CA1051027A - Process for the production of new phenylformamidines - Google Patents

Process for the production of new phenylformamidines

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Publication number
CA1051027A
CA1051027A CA166,698A CA166698A CA1051027A CA 1051027 A CA1051027 A CA 1051027A CA 166698 A CA166698 A CA 166698A CA 1051027 A CA1051027 A CA 1051027A
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Prior art keywords
carbon atoms
methyl
dimethyl
alkyl
formamidine
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CA166,698A
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French (fr)
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CA166698S (en
Inventor
Dieter Durr
Georg Pissiotas
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Novartis AG
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Ciba Geigy AG
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Priority claimed from CH473172A external-priority patent/CH564305A5/en
Priority claimed from CH473072A external-priority patent/CH564304A5/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/18—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to carbon atoms of six-membered aromatic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

ABSTRACT: of the Disclosure Compounds of the formula

Description

The present invention relates to phenylfor~amidines, to processes for their production, and to their use ~n pest control. :~
The phenylformamidlnes correspond to the formula ~:
. R4 / R

/~--<
S R5 ~ -N = CH - N \ (I) 3 . . ~.
or to the formula R5 ~ ~ K = CH - N~ HX (I~

wherein Rl represents alkyl having 1 to 4 carbon atoms, alkenyl having 3 to 5 carbon atoms, or al.kynyl having 3 to 6 carbon atoms, R2 represents hydrogen, alkyl having 1 to 4 carbon atoms, :;
alkenyL having 3 to 5 carbon atoms, or alkynyl ~;
having 3 to 6 carbon atoms, :
lS R3 represents alkyl having 1 to 4 carbon atoms, R4 represents alkyl having 1 to 4 carbon.atoms, and ~ ?~
~ R~ represents hydrogen, or alkyl having 1 to 4 carbon : atoms, and .
¦ X represents an inorganic or organic acid radical.
- 2 - :

.~ ' . ' ' ~ 'Z'7 The alkyl, alkenyl, alkynyl or alkoxy groups applicable for formula I can be straight-chain or branched, interrupted with hetero atoms, msubstituted, or substituted, e.g.
with halogen. Halogen is fluorine, chlorine, bromine and/or iodine Examples of such groups are inter al~a: methyl, methoxy, trifluoromethyl, ethyl, ethoxy, 2-chloroethyl, propyl, propoxy, isopropyl, isopropoxy~ n-butyl, n-butoxy, i-, sec.- ~r tert~bu~yl, allyl, me~hallyl, ~-chloroallyl, 2-chloroallyl, l-butenyl, 2-butenyl, 3-butenyl, propargyl or isobutynyl.

Compounds of formula I and Ia preferred because of their action are such compounds wherein Rl represents methyl, ethyl, propyl, isopropyl or n-butyl, R2 represents hydrogen, methyl, ethyl, propyl, isopropyl or n-butyl, R3 represents methyl, ethyl or isopropyl, R4 represents methyl, ethyl, propyl, isopropyl, sec.-butyl or tert.-bu~yl, and X represents an inorganic or organic acid radical.

The compounds of formula I and Ia can be produced by methods known per se; for example, by the following method:

.' ., :

:, ' .

~ 3 .1 . , .

i , .
. .

,, ..... ., , .. ,, .. . , . .'. , ' ' . ,', ' ',, ., . ''', ," ' ' ,. ""' `.' ' ' " " . ,' . " ~

._ ~ 4 /Rl c) POC13 ~ :
R ~ ~ N~12 ~ o Cll ~ e) PClr (II) ~III) g) Cl-~02 ~4- CH3 In formulae II and III, the symbols Rl to R4 have the meanings given for formula I. The starting materials of formulae II and III are known, and can be produced by methods analogous to known methods. `

The compounds of formula I have a broad biocidal action, and can be used for the control of parastic pests on domestic and productive animals. The compounds of formula I possess ~ in particular, acaricidal properties.

Surprisingly, the compounds according to the invention are appreciably more stable than analo~ous compounds disclosed in the literature, and have therefore a clearly ~;
1 more persistent action against all development stages, such as eggs, larvae and adults of members of the order acarina, particularly of mites 9 red spider mites and ticks, such as, e.g. of the families Ixodidae, Argasidae, Tetranychidae and Dermanyssidae. ;
,, ' , ` ` ` ~.

1~ - ` ' ' ' ' ', .

.. , ` ~' .
i ' .

~ 4 '' .
.:

~, .

1~5~Z7 The acaricidal action of the said compounds can be substantially broadened and adapted to suit the given cir-cumstances by the addition o~ other biocidal compounds. Suitable additives include the following active substances:

Organic phosphorus~compounds Bis-0,0-diethylphosphoric acid anhydride tTEPp) Dimethyl-(2,2,2-trichloro-1-hydroxyethyl)-phosphonate .;
:~ (TRICHLORFON) 1,2-dibromo-2,2-dichloroethyldimethylphosphate (NALED) 2,2-dichlorovinyldimethylphosphate (DICHLORVOS) 2-methyoxycarbamyl-1-methylvinyldimethylphosphate (MEVINPHOS) Dimethyl-l-methyl-2-(methylcar~amoyl~-vinylphosphate cis (MONOCROTOPHOS~
3-(dimethoxyphosphinyloxy)-N,N-dimethyl-cis-crotonamide ~ (DICROTOPHOS) :, 2-chloro-2-diethylcarbamoyl-1-methylvinyldimethylphosphate (PHOSPH~MIDON~
~'~ O,0-diethyl-0(or S)-2-(ethylthio~-ethylthiophosphate (DEMETON) i~ S-ethylthioethyl-0,0-dimethyl-dithiophosph~te (THIOMETON~
., 20 010-diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE) ~i 0,0-diethyl-S-2-(ethylthio)ethyldithioph~sphate (DISULFOTON) j 0,0-dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate ., .
~ OXYDEMETON MEI'HYL~

.~ O,0-dimethyl-S-(1,2-dicarbethoxyethyldithiophosphate (MALATHION) .'~j . :~
:! :

,-_5_ .. ~ : . . . . . ~ . .
: - . , . . . . . - , . , 9 05~0'X7 0,Q,0,0-tetraethyl-S,S'-methylene-bis-dithiopho$phate (ETHION) 0-ethyl-S,S-dipropyldithiophosphate 0,0-dimethyl-S-(:N~methyl-N-formylcarbamoylmethyl)-dithiophosphate (FORMOTHION) 0,0-dimethyl-S-~N-methylcarbamoylmethyl~dithiophosphate ( D IMETHO~TE ) O,0-dimethyl-0-p-nitrophenylthiophosphate (PARATHION-METHYL) O,0-diethyl-0-p-nitrophenylthiophosphate (PARATHION) 0-ethyl-0-p-nitrophenylphenylthiophosphate (EPN~
0,0-dimethyl-0-(4-nitro-m-tolyl)thiophosphate (FENITROTHION) .:
0,0-dimethyl-0-2,4,5-trichlorophenylthiophosphate (RONNEL) , 0-ethyl-0,2,4,5-trichlorophenylethylthiophosphate (.TRICHLORONATE) 0,0-dimethyl-0-2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS) O,0-dime~hyl 0-(2,5-dichloro-4-iodophenyl)-thiophosphate (JODOFENPHOS)
4-tert.butyl-2-chlorophenyl-N-methyl-0-methylamidophosphate . ~
. (CRUYOMATE) ~ .
0,0-dimethyl-0-(3-methyl-4~methylmercaptophenyl)thiophosphate 20~ (FENTHION) . ~:
Isopropylamino-0-ethyl-0-(4-me-thylmercapto-3-methylphenyl)-phosphate ;
. 0,0-diethyl-0-p-(methylsulphînyl~phenyl-thiophosphate . !, (FENSULFOTHION) 0-p-(dimethylsulphamido)phenyl-0,0-dimethylthiophosphate (FAMPHUR) 0,0,0',0'-tetramethyl-0,0'-thiodi-p-phenylenethiophosphate 0-ethyl-S-phenyl-ethyldithiophosphate 0,0-dimethyl-0~ methylbenzyl-3-hydroxycrotonyl)phosphate 3Q 2-chloro-1-(2,4-dichlorophenyl~vinyl-diethylphosphate (CHLORFENVINPHOS) : .

-6 ; :.~

0'~'7 2-chloro-l-(2,4,5-trichloxophenyl~vinyl~di~ethylphosphate 0-[2-chloro-1-(2,5-dichlorophenyl~]vinyl-0,0-diethylthio-phosphate Phenylglyoxylonitriloxime-0,0-diethylthiophosphate (PHOXIM) 0,0-diethyl-0-(3-chloro-4-methyl-2-oxo-2-EI-l-benæopyran-7-yl)-thiophosphate (COUMAPHOS) 2,3-p-dioxandithiol-S,S-bis(0,0-diethyldithiophosphat~) ~DIOXATHION)
5-[(6-chloro-2-oxo 3-benzoxazolinyl)methyl~0,0-diethyldithio-phosphate (PHOSALONE) 2-(diethoxyphosphinylimino)-1,3-dithiol.ane 0,0-dimethyl-S-[2-methoxy-1,3,4-thiadiazol-5-(4H)-onyl-(4)-methyl]dithiophosphate 0,0-dimethyl-S-phthalimidomethyl-dithiophosphate (I~IDAN) 0,0-diethyl-0-(3,5,6-trichloro-2-pyridyl)thiophosphate 0,0-diethyl-0-2-pyrazinylthiophosphate (THIONAZIN) 1 0,0-diethyl-0-(2-isopropyl-4-methyl-6-pyrimidyl~thiophosphate i (DIAZINON) i 0,0-diethyl-0-~2-quinoxAlyl)thiopho~phate :~
2Q 0,0-dimethyl-S-(4-oxo-1,2,3-benzotriazin-3(4H)-ylmethyl)-dithiophosphate (AZINPHOSMETHYL) 0j0-diethyl-S-(4-oxo-1,2,3-benzotriazin-3(4H)-ylmethyl)-dit.hiophosphate (AZINPHOSETHYL) S-~(4,6-diamino-s-triazin-2-yl)methyl~-0,0-dimethyldithiophos-phate (MENAZON) 0,0-dimethyl-0-(3-chloro-4-nitrophenyl)thiophosphate (CHI,ORTHION) 0,0-dimethyl-0(or S)-2-(ethylthioethyl)thiophosphate .
(DEMETON-S-METHYL) ':

_7_ :
~ , , .

. j, . . ~ ~ . . .. . . .

2-(0,0-dimethyl-phosphoryl-thiomethyl)-5-methQxy-pyrone-4-3,4-dichlorobenzyl-triphenylphosphoniumchloride 0,0-diethyl-S-(2,5-dichlorophenylthiomethyl)dithiophosphate (PHENKAPTON) O,0-diethyl-0-(4-methyl-cumarinyl-7-)-thiophosphate (POTASAN) 5-amino-bis(dimethylamido)phosphinyl-3-phenyl-1,2,4-triazole (TRIAMIPHOS) ~ ::
N-methyl-5-(0,0-dimethylthiolphosphoryl)-3-thiavaleramide (VAMIDOTHION) : 10 0,0-diethyl-0- L 2-dimethylamino-4-methylpyrimidyl-(6)]-thio-phosphate (DIOCTHYL) 0,0-dimethyl-S-(methylcarbamoylmethyl)-thiophosphate (OMETHOATE) 0-ethyl-0-(8-quinolinyl)-phenylthiophosphonate (OXINOTHIOPHOS) 0-methyl-S-methyl-amidothiophosphate (MONITOR) i 0-methyl-0-(2,5-dichloro-4-bromophenyl)-benzothiophosphate :
:, (PHOSVEL) -;'~ 0,0,0,0-tetrapropyldithiophosphate `~
3-(dimethoxyphosphinyloxy)-N-methyl-N-methoxy-cis-crotonamide ~:
0,0-dimethyl-S-(N-ethylcarbamoylmethyl)dithiophosphate 2 a (ETHOATE-METHYL) 0,0-diethyl-S-(N-isopropylcarbamoylmethyl)-dithiophosphate (PROTHOATE) S-N~ cyano-l-methylethyl)carbamoylmethyldiethylthiolphosphate '~ (C~ANTHOATE) :` S-(2-acetamidoethyl~-0,0-dimethyldithiophosphate Hexamethylphosphoric acid triamide (HEMPA) 0,0-dimethyl-0-(2-chloro-4-nitrophenyl)thiophosphate (DICAPTHON) ~` .
0,0-dimethyl 0-p-cyanophenyl thiophosphate (CYANOX) .',, .- ,'~,.
'~ ' ':~., ' : -8-0-ethyl-Q-p-cyanophenylthiophosphonate O,0-die-thyl-Q-2,4~dichlorophenylthiophosphate (DICHLORFENTHION) 0,2,4-dichlorophenyl-0-methylisopropylam~dothiophosphate 0,0-diethyl-0-2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS-ETHYL) dimethyl-p-(.methylthio)phenylphosphate ~-.
0,0-dimethyl-0-p-sulphamidophenylthîophosphate ~.
0-~p-(p-chlorophenyl)azophenyl]Q,0-dimethylthiophosphate (AZOTHOATE~
0 ethyl-S-4-~hlorophenyl-ethyldithiophosphate Q-isobutyl-S-p-chlorophenyl-ethyldithiophosphate 0,0-dimethyl-S-p-chlorophenylthiophosphate n, 0-dimethyl-S-(p chlorophenylthiomethylldithiophosphate 0,0-diethyl-p-chlorophenylmercaptomethyl-dithiophosphate (CARBOPHENOTHION) 0,0-diethyl-S-p-chlorophenylthiomethyl-thiophosphate 0,0-dimethyl S-~carbethoxy-phenylmethyl)dithiophosphate (~HENTHOATE) :~
~ :`
0,0-diethyl S-(carbofluorethoxy-phenylmethyl~dithiophosphate 0,0-dimethyl-S-carboisopropoxy-phenylmethyl)-dithiophosphate O,0-diethyl-7-hydroxy-3,4-tetramethylene-coumarinyl-thiophos-phate (:COUMITHOA~El 2-methoxy-4-H-1,3,2-benzodioxaphosphorin-2-sulphide Q,0-diethyl-0-(5-phenyl-3-isooxazolyl~thiophosphate 2-(diethoxyphosphinylimino~-4-methyl-1,3-dithiolane :~ .
tris-(2-methyl-1-aziridinyl)-phosphine oxide (METEPA) S-(2-chLoro-l-phthalimidoethyl~-0~0-diethyldithiophosphate N-hydroxynaphthalimido-diethylphosphate , ' ~

_g _ . .
, - ~ ... , ~ : : . : .. . .. .

~ l~SlQ~Z7 dimethyl-3,5,6-trichloro-2-pyridylphosphate 0,0-dimethyl~0-(,3,5,6-trichloro-2-pyridyllthiophosphate S-2-(ethylsulphonyl)ethyl dimethylthiolphosphate (DIOXYDEMETON-S-METHYL) diethyl-S-2-(ethylsulphinyl)ethyl dithiophosphate (OXIDISULFOTON) bis-Q,0-diethylthiophosphoric acid anhydride (SULFOTEP~
dimethyl~l,3-di(,carbomethoxy)-1-propen-2-yl-phosphate ~.
dimethyl-(.2,2,2-trichloro-1-butyroyloxyethyl)phosphate (BUTONATE~
0,Q-dimethyl-0-(,2,2-dichloro-1-methoxy-vinyl~phosphate bis-~dimethylamido~fluorphosphate ~,DIMEFOX) 3,4-dichlorobenzyl-triphenylphosphoniumchloride .
dimethyl-N-methoxymethylcarbamoylmethyl-dith.iophosphate (FORMOCARBAM) ~, a, 0-diethyl-0-(2,2-dichloro-1-chloroethoxy~inyl)phosphate 0,0-dimethyl-0-(2,2-dichloro-;-chloroethoxyvinyl)phosphate ' ,'1 0-ethyl-S,S-di.phenyldithiolphosphate ~
0-ethyl-S-benzyl-phenyldithiophosphonate : , 0,0-diethyl-S-benzyl-th,iolphosphate 20, 0,0-dimethyl-S-(,4-chlorophenylthiomethyl)dithiophosphate ~,METHYLCARBOPHENOTHION) , a, 0-dimethyl-S-(.ethylthiomethyl~dithiophosphate , diisopropylaminofluorophosphate (MIPAFOX) ~ ' 0,0-dimethyl-S-(morpholinylcarbamoylmethyl)dithiophosphate : ' :
(,MORPHOTHIONI , ; bismethylamido-phenylphosphate ,~ , .
0,0-dimethyl-S-(.benzenesulphonyl)dithiophosphate ,-' ~' ~ 0,0-dimethyl-($ and O~-ethylsulphinylethylthiophosphate .. ~:':
.~ ..
:. ~

' :.,~. ' :' , --10-- ~ , ':

., ,. . ,. -. ... .~ .. ,.. ~ , .. " ,; . : . - -~0~2~
Q,0-diethyl-0-4-nitrophenylphosphate triethoxy-isopropoxy-bis(thiophosphinyl~disulphide 2-methoxy-4~I-1,3,2-~enzodioxaphosphorin 2-oxide octamethylpyrophosphoramide (SCHRADAN) bis-(dim~thoxyth~ophosphinylsulphido~-phenylmethane N,N,N',N'-tetramethyldiamidofluorophosphate (PIMEFOX) Q-phenyl-0-p-nitrophenyl-methanethiophosphonate (COLEP~
0-methyl-0-(:2-chloro-4-tert.butyl-phenyl)-N-methylamidothio-phosphate ('NA~LENEl 0-ethyl 0-(2,4-dichlorophenyl)-phenylthiophosphonate 0,0-diethyl-0-(4-methylmercapto-3,5-dimethylphenyl)-thiophosphate 4,4'-bis-(0,0-dimethylthiophosphoryloxy)-diphenyl disulphide 0,0-di-(~-chloroethyl)-0-(3-chloro-4-methyl-coumarinyl-7)-phosphate S-(l-phthalimidoethyl)-0,0-diethyldithiophosphate ~,0-dimethyl-0-(3-chloro-4-diethylsulphamylphenyl)-thiophosphate 0-methyl-0-(2-carbisopropoxyphenyl)-amidothiophosphate 5-(0,0-dimethylphosphoryl)-6-chloro-bicyclo(3~2.0)-heptadiene-(1,5~
0-methyl-0-(2-i-propoxycarbonyl-1-methylvinyl~-ethylamido-thiophosphate.
Nitrophenols and derivatives 4,6-dinitro-6-methylphenol, sodium salt [Dinitrocresol]
dinitrobutylphenol-(2,2',2"~-triethanolamine salt 2-cyclohexyl-4,6-dinitrophenyl [Dinex]
2-(1-methylheptyl)-4,5-dinitrophenyl-crotonate [Dinocap] ~ ' 2-sec.-butyl-4,6-dinitrophenyl-3-methyl-butenoate [Binapacryl]
2-sec.-butyl-4,6-dinitrophenyl-cyclopropionate 2-sec.-butyl-4,6-dinitrophenylisopropylcarbonate ~Dinobuton ., .

.
~, -11-LCI'X7 Miscellaneous -pyrethin I :
pyrethin II
3-allyl-2-me~hyl-4-oxo-2-cyclopentan-1-yl-chrysanthemumate (Allethrin)
6-chloropiperonyl-chrysanthemumate (Barthrin) 2,4-dimethylbenzyl-chrysanthemumate (Dimethrin) 2,3,4,5-tetrahydrophthalimidomethylchrysanthemumate 4-chlorobenzyl-4-chlorophenylsulphide [Chlorobensid]
6-methyl~2-oxo-1,3-dithiolo-[4,5-b]-quinoxaline (Quinomethionate) : ':
(I)-3-(2-furfuryl)-2-methyl-4-oxocyclopent-2-enyl(I)-(cis-~trans)-chrysanthemum-monocarboxylate [Furethrin]
_ 2-pivaloyl-indane-1,3-dione [Pindon]
N'-(4-chloro-2-methylphenyl)-N,N-dimethylformamidine [Chlorophenamidin]
4-chlorobenzyl-4-fluorophenyl-sulphide [Fluorobenside]
5,6-dichloro-1-phenoxycarbamyl-2-trifluoromethyl-benzimidazole ~Fenozaflor] . :
p-chlorophenyl-p-chlorobenzenesulphonate [Ovex] . ~:
20~ p-chlorophenyl-benzenesulphonate [Fenson] . :
p-chlorophenyl-2,4,5-trichlorophenylsulphone [Tetradifon] . ::
p-chlorophenyl-2,4~5-trichlorophenylsulphide [Tetrasul} ~:
p-chlorobenzyl-p-chlorophenylsulphide ~Chlorobenside] .
2-thio-1,3-dithiolo-(5,6)-quinoxaline [Thiochinox]
prop-2-ynyl-~4-t-butylphenoxy)-cyclohexylsulphite [Propargil].
: Formamidines l-dimethyl-2-t2'-methyl-4'-chlorophenyl)-formamidine (C~I,ORP~ENAMIDIN) ~ .

, ~ , .,. . ~ - . , . . . .. . . ., .. , . ~ . . .... . . .

~5~

l-methyl-2~(2'-methyl-4'-chlorophenylj-formamidine l-methyl-2-(2'-methyl-4'-bromophenyl)-~ormamidine l-methyl-2-(2',4'-dimethylphenyl)~formamidine l-n-butyl-l-methyl-2-(2'-methyl-4'-chlorophenyl)-formamidine l-methyl-1-(2'-methyl-4'-chl~roanilino-methylene)-formamidine 2-(2"-methyl-4"-chlorophenyl-formamidine l-n-butyl-2-(2'-methyl-4'-chlorophenyl-imino)-pyrolidine.
Urea ; N-2-methyl-4-chlorophenyl-N',N'-dimethyl-thiourea. ~ :
Carbamates l-naphthyl-N-methylcarbamate (CARBARYL) 2-butinyl-4-chlorophenylcarbamate 4-dimethylamino-3,5-xylyl-N-methylcarbamate 4-dimethylamino-3-tolyl-N-methylcarbamate (AMINOCA~B) 4-methylthio-3,5-xylyl-N-methylcarbamate (.METHIOC~RB) 3,4,5-trimethylphenyl-N-methylcarbamate .:
2-chlorophenyl-N-methylcarbamate (CPMCI
5-chloro-6-oxo-2-norborane-carbonitrile-0-(methylcarbamoyl~-oxime -Cdimethylcarbamoyl~-5-methyl-3-pyrazolyl-N,N-dimethylcarbamate 2a (DIMETILAN~ :
2,3-dihydro-2,2-dimethyl-7-benzo~uranyl-N-methylcarbamate (CARBOFURANl 2-methyl-2-methylth.io-propionaldehyde-0-(methylcarbamoyl)-oxime ..
(:ALDICARB) 8-quinaldyl-N~methylcarbamate and its salts ~.`.
methyl-2-isopropyl-4-(methylcarbamoyloxy~carbanilate m-(l-ethylpropyl~phenyl-N-methylcarbamate . :
3,5-di-tert.butyl-N-methylcarbamate ~' ~''. - ~' ., :
. 1 .
:: .
~ -13-- , . ., .;.,.: ., ... . . , . -:

~ ~5:1.~01.Z~7 m~ methylbutyl 2 phenyl-N-methylcarbamate 2-isopropylphenyl-N-methylcarbamate ~ .:
2-sec.butylphenyl-N-methylcarbamate ~ :
m-tolyl-N-m~thylcarbamate ~ ~
2,3-xylyl-N~methylcar~amata ; ~`
3-isopropylphenyl-N-methylcarbamate 3-tert.butylphenyl-N-methylcarbamate 3-sec.butylphenyl-N-methylcarbamate 3-isopropyl-5-methylphenyl-N-methylcarbamate (.PROMECARB) 3,5-diisoprop~lphenyl-N-methylcarhamate `:
2-chloro-5-isopropylphenyl-N-methylcarbamate :, .; ': , 2-chloro-4,5-dimethylphenyl~N-methylcarbamate .~.

2-(1,3-dioxolan-2-yl~phenyl-N-methylcarbamate (DIOXACARB) ; 2-(4,5-dimethyl-1,3-dioxolan-2-yl~phenyl-N-methylcarbamate ~:
,, 2-(:1.,3-dioxolan-2-yllphenyl-N,N-dimethylcarbamate ,;`
2-(.1.,3-dithiolan-2-yl~-N,N-dimethylcar~amate .~
2-(.1.,3-dithiolan-2-yl~phenyl-N,N-dimethylcarbamate ~ ~:
2-isopropoxyphenyl-N-methylcarbamate (~PROCARB).
~ -(2~propin~10xy~phenyl-N-methylcarbamate - 20 3-t2-propinylo~y~phenyl-N-methylcarbamate : ~:
2-dimethylaminoph.enyl~N-methylcarbamate 2-diallylaminophenyl-N-methylcarbamate ~ ;~
:~ 4-diallylamino-3~5-xylyl-N-methylcarbamate (ALLYXICARB~
4-benzothienyl-N-methylcarbamate 2,3-dihydro-2-me.thyl-7-benzofuranyl-N~methy.lcarbamate ~ .3-methyl-1-phenylpyrazol-5-yl-N,N-dimethylcarbamate .l l-isapropyl-3-methylpyrazoI-5-yl-N,N~dimethylcarbamate (ISOLAN) :l .
:1 2-dimethylamino-5,6-d~methylpyrimidin-4-yl-N,N-dimethyl-carbamate .~ ~

.

', 3-methyl-4-dimethylaminomethyleneiminophen~l N-~ethylcarbamate 3,4-dimethylphenyl-N-meth~lcarbamate 2-cyclopentylphenyl-N-methylcarbamate 3-dimethylamino-methyleneiminophenyl-N-methylcarbamate (FORMETANATE) and its salts l-methylthio-ethylimino-N-methylcarbamate (M~T~IOMYL) 2-methylcarbamoyloximino-1,3-dithiolane 5-methyl-2-methylcarbamoyloximino-1,3-oxythiolane 2~ methoxy-2-propoxy~phenyl-N-methylcarbamate ~.
2-(1-butin-3-yl-oxy~pheny].-M-methylcarbamate l-dimethylcarbamyl-l-methylthio~0-methylcarbamyl-formoxime .
1-(2'-cyanoethylthio)-0-methylcarbamyl-acetaldoxime ~.
l-methylthio-0-carbamyl-acetaldoxime 0-(.3-sec.butylphenyl~-N-phenylthio-M-methylcarbamate 2,5-dimethyl-1,3-dithiolane-2-(0-methylcarbamyl)-aldoxime) :
0-2-diphenyl-N-methylcarbamate 2-(.N-methylcarbamyl-oximino)-3-chloro-bicyclo[2.2.1]heptane 2-(N-methylcarbamyl-oximino)-bicyclo[2.2.1~heptane 3-is.opropylphenyl-N-methyl-N-chloroacetal-carbamate :~
20 .3-isopropylphenyl-N-methyl-N-methylthîomethyl-carbamate `~
Q-(.2,2-dimethyl-4-chloro-2,3-dihydro-7-benzofuranyl)-N-methyl- .
carbamate 0-(:2,2,4-trimethyl-2,3-dihydro-7-benzo~uranyl)-N-methylcarbamate .
Q-naphthyl-N-methyl-N-acetal-carbamate .
0-5,6,7,8-tetrahydronaphthyl-N methyl-carbamate 3-isopropyl-4-methylthio-phenyl-N-methylcar~amate 3,5-dimethyl-4-methoxy-phenyl-N-methylcarbamate 3-methoxymethoxy-phenyl-N-methylcarhamate ~ `

L0'2~7 3-allyloxypheIlyl-N-methylcarbamate ~ ;
2-propargyloxymethoxy-phenyl-N-methy:l-carbamate 2-allyloxyphenyl-N-methyl-carbamate 4-methoxycarbonylamino-3-.isopropylphenyl-N-methyl-carbamate 3,5-dimethyl-4-methoxycarbonylamino~phenyl-N-methyl-carbamate ~:
2-~methylthiopropylphenyl-N-methyl-carbamate 3-(.a-methoxymethyl-2-propenyl)~phQnyl-N-methyl-carbamate 2-chloro-5 tert.-butyl-phenyl-N-methyl-carbamate 4-(methyl-propargylamino-3,5-xylyl-N-methyl-carbamate 4-(methyl-~-chloroallylamino~-3,5-xylyl-N-methyl-carbamate ~ .
4-(methyl-~-chloroallylamino)-3,5-xylyl-N-methyl-carbamate -ethoxycarbonylethyl~-3-methyl 5-pyrazolyl-N,N-dimethyl- .
, carbamate :: :

; 3-methyl-4-(.dimethylamino-methylmercapto-methyleneimino)phenyl- ..

:, N-methylcarbamate , .
.~ 1,3-bis(.carbamoylthio)-2-(N,N-dimethylamino)-propanehydrochloride ' 5,5-dimethy.lhydroresorcinoldimethylcarbamate ~.

:J 2-[ethyl-propargylamino]-phenyl-N-methylcarbamate .~ 2-[methyl-propargylamino~-phenyl-N-methylcarbamate . -20~ 2-:[dlpropargylamino]-phenyl-N-methylcarbamate 4-[dipropargylamino]-3-tolyl-N methylcarbamate ; :.

4-[dipropargylamino]-3,5-xylyl-N-methylcarbamate 1 2-[allyl-~sopropylamino~phenyl-N-methylcarbamate : .3-[allyl-~sopropylamino]-phenyl-N-methylcarbamate !
~: C~lolr~nate-a~ydroc~ar~ ns y-he.xach.lorocyclohexane [GAMMEXANE; LINDAN; r HCH] .

~ 1,2,4,5,6,7,8,8-octachloro-3a,4,7,7a'tetrahydro-4,7-methylene .1 indane ICHLORDAN]

`! :

, ', : -, . . . - . ~, , . . ., ~ . -, . . .

105~0;Z~7 1,4,5,6,7,8,8-heptachloro,3~,4,7,7~-tetrahydro-4,7-methylene indane ~E~EPTACHLOR]
1,2,3,4,10,10-hexachloro-1,4,4~,5,8,8-hexahydro-endo-1,4-exo-5,8-dimethanonaphthalene ~ALDRIN~
1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4~,5,6,7,8,8~octa-hydro-exo-1,4-endo-5,8-dimethanonaphthalene ~DIELDRIN~ ~
1,2,3,4,10,10-hexachloro-5,7-epoxy-1,4,4a,5,6,7,8,8a-octa- :.
hydro-endo-endo-5,8-dimethanonaphthalene [ENDRIN]. ;

: ' ' . ~

, , ;,~

: .

~53 ~fZ~7 The con-l)ouncls o~ ~ormul~ I and Ia cal- be used on their own :.
or together wi~h sui~ab]e carriers and/or addit;ves.
Suita~le carriers and additives may be solid or liquid, . and corrcspond to ~he substances common in formulation practi.ce, such as~ e.g. natural. and regenerated substances~
solvents, dispers.ing agents~ wetting agents~ adhesivesJ ;~
thickenersJ binders and/or fertil.isers, For applicati.on, the compounds of formulae I and Ia can be processed into ~h.e ~orm o dusts, emulsion concentrates~ ~.
granulates~ dispersions~ spraysJ or solutions, the .~ :
formulation o~ these preparations being ef~ected in a ; manner commonly known in practice. A150 to be m~ntioned l are cattle dips and spray races, in which aqueous i. preparations are used.
: 15 The agents according to the i.nventlon are produced in a manner known per se by the intimate mixing and/or .: grinding of active substances of formulae I and Ia wi.th the : suitable carriers, optionally with the addition o~ dispersing agents or solvents which are inert to the active substances.
The active substances can be obtained and used in the ~ folLowing prepara~ion forms: ~ :
solid preparations: dusts~ 9cattering agentsl granul.a~es, coated granulates~ impregnated granulates and homogeneous granulates;
liquid preparation$: ~
a) water dispersible active substance concentrates: ~.. -wettable powders, pastes, emulsions;
b) solutions.

: - , , :

.
.. ..
1,, , . . . . . . ... . .. , . ., ,. ~ . .. . . .

The so].id prepclrations (dllsts, scattering agen~s) are produced by ~he mixing of ~he active subs~.ances with solid carriers. Sui.~able carriers are, e.g. kaolin, talc~lm, bole~ loess, chalk~ limestone, ground limestQne, attapulgite> dol.omi~e~ diatomaceous earth, precipitated silicic acid~ alkaline earth. silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, ferti.lisers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products such as bran; bark dust, sawdust, ground nutshells, cellulose powder, residues o~ plant .;
extractions~ active charcoal, etc., alone or in admixture with each other.
. 15 Granulates can be very easily prepaled by a process in : which an active substance of formula I or Ia is dissolved in an organic solvent, the thus obtained solution applied to a l granulated mineral, e.g. attapulgite> SiO29 granicalcium, - bentonite, etc., and the organic solvent then evaporated off.
It is possible also to produce polymer granulates; in this . case th.e active substances o formula I or Ia are mixe.d with polymeri.sable compounds (urea/formaldehyde; dicyandiamide/
formaldehyde; melamine/formaldehyde, or others); polymerisation is then carefully .carried out in a manner which leaves the active substances unaffected, and granulation performed actually during the gel forming process. It is more favourable, however, ' , ' , , ' ':
:, , . ' ' ~ 7 to impregna~e ~inished porous polymer granules (urea/ ~ , formaldehyde, polyacrylonitrile, polyester and others)~
having a specific surface area and a ~avourable predeterminable `
àdsorption/desorption ratio, with the active substances~
e.g. in the ~orm o~ their solutions (in a low-boiling '"'''-solvent), and to then remove the solveot.Polymer granulates of this kind can be also sprayed ïn the form of microgranulates, having bulk weights of preferably 300 g/litre to 600 g/litre, with the aid of spray apparatus. Spraying can be carried `~
out over extensive areas of useful plan~ crops by the use ~ -of aeroplanes.
Granulates can also be obtained by the compacting of I the carrier material with the active substances and additives, ,, and a subsequent reducing operation.
Moreover, it is possible to add to these mixtures addi~ives stabilising the active subs~ance and/or nonionic, anion~active and cation-active substances which improve, e.g.
~, ~ the adhesiveness of the a~,tive substances on plants and ;~
parts of plants (adhesives and agglutinants), and/or ensure a better we~tability (wetting agents~ as well as dispersibility (dispersing agents).
The ollowing substances are, for example, suitable:
;~:

' `, , , ' ' .
: ~ .
~ 20 -, ~, ,.

olein/lime mi.~:t.ure, cel].~llose dcrivat:ives (methyl cellulosc, car~oxymethyl cellulose~, hydro~yethylene glycol ethers o~ monoalkyl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in tile alkyl radical, lignin-sulphonic acid~ the alkali metal and alkaline-earth metal salts thereof~ polyethylene glycol etl~ers rbol~e,s ~ ", ; (~Y~3e~-e~), fatty alcohol polyglycol ethers h.aving 5 to 20 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety; condensation . products of ethylene oxide, propylene oxide~ polyvinyl~
.- pyrrolidones, polyvinyl alcohols, condensation products - of urea and formaldehyde, as well as latex products.
Water-dispersible concen~rates of active substances~
i.e, wettable powders, pastes and emulsi.on concentrates, are agents which can be diluted with water to ob~ain any desired concentration. They consist of active substance, ., .
l carrier, optionally additives which stabilise the active . substance, surface-active substances~ and.anti-foam agents and, optionally~ solvents.
The wettable powders and pastes are ohtained by the mixing and grinding of the active substances with dispersing agen~s and pulverulent carriers, in suitable devices, until h.omogeneity is obtained. Suitable carriers are, e.g.
those previously mentioned in the case of solid preparations.
It: is advantageous in some cases to use mixtures o~
different carriers, As dispersing agents it is possible to ~ ~r ac/~h7a~k ~ ~

` - 21 - -.

.. . . . . .

~. ~

,use, e.g.: con~ensa~ion products o~ sulphonated naphthalene ~nd sulphona~ed naph~halene clerivatives witll formaldehyde, condensa~ion produc~s oE naphthalene or of naphthalene- ~;
sulphonic acids with phenol and formalclehyde, as well as i alk~li, ammonium and ~lkaline-earth metal salts o ligninsulphonic acid~ also alkylarylsulphonates, alkali metal salts and alkaline-ear~h metal salts of dibutyl naphthalenesulphonic acid, fatty alcohol sulphates such as salts of sulphated hexadecanols~ heptadecanols, octadecanols, and salts o sulphated ~at~y alcohol glycol ethers, the sodium salt of oley] methyl tauride~
ditertiary ethylene glycols, dialkyl dilauryl ammonium ;'l .
chloride, and fatty ~cid alkali-metal and alkaline-earth metaI salts.
Suitable anti-foam agents are, e.g. silicones.
The active substances are so mixed, ground, sieved and strained with the above mentioned additives that the solid constituent in the case of wettable powders has a ;~ particle size not exceeding 0.02 to 0.04 mm~ and in the case of pastes not exceeding 0.03 mm. For the preparation of emulsion concentrates and pastes, dispersing agents are used such as those mentioned in the preceding paragraphs, - organic solvents and water. Suitable solvents are, e.g.
alcohols, benzene, xylene, toluene, dimethylsulphoxide, and mineral oil ~ractions boiling in the range of 120 to 350C. The solvents must be practically odourless~ non~
phytotoxic~ and inert to the active substances.
.. . ' ~ ~

~ 22 - ~

,.: , .

F~lrthcL-Inore, the agen~s accordîng to the invention ~:
can be used :I.n tlle ~orm cf sol-ltions. For this purpose, the active s~lbstance, or several active substances, o~
the general ~orm~lla I and/or Ia is dissolved in suitable organic ~.
.S solvents, solvent mixtures, or water. As organic solvents it is possible to use aliph.atic and aromatic hydrocarbons their chlorinated derivatives~ alkylnaphthalenes, mineral oils on ~-heir own or in admixture with each other.
The content of active substance in the above described agents is between 0.1 and ~5%; it is to be mentioned in th.is connection that in the case of application of the agents from an aeroplane, or by means of some other suitable application devices~ cOncentrations of up to 99.5%
can be used, or even the pure active substance.
The active substances of ~ormulae I and Ia are prepared, e.g. as follows:
Dus~s The followin~ substances are used for the preparation .
of a~ a 5% dust, and b) a 2~/o dust:
a) S parts of active substance 95 parts of talcum. ~ :
. b) ... 2 part.s of active substance l part o~ highly dispersed silicic acid ..
97 par~s of talcum, .
. 25 The active substances are mixed and ground with the carriers.

~ 23 ~

~, - .. . . . - . . . . . . . .

Gran~llcl~e The following substances are used to produce a ;~
5% granulate:
5 parts of active substance~
0.25 parts o~ epichlorhydrin, 0.25 parts of cetyl polyglycol ether~
3,50 parts of polyethylene gly~ol, .
. .
91 parts of kaolin ( particle si~e 0.3 - 0,8 ~m). ~:
:` The active suhstance is mixed with epichlorhydrin :~
. : and dissolved ~lith 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The : thus obtained solution is sprayed on to kaolin, and ~ the acetone subsequently evaporated in vacuo, ~ .
, Wettable powder ~:;. The following constituents are used for the preparation . . ~ .
lS of a) a 40%, b) and c) a 25%, and d) a 10% wettable powder~
a) 40 parts of active substanceg parts o~ sodium lignin sulphonate, 1 part of sodium dibutyl-naphthalene sulphonate, , . 54 parts of silicic acid, b) 25 parts o~ active substance, 4,5 parts of calci~tm lignin sulphonat~ ;~
I; . 1,9 parts of Champagne chalk/hydroxyethyl cellulose .l mixture ~1:1), `
1.5 parts of sodium dibutyl naphthalene sulphonate, ~.
19,5 parts of silicic acid, ~
,: ~

: - 2~
.: ' ' . .

1'~$~7 :
19.5 parts of Champagne chalk~
28.1 parts of kaolin.
c) 25 parts of active substance~ `~
2.5 parts of isooc~ylphenoxy-polyoxyethylene-ethanol, 1.7 parts of Champagne chalk/~ydroxyethyl cellulose mixture (1:1)J
8.3 parts of sodium aluminium silicate, 16,5 parts of kieselguhr~ ~
46 parts of kaolin. `
d) 10 parts of active substance, ~-3 parts of a mixture of the sodium salts of , .
saturated ~atty alcohol sulphates, ` 5 par~s of naphth;alenesulphonic acidtformaldehyde condensate, ;~ ;
82 parts of kaolin. ~-~
~; The active substances are intimately mixed, in suitable I~ mixers, with the additives, the mixture being then ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentra~ion.
i Emulsifiable concentrates The following substances are used to produce a) a 10%
and b) a 25% emulsi~iable concentrate: -i a) 10 parts of active substance, ~; 25 3,4 parts o~ epoxidised vegetable oil9 :

-- 25 ~
, . '''.
i , ~ ~ - - .

3L~5~ t7 ',.
13,4 parts of a combination emulsi~ier consisting of fat~y alcohol polyglycol ether and alkylaryl-sulphona~e calcium salt~
40 parts of dimethylformamideJ
':~
~ 5 43,2 parts of xylene.
.. . ~:
b) 25 parts of active substanceJ
: 2.5 parts of epoxidised vegetable oilJ -~
. ~ .
parts of an~alkylarylsulph.onatelLatty alcohol . polyglycol ether mixture }
parts of dimethylformamide 57.5 parts of xylene. :
; ' .
: ~rom these concentrates it is possible to produce, by dilution with water, emulsions o any desired concentration, . ~.'' Spray: . ~
,~ .
`I : 15 The following constituents are used to prepare a :
,~ 5%~spray: ~.
!: ::
5 :parts of active substance, ~: 1 part of epichlorhydrinJ ~
~ 94 parts of ligroin (boiling limits 160-190C), ~:
1 ;
-- .
,, .
- .
, ., , ' .: , , - ~

.. , ~ . .
7 :~

Production of N,N-dimethyl-N'-(2,6-diethylphenyl)-formamidine.
Production of the compound of the ~ormula ~2H5 .~ < / ~13 Cl~
C2~15 3 40 ml o dimethylformamide and 40 ml of thionyl chloride are stirred for 2 hours in 200 ml of absolute toluene a~ 40C; an addition is then made dropwise at 40-50C of 59.8 g of 2,6-diethylaniline diluted with 200 ml of anhydrous toluene. The reaction mi~ture is ~`
heated slowly for ~ hours to the boiling point, and refluxed for a further 5 hours. The reaction mixture is cooled;
. 1 '.`!'~` ice water is added~ the whole rendered alkaline with sodium hydroxide solution, and the organic phase~separated ~
and dried over~ sodium sulphate. Distillation yields the ~ i lS product in ca. 85% yield; B.P.: 77-79C/0.03 Torr.
"
;~l The following urther compounds are prodiuced in an 1 analogous manner: ~ `
'`I , -~

!
~: ' , . .

- 27 ~
~; .

: j : . !

)5~Z7 N,N-dimethyl-N'-(2,6-dimethylphenyl)-formamidine, B.P. 132C/ll Torr N-methyl-N-butyl-N'-(2,6-dimethylphenyl)-formamidine, B.P. 93C/0.02 Torr N-methyl-N'-(2,6-dime~hylphenyl)-formamidine, M.P. 82 - 83C
N-methyl-N'-(2,6-diisopropylphenyl)-formamidine, ~ M.P. G2 - 63C
N-methyl-N'-(2~6-diethylphenyl~-formamidine, M.P. 165 - 166C
N~methyl-N'-(2,6-dimethylphenyl) formamidine, M.P. 186 - 187C
N-allyl-N'~(2,6-dimethylphenyl)-formamidine, M.P 45C
N-propargyl-N'-(2,6-dimethylphenyl) formamidine~ oil N,N-dimethyl-N'-(2,4,6-trimethylphenyl~-formamidine, B.P.72-73C/0.09 Torr N'-methyl.-N'-(2,4,6-trimethylphenyl)-formamidine, M.P. 123 - 124C
N,N-dimethyl-N'-(2-ethyl-6-sec.butyl-phenyl)-formamidine, .
N-methyl~N-n-butyl-N'-(2-ethyl-6-n-butyl-phenyl)-~ormamidine, 25 N,N-dimethyl-N'-~2-ethyl-6-isopropylphenyl)-formamidine, ~:
28 - ~

.

. :- . . , .. - . - . . - - -~5~)Z';~
N-methyl-N-n-bu~yl-N'-(2-ethyl-6-isopropylphenyl)--formamidine, N,N-dimethyl-N'-t2-methyl-6-tert. butylphenyl)-formamicline, -~
N-methyl-N-n-butyl-N'-(Z,6-diethylphenyl)-formamidine, n23 1.5251, B. P. 114-119C/0.05 Torr -N,N-dimethyl-N-(2-methyl-6-ethylphenyl)-formamidine3 B. P. 72C/0.005 Torr N,N-dimethyl-N'-(2,6-diisopropylphenyl)~formamidine, ~-N-methyl-N-n-butyl-N'-(2-methyl-6-isopropylphenyl)-formamidine. ~

.,' ,~ '~
.

~ !

.

.~ , ` '''~'` ~

" ' '~

,~

~o~
Example 2 Action_a~ainst _ A~ E~ halus bursa In each case, 5 adults ox 50 tick larvae were placed into a small glass test tube, and the test tubes then immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion from a dilution series of 100, 10, 1 and 0.1 ppm of test substance. The tubes were then sealed with a standardised cot~on plug, and inverted so that the active subs~ance emulsion could be absorbed by the -~
: .
lG cotton wool.
An evaluation in the case of the adults was made ater 2 weeks, and in the case of the larvae after 2 days.
There were two repeats for each test.
The compounds according to Example 1 were effective, ~ 15 in the above test, against adults and larvae of i~ Rhipicephalus bursa.
`i:
B) Boophilus microplus (larvae) With a dilution series analogous to that in Test A, l~ tests were carried out in each case with 20 OP-sensitive 1 20 larvae.
Il The compounds according to Example L were effective ` `
ll in the above test against sensitive larvae of Boophilus microplus.

. ' ' ' _ 30 _ , :

~ f - ~

'' .' ' . ' ' ~ ' ' " ' '' ''' ~` ' ~ "' '' ' ' '.. '' ` ' ' '

Claims (10)

CLAIMS:
1. Compounds of the formula (I) or (Ia) wherein X represents an inorganic or organic acid radical, R1 represents alkyl having 1 to 4 carbon atoms, alkenyl having 3 to 5 carbon atoms, or alkynyl having 3 to 6 carbon atoms, R2 represent hydrogen, alkyl having 1 to 4 carbon atoms, alkenyl having 3 to 5 carbon atoms, or alkynyl having 3 to 6 carbon atoms and either:
I) R3, R4 and R5 are simultaneously CH3 or:
II) R3 represents alkyl having 2 to 4 carbon atoms, R4 represents alkyl having 1 to 4 carbon atoms and R5 represents hydrogen or alkyl having 1 to 4 carbon atoms.
2. Compounds according to claim 1, wherein R1 represents methyl, ethyl, propyl, isopropyl or n-butyl, R2 represents hydrogen, methyl, ethyl, propyl, isopropyl or n-butyl, R3 represents methyl, ethyl or isopropyl, R4 represents methyl, ethyl, propyl, isopropyl, sec.butyl or tert.butyl, R5 represents hydrogen and X represents an inorganic or organic acid radical.
3. N,N-Dimethyl-N'-(2,6-diethylphenyl)-formamidine.
4. N-Methyl-N-n-butyl-N'-(2,6-diethylphenyl)-formamidine.
5. N,N-dimethyl-N'-(2-methyl-6-ethylphenyl)-formamidine.
6. N-Methyl-N'-(2,6-diisopropylphenyl)-formamidine.
7. N-Methyl-N'-(2,6-diethylphenyl)-formamidine.
8. Process for the production of compounds of hte formula (I) or (Ia) wherein X represents an inorganic or organic acid radical.
R1 represents alkyl having 1 to 4 carbon atoms, alkenyl.
having 3 to 5 carbon atoms, or alkynyl having 3 to 6 carbon atoms, R2 represents hydrogen, alkyl having 1 to 4 carbon atoms, alkenyl having 3 to 5 carbon atoms, or alkynyl having 3 to 6 carbon atoms and either:
I) R3, R4 and R5 are simultaneously CH3 or:
II) R3 represents alkyl having 2 to 4 carbon atoms, R4 represents alkyl having 1 to 4 carbon atoms and R5 represents hydrogen or alkyl having 1 to 4 carbon atoms, the said process comprising the reaction of a compound of the formula with a compound of the formula in the presence of SOCl2, COCL2, POCl3, PCl3, PCl5, (CH3)2SO4 or , wherein R1 to R4 have the above given meanings.
9. A method for combating parasitic pests on domestic and productive animals which comprises applying to said animals a compound as defined in claim 1.
10. A method as claimed in claim 9 wherein said compound is applied to an animal infested with or threatened with infestation with a member of the order acarina.
CA166,698A 1972-03-29 1973-03-21 Process for the production of new phenylformamidines Expired CA1051027A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH473172A CH564305A5 (en) 1972-03-29 1972-03-29 Substd phenylformamidines - acaricides
CH473072A CH564304A5 (en) 1972-03-29 1972-03-29 Substd phenylformamidines

Publications (1)

Publication Number Publication Date
CA1051027A true CA1051027A (en) 1979-03-20

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AR (1) AR217029A1 (en)
AT (1) AT320611B (en)
BE (1) BE797442A (en)
BR (1) BR7302283D0 (en)
CA (1) CA1051027A (en)
CS (1) CS189605B2 (en)
DD (1) DD107907A5 (en)
DE (1) DE2315041A1 (en)
FR (1) FR2178117A1 (en)
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IT (1) IT988616B (en)
KE (1) KE2917A (en)
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US4071556A (en) * 1974-03-11 1978-01-31 Stauffer Chemical Company Formamidine insecticidal compounds
SE418513B (en) * 1975-02-05 1981-06-09 Huyck Corp MULTIPLE-PAPER PAPER MACHINE COATED AS WELL AS MANUFACTURED
JPS5516913A (en) * 1978-07-18 1980-02-06 Imaizumi Shigiyou Kk Paper making blanket in paper making machine and production
EP0015440A1 (en) * 1979-02-23 1980-09-17 Hoechst Aktiengesellschaft Substituted N1-vinyl-N1-methyl-N2-aryl-formamidines, process for their preparation and their application as pesticides
GB9902592D0 (en) * 1999-02-06 1999-03-24 Hoechst Schering Agrevo Gmbh Fungicides
CN111925303A (en) * 2020-08-12 2020-11-13 广东嘉博制药有限公司 Preparation method of ropivacaine hydrochloride impurity

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NL253634A (en) * 1959-07-10
CH432929A (en) * 1962-03-08 1967-03-31 Ciba Geigy Pesticides
GB1212454A (en) * 1967-03-04 1970-11-18 Egyt Gyogyszervegyeszeti Gyar N,n'-substituted formamidines

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AT320611B (en) 1975-02-25
IT988616B (en) 1975-04-30
BR7302283D0 (en) 1974-06-27
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YU82473A (en) 1981-06-30
YU36156B (en) 1982-02-25
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SU651643A3 (en) 1979-03-05
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US3929883A (en) 1975-12-30
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