Note: Descriptions are shown in the official language in which they were submitted.
1055511
The invention relates to substituted phenyl
derivatives, their manufacture, and their use in pest
control.
The compounds correspond to the general formula
R ~ 8
, ,2
~ Z-CH-C=CH-R3 (I)
wherein Rl represents cyclohexyl, cyclohexyloxy or the group
R7 ~
~ ~ -Y- , in which Y represents -O-, -C-, -CH2-,
,CH3
-CH-, -CH2O, -OCH2-, -NH-, -N- or the direct bond;
R5
Z represents -O-, -NH- or -N-;
R5
R2 represents hydrogen or Cl-C3-alkyl; R3 represents -COOH,
(Cl-C5-alkoxy)carbonyl, (C3-C5-alkenyloxy)-carbonyl,
(C3-C5-alkinyloxy)carbonyl, cyclohexyloxycarbonyl, phenoxy-
carbonyl, the cyano group, a carbamoyl group which is mono-
or disubstituted by Cl-C5-alkyl or monosubstituted by
C3-C5-alkenyl, it being possible for the substituents of the
carbamoyl group together with the nitrogen atom to which
they are bound to form a saturated 6-membered heterocyclic
ring which can contain in addition an oxygen atom;
R4 represents hydrogen or methyl; R5 represents formyl;
R7 represents hydrogen, halogen, Cl-C5-alkoxy or Cl-C5-
alkyl; R8 represents hydrogen, halogen or methyl.
B 2 -
1055511
Halogen is to be understood as meaning fluorine, chlorine,
bromine, or iodine.
The alkyl or alkoxy groups represented by R5, R6,
and R7 can be straight-chain or branched. Examples of
such groups include: methyl, ethyl, n-propyl, isopropyl,
i-, n-, sec.- and tert.-butyl, n-, sec.- and iso-pentyl,
methoxy, ethoxy, propoxy, n-, iso- and sec.-butoxy, n-
pentoxy.
The alkoxy, alkenyloxy, alkinyloxy and haloalkenyl-
oxy moieties of an alkoxycarbonyl, alkenyloxycarbonyl,
alkinyloxycarbonyl or haloalkenyloxycarbonyl group R3 can
be straight-chain or branched. Examples of such moiety
groups include: methoxy, ethoxy, n-propoxy, isopropoxy,
sec.-butoxy, allyloxy, methallyloxy, propargyloxy, chlor-
allyloxy. The alkyl, alkenyl or alkinyl substituents of
a carbamoyl group R3 can be straight-chain or branched.
Examples of such a carbamoyl group R3 include: mono-
methylcarbamoyl, monoethylcarbamoyl, dimethylcarbamoyl,
diethylcarbamoyl, monoallylcarbamoyl, monoisopropylcar-
bamoyl, diallylcarbamoyl, 2-but-3-inyl-carbamoyl.
Examples of the heterocyclic rings formed with the
substituents of the carbamoyl group R3 together with the
nitrOgen atom to which they are bonded and optionally with
a further heteroatom include the morpholine, piperidine,
or pyrrolidine ring.
Compounds to be highlighted are those of the general
formula I, wherein R2 represents hydrogen, methyl or ethyl,
- 3 -
1055511
R3 represents carboxyl,methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl,
sec.-butoxycarbonyl, cyclohexyloxycarbonyl, phenoxycarbonyl, allyloxy-
carbonyl, propargyloxycarbonyl, monomethylcarbamoyl, monoethylcarbamoyl,
monoisopropylcarba~oyl, mono-sec. butylcarbamoyl, monoallylcarbamoyl,
diethylcarbamoyl, diallylcarbamoyl, 2-but-in-inylcarbamoyl, n-piperidino-
carbonyl, n-morpholinocarbonyl, or cyano; R4 represents hydrogen or
methyl, R5 represents formyl or acetyl, R6 represents hydrogen or
methyl, R7 represents hydrogen, Cl-C3-alkyl, chlorine, methoxy or ethoxy,
and R8 represents chlorine or methyl.
Preferred compounds on account of their action are those of
the general formula I, wherein Rl represents
R7
the group ~ Y , in which Y represents -O-,
CHO
-C- or -CH2-, Z represents -O-, -NH- or -N-,
o
R2 represents methyl or ethyl, R3 represents methoxycarbonyl, ethoxy-
carbonyl, isopropoxycarbonyl, sec.-butoxycarbonyl, cyclohexyloxycarbonyl,
monoethylcarbamoyl, diethylcarbamoyl, monoisopropylcarbamoyl, monoallyl-
carbamoyl, N-piperidinocarbonyl or
C
1055511
cyano, R4 ,epresents hydrogen or methyl, and R7 represents
hydrogen, methyl, ethyl, chlorine, methoxy or ethoxy.
A particularly preferred group of compounds is that
Or the formula I, wherein Rl represents the group
7 ~ , Z represents -O- , R2 represents methyl
or ethyl, R~ represents methoxycarbonyl, ethoxycarbonyl,
isopropoxycarbonyl, sec.butoxycarbonyl, diethylcarbamoyl,
monoethylcarbamoyl or cyano, R4 represents hydrogen, and
R7 represents hydrogen, chlorine, or ethyl.
A further preferred group of compounds is that of
the formula I, wherein Rl represents unsubstituted
benzyl, Z represents -O-, R2 represents methyl, R3 repre-
sents methoxycarbonyl, ethoxycarbonyl, diethylcarbamoyl
or cyano, and R4 represents hydrogen.
The compounds of the formula I are manufactured in
known manner, e.g. by the following methods:
Rl ~ R8 R14 Rl2 Base >
A) ~ ZH + X CH-C=CH-R3
(II) (III)
B)
Rl ~ R8 l4 ll ~ase
~ ZH + XC~ R2 > V
(II) (IV)
oder
1055S~l
R ~ R R . HgO/B~ (C2H5)2/R2~
4 2. H O ~ (VIl)
-C-CH --3~ > V
(VI)
und
~-C~ C-R + (R90)2P-CH--R3- Me ~ > I
(V) (VIII)
Rl ~ R8R4 R2 R OH/H ~
Z-CH-C=CH-COOH 10 --- -> I
(IX) or RlOX/Base
In the formula II to IX, Z and Rl to Rlo have the
meanings given for the formula I, X represents halogen,
in particular chlorine or bromine, Rg represents Cl-C5-
alkyl, phenyl or p-chlorophenyl, Me represents alkali metal,
in particular sodium or potassium, and Rlo represents
Cl-C4-alkylg C3-C4-alkenyl, C3-C4-alkinylJ or cyclohexyl.
Suitable bases in the reactions A, B and C are
hydridesJ amidesJ alkoxidesJ hydroxidesJ or carbonates of
alkali or alkaline earth metals.
The starting materials of the formula IX are
appropriately obtained by alkaline hydrolysis of a
corresponding ester.
According to process B, the compounds of the formula I
are manufactured by reacting a ketone of the formula IV with
the anion Or a dialkylphosphonic acid derivative in an inert
solvent (Horner reactionJ e.g. J.Org. Chem. 25J 1232-34 (1960)
and J. Org. Chem. ~0, 680 ff (1965)~.
--6_
~055511
D) The ccmpounds of the formula I, wherein Y and/or
Z represents the group -N- are appropriately manu-
~actured by acylation R5 or alkylation of a -NH
group accordir:g to the following equations:
R R4 R2
5R'l-NH ~ Z'-CH-C=CH-R3 acylatlng reagent
(X) or alkylating agent
15 ~ R8 R14 R12
R' -N ~ Zl-CH-C=CH-R3 or
(I)
R8 R14 R12 acylating reagent
Y ~ ~l-cH-c=cH-R3 or alkylating agent
(XI)
~ R8R1 5 l4 l2
1 ~ N - CH-C=CH-R3
in which formulae R2 to R8 have the meanings given for
formula I, R'l represents cyclohexyl or the group ~ ,
Z' represents -0-, -1- or -CH0-, the 7
lR6 R5 R6
-CH-group being bonded to the phenyl nucleus, and Y'
0 CH CH
t, 1 3 1 3
represents -0-, -1-, -C-, -CH2-, -CH-, -C-, -CH20-,
R5 CH3
-OCH2- or the direct bond.
As acylating reagent there is used for example acetic
acid-formic acid anhydride, acetic anhydride, or acetyl
chloride in the presence of a base, such as a tertiary
amine.
The reactions to the active substances of the formula
I are carried out at normal pressure and in solvents and
1055Sll
diluents which are inert towards the reactants, for
example in aromatic hydrocarbons such as benzene,
toluene, xylene; also in tetrahydrofuran, dioxan,
dialkyl ethers; N,N-dialkylated amides, such as dimethyl
formamide; in alcohols, such as methanol, ethanolJ propa-
nol, isopropanol, Gr butanols, sulphoxides, ketones, such
as acetone, methyl ethyl ketone, or cyclohexanone. The
reaction temperatures are in the range from O -140 C,but
are preferably in the range from 10 -70 C.
The starting materials of the formulae II, III, IV,
VI and VIII are known compounds. The compounds of the
formula VII for example can be manufactured by the process
disclosedin J.Org. Chem. 24,434 (1959). During the manu-
facture of the compounds of the formula I by processes
A, B and C, both possible geometrical isomers are formed
in varying ratios.
The described compounds partly constitute mixtures of
these cis- and trans-isomers such as occur during the
synthesis or after the purification.
Pure trans-isomers of the formula I can be obtained
e.g. by the use of pure 3-alkyl-(or 3,4-dialkyl-)4-halogeno-
2-trans-butenecarboxylic acid derivatives (J.A.C.S. ~0
6225 [1968]) in the synthesis of the active substances,
or by fractionated crystallisation, fractionated
distillation, gas or adsorption chromatographic methods
of separating cis/trans-isomer mixtures.
1055511
The compounds of the for~ula I can be uset for
combating animal and plant pests In particular they are
suitable for combating insects of the fa~ilies
Tettigonitae, Gryllidae, Gryllotalpidae, Blattidae,
Reduviidae, Pyrrhocoridae, Cimicidae, Delphacidae,
Aphididae, Diaspididae, Pseudococcidae, Scarabaeidae,
Der estidae, Coccinellidae, Tenebrionidae, Chrysomelidae,
Bruchidae, Tineidae, Noctuidae, Ly~antriidae, Pyralidae,
Culicidae, Tipulidae, Stomoxydae, Trypetidae, Muscidae,
Calliphoridae and Pulicidae
The insecticidal action can be substantanti-lly
broadened and adapted to suit the particular circumstances
by the addition of othor insecticides and/or acaricides as
~ell as insect baits Exa ples of suitable additives include
the follo~ing known additi~es
Organic phosphorus co pounds
Bis-O,O-diethylphosphoric acid anhydride
Di~ethyl-(2,2,2-trichloro-1-hydroxyethyl)-phosphonate
1,2-dibromo-2,2-dichloroethyldimethylphosphate
2,2-dichlorovinyldimethylphosphate
2-nethoxycarbamyl-1--ethylvinyldimethylphosphate
Cimethyl-l-methyl-2-(Rethylcarbamoyl)-vinylphosphate cis
3-tdimethoxyphosphinyloxy)-N,N-dimethyl-cis-crotonamide
2-chloro-2-diethylcarbamoyl-1-methylvinyldimethylphosphate
O,O-diethyl-Otor S)-2-(ethylthio)-ethylthiophosphate
S-ethylthioethyl-O,O-di~ethyl-dithiophosphate
O,O-diethyl-S-ethylmercaptomethyldithiophosphate
O,O-diethyl-S-2-(ethylthio)ethyldithiophosphate
_ g _
lOSSSll
0,0-tiaethyl-S-2-(ethylsulphinyl)ethylthiophosphate
0,0-timethyl-S-tl,2-ticarbethoxyethyltithiophosphate
0,0,0,0-tetraethyl-S,S'-methylene-bis-tithiophosphate
0-ethyl-S,S-dipropyldithiophosphate
0,0-dimethyl-S-(N-methyl-N-for ylcarbamoylmethyl)-dithiophos-
phate
0,0-tiaethyl-S-(N-methylcsrba~oylmethyl)-dithiophosphate
0,0-timethyl-0-p-nitrophenylthiophosphate
0,0-diethyl-0-p-nitrophenylthiophosphate
0-othyl-0-p-nitrophenylphenylthiophosphate -
0,0-dimethyl-0-(4-nitro-m-tolyl)-thiophosphate
0,0-dimethyl-0-2,4,5-trichlorophonylthiophosphate
0-ethyl-0-2,4,5-trichlorophonylethylthiophosphate
0,0-dimethyl-0-2,5-dichloro-4-bromophenylthiophosphate
0,0-dimethyl-0-(2,5-dichloro-4-iodophenyl)-thiophosphate
4-tert butyl-2-chlorophenyl-N-methyl-0- ethyla idophosphate
0,0-dimethyl-0-t3-mothyl-4-methylmercaptophenyl)-thiophosphate
_ 10 -
1055511
Isopropylamino-0-ethyl-0-(4-methylmercapto-3-methylphenyl)-
phosphate
0,0-diethyl-0-p-(methylsulphinyl)phenyl-thiophosphate
0-p-(dimethylsulphamido)-phenyl-0,0-dimethylthiophosphate
0,0,0',0'-tetramethyl-0,0'-thiodi-p-phenylenethiophosphate
0-ethyl-S-phenyl-ethyldithiophosphate
0,0-dimethyl-0-(-methylbenzyl-3-hydroxycrotonyl)phosphate
2-chloro-1-(2,4-dichlorophenyl)vinyl-diethylphosphate
l-chloro-1-(2,4,5-trichlorophenyl)~inyl-dimethylphosphate
0-[2-chloro-1-(2,5-dichlorophenyl)] ~inyl-0,0-diethylthio-
phosphate
Phenylglyoxylonitriloxime-0,0-diethylthiophosphate
0,0-diethyl-0-(3-chloro-4-methyl-2-oxo-2-H-l-benzopyran-7-yl)-
thiophosphate
2,3-p-dioxandithiol-S,S-bis(0,0-diethyldithiophosphate)
5-1(6-chloro-2-oxo-3-benzoxazolinyl)mothyl]0,0-diethyldithio-
phosphate
2-~diethoxyphosphinylimino)-1,3-dithiolane
0,0-dimethyl-S-[2-methoxy-1,3,4-thiadiazol-5-(4H)-onyl-(4)-
methyl]dithiophosphate
0,0-dimethyl-S-phthalimidomethyl-dithiophosphate
1055511
0,0-diethyl-0-(3,5,6-trichloro-2-pyridyl)thiophosphate
0,0-diethyl-0-2-pyrazinylthiophosphate
0,0-diethyl-0-(2-isopropyl-4-methyl-6-pyrimidyl)thiophosphate
0,0-diethyl-0-(2-quinoxalyl)thiophosphate
0,0-dimethyl-S-(4-oxo-1,2,3-benzotriazin-3~4H)-ylmethyl)-
dithiophosphate
0,0-diethyl-S-(4-oxo-1,2,3-benzotriazin-3t4H)-ylmethyl)-
dithiophosphate
S-[(4,6-diamino-s-triazin-2-yl)methyl]-0,0-dimethyldithio-
phosphate
0,0-dimethyl-0-(3-chloro-4-nitrophenyl)thiophosphate
0,0-dimethyl-O(or S)-2-(ethylthioethyl)thiophosphate
2-tO,0-dimethyl-phosphoryl-thiomethyl)-5-methoxy-pyrone-
4-3,4-dichlorobenzyl-triphenylphosphoniumchloride
0,0-diethyl-S-(2,5-dichlorophenylthiomethyl)dithiophosphate
0,0-diethyl-0-(4-methy~coumarinyl-7)-thiophosphate
5-amino-bis(dimethylamido)phosphinyl-3-phenyl-1,2,4-triazole
N-methyl-5-(0,0-dimethylthiolphosphoryl)-3-thiavaleramide
0,0-diethyl-0-[2-dimethylamino-4-methylpyrimidyl-(6)]-thio-
phosphate
- 12 -
1055511
0,0-dimethyl-S-(methylcarbamoylmethyl)-thiophosphate
0-ethyl-0-(8-quinolinyl)-phenylthiophosphonate
0-methyl-S-methyl-amidothiophosphate
0-methyl-0-(2,5-dichloro-4-bromophenyl)-benzothiophosphate
0,0,0,0-tetrapropyldithiophosphate
3-(dimethoxyphosphinyloxy)-N-methyl-N-methoxy-cis-crotonamide
0,0-dimethyl-S-(N-ethylcarbamoylmethyl)dithiophosphate
0,0-diethyl-S-(N-isopropylcarbamoylmethyl)-dithiophosphate
S-N-(l-cyano-l-methylethyl)carbamoylmethyldiethylthiolphosphate
S-(2-acetamidoethyl)-0,0-dimethyldithiophosphate
Hexamethylphosphoric acid triamide
0,0-dimethyl-0-(2-chloro-4-nitrophenyl)thiophosphate
0,0-dimethyl-0-p-cyanophenyl thiophosphate
0-ethyl-0-p-cyanophenylthiophosphonate
0,0-diethyl-0-2,4-dichlorophenylthiophosphate
0-2,4-dichlorophenyl-0-methylisopropylamidothiophosphate
0,0-diethyl-0-2,5-dichloro-4-bromophenylthiophosphate
dimethyl-p-(methylthio)phenylphosphate
0,0-dimethyl-0-p-sulphamidophenylthiophosphate
1055511
0-rp-(p-chlorophenyl)-azophenyl]0,0-dimethylthiophosphate
0-ethyl-S-4-chlorophenyl-ethyldithiophosphate
0-isobutyl-S-p-chlorophenyl-ethyldithiophosphate
0,0-dimethyl-S-p-chlorophenylthiophosphate
0,0-dimethyl-S-(p-chlorophenylthiomethyl)dithiophosphate
0,0-diethyl-p-chlorophenylmercaptomethyl-dithiophosphate
0,0-diethyl-S-p-chlorophenylthiomethyl-thiophosphate
0,0-dimethyl-S-tcarbethoxy-phenylmethyl)dithiophosphate
0~O-diethyl-S-~carbofluorethoxy-phenylmethyl)-di~hiophosphate
0,0-dimethyl-S-carboisopropoxy-phenylmethyl)-dithiophosphate
0,0-diethyl-7-hydroxy-3,4-tetramethylene-coumarinyl-thiophos-
phate
2-methoxy-4-H-1,3,2-benzodioxaphosphorin-2-sulphide
0,0-d,ethyl-0-(5-phenyl-3-isooxazolyl)thiophosphate
2-(diethoxyphosphinylimino)-4-methyl-1,3-dithiolane
tris-(2-methyl-1-aziridinyl)-phosphine oxide
S-(2-chloro-1-phthalimidoethyl)-0,0-diethyldithiophosphate
N-hydroxynaphthalimido-diethylphosphate
dimethyl-3,5,6-trichloro-2-pyridylphosphate
0,0-dimethyl-0-(3,5,6-trichloro-2-pyridyl~thiophosphate
S-2-(ethylsulphonyl)ethyl dimethylthiolphosphate
- 14 -
1055511
diethyl-S-2-tethylsulphinyl)ethyl dithiophosphate
bis-0,0-diethylthiophosphoric acid anhydride
dimethyl-1,3-di(carbomethoxy)-1-propen-2-yl-phosphate
dimethyl-(2,2,2-trichloro-1-butyroyloxyethyl)phosphate
0,0-dimethyl-0-(2,2-dichloro-1-methoxy-vinyl)phosphate
bis-(dimethylamido)fluorphosphate
3,4-dichlorobenzyl-triphenylphosphoniumchloride
dimethyl-N-methoxymethylcarba~oylmethyl-dithiophosphate
0,0-diethyl-0-(2,2-dichloro-1-chloroethoxyvinyl)-phosphate
0,0-dimethyl-0-(2,2-dichloro-1-chloroethoxy~inyl)-phosphate
0-ethyl-S,S-diphenyldithiolphosphate
0-ethyl-S-benzyl-phenyldithiophosphonate
0,0-diethyl-S-benzyl-thiolphosphate
0,0-dimethyl-S-(4-chlorophenylthiomethyl)dithiophosphate
0,0-dimethyl-S-(ethylthiomethyl)dithiophosphate
diisopropylaminofluorophosphate
0,0-dimethyl-S-(morpholinylcarbamoylmethyl)dithiophosphate
bismethylamido-phenylphosphate
0,0-dimethyl-S-(benzenesulphonly)dithiophosphate
0,0-dimethyl-(S and 0)-ethylsulphinylethylthiophosphate
1055511
0,0-diethyl-0-4-nitrophenylphosphate
triethoxy-isopropoxy-bis(thiophosphinyl)disulphide
2-methoxy-4H-1,3,2-benzodioxaphosphorin-2-oxide
octamethylpyrophosphoramide
bis-(dimethoxythiophosphinylsulphido)-phenylmethane
N,N,N',N'-tetramethyldiamidofluorophosphate
0-phenyl-0-p-nitrophenyl-methanethiophosphonate
0-methyl-0-(2-chloro-4-tert.butyl-phenyl)-N-methylamidothio-
phosphate
0-ethyl-0-(2,4-dichlorophenyl)-phenylthiophosphonate
0,0-diethyl-0-(4-methylmercapto-3,5-dimethylphenyl)-thiophos-
phate
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
0,0-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
- 16 -
105S511
2-1-methylheptyl)-4,6-dinitrophenyl-crotonate
2-sec.butyl-4,6-dinitrophenyl-3-methyl-butenoate
2-sec.butyl-4,6-dinitrophenyl-cyclopropionate
2-sec.butyl-4,6-dinitrophenylisopropylcarbonate
Miscellaneous
pyrethrin I
pyrethrin II
3-allyl-2-methyl-4-Dxo-2-cyclopentan-1-yl-chrysanthemulDate
6-chloropiperonyl-chrysanthemumate
2,4-dimethylbenzyl-chrysanthemumate
2,3,4,5-tetrahydrophthalimidomethylchrysanthemumate
4-chlorobenzyl-4-chlorophenylsulphide
6-methyl-2-oxo-1,3-dithiolo-[4,5-b]-quinoxaline
(I)-3-(2-furfuryl)-2-methyl-4-oxocyclopent-2-enyl(I)-(cis
trans)-chrysanthemum-monocarboxylate
2-pivaloyl-indane-1,3-dione
4-chlorobenzyl-4-fluorophenyl-sulphide
S,6-dichloro-1-phenoxycarbamyl-2-trifluoromethyl-benzimitazole
p-chlorophenyl-p-chlorobenzenesulphonate
p-chlorophenyl-benzenesulphonate
1055511
p-chlorophenyl-2,4,5-trichlorophenylsulphone
p-chlorophenyl-2,4,5-trichlorophenylsulphide
p-chlorobenzyl-p-chlorophenylsulphide
2-thio-1,3-dithiolo-(5,6)-quinoxaline
prop-2-ynyl-(4-t-butylphenoxy)-cyclohexylsulphite
Formamidines
l-dimethyl-2-(2'-methyl-4'-chlorophenyl)-formamidine
l-methyl-2-(2'-methyl-4'-chlorophenyl)-formamidine
l-methyl-2-(2'-methyl-4'-bromophenyl)-formamidine
1-methyl-2-(2',4'-dimethylphenyl)-formamidine
l-n-butyl-l-methyl-2-(2'-methyl-4'-chlorophenyl)-formamidine
l-methyl-1-(2'-methyl-4'-chloroaniline-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'JN'-dimethyl-thiourea.
Carbamates
l-naphthyl-N-methylcarbamate
2-butinyl-4-chlorophenylcarbamate
4-dimethylamino-3,5-xylyl-N-methylcarbamate
4-dimethylamino-3-tolyl-N-methylcarbamate
4-methylthio-3,5-xylyl-N-methylcarbamate
3,4,5-trimethylphenyl-N-methylcarbamate
2-chlorophenyl-N-methylcarbamate
105551~
5-chloro-6-oxo-2-norborane-carbonitrile-0-(methylcarbamoyl)-
oxime
l-(dimethylcarbamoyl-5-methyl-3-pyrazolyl-N,N-dimethylcarba-
mate
2,3-dihydro-2,2-dimethyl-7-benzofuranyl-N-methylcarbamate
2-methyl-2-methylthio-propionaldehyde-0-(methylcarbamoyl)-
oxime
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
m-(l-methylbutyl)phenyl-N-methylcarbamate
2-isopropylphenyl-N-methylcarbamate
2-sec.butylphenyl-N-methylcarbamate
m-tolyl-N-methylcarbamate
2,3-xylyl-N-methylcarbamate
3-isopropylphenyl-N-methylcarbamate
3-tert.butylphenyl-N-methylcarbamate
3-sec.butylphenyl-N-methylcarbamate
3-isopropyl-5-methylphenyl-N-methylcarbamate
3,5-diisopropylphenyl-N-methylcarbamate
2-chloro-5-isopropylphenyl-N-methylcarbamate
2-chloro-4,5-dimethylphenyl-N-methylcarbamate
2-(1,3-dioxolan-2-yl)phenyl-N-methylcarbamate
- 19 -
1055511
2-(4,5-dimethyl-1,3-dioxolan-2-yl)-phenyl-N-methylcarbamate
2-(1,3-dioxolan-2-yl)phenyl-N,N-dimethylcarbamate
2-(1,3-dithiolan-2-yl)-N,N-dimethylcarbamate
2-(1,3-dithiolan-2-yl)phenyl-N,N-dimethylcarbamate
2-isopropoxyphenyl-N-methylcarbamate
2-(2-propinyloxy)phenyl-N-methylcarbamate
3-(2-propinyloxy)phenyl-N-methylcarbamate
2-dimethylaminophenyl-N-methylcarbamate
2-diallylaminophenyl-N-methylcarbamate
4-diallylamino-3,5-xylyl-N-methylcarbamate
4-benzothienyl-N-methylcarbamate
2,3-dihydro-2-methyl-7-benzofuranyl-N-methylcarbamate
3-methyl-1-phenylpyrazol-5-yl-N,N-dimethylcarbamate
l-isopropyl-3-methylpyrazol-5-yl-N,N-dimethylcarbamate
2-dimethylamino-5,6-dimethylpyrimidin-4-yl-N,N-dimethyl-
carbamate
3-methyl-4-dimethylaminomethyleneiminophenyl-N-methyl-
carbamate
3,4-dimethylphenyl-N-methylcarbamate
2-cyclopentylphenyl-N-methylcarbamate
3-dimethylamino methyleneiminophenyl-N-methylcarbamate
and its salts
l-methylthio-ethylimino-N-methylcarbamate
2-methylcarbamoyloximino-1,3-dithiolane
5-methyl-2-methylcarbamoyloximino-1,3-oxythiolane
- 20 -
1055Sll
2~ methoxy-2-propoxy)phenyl-N-methylcarbamate
2-(1-butin-3-yl-oxy)phenyl-N-methylcarbamate
l-dimet:hylcarbamyl-l-methyltllio-O-methylcarbamyl-formoxime
1-(2'-cyanoethylthio)-0-methylcarbamyl-acetaldoxime
l-methylthio-0-carbamyl-acetaldoxime
0-(3-sec.butylphenyl)-N-phenylthio-N-methylcarbamate
2,5-dimethyl-1,3-dithiolane-2-(0-methylcarbamyl)-aldoxime)
0-2-diphenyl-N-methylcarbamate
2-(N-methylcarbamyl-oximino)-3-cllloro-bicyclo[2.2.1]heptane
2-(N-methylcarbamyl-oximino)-bicyclo[2,2,1]heptane
3-isopropylphenyl-N-methyl-N-chloroacetal-carbamate
3-isopropylphenyl-N-methyl-N-methylthiomethyl-carbamate
0-(2j2-dimethyl-4-chloro-2,3-dihydro-7-benzo~uranyl)-N-methyl
carbamate
0-(2,2,4-trimethyl-2,3-dihydro-7-benzofuranyl)-N-methylcarba-
mate
0-naphthyl-N-methyl-N-acetal-carbamate
0-5,6,7,8-tetrahydronaphthyl-N-methyl-carbamate
3-isopropyl-4-methylthio-phenyl-N-methylcarbamate
3,5-dimethyl-4-methoxy-phenyl-N-methylcarbamate
3-methoxymethoxy-phenyl-N-methylcarbamate
3-allyloxyphenyl-N-methylcarbamate
2-propargyloxymethoxy-phenyl-N-methyl-carbamate
2-allyloxyphenyl-N-methyl-carbamate
4-methoxycarbonylamino-3-isopropylphenyl-N-methyl-carbamate
- 21 -
, . .. . , , . , ~ .. , . .. . . ... . ~ . .... . . . . . . . . . . . .. . . ..
1055511
3,5-dimethyl-4-metho~ycarbonylamino-phenyl-N-methyl-carbamate
2-y-methylthiopropylphenyl-~-methyl-carbamate
3-(a-methoxymethyl-2-propenyl)-phenyl-N-methyl-carbamate
2-chloro-5-tert.-butyl-phenyl-N-methyl-carbamate
4-(methyl-propargylamino-3,5-xylyl-N-methyl-carbamate
4-(methyl-y-chloroallylamino)-3,5-xylyl-N-methyl-carbamate
4-(methyl-~-chloroallylamino)-3,5-xylyl-N-methyl-carbamate
l-(~-ethoxycarbonylethyl)-3-methyl-5-pyrazolyl-N,N-dimethyl-
carbamate
3- methyl-4-(dimethylamino-methylmercapto-methyleneimino)-
phenyl-N-methyl-carbamate
1,3-bis(carbamoylthio)-2-(N,N-dimethylamino)-propanehydro-
chloride
5,5-dimethylhydroresorcinoldimethylcarbamate
2-[ethyl-propargylamino]-phenyl-N-methylcarbamate
2-[methyl-propargylamino]-phenyl-N-methylcarbamate
4-[dipropargylamino]-3-tolyl-N-methylcarbamate
4-ldipropaL-gylamino]-3~5-xylyl-N-methylcarbamate
2-~allyl-isopropylamino~-phenyl-N-methylcarbamate
3-[allyl-isopropylamino]-phenyl-N-methylcarbamate
Chlorinated Hydrocarbons
B y-hexachlorocyclohexane [G~ AI~j LIND~Nj y HCIl]
1,2,4,5,6,7,8,8-octachloro-3a,4,7,7a -tetrahydro-4,7-
methylene indanc [CMLO~D~N]
1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-
- 22 -
1055511
methylene indane
1,2,3,4,10,10-hexachloro-1,4,4,5,8,8-hexahydro-endo-1,4-
exo-5,8-dimethanonaphthalene
1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a,5,6,7,8,8-octa-
hydro-exo-1,4-endo-5,8-dimethanonaphthalene
1,2,3,4,10,10-hexachloro-5,7-epoxy-1,4,4a,5,6,7,8,S-octa-
hydro-endo-endo-5,8-dimethanonaphthalene
The compounds of the formula I may be used as pure
active substance or together with suitable carriers and/or
additives. Suitable carriers and additives can be solid or
liquid and correspond to the substances conventionally used
1055511
in foL~nula~ion tecllnique such, for example, as solvents,
dispersants, wetting agents, adhesives, thickeners, binders
and/or fertilisers.
For application, the compounds of the formula I may
be processed to dusts, emulsion concentrates, granules, dis-
persions, sprays, to solutions, or suspensions, in the con-
ventional formulation which is commonly employed in appli-
cation technology. Mention may also be made of cattle dips
and spray races, in which aqueous preparations are used.
The agents according to the invention are manufac-
tured in kno~7n manner by intimately mixing and/or grinding
active substances of the formula I with the suitable carriers,
optionally with the addition of dispersants or solvents
which are inert towards the active substances. The active
substances may take, and be used in, the following forms:
Solid forms:
Dusts, tracking agents, granules, coated granules,
impregnated granules and homogeneous granules.
Liquid forms:
a) active substances which are dispersible in water:
wettable po~7ders, pasts, emulsions;
b) solutions.
To manufacture solid forms (dusts, tracking agents),
the active substances are mixed with solid carriers. Suit-
able carriers are, for example: kaolin, talcum, bolus, loess,
- 24 -
.... . . .. . . ..
105551~
chalk, limestone, ground limesi~one, attaclay, dolomite,
diatomaceous ear~h, precipitated silica, alkaline earth
silicates, sodium and potassium alumini.um silicates (feld-
spar and mica), calcium ~d magnesium sulphates, magnesium
S oxide, ground synthetic materials, fer~ilisers, for example
ammonium sulphate, ammonium phosphate, ammonium nitrate,
urea, ground vegetable products, such as corn meal, bark
dust, sawdust, nutshell meal, cellulose powder, resi.dues o~
plant extractions, activated charcoal etc. These substances
can either be used singly or in admixture with one another.
Granules can be very easily manufac~ured by dissol-
ving an active substance of the formula I in an organic
solvent and applying the resulting solu~ion to a granulated
material~ for example attapulgite, SI02, granicalcium,
bentonite etc.and then evaporating the solvent.
Polymer granu].es can also be manufactured by mixing
the active substances of the formula I with polymerisable
compounds (urea/formaldehyde; dicyandiamide/formaldehyde;
melamine/formaldehyde or others), whereupon a mild polymeri-
sation is carried out that does not affect the activesubstances and in the process of which the granulation is
carried out during the gel formation. It is more advantageous
to impregnate finished, porous polymer granules (urea/
formaldehyde, polyacrylonitrile, polyester or others) which
have a specific surface area and a favourable predeterminable
- 25 -
1055511
adsorption/desorp~ion ratio, with ~he active substances, for
example in the form of t.heir solu~ions (in a low boiling
solvent) and to remove the solvent. Polymer granules of this
kind in tlle form of microgranules having a bulk density o~
300 g/liter to 600 g/liter can also be manufactured with the
ai~ of atomisers. The dusting can bc carried out from aircraft
over extensive areas of cultures of useful plants.
It is also possible to obtain granules by compacting
the carrier witl the active substance and carriers and subse-
quently comminuting the product.
To these mixtures can also be added additives which
stabilise the active substance and/or non-ionic, anionic and
cationic. surface active substances, which, for example,
improve the adhesion of the active ingredients on plants or
parts of plants (adhesives and agglutinants) and/or ensure a
better wcttability (wetting agents) and dispersibility
(dispersil~ agents). Examples of suitable adhesives are the
following: olei.n/chalk mixture, cellulose derivatives (methyl
cellulose, carboxymethyl cellulose), hydroxyethyl glycol
. ethers of monoalkyl and dialkyl phenols having 5 to 15
ethylene oxide radicals per molecule and 8 to 9 carbon atoms
in the alkyl radical, lignin sulphonic acids, their alkali
metal and alkaline earth metal salts, polyethylene glycol
ethers (carbowaxes), fatty alcohol polyethylene glycol ethers
having 5 to 20 ethylene oxide radicals per molecule and 8 to
- 26 -
.. . . . . . . .. .
1055Sll
18 carbon atoms in the fatty alcohol moie~y, condensation
products of ethylene oxide/propylene oxide, polyvinyl pyrro-
lidones, pol~7inyl alcohols, condensation products of urea
and formaldehyde, and also latex products.
The water dispersible concentrates of the active
substance, i,e wettable powders, pastes and emulsi~iable
concentrates, are agents which can be diluted with water to
any concentration desired. They consist of active substance,
carrier, optionally additives which stabilise the active
substance, surface-active substance and anti-foam agents
and, optionally,solvents.
Wetta~le powders and pastes are obtained by mixing
and grind ng the active substances with dispersing agen~s and
pulverulent carriers in suitable apparatus until homogeneity
is attained. Suitable carriers are, for example, those men-
tioned for tlle solid forms of application. In son-e cases it
is advantageous to use mixtures of different carriers. As
dispersing agents there can be used, for cxample, condensa~ion
products of sulphonated naphthalene and sulphonated naphtha-
lene derivatives with formaldehyde, condensation products of
naphthalene or naphthalene sulphonic acids with phenol and
formaldehyde, as well as alkali, ammonium and alkaline earth
metal salts of lignin sulphonic acid, in addition, alkylaryl
sulphonates, alkali and alkaline earth metal salts of dibutyl
naphthalene sulphonic acid, fatty alcohol sulphates such as
1055511
salts of su]phated hexadecanols, hep,adecanols, octadecanols,
and salts of sulphated fat~y alcohol glycol ethers, the
sodium salt of oleoyl et~lionate, the sodium salts of olcoyl
methyl tauride, ditertiary acetylene glycols, dialkyl di-
lauryl ammonium chloride and fatty acid alkali and alkalineearth metal salts.
Suitable anti-foam agents are silicones.
The active substances are mixed, ground, sieved and
strained ~ith the additives cited hereinabove, in such a
manner that, the siæe of the solid particles does not exceed
0 02 to 0 04~ in wettable po~ders, and 0 03~l in pastes
To produce emulsifiable concentrates and past~s, dispersing
agents such as those cited above, organic solvents5 and water
are used. Examples of suitable solvents are: alcohols, benzene,
xylene, toluene, dimethyl sulphoxide, and mineral oil fractions
which boil between 120 and 350C~ The solvents must be
practically odourless, not phytotoxic, and inert to the active
substances.
Furthermore, the agents according to the invention
can be applied in the form of solutions. For this purpose
the active substances, or several active substances of the
general formula I, are dissolved in suitable organic solvents,
mixtures of solvents or in water. Aliphatic and aromatic hy-
drocarbons, chlorinated derivatives thereof, alkyl naphthalene~
and mineral oils, singly or in admixture with each other, can
.
- 28 -
~ 055511
be used as organic solvents.
The content of active substance in the above des-
cribed agents is bet~een 0.1% to 95%, in which connection it
should be mentioned that, in the case of application from
aircraft or some other suitable means of application, it is
possible to use concentrations of up to 99.5% or even pure
active subst.ance.
The active substances of the formula I can, for
example, be formulated as follows:
Dusts
The following substances are used to manufacture a)
a 5% and b) a 2% dust:
a) 5 parts of active substance
95 parts of talcum
b) 2 parts of active substance
1 part of highly disperse silicic acid
97 parts of talcum.
The active suhstances are mixed with the carriers
and ground.
Gral~ules
The following substances are used to produce 5%
granules: -
5 parts of active substance,
0.25 parts of epichlorohydrin,
0.25 parts of cetyl poly~lycol ether,
- 29 _
.. . . .. .. . . . . . .. . ... . . . ... . . .. ..... . . ..
105551~
~.50 parts of polyethylene glycol,
91 parts of kaolin (particle size 0.3 - 0.8 mm).
The active substance is mixed with epichlorohydrin
and dissolved with 6 parts of acetone; the polyethylene
glycol and cetyl polyglycol ether are ~hen added. The thus
obtained solution is sprayed on kaolin, and the acetone
subsequently evaporated in vacuo.
Wettable powder:
The following constituents are used for the pre-
paration of a) a 40%, b) and c) a 25%, and d) a 10% wettable
powder:
a)40 parts of active substance,
5 parts of sodium lignin sulphonate,
1 part of sodium dibutyl-naphthalene sulphonate,
15 54 parts of silicic acid.
b)25 parts of active substance,
4.5 parts of calcium lignin sulphonat~,
1.9 parts of Champagne chalk/hydroxyethyl cellulose
mixture (1:1),
1.5 parts of sodium dibutyl naphthalene sulphonate,
19.5 parts of silicic acid,
19.5 parts o~ Champagne chalk,
28,1 parts of kaolin.
c)25 parts of active substance,
2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, I
- 30 -
..... .. . . .. . . . . .. . . ... . .. . . .. .. .. ... . .. . . ., .. . , . . .. . . ~ .. . .. . . . .. .. . . . . . .. . .. . .
.. . . .. . . .... . ~ ... . . . . .
1055511
1.7 parts of Champagne chalk/hydro~yethyl cellulose
mixture (1:1),
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 fatty alcohol sulphates,
5 parts of naphthalenesulphonic acid/fonnaldehyde
condensate,
82 parts of kaolin.
The active substances are intimately mixed~ in suit-
able 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 concentration.
Emulsifi.able concentrates:
The following substances are used to produce a) a
10% and b) a 25% emulsifiable concentrate:
a)10 parts of active substance,
3 4 parts of epoxidised vegetable oil,
13.4 parts of a combination emulsifier consisting
of fatty alcohol polyglycol ether and alkyl-
arylsulphonate calcium salt,
40 parts of dimethylformamide,
105~511
43.2 parts of xylene.
b) 25 parts of active substance,
2.5 parts of epoxidised vegetable oil,
10 parts of an alkylarylsu].phonate/fatty alcohol-
polyglycol ether mixture,
5 parts of dimethylformamide,
57.5 par,s of xylene.
From these concentrates it is possible to produce,
by dilution with water, emulsions of any desired concentra-
tion.
Spray:
The following constituents are used to prepare a
5~/0 spray:
parts of acti.ve substance,
1 part of epichlorohydrin,
94 parts of benzine ~boiling limits 160 - 190C).
- 32 -
lOSSSll
The following Examples will serve to illustrate the
manufacture of the compounds of the formula I.
Example 1
To a solution of 19.8 g of 4-hydroxy-diphenyl ether
in 80 ml of acetone were added 16.5 g of anhydrous pul-
verised potassium carbonate and then, while stirring,
20.8 g of 3-methyl-4-bromo-2-butenoic acid ethyl ester
(mixture of 80% trans- and 20% of cis-compound) ~ere
added dropwise within one hour at the boiling temperature
of the mixture. Stirring was continued for 8 hours at
reflux temperature after addition of the bromide. The
reaction mixture was processed by filte~ ng of the acetone
solution from the precipitate with suction, washing the
residue with acetone, and removing the acetone in vacuo.
The residue was taken up in 20 ml of ether/hexane (1:5) and
this solution was washed firstly 4 times with 50 ml of 5%
ice-cold, aqueous potassium hydroxide solution, and
subsequently 4 times with water. The organic phase was
dried over sodium sulphate and the solvent and readily
volatile constituents were completely removed in vacuo,
to leave as residue pure 4-[4-(phenoxy)-phenoxy]-3-methyl-
2-butenoic acid ethyl ester (cis/trans). nD20 = 1.5598.
Example 2
To a solùtion of 18.6 g of 4-amino-diphenyl ether in
100 ml of 1,2-dimethoxy ethane were added 15.6 g ofethyl
diisopropylamine and then, while stirring, a solution of
19.3 g of 3-methyl-4-bromo-2-trans-butenoic acid methyl
lOS5511
ester in ~0 ml of 1,2-dimethoxy ethane was added at room
temperature within 8 hours. Stirring was then continued
for 20 hours at room temperature. The reaction mixture was
processed by filtering of precipitated ethyl diisopropyl-
ammonium bromide, washing with ether and freeing the
filtrate from solvent in vacuo. The resulting crude product
was further purified by chromatography on silica gel (eluant:
ether/hexane 1:2) to yield pure 4-[4-(phenoxy)-anilino]-3-
methyl-2-trans-butenoic acid methyl ester. n~20 = 1.5891.
Example 3
While stirring, a solution of 6 g of 4-[4-(phenoxy)-
anilino~-3-methyl-2-trans-butenoic acid methyl ester in
5 ml of anhydrous formic acid was added dropwise at 0C
and within about 30 minutes to 12 ml of a mixture of 102
parts of acetic anhydride and 92 parts of anhydrous
formic acid (which mixture had been heated for 1 hour
to 45 C before the formation of the mixed acetic acid/
formic acid anhydride)0 The reaction mixture was sub-
sequently kept at 0 to 5C for 6 hours and at 30C for
a further 24 hours. The reaction mixture was then treated
with 50 ml of water while gently cooling with ice and
stirred for 1 hour at 10-15C. The reaction mixture was
then repeatedly extracted with ether and the combined
ether phases were washed neutral first with saturated
sodium hydrogen carbonate solution and subsequently
with water. After ethereal solution had been dried over
sodium sulphate and the solvent completely removed in
vacuo/ the residual 4-[4-(phenoxy)-N-formylanilinoj-
3-methyl-2-trans-butenoi^ acid methyl ester was further
' _ 34 _
1055511
purified by chromatography on silica gel. Melting point:
93 -95 C.
Example 4
~ g of about 50% sodium hydride in mineral oil was
washed repeatedly with hexane and put into a sulphurating
flask in ~0 ml of absolute tetrahydrofuran. While stirring,
16.6 g Or diethylphosphonoacetic acid diethylamide in 20 ml
of absolute tetrahydrofuran were added dropwise at 0 -5C
within about 45 minutes. The mixture was heated to room
temperature and stirring continued for 30 minutes. It was
then cooled again to 5C and, while stirring, a solution
of 14.4 g of 1-[4-(benzyl)phenoxy]-propan-2-one in 40 ml
Or absolute tetrahydrofuran was added dropwise within 1 hour.
After 2 hours the reaction mixture was heated to 30C and
kept for 2 hours at this temperature. The reaction mixture
was processed by distilling off the bulk of the tetrahydro-
furan in vacuo, partitioning the residue between water and
diethyl ether, and repeatedly washing the aqueous phase
with ether. The combined ethereal phases were dried over
sodium sulphate and the solvent was distilled off. The
residue was further purified on silica gel by chromato-
graphy (eluant: methyl acetate/diethyl ether/hexane 1:4:2)
to yield pure 4-[4-(benzyl)-phenoxy]-3-methyl-2-cis/trans-
butenoic acid diethyl amide. n~20 = 1.5596.
In the same way, e.g. by reacting 1-[4-(benzyl)-phenoxy]-
propan-2-one with diethylphosphonoacetic acid isopropyl ester
and subsequent chromatography on silica gel, 4-[4-benzyl)-
phenoxy]-3-methyl-2-trans-butenoic acid isopropyl ester
(n~20 = 1.5512) and 4-L4-(benzyl)-phenoxy]-3-methyl-2-cis-
- 35 -
.
10555~1
butenoic acid isopropyl ester (n~20 = 1.5451) were obtained.
The 1-[4-(benzyl)-phenoxy]-propan-2-one used as
starting product was manufactured as follows:
While stirring, a previously prepared mixture of 22.3 g
of mercury oxide, o.8 g of trichloroacetic, 8 ml of boron
trifluoride diethyl etherate and 20 ml of absolute methanol
was added all at once to a solution, cooled ~ -5C, of
11.1 g of 4-benzylpropargyloxybenzene (n~20 = 1.5807) in
400 ml of absolute methanol. After about 10 minutes the
external cooling was reduced so that the temperature Gf the
reaction mixture (exothermic reaction) was slowly able to
rise to a maximum of 45C . The external cooling was again
intensified at this temperature and the reaction mixture
kept for a further 3 hours at about 20-25C. During the
course of the reaction the colour of the mixture turned
from orange to pale grey. The diethyl ketal formed was
isolated by pouring the contents of the flask, cooled to
about 0C, on the mixture of 125 ml of 2 normal sodium
carbonate solution and 500 g of ice. After stirring for about
10 minutes the whole mixture was acidified with 750 ml of
2 normal phosphoric acid and treated with 700 ml of diethyl
ether. The batch was filtered through a layer of diatomaceous
earth, the ether phase isolated, and the aqueous phase extrac-
ted 3 times with diethyl ether. The combined ethereal phases
were washed with 200 ml of 5% ice-cold potassium hydroxide
solution and 3 times with 300 ml of saturated sodium
chloride solution. The organic phase was dried over sodium
sulphate and the solvent then completely distilled off. The
resulting 1-[4-(benzyl)phenoxy]-propan-2-on-dimethyl ketal
- 36 -
1055511
was immediately dissolved in a mixture of 600 ml of
acetone, 100 ml Or water, and 35 ml of normal hydro-
chloric acid and hydrolysed to the ketone by being left
to stand for 5 hours at room temperature. The ketone was
isolated by pouring the reaction mixture into 600 ml of
saturated sodium chloride solution~ isolating the oragnic
phase, and washing the aqueous phase 3 times with diethyl
ether. The combined organic phases were washed finally
3 times with saturated sodium chloride solution, dried over
sodium sulphate, and the solvent was completely removed in
vacuo. The crude ketone, which congeals at once in
crystalline form, was recrystallised from isopropanol to
yield pure 1-[4-(benzyl)-phenoxy]-propan-2-one which rnelts
at 51-52C.
In wholly analogous manner it is possible to manufacture
from 4-propargyloxy-diphenyl ether (n~20 = 1.5825), 4-pro-
pargyloxybenzophenone (m.p. 72-73C) and 2-[4-(phenoxy)-
phenoxy]-3-butine (m.p. 53-54C) the following ketones
which are used as intermediates: l-[4-(phenoxy)-phenoxy]-
propan-2-one (m.p. 47 -48 C), 1-[4-(benzoyl)-phenoxy]-
propan-2-one (m.p. 51-52 C), and 2-[4-(phenoxy)-phenoxy]-
butan-3-one (m.p. 36-37C).
The following compounds are also manufactured in
analogous manner as described in Example 1 to 4:
~ 37 -
.. . .. . . . ...
1055511
H?-~--CJi~OOCH3 m.p.~ 55-56C
¢1~LO-CII--C--CII--COOC H m. p . : ~, 6-48C
C1~3
3-o~H2--C=CH{~OGC21i5 nD : lS5560
C~3
80% trans + ~20% cis
213_ ' ' '' '
0-CH2--C=CII--COCC2H5 m . p .: 74-76C
o
~3 ~L~C~J2 cl=c~ COOCH3 m.p. 105-107C
CH3
~1_0-CH2--C-Ci;--COuCH~; m-. p-.: GS-6'7C
- C~J3 .
- 38 -
.. . . . . .. . . .... .
1055Sll
CIIO
3 C~2 C .C~s COOCII3 m.p.~101 102C
CII3
ClJ~lT~--C~2--f--C~ ~OOCH3 nD : 1, 5~155
C}I3
1'. CH--f~CI~--COOCH m. p.: 6~3-69~C
C~I3
2 Cl=~ COOCH3 nD20 : 1,588
CH3
O
3 ~¢L~I--C~2--C=C~I--COOCH3 m p 100-1020C
~ 3
O
~C~ C!IO . .
W ~ 2 Cl =C~ COOC~3 m . p .: 110--112 C
CH~
~ 39 ~
1055511
~ 13 O~I2 f--C~-COOC~I3 nD20 : 1,5553
c~3
3 ~ H ~, I C~ COOCH3 nD20 1,5621
CII~
~CH2--9---c~- OOC3H7 ( i) n20 : 1, 5470
CH3
~_ ~9 cis~isomere 20
~O-CH2 1 .- CH~00C3~7 ( i ) nl~ : 1, 5522
CH3
trans- isomere
~Lo CHz~-lC-C~ COOClI2--C'l=CI'2 nD20 1 1,5571
0~?--C - CH--COOCH2 C -CH nl~20 : 1, 5640
(~113
L~CH2--f CH-CON(C~iI )2 n~20 : 1,5610
C~3
- 40 -
1055511
CH2 ~ 0C~2-C-C~-C_N nD = 1,5732
CH3
Cl ~ ~ OCH2-Cl=CH-CooC2H5 m~.p.~ 45 - 47C
CH3
Cl ~ ~ OCH2-CI=Cl~-cOOc3H7(i) m.p.: 49 - 50C
CH3
OCH2-C=CH-C-N\__~0m.p.: 69 - 70C
CH3
CH2 ~ OCH2-C=C~ N\__/0m.p.: ~0 - 81C
c~3
Cl ~ OCH2-CI--cl~-cooc3H7(i) m.p.: 85 - 87C
CH3
- 41 -
1055511
C2H5JJ W OCH2--C-CH--COOC3I-37(i) nD = 1,5~6
CH3
~ ¢L m.p. s ].17 - 119C
OCH2--C-C~ COOH
CH3
~io--CH2--C=C~I-C 10CH3 nD = 1, 538~3
CH3
~OC~I2--C--C~--COOC~3 nD - 1, 5294
C~I3
~-OCH2--Cl--CH--C-N m.p. :- 59 - 62 C
CH3
¢l13~0CH2--Cl-CH O N(C2H5)2 nD -- 1,5328
~H3
2 --
105551~
[~C~I2 ¢LO-CH2--C--CH--C-N m.p. ]02 - 104C
CH3
2~ m . p . ' 64 - 66C
OCH2--Cl-CH--C N (C2H5 ) 2
C~I3
Lo CH2--C=C~ C~ nD = :1, 5732
2 ¢L n20 .- ] ,5815
O-CH2--C=CH--C--N ~0
C~
C 1~ oJ3 13 o C~2 C=5~COOC2H5 m.p.: 63 - 65 C
CH3
~~ m.p. :~ 56 - 57C
C2H50~ ~0-CH2--Cl-CH--COOC3H7 ( i )
-43 -
105551~
~'}13 CH l=CH COOC2I~5 m.p. 45 - 47C
C2H5
LOCX~,--C=CH-COOC2~15 n20 = 1,542B
CH3
[3~ ¢LO_CH2--C=C~I--COOC2~15 nD = 1, 5623
~Lo CH2--CH=CH--COOC2H5
~3 O~CH2 CH=CH COOCH3 m.p.: 6~ - 66C
~¢Lo CH2 CH=CH--COOC3H7(i) m-p- 73 - 75 C
- 44 -
10555~1
CH
~1 ~0-CH2--C=CII--COOC2H
CH3
¢L0-CH2--C=CII--COOC4Hg (sek ) nD 1, 5480
C~I3
~(~¢LO-CH2--C=C~--COO~ nD = 1, 55~3
CH3
L9~:~C=CI~ COOC2H5 C = 1,5535
CH3
-CII C--~CH2--CH=CH2 m-p~ 8G - 87 C
~ ¢LCI~2-C=C~I-C I~C2~5 m.p. 95 - 96 C
. CH3
~ 45 -
105551~
[~0 CH2~C=CH--C--N(C2H ) m.p.- 78 - 80C
~1~CH2--C--CH--Coo~3
1 3 ~ ¢ L ~CH2--C-CH--C~T ~ >
B ~ ~)Cu ,, C~2 Cl=CH--COOC2H5
- CH3
~oc~2l3-
~CH2--C=CH--C OOC 2H5
CH3
¢~LO-CH2--C=CH--COO--CH2--CH=CH--Cl
CH3
- 46 -
. ~. .
1055511
0-CH?-C=CII-C0-NH- C3Hr7 ( i )
CH3
0-CH2-~=CH- COOC3H7 ( i )
C~I3
~CH3
? Cl=C~I--COOC2~i5
CH3
Example 5
A) ToPical action on ~ysdercus fasciatus larvae
10 ~ysdercus fasciatus larvae were treated topically
with solutions of active substance in acetone 8-10 days
before they were due to shed and emerge to the adult stage.
The larvae were then kept at 28C and 80-90% relative
humidity. They were fed with meal made from premoistened
cotton seeds. After about 10 days, i.e. as soon as the
untreated larvae had shed, the test subjects were examined
for the number of normal adults.
B) Contact action on D~sdercus fasciatus larvae
A specific amount of a 0.1% solution of active
substance in acetone (corresponding to 10 mg/of active
substance/m2) was pipetted into an aluminium dish and evenly
distributed.
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1055511
After the acetone had evaporated, 10 larvae of the
5th. stage of ~ysdercus fasciatus were put into the treated
dish which contained feed and moist cotton wool. The dish
was then covered with a sieve cover. After about 10 days,
i.e. as soon as the control larvae had shed and emerged
to the adult stage, the test subjects were examined for the
number of normal larvae. In the above tests A and B the
compounds according to Examples 1 to 4 displayed good action.
Example 6
-
Topical action on Dermestes iardarius pu~ae
10 fresh pupae of ~ermestes lardarius were treated
topically with solutions of active substance in acetone.
The pupae were then kept at 28C and 80-go~ relative
humidity. After about 10 days, i.e. as soon as the controls
had left their cocoons as Imagines, the test subjects were
examined ror the number of normal adults. In the above test
the compounds according to Examples 1 to 4 displayed good
action.
Example 7
Contact action on Aëdes ae~pti larvae
About 20 two day old larvae of the yellow fly
(Aëdes aegypti) were put into a beaker containing a
solution of the active substance (concentration 5ppm).
The beaker was then covered with a sieve cover. After
the controls had shed and emerged to the adult stage,
the test subjects were examined and the percentage number
- 48 -
1055511
of normal adults ascertained in comparison to the control.
In the above test the compounds according to Examples
1 to 4 displayed good action.
Example 8
.
Contact action on Tenebrio molitor pupae
A specific amount of a solution of active substance
in acetone (corresponding to 10 mg of active substance/m )
was pipetted into an aluminium dish and evenly distributed.
After the acetone had evaporated, 10 freshly shed pupae
were laid on the treated sur~ace. The dish was covered
with a sieve cover.
After the controls had left their cocoons as Imagines
the test subjects were examined for the number of normal
adults.
In the above test the compounds according to Examples
1 to 4 displayed good action.
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