DE2226523A1 - - Google Patents

Description

Dipl.-Infl. P. WirtK Dr. V. Schmied-KowarzJc Dipl.-Ing. G. Dannenberg Dr. P. Weinhold, Dr. D. Gudei

6 FrqnWurt / M., Gr. ΕκΒμΙμπμγ Str.3Sf

SANDOZ A.G.

η «,« «*! / Switzerland

Pest control agents

The present invention relates to novel bindings. the general formula I.

R ₀ R ₇

X il Π ι JL ei Λ

ORIGINAL BATHROOM 209851/1269

wherein R is a branched or unbranched, saturated or mono- or polyunsaturated aliphatic or alicyclic radical or a cycloalkylalkyl radical having 1 to carbon atoms and wherein R _? and R>, which can be the same or different, are hydrogen or a lower alkyl group having 1 to 4 carbon atoms, Q is an oxygen or sulfur atom and Z is an oxygen or sulfur atom or a group -CH-, with the Γ-allowance that A

and B each stand for hydrogen or that A and B together should mean a CC bond (ie the compound of the general formula I ^ _(CK j J ^ HC ^ CKfUcH-Y should ^mean ), and where Y is a cyano group, a group - p in which R. and R, which can be identical or different, stand for hydrogen or for an alkyl group with 1 to 4 carbon atoms, or, with inclusion of the nitrogen atom, can form a heterocyclic ring, a group -COORg, in which R, - for an alkyl group with 1 to 5 carbon atoms, or a group -C0R "> in which R _{7 stands} for an alkyl group with up to 5 carbon atoms, and in which η stands for 1, 2 or j5, which are used for pest control.

The compounds of general formula I can be, for example

a) by reacting a compound of the general formula II

R ₀ R,.

R ₁ Q- (CHg) -CZ ₁ -CH ₂ -CH ₂ -C = O II

in which R 1, R 1> R ₇ , Q, Z, A and η have the meanings given above, with a compound of the general formula III

209851/1269

Ro-P-CH ₀ X. Ill

ο, 2

in which Rg and Rg, which can be identical or different, stand for a phenyl group, an alkoxy group or an aryloxy group and in which X is a cyano group, a group -COORg, in which Rg has the meaning given above, a group -CONRkRj- * in which Rv and R_ have the meanings indicated above, or a group -COR ₇ , in which R _{7 has} the meaning indicated above, under Viittig-Horner conditions (see Houben-IJeyl, Methods of Organic Chemistry, Sd. E. Muller, Vol. V lc, p. 603 [1970]), ie in the presence of suitable strong bases

or

b) by implementing a compound of general

have designated meanings with a compound

Formula II, in which R ₁ , R ₀ , R.,., Q, Z ₁ , A and η correspond to the above of the general formula IV
R,

10

R ₁ , - ^N P = CHX IV

11 /

12th

wherein X has the meaning given above und.R ₅₀ , R and R 'mean aryl or dialkylamino, or

c) if Y in the general formula I is a group COR ₇ and Z is a group -CH-, by reaction

6 ·

r; iri'jT · <1ν1 p; r) f) rd pre-binding of the "general" formula V

209851/1269

BATH ORIGINAL

? 2
R ₁ Q- (CHg) _n -C-CH-CH ₂ CH ₂ MgX

AWAY

in which R-, > Rp, Q, A, B and η have the meanings given above and X is chlorine or bromine with a compound of the general formula VI

1 λ

in which R- and R have the meanings given above and R ₁ - is a lower alkyl radical with 1 to 4 carbon atoms and subsequent acid hydrolysis of the resulting magnesium salt and enol ether and simultaneous elimination of water.

The compounds of the general formula I in which Y is -CONRjlRc can also be prepared, for example, by reaction a compound of the general formula I, in which Y stands for COORg, with an AmIn of the general formula VII

HNR..R, - VII

where Rj. and R have the meanings given above, produce.

209851/1269

The implementation according to process variant a) can as be carried out as follows:

You give the appropriate strong base in one, for the implementation suitable solvents such as sodium hydride in a suitable ether such as dimethoxyethane, tetrahydrofuran, Diethyl ether ,. Dioxane, or in an amide; such as dimethylformamide or potassium tert-butoxide, in a suitable Solvents such as benzene, toluene, tetra-. hydrofuran or sodium alcoholate in dimethylformamide, optionally in the form of a suspension with the compound of the general formula III, preferably with stirring Room temperature, together, preferably leaves one more

certain time. e.g. stir for 8 hours and give the connection of the general formula II, preferably in a suitable solvent, such as that for the Reaction with the base used.

After a certain period of time, e.g. 20 hours, Was stirred at room temperature, water is added with cooling and in the usual way, for example by Extraction with 3enzol, worked up.

The implementation according to process variant b) can be as follows be carried out as follows:

The compound of the general formula II is in a suitable solvent, for example an ether such as dioxane or tetrahydrofuran, optionally at an elevated temperature, v / ie e.g. reflux temperature, preferably above a certain period of time, such as 2 ^ hours, with the connection of the general formula IV implemented, depending on the

209851/1269

BATH

Properties of the compound of the formula IV the isolated compound of the formula IV or the compound of the formula IV prepared in situ is used can be. Working up is carried out in the usual way.

The implementation according to process variant c) can be as follows be performed:

For the Grignard reagent of the general formula V in a suitable one Solvent such as an ether such as diethyl ether or tetrahydrofuran is the compound of the general formula VI admitted. After a certain time, e.g. 2-6 hours, preferably at room temperature, dilute mineral acid becomes such as dil. hydrochloric acid or sulfuric acid added, whereby the magnesium salt formed and the enol ether group are hydrolyzed and water is split off at the same time. The work-up of the α, ß-unsaturated ketones formed takes place in the usual way.

The compounds of general formula II, wherein Z, for a

Group - (J) H- and A with B together means a C-C bond-B

tet, can be, for example, in a known V / ise by reacting a compound of the general formula VIII

R ₁ Q- (CH ₂ ) _n -C -CH = CH ₂
OH

with methyl or ethyl acetoacetate

The compounds of the general formula II in which A is hydrogen and Z, for oxygen or sleep el, can be e.g. by etherification of the alcohol or thioalcohol of the general formula IX

2098 & 1/1269

- Ί - 130-5520

CZ ₂ H IX

in which R ,, R ₂ , Q and η have the meanings indicated and Z _{2 stands} for oxygen or sulfur, for example by reaction with an α, β - unsaturated ketone of the general formula X

Il

CH ₂ = CH-CR X

produce.

Compounds of the general formula II wherein Z ^ for a Group -CH- can, for example, be known per se

Way by condensation of a compound of general Formula ΧΓ

R ₁ Q (CH ₀ ) C-CH-CH ₀ -HaI "XI

χ d. η t ι c.

AWAY

in which R, R ₀ , Q, A, B and η have the meanings indicated above "* and Hal stands for chlorine or bromine with acetoacetic ester and subsequent hydrolysis and decarboxylation.

The compounds of general formula II, wherein Z, for a

Group -CH-, A together with B means a C-C bond

and R is hydrogen, can for example by Um- · Settlement of a compound of the general formula VIII with alkyl vinyl ether in the presence of mercury acetate at increased

209851/1269

, Are preferably made over a certain period, for example 4 days and subsequent rearrangement by briefly heating at l60 ° to 19O ⁰ C, preferably for 1 to hours, temperature.

The compounds of the general formula II in which A is hydrogen and Z, is a group -CH-, in which B is hydrogen

means can be, for example, by hydrogenation of the compounds of the general formula II, in which A and B together form a C-C bond.

The unsaturated alcohols of the general formula VIII can be, for example, by reacting the compound of the general Formula XII

R ₁ Q- (CH ^) _n -CR ₂ XII

before R, R, Q and η have the meanings given above, produce with vinyl magnesium bromide or chloride.

The compounds of the general formulas III, IV, V, VI, VII, IX, X, XI and XII are known or can be prepared according to known Process are produced.

The compounds of general formula I are colorless oils. You know in the usual way, for example by distillation or chromatography purified and characterized. ■ • ground.

2Ü9651 / 1269 BADORiGlNAL

As compounds of the general formula I according to the invention selenium named for example:

9-sec-Butoxy-3,7-dimethyl-2,6-nonadienoic acid methyl ester, g-Isopropoxy - ^ - dimethyl ^ o-nonadienoic acid methyl ester, 5- (4-isopropoxy-2-butyloxy) -3-methyl- 2-pentenoic acid; methyl ester, 5- (l-sec-butoxy-3-pentyloxy) -3-methyl-2-pentenoic acid methyl ester _i lO-isopropoxy-S-methyl - ^ - decadie-n - ^ - on, g_ _sec _B _U toxy-3 _J 7-dimethyl-2,6-nonadiene-1-nitrile, 10-isopropoxy - ^ - methyl ^ -decenoic acid ethyl ester, g-isopropoxy-jj ^ -dimethyl ^ -nonensäure-ethyl ester, 10 ~ Isopropoxy-4,8-dimethyl-3,7-decadien ~ 2-one ..

It has now been found that the compounds according to the invention the general formula I. the development of insects and Inhibit spider mites. If an immature form of certain insects or spider mites is treated with a compound according to the invention, in this way their transition into the subsequent manifestation is prevented.

This development inhibition can in certain insects and Spider mites cause immediate death. In other examples, there is contact with the compounds according to the invention to reduced oviposition or to prevent copulation.

The compounds according to the invention act upon absorption through the immature forms of the insects or when they come into contact with them. The compounds according to the invention of the general Formula I are therefore ideal for pest control. They are particularly distinguished by the fact that they are practically non-toxic to warm-blooded animals.

2 0 9 8 5 1/12 6 9

- ίο - ^y 130-3520

For use as pesticides, the compounds of the general formula I according to the invention can be used in In the form of dusts or sprays, e.g. as solutions or dispersions mixed with water or suitable organic Solvents such as alcohols, petroleum, tar distillers and others, as well as emulsifiers such as liquid polyglycol ethers, which have arisen from higher molecular weight alcohols, mercaptans or alkylphenols through the addition of alkylene oxide will. Suitable organic solvents, such as ketones, aromatic, optionally halogenated hydrocarbons, mineral oils, etc., are added as solubilizers.

The spraying and dusting agents can be the usual inert carriers, such as talc, kieselguhr, bentonite, pumice stone, or other additives such as cellulose derivatives and the like, also to improve the wetting ability and adhesive strength contain the usual wetting agents and adhesives.

The active compounds according to the invention can be used in the formulations and in the spray liquors in mixtures with other known ones Active ingredients are present. The formulations generally contain between 2 and 90 percent by weight of active ingredient, preferably between $ 5 and $ 50. In general, it is sufficient in the use broths a concentration between 0.01 and 0.1 percent by weight of active ingredient for effective pest control.

209 851/1269

_ _1λ _ ^ "OD ^ 130-5520

The active ingredient cancellations can be made in a known manner be, e.g .:

a) 25 parts by weight of a compound of the general formula I are mixed with 25 parts by weight of isooctylphenyl decaglycol ether and 50 parts by weight of xylene are mixed, whereby a clear solution is obtained which is easily emulsifiable in water / water. ■ The concentrate is diluted with water to the desired concentration.

b) 25 parts by weight of a compound of general formula I are mixed with J50 parts by weight Isooctylphenyloctaglykoläther and 45 parts by weight of a petroleum fraction of boiling point 21O ° -28o ° '(D ^_20: °' ^mixed 9 ² ^ - Bas concentrate is diluted with water to the desired concentration.

c) 50 parts by weight of a compound of the general formula I are mixed with 50 parts by weight of isooctylphenyloctaglycol ether. A clear concentrate is obtained that is easily emulsifiable in water and is diluted with water to the desired concentration.

The following application examples serve to explain the The excellent effectiveness of the compounds according to the invention are not intended to restrict the invention in any way.

209851/1 269

Active ingredient Active ingredient Dosage: 2
0.1 mg / cm a) ti It b)

Example a: Insecticidal effect on Dysdercus fasciatus-

Larvae (cotton bug)

Filter paper) of 9-sec-butoxy-3,7 "," 2,6-dirnethyl-nonadiene with a solution of a) 9 ~ ^sec ~ B ~ ^u Toxy 3,7-dimethyl-2,6-nonadienoic acid-methylester, or b -l-nitrile soaked. A box made of polystyrene (2OOxlOOx85mm) is lined with the filter paper treated in this way. A folded filter paper, which has also been impregnated, is placed in this box and filled with approx. JO Dysdercus larvae in the 4th larval stage. You add crushed cotton seeds and a drinking vessel as feed. The mortality is given in #.

Mortality of Dysdercus larvae After 10 days:

100 <fo 100 %

Example b:

The effect of was analogous to that described in example a Methyl 9-isopropoxy-5,7-dimethyl-2,6-nonadienoic acid Dysdorcus fasciatus ~ La, rven determined.

Drug mortality of Dysdercui

Dosage: Larvae after 10 days:

0.1 mg / cm ² . 97 %

Example c ; Effect on the development of Prodonia lit-tura-Laryen (cotton owl) into adults

Filter paper is impregnated with a solution of 9-sec-butoxy ~, 7 · methyl-2 _# 6-d-.lenGi'.ure-inet.hy! .Ester. With that

209851/1269
BATH ORIGINAL

- 13 - 130-5520

treated paper, the compartments of a plastic box are lined. A Prodenia caterpillar is placed in each compartment set and added a piece of art medium as feed. The number of normally developed adults is given in #.

Active ingredient development rate of the ProDosing: denia larvae to adults:

0.1 mg / cm ² 0 #

Example d;

The rate of development from Prodenia larvae to adults when using was analogous to that described in Example c 9-Isopropoxy-3i7-diraethyl-2,6-nonadienoic acid methyl ester certainly.

Drug development rate of the pro-

Dosage: denia larvae to adults:

0.1 mg / ren ² 5 %

ι
The following examples serve to illustrate the preparation of the compounds of the general formula I, but are not intended to restrict the invention in any way. The temperatures are given in degrees Celsius.

209851/1269

BAU ORfGiNAL

Example 1: 9-5ec-butoxy-3 »7-dimethyl-2,6-nonadienoic acid methyl ester

1.31 S (0.03 mol) of a 55% sodium hydride emulsion in Mineral oil are washed with hexane and suspended in 45 ml of 1,2-dimethoxyethane under nitrogen. While stirring at 20 - 25 ° become 6.3 S (0.03 mol) in the course of one hour (0,0-diethyl-phosphono) acetic acid methyl ester added. After 8 hours, 4.24 g (0.02 mol) of 8-sec-butoxy-6-methyl-5-octen-2-one are obtained in 6 ml of 1,2-dimethoxyethane was added dropwise and the mixture was stirred at 20-25 ° for 20 hours.

For working up, 100 ml of water are added dropwise with cooling. The organic .Anteile are extracted with benzene; the benzoin extract is concentrated to 60 ml, filtered through 30 g of aluminum oxide (activity II) and the filtrate evaporated. Of the. The residue can be purified by chromatography on silica gel [solvent hexane / ethyl acetate (9: I]) J be, with a cis / trans isomer mixture of 9-sec ~ butoxy-5,7-dimethyl-2,6-nonadienoic acid methyl ester is obtained.

n ^ ° = 1.4678

Analysis: ^c 16 ^H 28 ° 3 Molecular weight: 268.4

calc. C 71.6 % H 10.5 % 0 17.9 % found 71.9 % 10.2 % 18.2 %

Example 2: 9-Isopropoxy-3,7-dichromethyl-2,6-nonadienoic acid methyl ester

Is prepared analogously to Example 1, but instead of 8-sec-butoxy-6-methyl-5-octen-2-one, the S-isopropoxy-6-

209851/1269

ir.ethyl-5-octen-2 "On is used»

n ^ ⁰ ~ 1.4691 '

Analysis: ^C i «-; ^H 26 ^O 3 molecular weight: - 254.4

calc. C 70.8 % H 10.3 %

found 71.2 % 10.4 %

Example 3: 5 - (^ - Is ° P ^ opoxy - 2-butyloxy) -3-methyl-2-pentenoic acid, methyl ester

Is prepared analogously to Example 1, except that 4- (4-isopropoxy-2- butyloxy) -2-butanone instead of 8-sec-butoxy-6-methyl-5-octene-2-ori is used.

n ^ ° = 1.4521

Analysis: ^c 14 ^H 26 ° 4 molecular weight: 258.4

above _t C 65.1 % H 10.1 % "

ge "f, 65.4 % 10.4 %

Example 4: 10-Isogropoxy - ^ - methyl-g-decenoic acid ethyl ester

V / ird is prepared analogously to Example 1, whereby instead of 8-sec-butoxy-6-methyl ~ 5-octen-2-one the 9-I ^so P ^ro PQxy-2-nonanone and instead of (0,0-diethylphosphono) - methyl acetate of the ■ (Ο, O-diethylphosphonoJ-ethyl acetate is used.

Molecular weight: 270.4

H 11.2 io 0 17.7 fo 11.2 $ 17.7 %

209851/1269

n ²⁰ = 1 , 4527 C. 16 ^H. 30 ° 3 Ana Iy ö e: C. 71 1 Cv
, J- / ° ber. 71 , 6 fo gof.

16-130-3520

Example 5: 5zii

methyl ester

Is synthesized analogously to Example 1. That instead of 8-sec-butoxy ~ 6-methyl-5-octen-2-one 4- (l-sec-butoxy-3-pentyloxy) -2-butanone used as starting material is according to Example 14 manufactured.

τξ ° = 1.4527

Analysis: ^c 16 ^H 30 ° 4 Molecular weight: 286.4

calc. C 67.1 # H 10.6 %

found 68.0 % 10.7 %

Example 6: 2ri§

ester

Is prepared analogously to Example 1, but instead of (0,0-diethylphosphono) -acetic acid methyl ester the (O, 0-diethylphos phono) -acetic acid ethyl ester and instead of 8-sec-butoxy-6-methyl-5-octen-2-one the 8-isopropoxy-6-methyl-2- octanone is used.

n £ ° = 1.4532

Analysis: ^C 16 ^H "50 ^O 5 Molar weight: 270.4

calc. C 71.1 % H 11.2 % 0 17.7 % found 70.7 & 10.8 % $ 18.4

Example 7: 10-isopropoxy-8-raethyl-3,7-decadion-2-one

1.84 g (0.01 mol) of 7-isopropoxy-5-methyl-4-heptenal are used together with 3.1 g (0.01 mol) of triphenyl-acetylmothylenephoran (S: np. 199.5-201.5 °) »manufactured according to D.B. Denney and S.T. Ross, J. Org. Chora. 27, 998 [1962], in 30 ml Tetrahydrofuran - boiled under reflux for 24 hours.

2 0 9 3 5 1/12 6 9

BATH ORIGINAL

-17 - 1 ^ 0-3520

The tetrahydrofuran is then evaporated, the residue is taken up in hexane, the insolubles are filtered off and the kexane is evaporated. The oily residue can be purified by chromatography on silica gel with benzene / methanol 96: 4. Pure 10-isopropoxy-8-methyl-3,7-decadien-2-one is obtained. η _β = I, 47l6.

Analysis: ^c 14 ^H 24 ° 2 Molecular weight: 224.3

calc. C 75.0 # H 10.8 %

found $ 75.1. . * 10.9 %

Example 8: 9- ^se cB ^u toxy-3,7-dimethyl-2,6-nonadiene-l-

nitrile

1.77 g (0.01 mol) of 0.0-diethyl cyanomethylphosphonate are added dropwise at 25 ° to a slurry of 0.48 g (0.01 mol) of 50% sodium hydride dispersion in 25 ml of absolute 1> 2-dimethoxyethane . After stirring for two hours at 25 °, 2.12 g (0.01 mol) of 8-sec-butoxy-6-methyl-5-octen-2-one are added and the mixture is stirred at 25 ° for 18 hours. Then 50 ml of ether and 150 ml of V / water are added and the aqueous phase is extracted with ether. The ether extract is washed with saturated sodium chloride solution, dried with sodium sulfate and evaporated. The residue is chromatographed on silica gel with chloroform as the mobile phase, the Q-sec-Butoxy-J, 7- dimethyl-2,6-nonadiene-1-nitrile as a colorless oil, consisting of approximately equal proportions of the cis and trans isomers 'is obtained.' n ^ ° = 1.4720

Analysis: C _1C -H, .NO Molar weight: 235.4

calcd. C 76.5 % H 10.7 # N 6.0 % found . 77.0 # $ 10.9> 5 * 6 %

209851/1269 BAD or, q _INAL

_ _l8 .

Example 9;

About the Grignard reagent _/ made from 0.46 g (0.019 mol) of magnesium and 4.5 g (0.019 mol) of 1-Brcm-6-isopropoxy-4-methyl-3-hexene in 60 ml of absolute ether, x is stirred a solution of 2.45 g (0.019 mol) of 4-ethoxy-3-penten-2-one in 3-0 ml of absolute ether was added dropwise at 5 ° in the course of 15 minutes. After stirring for four hours at 20 °, it is poured onto ice-cold 2N sulfuric acid and extracted with ether. The ether extract is washed with saturated sodium bicarbonate solution, water and saturated sodium chloride solution, dried over sodium sulfate and evaporated. The residue is chromatographed on 200 g of silica gel with hexane / ethyl acetate (9: 1) as the mobile phase, 10-isopropoxy-4,8-dimethyl-3 , 7-decadien-2-one obtained as a colorless oil.

n ^ ° = 1.4726

Analysis: ^C 15 ^H 26 ° 2 · Molecular weight: 238.4

calc. C 75.5 % H 10.9 %

found $ 74.6 'io, 9 %

For the representation of the .used as starting products The following procedures can be used for ketones of the general formula II:

Example 10 : B-sec-Butoxy-o-methylyl · -5 ^ octen-2 ~ one

8.60 g (0.05 mol) of 5-sec-butoxy-3-methyl-l-penten-3-ol and 11.6 β (0.1 mol) methyl acetate are under Nitrogen heated to 135 ° in a round bottom flask with a distillation attachment. The one set free by the reaction Methyl alcohol distilled into the template. After 1 hour

209851/1269

130-3520

the reaction ^{temperature is increased to 182-185 or} and held at this temperature for 5 hours. After cooling, the reaction mixture is fractionally distilled under reduced pressure. In addition to methyl acetoacetate, a 5-cis / trans mixture of 8-sec-butoxy-6-methyl-5-octen-'2-one is obtained. 1O5-1O9 ° / o iron, ^8, n ^ ° = 1.4534

Analysis:

Molecular weight: 212.3

ber.
found

C 73.5 73 Λ

H 11.4 %

OK, 9 %

Example 11: 8-Isopropoxy-6-methyl-5-octen-2-one

The compound is prepared analogously to Example 10, except that 5-isopropoxy-3-methyl-1-penten-3-ol instead of 5-sec-butoxy-3-methyl-1-penten-3-ol is used.

PO

Bp. 117 ^o -119 ° / 8 mrn, nir = 1.4473

Analysis:

b he.
found

^C 12 ^H 22 ° 2

C 72.7 $ 72.4 yrs

Molgev; icht: 198.3

H 11.2, Jg 11.0 $

Example 12: 8-Isopropylthio-6-methyl-5-octen-2-one

V / is prepared analogously to Example 10, except that instead of 5-sec-butoxy-3-methyl-1-penten-3-ol, 5-isopropylthio-3-methyl-1-penten-3-ol is used, and the reaction mixture not by distillation, but by chromatography on silica gel with hexane / ethyl acetate (9: 1) as eluent · cleaned v / ird.

nf = 1.4883

Analysis:

Molecular Weight: 214.4

209851/1 269

calcd. C 67.3 % H 10.2 # S 15.0 % found . 66.4 % 9.7 % 15.0 <f>

Example. 13: 4- (4-isopropoxy-2-butyloxy) -2-butanone

20 g (0.154 mol) 4-isopropoxy-2-butanone, dissolved in 200 ml 10 g (0.26 mol) of sodium borohydride are added to ethanol at 20 ° -25 ° in the course of 2 hours. After another 2 hours the reaction mixture is reduced to 50 ml under reduced pressure concentrated, poured into 400 ml of water and extracted with ether. The ethereal solution is dried with sodium sulfate and evaporated. The residue is distilled at 35 mm, 4-isopropoxy-2-butanol having a bp of 88 ° / 35 mm.

To 3.3 g (0.025 mol) of 4-isopropoxy-2-butanol and 0.4 g of conc. Sulfuric acid is added dropwise to a mixture of 9.9 g (0.075 mol) of 4-isopropoxy-2-butanol and 7.0 g (0.1 mol) of methyl vinyl ketone at 20 ° -30 ° in the course of 30 minutes. After stirring for 24 hours at 20 ° -25 °, 0.7 g of potassium carbonate and 0.1 g of water are added. The reaction mixture is stirred vigorously for 3 hours at room temperature, filtered and distilled. The 4- (4-isopropoxy-2-butyloxy) -2-butanone obtained has a bp of 75 ° -76 ° / 1.0 mm. nj: ⁰ = 1.4268

Analysis:. ^C n ^H 22 ° '^; 5 molecular weight: 202.3

calc. C 65.3 % H 11.0 %

found 65.0 # 1.1.0 %

Example l4 :

is prepared analogously to Example I3, with 1-isopropoxy-3-pentanone being used instead of 4-isopropoxy-2-butanone. Bp 95 ° -97%> 2 mm. n ^ ⁰ = 1.4306

209851/1269

130-3520

Analysis:

ber.

found

^C 13 ^H 26 ° 3

C 67.8 % 67.8 pounds

Molecular weight: 230.3

H 11.4 % 11.2 %

Example 15: 7-Isogropoxy ^ 5-methyl-4 ~ heptenal

15.8 g (0.1 mol) of S-isopropoxy - ^ - methyl-l-pentene - ^ - ol and 20.0 g of mercury acetate are kept in 180 ml of ethyl vinyl ether for 4 days at reflux temperature. 0.9 ml of glacial acetic acid are added at 20 ° to the now cloudy solution. After 3 hours, 150 ml of 5% potassium carbonate solution are added and the mixture is extracted with hexane. The hexane extract is dried with sodium sulfate and evaporated. The residue is heated without further purification under nitrogen for 1 1/2 hours at ⁰ I65 -l68 ° and then distilled under reduced pressure. Bp of 7-isopropoxy-5-methyl- ⁱ l-heptenal: 70 ° -73 ° / 0.8 mm, 20

n ~ - = 1.4476

Analysis:

ber.

found

^C ll ^H 20 ° 2

C $ 71.7 $ 71.7

Molecular weight: 184.3

H $ 10.9> 10.8 %

Example 16 '.

9-isopropoxy-2-nonanone

1.4 g (0.025 KoI) solid potassium hydroxide are in 30 ml 50 $ dissolved in aqueous methanol. 4.1 g are added to this solution (0.015 mol) 3-carbaethoxy-9-isopropoxy-2-nonanone added and the mixture is heated to boiling temperature. After 1 hour on The reaction mixture is cooled to reflux to 50 °, with $ 50 Sulfuric acid neutralized, cooled to room temperature after 10 minutes and treated with 50 ml of water. The heterogeneous mixture

209851/12 69

is extracted with ether, the ether extract is washed with saturated sodium chloride solution, dried with sodium sulfate and evaporated. The residue is chromatographed on silica gel with hexane-liquid ester 9: 1. Kan receives uniform 9-isopropoxy-2-nonanone as a colorless oil.
n £ ^u = 1.4309

Analysis: ^c 'i2 ^iI 24 ° 2 molecular weight: 200.3

calc. C 72.0 # H 12.1 % 0.16.0 56 found. . 71.7 % 11.9 % 16.2 %

Example 17: 8-Isopropoxy-6-methyl-2-octanone

The connection is shown analogously to Example ΐβ, where instead 3-carbaethoxy from 3-carbaethoxy-9-isopropoxy-2-nonanone -8-isopropoxy-6-methyl-2-octanone is used, bp 127-129 ° / 15 mm

Analysis: C, _O H nh ° o Molecular weight: 200.3

calc. C 72.0 $ H 12.1 $ 0 16.0 # found. 71.3 % 11.8 $ YJ, 1) io

The condensation of the compounds of general formula XI with ethyl acetoacetate can forgiveness by the following ^example: are taken:

Example 18 : 3-Carbaethoxy-9-isopropoxy-2-nonanone

0.69 g (0.03 mol) of sodium are absolute at 20 ° in 20 ml Ethanol registered. After the reaction is complete, 3.9 g (0.03 mol) of acetoacetic acid are added dropwise to the solution at 25 °. The clear solution is then heated to 80 ° and 6.7 g are added over the course of an hour at the reflux temperature (0.03 mol) of 1-bromo-6-isopropoxy-hexane were added dropwise. The cloudy

209851/1269 BADOR ₁ G ₁ NAL

The mixture is refluxed for 16 hours and then cooled to 20 ° and neutralized with alcoholic hydrochloric acid. After adding 20 ml of ether, the reaction mixture is filtered and the filtrate is evaporated. The residue is distilled, with 3-carbaethoxy-9-isopropoxy-2-nonanone having a bp 125 ° -130 ° / ⁰ '8 mm. accrues. .

Analysis: ^C i5 ^H 28 ° 4 "Molecular Weight: 272.4

calc. C 66.1 % H 10.4 £ 0 23.5 f found . 65.8 i 10.4 % 24.1 <fo

The following compound can also be prepared analogously to Example 18, with 1-bromo-5-isopropoxy-3-methylpentane instead of 1-bromo-6-isopropoxy-hexane is used.

Example IQ : 3-Carbaethoxy-8-isopropoxy-6-methyl-octanone

Bp 92 ° -94 ° / 10 ~ ⁴ mm.

Analysis: ^C 15 ^H 28 ° 4 Molecular weight: 272.4

calc. C 66.1 % H 10.4 % 0 23.5 % found 66, ι ^ ιο, ο % 23.9 %

The compounds of the general formula XI can be prepared according to the following examples 20-21:

Example 20 : 1-bromo-6-isopropoxy-hexane

1.15 g (0.05 mol) of finely chopped sodium are introduced into 30 g (0.5 mol) of absolute isopropanol under nitrogen and stirred at 60 ° for 16 hours to completely dissolve the sodium. After cooling to 20 °, 12.2 g (0.05 mol)

20985 1/1269

130-5520

1,6-dibromohexane was added and the mixture was stirred at reflux temperature for 18 hours. The precipitated sodium bromide is filtered off, the filtrate is freed from excess isopropanol in vacuo and distilled. The main fraction (6.0 g) with a bp. 96 ° -98 ° / 15 mm is chromatographed on 300 g of silica gel with hexane-ethyl acetate (99 * 1), 1-bromo-6-isopropoxyhexane being obtained as a uniform, colorless oil . Analysis: C _n H _1n BrO Molar weight: 223.2

calc. C 48.4 % H 8.6 % Br 35.8 $ found. 48.7 fo $ 8.4 35.9 %

0 7.2 7.6

Example 21:

1-bromo-5-isopropoxy-3-methyl-pentane

A mixture is added to 10.9 S (0.04 mol) of phosphorus tribromide at 0 ° of 16 g (0.1 mol) of 5-isopropoxy-3-methyl-1-pentanol and 2 g (0.25 mol) of pyridine were added dropwise. The mixture is then stirred for 2 hours at 25 ° and then at 12 mm / 160 ° bath temperature in a receiver of saturated sodium bicarbonate * distilled (bp 100 ° -110 ° / 12mm).

The content of the template is taken up with ether and one after the other with saturated sodium bicarbonate solution, 2 N sulfuric acid and saturated saline solution, and dried with sodium sulfate. After evaporation of the ether, the remaining 1-bromo-5-isopropoxy-3-methyl-pentane is distilled cleaned. Sdp. 90 ° -91 ° / 12 mm.

Analysis:

ber.
found

C ₉ II ₁₉ BrO

C 48.4 yrs 48.4 %

Molecular Weight: 223.2

H 8.6 7.9

Br 35.8 $ 35.6 fo

0 7.2 $ 7.7 #

209851/1269

The alcohols used for the preparation of the compounds of the general formula XI can by known processes, for example set up as described in the following example:

Example 22: 5-isopropoxy-3-methyl-pentanol

To 28.4 g (0.105 mol) of phosphorus tribromide with stirring at 0 ⁰ C a mixture of 34.4 g (0,26l mol) of 4-isopropoxy-2-butanol and 5 * 07 g (0.064 mol) of absolute pyridine in the course added dropwise from 15 min. After stirring for 2 hours at room temperature, the reaction mixture is rapidly distilled in vacuo (bp. 35-60 ° C./12 mm). The distillate taken up in ether is washed successively with ice-cold dilute sodium bicarbonate solution, water, ice-cold 2N sulfuric acid, water and saturated sodium chloride solution, dried over sodium sulphate and freed from ether over a column.

Fractional distillation of the residue gives 2-bromo-4-isopropoxy-butane with a bp of 69 ~ 70 ° C / 24 mm.

To the ethanolic sodium ethylate solution, prepared from 9 * ^ - 5 g of sodium and 200 ml of absolute ethanol, v / earth under nitrogen and stirring at 50 ⁰ C within 15 minutes. 67.7 g (0.423 mol) of malonic acid ethyl ester were added dropwise, followed by 80.0 g (0.4lo mol) of 2-bromo-4-isopropoxy-butane, in the course of a further 15 minutes. The mixture is refluxed for 24 hours, then neutralized with glacial acetic acid and freed from the bulk of the ethanol by distillation.

The ether extract of the residue treated with ice water is washed with water and saturated sodium chloride solution over Dried sodium sulfate and evaporated in vacuo. The resulting crude 2-carbaethoxy-5-i5opropoxy-3-methyl-n-valerian-

20985Ί / 1269

26 - '130-5520

ethyl acid ester can be reacted further without additional purification.

110 g of crude ester are converted into 18o g of 50 percent strength over the course of 15 minutes with stirring at 6O ^{0 C.} KOH (1.60 mol) was added dropwise and the mixture was refluxed for 2 hours. After adding 100 ml v / water, the ethanol formed during the hydrolysis is distilled off at normal pressure. The acidified at 10 ⁰ C with 250 ml of sulfuric acid with stirring β η residue is extracted with ether, the ether extract washed with a little water and saturated sodium chloride solution, and dried over sodium sulfate evaporated. The crude dicarboxylic acid that remains is ^{stirred at 190 °} C. for 1 hour for decarboxylation and the product is then distilled in vacuo. This gives 5-isopropoxy-3-methyl-n-valeric acid with a boiling point of 89-91 ° C./0.1 mm.

Analysis: C _g H _Q 0 ^ Molecular weight: 174.2

calc. C 62.0 % H 10.4 <? o 0 27.5 $ found. 62.0 % 10.4 # 27.6 %

A solution of 19 * 8 g (0.14 mol) of S-isopropoxy - ^ - methyl-n-valeric acid in 120 ml of absolute benzene is added to 96 ml (0.14 mol) of 70 percent in the course of one hour. Sodium bis (2-methoxyethoxy) alurainium dihydride was added dropwise to 220 ml of absolute benzene. The mixture is boiled for 2 hours under reflux, cooled to 1O ^ ⁰ C, acidified with stirring with 2 η sulfuric acid and extracted with ether. The extract is washed with a little water and saturated sodium chloride solution, dried over sodium sulfate and evaporated.

When the residue is chromatographed with hexane: ethyl acetate = 9: 1 on 600 g of silica gel, 5-isopropoxy-O-methyl-pentanol is used as colorless oil obtained.

209851/1269

- 27 - ·. 150-3520

Analysis: ^C q ^H 20 °? Molecular weight: ϊ6θ, 3

calc. C 67.5 % H $ 12.6> $ 0-20.0

found 67.3 % 12.7 % 20.2 %

The halogen precursor to the Grignard compound required for the preparation of the compound of the general formula I according to process c of the general formula V can be prepared, for example, according to the following example:

Example 23: 1-Bromo-6-isopropoxy-4-methyl-3-hexane

The Grignard reagent [prepared according to E. Renk et. al. J. Am, Chem. Soc. 8j5, I987 (196I)] made from 9.06 g (0.37 mol) Magnesium and 42.8 g (0.35 mol) Cyelopropylbromld in 46o ml of absolute tetrahydrofuran, is under nitrogen and stirring 5 ° C., a solution of 46 g (0.35 mol) of 4-isopropoxy-2-butanone in 100 ml of absolute tetrahydrofuran was added dropwise in the course of 10 minutes. After stirring for 20 hours at room temperature, the reaction mixture is mixed with saturated ammonium chloride solution and ice added and extracted with ether. The ether extract is washed with saturated sodium chloride solution and dried over sodium sulfate and evaporated »The resulting 2-cyclopropyl-4-isopropoxy-2-butanol is obtained as a colorless oil after distillation at 75 ° -77 ° / 12 mm.

Ig ml of 48 $ hydrogen bromide to be 27.7 g of 2-cyclopropyl-4-isopropoxy-2-butanol with stirring at 0 ⁰ C over 15 min. Zugotropft acid [Method of M. Julia et al ..-. , Bull. Soc. -Chün. France 1072 (1960)]. The mixture is stirred for 30 minutes at 0 ° to 5 ° and then extracted with ether. The ! \ ΟΛΛ \ <ίν! -, \\ ί-.7Μ; <; is mixed with water, saturated sodium bicarbonate solution

209851/1269

: ■ r Λ λ

ο ο ζ ο

130-3520.

solution and saturated saline solution, dried over sodium sulfate and evaporated. The residue is treated with hexane / ethyl acetate (98: 2 and 95: 5) Chronographed silica gel. The chromatographically uniform mixture of the cis-trans isomers of l-bromo-6-isopropoxy-4-methyl-3-hexene is thereby obtained obtained as a colorless oil. n ^ ° = 1.4802

Analysis: C ₁₀ H ₁₉ BrO Molar weight: 235.2

Calcd. C 51.1 ^ H 8.1 % Br 34, O- # found. 51.1 % 8.3 % 33.2 %

The ketones of the general formula XII * in which R _{0 is} a lower alkyl group with 1 to 4 carbon atoms can be represented according to the following examples:

Example 24 i 4-Isopropoxy-2- butanone.

To 7.2 g (0.12 mol) of isopropanol, 0.3 g of conc. sulfuric acid given. While stirring to room temperature, a mixture of 21 g (0.33 mol) of vinyl methyl ketone is obtained in the course of one hour and 36 g (0.6'Mol) of isopropanol are added dropwise, being careful that the temperature does not exceed 30 ° increases. After 24 hours, 1.6 g are obtained at room temperature

Potassium carbonate and 2 drops of water are added to the mixture Stirred intensively for 2 hours, filtered and the clear, now neutrally reacting piltrate fractionated at 36 mm. After this the excess isopropanol has passed over, 4-isopropoxy-2-initanone is distilled at 73-76 ° / 36 mm.

Λ '"; <Ί ■"

Ü Ό ti O

BAD ORfGJNAL

Example 25: Propylthio-2-butanone

Is prepared analogously to Example 24, except that isopropyl mercaptan is used instead of isopropanol, bp 94-96V17 mm.

The alcohols of the general formula VIII can according to the following Examples are produced:

Example 2§j_ Sr

12 g (0.5 mol) of magnesium shavings are in a stirrer and reflux condenser covered flask under nitrogen with 60 ml of absolute tetrahydrofuran and on Heated 4o to 45 °. From a dropping funnel are 5 nil a solution of 53. » 5 S (0.5 mol) vinyl bromide in 100 ml absolute tetrahydrofuran was added dropwise, whereupon an exo- · thermal reaction begins. The remaining vinyl bromide solution is just added dropwise so quickly that a temperature of the reaction mixture of 45 to 50 ° is maintained (approx. 1 to 1 1/2 hours). The mixture is then stirred for one hour at 50 ° and then cooled to 0 °. Under vigorous stirring are now 52 g in the course of 45 minutes (0.4 mol) 4-isopropoxy ~ 2 "butanone in 100 ml of absolute tetrahydrofuran added dropwise and then the reaction mixture is stirred for 16 hours at room temperature. At this time, 250 ml are added over 15 minutes 20 # ammonium chloride solution to the cooled to 5 to 10 ° Reaction mixture added. The mixture is stirred for 15 minutes and extracted with ether. The Aetherex

209851/1269

tract is washed in the separating funnel rait water, with Dried sodium sulfate and evaporated. The residue

is fractionated at 13 mm pressure, the 5-isopropoxy- ' 2-methyl ~ 1-penten-> ol distilled at 72-73 °. n ^ ° = 1.4297-

Analysis: ^c g ^H 18 ° P Molecular weight: 158.2

calc. C 68.3 % H 11.5 %

found 68.1 % 11.4 %

Example 27: ^ -Isopropylthio - ^ - methyl-1-pentene - ^ - ol

Is prepared analogously to Example 26, except that 4-isopropylthio-2-butanone instead of 4-isopropoxy-2-butanone is used. 79-80 ° / 1.2 mm, njf β 1.4813

Analysis: CJi gOS molecular weight: 174.3

found 61.5 % 10.4 % '18 .9

209 851/1269. ^ßÄD ORIGINAL

Claims (8)

130-3520 'claims; Process for the preparation of compounds of the general formula 1 Ya h R ₁ Q- (CH ₀ ) -CZ ₁ -Ch * -CH ₀ -C = CH-Y A in which R. denotes a branched or unbranched, saturated or mono- or polyunsaturated aliphatic or alicyclic radical or a cycloalkylalkyl radical with 1 to 3.0 carbon atoms and in which _{'R 2} ' and Ry, which can be the same or different, denote hydrogen or a lower alkyl group with 1 to 4 carbon atoms, Q is an oxygen or sulfur atom and Z_ is an oxygen or sulfur atom or a group -CH-, with the proviso _s that A and B each stand for oxygen or that A and B together should mean a CC bond (ie the compounds of the general formula I ^ il should mean), and v / orin Y a cyano group, a group -CONRuRf-, in which R ^, and R ₁ -, which can be the same or different, are hydrogen or an alkyl group having 1 to carbon atoms, or can form a heterocyclic ring with the inclusion of the nitrogen atom, a group -COOR, -, in which Rg is an alkyl group with 1 to 5 carbon atoms, or a group-COR ₁₇ , in which R "is an alkyl group having 1 to 5 carbon atoms * and in which η is 1, 2 or 3, is characterized in that one
a) a compound of the general formula II 209851/1269. ¹ BADORIGINAt 130-3520 R ₀ R R ₁ Q- (GH ₀ ) -CZ ₁ -CH ^ -CH ₀ -C = O. II A wherein R,, Rp, R-, Q, Z ", A and η are those indicated above Have meanings in the presence of strong bases with a compound of the general formula III ? " ^CH 2 ^{X 1 τ} where Ro and Rq, which can be the same or different, stand for a phenyl group, an alkoxy group or an aryloxy group and v; orin X has a cyan group, a group -COORg, v? oriii R ^ dia has the meaning given above, a group -CCNRJL -, in which IU and R ₁ - those designated above. Have meanings, or e group -CO
has meaning, a group -COR ₇ , in which R _{17 is} the above-identified Be b) -3 a compound of the general formula II, in which R., R ₀ , R_ ,, Q, Z ₁ , Λ and η have the meanings given above, with a compound of the general formula IV IO
- ^x P-CHX IV 33-130-3520 wherein X has the meaning indicated above and R-, _n > R ₁ and R ₁₂ mean aryl or dialkylamino, or that one c) if Y in the general formula I is a group COR ₇ and Z is a group -CH- _} a Grignard Ver Compound of the general formula V ? 2 R ₁ Q- (CH ₀ VC-CH-CH ₀ CH ₀ MgX V 1 d η tt d. d AWAY ₀ V d η in which R ₁ , R 2, Q, A, B and η have the meanings given above and X is chlorine or bromine with a compound of the general formula VI VI where R ₇ and IL · have the meanings given above and R_ stands for a lower alkyl radical with 1 to 4 carbon atoms and subsequent · acid hydrolysis of the resulting magnesium salac and enol ether and simultaneous elimination of V.'assor. 2. Process for the preparation of compounds of the general Formula I according to claim 1 a), characterized in that that sodium hydride is used as the base. 3. Compounds of the general formula I R ₁ Q- (CHg) _n -CZ ₃ -CH ₂ -CH ₂ -C = CH-Y 209851/1269 BAD original 34-130-3520 wherein R _{1 is} a branched or unbranched, saturated or mono- or polyunsaturated aliphatic or alicyclic radical or a cycloalkylalkyl radical with 1 to 10 carbon atoms and wherein R and R, which can be the same or different, represent hydrogen or a lower alkyl group with 1 to 4 carbon atoms, Q is an oxygen or sulfur atom and Z _{1 is} an oxygen or sulfur atom or a group -CII-, with the proviso, that A and B are each hydrogen or that A and B together represent a CC bond are intended to mean (ie, the compound of the general formula I _R ^ _ (CH ^ Sch-CH ^ H ^ cH-Y ^be "point to), and in which Y is a cyano group, a group -COMR ^ .R _r in which Rj, and R ₁ -, which can be the same or different, represent hydrogen or an alkyl group having 1 to 4 carbon atoms, or, including the nitrogen atoms, a heterocyclic ring know, a group -CCOR, -, in which R ^ stands for an alkyl group with 1 to 5 carbon atoms, or a group -COR ", in which R" stands for an alkyl group with 1 to 5 carbon atoms, and where η stands for 1.2 or 3 means. 4. 9-sec-7iutoxy-3,7-dimethyl-2,6-nonaaenoic acid-n-ethyl ester 5. 9-isopropoxy-3 _J-7 dimfii; hyl -2,6-nonadien3äure-methylc3ter 6. 5- (4-Isopropoxy-2-butyloxy) -3 "methyl-2" pentenoic acid riethyl ester. 7. 5- (1-sec-Butoxy-5-pentyloxy) -3-methy.l-2-peritic acid--; ₁ iothyl ester. 8. 10-Isopropoxy-8-r: iethyl-3i7-dec3dien-2-one. 2 0 9 8 5 1/12 6 9 F.
^ßAD . - 35 - '■ 130-3520 9 »9 ~ ^sec ~ B ^u Toxy-3I7-ö.imethyl-2j, 6-nonadien-l-nlt: ril. 10. 10 ~ Isopropoxy ~ 3-methyl-2-decenoic acid ethyl ester. 11. g-Isopropoxy - ^^ - dimethyl - ^ - nonenoic acid ethyl ester. 12. 10-Isopropoxy-4,8-dimethyl-3 * 7-decadien-2-one. 13. Pesticides, characterized that they contain one or more compounds of the general formula I according to claim 1 as active ingredient, 14. Pesticides, characterized in that it _s 9-see-butoxy-3 _i 7-dimethyl-2 _j, 6-nonadiensäuremethylester contains, as active substance, 15. Schädlingsbekämpfungsmittelj characterized in that it is _a 9-isopropoxy _i ~ 3J7-dimethyl-2, 6-nonadiensäuremethylester contains as active substance " 16. Pesticides _3, characterized in that it contains 5- (4-isopropoxy ~ 2-butyloxy) -3-methyl-2-pentenoic acid methyl ester as active ingredient, 17. Pest control agent, characterized ^ that it contains '-) - ■ (l-3ee-butoxy-3 ~ pentyloxy') - 3-niethyl-2 ~ pentenoic acid methyl ester as active ingredient « 1.8. So'n. ^: idiinc3bekä?;} care agent, dadurcli marked "Jtasn ea 10-I" ^ opropoxy-8-mothyl-3,7-decad'ien-2-one contains as Aktlvutofr. 209851/1289 150-5520 That 9 ~ ^se c-butoxy · 19 pesticides, characterized in that - 5J7-di ^me thyl ~ 2, o-nonadien-lnitril contains as active substance. 20. Pesticides, characterized in that that it is 10-isopropoxy-5-methyl ~ 2-decenoic acid ethyl ester contains as an active ingredient. 21. Pesticides, characterized in that it contains 9 ~ I ^so P ^ro P ^ox y ~ 5i7-dimethyl-2-nonenoic acid ethyl ester as active ingredient. 22. Pesticides, characterized in that dasG es 10-isopropoxy-4,8-dimethyl-5,7 ~ il, 2cadien-2-one contains as an active ingredient. DeT patent attorney » BAD ORiGINAL 209851/1269