Note: Descriptions are shown in the official language in which they were submitted.
~4~
The invention relates to derivatives of 4-alkoxydiphenyl
ethers or 4-alkoxymetllyldiphenyl ethers, or of l-cyclohexyl-
oxy-4-alkoxybenzenes or 1-cyclohexyloxy-4-alkoxymethyl-
benzenes, unsubstituted or substituted in the phenyl rings, to
their production, and to their use for the control of
the development of insects and members of the order
acarina.
The compounds correspond to the formula
. . ", .:
L ~ 1
wherein
Rl represents hydrogen, halogen, Cl-C4-alkyl, vinyl or ~ :
ethynyl,:
R2 represents hydrogen, halogen, methyl or ethyl, or
Rl and R2 together represent the cyclopentyl or cyclo-
~5 hexyl ring,
R3 ~ represents hydrogen, halogen, methyl, ethyl or ~
Cl-C4-alkoxy, , . ; .
.
R4 ~represents hydrogen, halogen or methyl,
R5 represents hydrogen or halogen, or
,; .
R3 and R5 together represent a carbon-carbon-bond, .
or an oxygen bridge,
R6 represents hydrogen, methyl or ethyl,
R7 represents cyclohexyl or the group ~ 8 , :
,~ . . .
:
. .
:
Sl~
R8 represents hydrogen, halogen, Cl-C4-alkyl or
cl-c4-alkoXY~ z z
y represents oxygen or the group -CHO-, whereby the CH-
group is bound to the phenyl ring,
S Z represents hydrogen or methyl, and
m and n each represent the number O or 1.
By halogen are meant fluorine, chlorine, bromine or
iodine, particularly, however, chlorine.
The alkyl and alkoxy groups in the case of Rl~ R3 and
R7 can be straight-chain or branched. Examples o~ such
groups include methyl, ethyl, n-propyl, isopropyl, i-,
n-, sec.-, tert.-butyl, methoxy and ethoxy.
Compounds forming a preferred group are compounds
of formula I wherein -
Rl represents hydrogen, chlorine, methyl, ethyl, n-propyl,
isopropyl, n-, i-, sec.-butyl, vinyl or ethynyl,
R2 represents hydrogen, chlorine or methyl, or
Rl and R2 together represent the cyclopentyl or cyclo
hexyl ring,
3 represènts hydrogen, methyl, ethyl, methoxy or ethoxy, i
R4 represents hydrogen, chlorine or methyl, ;
R5 represents hydrogen, or
~R3 and R5 together represent a carbon-carbon-bond
~ or an oxygen bridge,
R6 represents hydrogen or methyl,
.
R7 represents cyclohexyl or the group
~ ~ R8 ~
., .
.,:
~0~5~
R8 represents hydrogen, chlorine, methyl, ethyl or
ethoxy,
Y represents oxygen, or the group -CH0, whereby the CH-
groùp is bound to the phenyl ring,
Z represents hydrogen or methyl, and
m and n each represent the number 0 or 1.
Compounds to be particularly emphasised because of
their effectiveness are compounds of formula I wherein
Rl represents hydrogen, chlorine, methyl, ethyl, n-propyl,
isopropyl, n-, i-, sec.-butyl, vinyl or ethynyl, -
R2 represents hydrogen, chlorine or methyl,
R3 represents hydrogen, methyl, ethyl, methoxy or ethoxy, .R4 represents hydrogen, chlorine or methyl,
R5 represent~ hydrogen, or .15 R3 and R5 together represent a carbon-carbon-bond, or
an oxygen bridge,
R6 represents hydrogen or methyl, `
. . :. .
R7 represents the group ~a
R8 represents hydrogen, chlorine, methyl, ethyl or ~ .
ethoxy,
Y~ represents oxygen, or the group -CH20-, whereby the CH2- ;;~
: group is bound to the phenyl ring, and
: :.
~ m and n each represent the number 0 or 1.
,-- ~,,
The compounds of formula I are produced in a manner
25~ known~per se by the following methods: ~:
-: : , ,~:
;' : "
,:
--' : '.,;
.
~ ~ 5 ~ 4 ~
1) Formation of the ether (O-alkylation) by condensation
of a halide of formula III with a compound of formula II:
X ¦ _ lla~-
(II) (III)
R7~ + ~X
(I)
whereby also in ~ormulae II and III, Rl to R7, Y, m and n :
have the meanings given for formula I; X stands for
chlorine, bromine or iodine, preferably for chlorine or .
bromine; M is a metal, especially the I. or II. main group
of the periodic system, or hydrogen
2) Epoxidation of a compound of formula IB:
ld-tl~n ~ ~, ;
(IB)
: ~ -
~ : '
:~ ~f~ (Ir)' ~
:whereby in formulae IB~and IC: Rl, R2, R4, R6~ R7, Y, m
: and:n have the meanings given for formula I.
.
~ S ,"~
. .
: ~ '':.,''.
: . .
~0~5~4~
3) Addit.ion of hydrogen halide to the olefinic - :
double bond of a compound o formula IB:
......
~IB) ~:
R7- ~
(IDa) H
whereby in formulae IB, IDa and IDb, Rl, R2, R4, R6, R7, .~i
Y, m and n have the meanings given for formula I; ~; ;
X stands for ha~ogen, preferably, however, for chlorine.
: 4) Epoxidation of an unsaturated halide to give an
~:~ 10 epoxy halide, and condensation thereo~ with a compound :
of formula II: : :
,'" ,
~ - 6 -
' , ' "'
~.~4S~44
X ~ R epOxidisin ~ o \
m 1 agent
(IV)
(V)
7 ~
tII YM
~ (IC)
whereby in formulae IC, II, IV and V, Rl, R2, R4, R6,
R7, Y, m, n and M have the meanings given in the case of ~
formula I or given above; X stands for halogen, ~ :-
especially for bromine or chlorine. `~. .
, ';
5) Hydrogenation of a compound IB: .:
'd
1 catal
(I~)
(IE) H
. . ...
' ~ ' . .' .,
ereby Rl,~R2, R4, R6, R7, Y, m and n have the meanings
given for ~formula I.
7 - :
.
~ .
:., :
",
1045~
6) Selective hydrogenation of a conjuga~ed triple bond
to a conjugated double bond:
R7-~
Lindlar-catalyst
(IF)
R - ~ ;
(IG)
whereby R2, R4, R6, R7, Y, m and n have the meanings
given for formula I. . .
7) Addition of an alcohol or water to a double bond: : .
- ' .': '~
7 ~ ~ R R2 .. -.
/ ~ ~ ~ R'30~ ~.
.. _ _ ~ I ~ ~ IIg(II)-salt
(IB) . ..
:
H ~ OH ~ water
.
..
- 8 - : .
~4S~4
R - ~ ~ OR~Rl
(IH)
whereby Rl, R2, R~, R6, R7, Y, m and n have the meanings
given for formula I, A represents the anion o~ an Hg(II)-
salt and R'3 represents a Cl-C4-alkyl radical or :
hydrogen. :-
The mercury ~ salt used is preferably mercury
acetate or mercury fluoroacetate.
8) Alkylation of an alcohol of formula IJ~
(IJ) 1 ~ ;
..,:
10R7--~ ~ R~jRl
(IH)
1 2~ ~ R6, R7, Y, m and n have the meanings
:given for formula I, X represents a halogen atom, and
R '3 represents a C~-C4-alkyL radical.
The alkylation of 4-hydroxydiphenyl ether and of ~ ~-
4-cyclohexyloxy-phenol, respectively, or of their derivatives
;'
; ,
5~44
substituted in the rings, can be performed with the
various saturated or unsaturated halides, depending on
the reactivity of the applied halide, in various solvents
and at various reaction temperatures, always, however,
in the presence of at least one mole of a base.
Suitable solvents are, in particular, acetone, methyl '
ethyl ketone, cyclohexanone, 1,2-dimethoxyethane,
tetrahydro~uran, dioxane, dialkyl etherl dimethylformamide,
dimethylsulphoxide, hexamethylphosphoric acid triamide,
sulpholane, inert hydrocarbons such as toluene, benzene,
xylene and suchlike. It is possible, however, to use
other solvents.
The necessary bases and acid acceptors, respectively, used -
in the case of ether formation from a compound of formula II
and a halide, are, in particular, alkali or alkaline-earth
hydroxides, alkali or alkaline`earth carbonates, alkali
or alkaline-earth hydrides and alkali alkoxides; it is
possible, however, also to use organic bases such as, e.g. ;
triethylamine, pyridlne, and so forth, as acid acceptors.
The reaction temperatures for the formation of
arylalkyl ethers are between -10 and 130C, mostly between
5 and 70C ( e.g. with application of solvents such as
dimethylsulphoxide, dimethylformamide, dioxane, sulpholane,
tetrahydrofuran, hexamethylphosphoric acid triamide, 1,2-
; dimethoxyethane, etc.); or the reaction is performed at
the boilLng temperature of the employed solvent (e.g.
in the case of ketones).
~ . . .
- 10-. , ~'' '
, ~' .~"
,
~04S149L
The conversion o-E compo~mds of ~ormula IB into the
corresponding epoxy derivatives is per~ormed preerably
in an inert solvent, advantageously in a chlorinated
hydrocarbon between -25C and room temperature, usually
between -5 and ~5C~ with the aid of an epoxidiising
agent, such as, e.g. a peroxy acid. The epoxy derivatives
of formula IC can also be obtained by way of the
corresponding halohydrides, by the cleavage of hydrogen
halide, the process comprising the conversion of an
alkenyl ether of formula IB with an N-halosuccinimide,
e.g. with N-bromosuccinimide, in a mixtwre of water and
a solvent such as tetrahydrofuran, 1,2-dimethoxyethane,
dioxane or tert.butanol in the homogeneous or heterogeneous
phase between -5C and room temperature, into bromohydrine;
and the obtainment, by the subsequent treatment of the
bromohydrin with an alkaline agent such as, e.g. alkali
carbonate or an alkali alkoxide, of the desired epoxy -
derivative. By alkali is meant, in particular, sodium or
potassium.
- 20 ~ The term "peroxy acid'i signifies principally lower
peroxyalkanoic acids having 1 to 6 carbon atoms, such as,
.. ..
- e.g. peroxyacetic acid, as well as aromatic peroxyacids
such as peroxybenzoic acid, monoperoxyphthalic acid,
;
~ ~particularly, however, 3-chloroperoxybenzoic acid.
., .
The processing and isolation of compounds of formula I
sre effected by known techniques; e.g., addition of water
or ice to the reaction mixture; subsequent extraction with
~ ;,
- 11 -
:~ i.!;;..'
:; :
~.~)4514~
a suitable solvent~ e~g. ether; washing of the organic
phase, e.g. with dilute alkali solution OL alkali
carbonate; and drying of the solution over anhydrous
sodium sulphate. ~fter removal of tlle solvent, the
obtained compound of formula I can, if necessary, be
purified by crystallisation, vacuum distillation, or ;
chromatography on silica gel or aluminium oxide.
Various reaction sequences can be employed to obtain
epoxidised compounds of formula IC: They are obtained
either by a process in which, as according to the stated
production processes, the hydroxyl group of 4-hydroxy
diphenyl-ether- or 4-cyclohexyloxyphenol-compounds
is firstly etherified, in the presence of a base, with ~-
an alkenyl halide, and in this arylalkenyl-ether the
olefinic double bond subsequently converted, as described
abo-ve9 into an epoxy; or the alkenyl halide firstly
epoxidised, with the exclusion of moisture, in a chlorinated
hydrocarbon, between -25C and room temperature,~with the
; aid of an epoxidising agent, such as, e.g. a peroxy acid,
and this epoxy halide reacted in the consequent reaction
with 4-hydroxydiphenyl ether and 4-cyclohexyloxy-phenol,
in the presence of an acid acceptor 9 to the final products,
.
an epoxLdised diphenyloxide-alkyl ether and 4-cyclohexyl-
oxyphenyl-alkyl ether, respectively.
The addition of hydrogen halide~ especially of hydrogen
.
chloride or bromide, to an aliphatic double bond is
effected preferably by the action of the anhydrous hydrogen
- 12 -
.
10~5~ 44halide on a ~-alkenyloxydiphenyl ether or on a 4-alkenyloxy-1-
cyclohexyloxyhenzene derivative in a suitable solvent,
such as, e.g. a chlorinated hydrocarbon, methanol,
ethanol, another alcohol, a dialkyl ether, glacial acetic
acid, etc.. The addi~ion of the hydrogen halide is
performed at ~ temperature of between -30 and ~25C.
The isolation of the yellowish halide is carried out
likewise by known techniques, such as addition o water
to the reaction mixture, extraction with an organic solvent,
and removal of the excess hydrogen halide by neutralisation
with a weak base, or by washing with water, whereby, after
removal of the solvent, the halide remaining can be
further purified by crystallisation, high vacuum distillation,
-or chromatography.
Unsaturated araliphatic ethers of formula IB can be
hydrogenated in a known manner to the saturated araliphatic
~ethers of formula IE, e.g. with catalytically activated
~hydrogen, advantageously between room and boiling temperature
~of the reaction mixture under normal or elevated pressure.
Suitable catalysts are preferably Raney nickel~ or noble
metals such as platinum or palladium. Applicable solvents
are, in particular, methyl and ethyl acetate,~dioxane,
or~alcohols such as~methanol, ethanol, and so forth. -
.
~Unsaturated araliphatic ethers of formula IF can be
;selectively partially hydrogenated, in a known manner,
to ethers of formula IG, e.g. with catalytically activated
hydrogen, at room temperature and normal pressure, until
,-. ::
.
' .:
~ ~ " ' ', "' .
,:
~ 5~4
one mole of hydro~en is absorbed. The catalyst preferably
employed is a Lindlar catalyst. Suitable solvents
are, e.g. ace~ic acid methyl and -ethyl ester, dimethoxy
ethane~ dioxane, or alcohols such as methanol or ethanol.
The reactions to the active substance of formula I
wherein R3 represents a Cl-C~-aLkoxy group are performed
under norrnal pressure and in an anhydrous alcohol R'30H,
and, if necessary, in solvents and diluents inert to
the reactants, e.g. in ethers such as tetrahydrofuran,
10 dioxane, diethyl ether, 1,2-dimethyloxyethane, etcIn
the 1. step ~ if R'3 = H - as well as in the 2. step,
the solvent can also be water.
The mercury-(II)-salts~preferably used are mercury-
(II)-acetate and mercury-(II)-trifluoroacetate. The
complex hydride employed is, e.g. MeBH4, wherein Me
- represents an alkali metal atom or alkaline-earth metal atom.
The reaction with complex hydride is performed in the
presence of alkali hydroxide and water. The reaction
'
temperatures are in the range of -10 to ~40C, preferably
~between 0 and -~25C.
A further method of obtaining compounds of formula I
: .
~wherein R3 represents a Cl-C4-alkoxy group comprises moreover
the etherification of an alcohol of formula IJ by reaction -
with a halide, depending on the reactivity of the applied
halide~ in various solvents and at different reaction
: : :
~ ~ ~temperatures, always, however, in the presence of at least
:: `
one mole of one of the above mentioned bases.
14~-
~ ~ ,
. ~, '
:
.
~(~45~4~
The obtained compounds occur, where this is, in
principle, possible, as cis/trarls-isomer mixtures. An
is~mer mixture can be separated, e.g. with the aid
of chromatographic separation methods into the isomeric
forms; for example, by adsorption on a separating
material having selective adsorption activity, such as, e.g
silica gel, aluminium oxide, and subsequent elution of
the separated isomers with a suitable solvent such as,
e.g. diethyl ether, hexane, methyl or ethyl acetate.
A further chromatographic separation method is gas --
chromatography. In certain cases, an isomer mixture can
be separated also by fractional distillation or by
fractional crystallisation.
The starting materials of ~ormulae II to V are known
compounds, which can be produced analogously to known
methods described in the literature.
The compounds of formula I are suitable for the control
of the most diverse animal pests.
They are suitable for the control of insects, and
- 20 members of the order acarina, principally, however, for ;~
the control of insects.
. .
Thus, the compounds of formula I can be used against,
for example, in.sects of the following orders and amilies.
Orthoptera Acrididae
Gryllidae
Blattidae
- 15 -
.
,, : ~'',
~= ~
5' '
~s~4
Isoptera Kalo~ermitidae ' :~
Hemiptera Miridae
Piesmidae
Lygaeidae
Pyrrhocoridae
Pentatomidae
Cimicidae J
Reduviidae
Jassidae
Eriosomatidae
Lecaniidae ¦ :
.
Coleoptera Carabidae '
Elateridae
Coccinellidae
Tenebrionidae .
Dermestidae
Cucujidae
Chrysomelidae
Curculionidae
: :. .
20 : Scolytidae
Scarabaeidae ~ :
Lepidoptera PyraIidae
Phyticidae : .
Pyraustidae
Crambidae
: Tortricidae
: . .
: ~Gralleriidae :
Lyonetiidae Noctuidae. :
: :~ Yponomeutidae Pieridae
- 30 ;:~ ~ Flutellidae Lymantriidae
Diptera ~ Culicidae
Simuliidae
Tipulidae
, .
.
: -:16 -
... . . , . .. . . -. . -
~L0~4~ ^~
The action of the compounds of formula I can be
appreciably broadened and enhanced, and adapted to suit given
circumstances, by the addition of other insecticides and/or ::
acaricides or insect bait.
Suitable additives include, for example, the follow- . .
ing active substances:
Organic phosphorus compounds
Bis-O,O-diethylphosphoric acid anhydride (TEPP)
Dimethyl-~2,2,2-trichloro-1-hydroxyethyl)-phosphonate .. ~ ~ :
(TRICHLORFON)
1,2-dibromo-2,2-dichloroethyldimethylphosphate ~NALED) .
2,2-dichIorovinyldimethylphosphate (DICHLORVOS)
2-methoxycarbamyl-l-methylvinyldimethylphosphate (MEVINPHOS)
Dimethyl-l-methyl-2-(methylcarbamoyl)-vinylphosphate cis `
(MONOCROTOPHOS) .. :
3-~dimethoxyphosphinyloxy)-N,N-dimethyl-cis-crotonamide
, :
(DICROTOPHOS)
2-chloro-2-diethylcarbamoyl-1-methylvinyldimethylphosphate
(PHOSPHAMIDON) ~ .
O,O-diethyl-O~or S)-2-~ethylthio)-ethylthiophosphate ~DEMETON) . :
S-ethylthioethyl-O,O-dimethyl-dithiophosphate ~THIOMETON)
O,O-diethyl-S-ethylmercaptomethyldithiophosphate ~PHORATE)
O,O-diethyl-S-2-~ethylthio)ethyldithiophosphate (DISULFOTON)
O,O-dimethyl-S-2-(ethylsulphinyl)ethylthiophospha~e
.. .. . ..
~OXYDEMETON METHYL) ~ :
: O,O-dimethyl-S-(1,2-dicarbethoxyethyldithiophosphate (MALATHION)
:,. .
.`. '' ', .
....
..., ,. ' " ...
,:. .: . ' .
.
.:
:,, .
7 ~ . .. ..
.. . ~
- 1~45~L~4
O,O,O,O-tetraethyl-S,S'-methylene-bis-dithiophosphate ~ETHION)
O-ethyl-S,S-dipropyldithiophosphate
O,O-dimethyl-S-~N-methyl-N-for.mylcarbamoylmethyl)-dithiophosphate
(FORMOTHION)
O,O-dimethyl-S-(N-methylcarbamoylmethyl)dithiophosphate ~.
(DIMETHOATE)
O,O-dimethyl-O-p-nitrophenylthiophosphate ~PARATHION-METHYL) :~
O,O-diethyl-O-p-nitrophenylthiophosphate ~PARATHION) ..
O-ethyl-O-p-nitrophenylphenylthiophosphate (EPN)
0,0-dimethyl-0-(4-nitro-m-tolyl)thiophosphate (FENITROTHION~
0,0-dimethyl-0-2,4,5-trichlorophenylthiophosphate (RONNEL)
O-ethyl-0,2,4,5-trichlorophenylethylthiophosphate (TRICHLORONATE) ::,
0,O-dimethyl-0-2j5-dichloro-4-bromophenylthiophosphate (BROMOPHOS) ~ :
0,0-dimethyl-0-(2,5-dichloro-4-iodophenyl)-thiophosphate `~
(JODOFENPHOS) - .
4-tert.butyl-2-chlorophenyl-N-methyl-O-methylamidophosphate .~. ~
(CRUPOMATE) ~ :
0,0-dimethyl-0-~3-methyl-4-methylmercaptophenyl)thiophosphate :
(FENTHION)
Isopropylamino-O-ethyl-0-~4-methylmercapto-3-methylphenyl)-
phosphate
O,O-diethyl-O-p-~methylsulphinyl)phenyl-thiophosphate :
~FENSULFOTHION) .~.;
O-p-(dimethylsulphamido)phenyl-O, _dimethylthiophosphate (FAMPHUR)
O,O,O',O~-tetramethyl-O,O'-thiodi-p-phenylenethiophosphate ~:
: O-ethyl-S-phenyl-ethyldithiophosphate
0,0-dimethy:L-O-:(o~-methylben~yl-3-hydroxycrotonyl)phosphate
: 2-chloro-1-~2,4-dichlorophenyl)vinyl-diethylphosphate
~ (CHLORFENVINPHOS)
. ,
' -' '
~ 18 -
:,::' ;' :
5~4
l-chloro-1~(2,4,5-trichlorophenyl)vinyl-dimethylphosphate
0-[2-chloro-1-~2,5-dichlorophenyl)]vinyl-0,0-diethylthio- ~ .
phosphate -~
Phenylglyoxylonitriloxime-O,O-di.ethylthiophosphate (PHOXIM) ;
0,0-diethyl-0-~3-chloro-4-methyl-2-oxo-2-H-l-benzopyran-7-yl)-
thiophosphate ~COUMAPHOS)
2,3-p-dioxandithiol-S,S-bis~O,O-diethyldithiophosphate~ ~ :
~DIOXATHION) c~
5-[~6-chloro-2-oxo-3-benzoxazolinyl)methyl]O,O-diethyldithio-
phosphate ~PHOSALONE)
2-~diethoxyphosphinylimino)-1,3-dithiolane .
0,0-dimethyl-S-[2-methoxy-1 J 3,4-thiadiazol-5-~4H)-onyl-~4)- :
methyl]dithiophosphate ; .
O,O-dimethyl-S-phthalimidomethyl-dlthiophosphate ~IMIDAN)
0,0-diethyl-0_~3,5,6-trichloro-2-pyridyl)thiophosphate .
0,0-diethyl-0-2-pyrazinylthiophosphate ~THIONAZIN) : :
0,0-diethyl-0-(2-isopropyl-4-methyl-6-pyrimidyl)thiophosphate` .
~DIAZINON) ~ . -
~ 0,0-diethyl-0-(2-quinoxalyl)thiophosphate
0,0-dimethyl-S-~4-oxo-1,2,3-benzotriazin-3~4H)-ylmethyl)- ;` ;
~dithiophosphate ~AZINPHOSMETHYL)
0,0-diethyl-S-~4-oxo-1,2,3-benzotriazin-3~4H)-ylmethyl)~ ;
dithiophosphate ~AZINPHOSETHYL) .
: S-[~4,6-diamino-s-triazin-2-yl)mothyl]-0,0-dimethyldithiophos-
phate ~(MENAZON)
: ~ 0,0-dimethy~-0-(3-chloro-4-nitrophenyl~thiophosphate ~CHLORTHION)
O,O-dimethyi-O~or S)-Z-(ethylthioethyl)thiophosphate
: (DEMBTON~S-METHYL)
:::
- 1 9 - ,: .
". ,' ':
, "
~045~4 ,:
2-(0,0-dimethyl phosphoryl-thioMethyl)-5-methoxy-pyrone-4-3,4-
dichlorobenzyl-triphenylphosphoniumchloride .
0,0-diethyl-S-~2,5-dichlorophenylthiomethyl)dithiophosphate
(PHENKApTON)
0,0-diethyl-0-~4~methyl-cumarinyl-7-)-thi.ophosphate ~POTASAN)
5_amino~bis(dimethylamido)phosphinyl-3-phenyl-1,2,4-triazole
(TRIAMIPHOS)
N-methyl-5-~0,0-dimethylthiolphosphoryl)-3-thiavaleramide
~AMIDOTHION)
0,0-diethyl-0-[2-dimethylamino-4-methylpyrimidyl-~6)]-thio-
phosphate (DIOCTHYL) ~-
O,O-dimethyl-S-(methylcarbamoylmethyl)-thiophosphate (OMETHOATE) .~:
O-ethyl-0-(8-quinolinyl)-phenylthiophosphonate (OXINOTHIOPHOS)
O-methyl-S-methyl-amidothiophosphate ~MONITOR) .
O-methyl-0-~2,5-dichloro-4-bromophenyl)-benzothiophosphate .
(PHOSVEL) ~.
O,O,O,O-tetrapropyldithiophosphate :
3-(dimethoxyphosphinyloxy~-N-methyl-N-methoxy-cis-crotonamide
O~O-dimethyl-S-(N-ethylcarbamoylmethyl)dithiophosphate
~ETHOATE-METHYL)
O,O-diethyl-S-(N-isopropylcarbamoylmethyl)-dithiophosphate
(PROTHOATE) ; -
: ~ S-N-(l-cyano-l-methylethyl)carbamoylmethyldiethylthiolphosphate
(CYANTHOATE~
~ , .
;~ 5-(2-acetamidoethyl)-0,0-dimethyldithiophosphate ~;
Hexamethylphosphoric acid triamide (HEMPA)
0,0-dimethyl-0-~2-chloro-4-nitrophenyl)thiophosphate ~DICAPTHON) .
O,O-dimethyl-O-p-cyanophenyl thiophosphate (CYANOX)
. :'
- 20 -
':
. ~ .
.. , , ~ . . . . .
~0451~
O-ethyl-O-p-cyanophenylthiophosphonate :
0,0-diethyl-0-2,4-dichlorophenylthiophosphate (DICHLORFENTIIION)
0,2,4-dichlorophenyl-0-methylisopropylamidothiophosphate
0,0-diethyl-0-2,5-dichloro-4-bromophenylthiophosphate ~ .
~BROMOPHOS-ETHYL) :~.
dimethyl-p-(methylthio)phenylphosphate
O,O-dimethyl-O-p-sulphamidophenylthiophosphate ..
O-[p-(p-chlorophenyl)azophenyl]O,O-dimethylthiophosphate ~ .
~AZOTHOATE) ~ ;
0-ethyl-S-4-chlorophenyl-ethyldithiophosphate
O-isobutyl-S-p-chlorophenyl-ethyldithiophosphate
O,O-dimethyl-S-p-chlorophenylthiophosphate . .
O,O-dimethyl-S-(p-chlorophenylthiomethyl)dithiophosphate
O,O-diethyl-p-chlorophenylmercaptomethyl-dithiophosphate
(CARBOPHENOTHION) :~ .
O,O-diethyl-S-p-chlorophenylthiomethyl-thiophosphate
O,O-dimethyl-S-~carbethoxy-phenylmethyl)dithiophosphate ~ :
(PHENTHOATE) ~:
O,O-diethyl-S-~carbofluorethoxy-phenylmethyl)-dithiophosphate ; ~ .
O,O-dimethyl-S-carboisopropoxy-phenylmethyl)-dithiophosphate :
0,0-diethyl-7-hydroxy-3,4-tetramethylene-coumarinyl-thiophos-
: phate ~COInMITHOATE) : ;
: 2-methoxy-4-H-1,3,2-benzodioxaphosphorin-2-sulphide
0,0-diethyl-0-(5-phenyl-3-isooxazolyl)thiophosphate
: 2-~diethoxyphosphinylimino)-4-methyl-1,3-diethiolane
,
trls-~2-methyl-1-aziridinyl~-phosphine oxide ~METEPA) .
5-~2-chloro-1-phthalimidoethyl)-0,0-diethyldithiophosphate
~: ~ N-hydroxynaphthalimido-diethylphosphate
:: ,~;:
:~.: .:. :,.
,,".
- 21 -
:''
lO~S~
dimethyl-3,5,6-trichloro-2-pyridy~lphosphate
O,O-dimeth~1-0-~3,5,6-trichloro-2-pyridyl)thiophosphate
S-2-~eth~lsulphonyl)ethyl dimethylthiolphosphate
(DIOXYDEMETON-S-METHYL~
dlethyl-S-2-~ethylsulphin~l)ethyl dithiophosphate ~OXIDISULFOTON)
bis-O,O-diethylthiophosphoric acid anhydride ~SULFOTEP)
dimethyl-1,3-di~carbomethoxy)-1-propen-7.-yl-phosphate
dime~hyl-~2,2,2-trichloro-1-butyroyloxyethyl)phosphate
(BUTONATE)
0,0-dimethyl-0-~2,2-dichloro-1-methoxy-vinyl)phosphate
: bis-~dimeithylamido)fluorphosphate ~DIMEFOX)
3,4-dichlorobenzyl-triphenylphosphoniumchloride
dimethyl-N-methoxymethylcarbamoylmethyl-dithiophosphate
;~ ~FORMOCARBAM)
0,0-diethyl-0-~2,2-dichloro-1-chloroethoxyvinyl)phosphate
0,0-dlmethyl-0-~2,2-dichloro-1-chloroethoxyvinyl)phosphate
O-ethyl-S,S-diphenyldithiolphosphate
O-ethyl-S-benzyl-phenyldithiophosphonate
. O,O-diethyl-S-benzyl-thiolphosphate
0,0-dimethyl-S-~4-chlorophenylthiomethyl)dithiophosphate
. ~METHYLCARBOPHENOTHION)
O,O-dimethyl-S-~ethylthiomethyl)dithiophosphate
diisopropylaminofluorophosphate CMIPAFOX)
. ~ O,O-dimethyl-S-~morpbolinylcarbamoylmethyl)dithiophosphate
: (MORPHOTHIONj
bismeth~lamido-phenylphosphate
O,O-dimethyl-S-(benzenesulphonyl)dithiophosphate
... ,.,-: :
; . ~ O,O-dimeth~ S and O)-ethylsulphinylethylthiophosphate
:~ .
, ~: ,
.. :
'~''','~'~
,"''`' ~ ~ '
~ .
~ - 22 -
.:
:: :
" ' ,;
~s~
0,0-dieth~1-0-4-nitrophenylphospha~e
trlethoxy-isopropoxy~bis~thiophosphinyl~disulphide
2-methoxy-4H-1,3,2-benzodioxaphosphorin-2-oxide
octameth~lpyrophosphoramide ~SCHRADAN)
bis-(dimethoxythlophosphinylsulphido)-phenylmethane
N,N,N',N'-tetramethyldiamidofluorophosphate ~DIMEFOX)
O-phenyl-O-p-nitrophenyl-methanethiophosphonate ~COLEP)
O-methyl-0-~2-chloro-4-tert,butyl-phenyl)-N~methylamidothio-
phosphate ~NARLENE)
0-ethyl-0-(2,4-dichlorophenyl)-phenylthiophosphonate
0,0-diethyl-0-~4-methylmercapto-3,5-dimethylphenyl)-thiophosphate
4,4'-bis(O,O-dimethylthiophosphoryloxy)-diphenyl disulphide
0,0-di-~-chloroethyl)-0-~3-chloro-4-methyl-coumarinyl-7)- ;
phosphate
S-(l-phthalimidoethyl)-O,O-diethyldithiophosphate
0,0-dimethyl-0-(3-chloro-4-diethylsulphamylphenyl)-thiophosphate :
O-methyl-0-~2-carbisopropoxyphenyl)-amidothiophosphate
5-~0,0-dimethylphosphoryl)-6-chloro-bicyclo~3.2.0)-heptadiene (1,5)
O-methyl-0-(2-i-propoxycarbonyl-1-methylvinyl)-ethylamidothio-
phosphate.
Nitrophenols and derivatives
.. .
4,6-dinitro-6-methylphenol, sodium salt [Dinitrocresol]
dinitrobutylphenol-~2,2',2")-triethanolamine salt `
2-cyclohexyl-4,6-dinitrophenyl ~Dinex] ~-
2-(l-methylheptyl)-4,6-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 rDinobuton]
S1~4
Miscella~eous
pyrethin I
pyrethin II
3-allyl-2-methyl-4-oxo-2-cyclopentan-1-yl-chrysanthemumate
~Allethrin~
6-chloropiperonyl-chrysanthemumate ~Barthrin)
Z,4-dimethylbenzyl-chrysanthemumate (Dimethrin) : :
2,3,4,5-tetrahydrophthalimidomethylchrysanthemumate ~
4-chlorobenzyl-4-chlorophenylsulphide [Chlorobenzid] - -
6-methyl-2-oxo-1,3-dithiolo-~4,5-b]-quinoxaline ~Quinomethionate)
~I~-3-~2-furfuryl)-2-methyl-4-oxocyclopent-2-enyl~ cis~trans)-
chrysanthemum-monocarboxylate [Furethrin]
2-pivaloyl-indane-1,3-dione ~Pindon] . ;
N'-~4-chloro-2-methylphenyl)-N,N-dimethylformamidine .
[Chlorophénamidin] :
4-chlorobenzyl-4-fluorophenyl-sulphide [Fluorobenside]
S,6-dichloro-1-phenoxycarbamyl-2-trifluoromethyl-benzimidazole
IFenozaflor]
p-chlorophenyl-p-chlorobenzenesulphonate ~Ovex] . .
p-chlorophenyl-benzenesulphonate ~Fenson]
p-chlorophenyl-2,4,5-trichlorophenylsulphone ~Tetradifon]
p-chlorophényl-2,4,5-trichlorophenylsulphide ~Tetrasul] :
p-chlorobenzyl-p-chlorophenylsulphide [Chlorobenzide]
2-thio-1 J 3-dithiolo-~5,6)-quinoxaline [Thiochinox]
: prop-2-ynyl-~4-t-butylphenoxy)-cyclohexylsulphite [Propargil]
Formamidines ~
l-dimeth~1-2-t2~-methyl-4'-chlorophenyl)-formamidine .~, .-".,
~ ~ ~ CcHLoRp~EN~M~DIN~
: ~ ": ,.
~, -
'.~
,
: - 24 _
, ,: .
.-, :
~45~4~
l-methyl-2-c2~-methylr4l-chlorophenyl~-formamidine
l-methyl-2-~2'-meth~1-4~-bromophenyl~-~ormamidine
l-methyl-2-(2'-4'-dimethylphenyl)-formamidine
l_n-butyl-l-methyl-2-~2'-me~hyl-4'-chlorophenyl)-formamidine :
l-methyl~ 2'-methyl-4'-chloroaniline-methylene)-formamidine . .
2-C2"-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 ~AMINOCARB) .
4-methylthio-3~5-xylyl-N-metbylcarbamate (MET~IOCARB) ~ . -
3,4,5-trimethylphenyl-N-methylcarbamate ;~
2-chlorophenyl-N-methylcarbamate ~CPMC) :;
5-chIoro-6-oxo-2-norborane-carbonltrile-O-~methylcarbamoyl)-oxime
dimethyicarbamoyl3-5-methyl-3-pyrazolyl-N,N-dimethylcarbamate
(DIMETI.LAN) .
2,3_dihydro-2,2-dimethyl-7-benzofuranyl-N-methylcarbamate
(CARB0FURAN)
: : 2-methyl-2-methylthio-propionaldehyde-O-~methylcarbamoyl)-oxime
ALD~CARB~
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-me~hylcarbamate
. .
~: , .
~ : ~ 25 - ~ :~
': '
,:. .:' '
. .. . . ... . . . . . . . :
1~5~
m~ methylbutyl~phenyl-N-methylcarbamate : :
2-isopropylphenyl-N-methylcarbamatP
2-sec.but~lphenyl-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 ~PROMECARB~ :
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 ~DIOXACARB) :
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 : ~ N
2-~1,3-dithiolan-2-yl)phenyl-N,N-dimethylcarbamate
2-isopropoxyphenyl-N-methylcarbamate ~APROCARB)
2-~2-propinyloxy)phenyl-N-methylcarbamate ;
3-~2-propinyloxy)phenyl-N-methylcarbamate
2-dimethylaminophenyl-N-methylcarbamate
?-diallylaminophenyl-N-methylcarbamate
4-diallylamino-3,5-xylyl-N-methylcarbamate ~ALLYXICARB) .
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 ~ISOLAN)
: .. . .
2-dimethylamino-5,6-dimethylpyrimidin-4-yl-N,N-dimethyl-carbamate
, . .
26 -
, ;!
.i
. ' ~ .
~13 45~
3-methyl-~-dimethylaminometh~leneiminophenyl-N-methylcarbamate : .
3,4-dimeth~lphen~l-N-methylcarbamate ,
2-cyclopentylphenyl-N-methylcarbamate
3-dimethylamino-methyleneiminophenyl-N-methylcarbamate
~FORMETANATE~ and its salts
l-methylthio-ethylimino-N-methylcarbamate ~MEI~IOMYL)
2-methylcarbamoyloximino-1,3-dithiolane
5-methyl-2-methylcarbamoyloximino-1,3-oxythiolane ~
2-(1-methoxy-2-propoxy)phenyl-N-methylcarbamate : .
2-~1-butin-3-yl-oxy)phenyl-N-methylcarbamate `. .
l-dimethylcarbamyl-l-methylthio-0-methylcarbamyl-formoxime : i
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-M-methylcarbamate
2-~N-methylcarbamyl-oximino)-3-chloro-bicyclo[2.2.1]heptàne
2-~N-methylcarbamyl-oximino)-bicyclo[2.2.1]heptane :
3-isopropylphenyl-N-methyl-N-chloroacetal-carbamate ;
3-isopropylphenyl-N-methyl-N-methylthiomethyl-carbamate
0-(2,2-dimethyl-4-chloro-2,3-dihydro-7-benzofuranyl)-N-methyl-
carbamate
0-~2,2,4-trimethyl-2,3-dihydro-7-benzofuranyl)-N-methylcarbamate
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
... . :
.'
: ~ 27 - ~
3-allyloxyphenyl_N-methylcarbamate
2-propargyloxymethoxy-phenyl-N-methyl~carbamate
2-allyloxyphen~l-N-methyl-carbamate
4-methoxycarbonylamino-3-isopropylphenyl-N-methyl-carbamate
3,5-dimethyl-4-methoxycarbonylamino-phen~l-N-methyl-carbamate
2-~r-methyithiopropylphenyl-N-methyl-carbamate
3-(cC-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~ ~ -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-dimethylhydroresorcinoldimethylcarbamate
2-~ethyl-propargylamino]-phenyl-N-methylcarbamate . -
,
2-rmethyl-propargylamino]-phenyl-N-methylcarbamate ,:'.. :'.:~':' '
4-[dipropargylamino]-3-tolyl-N-methylcarbamate ~ : -
4-[dipropargylamino]-3 ? 5-xylyl-N-methylcarbamate -~ 4
2-[allyl-isopropylamino]-phenyl-N-methylcarhamate
3-[allyl-1sopropylamino]~-phenyl-N-methylcarbamate .,. ;. ,
,"~g~,...
-hexachlorocyclohexane ~GAMMEXANE; LI~DAN; ~f HCH]
1,2,4,5,6?7,8?8-octachloro-50l~4,7,70('tetrahydro-4,7-methylene ,'~. ;
indane ~CHI.ORDAN]
1,,4,5,6,7,&,8-heptachloro,3~X,4,7?7(-tetrahydro-4,7-methylene '
.
.. ..
28 -
' ' : :;'
.. .. .
1~45
indane [~I~PT~CHLOR]
1,2,3,4,10,10-IIexachloro-1,4,4a~5,8,8a hexahydro endo-1,4-exo-
5,8-dimethanonaphthalene [ALDRIN]
1,2,3,4,10~10-hexachloro-6,7-epoxy-1,4,4a,5,6,7,$,8a-octa-
hydro-exo-1,4~endo~5,8--dimethanonaphthalene EDIFLORIN]
1,2,3,4,10,10-hexachloro-5,7-epoxy-1,4,4~,5, 6,7,8,8a-octy-
hydro-endo-endo-5,8-di~ethanonaphthalene [ENDRIN].
The compounds of formula I can be used on their own
or together with suitable carriers and/or additives.
Suitable carriers and additives can be solid or liquid
and correspond to the substances common in formulation
practice, such as, e.g. natural or regenerated substances, ~ :solvents, dispersing agents, wetting agents, adIlesives,
thickeners, bonding agents and/or fertilisers. For application,
the compounds of formula I can be processed into the
form of dusts~ emulsion concentrates, granulates ?
dispersions, sprays or solutions, the formulation of the
said preparations being effected in a manner commonly
known in practice.
The agents according to the invention are produced
in a manner known per se by the intimate mixing and/or
grinding of active substances of formula I with suitable
carriers, optionally with the addition of dispersing agents
or solvents which are inert to the active substances.
The active substances can be obtained and used in the
following preparation forms:
- 29 -
.
'
.. , , .. .. , . . . , ~ . . . . . . . .. . . . . . .
~)4S14~ ~
Sol~d forms: , -
Dusts, scattering agentsJ granules, coated granules,
impregna~ed granules and homogeneous granules.
Liquid forms:
a) active substances which are dispersible in water: -~
~ettable powders, pasts, emulsions;
b) solutions.
To manufacture solid forms ~dusts, scat~ering agents),
the active substances are mixed with solid carriers. Suitable
carriers are, for example: kaolin, talcum, bolus, loess, chalk, ~ ~ ;
limestone, ground limestone, attaclay, dolomite, diatomaceous
earth, precipitated silica~ alkaline earth silicates, sodium and
potassium aluminium silicates ~feldspar and mica), calcium and
magnesium sulphates, magnesium oxide, ground synthetic materials, ;
fertilisers, for example ammonium sulphate, ammonium phosphate, ~; ;
ammonium nitrate, urea, ground vegetable products, such as corn
meal, bark dust, sawdust, nutshell meal, cellulose powder, residues -
of plant extractions, activated charcoal etc. These substances ~ ;
can either be used singly~or in admixture with one another. ~ ~
20 ~ Granules can be very easily manufactured by dissolving . ~ -
an acti~e substance of the formula I in an organic solv~nt and `-
apply~ing the resulting solution to a granulated material, for
example attapulgite, SI02, granicalcium, bentonite etc. and then
evaporating the solvent.
Polymer granules can also be manufactured by mixing
the active substances of the formula I with polymerisable com~
.:
pounds ~urea/formaldehyde; dicyandiamide~formaldehyde; melamine/
: -, ~ ' .~. .
,,.. ,.: ,:. ;~
.: . . . ,:
- 30 - ,
.,:
'..:
~ ' :.: '. .'
~0~s~
formaldehyde or others), whereupon a mild polymerisation is
carried out that does not a~fect the active substances 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 adsorption~desorption ratio, with the
active substances, for example in the form of their solutions -
~in a low boiling solvent) and to remove the solvent. Polymer
granules of this kind in the form of microgranules having a
bulk denslty of 300 g/liter to 600 g/liter can also be manufac-
tured with the aid of atomisers. The dusting can be carried out ~ `
from aircraft over extensive areas of cultures of useful plants. `~
It is also possible to obtain granules by compacting ~
the carrier with 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 wett-
ability (wetting agents) and dispersibility ~dispersing agents).
Examples of suitable adhesives are the following: -
olein/chalk mixture, cellulose derivatives (methyl cellulose,
carboxymethyl cellulose), hydroxyethyl glycol ethers of mono-
alkyl and dialkyl phenols having 5 to 15 ethylene oxide radicals
.:
~ per molecule and 8 to 9 carbon atoms in the alkyl radical,
;,
: '
31 ~ ~
.
,j ~
. . ~ . - ,- , - . .
: - .. ,., .- . .. ,. : . :,, ,. ,;, ,. ~, . ~ ., : : .
~045~
lignin sulphonic acids, their alkali metal and alkaline earth
metal salts, polyethylene glycol ethers carbowaxes*, fatt~
alcohol pol~ethylene glycol ethers having 5 to 20 ethylene oxide
radicals per molecule and 8 to 18 carbon atoms in the fatty
alcohol moiet~, condensation products of ethylene oxide/propylene
oxide~ polyv~nyl pyrrolidones, polyvinyl 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 emulsifiable con-
centrates, are agents which can be diluted with water to any
concentration desired. They consist of active substance, carrier, -
optionall~ additives which stabilise the active substance, surface-
active substance and anti-foam agents and, optionally, solvents.
Wettable powders and pastes are obtained by mixing
and grinding the active substances with dispersing agents and
pulverulent carriers in suitable apparatus until homogeneity
is attained. Suitable carriers are, fbr example, those mentioned
for the solid forms of application. In some cases it is advan- `
tageous to use mixtures of different carriers. As dispersing
agents there can be used, ~or example, condensation products
of~sulphonated naphthalene and sulphonated naphthalene derivatives -
with formaldehyde, condensation products of naphthalene or naphtha-
lene sulphonic acids with phenol and formaldehyde, as well as
aIkali, ammonium and alkaline earth metal salts of lignin sul-
.;, ,~.
phonic acid, in addition, alkylaryl sulphonates, alkali and
alkaline earth metal salts of dibutyl naphthalene sulphonic acid,
fatty alcohol sulphates such as salts of sulphated hexadecanols,
*Trademark -
;,. . ~.',,, .': .'
,
~ 32 ~ ;~
,: , :,,
~s~
heptadecanols, octadecanols, and salts of sulphated fatty alcohol
glycol ethers, the sodlum salt of oleo~l ethionate, the sodium
salts of oleoyl methyl tauride, ditertiary~ acetylene glycols,
dialkyl dilauryl ammonium chloride and fatty acid alkali and
alkaline earth metal salts.
Suitable anti-foam agents are silicones.
The active substances are mixed, ground, sieved and
strained with the additives cited hereinabove in such a manner
that, the size of the solid particles does not exceed 0.02 to ,
0.04 ~ in wettable powders, and 0.03 ~ in pastes. To produce
emulsifiable concentrates and pastes, dispersing agents such as
those cited above, organic solvents, 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
20~ formula l are dissolved in suitable organic solvents, mlxtures of
solvents or in water. Aliphatic and aromatic hydrocarbons, chlori-
: ~
nated derivatives thereof, alkyl naphthalenes, and mineral oils
singly or in admixture with each other, can be used as organic ;
solvents.
The content of active substance in the above described
agents is between 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 appllcation, it is possible to use
:
: ~ . ':.
- 33
,
:
1(~45~
concentratlons o~ up to 99.5% or even pure active substance.
The actlve 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 paTt of highly disperse sllicic acid
97 parts of talcum.
The active substances are mixed with the carriers and
ground. ..
Granules
The following substances are used to produce 5%
granules:
5 parts of active substance, ; -
0.25 parts of eplchlorohydrin,
0.25 parts of cetyl polyglycol ether, .: -
2~0 3.50 parts of polyethylene glycol, ~;.
91 parts of kaolin (particle size 0.3 - 0.8 mm~
The active substance is mixed with epichlorohydrin
and di~ssolved with 6 parts of acetone; the polyethylene glycol
;and cetyl poiyglycol ether are then added. The thus obtained
solutlon~is sprayed on kaolin, and the acetone subsequently ~-~
evaporated in vacuo.
Wettable po~der:
The following constituents are used ~or the prepara-
_ ;
:
':
345~
tion o a2 a 40%, b2 and c~ a 25~ and d~ a 10% wettable powder:
a2 40 parts of active su~stance,
5 parts o sodium lignin sulphonate,
1 part o sodium dibut~l-naphthalene sulphonate,
54 parts of silicic acid. :~
b) 25 parts of active substance,
4.5 parts of calcium lignin sulphonate,
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 of Champagne chalk, -
28.1 parts of kaolin.
C2 25 parts of active substance,
2.5 parts of isooctylphenoxy-polyoxyethy~lene-ethanolg ~-
1.7 parts of Champagne chalk~hydroxyethyl cellulose
mixture ~1:1),
8.3 parts~of sodium aluDmium silicate
16.5 parts of kieselguhr, :
46 parts of kaolin.
d) ~IO~parts of active substance,
3 parts of a mixture of the sodium salts of satu- ,
rated fatty~alcohol sulphates,
S parts of naphthalenesulphonlc acld/formaldehyde~
condensate, -
82 parts of kaolin.
The active~substances are intimately mixed, in suitable
; mlxers, with ths~ addltires, the mlxture being then ground
: ~ : ,
, ~ ;.
~ - 3S -
.,
:.:
.
,~ .. . .
~0~5~
in the appropriate mills and rollers. Wettable powders are ob- -
tained which can be diluted with water to give suspensions of
any desired concentration.
Emulsifiable 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 alkylaryl-
sulphonate calcium salt, -
40 parts of dimethylformamide,
43.2 parts of xylene, ;;
25 parts of active substance, ;
2.5 parts of epoxidised vegetable oil,
10 parts of an alkylarylsulphonate/fatty alcohol-
polyglycol ether mixture
5 parts of dimethylformamide,
.. ... .
57.5 parts of xylene.
~ i ,
From ~hese concentrates it is possible to produce, by :
dilution with water, emulsions of any desired concentration. -
Spray:
, ' ~, .
The following constituents are used to prepare a 5% ~
.
~ spray:
.
5 parts of active substance,
1 part of epichlorohydrin,
94 parts of benzine (boiling limits 160 - 130C~.
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.
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Example 1
The solution of 6.4 g of ca. 90~/0 potassium hydroxide
in 90 ml of absolute ethanol was added dropwise at room
temperature in the course of 6 hours, with stirring, to
a solution of 19.2 g of 4-cyclohexyloxy-phenol and
16.4 g of 1-bromo-3-methyl-2-pentene in lS0 ml of 1,2-
dimethoxyethane. After the addition of the base, s~irring
was continued for a further 15 hours at room temperature.
The precipitated potassium bromide was filtered off in
subsequent processing, the filtrate concentrated in vacuo,
the residue taken up in hexane, washed three times with
ice cold 10% potassium hydroxide solution and then with
water until neutral. After drying of the organic phase
over sodium sulphate, ~iltration, and complete removal ;
of the solvent in vacuo, there remained pure l-cyclohexyl-
oxy-4-(3-methyl-2-pentenyl-1-oxy)-benzene; n20 : 1 5265.
Example 2
The solution of L0.3 g of 84% 3-chloroperoxybenzoic
acid in 100 ml of methylene chloride diethyl ether (9:1)
was added dropwise at -5C in the course of ca. S hours
to a solution of 13.7 g of 1-cyclohexyloxy-4-(3-methyl-2-
pentenyl-l-oxy~-benzene in lS0 ml of methylene chloride.
The~temperature was maintained at 0C overnight; n hexane
was therl added to the reaction mixture, and the whole
washed thrée times with ice cold 10% potassium hydroxide
solution and subsequently with water until neutral. After
` 37 -
- ' : ,,:
:
i ~ -
:
' ;
104519~4
drying of the organic solution over sodium sulphate,
filtration was performed, the solvent removed in vacuo,
and the oily residue purified by chromatography on
silica gel (eluting agent: ether/hexane 1:4) to thus
obtain pure 1-cyclohexyloxy-4-(2,3-epoxy-3-methyl~pentyl-
l-oxy)-benzene; n20 : 1.5180. -
Example 3
The solution of 10.7 g of 1-(p-phenoxy)-phenoxy-3-
methyl-2-pentene in 50 ml of absolute methanol was added
- in 10 minutes, with vigorous stirring, to a suspension
cooled to -2C of 12.7 g of pulverised mercury(II)-
acetate in 80 ml of absolute methanol. Thirty minutes -
after addition of the alkene, additions were made, to
.
the reaction mixture at -2C, o 40 ml of a 3N aqueous ~
sodium hydroxide solution and, immediately afterwards, `
of 40 ml of a 0.5 molar sodium hydride solution in 3N
sodium hydroxide solution, the temperature consequently
rising to ca. 25C. Stirring was subsequently continued
for 2 hours at 15-20C. In further processing, the reaction
mixture was decanted from the precipitated mercury, the
overlying solution poured on 500 ml of saturated sodium
,
chloride solution, and the whole extracted four times with
diethyl ether. The combined ether solutions were washed
.
with~sodium chloride solution, dried over sodium sulphate,
and the solvent completely removed in vacuo. The oily
.~ ., .
~ 25 residue was further purified by chromatography on silica gel
' ~ ~ .'"'
.. ' :.
: ~
5~
(eluant: diethyl ether/hexane 1:5) to obtain pure l-(p-
phenoxy)-phenoxy-3-methyl-3-methoxypentane;
n20 : 1.5440.
Example 4
An amount of 22 g of 1,3-dichloropropene was added
dropwise at 55C within 30 minutes, with stirring, to
the mixture of 28 g of 4-hydroxydiphenyl ether, 150 ml
of acetone, 26.6 g of anhydrous pulverised potassium
carbonate and 50 ml of hexamethylphosphoric acid
triamide, and the mixture held for a further 18 hours
lQ at the reflux temperature. The reaction mixture was
subsequently poured on ca. 1.5 litres of ice water, and
repeatedly extracted with diethyl ether. The combined
ether solutions were washed ~our times with 10% potassium
hydroxide solution and repeatedly, to obtain a neutral
~ reaction, with saturated sodium chloride solution. After
drying of the ether soIution over sodium sulphate, the
solvent was fully removed in vacuo to obtain pure 3-(p-
; phenoxy)-phenoxy-l-chloro-l-propene; n20 ~ 819.
Example~5 . .
13.2 g of 5-(p-phenoxy)-phenoxy-3-methyl-3-penten~l-ine
~(produced rom 4-hydroxydiphenyl ether and 1-bromo-3-methyL-
~2-penten-1-ine in the presence of po~assium carbonate
in acetone;~nD20 : 1.5814) was taken up in 140 ml of 95%
ethanol; and hydrogenated, at low-pressure and at room
temperature; with 1.3 g of Lindlar catalyst~ with addition
- 39 - -
.
.:
,,...... :
~o~s~
of 0.5 g of quinoline, until hydrogerl absorption ceased.
In subsequent processing, the catalyst was filtered off,
the ethanol distilled off from the filtrate, the
residue taken up in ether/hexane (1:2), and this solution
firstly repeatedly washed with :ice-cold N-hydrochloric
acid, and finally with water until neutral. After
drying of the ether solution over sodium sulphate, the
solvent was completely removed, and the oily 5 (p-
phenoxy)-phenoxy-3-methyl-1,3-pentadiene further purified
by chromatography on silica gel (eluant: ether/hexane 1:4);
n20 : 1.5710.
Exam~le 6
6.3 g of 90% pulverised potassium hydroxide was added
in portions at ca. 10C to the solution of 18.6 g of
4-hydroxydiphenyl ether in 125 ml of dimethylsulphoxide,
and dissolved. To this solution there was then added
dropwise within 3 hours at 10-15C, with stirring, : `:
17.~ g of 1-bromo-4-methyl-3-hexene. After addition of
the halide, stirring was continued for a further 20
hours~at room temperature. In subsequent processing, the
reaction mixture was poured into ca. 1 litre of ice water, ,-
~and the mixture repeatedly extracted with diethyl ether.
The combined ether phases were washed twice with water,
four times with~20% aqueous potassium hydroxide solution,
~and~finally again with water, until neutral. After drying
of the ethér phase over sodium sulphate, the solvent was
~ - 40 - ~;
,
: , ' . '
. ':
: . ;
~4S~44 -
distilled of~, and the oil-lilce product remaining further
purified ~y chromatography on silica gel (eluant:
ether/hexane 1:5) to obtain pure l-(p-phenoxy)-phenoxy-
4-methyl-3~hexene; n20 : 1.5580.
The ~ollowing compounds are produced in a manner
analogous to that described in Examples 1 to 6:
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, ., . ;., ., .. , .. ., ., ".. . . ,. , , ., , ~ . ;; ; , ., -,
. . ... ,, ~;. , . . . ., .. .. . . .. ~. . ,.~.- ,, ,. .,,, .,.;.. i , .. ...... . . . ... . . . .
~45~
. . ~
Active substance ~ data . :
.,.~ ~ - .. ~ , ,.
¦ ~ O ~ 1'H3 ~ ¦
O-CH2--CH=C nD20 : 1,566~ .
~ /CH3
_ ¦ 2 ~C/ \CH ¦M.P.: 40-~lGC ¦
~ C CH -CH=C CH2-CH3 ¦ nD20 : ~,55~9 ¦
. i '~
I ~ ~ C C / 3 ~ ~
(~3 ~ - 9
: I O CH CH - 9 CH ¦ nD2C : 1~5399 ¦ ~
. .
: ~ 1,5
.
.
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.
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~L0453~4~ .
,~
Active substance data
_ _ _ . __ _ . _. , .
~ ~ 3 !~o CH2 C~=C ~ D2C : 1,5770
0 C~l CN,-CE2 CH=C\ ¦ nD20 ~ 1~5436
. CH3
9H Cll~ CH2 C\- o\ ~ D20 : 1,5413
0 CH -'H CH ¦ nD2C : 1,5453
CH3
~0 CH CH -CH=C/ 3 ¦ nD20 : 1,5581
: ~ CH3
¦ ~ ~ Lo C~l -CH - C C=CH ¦ M-P-: 45-47C ¦
: ' . .' ,':,;',',.:'
~ ~-- ... . . ~
~'.
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~045~
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ActitJe substance Phys cal :
.. . . . . ~ . . . . , _ :
CH2 CH=C M.P.: 31-~2C
0 CH2-CH- ~ ¦ M.P.: 55-57C ¦
.
¦ ~ ~ -0 CH2 C ~ ¦ M.P.: 82-84C ¦ ~
. -. .
-0 CH2 CH=CH ¦ nD-0 : 1~5887 ¦
¦ ~ ~ - CH2 C=CH2 ¦ M.P.: ~0-~2C
; ~ : ~H3 .
~' ~ _ '~ '
' ; ~ ' ,
~ : 44
~(~45~
~ _
. Active substance da-ta
. _ . _ .. _ . . _ . _ . . _ .
CH2-CH=CH-c113 ¦ M.P.: 39-41C
~ CH}-3-cH2 nD ~ ~ ;
~ ~ V/LO CH2-CH=CH2 nD20 : 1,5739
¦ ~ ~ 2 \ ¦ nD2C : 1~5364
I CH2-~H3 .:~
~ ~: ~ ~ L CIH3 CIH3 .
: ~ -aH-aH2-CH2-cH2 C-OCH3 nD20 : 1,5350
: CH ~CH
~: ~ ' ~ _ ' ~ '.
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Active substance - d ~ -
..~
. ,. '.'''
C CH2 CH2-cH2-C-CH nD20 : 1,5652
H3
O CH2-C12 1-O CH2 CHg nD20 : 1,5444
12 ~ \ {.P.: 6~1~6ac
L ~ ~ O-CE2 Cl~=CH Cl ¦ M.P,~ 35C
~: ~ cis/trans nD20 : 1,5905
: . (undercooled
; melt)
; ~ 3 .
~ ~H2-~ }OCH3 D20 : 1,545a
.. . ..
~: - 46 - :
:
~ Act ive s ubs tance - data
0~
¦ 2N5 ~ ~ ~ O CH2 CH2-C OCI3¦ nD20 : 1,53B5
CH2-CH3 ~ .
C2H ~ 13 CH2 C-=C\ nD20 : 1,5662 ~ ~;
¦ ~ ~ O CH2 CH C OH2 CH¦ b20 : 1,5475 ¦
CH3 . :
O CH CH2-CH¦ nD20 : 1,5935 ¦
CH3 :
. ~ . ._
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~1)4519~
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Active substance Pllysical :. .
data
._ .~ ~... _ .. ... _ ...
¦ ~ 3 o CH2-CE2 C CH2C113 ¦ nD20 1,5369
aH
O CE2 CH2 CN2 1 OCH3 ¦ nD20 1~53B8 ¦ ~ ~
, CH2- CH3 ~ .
3 alH3C
~-CH-CH2-aH2 aH2 1 3 nD20 : 1,5350
, ~ aH2--CH3 ; ~
: : CH-O-CH2 a nD20 : 1,5602 ~ :
: ~ . . .
~ ~ 3 s ~ 1 3:
: ~ ¦~ CE-O CH2-CI=C CH2 CH~ ¦ nD20 : 1~5~68
~: ~: : .
, ~ . . .... ~
...
: - 48 -
.
, : ~
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~045~44
-~ ~~ ~ Physical
Active su~stance data
_ .__ :
__ . .. _ . .. __
~ C~12-CH2-C-0-CH2-CH3 ~ nD : 1,5360
CH2-CH ~ ~
O-cH2-cH
2-CH3 :
,0~ F~'3 - :
C2H50 0-CH2-C~I=C-CH2-CH3
. , I
. ''~: :
~2H5 ~ CH2 CH3 nD : 1,5347
-CH2-cH=
~ : ' '`' ' . .
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,
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Ac~ive substance Physical ::
data
,, .:.
....
,
g ~ ~LO_CH2_C~Z~
OCH3 . i:
''' . "~' ',
~ ~ ~ L O-CH2-CH=C-CH2-CH3 ~ ~ ~
. .
~'
~ t ~LO-CH2-CH C~C~2-C~13
' : ' "' `:
. ;..'','
~ ~L ~ H~O-~U ~ H-C
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Inhibitory effect on larvae oE I~ cus fasciatus
Ten larvae of Dysdercus fasciatus, which were ~ - lO
days before moulting into the adult stage, were topically
treated with acetonic active-substance solutions. The ..
larvae were then kept at 28C with ~0 - 90% relative
humidity; they were fed on the shred o-~ presoaked
cottonseed. After ca. lO days, i.e. as soon as the test
insects had completed moultlng, the insects were examined
to determine the number of normal adults. The compounds
according to Examples l to 6 exhibited a high degree
of effectiveness in the above test.
'. .
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: : - 51 ~
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Inhibitory_effect in ~ as phase on the eg~s of
~_ ,.
Into one 130 ml flask with ground glass stopper were
placed 40 mg of active substance, and into another of
175 ml content 100 eggs of Spodoptera littoralis. The
two flasks were connected with a connecting memberg
and maintained at 25C.
The evaluation of the inhibitory effect was made
after 5 to 6 days.
Compounds according to Examples 1 to 6 displayed a
high degree of effectiveness in the above test.
' ' ' , . . ' ~ . ! ' '
