is particularly effective Method when the toxins in such a physical In the form of a so-called "low volume application" can perform, d. H. when the compounds are in liquid form or substantially at a higher level

709827/1081

Dissolve the boiling solvent.

The amount of application depends of course on the pesticidal purpose, the amidophosphoric acid ester used, the frequency of the Order and possibly also on other factors.

The term "agriculturally acceptable or acceptable carrier material" means any substance that is used to do so can be used to dissolve, disperse, or distribute the chemicals without affecting the effectiveness of the toxin is, and without this carrier material permanent damage to the environment, such as the floor, the devices and agricultural crops.

Diluted spray preparations can be used to combat insects and mites Apply about 0.012 g to about 24.0 g · of the active amidophosphoric acid ester per liter of the spray preparation Contains (0.1 to 20 pounds per 100 US gallons). The spray preparations are usually in concentrations of about 0.12 up to about 6.0 g / L (0.1 to 5 pounds per 100 US gallons). In the case of more concentrated spray preparations, the concentration of the active substance increased by a factor of about 2 to about 12. This is done when using diluted spray preparations Usually applied to the plants until the preparation runs off, while with more concentrated spray preparations, which are applied in smaller volumes, the materials are used in the form of spray mist.

The compounds according to the invention can be used as fungicides be used in the form of fungicidal spray preparations which are applied in the usual manner, for example by Hydraulic spraying of high volumes of the spray preparations, spraying of the spray preparations in small volumes by spraying by air spraying, by air spraying and by dusting. The dilution and the amount applied depend on the type of device used, the method of application and the diseases to be combated, although this must be said is that the preferred effective amount of active ingredient is generally

709827/1081

is about 0.112 to 56.0 kg / ha.

When used as a fungicidal seed protection agent the amount in which the toxin is applied to the seed is, generally about 0.63 g to about 12.5 g / kg of the seeds (0.1 to 20 ounces per hundred pounds). The active ingredient can be used as a soil fungicide in an amount of about 0.112 to about 56.0 kg / ha (0.1 to 50 lbs. Per acre) incorporated into the ground or can be applied to the surface of the soil. As a foliar fungicide, the active ingredient is usually used in an amount of about 0.28 to about 11.2 kg / ha (0.25 to 10 lbs. per acre) applied to the growing plants.

When used as a nematocide, as a systemic agent or The amidophosphoric acid esters can be used as soil insecticide in the form of solid formulations, preferably in the form of granules, or in the form of diluted liquid. Preparations by broad-based Spreading, by side fertilization in rows, by working into the soil or by treating the seeds on be brought. The amidophosphoric acid esters according to the invention transplant water can also be added or can be used as immersion or soaking preparations for parts of plants to be propagated be used, for example, for seeds, tubers, roots, seedlings, etc., in order to disinfect them in this way to achieve and / or protection against roundworms, terrestrial insects (and mites) and against a systemic uptake of To reach leaf pests. The application rate can be about 0.56 to about 56.0 kg / ha (0.5 to 50 pounds per acre), although you can also use higher application quantities. The preferred amount ranges from about 1.12 to about 28.0 kg / ha (1 to 25 pounds per acre). The amidophosphoric acid esters according to the invention can be incorporated into the soil Mix with the soil in such an amount that an active ingredient concentration of about 1 to about 100 ppm results.

The amidophosphoric acid esters according to the invention can be used as the sole pesticidal agent, or they can be used in Combination with other pesticides such as bactericides, fungicides,

709827/108 1

Use herbicides, insecticides, acaricides and nematocides.

Particularly noteworthy are the compounds of the general formula CI) r according to the invention in

A is a phenyl group or a naphthyl group, which is optionally substituted by 1, 2 or 3 identical or different substituents from the group consisting of cyano groups, nitro groups. Halogen atoms, C ₁ -C 6 -alkyl groups, C 1 -C 6 -alkoxy groups, Cj-Cg-alkylthio groups, (C.-Cg-alkyl) -aminocarbonyl groups, (di-C ₁ -Cg-alkyl) -aminocarbonyl groups, C-Cg Groups comprising haloalkyl groups, phenyl groups, phenoxy groups and phenylthio groups are substituted;

R represents a hydrogen atom or a Cj-C alkyl group;

! R (a) a _C1 -CG-alkylene group optionally substituted by a substituent from the cyano groups, nitro groups, C, -CG-alkoxy groups, C ₁ -C _ß alkylthio groups, C ₁ -CG-alkylsulfinyl, C ₁ - Cg-Alkylsulfony! groups, (C.-C _g alkyl) -carbonyl, -carbonyl (C ₁ -CG-alkoxy), (C ₁ -C _ß alkyl) -carbonyloxygruppen, (mono- or di-C.- Cg-alkyl) aminocarbonyl groups, phenoxy groups, phenylthio groups, phenylsulfinyl groups ,. Phenylsulfonyl groups, phenylcarbonyl groups, phenoxycarbonyl groups, phenoxycarbonyloxy groups, phenylaminocarbonyl groups., Group comprising benzyl groups and phenethyl groups is substituted,

(b) a C ₃ -C 6 -cycloalkyl group, which is optionally substituted with one, two or three similar or different substituents from one of the groups of substituents given above for the phenyl group or the naphthyl group A,

(c) a C ^ -Cg-alkenyl group which is optionally substituted with one or two identical or different substituents from the group _{comprising cyano groups, halogen atoms, (C 1} -Cg-AlkOXy) carbonyl groups and phenyl groups, and

(d) a C ₃ -C 6 alkynyl group;

709827/1081

R is a Cj-Cg alkyl group; R is a C 1 -C 6 alkyl group and X represents an oxygen atom or a '"sulfur atom.

3In the above-defined subclass of preferred compounds according to the invention, those compounds of the general formula (I) are particularly preferred / in which A represents a phenyl group or one with 1, 2 or 3 identical or different substituents from the C 1-6 alkyl groups, Halogen atoms, preferably chlorine atoms, or groups comprising nitro groups, substituted phenyl group; R is a hydrogen atom or a C ^ -C ^ -alkyl group; R is a C ₁ -CU ~ alkyl group

i 4 2 3

pe or C_-C ₄ alkenyl group; R is a Cj-C ^ alkyl group; R is a Cv-C ^ -alkyl group and X is an oxygen atom.

In these representative compounds, the substituents occupied of the phenyl ring of group A generally the positions 2, 4 or 6.

709827/1081

Claims (25)

Claims in the A is an optionally substituted aryl group, its aryl radical has up to 12 aromatic ring carbon atoms, R is a hydrogen atom, a Cj-Cg-alkyl group, a di-C ₁ -Cgalkylamino group, a saturated or unsaturated heterocyclic group having 4 to 6 carbon atoms, the (a) one or two nitrogen atoms and optionally additionally one. Contains an oxygen atom or a sulfur atom, a Cj-Cg -alkoxy group, a Cj-Cg-alkylthio group or a cyano group ;. R a) an optionally monosubstituted C.-Cg-alkyl group, b) an optionally substituted C ^ -Cg -cycloalkyl group, c) an optionally substituted C-j-Cg-alkenyl group, d) an optionally substituted C.-Cg cycloalkenyl group or e) a Cg-Cg-alkynyl group; R is a Cj-Cg-alkyl group, 3
R is a C - Cg alkyl group and X represents an oxygen atom or a sulfur atom. 709827/1081 ORIGINAL INSPECTED 2. Compounds according to claim 1, characterized in that R is a hydrogen atom. 3. Compounds according to claim 1, characterized in that the substituent A of the following formula corresponds to, in the. Y, Υ ¹ and Y ", which can be identical or different, hydrogen atoms, C.-Cg-alkyl groups, halogen atoms, C.-Cg-alkoxy groups, Cj-Cg-alkylthio groups., Nitro groups, cyano groups, (C ₁ -Cg- AlkOXy) -carbony! Groups, di-C ₁ -C ₄ -alkylamino groups, (Cj-Cg-alkyl) -carbony! Groups, di-Cj-C-alkylaminocarbonyl groups, arylthio groups or aryloxy groups. 4. Compounds according to claim 3, characterized in that R is a hydrogen atom, a C ₁ -C ₄ -alkyl group, a di-C 1 -C 4 -alkylamino group, a C 1 -C 4 -alkoxy group, a C 1 -C 4 -alkylthio group, a cyano group or a heterocyclic group; Pure a) optionally substituted Cj-C ^ -alkyl group, b) optionally substituted Cg-C ^ cycloalkyl group, c) optionally substituted C ₃ -C ₄ alkenyl group, d) optionally substituted Cg-Cg-cycloalkenyl group or e) C ₃ ~ C ₄ alkynyl group; R is a C ₁ -C ^ alkyl group and R is a C ₁ -C ₄ alkyl group. 5. Compounds according to claim 4, characterized in that R is for represents a hydrogen atom. 6. Compounds according to claim 4 or 5, characterized in that R represents a Cy-Cg-aralkyl group. 709827/1081 7. Compounds according to claim 4 or 5, characterized in that Y, Y ¹ and Y ", which can be identical or different, hydrogen atoms, C-. -C ^ -alkyl groups, cyano groups, halogenatoins, nitro groups, C.-C ^ alkylthio groups, di-Cj-C ₃ -alkylamino groups, Cj-C ₄ alkoxy groups, phenylthio groups or phenoxy groups; R is a C ₁ -C. -alkyl group, a cyano-Cj-Cg-alkyl group, a phenylthio-Cj-C ^ alkyl group, a (Cj-C ₄ -AlkOXy) -carbonyl Cj-C ^ -alkyl group, a furfuryl group, a C ₃ -C ₄ -alkenyl group, a C ₃ -C ₄ -AIkXnYlgruppe, a C ^ -Cy -cycloalkyl group, a ^ -C ^ alkenyloxy-Cj-C ^ alkyl group, a C ₇ -C aralkyl group or a (C ₃ -C ₄ -alkenyl) -oxycarbonyl-Cj-C ₃ -alkyl group; R is a methyl group or an ethyl group and R is a C 1 -C 4 alkyl group. 8. Compounds according to claim. 7, characterized in that Y, Y ¹ and Y ", which can be identical or different, denote hydrogen atoms, methyl groups, chlorine atoms, methylthio groups or nitro groups. 9. Compounds according to claim 8, characterized in that R is a hydrogen atom> represents an alkyl group, an alkoxy group or a bialkylamino group. 10. Compounds according to claim 8 or 9, characterized in that that R is an alkyl group, an alkenyl group * an alkynyl group, a cycloalkyl group, an alkoxycarbonylalkyl group, an arylthioalkyl group, a cyanoalkyl group, a furfuryl group or a dialkylaminoalkyl group and X represent an oxygen atom. 70982771081 11. Compounds of the general formula (III) N = C-N R * (III) OR * SR ' in the R is a hydrogen atom or a C, -C.-alkyl group, R is a C.-C - alkyl group, a cyclohexyl group, a C ₃ -C ₄ -alkenyl group, a propargyl group, a phenylthio-C - C - alkyl group, a cyano-Cj-C.-alkyl group, a (C- -C - alkoxy) carbonyl-Cj-C ^ alkyl group, a furfuryl group or a benzyl group; R is an ethyl group; R is an n-propyl group, an isobutyl group or a sec-butyl group; and X, Y ¹ and Y ″, which can be identical or different, denote hydrogen atoms, methyl groups> chlorine atoms, nitro groups or methylthio groups. 12. Compounds of the general formula in which R stands for an n-propyl group or an isobutyl group stands. 709827/1081 13. Compounds of the general formula in which R stands for an n-propyl group or a sec-butyl group stands. 14. Compounds of the general formula in which R stands for an n-propyl group or a sec-butyl group stands. 15. Compounds of the general formula N = C-N " CH ₂ CH = CH ₂ %. ^OC 2 ^H 5 in which R stands for an n-propyl group or a sec-butyl group. 709827/1081 16. Compound of Formula N = C-N- ^OC 2 ^H 5 17. Compound of formula N = C-N- .CH. OC ₂ H ₅ O ^ ^ SC ₄ H _Q -sec 18. Compound of Formula • N = C-N .UU-Cn. 19. Compounds of the general formula (I) 709827/1081 I .R ¹ A-N = C-N ^. (I) ^; : "SR ³ in the A is a phenyl group or a naphthyl group, each optionally with one, two or three similar or different substituents from cyano groups, nitro groups, halogen atoms, Cj-Cg-alkyl groups, C-Cg-alkoxy groups / C - Cg-alkylthio groups, _C1 -CG alkyl) aminocarbonyl groups, (di-C - Cg-alkyl) aminocarbonyl groups, C ^ -CG-haloalkyl groups, phenyl groups, phenoxy groups and _f phenylthio group comprising substituted; R is a hydrogen atom or a C -C alkyl group; a) a C - Cg alkyl group, optionally with a substituent from the cyano groups, nitro groups, C - Cg alkoxy groups, C - Cg alkylthio groups, C - Cg alkylsulfinyl groups, C - Cg alkylsulfonyl groups, ( C - Cg-alkyl) carbonyl groups, (C - Cg-alkoxy.) - carbonyl groups, (C ₁ -Cg-alkyl) -carbonyloxy groups, (mono- or di-C, -Cg-alkyl) -aminocarbonyl groups, phenoxy groups , .Phenylthio groups, phenylsulfinyl groups, phenylsulfonyl groups, phenylcarbonyl groups, phenoxycarbonyl groups, phenoxycarbonyloxy groups, phenylaminocarbonyl groups, benzyl groups and phenethyl groups is substituted, b) a C ^ -Cg -cycloalkyl group, optionally with a, two or three similar. or different Substituents such as those specified above with respect to the phenyl group. Or naphthyl group A is substituted are, c) a C-j-C ^ alkenyl group, optionally with a or two identical or different substituents 709827/1081,. , is substituted from the group consisting of cyano groups, halogen atoms, carbonyl groups and phenyl groups, or d) a C 1 -C 6 alkynyl group; R is a C. to Cg alkyl group; ! R is a C ₁ -C _fi -Alky group; and X represents an oxygen atom or a sulfur atom. 20. Compounds of the general formula (I) A-N = C-N- _ in the A is a phenyl group or a phenyl group which is substituted by one, two or three similar or different substituents from the _{group comprising C 1} -C ₃ -alky groups, halogen atoms and nitro groups; R is a hydrogen atom or a C, -C, -alky! Group; a C ₁ -C ₃ alky group or a C 1 -C 3 alkenyl group; R is a Cj-C 1-4 alkyl group; R is a C ₃ -C alkyl group; and X represent an oxygen atom. 21. Compounds according to claim 20, characterized in that A represents a substituted phenyl group in which the substituents are in the 2-, 4- or 6-position. 22. A process for the preparation of the compounds according to any one of the claims 1 to 21, characterized in that there is a connection the general formula 709827/1081 AN = C ^ with a compound of the following general formula X (R ² O) (R ³ S) -P-Cl converts, where in the above general formulas the substituents 1 2 tuenten A, R, R, R, have meanings. 12 3 A, R, R, R, R and X are those indicated in claim 1 23. Pesticidal agent, characterized in that it contains at least one compound according to any one of claims 1 to 21 as an active ingredient and contains an agriculturally acceptable carrier material. 24. Means according to claim 23 " characterized in that it a) is in the form of a dust preparation or in the form of granules, or b) contains a surface-active agent and in the form of a crosslinkable powder, an emulsifiable concentrate or a flowable emulsion concentrate is present. 25. Methods of combating pests in the form of fungi, Arthropods and / or roundworms, characterized in that one looks at the pests or the area that is affected by the pests to be freed or protected against pest infestation, a pesticidally effective amount of at least one compound according to any one of claims 1 to 21 applies. 709827/1081