DE1618925C - Cyclopentenolone cyclopropanecarboxylate, process for their preparation and insecticidal agents containing these compounds - Google Patents

Description

R ³ -C

. CH ³
C.

IO

CH-C-O-CH

• CR ⁵

I I

CH ₂ -C = O

20th

in which R ^{1 is} a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, a phenyl group, a phenyl group substituted by alkyl or alkoxy groups with 1 to 4 carbon atoms, R ² , R ³ and R ^{4 are alkyl groups with 1 to 4 carbon atoms} 4 carbon atoms and R ^{5 is} an alkyl group with 1 to 4 carbon atoms, an alkenyl group with 3 to 4 carbon atoms, a cyclopentenyl group, _v a benzyl group, a penta-2,4-dienyl (l) group or r is the furfuryl group.

2. Process for the preparation of cyclopropane "ca'rbonsäurecyclopentenolonestern according to" claim 1, characterized in that one R ² -

R ¹

I.
-c

CHCOOH

R ⁴

in which R ¹ , R ² , R ³ and R ^{4 have} the meaning given in claim 1, or their lower alkyl esters, halide or acid anhydride, with a cyclopentenolone compound of the general formula

■ CH ³

HO-CH CR ⁵

CH ₂ -C = O

in which R ^{5 has} the meaning given in claim 1, esterified by methods known per se. • '· 3. Insecticidal agents, characterized by a content of at least one cyclopropanecarboxylic acid cyclopentenolone ester according to claim 1 as "active ingredient."

The invention relates to cyclopropanecarboxylic acid, a cyclopropanecarboxylic acid of the general formula cyclopentenolone esters of the general formula

_R i ■

R ¹
R ² -C

R ³ -C

R ⁴

CH ₃
C,
CH-C-O-CH CR ⁵

CH ₂ -C = O '

R ² -C

45

CHCOOH

(ID

in which R ^{1 is} a hydrogen atom, an alkyl group with up to 4 carbon atoms, a phenyl group or a phenyl group substituted by alkyl or alkoxy groups with 1 to 4 carbon atoms, R ² , R ³ and R ^{4 are} alkyl groups with 1 to 4 carbon atoms Atomen undR ⁵ denotes an alky group with up to 4 carbon atoms, an alkenyl group with 3 to carbon atoms, a cyclopentenyl group, a benzyl group, a penta-2,4-dienyl (I) group or the furfuryl group, processes for their preparation and insecticidal agents containing these compounds.

The cyclopropanecarboxylic acid cyclopentenolone esters of the above general formula can be prepared according to the invention by adding R ³ -C

in which R. ¹ , R ² , R ³ and R ^{4 have} the above meanings, or their lower alkyl esters, acid halide or acid anhydride with a cyclopentenolone compound of the general formula

CH ₃
¹ C

/ \
HIGH-HIGH CR ⁵

I I

CH ₂ -C = O

(in)

in which R ^{5 has} the above meaning, esterified by methods known per se.

Pyrethrum extracts have long been used as insecticides used because they are harmless to warm-blooded animals. In more recent times an analogue of the Active ingredients of pyrethrum extracts, i.e. pyrethrin and cinerin, manufactured synthetically and as an insecticide put on the market. This substance is called "allethrin" (cf. M. S. Sch.echter and Collaborator, Journal of the American Chemical Society, Vol. 71 [1949], pp. 1517 and 3165, and H. J. * Sanders and A. W. Ta ff [Industrial and Engi- ίο neering Chemistry], Vol. 46 [1954], p. 414). The active ingredients are due to their high insecticidal effectiveness, especially their rapid effect, valuable, and they are characterized in that the Insects develop little or no resistance to these compounds.

Because of the complexity of manufacturing, the connections are very expensive, and at most they can be im Household against flies and other vermin can be used.

'The cyclopropanecarboxylic acid esters of the ^ general formula I have a high insecticidal activity, are harmless to mammals and plants and can be made from easily accessible starting compounds can be produced by a simple and inexpensive process. The connections of the Invention have a comparison with pyrethrum extracts and synthetic products of the pyrethrin type higher insecticidal activity, e.g. B. against mosquitoes (Culex pipiens pallens).

Examples of particularly preferred cyclopropanecarboxylic acid esters of the general formula I are:

connection
No.

CH ₃ .

CH ₃ C

CH ₃ -C

CH, -C

CH-C-O-CH / Il \

.C-CH ₂ -CH = S = CH ₂

CH ₇ -C.

CH,

2,2,3,3-tetramethylcyclopropane-carboxylic acid 3'-allyl-2'-methyl-4'-oxo-2'-cyclopentenyl ester

CH ₃

CH ₃ -C

V CH-C-O-CH

/ Il

CH ₃ -C 0

CH,

C-CH ₂ - C = CH - CH = JCH
CH ₂ -C. "O'

2,2,3,3-tetramethylcyclopropane-carboxylic acid 3'-furfuryl-2'-methyl-4'-oxo-2'-cyclopentenyl ester

CH

2,2,3,3-Tetramethylcyclopropane-carboxylic acid 3 '- (2 "-cyclopentenyl) -2'-methyl-4'-oxo-2'-cyclopentenyl ester

continuation

Connection no.

CH3 HC

CH-C-O-CH

CH ₃ -CO CH ₂ -C

C-CH ₇ -CH = CH ₂

CH ₃

2,2,3-Trimethylcyclopropane-carboxylic acid 3'-allyl-2'-methyl-4'-oxo-2'-cyclopentenyl ester

CH ₃ C

CH ₃ -HC

CH ₃ -C

CH-C-O-CH

CH ₃ CH ₂ -C
. V

C - CH, - C = CH - CH = CH

2,2,3-Trimethylcyclopropane-carboxylic acid-S'-furfuryW-methyM'-oxo ^ '- cyclopentenyl ester

CH ₃ C CH

CH ₃ -HC

CH-C-O-CH C-CH

' Il ■ \ / \ ■

CH ₃ -CO CH ₂ -C CH ₂ CH ₂

CH,

2,2,3-Trimethylcyclopropane-carboxylic acid 3 '- (2 "-cyclopentenyl) -2'-methyl-4'-oxo-2'-cyclopentenyl ester

CH ₃ C

CH ₃ -C

CH-C-O-CH

/ Il \

CH ₃ -CO CH ₂ -C

C-CH ₂ -CH = CH ₂

CH,

2,3,3-Trimethyl-2-phenylcyclopropane-carboxylic acid 3'-allyl-2'-methyl-4'-oxo-2'-cyclopentenyl ester

continuation

connection
'No.

10

11th

CH,

C ₂ H ₅ -C

CH-C-O-CH

CH ₃ -C

CH-C

OrA - OJnU

CH ₃

S ^ -Dimethyl ^ -äthyW-phenylcyclopropane-carboxylic acid 3'-allyl-2'-methyl-4'-oxo-2'-cyclopentenyl ester

CH,

CH ₃ C

CH ₃ -C

C ₂ H ₅ -C

CH-CO-CH '^ C-CH ₂ -CH = CH ₂

/ Il \. χ /

CH ₂ -C

CH,

V. O

2,2,3-Trimethyl-3-ethylcyclopropane-carboxylic acid-S'-allyl ^ '- methyW-oxo - ^' - cyclopentenyl ester

CH,

CH ₃ C

CH ₃ C

CH-CO-CH .C-CH ₃

/ Il \ /

CH ₃ -C 0 CH ₂ -C -

CH,

^ S ^ -Tetramethylcyclopropane-carboxylic acid-2 ', 3'-dimethyl-4'-oxo-2'-cyclopentenyl ester

CH ₃

CH ₃

CH ₃ C
'- CH-CO-CH

/ Il \

CH ₃ -C 0 CH ₂ -C

CH ₃

2,2,3,3-tetramethylcyclopropane-carboxylic acid-S'-benzyl ^ '- methyM'-oxo-Z'-cyclopentenyl ester

continuation

10

connection
No.

CH ₃

C 'CH ₃ -C

CH-C-O-CH

/ Il \

CH ₃ -CO CH ₂ -C

CH,

C - CH, - CH - CH-

2,3,3-Trimethyl-2- (p-tolyl) -cyclopropane-carboxylic acid 3'-allyl-2'-methyl-4'-oxo-2'-cyclopentenyl ester

CH ₃

CH ₃ C

CH, -C

CH-C-O-CH

'Il. \

CH ₃ -C 0 CH ₂ -C _n

CH,

C - CH, - CH = CH - CH = CH ₂

2,2,3,3-Tetramethylcyclopropanecarboxylic acid 3 '- [2 ", 4" -pentadienyl- (1)] - 2'-methyl-4'-oxo-2'-cyclopentenyl ester

CH,

CH ₃ C

CH, -C

CH-C-O-CH ■

/ Il ■ \ ■

CH ₃ -C O. CH ₂ -C

C-CH ₂ -CH = CH-CH ₃

CH,

2,2,3,3-Tetramethylcyclopropane-carboxylic acid 3 '- (2 "-butenyl) -2'-methyl-4'-oxo-2'-cyclopentenyl ester

- C ₂ H ₅

CH ₃ C

CH-C-O-CH

CH ₃ C

CH ₂ -C

C—.CH, -CH = CH,

CH,

2,2-Diethyl-3,3-dimethylcyclopropane-carboxylic acid 3'-allyl-2'-methyl-4'-oxo-2 ^/ -cyclopentenyl ester

11th

Continued 12

connection
No.

C ₂ H ₅

CH ₃ C

C ₂ H ₅ -C

16

C ₂ H ₅ -

CH-C-O-CH

Il \

0 CH ₂ -

C ₂ H ₅

C - CH, - CH = CH,

2,2,3,3-Tetramethylcyclopropane-carboxylic acid- ■ 3'-aUyl-2'-methyl-4'-oxo-2'-cyclopentenyl ester

CH,

CH ₃ C

CH, -C

17th

CH-C-O-CH

C-QH ₅

CH, C

/ Il

CH ₃ -C 0

- CH ₃ "0

2,2,3,3-Tetramethylcyclopropane-carboxylic acid 3'-ethyl-2'-methyl-4'-oxo-2'-cyclopentenyl ester

The for the production of the new Cyclopropancarbonsäureester'r Usable cyclopropanecarboxylic acids of the general formula II can according to customary Process are produced. For example, is tetramethylcyclopropanecarboxylic acid easily accessible according to the following reaction scheme:

CH

CH,

C = C

CH,

CH ₃

CH,

+ N ₂ CHCOOQH ₅

CH,

45

CH ₃

CH,

CH ₃

CH CH ₃

COOQH ₅

CH ₃

ι f ~ \

CH CH ₃

COOH

55

Ver R ¹ H R ² R ³ R ⁴ binding
No. CH ₃ \ CH ₃ CH ₃ CH ₃ '18 QH ₅ - CH ₃ CH ₃ CH ₃ ' "19th QH ₅ CH ₃ CH ₃ CH ₃ 20th QH ₅ QH ₅ CH ₃ CH ₃ 21 QH ₅ ^: QH ₅ QH ₅ QH ₅ 22nd QH ₅ CH ₃ ' CH ₃ CH ₃ ■ 23 QH ₅ CH ₃ ' CH ₃ 24 CH ₃ O - ^ ~ \ - CH ₃ ' CH ₃ CH ₃ 25th CH ₃ CH ₃ CH ₃ 26th

Examples of cyclopentenolone compounds used according to the process of the general formula III are compiled in the table below :.

60

Connection no.

Examples of cyclopropanecarboxylic acids of the general formula II which can be used according to the process are compiled in the table below.

65

27 28 29 R ⁵

CH ₃
QH ₅
-CH ₂ CH = CH ₂

continuation = CH-CH ₃ O - CH ₂ - < connection
No. • - CH ₂ CH = CH • CH = CH ₂ O . R ⁵ CH = CH 30th - CH / 31 - CH ₂ CH CH ₂ -CH ₂
ι 1 32 -CH ₂ T ^ \ / 33 I. 34

IO

20th

30th

The compounds of the invention can be prepared in a number of ways. For example the compounds can be obtained by reacting a cyclopropanecarboxylic acid of the general formula II with a cyclopentenolone compound of the general formula III in the presence of a dehydrating agent Means, such as Dicyclohe.jcylcarbodiimid, in an inert Solvent can be prepared at room temperature. You can also use a lower alkyl ester of the Cyclopropanecarboxylic acid in the presence of a basic catalyst such as sodium, potassium, sodium alcoholate or potassium alcoholate, heat with the cyclopentenolone compound and this continuously distil off the lower alcohol formed during the transesterification from the reaction system. Examples of the lower alkyl esters are the methyl, ethyl, n-propyl and isopropyl esters.

After the particularly preferred esterification process, the Cyclopentenolonverbmdung with a Cyclopropanecarboxylic acid halide in an inert organic solvent such as benzene, toluene or η-hexane, and preferably in the presence of a hydrogen halide acceptor such as pyridine or triethylamine or another tertiary amine, at room temperature or below, acylated. As a cyclopropanecarboxylic acid halide the chloride is particularly preferred, but the bromide and the iodide can also be used be used. The cyclopropanecarboxylic acid halide can be obtained from the free carboxylic acid by treatment with a halogenating agent, e.g. B. a thionyl halide, phosphorus trihalide or phosgene, getting produced.

The cyclopentenolone compound can also be esterified with a cyclopropanecarboxylic anhydride will. This creates the desired ester and the free one. Cyclopropanecarboxylic acid, which is separated and again converted to the anhydride, e.g. B. by treatment with acetic anhydride or acetyl chloride. This esterification reaction is preferably carried out under reflux and in an inert solvent, such as toluene or xylene. The reaction is over within a short time.

Insecticidal agents which contain compounds of general formula I as active ingredient can be used in Form of ul solutions, emulsifiable concentrates, aerosols, wettable powders, mosquito coils, Granules, baits, dusts that contain one or more attractants, or others Application forms can be used with the aid of conventional auxiliaries.

Depending on the type of formulation, e.g. B. with dusts, baits or mosquito coils, can the active ingredient in the form of a solution in an organic solvent such as xylene, .Methylnaphthalin or acetone, can be used in a manner known per se.

The examples illustrate the invention.

example 1

2.0 g of the cyclopentenolone compound designated as Allethrolone No. 29 are dissolved in 10 ml of anhydrous benzene. The solution is mixed with 2.5 ml of pyridine and then with a solution of 2.5 g of 2,2,3,3- Tetramethylcyclopropanecarboxylic acid chloride is added to 10 ml of benzene. The reaction vessel is tightly closed and left to stand at room temperature. After 3 hours, the reaction mixture is poured into ice water and washed successively with dilute hydrochloric acid, aqueous sodium bicarbonate solution and water. The benzene solution is then dried with sodium sulfate and the benzene is distilled off under reduced pressure. 3.8 g of practically pure ester remain. Part of this ester is distilled for further purification. Bp ₀₁ 106 ° C; n? 1.5050; IR absorption at -1717 cm " ¹ '(ester), 3095, 1640 and 990 cm" ¹ .

approx.

CH ₃ -C

CH, -C

CH-C-O-i

CH,

-CH

C-CH ₂ CH = CH ₂

CH ₂ -C

\ O

Example-2

3.0 g of allethrolone are mixed with 5.5 g of 2,2,3,3-tetramethylcyclopropanecarboxylic acid anhydride mixed and left to stand at room temperature for 72 hours. Thereafter, the reaction product according to Example 1 worked up. 4.3 g of the ester described in Example 1 are obtained.

Example 3

From 2.3 g of compound no. 31.2.5 g of 2,2,3,3-tetramethylcyclopropanecarboxylic acid chloride and 3.0 ml of triethylamine, according to Example 1, the compound no. corresponding esters obtained in a yield of 3.8 g. Part of the product is distilled for purification. Kp. _{0% 1} 13O ⁰ C with partially

wise decomposition; ni °

1.5185; IR absorption at ι '

1718 cm " ¹ (ester), 3095, 6040 and 990 cm CH ₃

CH-

CH ₃ -C

CH ₃

■ C - Ο - ι

Il ο

IO

CH ₇ CH = CH ■ CH = CH ₂

20th

CH ₇ -C

O

Example 4

In the same manner as in Example 1, 2.15 g of cinerolone (Compound No. 30) are treated with 2.5 g of 2,2,3,3-tetramethylcyclopropanecarboxylic acid chloride in the presence of pyridine. 4 g of the ester are obtained. Part of the ester is distilled for purification. Bp. _D-1 170 ⁰ C with partial decomposition; nl ° 1.5123; IR absorption at 1718 cm " ¹ (ester) and 1300 cm" ¹ . .

CH ₃

CH ₃ -C

CH- C - Ο—,

CH ₃ -C

CH ₃

40

45

CH ₃
C.

-CH
\

C - CH ₂ · CH = CH · CH,

CH ₂ -C

\ O

Example 5

55

60

2.0 g of allethrolone and 1.9 g of 2,2,3,3-tetramethyl cyclopropane carboxylic acid (mp. 121 ⁰ C) are dissolved in 40 ml of dichloromethane. The solution is mixed with 3 g of dicyclohexylcarbodiimide and left to stand for 24 hours at room temperature. The precipitated dicyclohexylurea is filtered off and the solution is worked up as in Example 1. 3.8 g of the same ester as in Example 1 are obtained.

-Example

3.0 g of allethrolone with 3.0 g 1,1,2-Trimethylcyclopropancarbonsäurechlorid be esterified (bp. 92 ° C _at 90 _of bis) in the presence of 2.5 g of pyridine in the same manner as in Example 1 '. The reaction product is worked up _{according to Example I 1.} 4.9 g of ester are obtained as an oil; η Ό ' 1.5040.

i ¹⁵ CH,

CH ₃

CH-C-Ö-1

CH,

CH,

C-CH ₂ CH = CH,

O
Example 7

In the same manner as in Example 5, 3.0 g allethrolone with 2.6 g of 1,1,2-Trimethylcyclopropancarbonsäure (Kp ₂ 72 to 75 ° C;. Ns 1.4510; anilide, mp 176 ° C.) In the presence treated by 4 g of dicyclohexylcarbodiimide. 4.5 g of the same ester as in Example 6 are obtained.

The following known compounds 1 to VI were made with compounds according to the invention in terms of their insecticidal activity. The tests were carried out as follows:

A solution of 0.5 g of the test compound in 20 ml of acetone is mixed with 99.5 g of a mosquito coil carrier [a mixture of taboo powder, the powder of the leaves or bark of the taboo tree (Machilus thunbergii Sieb, et Zucc), which belongs to the camphor tree family, and pyrethrun pulp and wood flour im Weight ratio 3: 5: 1] evenly mixed. After the acetone has evaporated, the mixture becomes kneaded with 150 ml of water. The kneaded product is extruded and dried. You get one Mosquito coil with 0.5% active ingredient.

About 20 common adult mosquitoes are placed in a cube-shaped glass box with an edge length of 70 cm. A gram piece of the 0.5% mosquito coil is hung horizontally in the center of the bottom of the box and lit at both ends. After 24 minutes, the number of immobile mosquitoes (knockdown number) is determined. These mosquitoes are moved to another chamber that has food in it. The mortality of these mosquitoes is determined after 24 hours. The experiment is repeated several times to determine the KT ₅₀ value (knockdown time), the relative effect on »allethrin (chrysanthemum ^{monocarboxylic acid 3 +} -allyl-2 ⁺ -methyl-4i-oxo-2 ⁺ -cyclopentenyl ester) (100) and determine knockdown mortality.

17 '

The results are compiled in the table below. CH ₃ -C
Cl-C CH ₃ -C Knockdow
KT ₅₀
(Min. Sec.) .- 54 Knockdown
Mortality,% Test compound no. \ / \ ■
CH-CO-CH C-CH ₂ -CH = CH ₂
/ Il \ /
: ο CH ₂ -C
² Il \ . / X
CH • C • O -CH C-CH ₂ -CH = CH ₂
/ Ii \ /
: ο ■ CH ₂ -C
Il ■ 4 ' n-effect
relative
effect 59 100 1 .'.· Il
Cl O. CH ₃ O '■ 5'36' ^r ■ " 188 44 100 2 Connection II according to the German Auslegeschrift 1 092 912 Compound III -
according to Belgian patent specification 676 754, example 1 6Ί8 " 134- 100 90 3 CH ₃ , CH ₃ _
C = CH-CH CH-CO-CH ₂ -f / N
/ \ / Il \ k)
CH ₃ CO
H ₃ C CH ₃ - 4'54 " 119 100 4th .... / O / \ · "Furethrin"
Chrysanthemum monocarboxylic acid
(3- (a-furfuryl) -2-methyl-4-oxo-2-cyclopentenyl ester) T 153 • 91 7th »Cyclethrin« ·. · ■
Chrysanthemum monocarboxylic acid
(3- (2'-cyclopentenyl) -2-methyl-4-oxo-2-cyclopentenyl ester) 6'36 " 107 9 ..'... "Allethrin"
Chrysanthemum monocarboxylic acid
(S-allyl ^ -methyl- ^ oxo - ^ - cyclopentenyl ester) 6'54 " 114 89 13th 6 ' 109 95 14 Γ 125 Connection I according to the German Auslegeschrift 1 154 463 / O k 17'24 " 61 43 > 20 ' - - 13 ' ■ . 85- ■ 12'42 " 88 16'54 " 67 7'30 " . 84 ■

Claims (1)

Patent claims: 1. Cyclopropanecarboxylic acid - cyclopentenolone ester of the general formula " Cyclopropanecarboxylic acid of the general formula R ¹
R ² -C