DE2907609A1 - NEW PYRETHROIDS, THEIR PRODUCTION AND USE - Google Patents

Description

The present invention relates to a new class of pyrethroids, especially new esters of 2,2-dimethylcyclopropanecarboxylic acids, those in the 3-position of the cyclopropyl ring are substituted by a saturated or unsaturated, polyhalogenated chain of 3 carbon atoms, and on their use as insecticides. The present invention further relates to the new, above-mentioned cyclopropanecarboxylic acids, their lower alkyl esters and processes for their preparation.

The pyrethrins (or pyrethrum), i.e. esters of chrysanthemum acid (2,2-dimethyl-3-isobutenyl-cyclopropanecarboxylic acid) with a retronolon (2-alkenyl-3-methyl-cyclopent-2-en-4-olone) are insecticides of natural origin, their properties are fast and high insecticidal activity along with low toxicity to humans and animals.

909837/0613

-Sh

i Pyrethrum, however, is light due to atmospheric influences

j decomposable, and this behavior makes pyrethrum protective

j agricultural crops unsuitable and limits its

5 Use for closed rooms. Furthermore it is cost-

j playful, partly due to the complex extra

; tion procedure and partly due to the need to use it

i to combine with suitable synergistic substances.

J ίο To overcome these problems are numerous, structurallyj

{Manufactured substances similar to pyrethrum (pyrethroids)

1 has been to the insecticidal effect and low toxicity]

\ to protect humans and animals and at the same time Mole-j

\ to obtain cools that are resistant to atmospheric agents

115 diger (see e.g. "Synthetic Pyrethroids", M. Elliot Ed.

: ACS Symposium, Series No. 42, Washingston 1977).

: Research focused on the synthesis of new derivatives

^{1 of} the 2,2-dimethylcyclopropanecarboxylic acid and analogous sub-

i2o punch as well as on the synthesis of alcohol analogs to the j

J cyclopentenolones and new groups with alcohol functions ^

: those with derivatives or analogs of 2,2-dimethyl-cyclo-?

j propanecarboxylic acid can be esterified. There are numerous

j rich, substituted in the 3-position derivatives of the 2,2-

) 25 dimethylcyclopropanecarboxylic acid. From the point of view of the stabili-!

j tat are particularly promising in the j

j 3-position contain a ß, ß-dihalovinyl group (J.Farkasj

; et al, Chem. Listy_52_, 688 (1958); M.Elliott et al, Nature

! (London) 246, 169 (1973); M.Elliott et al, J. Chem. Soc,

j30 Perkin 1, 1974 , 2470).

\ The following table 1 lists some of the synthetic pyrene

: throids with interesting properties:

909837/0613

Table 1

CH

Common name

Pyrethrin I HC

H.

All of you

" ¹ V

Resmethrin

HC

.W

Tetraznethrin HC

³ W-

H ₃ C /

C-Z

If

Reference

■ ° <J

of natural origin Schechter et al. J.A.Ci

»31IS5 (1949)

Elliott et al., Nature
(London), 213, "493 (1967

Kato et al., Agric.Biol, Chem. ^ 8, 914 (1964)

co ' cd,

Table 1 continued

Phenothrin

η σ

Fujimoto et al., Agric. V Biol. Chem., 2Z> 26Sl (1973)

Pfcrmethrin

(O O CO OO

Cypermethrin

Cl

c /

M.Elliott et al. , Nature (London) j 246 , 109 (1973) " ^C 6 ^M - Pestic.Sci., ^, 537 (1975)

M. Elliott - ACS Symposium Series n ° 42 - Wasl i 1977

De c amet h ri η

M. Elliott - ACS Sympo; sium Series n ° 42 -Wash ington 1977 ~

CD O ί £>

r

'"" 2OT76Q9

The aim of the present invention are new pyrethroids of the general formula:

^H 3 ^C / ^H 3 C

A-CH- -C-OR

If 0

(D

where A =

(X »H, F, Cl, Br · Y = Cl, Br)

CF-C = CH-, CF-C-CH, ο ι ⁱ

R = _ CH-

- Cl

R ⁷ R ⁸

CH-C = C-CH -R

(the group -CH- is attached to the J heterocyclic ring in the 2- or 3-position)

- CH-C = C-CH-R ; 2i 2t

909837/0613

whereby
R ¹ = H, CN, C s CH

2
R = 3-phenoxy, 3-benzyl, 4-allyl, 4-propargyl

3
R = H, alkyl bonded to the heterocyclic ring in the 3- or 2-position;

4th
R = (in the 4- or 5-position of the heterocyclic ring) =

Benzyl, benzoyl, phenoxy, allyl, propargyl;

,

Y = 0, S.

R ⁵ and R = alkyl C ₁ -C ₃ , or R ⁵ and R ⁶ together form an orthocondensed, aromatic, heteroaromatic or aliphatic (ge

20 saturated or unsaturated) ring; ι

R and R = (identical or different from one another) = · H, halogen, CH ₇

9
R = phenyl, vinyl, substituted vinyl, phenoxy. ;

The compounds of general formula I have a high insecticidal and acaricidal activity.

The present invention is also directed to new derivatives of 2,2-dimethyl-cyclopropanecarboxylic acid of all-30 common formula (II): HC, CH,

H,
3- ^Cs A / \ C - OR » X
CF-C-CH ₂ - Il
0 Y where: R ¹ =
A = CF • X « low
C-, Alkyl
^CF 3 X
-C = CH-, Cl, Br). (whereby = H, F, Cl, Br And Y =

909837/0613

S The compounds of general formula (II) are valuable intermediates for the synthesis of the new pyrethroids of general formula (I).

One of the processes according to the invention for the preparation of the derivatives of the general formula (II) is characterized in that a halogenated polyfluoroethane of the formula:
CF ₃ - C (X) Y ₂

(where X and Y have the meanings given for formula (I)) and then those shown in Reaction Scheme 1 Stages.

909837/0613

Scheme 1 (R, X and Y have the meaning given above)

CF ₃ -CXY ₂ + CH ₂ = CH-

) ₂ -CH ₂ -C00Rf - ^ CF ₃ -C-CH ₂ -CjH-C (CH ₃ ), -COOR '

CF ^ CX = CH-CH-C (CH,)

.Y

• (-hy)

CF, -CH = CH-CH ^ii: - -CH-COOr '^

(IV, X β H)

H, C CH

CF-C-CH ₂ -CH ^

³ (-HY)
(IV)

(-HX, X + H)

/ ^CH 3

-CF ₃ -C = CC

■ *

: h-coor ^; (in)

-CH-COOR '

(V)

CD CD -J

29O7609

1) Addition of a CF-Z-C (X) Yp compound to the double bond of an ester of 3,3-dimethyl-4-pentenoic acid in property-j called a radical reaction accelerator according to the equation:

X

2) Cyclization of the adduct thus obtained in the presence to

a base:

Base f

ff Base f \ ζ

CF- C ^ \ <y \ OWT ^ Y CF ₃ -C-CH COOR ' _(m)

³ Iy y

Y ^YX

3) Dehydrohalogenation by further treatment with a base

f \ ^ ^Base V '

CF- C - CIT COOK> CF-C (X) = CH - ^ - COOR '

³ · ² -HY ³

(II)

Depending on the conditions under which the last two reactions are carried out and on nature I of the halogen Y, stage 3) can take place in the course of stage 2) I or precede it, in accordance with the following}! Scheme:

* D S

CF "- C / Y ^ / \ OR '^ CF -C (X) = CH - / n / n OR ¹

3 ι '-HY' 3

Yi Y

so HY

-HY

CF - C ' X ^ X / \ OR ¹

909837/0613

If in the compounds of the general formula (IV) X is a halogen, the compounds according to the following can Equation subjected to further dehydrohalogenation will:

4) CF ^ -C (X) = CH S \ COOR ' ^BaSe v CF-C = C 2x_C00R «

³ -HX ' ^J

(IV) (V)

The last-mentioned reaction can optionally also be carried out together with stages 2 and 3 without isolating the compounds the general formula (IV) take place.

The starting compounds of the formula CF ₇₅ -C (X) Y ₂ are known products and can easily be prepared from halogenated, commercially available polyfluoroethanes by known rearrangement reactions. Compounds of the formula CF ₃ -C (X) Y ₂ are, for example:

20 CF ₃ -CFDr ₂

CF-CClBr 3 *

CF ₀ -CHClBr

2b -i

Suitable accelerators for the addition reaction 1) are organic peroxides such as tert-butyl peroxide, benzoyl peroxide or diacetyl peroxide, adzo derivatives such as azo-bis-isobutyronitrile, Complexes that contain transition metals and how they are formed e.g. by iron or copper salts with aliphatic Amines are formed, or redox transmission systems.

35 The reaction 1) takes place by, in the presence of a

catalytic amount of one of the above radical reactions accelerates the polyhaloethane with an ester of 3,3-diinethylpentenic acid, preferably in a molar ratio of polyhaloethane / ester above 1 at temperatures

909837/0813

290760?

between 50 and 200 C. The reaction can advantageously be carried out in an autoclave under autogenous pressure or at atmospheric pressure Pressure in an inert solvent at back

5 flow temperature can be carried out.

\ The cyclization reaction 2) takes place under the action of a

! strong base, e.g. an alkali alcoholate or

j sodium hydride, in a polar solvent and at Tempej io ratures between -20 and + 50 ⁰ G. A longer treatment with the same base or under somewhat more severe temperature conditions can be a further dehydrohalogenation according to j equation 3) and - if X stands for a halogen atom - according to

I of equation 4).

j -

I 15 "

The elimination reaction of the HY acid can also be carried out before and after the cyclization stage by the action of an inorganic Base or an acid acceptor amine

The compounds prepared by the process described above are usually ethyl or methyl esters which the corresponding acids can easily be obtained by conventional hydrolysis.

If the elimination of the HY acids and HX acids with a Inorganic base, such as sodium or potassium hydroxide, results in hydrolysis of the esterj at the same time group, so that the compounds are obtained directly in the form of the free acid by subsequent acidification.

The compounds of the formula (II) can also be prepared by a further process according to the invention, the first stage of which is the addition of a compound of the formula CF ^ -CXY ₂ to an ester of 2-alkoxycarbonyl-3,3-dimethyl-

35 4-pentenoic acid of the formula:

CH ₀ = CH-C (CH,) -p-CH-COOR ¹

COOR ¹

is what, depending on the 3-position of the Cyclopropylringes desired substituent A different-

909837/0613

is borrowed procedure. The starting compound, i.e. the 2-alkoxycarbonyl-3,3-dimethyl-4-pentenoic acid ester, is easily obtained by reacting 3-chloro-3-methyl-butene (1) and a malonic ester (see BeIg. PS 851 524).

The following scheme summarizes the process steps that result from this second process to the compounds the general formula (II) lead.

909837/0613

Scheme 2 (R ¹ , X and Y have the meaning given above)

(D

CF, -CXY _o + CH ₉ - = CH-C (CH-) _o -CH (C00R). CF ₃ -CXY-CH ₂ -CHY-C (CH ₃ J ₂ -CH (COOR) ₂ (B)

C 2 λ /

V -HY

CF ₃ -CXY-CH ₂ - CH

C-COOR ¹ (C)
COOR '

H.

CF ₃ -CX = CH-CH ^ ΊΕ - COOR ¹ (D)

COOR ¹ -CO

1

CH

-HX + H.

CF ₃ -CXY-CH ₂ -CH

> H-COOR '(III)

CF ₃ -CHY-CH ₂ -I I C-COOR (F)
COOR ¹

(IV)

(E) (6) J-HY

Scheme 2 (continued)

(8th)

CO,

(4ψ-

-HX H ^ C CH,

CO O CO 00

CF ₃ -CX = CH-

(IV)

^ H-

CF. COOR ^r

^ -C ^ C-CH- ¹ CC

COOR '

oor '

(8) / -CO ₂

CF-C HC-CH

Ή-COOR '

(V)

(F)

(6)

+ H

-HY

, CH,

(8th)

C-COOR '

COOi ^

-COo

(G)

■ V

(ir)

CH-COOR ¹

CJD O - «J

The various stages summarized in scheme 2) take place in detail:
Reaction 1 (scheme 2)

Reaction 1 takes place in the presence of a radical reaction accelerator, for example organic peroxides, such as tert-butyl peroxide, benzoyl peroxide or diacetyl peroxide; Azo {derivatives, such as azo-bis-isobutyronitrile, complexes, the salts! of transition metals, such as those formed by iron or copper salts with aliphatic amines,! or redox transmission systems. Reaction 1 takes place by adding a polyhaloethane in the presence of catalytic amounts of one of the radical reaction accelerators mentioned. j of formula CF ₃ -CXY ₂ 3,3-dimethyl-4-pentenoic acid with an ester of 2-Alkoxycarbonylj 15, preferably reacted in a molar ratio of Polyhalogenäthan / ester over 1 at temperatures between 50 and 200 ⁰ C. The reaction is expediently carried out in an autoclave under autogenous pressure or under atmospheric pressure in an inert solvent -20 at reflux temperature.

X reaction 2 (scheme 2)

: It is carried out by treating the 1 (B) obtained \ adduct with one equivalent of an alkaline base (NaHCO-, J Na ₂ CO _3, K ₂ CO ₃ Jj KOH, NaOH, C ₂ H ₅ ONa!) In an organic in reaction \ Solvent. The diester of 1,1-cyclopropanedicarboxylic acid (C) is thus obtained in Scheme 2. Starting from compound (C) one can proceed in various ways: around the polyhalogenated chain in the 3-position of the cyclopropyl; to modify the ring and to carry out the decarboxylation

to lead.

909837/0613

■ reaction 3 (scheme 2)

: The cyclopropane derivative obtained in stage 2 is

I treatment with one equivalent of an alkaline base, pre-

'\ 5 preferably a sodium, dehydrohalogenation. Optional

j se one can also obtain the same intermediate product by adding

1 one starts directly from the adduct described in step 1,

: by treatment with two equivalents of an alkali

i lischen base. This gives the cyclopropanedicarboxylate (D).

\ Reaction 4 (Scheme 2)

I The compound (D) (if X = Cl, Br) is obtained by treatment with!

\ an excess base, preferably an alkali j

\ alcoholate, or by NaNH ₉ in an organic solution \

1 15 medium further dehydrohalogenation and supplies the intermediate j

? Products). j

i reaction 5 (Scheme 2)

The cyclopropanedicarboxylate (C) is by the action of

! 20 zinc powder in hydrochloric acid, acetic acid or methyl

I or ethyl alcohol to form the intermediate (F)

\ hydrogenated. This reaction takes place when X = Cl, Br and leads

j to introduce a hydrogen atom instead of a halo

(genatoms (X = H).

\ Reaction 6 (Scheme 2)

; The intermediate (F) is made under the same conditions as

I reaction 3 dehydrohalogenates and provides the intermediate; product (G) that can also be obtained by catalytic hydrogenation ^? 3o (reaction 7, scheme 2) of the triple bond of the chain in i 3-position of the cyclopropyl ring of intermediate (E) i can be obtained. The catalytic system used in reaction 7 can be any conventional system for the selective reduction of the triple bond to a double bond, such as:

j 35 hydrogen on poisoned palladium catalyst;

: Na / liquid NH,

j Hydroboration with subsequent hydrolysis using an \ aliphatic acid (Tetrahedron 1977, 33, page 1845).

909837/0613

: With the reactions described so far, one obtains Cyclo- j

j propanedicarboxylate (C, D, E, F and G), which were already mentioned in J.

I 3-position the polyhalogenxerted chains according to the J.

1 5 different meanings of the substituent A of formula (i)

: contain. These are obtained by decarboxylation

ι (reaction 8) the compounds of formula (II).

: Reaction 8 (Scheme 2) j

In the intermediate products (C, D, E, F and G) are under a}

= decarboxylated under the following conditions: J

\ 8a) Total or partial hydrolysis with acids or alkalis in

\ Alcohol with subsequent heating of the appropriate

? Acids in neutral or basic organic solutions

s 15 average to temperatures between 100 and 250 ° C. i

I 8b) hydrolysis as in 8a) with subsequent heating in j

j quinoline in the presence of copper to temperatures ί

[between 100 and 250 ⁰ C. |

] 8c) heating in an aprotic, polar solvent, J

(20 like dimethyl sulfoxide, in the presence of an alkali \

} halides or -cyanides and stoichiometric J

j amounts of water (2 equivalents).

I This is how the compounds of the general formula (II) were obtained

j 25 in the form of the carboxylic acids (R = H), from which one given- I

j if the corresponding esters are obtained by conventional esterification

can be produced, or in the form of the esters from which one can produce

<if necessary, the corresponding acids using conventional

I can produce hydrolysis. j

J30 j

! The reactions are summarized in Table 2 below

j, which, according to the procedure of Scheme 2, to the various

: lead to compounds of general formula (II).

909837/0613

Table 2 Reactions for the preparation of the compounds of the formula:

A - CH CH - COOR ¹

I (R ¹ = H, lower alkyl)

; Substitucnt A reactions

; CF ₃ -c_, c-1-2-3-4-S

: CF ₃ -ex = CH-1-2-3-8

p5 CF ₃ - CH = CH - Jl - 2 - 5 - Ö - 8

: ^{(X = H)} | i_2 ~ 3--4-7 ~ 8

; CF ₃ - _CXY _ _CH2 ! - ₂ _

j According to the method described above in the following table were J compounds of the general \ 3 listed my formula (II) are prepared:

909837 / 0S13

Table of compounds of the general formula (II)

Connection formula Labelling Ms ( ^a ) a CF ₀ -CF = CH-CH ^ - CH-COOC-H ₁ .
ο £ 5 ^(C li ^H l4 ^P 4 ° 2 ⁾ 254 (m £, 1.68 $ O 209 (M] J] -CH ^ CH ₂ O) 18l (M ⁺ -Co8c ₂ H5,
100 ^) b 3 ^ V ^ 3
CF ₀ -CFBr-CH ₀ -CH -— CH-COOC.H Ms ( ^a)
(C ll ^H l5 ^F 4 ^Br0 2 ⁾ 334-336 (Mto, 16} i, 0.2456]
289-291 (M-CH ₃ CH ₂ O)
2 55 (Mt-Br)
247,249,227,209) ^H 3 ^C \ _C / ^CH 3 I C CF -CF = CH-CH ^ - ^ CH-COOH n ^2O = 1.4l8O
D '

CD -J CD

d e ^H 3 \ / "3
CF -CBr = CH-CH- ^ CH-COOC H
3 ^Δ -5 MS ^U)
(C ₁₁ H ₁₄ F ₃ BrO ₂ )
3ΐ4-31ό (Μ + 0.15 ^, 0. L6iS)
269-271 (M ⁺ -CH ₃ CH ₂ O)
241-243 (M ⁺ -COOC ₂ H ₅ )
235 (M ⁺ -Br)
207 (M ⁺ -CH Br)
2 4 f 3 \ y 3
C.
CF -CBr ₇ CH ₅ CH -i-CH-COOC H MS ^(a ^
(C ₁₁ H ₁ -F ₃ Br ₂ O ₂ )
394-390-398 (M ⁺ , 3, 4 ^, S, 95S, 3.456)
313-315 (M ⁺ -Br)
314-316 (M ⁺ -HBr) H ^ C _X CH
3 κ / 3
CF ^ -C = C ^^^^ ^ H _B
h 'COOCH ₀ CH ₀
(trans isomer) MS ^(a )
(C ₁₁ H ₁₃ F ₃ O ₂ ) 234 (Μ ⁺ , Ο.15 £)
206 (M ⁺ -C ₂ H ₄ )
189 (M ⁺ -CH ₃ CH ₂ O)
161 (M ⁺ -COOC ₂ H ₅ )
141 (M ⁺ -C ₃ F ₃ )
NMR ^(C) (ςζ ', ppm)
1.23 (t, 3H, CH ₃ -CH,)
1.3 (6H, geminal "methyl groups;
l, 7-2, l (m, 2H, H _A + H _B )
4.1 (q, 2H, CH ₂ -CH ₃ )

α »ο Φ ω

H C CH C. NMR ^(C. ( 6> ppm) 3 \ 1.2-1 , 4 (9H, geminal methyl groups) S. CF-CCl = CH-CH ^
ο CA tind CH ₃ -CH ₂ ) 1.5-2 .8 (2H, H _A + H _B ) 4.06- 4, l2 (q , 2H, CH3-CH ₂ ) 5.5-7 (1H, H _C ^} NMR ^{(C. }} (S, ppm) - CHb-COOC ₂ H ₅ 1.28 (t, 3H, CH ₃ -CH ₂ ) H CF-C ^ C-CHf-
3 ^A 1.3-1 .45 (6H , geminal methyl groups) 1.7-2 , I5 (m, 2H, H _A + H _B ) 4.15 (q, 2H, CH ₂ -CH ₃ ) 2250 (C = C) 1320 (C = O)

ο
Φ
α »

^H D _V / ^H C
^N C = CH ₀ C CH. (c) , c
NMR (Ö > PP ^m ) _mp (^ = 49-5O ° C i CF ^ \ ³ ) XT ³ 1.2 8 (t, 3H, CH ₃ -CH ₂ ) 1 _f 2 4 (6H, geminal methyl groups) / ' COOCH ₀ -CH. l, 65 (d, lH, H _B ) H _A 2 3 2.4 (m, lH, H _A ) 4.15 (q _i 2H, CH ₂ -CH ₃ ) (trans isomer) 5.75 (m, 2H, H _c + H _D ) J (Ha-Hb) - ^{s HZ} J (h _a -h _c ) = 9 HZ J (CH ₂ -CH ₃ ) = 7 Hz / "19F NMR ^(e) 59.5 (d _i 3F ₃ CF ₃ ) 1650 (C = C), no bands at 2260 (C = C) ^H 3 ^C \ _C / ^CH 3 3 CF -CH = CH-CH ^ ^ CH-COOH
3

k CF -CHCl-CH ₂ -CH ^ - ^ - CH -COOCH ₂ -CH (c) _r
NMR (Q, ppm)
1.2 (m, 9H, geminal methyl groups +
CH ₃ -CH ₂ )
1.7-2.7 (m, 2H, H _A + H _B )
1.5-2.2 (m, 2H _s CH ₂ -CHCl) 1 J ^ - - ^. HOOCH ₂ -CH '
^H AV NMR ^(c) (rT _jP pm)
1.25 (t, 3H, CH ₃ -CH ₂ )
1.3 (s ^ 6H, geminal methyl groups)
2.15 (d, d, lH, H _A )
4.15 (q, 2H, CH ₂ -CH ₃ )
6 (m, 2H, H _c + H _D )
³ ₃ <V » _B ' ^{= 5 Hz}
/ ptl / - * U \ *
y LII. "-V / Π J
j Qj
rip ³ = 1.4206

1907609

! In Table 3 above:

: (a) MS = mass spectrum data; only the main ions would

j specified

i 5 (b) R.I. = refractive index

J (c) NMR = ¹ H NMR data; the NMR spectrum was

! use of CDCl as a solvent and TMS as

j internal standard

s = singlet, d = duplet, t = triplet, q. = Quartet, ■ ίο πι- »multiplet; J = coupling constant

i (d) IR = IR spectrum data; only the significant-1 bands were listed

I (e) ¹ ^ F NMR spectra were recorded with DCDCl, as solvent ■ and CFCl ^ as internal standard;

116 d = dowel

■ _: (f) = the melting point has not been corrected

The pyrethroids of the general formula (i) are easily obtained

1 by the usual methods of organic chemistry from the

! 20 Cyclopropanecarboxylic acids and esters of the general formula

j (II). For example, the acids and esters of the general

j Formula (II) converted into the corresponding acyl halides

! and then with an alcohol of the formula

I R-OH (R = the meaning given for formula (I))

ί 25 put, making the connections of the general

j formula (I) is obtained.

\ The special structure of the acids and esters of the general I formula (II) allows the existence of various geometric:

; ³⁰ and configurational isomer due to the following j factors:

ί - asymmetric nature of the carbon atoms 1 and 3 of the cyclopropyl

; ringes (enantiomers);

j - relative spatial arrangement of the COOR ¹ group and the Substi-I ³⁵ A tuenten respect to the given through the cyclopropyl ring

j level (ice or trans);

= - cis or trans isomerism of the on the double bond

f essential substituents when A = CF ^ -C = CH-.

909837/0613

The separation of the various isomer mixtures into the corresponding Stereoisomers and their enantiomers are obtained by conventional methods, e.g., chromatography or precipitation of the salts with any active bases. The present invention also includes isolation and Use of all steric and / or configurational isomers from a prepared by the process described Mixture of compounds of the formula (II) as well as

ίο the use of the mixes themselves and the through part or complete separation of materials obtained in stereoisomers for the synthesis of the compounds of general Formula (i).

Due to the presence of asymmetric centers, and the possibility of a cis-trans isomerism the new I pyrethroids of the general formula (I) may be present as mixtures of isomers and j. A special characteristic of these mixtures is the fact that the separation of the components - J.

so th by simple chemical processes, such as column or S Thin layer chromatography, can be done. I.

The present invention also encompasses the isolation and use of the steric or configurational isomers as well as the direct use of the mixed mixtures obtained by the synthesis or an incomplete separation of the isomers as insecticides.

In addition to a very high activity against insects, most harmful in agricultural or private areas Species such as Hemiptera, Lepidoptera, Coleoptera, Diptera and Blattoids show the compounds according to the invention of formula (i) also have a satisfactory acaricidal activity well above that of most known Pyrethroids lies.

909837/0613

The compounds of the invention are particularly valuable because of their high insecticidal activity along with very low acute toxicity, as can be seen from data 5 of Table 4 (which also compares with two known synthetic pyrethroids). Reference is also made to Example 30.

The pyrethroids according to the invention also show, as in Beiio game 31 shows the necessary, good resistance.

The following examples illustrate the present invention.

example 1
! 15 Preparation of 3,3-dimethyl-4,6-dibromo-6,7,7,7-tetra-; fluoroheptanoic acid ethyl ester (intermediate)

j In a 200 ccm autoclave under a nitrogen

j atmosphere 17 g of the ethyl ester of 3,3-dimethyl-3-pentene

Uo acid (0.105 mol), 55 g 1,1,1,2-tetrafluorodibromoethane

\ (0.21 mol) and 0.5 ecm of tert-butyl peroxide introduced.

j The autoclave was then immersed in an oil bath and 5

Mechanically shaken at 120 ^{° C. for hours.} After cooling, the contents of 100 ecm CHgClg were diluted, the solution I was washed 3 times with 50 ecm water each containing small amounts of FeSO ^ 1, dried _{with anhydrous CaCl 2 and!} the solvent evaporated in vacuo. So you got

43.3 g of crude product, which was distilled under vacuum and .30 a fraction boiling between 97 and 99 ° C / 0.25 mm Hg delivered. In this way 39 g of ethyl 3,3-diraethyl-4,6-dibromi 6,7,7,7-tetrafluoroheptanoate were obtained.

Elemental analysis:

ber .: Br 38.41 %
; 35 found: Br 37.83 %

909837/0613

Example 2

Production of the ethyl ester of 2,2-dimethyl-3- (ß-fluoro-ßtrifluoromethylvinyl) -cyclopropanecarboxylic acid and the free acid

A solution of 25 g (0.06 mol) of the ethyl 3,3-dimethyl-4 ₁ 6-dibromo-6,7,7,7-tetrafluoroheptanoate obtained in Example 1 in 50 ecm of ethanol was added at a temperature between 23 and 32 ° C with stirring 0.132 mol of a sodium ethylate solution in 150 ecm of ethanol was added.

After the addition was complete, the resulting solution was kept at room temperature for 3 hours. Of the solution, 50 ecm, which were concentrated in a small volume. Then the solution obtained was poured into ice water. poured with 50 ecm CHpCIp extracted and the organic Phase washed with water until neutral pH. Then it was dried with anhydrous CaClp and that

20 Solvent removed under vacuum.

! This gave 3.6 g of crude product which, according to gas chromatography together with mass spectrometry, predominantly consists of the ethyl ester of 2,2-dimethyl-3- (ß-fluoro-ß-trifluoromethylvinyl) cyclopropanecarboxylic acid (compound a of Table 3), the can be isolated from the crude product by column chromatography, and the ethyl ester of 2,2-dimethyl-3 ~ (ßbr om-ß, ^ *, ^ -, ^ - tetrafluoropropyl) -cyclopropanecarboxylic acid (about 20 % of the crude product) consisted ( Compound b of Table 3).

The remaining part of the ethanol solution, of which the 50 ecm were removed, was treated with 6 g of 85% KOH in 30 ecm of ethanol.

SQ9837 / 0613

; The reaction mixture was then refluxed for 2 hours in order to hydrolyze the ester and to terminate the dehydrobromination of the β-bromo-β, Ϋ ", !"',Γ'-tetrafluoropropyl group. The reaction mixture was concentrated on a small flower and poured into ice water; then the mixture was _{acidified with dilute H 2} SO ^, extracted 3 times with 50 ecm CH ₂ Cl ₂ each time and the organic phase was extracted 2 times with 100 ecm each

; an aqueous NaCl solution and washed over anhydrous ίο CaCl ^ dried. The solvent was removed under vacuum

^; removed and delivered as 8 g of 2,2-dimethyl-3- (ß-fluoro-.beta.-trifluormethylvinylj-cyclopropane carboxylic acid of a viscous form, straw-yellow oil (Compound c of Table 3). In Game 3

, 15 Preparation of the 3,3-dimethyl-4,6,6-tribromo-7 _} 7,7-trifluoroheptanoic acid ethyl ester (intermediate)

j In a 200 ecm autoclave under a nitrogen atmosphere 13 g of the ethyl ester of 3,3-dimethyl-4-pentenoic acid (0.083 moles), 53 grams of 1,1, i-trifluoro-2,2,2-tribromoethane

so (0.166 mol) and 0.5 ecm of tert-butyl peroxide introduced.

Then the autoclave was placed in an oil bath and 5 hours; Shaken mechanically at 120 ^° C. and at 130 ^{° C. for 1 hour.} After cooling, the contents with 100 cc ■ methylene chloride was diluted, the solution was ecm 3 times with 50: containing water, the small amounts of Fe (SO ^) _2, washed \ and dried over anhydrous CaCl. ₂ After evaporation of the solvent, the crude product was distilled under vacuum and yielded a fraction with a boiling point _Q 4 K _n J _1n 117-118 ° b,

30 from 31.3 g of 3,3-dimethyl-4,6,6-tribromo-7,7,7-trifluoroheptanoic acid ethyl ester duration.

Elemental analysis:
] ber .: Br. 50.26 %
• found: Br 48.57 %

909837/0613

1907609

^: Example 4

To a solution of 4.7 g of the I 3 »3-dimethyl-4,6,6-tribromo-7,7,7-trifluoroheptanoic acid ethyl 'prepared in Example 3 5 esters in 10 ecm ethanol became a solution with stirring ; added from 0.022 mol of sodium ethylate in 60 ecm of ethanol,

the temperature was kept between 19 and 23 ° C. ^: The obtained solution was left at room temperature for 3 hours

held until the gas-chromatic control was complete! ho indicated the disappearance of the initial ester.

ξ Then the solution was concentrated to a small volume: poured into ice water and extracted 3 times with 40 ecm CHpCIp each time. The organic solution became neutral with water. Wash 16 and dry over anhydrous CaCl ₂ . The solution j; medium was removed under vacuum to give 2.6 g as {crude product which by column chromatography in 4 Fraktio

nen was separated. Three of these analyzed by gas chromatography i and analyzed by gas chromatography together with; ? .o mass spectrometry identified fractions showed the following composition:

<Fraction I (0.3 g) = ethyl ester of 2,2-dimethyl-3- (ß-bromo- ' ß-trifluoromethylvinyl) -cyclopropane-

^: carboxylic acid (compound d from table

Us fraction II (0.5 g) = mixture of about 55 % compound d,

about 20% of bilden- the fraction III (f compound) i the fraction and about

25 % of the ethyl ester of 2,2-dimethyl

: 3- (ß, ß-dibromo- ^, f, | <-trifluoropropyl) -

• so cyclopropanecarboxylic acid (compound e

from table 3) '-

Fraction III (0.6 g) = ethyl ester of 2,2-dimethyl-3- (ß-

trifluoromethylethinyl) cyclopropanecarboxylic acid (compound f from Table i ³⁵ (trans isomer)

909837/061 $

-ttfU - -: =.

i Example 5

Preparation of the 3,3-Diinethyl-4,6,6-trichloro-7,7> 7-trifluor- ■ ethyl heptanoate (intermediate)

; In a 100 cc flask "sphere was added under Stickstoffatmo- 7.8 g of the ethyl ester of 3, 3-dimethyl-4-pentenoic acid (0.05 mol), 18.75 g 1,1,1-trifluorotrichloroethane (0 0.25 g of cuprous chloride, 3.5 ecm of ethanolamine and 50 ecm of tertiary butyl alcohol were introduced. The reaction mixture was then refluxed for 10 hours, cooled and the tertiary butyl alcohol evaporated.

• The residue diluted with 50 ecm of diethyl ether was treated ^{with dilute HCl: up to 15 to achieve an acidic pH.} The ethereal phase was washed with water, \ with NaHCO, neutralized, dried over anhydrous NapSO; net and the solvent evaporated; this gave 17 * 2 g; of an oil which after vacuum distillation 13.2 g of a frac tion J2O with a Kp. _Q 6mm ^1O5 ~ ^11O ° ^{C from} 3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluorheptansäure ethyl ester (gas-chroma-

graphical titer = 93 %) . : Eleraental analysis

Calculated: Cl 30.96 % • as found: Cl 30.36 % : The IR and NMR spectra of this product corresponded to the structure indicated.

Example 6

- Preparation of the ethyl ester of (i) -cis-trans-2,2-dimethyl- ³⁰ 3- (ß-chloro-ß-trifluoromethylvinyl) -cyclopropanecarboxylic acid i (mixture of isomers; compound g)

i To a solution of 0.06 mol of sodium ethylate in 30 ecm abs.

Ethanol was at a temperature of -20 ⁰ C a solution ³⁰ of 11 g of the intermediate prepared in Example 5; (0.03 mol) in 10 ecm of ethanol was added. The reaction mixture

was stirred for 1 hour at 0 ° C and stirred after standing ⁵ night, again for 2 hours at 50 to 60 ⁰ C.

909837/0613

; After cooling and filtering off the 3.8 g of sodium j

i chloride, the solution was poured into ice water and 3 times

! extracted with 30 ecm diethyl ether each. The organic ex-

J 5 tract was washed with water and anhydrous

\ NapSO ^ dried. After evaporation of the solvent obtained j

\ man 8.1 g of an oil that, according to gas chromatography and

\ Mass spectrometry predominantly from the isomers of

i compound g (about 83 %} and a smaller amount (about

ho 12 %) compound f existed. The IR spectrum of this mixture

\ showed the one for the double bond C = C Q = 1650 cm "), the

j triple bond C = C (^ = 2250 cm) and the C = O ester group

j (O = 1720 cm ") characteristic absorption features.

j Example 7

i15 Preparation of the ethyl ester of (i) -cis-trans-2,2-dimethyl-

- 3- (ß-trifluoromethyläthinyl) -cyclopropanecarboxylic acid (mixture

j of the isomers)

\ Put in a thoroughly dried, reflux condenser

8 g of a 25% strength sodium amide suspension in Degussa oil under 50 ecm of anhydrous benzene were introduced into the 250 cc round bottom flask, whereupon ^{the following reactants were added at 0} ° C. under a nitrogen atmosphere: 13.5 g of the ethyl ester of 2,2-dimethyl-3- (ß-chloro-! 25 ß-trifluoromethylvinylj-cyclopropanecarboxylic acid (mixture of the I isomers), 5 ecm tert-butanol and 5 ecm anhydrous benzo! The reaction mixture was cooled by means of a external ice-water bath at 15 to 20 ° C. until no further heat developed (about 1 hour). It was then kept at reflux temperature for 6 hours and, after cooling to room temperature, poured into 100 ecm of an aqueous 2N hydrogen chloride solution separated off, washed neutral with water, _{dried on anhydrous Na 2} SO ^ and filtered.Then the organic solvent was removed under vacuum and yielded 12.5 g of crude product, which on a Vigreu x column was distilled from a height of 10 cm and delivered a ^{fraction boiling at 93 to 99 0} C (35 now Hg) which consisted of the desired product (compound h in Table 3).

909837/0613

ί A comparison of the NMR data (see Table 3) for compound ! h and f show that the latter is the trans isomer.

I B eis ρ ie 1 8

■ 5 production of the ethyl ester of (-) - trans-2,2-dimethyl-3-; (ß-trifluoromethyl (Z) vinyl) -cyclopropanecarboxylic acid _(connect: i dung in Table 3) and the corresponding free acid (compound j in Table 3)

io In a 500 cc round bottom flask were under a nitrogen

atmosphere 11.5 g of the ethyl ester of 2,2-dimethyl-3- (ß- ^! trifluoromethyläthinyl) -cyclopropanecarboxylic acid (compound f) 200 ecm η-hexane and 2 g palladium on calcium carbonate (Pd / CaCO ^) (poisoned with lead) and according to Urg.Synthesis, Coll is Vol. V, 880, John Wiley & Sons, 1973). The flask was connected to a hydrogenation device and its contents were vigorously stirred for several hours until no further one

More hydrogen was absorbed. Then the reaction; mixture filtered on Celite and the solvent evaporated; 2ü; so there was obtained 10.5 g of crude product which was distilled under vermin- \ dertem pressure. The fraction collected at 88 C / 16 mm Hg i was found to be compound i according to analysis by IR and ί NMR spectroscopy (purity ^ 90 % according to; gas-liquid chromatography).

To 7 g of the compound i, 4 g of KOH (85 % concentration) and 50 ecm of 95% ethanol were added and the ^! Heated to reflux. Then, the size of part of the solvent was 'evaporated by, and 50 cc of water, and the obtained mixture to 30 10 g of an aqueous 1: 1 sulfuric acid' solution was added, followed by extraction with methylene ^chloride: was. The organic phase was _{dried over anhydrous Na 2} SO ^ ' and filtered. After removal of the solvent \ in vacuo gave 5.9 g of an oil which after stallisation Umkri-3b from n-pentane, the compound j as a white solid: fabric (F. 49-50 ⁰ C.) afforded.

909837/0613

- 1907609

Example 9

Preparation of the ethyl ester of 2,2-dimethyl-3- (2-chloro-3,3,3-trifluoropropylJ-cyclopropanecarboxylic acid 1

j a nitrogen atmosphere, 15.6 g (0.1 mol) of the ethyl ester j of 3,3-dimethyl-4-pentenoic acid In a tube made of Pyrex glass for pressure responses under \, 59.2 g (0.3 mole) of 1 , 1,1-tri- j fluorochlorobromoethane, 3 ecm ethanolamine and 0.6 g CuCl j

ίο introduced. The glass tube was closed with a flame! and shaken to achieve a homogeneous mixture. Then it was placed in an autoclave with water on it contained about 2/3 of its volume. The autoclave was closed and heated to 120 to 140 ° C. for 20 hours. After this!

The glass tube was opened to cool and the excess 1,1,1-trifluorochlorobromoethane was distilled off in vacuo. The residue was collected with diethyl ether, washed neutral with a 2N hydrogen chloride solution and then with water and filtered. The organic phase was _{dried over anhydrous Na 2} SO / and the solvent was removed in vacuo. The residue was distilled under reduced pressure and yielded 20 g of a fraction which boiled at 70 to 75 ° C. (0.06 mm Hg) and which was obtained from the ethyl ester of 3,3-di-jraethyl- ^ bromo-ö-chloro-y ^ y-trifluoroheptanoic acid consisted of. I (n _D = 1.4415; elemental analysis, IR and NMR spectra correspond to the assumed structure). j

10 g of this intermediate were in 10 ecm abs. Ethanol dissolved and the resulting solution at room temperature to a solution of sodium ethylate (prepared by dissolving ί of 1.5 g of sodium in 55 ecm abs. Ethanol) added. Then j

; the reaction mixture was refluxed for 1.5 hours!

; the solvent was removed in vacuo and 100 ecm of water were added to the residue. The organic one

; ₃ 5 material was extracted 3 times with 75 cm diethyl ether each time.

; The organic phase was washed neutral with water, _{dried over anhydrous Na 2} SO ^ and the solvent was evaporated off under vacuum. 6.3 g of the ethyl ester were obtained in this way

909837/0613

- 29Q76Q9

2,2-Dimethyl-3- (2-chloro-3,3,3-trifluoropropyl) -cyclopropanecarboxylic acid as a mixture of the cis, trans isomers (approx. 1: 1; Compound k in Table 3).

5 Example 10

^; Production of the ethyl ester of (+) - cis, trans-2,2-dimethyl-3- (i3-trifluoromethyl-E-vinyl) -cyclopropanecarboxylic acid

: 2.5 g CpH ^ ONa were at -15 ⁰ C in 80 cc of dimethylformamide

¹⁰ dissolved and to this solution a solution of 6.3 g of the ethyl

) esters of (+) - cis, trans-2,2-dimethyl-3- (2-chloro-3,3,3-trifluoropropyl ^ cyclopropanecarboxylic acid in 20 ecm dimethylform

j amide added. The reaction mixture slowly became from

■ warmed -15 ° C to ⁰ ° C within 3 hours, then 100 cc of water were added ^{lu 0} C at O, the organic material

; was extracted 3 times with 100 ecm diethyl ether and the

organic solution then washed neutral with water, dried with '■ anhydrous CaCl ₂ and the solvent under

■ Vacuum removed. In this way 5 g of the ethyl ester were obtained

'< 20 (+) - cis, trans-2,2-dimethyl-3- (ß-trifluoromethyl-E-vinyl) - ^: cyclopropanecarboxylic acid as a mixture of the cis, trans isomers in a ratio of about 1: 1 (compound 1 in Table 3).

The same reaction was carried out at ⁰ ° C. for 15 hours. A product was thus obtained which consisted of about 90% of the trans isomer, demonstrated by the disappearance of the signal at 1.85 ppm corresponding to the proton Hg of the cis isomer in the NMR spectrum (cf. Table 3).

Example 1_1_

130 Production of CF ^ -CFBr-CHp-CHBr-C (CH -,) P-CH (CO ₉ C ₅ Hp ₁ ) _o

In a 250cc car equipped with a shaker

Hastelloy C claves were placed under a nitrogen atmosphere, 208 g of CF ₃ -CFBr ₂ (0.8 mol), 91.2 g (0.4 mol) of ^3S CH ₂ = CH-C (CE ₅ ^ -CH (CO ₂ Et) ₂ and 6 ecm di-tert-butyl peroxide

introduced. The autoclave was heated to 140 ° C. and 2; Held at this temperature for hours. After cooling, the contents were taken out, the excess CF ₃ -CFBr ₂ was evaporated, then the contents of the autoclave became

909837/0613

M- - - · ■■ - ^: ■

subjected to a molecular distillation and delivered a fraction with a b.p. of 90? C (10 ~ ^ mm Hg), which from

120 g of ethyl (i, 1-dimethyl-2,4-dibromo-4,5,5,5-tetrafluoro) pentyl malonate; n _ß = 1.4513. The IR analysis corresponded to that

adopted structure.

Elemental analysis:

calc .: C 34.5 H 4.1 F 15.6 Br 32.8 %

obtained .: C 34.9 H 4.2 F 15.4 Br 31.9 % ίο Example 12.

Manufacture of CH CH

³ ^ ³

CF-CFBr-CH-CH C -CO C H j

3 2 j II 5 UJ ₁ (J _from j

CH, CH, ^CO 2 ^C 2 ^H 5 I.

³ V ^ ³ f

CF -CF = CH-CH-C-CO C H

^C0 2 ^C 2 ^B S

48.8 g (0.1 mol) of ethyl (1,1-dimethyl-2,4-dibromo-4,5,5,5-tetrafluoro) pentylmalonate (prepared as in Example 11) in 100 ecm anhydrous ethanol were added with stirring an ethanolic sodium ethylate solution (made from 2.4 g sodium and 100 ecm anhydrous ethanol) is added dropwise. When the addition was complete, a sample was taken from the mixture; according to the gas mass analysis, the cyclization was already completely finished and delivered the connection:

³⁰ CF, -CFBr-CH., - CH-C - CO CH _r

3 ^Δ ι 2 2 5

CO ₂ C ₂ H ₅

909837/0813

-νβ-

Mass division:

(CHF DrO ) : 4O6 (M) ^ 14 19 4 4

3,27 (M ⁺ -Br) 361 (M ⁺ -C ₂ H ₅ O); 213 (M ⁺ -C ₃ F ₄ BrH ₂ )

; 315

; 185

"5 167

\ 43

i At this point a further amount of sodium ethylate was added to : Ethanol (equal to the previous amount) was added, then the reaction mixture was stirred at 40 ° C. for 5 hours.

; After neutralization with 1: 1 HCl and subsequent filtration; Then the solution was concentrated to a small volume; there were added 200 cc of water was added, then 2 times, extracted with 150 cc of CHCl 2s. The chloroform extract was dried on CaClo and evaporated and yielded 31.4 g of the diethyl ester of 2,2-dimethyl-3- (i3-fluoro-β-trifluoromethylvinyl) -cyclopropane-1,1-dicarboxylic acid; n ^ = 1.4303

^ 3 I.

CF ₃ -CF = CH-CH-C-CO ₂ C ₂ H ₅ j

909837/0613

Division of the lakes:

: ⁵ (C HF O): 326 (M ⁺ ) 14 Io 4 4

- 281 (M ⁺ -CHO)

2

253 ( ^{M +} - ^C 3 ^H 5 ° 2 ⁾

nor ί OCI Π Τϊ ^

235 207

- 179

167; l6o

1 ¹¹⁵

j Example 13

I 3χ "

ϊ Making CF-CF = CH-CIi-CH-CO ₀ C ₀ H.

\ ο 2, λ

j In an immersed in an oil bath, equipped with a reflux condenser ; The flasks seen became 5 g under a nitrogen atmosphere I of the compound prepared in Example 12

CF -CF = CH-CH-C-CO C H 3 j 2 2

1 g of NaCl, 12 ecm of dimethyl sulfoxide and 0.6 ecm of water were introduced. The reaction mixture was then ^{heated to 165 to 167 °} C. for 9 hours. After cooling down it had become noisy; Gas chromatographic analysis formed the compound with a conversion of 75 % and with a cis / trans ratio on the ring of about 1: 1.

909837/0613

Example Vi

Preparation of CF ₃ -CCI ₂ -CH ₂ -CHCl-C (CH ₃ ) ₂ -CH (CO ₂ C ₂ H ₅ ) ₂

5 In a mechanically stirred autoclave made of Hastelloy C; 23 g (0.1 mol) of j CH ₂ = CH-C (CH ₃ ) ₂ -CH (CO ₂ C ₂ H ₅ ) ₂ , 82.5 g of CF ₃ -CCl ₃ (0.4 mol ),

0.1 g CuCl, 3.5 g ethanolamine and 115 ecm tert-butyl alcohol were introduced. The autoclave was ίο 2 hours at 100 ⁰ C and then heated for a further 7 hours at 110 ⁰ C. After cooling, the reaction mixture was filtered and, after removing the excess CF ₃ CCl _3, the solution was distilled by evaporation under reduced pressure. Thus there was obtained 20 g of a fraction having a Kp.qo rnm ^ '"^ ⁰ ^' ^ ^e is ^from ethyl- (1,1-dimethyl-2,4,4-trichloro-5,5,5-trifluoro) - pentyl malonate.

IR (neat sample): 1720 and 1740 cm " ¹ (C = O); other bands at 1460, 1362, 1300, 1255, 1227, 1205, 1175, 1040 cm" ¹
Elemental analysis:

calc .: C 40.4 H 4.8 F 13.7 Cl 25.6 % found : C 41.1 H 4.9 F 13.2 Cl 25.1 %

Example Ij?

Preparation of the m-phenoxybenzyl ester of (+) - cis, trans-25 2,2-dimethyl-3- (ß-fluoro-ß-trifluoromethylvinyl) -cyclo-

propanecarboxylic acid and partial separation of the geometric isomers

9.5 g of 2,2-dimethyl-3- (ß-fluoro-ß-trifluoromethylvinyl) - 'cyclopropanecarboxylic _{acid were converted into the acid chloride by treatment with 9.7 g of PCl 1} - in 200 ecm of CCl ^ at 23 to 24 ° C - j delt. Distillation under vacuum gave 6.2 g of acid chloride (elemental analysis: calculated: Cl 14.49%, found Cl 14.29 %). |

2.2 g of the acid chloride thus obtained were 2.2 gj 3-phenoxybenzyl alcohol in 100 cc of anhydrous benzene containing 2 cc of pyridine, esterified at 18 to 24 ⁰ C.

909837/0613

- 29Ü76Ö9

After filtration of the pyridinium salt, the solution was charged with 80 cc of an aqueous HCl solution, and then washed with water at 0 ⁰ C neutral. After drying, the solvent was evaporated off in vacuo and so gave 4.1 g of crude 3-phenoxybenzyl ester of (+) - cis, trans-2,2-dimethyl-3- (ßfluoro-ß-trifluoromethylvinylj-cyclopropanecarboxylic acid.

For partial separation of the geometric isomers, the product thus obtained was placed on a silica gel column (filler: silica gel G (type 60) from Merck and an analogous product, code 453332, from C. Erba in a weight ratio of 1: 2; column length 20 cm , Column diameter 2.4 cm; eluent: 2: 1 n-hexane / benzene at room temperature) chromatograph! How did you get the following factions?
Fraction I sample 1-A 61 g)
Fraction II sample 1-M (0.6 g)
Fraction III sample 1-B (1.2 g).

According to NMR analysis, sample 1-A consisted predominantly (at least 90%) of the isomeric 3-phenoxybenzyl ester of (+) - cis-2,2-dimethyl-3- (ß-fluoro-ß-trifluoromethyl (E) vinyl) -cyclopropanecarboxylic acid.

Sample 1-B consisted predominantly (at least 80 %) of the isomeric 3-phenoxybenzyl ester of (+) - trans-2,2-dimethylj-

3- (ß-fluoro-ß-trifluoromethyl (E) vinylJ-cyclopropanecarboxylic acid.i

Sample 1-M was found to be a mixture of the above two th isomers in a cis / trans ratio of about 1/3

The properties of these samples were as follows:

909837/0613

--SÄ-

- lrtf -

29Q76Q9

H,

j CH

j II

Compound 1-A

COO-CH ₂ -

NMR ( ö .ppm) (* '

2 (m, H _A + H _B )

6.1 (dd, H) 1.23 (s, geminal methyl groups)

5-06 (s, CH) 6.8-7.5 (m, aromatic protons) J (H, F trans) = 33 Hz J (H _c , H _A ) = 9 Hz

COO-CH ₂ -

Compound 1-B

1.7 (d, H) 2.33 (dd, H _A )

5-23 (dd, H _c )

1.16 (s, CH) ■ 1.25 (s, CH ₃ )

5.Ο5 (s, CH ,,) 6.8-7.4 (m, aromatic protons) J (H _c , H _A ) = 9 Hz

J (H _A , H _ß ) * 5 Hz

J (H, F trans) = 31 Hz

909837/0613

| 9Ο7 ~ 6Θ3 ι

* s = singlet, d = duplet, dd = duplet of a duple,!

m = multiplet; J = coupling constant 1

Example 16 \

Preparation of the 2-methyl-5-benzyl-3-furylmethyl ester of j

(+) - cis, trans-2,2-dimethyl-3- (ß-fluoro-ß-trifluoromethyl- \

vinyl) ~ cyclopropanecarboxylic acid and separation of the geometrical '

Isomers:

The above compound was obtained by the method of

Example 15 starting from 2.2 g of the chloride of 2,2-dimethyl- ^ 3- (ß-fluoro-ß ~ trifluoromethylvinyl) -cyclopropanecarboxylic acid

and 2.3 g of 2-methyl-5-benzyl-3-furylmethyl alcohol. · J

After similar work, 4.3 g of the crude 2-methyl-; 5-benzyl-3-furylmethyl ester of (+) - cis, trans-2,2-diniethyl-J 3- (ß-fluoro-ß-trifluoromethyl (E) vinylJ-cyclopropanecarboxylic acid { (NMR spectrum corresponded to the structure). !

By chromatography on a silica gel column under?

under the conditions described in Example 15, the raw!

Ester in the following two, geometric isomers to- ·

separated: ' ;

Fraction I sample 2-A (0.7 g) (cis) j

Fraction II sample 2-B (1.8 g) (trans)!

According to NMR analysis, sample 2-A was predominant (JL 90 %) \

from the isomeric 2-methyl-5-benzyl-3-furylmethyl ester of \

(+) - cis-2,2-dimethyl-3- (ß-fluoro-ß-trifluoromethyl (E) vinyl) - I.

cyclopropanecarboxylic acid. j

j Sample 2-B consisted predominantly (90 %) of the isomer j

j 2-methyl-5-benzyl-3-furylmethyl ester of (+) - trans-2,2- j

Dimethyl ~ 3- (ß-fluoro-ß-trifluoromethyl (E) vinyl) -cyclopropane-!

35 acid.

The NMR data for the above two samples were as follows:

90 9 8 37/0813

- ^; ° ύυ

^> COO- CH J! ! I

ar ^ h

Compound 2-Α

NMR ({fppm)

1f2 (s, geminal methyl groups)

1.5 + 2 (β, H _A e H ₃ ) 2.2 (s, CH ₃ -C = C) 3.8 (s, CH ₂ ) 4.75 (s, OCH ₂ ) 5.8 (s , H _D ) 6.05 (dd, H ₀ ) 7.1 (aromatic protons)

J (H _c , H _A ) = 8 Hz J (H ₀ , F) = 33 Hz

Compound 2-B

* = see above 1.15; 12.3 (s, geminal methyl groups)

1.57 (d, H _B ) 2.27 (s, CH ₃ -C = C) 2.27 (dd, H _A ) 3.8 (s, CH ₂ )

4.75 (s, OCH ₂ ) 5.2 (dd, H ₀ )

5.76 (s, H _D )

7.1 (aromatic protons)

J (H _A ,
J (Η _Λ

H _B )

5 Hz H ₀ ) = 9 Hz

J (Hp, F) = 33 Hz

9Q9837 / QS13

example

■ According to Example 1, 2,2-dimethyl-3- (ß-fluoro-ß- ! trifluoromethylvinyl) cyclopropanecarboxylic acid and o (-Cyan-3- ? 5 phenoxybenzyl alcohol the ot-cyano-3-phenoxybenzyl ester of ! (+) - ei s, trans-2,2-dimethyl-3- (ß-fluoro-ß-tri fluo rm e thylviny1)

■ cyclopropanecarboxylic acid.

The partial separation of the geometric isomers by; to chromatography on silica gel according to Example.15 resulted s the following samples:

I 3-A cis isomer, purity according to NMR> 90 % \ 3-B tr ans isomer s, purity according to NMR £ -90 % \ 3-M Mixture of isomers 3-A and 3-B in a ratio of! ie about 3: 5; Refractive index n ^ ' ⁵ = 1.5097

The IWR data of Sample 3-A and 3-B were as follows:

I FC HCH

NMR (<£ _PP ,) "

ρ Compound 3-A

²⁵ 1.8 * 2.35 (m, 2Hi ^H _A ^{+ H} _B )

■ 5-9 (dd, lHjttc)

i 1.3 '( ^s > ^6li ? geminale

Methyl groups)

6 .22 (IH, CH-CN)

6.8 * 7.5 (m, 9H, aromatic : Protons)

\ J (H. - H) »9 Hz j

ί A C ι

I J ( ^H C " ^F trans) = 31 Hz

j 35 Γ ""

ί I

909837/0613

-SG-

COO-CH (CN) -

Compound 3-B

- ^C 6 ^H 5

2.32 (dd, 1II, H _A )

1.7 (d, IH, H _B ) 5.23 (dd, IHi H _c ) 1.22 (s, 3H, CH) 1.32 (s, 3H, CII) 6.25 (d, IH, CII-CN )

6.8 * 7.5 (m, 9H, aromatic

Protons)

J (1I _A -H _B ) =

J (» _A - ^H _c ) =

C trans) = 32 Hz

example

18th

According to one example 15erhielt of ^{2,2-dimethyl-3-trifluoro: b} rnethyläthlnyl-cyclopropane carboxylic acid and e <-cyano-3-phenoxybenzylaikohol the o (-cyano-3-phenoxybenzy3.ester of (+) - trans-2, 2-Dimethyl-3-trifluoromethylätllinyl-cyc.lopropanecarboxylic acid; with the following NMR data:

NMR

Q ppm)

II

Connection 1.83-2.2 (m, 2Π, II + H)

AWAY

1 | 3 (s, 3H, CII ₃ )

1.35 (s, 3H, CH ₃ )

6.3S (s, IH, CII-CN)

6.8-7> 7 (in, 9II, aromati

cal protons)

909837/0613

-51-

- & - 29076Q9

■ Example 1J9

According to Example 1, 2,2-dimethyl-3- (β-chloro-β-; trifluoromethyivinyl) cyclopropanecarboxylic acid and 3-phenoxy were obtained > benzyl alcohol the 3-phenoxybenzyl ester of (+) - cis, trans-2,2-dimethyl-3 (ß-chloro-ß-trifluoromethylvinyl) -cyclopropane- carboxylic acid.

Partial separation of the geometric isomers by chromatography on silica gel according to Example 15 gave the following samples:

5-A cis isomer, purity according to NMR ^ 90 % 5-ß trans isomer, purity according to NMR ^ -90% 5-M Mixture of isomers 5-A and S) -B in a ratio of about 3: 7; Refractive index nf: = 1.5> 266.

The NMR data of Samples 5-A and 5-B were as follows:

Compound 5-A

_NM R

1.6-2.7 (m, 2H, H + Η)

.AU

1.22 (s, 6η, geminate methylgr.) 5.03 (s, 2H, CH ₂ J

6.7-7.5 (in, 1OH, aromatic

Protons + π) c

909837/0613

^HC CH, GH ^CF 3- "Λ V / C-- ' ^Hb Y- - \
N: oo-CH - ^H A -C (Cl) -

Compound 5-B 2,4 (dd, iii, h _a )

1.8 (d, IH, H)

I ¹ I ² I 2 doublets, IH, Hc eis ¹ (+ trans on the double bond)

1.20 (s, 3H, CH ₃ )

1.30 (s, 3H, CH ₃ ) 5.08 (s, 2H, CH)

6.8-7.5 (m, 9H, aromatics)

Ϊ25 Example 20

According to Example 15, 2,2-dimethyl-3- (ß-chloro-ß- : trifluoromethylvinyl ^ cyclopropanecarboxylic acid and iX-cyano-3-;

phenoxybenzyl alcohol the oC-cyano-3-phenoxybenzyl ester of \ ; (+) - ice, trans-2,2-dimethyl-3- (ß-chloro-ß-trifluoromethylviny1) -: 30 cyclopropanecarboxylic acid. %

\ A partial separation of the geometric isomers by chromatography on a silica gel column according to Example 15 gave the following samples: ■ 35 6-A cis isomer, purity according to NMR ^ 90 % ■ 6-B trans isomer, purity according to NMR> 90 %

6-M Mixture of isomers 6-A and 6-B in a ratio of about 3: 7; Refractive index n _n = 1.5256

909837/0613

29076Q9

The isomer mixture (E + z) -trans isolated (compound 6-C).

The NMR data of Samples 6-A, 6-B and 6-C were as follows:

H CF-C (Cl) JcH ₃ ^ H

^{Λ K xx} ° coo-ch (cnO- (o

H'

Compound 6-A

NMR

f /. ppm)

^CF

^H /

CH

egg

-C

CN

OO-CH- (O

Compound 6-B

35 1.95-2.45 (m, 211, H _A + H _ß )

13 (s, 6H, geminal methyl groups)

6.22 (s, s, IH, CH-CN

6.28 (

6.7 - 7.6 (m, 1OH, aromatic tables

Protons "+ η) c

2.4 (d, d, IH ₁ H ^ 1.8 (d, IH, H _B )

6.1 (d, IH, H _c - a single . Isomer)

1 ^ 2-1.37 (s, s, 6H, geminale

Methyl groups)

^{> 3}
6.37

i CH-CN)

6.8-7.6 (m, 9H _Λ aromatic protons)

J (H -H) - 5Hz A ο

J (H _A -H _C ) = 9 Hz

909837/0613

13Ö76Ö9

II

CF-C (Cl) =

II '

:; oo-CH-

Compound 6-C

l _r 2-1.4 (6li, geminal methyl

groups) 1.76 (d, IH, H _B )

2 _; 4 (dd, IH, H) '

{(IH, H) 6 _f O8 (d) ( ^c

6.27 (IH, CH-CN)

6.8-7 _r s5 (m, 9H, aromatic protons)

example

21st

I According to Example 15 there was obtained from 2,2-dimethyl-3- (.beta.-bromo-.beta.-trifluoromethylvinyl!) Cyclopropanecarboxylic acid and 3-phenoxy \ benzyl alcohol 3-phenoxybenzyl ester of (+) - cis, trans
; 25 2,2-Dimethy1-3- (β-bromo-β-trifluoromethylvinyl) -cyclopropane-; carboxylic acid.

A partial separation of the geometric isomers by
Chromatography on a silica gel column according to Example 15 gave the following samples:
I 7-B trans isomers, purity according to NMR ^ 90 % I 7-M mixture of the cis, trans isomers in a ratio of about 1: 1.2; n ^ = 1.5326

909837/0613

Connection 7-Β ¹⁰

2.25 (dd, IH, Η _Α ) 1.8 (d, IH, Η _Β )

5.1 (s, IH, H)

1.2 (s, 311, CH ₃ )

1.3 (s, .3ii, CH)

6.5 (d, 21!, CH ₂ )

6.8 * 7.55 (m, 9H, aromatem)

J (H _A -H _B ) - 5 Hz J (H _A -H _C ) - 9 Hz

Example 22

According to Example 15, 2,2-dimethyl-3- (β-bromo-β-trifluoromethylvinyl-cyclopropanecarboxylic acid was obtained and o (-Cyan-3-phenoxybenzyl alcohol the <X-cyano-3-phenoxybenzyl ester of (j -) - cis, trans-2,2-dimethyl-3 (ß-bromo-ß-trifluoromethylvinyl) -cyclopropanecarboxylic acid.

Partial separation of the geometric isomers by chromatography on silica gel according to Example 15 gave the following samples:

8-B trans isomers, purity according to NMR } 90% 8-M mixture of the cis, trans isomers in the ratio of

24 about 1: 1.2; Refractive index n _Q = 1.5310

909837/0613

CH

IK COO-CH (CN)

Compound 8-B

EU * (»» Ppm)

2.2-2.6 (m, IH, H _A ) 1.8 (d, IHiH ₀ )

6.4 C 211, H + CH-CN) c

1 , 2-1, 33 (m, 6H, ii

Methyl groups)

6.9-7 _? 6 (m, 9H, aromatic protons)

J (H _A -H _B ) J (H _A -H _C )

9 Hz

example

23

\ According to Example 15, (+) - trans-2,2-dimethyl-3-

\ (ß-trifluoromethyl-Z-vinylJ-cyclopropanecarboxylic acid and

j 25 3-phenoxybenzyl alcohol the 3-phenoxybenzyl ester of (+) -

; trans-2,2-dimethyl-3 (ß-trifluoromethyl-Z-vinylJ-cyclopropane-

; carboxylic acid (compound 9-B) »

C -

CF,

COOCH -

0-C ₆ H ₅

Compound 9-B

909837 ^ 0613

NMR (J, ppm)

2.45 (dd, IH ₃ H.) 1.7 Cd, -IH, H _B ) 5.65 (m, 2H, H _c + H _d )

1.23 (d, 6H, geminale

Methyl groups) to

5.1 (s, 2H, CH ₂ )

6.8-7.6 (m, 9H, aromatic Protons)

15 J (H-H) = 5Hz

AWAY

Example 24

According to Example 15, (+) - trans-2,2-dimethyl-3- (β-trifluoromethyl-Z-vinyl) -cyclopropanecarboxylic acid was obtained and Ot-cyano-3-phenoxybenzyl alcohol denotes oC-cyano-3-phenoxybenzyl-20 ester of (+) - trans-2,2-dimethyl-3- (ß-trifluoromethyl-Z-

vinyl) cyclopropanecarboxylic acid (Compound 10-B). H

^H Dv / H_C CH,

C - < ³ X

er '\ y \ y cn

^x : oo-cn-

“A

Compound 10-B

'NMR 1, 45 f Γ ν "" ■
idf PP ^m / OC, H _r Sy 7th (dd, IH, H) If 65 (d, IH, H _B ) 23 (m, 2H, H _C + H _D ) (d, 6h, geminale
Methyl groups)

35 6.3 Cs, IH, CH-CN)

6,8-7j6 (m, 8h, aromatic protons)

J Ch _a -H _b ) = 5 H ^

909837/0613

-M-

- se- - 29Ö76Ö3

Example 25

According to Example 15, the cK-cyano-3-phenoxybenzyl ester of ( +) - trans-2,2-dimethyl-3- (ß-trifluoromethyl-E-vinyl) -cyclopropanecarboxylic acid (compound 11-B); ηψ = 1.52 2 h

^H c

¹ D / Λ CN

H . COO-CH A

_u,. ,. . _T , NMR (σ, ppm)

Connection 11-B ' ^K

1.15-1.3 (OH, geminale.

Methyl groups)

■ 1.75 (d, IH, H _B )

• 2.1 (dd, IH, H _A )

5.9 (m, 211, H _C + H _D )

6.3 (s, IH, CH-CN)

7} 1 (m, 9H, aromatic ; see protons)

J (» _A -» _c ) = 9 Hz Example 26

Production of the öuCyan-3-phenoxybenzyl ester of the (+) - cis, trans-2,2-dimethyl-3- (2-chloro ~ 3,3 »3-" trifluoropropyl) -cyclo propanecarboxylic acid (compound 12)

909837 / 0S13

A solution of 3 g of (+) - cis, trans ~ 2,2-dimethyl-3- (2-chloro- j 3,3,3-trifluoropropyl / cyclopropanecarboxylic acid chloride (obtained from j th from the corresponding ethyl ester by hydrolysis and i reaction with SOCIp) in 50 ecm anhydrous benzene

with a solution of 2.9 g of oi.-cyano-3-phenoxybenzyl ^{alcohol in:} 50 ecm of anhydrous benzene. To the resulting solution \ 2 cc of pyridine were added, then the solution was 24
Maintained at room temperature for hours, neutral with water

ό washed, the organic phase was separated and dried * net and the solvent evaporated under vacuum. So

5.1 g of the desired product were obtained as a yellow vis-

24
koses 01 (refractive index np. = 1.5125; elemental analysis _.:

and IR data corresponded to the assumed structure).

H ₁ Q CH

CF -CHCl-CII -CH-CH-COO-ClI-

D-C 'Il

? "· 6 5

Connection 12

Example 27 ■

Preparation of the 3-phenoxybenzyl ester of (+) - cis, trans-2,2-dimethyl-3- (2-chloro-3,3,3-trifluoropropyl) -cyclopropane-
carboxylic acid (compound 13)

According to Example 26, the reaction of 3 g gave: (+) - ice, trans-2,2-dimethyl-3- (2-chloro-3> 3,3-trifluoropropyl) cyclopropanecarboxylic acid chloride with 3-phenoxybenzyl alcohol

5 ζ of the desired product in the form of a viscous, coloring. loose oil (refractive index n _Q = 1.5160; IR data correspond to the assumed structure)

^{; H} 3 ^C \ / ^CH 3 i

CF -CHCl-CH -CH-CH-COO-CH -

3 2 Δ

Connection 13

909837 / 0S13

- 29Q76Q9

The product thus obtained was then on a silica _: gel column using a 95: 5 mixture of n-hexane; and diethyl ether as the eluent.

The following two samples 5 were obtained: ■ A 13-cis-Isoraeres; η ~ = 1.5169 13-B trans isomer; n ~ = 1.5171 Example 28

Production of the o (-Cyan-3 ~ phenoxybenzyl ester of the (+) - cis, ίο trans-2,2-dimethyl-3- (2,2-dibromo-3,3,3-trifluoropropyl) -

cyclopropanecarboxylic acid (compound 14)

According to Example 26, the reaction of 3 g of (+) - cis, trans-2,2-dimethyl-3- (2,2-dibromo-3,3,3-trifluorine> propylj-cyclopropanecarboxylic acid chloride with o ( -Cyan- 3-phenoxybenzyl alcohol 4.5 g of the desired product in the form of a viscous oil (elemental analysis and IR data corresponded to the assumed structure),

H "C CH: 3 _χ / 3

CN

CF -CBr -CII -CH-CH-COOCH- / Q 3 2 2

Connection 14

1.2-2.7 (10Η, protons of the acyl part) 6.3 (s, 1H, CH-CN) 6.7-7.6 (m, 9H, aromatic protons)

Example 29 Insecticidal Activity of the Compounds According to the Invention

The compounds according to the invention were prepared by the methods listed below, the data of which are summarized in Table A. are, on larvae and adults of the following phytophagous species tested.

909837 / 0S13

- 29Ό7609

α) Biological activity in Macrosiphum euphorbiae

(Aphids) -

Small potato plants grown in pots were included adult female aphids and infected after a few hours with an aqueous dispersion of the test products sprayed (see Table 4). Percent mortality was rated 24 hours after treatment (Aphid mortality on untreated plants = O).

B) Biological activity in Pieris brassicae (Lepidoptera) Cut cauliflower leaves were sprayed with an aqueous dispersion of the test products (cf. Table 4). After drying, the leaves were infected with 5-day-old larvae. The percentage mortality of the larvae (in the case of untreated leaves = O) was determined 48 hours after the treatment.

C) Biological activity in Leptinotarsa decemlineata

ι (Coleoptera)

Small potato plants grown in pots were infected with 4 day old larvae and then with an aqueous one Sprayed dispersion of the test products (see Table 4). Forty-eight hours after treatment, the percent mortality rate was found determined (for untreated plants = 0).

D) Biological activity in Musca domestica (Dyptera) 4-day-old adults were treated with an acetone solution of the test products by applying locally using a microsyringe (cf. Table 4). The percentage mortality (for insects treated only with acetone = 0) was determined 24 hours after the treatment.

E) Biological activity in adult Culex pipiens

(Dyptera) -

Rectangular strips of Whatman No. 1 paper were uniformly treated with an acetone solution of the test products (see Table 4).

909837/0613

I After evaporation of the solvent, the inner part became a

^; Perspex cylinder (model OMS) with the treated paper

I lined it up and locked it with a net. Then were

1 5 in cylinders 2 to 3 day old adult insects

1 introduced. One hour after the start of contact, the in-

• sects in an identical one, treated with untreated paper

I dressed cylinder transferred and with a sugar

^; solution fed. The percentage mortality (with un-

\ io treated insects = o) 24 hours after treatment4

! start determined.

I F) Biological activity in Blatta orientalis (Ortoptera)

I the bottom and walls of the glass cylinder were uniform with

i treated with an acetone solution of the test products (cf.

• is table 4). After evaporation of the solvent was in

j introduced each cylinder 80 to 100 days old Neanids

\ and the cylinder with a lid made of a metal mesh

i locked. 24 hours after the start of treatment

} the insects are transferred into similar, untreated cylinders

J20 leads and fed accordingly. The percentage of death

{possibility (with untreated insects = 0) was 48 hours

j determined after the start of treatment.

\ G) Biological activity in adult Tetranychus

urticae (Acari)

125 leaf sheaths from bean plants were grown with adults

\ Acaren infected and then with an aqueous dispersion

j of the test products sprayed (see Table 4). The percentage

ι mortality (with untreated leaf disks = 0) was

i determined 24 hours after treatment.

909837/0613

Table 4 (Insecticidal and acaricidal activity (expressed as% mortality at given doses)

Macrosiphum

Dose of cort. (tfo) W

Pieris

Dose of mort. (*>) (%)

Leptinotarsa

D dose Mort.

Musca

D.
dose

Mort. 00

1-A

1-B

1-M

0.01
0.005

100 100

0.01

100

0.005
0.001

100 100

0.01
0.005

100 100

0.01

100

0.005
0.001

100 95

0.01

100

0.01

100

0.05
0.01

0.05
0.01

0.05
0.01

100 100

100 82

100 80

0.005 100 0.005
0.001 100
100 0.01 35 0.05
0.01 100
90 2-A 0.01
0.005 100
91 0.005
0.001 100
50 0.01 85 0.05 92 2 B 0.01
0.005 100
93 0.005 55

, to

CD O

to

Table 4 continued

3-A ° , 005 100 100
76 0
0 , 005 100
, 001 100 100 0 , 01 ο, 01 100 100 0, 01 100 100 3-B ° , 005 100 60 0
0 , 005 100
, 001 100 100 0 , 01 0, 01 100 10 O, 01 100 100 3-M O , 005 100 100 0 , 005 100 100
100 0 , 01 0, 01 100 1oo 0,
0, 05
01 100
100 100 809837 4th 0.01
0.005 53 0.005 0 0, 01 0 0.05 70 / 0613 9-B 0.01 0.005 0.05 10-B 0.01 0.005
0.001 0.05 Phenothrin
(Comparative
links) 0.01 0.005 0.05

Pennethrin 0.05 100

° ^{'01 10} ° °' ^{01 77} ° ^'01 32

0.005 96 0.005 100

0.001 83

Table 4 (Continuation)
Culex
I P. (ad.
dose
(g / m ² ) )
Mort.
(Ji) Blatta
dose
(g / m ² ) 0.
Mort.
00 Tetranychus
U. (ad,)
Dose of mort.
(* o) (*) 1-A 0.2 100 0.1
0.01 100
100 0.1 100 909837 / 1-B 0.2 57 0.1
0.01 100
65 0.1 90 ^f 0813 1-M 0.2 100 0.1
0.01 100
100 0.1 ρ6

2-A 0.2 100 0.1
0.01 100
100 0.1 60 2 B 0.2 50 0.1 8 0 0.1 37 3-A i
'I. 0.2 100 0.01 100 0.1 100

CD ί £>

Table 4 continued

0.2 100 0.01 100 0.1 100

3-M 0.2 100 0.01 100 0.1 81 4th 0.2 44 0.01 100 0.1 100 9-B 0.2 100 0.1 40 10-B 0.2 100 0.1 80 Phenothrin
(Comparative
links) 0.2 0 0.1 0 Permethrin
(Comparative
Links) 0.2 28 0.1
0.01 100
77 0.1 47

CD - CD

- 29Ö7609

^; Example 30

; Acute oral toxicity in rats-Ais Test animals were half male and half female

'5 albino rats of the Wistar strain used. After a start-up period, the animals were fasted 6 hours before to 2 hours after treatment and then observed continuously for 14 days, being fed with calibrated food and water ad libitum. The treatment was carried out by introducing fixed amounts of test product into the animals by means of a gastric tube connected to a Mei3 syringe.

During the entire observation period, mortality and all possible symptoms of poisoning were noted.

Compound 1-B was prepared in a Dose of 200 mg of active substance per kg of live weight tested on rats without any mortality after the test.

20 probability was observed in the test animals.

: Example 31.

Field test of activity and duration of action in Acaren The test was carried out outdoors to determine activity and duration of action different, representative compounds against Acaren (Tetranychus urticae) to be found against the commonly used insecticides are resistant.

The compounds were in the form of an aqueous-acetonic dispersion with addition of a wetting agent ( "Fitofil" Montedison in 0.5% _ö sodium concentration) was applied by the cultures until dripping uniformly einnebelte (active ingredient concentration = 0 , 3 ⁰ M).

At time intervals from the start of treatment, the number of those present on the appropriately marked leaves was awakened Acaren noted.

909837/0613

As is known, subject to the above conditions gen all pyrethroids listed in Table 1 with the exception of permethrin, cypermethrin and decamethrin a rapid Decomposition and become completely inactive after a very short time.

The tests according to the invention showed that permethrin and cypermethrin were completely inactive after 14 days. In contrast, the compounds according to the invention still showed a remarkable one after the same period of time Activity.

In the above formulas, e.g.

R H or in particular an alkyl group with 1-4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, Isobutyl, sec-butyl, tert-butyl

R * and R are e.g. methyl, ethyl, propyl, isopropyl

7 8 20 R and R, insofar as they are halogen, in particular F, Cl and Br.

R ^ and R can be used together with the

-HpC-Wji Group

e.g. also an N-methylene-substituted phthalic acid imide di- or tetrahydrophthalic acid imide or pyridine-2,3-

form dicarboximide residue,

R means, insofar as it represents a substituted vinyl group, in particular one by halogen, especially F, Cl and Br, methyl, ethyl or phenyl substituted vinyl group,

R ¹ is in particular a lower alkyl group, as defined under R, for example.

909837/0613

Claims (1)

claims 1. -I Process for the production of insecticidal and ncaricidal compounds of the general formula: ^H 3 ^C \ / ^H 3 ^X C ^/ A (D [- CH - C-OR OH O (where: A = CF ₀ -C = C-, CF ₀ -C = CH-, CF _n -C-CH. and 3 ~~ ο 3, * Y where: χ = π, F, Cl, Br and Y = Cl, Br) ! R = -CH - '< t R ² (where: R ¹ = H, CN, C = CH and R ² = 3-phenoxy, 3-uenzyl, 4-allyl, 4-propargyl); ί (where: R = H, CN, C = CH, R = H, alkyl; I ₄ ~~ " R = benzyl, benzoyl, phenoxy, allyl, propargyl; Y ¹ = 0, S; the group CH is in the 2- or 3-position on ? i bonded to the heterocyclic ring, R ³ is in 3- or 2- | Position attached to the heterocyclic ring, and R ^ j is attached to the heterocyclic ring in the A or 5 position) " 909837 ^ 0613 where * ~ 9 1 * Ά- R = H, CN, C S CH 2
R = 3-phenoxy, 3-eenzyl, 4-AHyI * 4-Pi * opargyl R = H, on the heterocyclic ring in 3- or 2- Position-attached alkyl; j ίο R = (in the 4- or 5-position of the higher ο cyclic ring) = j benzyl, benzoyl, phenoxy, allyl, propargyl; ^: γ = ο, S R and R = alkyl C ₁ -C ^, or R and R together form '-> an orthocondensed, aromatic, heteroaromatic or aliphatic (saturated or unsaturated) ring; R 'and R = (identical or different from one another) = H, halogen, CH-, *> - R ^ = phenyl, vinyl, substituted vinyl, phenoxy. 2. Compounds according to claim 1 with the formula J ³ \ / ³ / ^C \ A-CH- CH - COOR where: A = CF-C = C-, CF-C = CH; CF-C-CH J ό Y R ¹ • the - CH ^ ^ O-C, H "", CN / CHo- ^ f (X = H, F, Cl, Br; Y = Cl, Br, R ¹ = H, CN) 909837 ^ 0613 3. Compounds according to claim 2 having the formula A - CH - CH - COOR wherein A has the meaning given in claim 2 and R = _ CH ² // W 265 ^is 4.- Compound according to claim 3, namely the 2-methyl-5-benzyl-3-furylmethyl ester of (+) - cis-2 _> 2-dimethyl-3- (ßfluoro-ß-trifluoromethyl (E) vinyl) -cyclopropanecarboxylic acid. J 5.- A compound according to claim 3, namely the 2-methyl-5-benzyl-3-furyl ester the (+) - trans-2,2-dimethyl-3- (ß-fluoro-β-trifluoromethyl (E) vinyl) -cyclopropanecarboxylic acid. ' 6.- Mixture of the two isomeric compounds of Claims 4 and 5. 7. Compounds according to claim 2 having the formula A-CH- CH - COO - CH - (Q 6 5 wherein A = CF-C = C- and R ¹ = H, CN. is. 909837/0613 - ** - 29Q7609 8.- Compound according to claim 7, namely the tf-cyano-3-phenoxybenzyl ester of (+) - cis-2,2-dimethyl-3-trifluoromethylethinylcyclopropanecarboxylic acid. 9.- A compound according to claim 7, namely the <tf-cyano-3-phenoxybenzyl ester of (+) - trans-2,2-dimethyl-3-trifluoromethylethinylcyclopropanecarboxylic acid. 10. Mixture of the two isomeric compounds of claims 8 and 9. 11. Compounds according to claim 2 having the formula 15 HC _v CH ³ \ / A - CH - CH - COO _ CH - (O ; 20 in which SA = CF-CH = CH- and R ^1. = H, CN 1st. ? ο 12.- Compound according to claim 11, namely the 3-phenoxybene J ²⁵ cyl ester of (+) - trans-2,2-dimethyl-3- (ß-trifluoromethyl- I Z-vinyl) -cyclopropanecarboxylic acid 13 · - Compound according to claim 11, namely the G ^ -Cyan - 3-phenoxybenzyl ester of (+) - trans-2,2-dimethyl-3- (β-tri- j fluoromethyl-Z-vinyl) -cyclopropanecarboxylic acid j 14.- Compound according to claim 11, namely the o / -Cyan-3-phen-j; oxybenzyl ester of (+) - trans-2,2-dimethyl-3- (β-trifluoro -I [ methy1-E-vinyl] -cyclopropanecarboxylic acid. 909837/0613 15 - Compounds according to claim 2 with the formula: A-CH- CH - COO - CH - / Q where oc, H _r 1 r I A = CF -C = CII- and R ¹ = H, CN. I. 16, - Compound according to claim 15, namely the 3-phenoxy \ benzyl ester of (+) - cis-2,2-dimethyl-3- (ß-fluoro-ß-tri- j fluoromethyl (E) vinyl) cyclopropanecarboxylic acid. ] 17.- Compound according to claim 15, namely the 3-phenoxy j benzyl ester of (+) - trans-2,2-dimethyl-3- (ß-fluoro-ß-tri- j fluoromethyl (E) vinyl) cyclopropanecarboxylic acid. i 18.- Mixture of the two isomeric compounds of claims 16 and 17. 19.- Compound according to claim 15, namely the o (-Cyan-3-phenoxybenzyl ester the (+) - cis-2,2-dimethyl-3- (ß-fluoro-β-trifluoromethylvinyl) -cyclopropanecarboxylic acid. 20.- Compound according to claim 15, namely the o (-Cyan-3-phenoxybenzyl ester the (+) - trans-2,2-dimethyl-3- (ß-fluoro-β-trifluoromethylvinyl) -cyclopropanecarboxylic acid. 21.- Mixture of the two isomeric compounds of claim
19 and 20. 909837/0613 I9076Q9 22.- Compounds according to claim 2 with the formula: HC CH j A - CH - CH - COO - CH - ^ Q wherein - ^ ο 5 Cl 10 A = CF-C = CH and R = H, CN. 23 · - Compound according to claim 22, namely the 3-phenoxybenzyl ester of (±) -cis-2,2-dimethyl-3- (ß-chloro-ß-trifluoromethylvinylJ-cyclopropanecarboxylic acid. 24.- Compound according to claim 22, namely the 3-phenoxy- [ benzyl ester of (+) - trans-2,2-dimethyl-3- (ß-chloro-ß-trifluoromethylvinyl) -cyclopropanecarboxylic acid. ; 20 25 · - Mixture of the two isomeric compounds of claim 23 and 24. ; 26.- Compound according to claim 22, namely the cA-cyano-3- phenoxybenzyl ester of (+) - cis-2,2-dimethyl-3- (ß-chloro-ß-J25 trifluoromethylvinylj-cyclopropanecarboxylic acid. 27. Compound according to Claim 22, namely the oc-cyano-3-phenoxybenzyl ester the (+) - trans-2,2-dimethyl-3- (ß-chloro-ßtrifluoromethylvinyl) -cyclopropanecarboxylic acid. 28.- Mixture of the two isomeric compounds of claims 26 and 27. 29.- Compounds according to claim 2 with the formula; 909837/0613 907609 A-CH-CH-COO-CH wherein. 6 ^H 5 10 A = CF Br -C = CH - and R ¹ = H, CN. 3 30, - Compound according to claim 29, namely the 3-phenoxy ; benzyl ester of (+) - cis-2,2-dimethyl-3- (ß-bromo-ß-trifluoromethylvinyl) -cyclopropanecarboxylic acid. 31.- A compound according to claim 29 "that is the 3-phenoxybenzyl ester of (+) - trans-2,2-dimethyl-3- (beta-bromo-beta-tri- f luormethylvinylj-cyclopropane carboxylic acid. 32.- Mixture of the two isomeric esters of claims 30 and 31 - 33 · - Compound according to claim 29 »namely the OC-cyano-3- j phenoxybenzyl ester of (+) - cis-2,2-dimethyl-3- (ß-bromo-ß- ! trifluoromethylvinyl ^ cyclopropanecarboxylic acid. 34. A compound according to claim 29, namely the (X-cyano-3-phenoxybenzyl ester of (+) - trans-2,2-dimethyl-3- (ß-bromo-ß-tri-; fluoromethylvinylj-cyclopropanecarboxylic acid. 35.- Mixture of the two isomeric compounds of claims 33 and 34. 36, - Compounds according to claim 2 with the formula 90983770613 H-C CIU ^{X /} R ¹ C * ^R A-CH- CH - COO -CH- Ο-CH ο 5 worm 10 χ A = CF -C-CH ₀ -; X = H, F, Cl, Br; Y = Cl, Br; 3, 2 R ¹ = H, CN. ¹⁵ 37 · - Compound according to claim 36, namely the oC-cyano-3-phenoxybenzyl ester of (+) - cis, trans-2,2-dimethyl-3- (2-; chloro-3,3,3-trifluoropropylJ-cyclopropanecarboxylic acid . 38, - Compound according to claim 36, namely the 3-phenoxy- ²⁰ benzyl ester of (+) - cis-2,2-dimethyl-3- (2-chloro-3 _f 3,3-trifluoropropyl) -cyclopropanecarboxylic acid. 39 · - Compound according to claim 36, namely the 3-phenoxy-; benzyl ester of (+) - trans-2,2-dimethyl-3- (2-chloro-3,3,3- ■ ²⁵ trifluoropropyl) -cyclopropanecarboxylic acid. 40r mixture of the two isomeric compounds of claim 38 and 39- ³⁰ 41.- A compound according to claim 36, namely, the o (-cyano-3-phenoxybenzyl ester of (+) - cis, trans-2,2-dimethyl-3- (2,2-dibromo-3,3,3-trifluoropropyl ) cyclopropanecarboxylic acid. 42.- 2,2-Dimethylcyclopropancarbonsäuren and esters of the general formula ³⁵ common: HC CII A-CH- CH - COOR '(II) 909837/0613 ν. ο at
R · - H, alkyl C ₁ -C _{4 χ} :> A = CF-C 1 -C 4-, CF-C = CH-, CF-C-CH-; YY 1 3 _f ζ X Y X = H, F, Cl, Br; Y = Cl, Br. 43 · - Compounds according to claim 42 with the formula HC CH ³ \ ³ CF- C = C - CH - CH - COOR ' 15 where: r «= h, C ₁ -H- * · 5 4,4, - Compounds according to claim 42 with the formula HC CH ³ \ ³ CF ₃ - CH = CII - CK - CK - COOR ¹ , where: R ¹ = H, CH 45.- Compounds according to claim 42 with the formula CF ₃ - C (F) = CII - CH - CH - COOR 'where: r> = h, C ₀ H 30 ^{L 5} 46.- Compounds according to claim 42 with the Fprmql, "3 ^C \ / ^CH 3 C ^ 3 ;, ^CF 3 - ^{C (C1} ) ^{= CH} - ^CH '- ^X CH - COOR · where: ri = h, C η. 909837/0613 47 · - Compounds according to claim 42 with the formula ^H 3 5 C CF - C (Br) = CH - CH - CH - COOR ¹ where: R '= n, c_H_ · * 5 i 10 48.- Compounds according to claim 42 with the formula: H ₁ C CH, ³ \ / ³ x ^N c / CF - C - CIL - CH - CH - COOR ¹ : 15 Y where: X = H, F, Cl, Br; Y = Cl, Br; R ¹ = HC _o H i * 5 49.- A method for the preparation of compounds according to claim 1 ¥ is 41 , characterized in that one binding the formula ^H 3 \ / ^H 3 ^N c ^ A - CH - CK - COOR '(II) (in which A has the meaning given in claim 1 and R ¹ = H, C _1-Zf alkyl) converted into the corresponding acyl halide and this binds the base in an inert solvent and in the presence of a hydrohalic acid with an alcohol of the general Formula R-OH (in which R has the meaning given in claim 1) is implemented. 50.- A process for the preparation of compounds according to claim 42 to 48, characterized in that a compound of the formula CF ^ -C (X) Y ₂ (in which X and Y have the meaning given in claim 42) with an ester of 3,3-dimethyl-4-pentenoic acid of the formula: 909837/0811 - 'Z * - 2907603 CH _A = CH - C (CHj) ₂ - CH ₂ -COOR ' (R ¹ = C _1- . Alkyl) in the presence of a radical reaction accelerator to form a compound of the formula: X CEv -C- CH ₂ -CH- C (CHj) ₂ - CH ₂ - COOR ¹ YY (in which X, Y and R ^{1 have} the above meaning), which is subjected to one or more successive dehydrohalogenations by subsequent treatment with an organic or inorganic base. 51.- A process for the preparation of compounds according to claims 42 to 48, characterized in that a compound of the formula CF ^ -C (X) Y ₂ (in which X and Y have the meaning given in claim 42) with a compound of formula CH ₂ = CH - C (CHj) ₂ - CH (C00R ^r ) ₂ (in which R ¹ = C ^ _ # alkyl) in the presence of a radical reaction accelerator to form a compound of Formula X CF, -C- CH ₉ - CH - C (CH,) ο - CH (COOR ¹ ) _o J f C- ι J C- C. YY (in which X, Y and R ^{1 have} the above meaning) converts \ 25 which by treatment with one equivalent of a base a (compound of the formula: HG ΓΗ ä γ C CF _x - C - CH ₉ - CH - C - - COOR ¹ 30 y COOR ¹ (in which X, Y and R ^{1 have} the above meanings) yields J ι from which you can finally selectively dehydrohalogenation! ί and / or hydrolysis with subsequent decarboxylation the Compounds according to claim 42 to 48 is obtained. 903837/0613 52.- Insecticidal and acaricidal preparations containing or comprising one or more compounds or mixtures of the isomeric compounds according to claims 1 to 41 as the active ingredient. The patent attorney: 909837/0613