DE2319573A1 - SCHAEDLING INHIBITORS - Google Patents

Description

The present invention relates to compounds of the general formula I.

R ₁ -YC- (CH ₂ ) ^ c- (CH _a ) _z -xa ₆ ι

wherein R- is a straight-chain or optionally branched alkyl radical with 1 to 11 carbon atoms, a straight-chain or branched, mono- or polyunsaturated, non-cyclic hydrocarbon radical with 3 to 11 carbon atoms, a Cyelcqlkylresfc or a, with a lower Alkyl.gru.ppe substituted Cyeloalkylresb with 5 to 7 carbon atoms and R ₃ , R ,, R ₄ and R ₅ independently of one another for hydrogen or a straight-chain or optionally branched alkyl radical with 1 to 6 carbon atoms and w and ζ

309846/1188

ORIGINAL INSPECTED

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stand for 0 or a number from 1 to 8 with the proviso that the sum w + ζ should mean a number from 1 to 8 and Y for oxygen or sulfur, X for oxygen, sulfur, an -OCH ₂ -, -SCH ₂ -. -OCHR-- or -SCHR_ group, where R- denotes a straight-chain or optionally branched alkyl radical having 1 to 4 carbon atoms

and in which R- is an aromatic radical Ar: ο ■ J-

an aromatic one
Residue Ar ₃ : ^u q

means, wherein ü is a lower alkyl, alkenyl, phenol, lower alkoxy, lower alkenyloxy, formyl, lower alkylcarbonyl, lower alkoxycarbonyl, mono- or di-lower alkyl-substituted carbamoyl, lower alkoxymethylene, lower alkylthio - Or a cyano group or chlorine or bromine and R _ft and R_ independently of one another for hydrogen or for a lower alkyl group and W for a nitro group and the individual substituents u can be different and in which m is

0,1 or 2, η stands for 0,1 2 or 3 and the sum m + η is to stand for a number from 1 to 5, ρ stands for 1 or 2 and q stands for 0, 1 or 2

with the proviso that R "should only stand for a straight-chain or optionally branched alkyl radical with 1 to 6 carbon atoms when X stands for -OCHR- or -SCHR ₇ -, or when X stands for -OCH ₂ - or -SCH ₂ - and R _fi at the same time has the meaning Ar ₃ tmd / or if ζ is a 2ah 1 from 1 to 4 and at the same time the sum w + ζ is a number from 1 to 4,

308846/11-ββ

130-3711

which are suitable for pest control. As used herein, "lower alkyl" refers to refers to a straight or branched chain alkyl group of up to 6 carbon atoms.

The compounds of general formula I can be, for example ·

a) by reacting a compound of the general formula II

wherein R,, R _n , R -, R ₁ ,, H ₁ - and Y as well as w and ζ are the above be-12345

Signed meanings and Q ^ for chlorine, bromine or a tosyl radical with a compound of the general formula III

M ₁ XR ,. III

in which Rg and X have the meanings given above, and M, stands for hydrogen, sodium or potassium, with the proviso that when M ₁ stands for hydrogen, the reaction is preferably carried out in the presence of an acid-binding agent, or

b) if X in the general formula Ϊ is oxygen and ζ is an integer from 1 to S by reacting a compound 'of the general formula IVa -

R, -YC- (GH ^) C- (CH ₀ ) ^ - OH IVa

IW R-

where R .. * R_, R ~, Rk, Rp. and Y as well as w the above Have meanings and ζ for an integer, from 1 to 8 stands with a compound of the general formula IHa

IIIa.

wherein Rg has the meaning given above with bicyclohexyl carbodiimide as a condensing agent, or c) if in the general formula I w + ζ for 2 to 8 and Y stand for oxygen, by attachment of a compound of general formula Va

HOR ₁ Va

where R. has the meanings given above, to which Compound of the general formula VI

/ d W-Xi d Z O ■

._ ■ R- '■

■ J * - 5. . .. ■■ "■ -

.worin, Η _Λ , R_, R,., Rr-, R ^, X, as well as w and z. the above

2 _5 H ■ _J O

have signed meanings, or

d) if the radical X in the compounds of the general formula I is -QCH ^, -SCH ₁ T, -OCHR ₇ - or -SCHR-, a compound of the general formula el-IV

<?>. *? *) c - '; -. {r> \ ή fß-, '■ ι'' 0 ''' i 'r'} S 'iä ^ J ^ iI ^ v y &' / _ jy 'S ^ 3

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where R ^, R-, R, R ^, R ₅ as well as w and ζ have the meanings given above and Z represents oxygen or sulfur and M_ represents hydrogen, sodium or potassium with a compound of the general formula VII

Q ₂ ^CHR 6 ^R io ^VI1

in which R, has the meaning indicated above, R is hydrogen or R ₇ and Q _{2 is} chlorine or bromine

with the proviso that, if M ₂ in the general formula ϊν is hydrogen, the reaction is carried out in the presence of an acid acceptor, or

e) if the substituent R ₃ in the general formula I is hydrogen, by reacting a compound of the general formula VIII

HR ₄
Q3C- (CH ^) _w C- (CH ₂ ) _z -XR ₆ VIII

where R ^ Rh iRj-jRgjX and w and ζ have the meanings given above and QJTür chlorine, bromine or a tosyl radical '
with the compound of the general formula V

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wherein R and Y have the meanings given above and M _{3 stands} for hydrogen, sodium or potassium, with the proviso that, if M ₃ stands for hydrogen, the reaction is carried out in the presence of an acid acceptor, or

f) if the substituent R ₃ in general formula I is hydrogen, by reaction of a compound of general formula IX

MjY-C- (CHg) ₁₁₁ C- (CHg) ₂ -XR ₆ IX

V '"5

wherein FL, R ^, R ₁ -, Rg ,. χ and Y, as well as w and ζ have the meanings given above, and M _{4 stands} for hydrogen, sodium or potassium, with the addition that, if M ₄ stands for hydrogen, the reaction is carried out in the presence of an acid acceptor, with a compound of the general formula X

^Q 4 ^R n

wherein Q. _{4 is} chlorine, bromine or a tosyl radical and R is a straight-chain or optionally branched primary or secondary alkyl radical with 1 to 11 carbon atoms, a straight-chain or branched, mono- or polyunsaturated non-cyclic primary or secondary hydrocarbon radical with 5 to 11 carbon atoms, a cycloalkyl radical or a cycloalkyl radical with 5 to 7 ring carbon atoms substituted with a lower alkyl group, with the proviso that the radical Q. is to be bonded to a primary or secondary carbon atom.

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The implementation according to method a) is carried out as follows will:

The compounds of the general formula III. is left in a suitable solvent, such as a carbon dioxide such as benzene, toluene, an ether such as dioxane, 1,2-dimethane, diethylene glycol dimethyl ether, a ketone such as acetone, a nitrile such as acetonitrile, an acid amide such as dimethylformamide or, if X in the general formula III means -OCHg- or -SCHg, Hexamethylphosphoric acid triemide or, if X is 0 or S, an alcohol such as ethanol, tert. Butanol or a suitable solvent mixture and if M in the formula III stands for hydrogen, in the presence of an acidic. agent such as sodium or potassium hydroxide, Sodium or potassium carbonate, potassium tert. Butoxide etc. at temperatures between preferably 0 and about 120 °, depending of the solvent used and with stirring for a certain period of time, such as 10-48 hours react with the compounds of general formula II. If necessary, sodium iodide can also be added to the reaction mixture catalytic amounts are added «

A preferred embodiment, especially when X in the general formula III -OCH ₂ -, -SQ ^ -, -CCHR ₇ - or -SCHR ₇ - consists in the implementation of the compound of the general formula III in which M ^ is water stiff With Natriumhydrld in 1,2-Diir.ethoxyäthan and further reaction in this solvent. The reaction product is worked up in the customary manner.

ORIGINAL INSPECTH>

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The implementation according to process b) can be carried out as follows v% * he the:

The compounds of the general formula IVa v / ground together with the compounds of the general formula HTa in a suitable inert solvent and without supply of heat, but preferably without a solvent and with heating, for example to 100-110 ° for a certain period, e.g. 18 to 72 Reacted hours with dicyclohexylcarbodiimide as a condensing agent.
Working up is carried out in the customary manner.

The implementation according to process c) can be carried out as follows v / earth:

The compounds of general formula Va are in ^s medium a suitable Lö'sungs such as an ether such as tetrahydrofuran or optionally in an excess of the compound of the general formula Va as a solvent with the compound of general formula VI with acid catalysis or preferably under catalysis by mercury II salts such as mercury II acetate, mercury II fluoroacetate, mercury II nitrate, mercury II chloride etc. and subsequent reduction of the organic mercury intermediate compound formed without prior isolation by a suitable reducing agent such as alkali borohydride, sodium amalgam hydrazine etc.C (cf. HC Brown and P. Geoghegan jr. J. Am-. Chem. Soc. 8 £, 1522 (1967)]. Working up is carried out in the usual way.

The implementation according to method d) can be carried out as follows will:

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The compound of the general formula IV 'is in a · suitable solvent such as 2.3. a hydrocarbon such as benzene, an ether such as dioxane, 1,2-di-methoxyethane, diethylene glycol dimethyl ether, a?: eton such as acetone, a nitrile such as acetonitrile, an acid amide such as dimethylformamide or, and especially if M ₂ in the compound of the general formula IV for hydrogen is, preferably without a solvent in the presence of an acid-binding agent such as sodium or potassium bicarbonate or sodium or potassium carbonate with stirring, optionally forming a suspension, reacted with the compound of the general formula VII. Stirring is continued for a certain period of time, for example 1-20 hours at room temperature and optionally at the end for example at 80 ° -120 ° and finally, after adding a little water, an even shorter time at room temperature.

Working up is done in the usual way.

The reaction according to process e) can be carried out analogously to the conditions described under synthetic route a) by reacting the compound of the general formula V, where M _{3 should} preferably be sodium or potassium, for example in one of the solvents mentioned there or, if appropriate, in a mixture of the compound of general formula V, where M ₃ stands for hydrogen and, if K ₃ stands for hydrogen, take place in the presence, for example, of one of the acid acceptors mentioned under synthesis route a) with the compound of general formula VIII.
The work-up is done in the usual way,

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The implementation according to process f) can be carried out as follows will:

The compound of the general formula IX is in a suitable Solvent such as an ether v; ie 1., 2-dimethoxyethane, Diethylene glycol dimethyl ether, a nitrile such as acetonitrile, in hexamethylphosphoric acid triamide, a suitable one Solvent mixture or optionally in a compound of the general formula IXa

HY-C- (CH ₂ ) _w -C- (CH ₂ ) _z -XR ₆ IXa

R ^ Rr-

where R_ ^ R ^ _t B., - * R / -> X and Y, as well as w and ζ have the meanings given above with the compound of the general formula X and provided that M- in the compound of the general formula IX is hydrogen, in the presence of an acid acceptor such as sodium or potassium hydroxide, sodium or potassium carbonate, potassium tert-butoxide, preferably with stirring over a certain period of time, for example at temperatures preferably between 0 and 60 °. Working up is done in the usual way.

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2mm

Some of the starting compounds of the general formula II are known or can be prepared, for example, by the following processes known per se: If Qi in the compounds of the general formula II is chlorine or bromine by reacting a compound of the general formula IVb ^-

? 2 ^R 4
R ₁ -YC- (CH ₂ ) _w -C- (CH ₂ ) _z -0H IVb

wherein R, R, R., IU, R and Y as well as w and ζ denoted at the beginning Have meaning, with suitable halogen-transferring reagents (see Houben-Weyl, Methods of Organic Chemie Vol. V / 4 p.36l-4ll (1960) and Vol. V / 3 862, 899, 905,932, etc. (1962), Georg Thieme) under conditions ^ which exclude an ether splitting, for example with Thionyl chloride or bromide with phosphoric chloride or bromides, or by exchanging the tosylate of the compound of the general formula IVb against bromide etc. The reactions can in each case under standard conditions take place.

ß: If Q ,, in the compound of the general formula II for Tosylate is by reacting a compound of the general formula. IVc-

^R 2 ^R 4
R -YC- (CH ₀ ) C- (CH ,.) -OM IVc

i I ei. Vl \ C. Z D.

R ₃ R ₅

v / orin R _{,, R 0} , R - ,, R,., R _c , Y as well as w and ζ denoted at the beginning-12345

Neten meanings and M _{5 stands} for hydrogen or a metal cation with tosyl chloride with the proviso that, when M ₅ stands for hydrogen, the reaction in the presence of an acid acceptor such as anhydrous sodium carbonate

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or in the presence of zinc oxide and optionally pyridine (cf. Houben-Wcyl, methods of Organic Chemistry Vol. IX pp. 663-668, Georg Thieme 1955). υ. The compounds of the general formula II

wherein the portion -C- (CH ₀ ) C- (CH ₀ ) - the

general formula II by suitable choice of the substituents Rp, R - ,, R ^, Rj- and w and ζ is symmetrical, for example when Rp, R_, R ^ and R ^ are hydrogen, or if 'Rp and R- stand for' hydrogen and w + 1 = έ-,

or when R _n and Ri _{1 are} hydrogen and R ^ and R ₁ -2 4 ■ "· ■ - '3 5

are identical, but otherwise the ones at the beginning
can have given meanings, and ζ for O
stands, know by reacting a compound of the general formula xi -

at

viorin the section '-C- (CH ₀ ) C- (CH ₀ ) - the

I d W1 d. 7,

R ™ Rf-3 5.

The above-mentioned requirement of symmetry is sufficient and Rp, R, Rl, Rp-, w and ζ have the meanings given above and Q is chlorine, bromine or tosylate with one
Equivalent to a compound of the general formula V
with the proviso that ^ if M stands for hydrogen, the process is carried out in the presence of an acid acceptor.

309846/1188

will be presented. C (VgI. Houben-VJeyl "Methods of organic Chemie "Vol. VI / 3, pp. 26ff (1965) and Vol. IX 105ff (1955)].

The preparation of the starting compounds of the general formula VII is known or can be carried out in analogy to known ones Procedures are made.

The starting compounds of general formulas IVa and IVb are known or can, for example, according to methods known per se be prepared as described below:
By reducing a compound of the general formula xii

where R _n , R_, R. ,, R,., R _cJ Y and w denote the initially-1 2 j? η 5

have neten meanings and ζ 'stands for an integer from 1 to 8 and R ^ for hydrogen, an alkyl -J ". group with 1 to 11 carbon atoms or an alkenyl group with 3 to 11 carbon atoms stands ₃ with Katriumbis - (2- methoxyethDxy) aluminum dihydride in a suitable inert solvent such as, for example, benzene C (cf. M. Cerny et. al., Coll. Czech. Chem. Commun. 4, 1025 (1969) 3 or

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if it applies to the compound of the general formula IVa and IVb that ζ = 0 and R _{4 is} hydrogen and R _{5 is} a straight-chain or optionally branched alkyl radical having 1 to 6 carbon atoms, by reacting a compound of the general formula XIII

R ₁ -YC-

in which R ,, R_, R_, Y and w have the meaning given at the beginning, with a compound of the general formula XIV

R ₁₃ MgHaI XIV

where R ₁ ^ denotes a straight-chain or optionally tri-branched alkyl radical having 1 to <5 carbon atoms
and Hai represents chlorine or bromine

in a suitable anhydrous solvent such as Diethyl ether or tetrahydrofuran, or

Sf & changes

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if it applies to the compound of the general formulas IVa or IVb that R ₂ and R ^ are a straight-chain or optionally branched alkyl radical having 1 to 6 carbon atoms, Y is oxygen and w is a number from 1 to 8 by addition of a compound of general formula Va

R ₁ OH · Va

wherein R, has the meaning indicated at the beginning, to the Compound of the general formula XV

where Rj ,, Rj- and ζ have the meanings given at the beginning and where R _p and R are a straight-chain or branched alkyl radical having 1 to 6 carbon atoms and w is an integer from 1 to 8 and Ac is an acyl radical such as 'For example, an acetyl group and subsequent cleavage of the protective group, or

if in the compound of the general formulas IVa or IVb Y is Is sulfur, by reacting a compound of the general formula XVI

M ₅ SC- (GH ₂ ) _w C- (CH ₂ ) _z -0H

where R _p , R, Rj., R "and w and ζ have the meanings given above and Mg for" hydrogen, sodium or

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Potassium, with the compound of the general formula X, with the proviso that, if hl is hydrogen, the reaction is preferably carried out in the presence of an equivalent of an acid acceptor, or if in the compound of the general formula IVa or IVb wherein Y stands for oxygen

the section -C- (CH ₀ ) C- (CH ₀ ) - by suitable

I d. W | d. Z

R ₃ R ₅

Choice of the substituents is symmetrical, as described under ~ &) , by reacting a compound of the general formula XVII. .

? 2 * 4
MO-C- (CH) C- (CH) -OH XVII

ο ι d Vv ι d Z

RTJ
-τ -Kr-

wherein-the designated portion -C- (CH ₀ ) C- (CH ₀ ) -

I c W | c. Z

. V ^R 5

dm. The symmetry requirements described under y--) are _{sufficient, R 0} or R stands for hydrogen and M _g for hydrogen, sodium or potassium, with the compound of the general formula X with the addition, that if i ^ for V / hydrogen, the reaction is preferably carried out in the presence of an equivalent of an acid acceptor, or 'if for the compound of the general formula IVaoderIVb that ζ + ν / - 1 and Rj, and R ^ are hydrogen, by reaction of a compound of the general formula XVIII

R ₂

C = CKCOORA ■

/ '* & XVIII

R / .309848 / 11 ÖJ ^ äncert _a ®mm

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wherein R ₂ and Η. _{Λ have} the meanings given at the beginning and R _{14 represents} hydrogen or a lower alkyl group with 1 to 6 carbon atoms with the compound of the general formula Va, in analogy to the process described under c) and subsequent reduction with sodium bis (2-methoxyethoxy ) aluminum dihydride in a suitable inert solvent such as benzene (cf. M. Cerny et. al. loc. cit.).

The compounds of the general formula IV, in which Z stands for sulfur, can be prepared in a manner known per se, for example by Reaction of the compounds of general formula II with thiourea in a suitable solvent such as, for example Ethanol preferably at an elevated temperature, e.g. under reflux and subsequent alkaline hydrolysis of the resulting S-substituted isothioureas, for example with alkali.

The compounds of the general formula XII are known or can be used in a manner known per se, for example by malonic ester condensation of suitable halogen ethers. or halogen thioethers or the corresponding tosylates the general formula

_χΐχ

where R ₁ , R ₀ , R ₁ , Ri 1, R _c and Y and w are the initially be-1 2 j> 4 5

Have the meanings shown and z "is an integer from 2 to 8, where if z" is 2, R ^ and R _{5 are} hydrogen and Q _{6 is} chlorine, bromine or tosylate

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followed by hydrolysis and decarboxylation (Lit. R. Adams and RM Kamm ^ Org. Synthesis Coll. Vol. ^, 250 (19 ** 1); Ξ.B. Vliet et al. Org. Synthesis Coll. Vol. 2 , 4ΐδ (19 ^ 3); .CP. Allen and MJ Kalra, Org.Synthesis Coll. Vol. * £, 6l8 (1965) and optionally conversion into the ester corresponding to the meaning of R ₁₂ in the compound of the general formula XII, getting produced.

The compounds of the general formula VI can analogously the method mentioned under a) with conversion of compounds of the general formula xx

^N C = CH (CHg) _w _J ₁ -C- (CH ₂ ) _Z -Q ₇ XX

g _w J ₁

where R _rt , R ,, Ri _1. , R ₁ - as well as w and 2-denotes the initially

2 3 ^ 5

have neten meanings and Q_ for chlorine, bromine or a tosyl radical, with the compound of the general Formula III, or, if X is 0, analogously to the method mentioned under b) by reacting a compound of the general Formula XXI

C = CH (CfI) -C- (CH) OH XXI.

eL Vi-L 1 d. Z ■

/ ^H 5

where R _g> R ^, R ^, R ^ and -w the entangi :; and ζ stands for an integer from 1 to 8 with the connection of the general Forrael HIa.

Unless the preparation of the starting compounds is described. " are these known or can be produced by processes known per se or analogously to those described here or analogously to processes known per se.

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The compounds of the general formula I are generally colorless oils or, in individual cases, also low-melting oils colorless crystals, which are characterized in the usual way permit.

It has now been found that the compounds according to the invention of general formula I inhibit the development of insects and spider mites .. Becomes an immature form of certain insects or spider mites are treated with a compound according to the invention, their transition into the subsequent appearance prevented.

This inhibition of development can lead to immediate death in certain insects and spider mites. In other Examples lead to contact with the compounds according to the invention to reduced oviposition or to prevent copulation.

The anti-ripening effect of the synthetically obtained Compounds of the formula I reach or exceed, for example, those of the natural Cecropia juvenile hormone, the however, cannot be obtained in a comparable economical manner.

The compounds of the invention act when ingested by or in contact with the immature forms of insects in order to. The compounds of the general formula I according to the invention are therefore outstandingly suitable for combating pests. They are particularly characterized by the fact that they are practically non-toxic to warm-blooded animals.

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Particular mention should be made of the compounds of the general formula I in which R 1 is a branched or a secondary alkyl radical. The compounds of the general formula I may be mentioned as preferred: in which R and R- are hydrogen, in particular the compounds in which R _{fi is} Ar. and U stands for a lower alkylthio group or a lower alkyl group and very particularly the compounds in which R _{g is} Ar “. Also of particular interest are the compounds of the general formula I in which X is a group -OCHR ₇ - or -SCHR ₇ -, inter alia with regard to acaricidal activity. . -

Also to be emphasized are the compounds of the general formula I in which X is a —OCH »- or —SCH ₃ group and R is a radical Ar«.

Examples of compounds of the general formula I according to the invention that may be mentioned are:

5- (5 "Isopropoxy-3-methyl-pentyloxy) -1, j5-kenzodioxole, 5" (5-sec-Butoxy-3-methyl-pentyloxy) -1, 5-t'enzodioxol _J.

5-L3- "'öfchy 1-5- (5-pentyloxy) -pentyloxy 3-1,3-benzodioxole, 5-tS-methyl-S- (2-pentyloxy) -pentyloxy] -1, 3-benzodioxole,

1- (5 "isopropoxy ~ 25-riethyl-pentyloxy) -4- (methylthio) -benzene,

5- (6-isopropoxy "hex.yloxy)" i _J j) -ben? _J odioxol

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1- (5-isopropoxy-pentyloxy) -4- (methylthio) -benzene, 4- (5-isopropoxy-pentyloxy) -biphenyl, (5-isopropoxy-pentyl) -piperonylether, 5- (3-isopentyloxy-butoxy) - 1,3-benzodioxole, 4- (3-isopentyloxy-butoxy) -benzoic acid methyl ester, 1- * ethyl-4- (6-isopropoxy-hexyloxy) -benzene

1-ethyl-4 (6-hatoxy-hexyloxy) -benzene 1-bromo-4- (5-isopropoxy-pentyloxy) -benzene

(6-Isopropoxy-hexyl) piperonyl ether (5-pentyloxy-pentyl) -piperonyl ether 1-Ethyl-4- [5- (2-pentyloxy) -pentyloxy] -benzene (6-isopropoxyhexyl) -cc-ethylpiperony lather (6-Isopropoxy-hexyl) - (3,4-dimethoxy-N-diethyl-benzyl) -ether (7-Methoxy-3,7-diraethyloctyl) -a-ethylpiperonyl ether

[3-methyl-5- (3-pentyloxy) pentyl] α-ethylpiperonyl ether 5- [3-Ylethyl-2-butenyloxy) butoxy] -1,3-benzodioxole (4-Isopropoxy-butyl) piperonyl ether 1-ethyl-4- (S-isopropoxy-S-methyl-pentyloxy) -benzene 5- (5-butoxy-3- methylpentyloxy) -1,3-benzodioxole 5- (4-isopropoxy-butoxy) -1,3-benzodioxole (6-Cyclopentyloxyhexyl) piperonyl ether (5-Allyloxy-2-hexyl) piperonyl ether

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2313573

The compounds of the general formula I according to the invention can be used as pesticides 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 distillates, etc., as well as emulsifiers, e.g. liquid Polyglycol ethers, which are made from higher molecular weight alcohols, mercaptans or alky! Phenols by the addition of Alkylene oxide are formed. Suitable organic solvents, such as Ketones, aromatic, optionally halogenated hydrocarbons, Mineral oils, etc., added as solubilizers will.

The spraying agents and dusts can be the customary inert ones 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 Adhesion strength contain the usual wetting agents and adhesives.

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The active ingredients according to the invention can be used in the formulations and are present in the spray liquors in mixtures with other known active ingredients. The formulations can also advantageous UV stabilizers and / or antioxidants and / or contain common evaporation-limiting additives. The formulations generally contain between 2 and 90 weight percent active ingredient, preferably between 5 and $ 50. In general, it is sufficient in the used broths a concentration between 0.01 and 0.4 percent by weight of active ingredient for effective pest control the end.

The active ingredient formulations "can be prepared in a known manner be, e.g .:

a) 25 parts by weight of a compound of general formula I are mixed with 25 parts by weight of isooctylphenyldeca-

• ^: Glycol ether and 50 parts by weight of xylene mixed, resulting in a clear solution that can be easily emulsified in water. The concentrate is diluted to the desired concentration with water.

b) 25 parts by weight of a compound of the general formula I are mixed with 30 parts by weight of isooctylphenyloctaglycol ether and 45 parts by weight of a petroleum fraction with a boiling point of 210-280 ° (D _2Q : 0.92). The concentrate is diluted with water to the desired concentration.

c) 50 parts by weight of a compound of the general formula I with 50 parts by weight of isooctylphenyloetaglycol ether mixed. You get a clear focus

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stepped, which is easily emulsifiable in water and is diluted with water to the desired concentration,

The following application examples serve to explain the excellent insecticidal and acaricidal effectiveness of the inventive Compounds, but are not intended to limit the invention in any way.

Beis p iel a:. Insecticidal effect on_Dysdercus> fasciatus-

Larvae (cotton bug)

Filter paper is soaked with a solution of the active ingredient of general formula I. With the filter paper treated in this way a can made of polystyrene (200 χ 100 χ 85 mm) lined. In this box is also given impregnated, folded filter paper and occupied with approx. 30 Dysdercus larvae in the 4th larval stage. You enter knotted cotton yarn and as tinsel Drinking vessel with it. "The indication of the number of normally developed Adulten takes place in ^.

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Drug development

Dosage: active ingredients ^aer _T ^D ^ ^s ~

f \ ι ™ ~ / ~ ™ ² 'dercus larvae

Q ' ^{1 m} ^ ^cm to adults

.5- (5-Isopropoxy-3-methyl-pentyloxy) -l., J5 benzodioxole,

benzodioxole,

1- (5-butoxy-3-methyl-pentyloxy) -4- (methylthio) benzene,

5 ~ (10-isopropoxy ~ decyloxy) -I _J 3-benzodioxole, 4- (5-isopropoxy-pentyloxy) -berizoic acid methyl ester, 1- (5-isopropoxy-pentyloxy) -2-isopropoxy-benzene, (5-isopropoxy- pentyl) piperonyl ether ._

4- (5-isopropoxypentylthio) toluene, 5- [4- (2-pentyloxy) -2-butoxy] -1, 3-benzodioxole, 0%

5- is> ~ (3-J "'ethyl-2 ~ butenyloxy) -butoxy] -1, 3-

benzodioxole. * O ^

1- (5-isopropoxy-pentyloxy) -3-methyl-4- (methylthio) -

benzene 0%

1-ethyl-4- [5- (2-pentyloxy) -pentyloxy3-benzene 0%

l-bromo-4- (5-isopropoxy-pentyloxy) -benzene 0%

309846/1188

Example b: Effect on the development of Prodenia littura larvae (cotton owl) into adults

Filter paper v / ird with a solution of the active ingredient of the general Formula I soaked. The compartments of a plastic box are lined with the paper treated in this way. In every subject a Prodenia caterpillar is set and a piece of Kuns.tmedium is used as a Feed added. The number of normally developed adults is given in ^.

Active ingredient dosage:

, 2

0.1 mg / cm

Active ingredient

Development rate of the Prodenia -Multi larvae:

5- (5-Isopropoxy-j5-methyl-pentyloxy) -l.,> Benzodioxole, -

5- (5-see ~ butoxy-; 5-methyl-perityloxy) -1, benzodioxole,

-5- (j5 ~ pentyloxy) -pentyloxy] -1 _t 3-benzbdioxol,

5- (6-Isopropoxy-hexyloxy) -1 _J 3-benzodioxole,

l- (5-isopropoxy-pentyloxy) -4- (methylthio) -benzene,

(5-Iscpropoxy-pentyl) -pipsronyl ether 1-Bromo-4- (5-isopropoxy-penthyloxy) -benzene 1-ethyl-4- (6-isopropoxy-hexyloxy) -benzene

309846/1188

0% 0%

- 27 - 150-3711

Example c: -effect suf the- development of Tenebrio moli-

tor pupae (meal beetles) to adults

The compounds of general formula I according to the invention are used in concentrations of 1% active ingredient in acetone solution. On the ventral side of the last three segments of fresh caterpillars (not older than 18 hours), 2 / μl substance solution, corresponding to 20 micrograms of active ingredient, is applied using a 1 ~ microliter pipette. 10 dolls are used for each test. The treated pupae are kept at 28 ° in plastic cups. Normally developed adults are paid out after 10 to 12 days. The number of normally developed adults is given in fo .

Active ingredient development rate

of the Tenebrio dolls to adults

5- (5-isopropoxy-; 5-methyl-pentyloxy) -1,; 5-benzodioxole, 5 ~ (5-see-butoxy-; 5-methyl-pentyloxy) -1,3-benzodioxol., 0 $ 5- [3-Kethyl-5 ~ C5-pentyloxy) -pentyloxyl-ljjj-bönzodioxol., 0 $ 1-ethyl-4- (5-isopropoxy-3-methyl-pentyloxy) -benzene,

1- (5-Isopropoxy-j5-methyl ~ pentyloxy) -4- (raethylthio) benzene,

5- (5-isopropoxy-psntyloxy) -1,5-benzodioxole, 4 ~ (5-13opropoxy-pentyloxy) -benzoic acid methyl ester, l-ethyl-4 ~ (5-isopropoxy-pentyloxy) -l, 3-benzodioxole, 5-C ^ -D-methyl-2-butenyloxy) -butoxy] -l, 3-bonzodioxole,

1-ethyl-ft - (^ - isopentyloxy-butoxy) -benzene. O ^

(5-pentyloxy-pentyl) -piperonylether 0%

(4-isoprapoxy-pentyloxy) -3-methyl-4- (methylthio) benzene 0%

309846/1188

Example d: Contact effect in Tetranychus urticae (red spider)

1 day before the treatment, 10 adult females of Tetranychus urticae are transferred into the inner area of two rings (diameter: / 5 cm) made of caterpillar glue on a leaf of a cotton plant using a fine brush. The cotton sheets are sprayed with a broth, each containing 0.1 $ active ingredient, by means of an atomizer until they drip off. After drying, the plants are kept at room temperature and in the dark. The dead and living animals are counted 6 days after the treatment. The effect is given as the ratio of the treated and an untreated population in % .

Active ingredient effect after

6 days

5- (10-isopropoxy-decyloxyJ-ljJ-benzodioxole, 9 ° $ (5-pentyloxy-pentyl) -piperonylether ⁼ "100%

4- (5-isopropoxy-pentyloxy) -1-biphenyl, $ 95

i-ethyl-4- (6-butyloxy-hexyloxy) -benzene 100%

4- (3-Isopentyloxy-butoxy) benzoic acid; ethyl ester, $ 90 5-C3-methyl "5- (2-pentyloxy) -pentyloxy] -1, 3-benzodioxole. "$ 100

(6-rsopropoxy-hexyl) -ci ~ äthylpiperony lather 100%

The following examples serve to illustrate the preparation · of the compounds of general formula I ₇ to the invention but in no way limit. The temperatures are given in degrees Celsius.

309846/1188

-29.- j.30-3711

Example It i ^

benzene (according to method a)

0.780 g (0.0052 mol) of 4-tert-butylphenol are added to 20 ml of absolute dimethylformamide at 20 ° for 40 minutes with 0.376 g (0.00β7 mol) potassium hydroxide stirred. After adding 1.05 S (0.0050 KoI) l-bromo-5-isopropoxypentane in 5 ml abs. Dimethylformamide the solution is stirred for a further 15 hours at 20 °. Water is added to the reaction mixture and the product with ether extracted. The one with cold 1 N sodium hydroxide solution and saturated sodium chloride solution washed ether extract is dried over sodium sulfate and evaporated. In the chromatography of the Residue on 60 g of silica gel with hexane-ethyl acetate (98: 2) becomes the l-tert-butyl-4- (5-isopropoxy-pentyloxy) benzene as colorless ~ ses OeI received.

χξ ° = 1.4862.

Analysis: ^{c 18 H} 3Q ° 2 Molecular weight: 278.4

calcd. C 77.6 # H 10.9 % 0 11.5 ^ found. 77.9 % 10.9 # $ 12.0

Example 2; 5i (4-isopropoxy-2-butox5r) _{> -1 A} 3-benzodioxole

(according to method a)

To 0.360 g (0.0082 mol) 55 percent. Sodium hydride dispersion in oil and 5 ml of absolute tetrahydrofuran are added dropwise with stirring at room temperature, 1.38 g (0.010 mol) of 3,4-methylenedioxy-phenol in 10 ml of absolute tetrahydrofuran, and the mixture is ^{stirred at 60 °} C. for 30 minutes. After cooling to 20 °, 1.95 g (0.010 mol) of 2-bromo-4-isopropoxybutane in 10 ml of absolute tetrahydrofuran are added dropwise in the course of 5 minutes, followed by 3 ml of absolute hexamethylphosphoric acid trlamide, and the mixture is refluxed for 18 hours cooked. The reaction product is taken up in ether with ice-cold 1N sodium hydroxide solution, water and saturated

309846/118 "

- 30 - 130-3711

2.31957a

Washed brine, dried with sodium sulfate and evaporated. The residue is purified by chromatography on 70 g of silica gel with hexane-ethyl acetate (100: 0 to 95: 5) and finally freed from volatile components for 4 hours at 60 ° in a high vacuum (10 mm Hg). This gives 5- (4-isopropoxy-2-butoxy) -1, 3-benzodioxole as a colorless oil.

20th
n * ^u = 1.5001.

Analysis: ^C i4 ^H 2O ^O 4 Molecular Weight: 252.3

calc. C 66.6% H 8.0 % 0 25.4 % found 67.0 % 7.8 $ 25.0 i>

Example 3: (5-Isopropoxypentyl) piperonyl ether

(according to method a)

To 0.240 g (0.0055 mol) 55 percent washed with absolute pentane, Sodium hydride dispersion in oil v / earth 10 ml hexamethylphosphoric acid triamide freshly distilled from molecular sieve (HMPT) and then with stirring at room temperature im Course of 10 min. Ο, 7δθ g (0.0050 KoI) piperonyl alcohol in 30 ml of HMPT were added dropwise. The mixture is stirred for one hour at 60 °, then cooled to 20 °, 1.045 -g (0.0050 mol) of l-bromo-5-isopropoxypentane added dropwise in 20 ml Hexarnethylphpsphorsauretriamid and continued stirring for 16 hours at 60 °. The reaction product is Poured onto ice and extracted with ether, the organic phase with 2 N sulfuric acid, water and saturated sodium chloride solution washed, dried with sodium sulfate and evaporated. When the residue is chromatographed on 80 g of silica gel with Ilexan-ethyl acetate (97: 3) pure (5-isopropoxy-pontyl) ~ piperonyl ether is obtained. ■

= 1.4970.

3Q9846 / 1 June 18

Analysis: ^C l6 ^H 24 ° 4 H 8
8th , $ 6 2319573
Molecular weight: 28θ.4 ber.
found C 68.5
68.7 % 0 22.8 #
23.2 # Example 4: 4 ~ ^ 5-Isopropox ^ -pentylthio) -toluene

(according to method a)

1.24 g (0.01 mol) of 4-mercaptotoluene and 0.5β g (0.01 mol) of potassium hydroxide are slurried under nitrogen in 50 ml of dimethylformamide and for 1 hour ·. stirred at 20 °. After that there a solution of 2.09 S (0.01 mol) l ~ bromo-5-isopropoxypentane in 10 ml of dimethylformamide to the slurry and stir the mixture for a further 18 hours.

100 ml of water are then added to the reaction mixture and the mixture is extracted with ether. The ether extract is with 1 N sodium hydroxide solution extracted, washed with saturated sodium chloride solution, dried with sodium sulfate and evaporated under reduced pressure.

The residue is on 200 g of silica gel with hexane-ethyl acetate (99; 1) Ehroniatographiert, with uniform 4- (5-isopropoxypentylthio) -toluene is obtained as a colorless oil.

n ²⁰ = 1.5142. "■

Analysis: ^C i5 ^H 24 ^{0S Molecular Weight} : 252.4

calc. C 71.4 £ H 9.6 $ S 12.7 found. 70.8 % 9.6 # 12.3

309848/1188

- 32 - 130-3711

Example 5?

To a suspension of 0.86 g (0.036 mol) of sodium hydride in 40 ml of dry 1,2-dimethoxyethane v / earth at 20 ° 5.4 g. (0.03 mol) ct ~ ethylpiperonyl alcohol was added dropwise. After two hours Stirring at 60 °, 8.03 g (0.036 mol) of 1-bromine -6-isopropoxyhexane dissolved in 20 ml of dry 1,2-dimethoxy athan, added over the course of 60 minutes and the mixture Stirred at 60 ° for hours.

The reaction mixture is then added at room temperature 1 ml of ethanol and then 100 ml of water were added. The mixture is extracted with ether, the ether phase washed with saturated sodium chloride solution, dried with sodium sulfate and evaporated.

The residue is fractionally distilled. You get a gas chromatographically uniform, colorless oil from

Sap. 140 - 141 ° / 5- 10 9 mm. Molgewi 20 _. 4890 9 0 20 "l% Analysis: C ₁₉ B 30 ° 4 19.8% ber. C 71 Λ% H ,1 % found 70 ,8th % , 4%

Analogously to Examples 1-5, but using the starting compounds listed in the table, can also the following compounds (compound no. 6 - 30 of the general formula I) are produced:

309846/1188

example
Mr . 7th 5- (7-isopropoxy-heptyloxy) Gross-
fcrmel Molge
weight 20th
n _D resp. analysis
ber.
found
C. H 8.9 $
S. / ma log
at
game
No. Output
connect,
example
No*. - »1,3-benzodioxole ^C 17 ^H 26 ° 4 294.4 M.p.
C ^c c 3 69.4 8.8 1 76 8th 5- [4- (2-pentyloxy) -2-butoxy 3 52 ° 69.2 8.6 -1,3-benzodioxole ^C 16 ^H 24 ⁰ 4 .280.4 68.6 8.5 2 67 9 1- (6-isopropoxy-hexyloxy) 1.4913 68.8 ■ 9O a) -4- (methylthio) benzene ^C 16 ^H 26 ° 2 ^S 282.4 68.0 9.1 · 11.4 1 77 JD
39 XO 1- (6-isopentyloxy-hexyloxy) 4> 44 ° 67.8 9.7 11.4 Ρ »
35
Ή, -4- (methylthio) benzene ^C 18 ^H 30 ° 2 ^S 510.5 69.6 9.7 10.3 1 83 » 11 1- (7-isopropoxy-heptyloxy) 1.5124 69.1 9.5 10.1 -4- (methylthio) benzene C ₁₇ H ₂₈ O ₂ S '296.5 68.9 9.5 10.8 1 76 12th l-chloro-4- (5-isopropoxy- 1/5183 69.0 7.8 10.9 pentylthio) benzene C ₁₄ H ₂₁ ClOS 272.8 61.6 7.8 11.8 4th 75 1- (5-isopropoxy-pentyloxy) - 1.5304 61.3 9/3 11.8 IO 3-methvlr4- (methylthio) benzene ^C 16 ^H 26 ° 2 ^S 282.4 68.0 9.1 αϊ, 4 1 U 1.5209 68.2 11.6

At-
game-
No. • Gross
formula Mole
ge
weight 20th Analysis%
ber.
found
CHS Br i
Analogue
at
game
No. Starting
connect
manure
example
No. 13th l-bromo-4- (5-isopropoxy-
pentyloxy) benzene ^C 14 ^H 21 ^BrO 2 301.2 1.5113 55.8 7.0 26.5
55.8 7.0 26.7 1 75 14th (6-isopropoxyhexyl) -
piperonyl ether ^C 17 ^H 26 ° 4 294.4 1.4936 69.4 8.9
69.2 8.7 3 * 77 15th l-ethyl-4- [6- (2-ethyl-hexyl-
oxy) -hexyloxy] -benzene ^C 22 ^H 38 ° 2 334.5 1.4824 79.0 11.4
78.7 11.1 1 79 16 (4-isopropoxybutyl) -
piperonyl thioether ^C 15 ^H 22 ° 3 ^S 282.4 1.5303 63.8 7.9 11.4
63.3 7.8 11.7 2 78 17th l-ethyl-4- (5-pentyloxy-
pentyloxy) benzene ^C 18 ^H 30 ° 2 278.4 1.4868 77.6 10.9
77.5 10.9 I ⁺ 84 18th (5-pentyloxypentyl) -pipero-
nylon ether ^C 18 ^H 28 ° 4 308.4 1.4972 70.1 9.2
70.4 9.3 3 * 68 19th l ~ ethyl ~ 4- (6-butyloxy ~
hexyloxy) benzene ^C 18 ^H 30 ° 2 278.4 1.4862 77.6 10.9
77.4 10.6 1 69 20th 1-ethyl-4- [5- (2-methylr
butyloxy) pentyloxy] benzene ^C 18 ^H 30 ° 2 278.4 1.4843 77.6 10.9
77.8 10.5 1 70 21 ■ '-Aethyl-4- [5- (2-pentyloxy) -
I entyloxy] benzene ^C 18 ^H 30 ° 2 278.4 1.4827 77.6 10.9
77.3 10.5 1 74

*) using 1,2-dimethoxyethane instead of Hexaraethylphosphorsäuretriairüd
+) using 5-pentyloxypentyl tosylate

CD UI

i z>
lO
t & at
game
No. co
co l-ethyl-4- (5-isopentyloxy-
pentyloxy) benzene Gross
formula Molge
weight "20th
ⁿ D Analysis%
ber.
found
CH Analogue
example
No. Starting
connection
example
No. i Jf-
O) 22nd 1-ethyl-4- (9-methoxy ~ nonyl-
oxy) benzene ^C 18 ^H 3Ö ° 2 278.4 1.4831 77.6 10.9
77.5 10.9 1 71 23 l-ethyl-4- (8-ethoxy-octyl-
oxy) benzene ^C 18 ^H 30 ° 2 278.4 1.4898 77.6 10.9
77.3 10.4 1 72 N)
OO 24 1- (6-isopropoxy-hexyloxy) -
3,4-dimethylbenzene ^C 18 ^H 30 ° 2 278.4 1.4876 77.6 10.9
77.8 10.5 1 73 CO 25th 1-ethyl ~ 4- (5-sec.butoxy-
pentyloxy) benzene ^C 17 ^H 28 ° 2 264.4 1.4904 77.2 10.7
77.7 10.4 1 "77 cn 26th (6-cyclopentyloxyhexyl) -
piperonyl ether ^C 17 ^H 28 ° 2 264.4 1.4868 77.2 10.7
77.4 10.4 1 80 27 l-ethyl-4- (6-isopropoxy-
hexyloxy) benzene ^C 19 ^H 28 ° 4 320.4 1.5100 71.2 8.8
71.2 8.5 3 82 28 (6-sec-butoxyhexyl) -pipero
ny lather ^C ri7 ^H 28 ° 2 264.4 1.4823 77.2 10.7
77.5 10.6 1 77 29 (6-isopropoxyhexyl) - (3,4-dimen-
thoxy-a-methylbenzyl) ether ^C 18 ^H 28 ° 4 308.4 70.1 9.2
70.0 9.1 3 * 81 30th ^C 19 ^H 32 ° 4 324.5 1.4902 70.3 9.9
70.4 9.9 5 77 *) using 1,2-dimethoxyethane instead of before χ Hexamethylphosphoric triamide

Example: 31; 5

(according to method b)

A mixture of 1.6 g (0.01 mol) of 5-isopentyloxy-1-butanol, 1 * 38 g (0/01 mol) of 3,4-methylene-dioxy-phenol and 2., o6 g (0.01 Mol) dicyclohexylcarbodiimide is kept at 105 ° for 20 hours. After cooling, 50 ml of ether are added, the precipitate is filtered off and the piltrate is evaporated. The residue is chromatographed on silica gel with hexane / ethyl acetate (14: 1). 5- (3-Isopentyloxy ^ butyloxy) -l _i 3-benzodioxole is obtained as a colorless oil *

Analysis: ^C i6 ^H 24 ° 4 Molecular weight:

calcd. C 68.5 % H 8.6 ^

found 68.6 ^ 9 * 0 #

Example 3 2: §- [ 5-Isogrοpox ^ - ^ - nj

"'zodioxol (according to method b)

A mixture of 1.92 g (0.012 mol) of 5-xsopropoxy-3-methyl-pentanol, 1.52 g (0.011 mol) of 3,4-mefchyl-dioxy-phenol and 2.57 g (0.115 mol) dicyclohexylcarbodiimide is used for 3 days at 100-110 ° C stirred. After cooling, the reaction mixture becomes chromatographed on 200 g of silica gel with hexane-ethyl acetate (98; 2). 5 ~ (5-Isopropoxy-3-sethy! ~ Pentylo>: y) -1,5-benzodioxole is obtained as a colorless oil.

= 1.4980

30984Θ / 1188

Analysis: ^C 16 ^H 24 ° 4 Molecular weight: 280.4

ger. C 68.5 % H 8.6 # 0 22.8 #

found 68.5 % 8.8 # 22.5 #

In a manner analogous to that described in Examples 31 and 32, but using the starting compounds of the general formula IVa listed in the table below, the following compounds of the general formula I can be prepared.

309846/1188

r ^iu '"
at
game
No. 5- (5-sec-butoxy-5-methyl-pentyl-
oxy) -1,5-benzodioxole Gross-
formula ■ Molge
weight ⁿ D analysis
ber.
CK 9.5
9.2 0 S. 8th
0 Starting
verb. s.
example
No. 33 3 ~ [5-methyl-5- (5 ~ pentyloxy) -
pentyloxy 3-1,5-benzodioxole C ₁₇ H ₂₆ O ₄ 296.5 1.4956 68.9
68.9 9.2
9.4 21.6
21.8 88 34 1-ethyl-4- (5-isopropoxy-5-
rriethyl-pentyloxy) -benzene ^C 18 ^H 28 ° 4 508.4 1.4947 70.1
70.5 10.7
10.7 20.8
20.5 5
7th 89 J 5 1- (5-isopropoxy ~ 5 ~ methyl-pen-
tyloxy) -4- (methylthio) benzene 264.4 1.4857 77.2
76.9 9.5
9.5 12.1
12.2 87 36 5- (5-butoxy-5 * -methyl-pentyl-
oxy) -1,5-benzodioxole C ₁₆ H ₂₆ O ₈ S 282.4 1,520.9 68.0
67.8 8.9
8.7 11.4
12.0 87 37 1- (5-butoxy-5-methyl-pentyl-.
oxy) -4- (methylthio) benzene ^C 17 ^H 26 ° 4 294.4 1.4908 69.4
69.5 9 ^ 6 22.4
21.9 90 38 5-t5-methyl-5- (2-pentyloxy) -
pentyloxyJ-1,5-benzodioxole ^C 17 ^H 28 ° 2 ^S 296.5 1.5162 68.9
69.4 9.2
9.5 10.8
10.8 10,
11 90, 39 1- [5-methyl-5- (2-pentyloxy) -
pentyloxy3-4- (methylthio) -benzene ^C 18 ^H 28 ° 4 508.4 1.4957 70.I
70.4 9.6
9.8 20.8
20.8 91 40 5- (5-isopropoxy-pentyloxy) -1, 5-
benzodioxole ^C 18 ^H 50 ° 2 ^S 510.5 1.5151 69.6
69.6 8.5
8.5 10.5
10.6 10,
10, 91 41 ^C 15 ^H 22 ° 4 266.5 1.5019 67.6
67.5 24.0
25.8 92 ho
Ca)
_ .— .. ίθ

Ott » «1» ι ** cn

ft.

Γ *

V)

TD

at
game
No. 5- (10-isopropoxy ~ decyloxy) -l, 3-
benzodioxole Gross
formula Molge
weight "20th
ⁿ D analysis
ber.
found
CH 9.6
9.6 t
0 ' S. * Starting
verb. s. ■
example
No. 42 5- (6 ~ isopropoxy ~ hexyloxy) -1,3 ~
benzodloxol ^C 20 ^H 32 ° 4 336.5 M.p.
[ ⁰ C 3 71.4
71.4 8.6
8.6 19.0
19.1 95 43 5- (4-isopropoxy-butyloxy) -1,3-
benzodioxole ^C 16 ^H 24 ° 4 280.4 45-45.5 ° 68.5
68.8 8.0
8.3 22.8
22.1 96 44 5- (3-isopropoxy-propoxy) -1, 3-
benzodioxole ^C 14 ^H 20 ° 4 252.3 1.4894 66 _f 6
66.7 7.6
7.5 25.4
25.4 11.9
12.2 97 45 1-ethyl-4- (5-isopropoxy ~ pen-
tyloxy) benzene <Wl8 ° 4 238.3 * 1 ^ 5028 65.5
65.8 10.5
10.5 26.9
26.7 98 46 1- (5-isopropoxy-pentyloxy) -4-.
(methylthio) benzene ^C 16 ^H 26 ° 2 250.4 1.5029 76.8
76.5 9.0
9.4 12.8
13.2 47 4- (5-isopropoxy-pentyloxy) ~
methyl benzoate ^C 15 ^H 24 ° 2 ^S 268.4 1.4848 67.1
67.0 8.6
8.6 11.9
11.8 92 48
ι 1 - (5-isopropoxy-pentyloxy) -2-
isopropylbenzene ^C i6 ^H 24 ° 4 280.4 1.5234 68.5
68.8 10.7
10.9 22.8
22.4 92 49
ί 5- [3- (3-methyl-2-butenyloxy) -
butoxy] -1,3-benzodioxole ^C 17 ^H 28 ° 2 264.4 1.4982 77.2
77.5 8.0
8.5 12.1
12.1 92 i 50 ^C 16 ^H 22 ° 4 278.3 1.4860 69.0
68.9 1.5130

cn Ca)

1
OT *
\ ft Wt O O V3 • ο - ' m HO m £ J CU O • Η · U-4 co co * η, u O in kDXi j
OJ -P to co m u i-i Ό τ-Ι O Ή ο <s> PQ t b-OJ "te *. O <~ i HH On O 4-5 Q>. OJ OJ t — VO • ν Η ω 4> ε t-co κ? · CJ \ OJ O O ί »k k O ti rH CQ ⁵ M. CO ON ro χ> O YES a vovo co ON O in VO IS OJ _O co in K \ ·> σ \ r « H r-l VO VO CVI OJ 0 ON CVl OJ O r-4 co OJ O OJ do VO W. OJ t-i O - b- O f I. I. O Xi t 1- I. Φ oxy O Xi t-i r-! 8 © ■ 'S " 4-S • Η Ή β 0 «p O φ Ci ■ 3 Ci, JQ ^ O I. I Φ ω • Η J ^ K W i O O <I> a O r-l ί O i-i O -P J ^ ft + * 0 β OJ O r-f O CO QJ P. E £ * j xi MXl O ti) Xi I I O 4 ^ t -ν in u H p to>} i t4 I O rH C ΓΛ W t- \ Vi I O ro CN in in H in

309846/1

- 41 - 130-3711

Example 54 j

(According to method d)

To a mixture of 1.98 g (0.01 mol) of crude α-ethylpiperonyl chloride and 2.82 g (0.015 mol) of 7-methoxy-3,7-dimethyloctanol is added, with stirring at 20-25 °, 1 g (0.012 mol) Sodium bicarbonate added. The heterogeneous mixture is stirred for 20 hours at room temperature and for 1 hour at 80 ^D , then cooled to room temperature, mixed with 10 ml of water and stirred for a further 30 minutes.

The reaction mixture is poured into 20 ml of water and extracted with hexane. The hexane extract is washed with saturated sodium chloride solution, dried with sodium sulfate and evaporated.

The residue is purified by chromatography on silica gel using hexane / ethyl acetate (19: 1) as the eluent, v; above the (7-methoxy-3,7-dimethyloctyl) -a-ethylpiperonyl ether. is obtained as a colorless oil. Bp .: 138 ~ 140 ° / 5-10 ~ mm.

nf = 1.4938

Analysis: ^C 2i ^H 34 ° 4 molecular weight 350.5

calcd. C 72.0% H 9.3ί _; % O 18.3 t found 72.2% 9.2% 18.6%

30334β / ΠβΙ

- 42 - 130-3711

Example 55 :

{According to method d>

To a Geraisch of 1.98 g (0.01 mol} of crude α-ethylpiperonyl chloride and 2.82 g (0.015 moles) of 3-methyl-5- {3-pentyloxy) pentanol 1 g (0.012 mol) of sodium bicarbonate is added with stirring at room temperature. The heterogeneous mixture is for 20 hours at 20 - 25 ° and then during Stirred at 80 ° for 1 hour. After cooling to room temperature 10 ml of water are added and the mixture is stirred for a further 30 minutes The reaction mixture is poured into 20 ml of water and mixed with Hexane extracted. The hexane extract is washed with saturated sodium chloride solution, dried with sodium sulfate and evaporated.

The residue is purified by chromatography on silica gel with hexane / ethyl acetate (19: 1) as the eluent, the [3-methyl ~ 5- {3-pentylGxy} -pentyl] -et-ethylpiperonyl ether being obtained as a colorless gel. Bp. 126 - 127 ° / lo ~ ⁴ mm.

ng = 1.4923

Analysis; C ₂₁ H ₃₄ Q ₄ Molecular Weight: 350.5

bar. e 72.0 t H 9.8 1 O 18.3%

found 72.3% 9.3 % 18.5%

-30 f 841 / tt Il

- 43 - 130-3711

Example 56: li

{According to procedure d)

To a suspension of 2.4 g (0 _f 05 mol) 50 percent. Sodium hydride, which has been freed from mineral oil with hexane, in 40 ml of dry 1,2-dimethoxyethane v / earth at 0 ° in the course of 40 minutes. 6.6 g (0.05 mol) of 4-isopropoxybutanol in 50 ml of dry 1, 2-dimethoxyethane was added dropwise. After stirring for two hours at 20-25 °, a solution of 10.75 g (0.05 mol) of piperonyl bromide is added dropwise in the course of 30 minutes at 0-5 °.

The mixture is for 2 hours at 20-25 ° and then Stirred at 40 ° for 16 hours. Then 150 ml of ether and the ether solution are added to the reaction mixture extracted with water in a separating funnel. The ether phase is dried over sodium sulfate and evaporated. The residue is distilled under reduced pressure, whereby (4-isopropoxybutyl) piperonyl ether is more uniform according to gas chromatography of bp 108-112 ° / 10 "mm as a colorless oil is obtained.

i \ i ° = 1.5002

Analysis: ^c 15 ^H 22 ° 4 Molecular weight: 266.4

here. C 67.7% H 8 _r 3% 0 24.0% found. 67.6% 8.4% 24.8%

309846/1188

130-3711

Example 57;

Is produced analogously to Example 56, except that 5-sec. Butoxypentanol is used instead of 4-isopropoxybutanol.

n ^ ° = 1.5014

Analysis: ^C ₁ 7 ^H ₂ 6 ° 4

Molecular weight 294.4

ber.

C 69.4% H 8.9% 69.3% 8.3%

Example 58 :

Is prepared analogously to Example 56, except that 7-methoxy 3,7-dimethyloctanol is used instead of 4-isopropoxybutanol.

: 1.4968

Analysis:

here. found

^c ₁ 9 ^H ₃₀ ° 4

C 70.8% 70.2%

Molecular Weight: 322.4

H 9.4%
9.4%

Example 59:

Is prepared analogously to Example 56, except that 5-allyloxy-2-hexanol is used in place of 4-isopropoxybutanol.

20th
nt " = 1.5032 bp 150-152 ° / 0.5 mn

Analysis: calc.

Molecular Weight: 292.4

C. 69.8 %

70.1%

H 8.3% 8.2%

309846/11

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Example 60:

(According to method d)

A mixture of 1.27 g (0.006 mol) of 6-chloromethylsafrole and 1.47 g (0.0078 mol) of 7-methoxy-3,7-diimethyloctanol is added with 0.75 g (0.0088 mol) of sodium bicarbonate are added and 18 hrs. stirred at 95 ° and then for 8 hours at 120 °. The reaction mixture is taken up in ether, twice extracted with saturated sodium chloride solution, dried over magnesium sulfate and evaporated. In chromatography the residue on 100 g of silica gel with hexane-acetone (98.5: 1.5) gives the 6-allylpiperonyl (7-methoxy ~ 3,7-dimethyloctyl) ether as a colorless oil which is uniform by gas chromatography.

n * ° - 1.5077

Analysis: C ₃₂ H ₃₄ O ₄ Molecular Weight: 362.5

calc. C 72.9% H 9.5% found. 72.7% 9.1%

Example 61 : ßiAllYlgigerony ^ l- ^ § ~ iso £ ro £ OX £ hexYl) _- ether

Is prepared analogously to Example 60, but using of 6-isopropoxyhexanol instead of 7-methoxy-3,7-dimethyloctanol.

n ^ ° = 1.5047

Analysis; C ₃₀ H ₃₀ O ₄ Molecular Weight: 334.5

calc. C 71.8% H 9.0% found. 72.0% 8.9%

308846/1188

Example 62: 4- (5-Isopropoxy-pentyloxy) -biphenyl

(according to method e) , - - -

To 6.0 g (0.110 mol) of isopropanol, 0.250 g (0.0057 mol) of 55-pros. Sodium hydride dispersion was added in oil and the mixture was stirred at 60 ° for 1 hour. After cooling, a solution of 1.465 g (0.005 mol) of 4- (5-brompentyloxy) biphenyl in 10 ml of isopropanol (0.23 mol) is added dropwise and the mixture is stirred at 60 ° for 16 hours. The reaction product is freed from excess isopropanol by distillation at 20 mm, mixed with water and extracted with ether. The organic phase is washed with saturated sodium chloride solution, dried with sodium sulfate and evaporated. In the chromatography of the residue on 60 g of silica gel with hexane-Essigester- (97; 3) ~ ^he holds 4- (5-Isopropaxy ~ pentyloxy) biphenyl from Sehmp.36-37 °

Analysis: ^C 20 ^H 26 ° 2 molecular weight; 298.4

ber, C 80.5 Jo ■ - ■ H 8.8 <p 0 10.7 # found. 80.5 & 9 * 0 % $ 10.8

Example 63? " ^ - (S ^^ rliZ ^ S ^^ P ^ iSiSi:

(according to "procedure e)

0.45 g (5 * 33 mmol) isopropylthiol v / earth in 10 tnl absolute Dimothylforniaraid 1 hour at 20 °. With 0.200 g (3 * 57cKal) potash up.-hydroxide tumbled. In the course of 5 min. 1.020 g (3.5 "6 nikol) 5- (5-bromopentyloxy) -1,3-benaodioxole in 5 ml abs. Pear-thylfornamid sugetropffc and the mixture for 20 hours, stirred at 20 °. The reaction product is mixed with water and extracted with ether, the extract with cold 1 ü Ha-.

30984871188

- 47 - 130-3711

tronlauge and saturated sodium chloride solution, dried with sodium sulfate and evaporated. In chromatography the residue on 120 g of silica gel with hexane-ethyl acetate (97: 3) and then recrystallization from petroleum ether one receives 5- (5-isopropylthio-perityloxy) -l, 3-bGnzodioxol vom M.p. 47.5- ^ 8 °.

Analysis; CJ _? 0 p. Handle weight: 282.4

calcd. C 63.8 % H 7.9 % S 11.4 $

found 63.5 % 7.7 f 11.2 #

Example 64: Ι§ΐ5Η!: 25Σ & ££ Υ: ο. ~ · 5ίΕ2Ε22 ¥! ^: Ίϊ £ Ε (according to method f)

To a mixture of 1.41 g (0.0103 mol) of 1-bromobutane and 2.0 g (0.0079 mol) 6-piperonylhexanol in 30 ml absolute 1,2-Dimethoxyethane are stirred at room temperature 0.31 g (0.0103 mol) 80 percent. Sodium hydride dispersion in oil added in portions. The suspension is stirred for 19 hours at 60 °, again with the same amounts of 1-bromobutane and Sodium hydride dispersion is added and the mixture is stirred for a further 4 hours at 65 °.

The reaction mixture is cooled to 20-25 °, water is added and the product is extracted three times with ether. the Organic extracts are washed three times with water and once with saturated sodium chloride solution, over magnesium sulfate dried and evaporated. In chromatography the residue on 100 g of silica gel with hexane-ethyl acetate (96: 4) is obtained which is chromatographically uniform (6-Butoxyhexyl) piperonyl ether as a colorless oil.

= ° - 1.4955

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- 48 - 130-3711

Analysis: ^C 18 ^H 28 ° 4 Molecular weight: 308.4

calc. C 70.1% H 9.2% O 20.8 I found. 70.5% 8.8% 21.1%

The compounds of the general formula II required for the preparation of the compounds of the general formula I can according to the following examples:

Example 65:

To 28.4 g (0.105 koi) Phosphortri.br ornid is "under stirring at 0 ° ~ a mixture of JH, H g (0.261 koi) 4-Isopropcxy-2-butanol and" j 5 07 g (0, Co4 Mol ) Added dropwise to absolute pyridine in the course of 15 min. After stirring for 2 hours at room temperature, the reaction mixture is rapidly distilled in vacuo (bp 55-60 ° / 12 mm). The distillate taken up in ether is washed successively with ice-cold dilute sodium carbonate acid, water, ice-cold 2N sulfuric acid, water and saturated sodium chloride solution, dried over sodium sulphate and freed from ether over a column. In the fractional distillation of the residue is 4-bromo-2-isopropoxybutsn, bp. 69-70 receive ^{0/2 2} I-mm.

Analysis: C ₇ H ₁₅ BrO Molecular weight: 195.1

ber. C. 43 ,1% H 7th .7% Br 41 , 0% found 42 .9% 7th .6% 41 , 4%

Analogously to Example 65, the following compounds (Examples 66-73 of the general formula. II are prepared .;

309846/1188

] At-
i game
! No. I. Gross
formula Molge
weight Boil
Point C. analysis
about _iT
found .% Starting
link i S. a K)
U)
—Λ l-bromo-5-isopropoxypentane I. 45.9
46.3 H Br I. j 5-isopentyloxy-
i pentanol
I. ■ to I
cn
-j 66 2-bromo-4 ~ (2-pentyloxy) -
butane CoH ₁ -BrO ■ 209.1 80-82 °
/ 12 mm 48.4
47.9 8.2
8.2 38.2
37.8 5-isopropoxy
pentanol 9-methoxy
nonanol
i 67 l-bromo-5-pentyloxypentane C ₉ H ₁₉ BrO 223.2 71-75 °
/ 12 mm 50.7
50.0 8.6
8.3 35.8
36, .3 4- (2-pentyl-
oxy) -2-butanol \
\ 8-ethoxy-
octanol 68 1-bromo-6-butyloxyhexane C ₁₀ H ₂₁ BrO 237.2 126-129 °
/ 16 mm 50.7
50.6 8.8
.8.7 33.7
31.0 5-pentyloxy
pentanol Γ
1 l-bromo-5- (2-methyl-butyl-
oxy) pentane C ₁₀ H ₂₁ BrO 237.2 130-132 °
/ 16 mm 50.7
50.7 8.9
9.0 33.7
31.4 6-butyloxy
hexanol ! 70 l-bromo-5-isopentyloxy-
pentane C ₁₀ H ₂₁ BrO ■ 237.2 ; 112-114 °
/ 12 * mm 50.7
50.7 8.9
8.8 33.7
33.9 5- (2-methyl-
i butyloxy) -pen-
i tanol 71 1-bromo-9-methoxynonane ^C 10 ^H 21 ^BrO 237/2 116-119 °
: / 13 mm
\ 50.7
50.5 8.9
9.3 33.7
34.0 72 1-bromo-8-ethoxyoctane ^C 10 ^H 21 ^BrO 237.2 :
138-142 °
/ 17 mm 50.7
50.3 8.9
9.1 33.7
33.3 73 C ₁₀ H ₂₁ BrO 237.2 123-125 °
/ 13 mm 8.9 33.7
33.9

- 50 - 130-3711

Example 74 _?

To a suspension of 5.8 g (0.132 mol) of a 55 percent. Sodium hydride dispersion in 200 ml of absolute toluene 17.6 g (0.2 mol) of 2-pentanol are added at 25 ° with stirring added dropwise. The mixture is refluxed for 5 hours, cooled to room temperature, treated with 30. € g (0.132 mol) of 1,5-dibromopentane and at Stirring at reflux temperature. Then the reaction mixture is cooled to room temperature, washed with water, dried over sodium sulfate and evaporated. The residue is distilled at 16 mm and the at The fraction boiling at 105 ° -125 ° was chromatographed on 1.3 kg of silica gel. Eluting with hexane / ethyl acetate (98.5: 1.5} gives l-bromo-5- (2- pentyloxy) pentane, which is uniform by gas chromatography, bp 115-118 ° / 16 mm

Analysis: C _Q H BrO Molecular Weight: 237.2

ber. 75: C. 50 .7% H 8th / 9% Br 33 .7% found 51 * 0% 9 _r l% 34 , 0% By S play ! -Br * O Rl— 5_ -isopi ΓΌΡΟ3 yp ⁽ änfcan

1.15 g (Ο, 05 mole) of finely cut sodium are entered absolute under nitrogen in 30.0 g (0.50 mol) of isopropanol and \ ^r OLLS tändigen resolution of sodium ISS hr. At 6o ° G stirred. After cooling to 20 ⁰ C 11.5 g (0.05 mol) I.r5-Dibronipentan are added and the mixture l8 SFCD. stirred at reflux temperature. The precipitated sodium bromide is filtered off, the filtrate is freed from excess isopropanol in vacuo and distilled. The main fraction, with a boiling point of 80-82 ° / 12 mm, is converted into hexane-ethyl acetate on 300 g of silica gel

30984S / 1188

(99 "x 1) chromatographed, * where l-Brocn-5-isopropoxypentane as colorless oil is obtained.

80.5 - 8l, 5 ° C / 12 mm

Analysis: CgH ₁₇ BrO Molecular weight: 209.1

calc. C- 45.9 £ H 8.2 £ Br ^ 8.2 % 0 7 / Γ

found, 46.1 ^ 8.2 ^ 38.7 ^ 8.0

In a manner analogous to that described for Example 75, also produce the following compounds of general formula II:

309846/1188

OO Co.

l-bromo-7-isopropoxy-
heptane Gross-
^! formula . "Mol
weight Boil
Point analysis 1-bromo-6-isopropoxyhexane ^C 10 ^H 21 ^BrO 237.2 92-94 °
/ 11 rniu ber. at
game
No. l-bromo-4-isopropoxybutane C ₉ H ₁₉ BrO 223.2 96-98 °
/ 15 mm found
CH Br 76 l-bromo-6- (2-ethyl-hexyl-
oxy) -hexane C ₇ H ₁₅ BrO 195.1 90-91 °
/ 34 mm 50.5 8.9 33.7
50.8 8.7 36.5 77 l-bromo-5-sec.butoxypentane C ₁₄ H ₂₉ BrO 293.3 115-120
/ 0.6 mm 48.4 8.6 35.8
48.7 8.4 35.9 78 1-bromo-6-sec, butoxyhexane C ₉ H ₁₉ BrO 223.2 92 ₇ 93 °
/ 8 'mm 43.1 7.7 41.0
43.2 7.6 41.3 79 l-bromo-6-cyclopentyloxy-
hexane ^C 10 ^H 21 ^Br ° 237.2 57.3 10.0 27.2
57.8 10.0 27.5 80 C _n H ₂₁ BrO 249.2 123-125
/ 1.4 mm 48.1 8.6 35.8
49.1 8.7. 35.1 81 50.6 8.9 33.7 82 '53, 0 8.5 32.1
53.3 8.5 32.7

- 53 - 130-3711

Example 83; l ^ chloro-ö-isopentyloxyhexane

1.8 g (0.08 mol) of sodium are added to 172 g (1.95 mol) of isopentanol. The mixture is stirred at 25 ° C. for three hours. After this time all the sodium has reacted and it is now four 17 * 8 g (0.115 mol) 1,6-dichlorohexane were added dropwise. The mixture

is three hours at 60 ° and then for 24 hours 100 ° stirred.

The excess isopentanol is distilled off at 2Cmm, the The residue was taken up in ether and washed with water. After drying with sodium sulfate, the ether solution is evaporated and the residue on 120 g of silica gel with hexane-Sssigester- (99 ^ 1) chromatographed. Uniform 1-chloro-6-isopentyloxy-hexane is obtained as a colorless oil.

= I, 4j587. Sdp. 102-103.5 ° / 12mm

ClO molecular weight: 2C6.8

• H 11.2 <fo 'Cl 17.1 $

11.1 Ji 17 * 2 #

Example 84:

Analysis: C ₁ L1 ^H 2 9 ber. C. 63, 1 gsf. 64,

To a mixture of 10.4 g (0.06 mol) of 5-pentyloxypentanol and 9.55 g (0.05 mol) of tosyl chloride in 20 ml of absolute chloroform 7.9 g (0.1 mol) of absolute pyridine are added dropwise over the course of 10 minutes at 0 ° with stirring. One is still stirring 3 hours at the cleared temperature, then mixed with 70 g Ice and 30 ml honey. Hydrochloric acid and separates the chloroform phase in a separating funnel. After washing five times with Water, the chloroform solution is dried over sodium sulfate and the solvent is distilled off. In chromatography the residue on 600 g of silica gel with chloroform-methanol (9: 1) is obtained uniformly by gas chromatography

309846/1188

- 54 - - 130-3711

5-pentyloxy-pentyl tosylate

Analysis: C. 62 8 ° 4 ^S H 8th Molecular weight .5% S. 9 , 7 ber. 63 , 2% 9 , 0% 9 ,1 ge f. A 9-
/ t O

The compounds of general formula IVa can, for example can be produced as follows:

Example 85 t 3-Xsopentylo: xy-1-butanol

0.96 g (0.02 mol) of 50 percent sodium hydride dispersion are added to 55.2 g (0.4 mol) of isopentanol. ! times 3O min. are added dropwise with Hühren at 25 ° over 30 min. 9.2 g (0.08 mole) Crotonsäureätir / lester, the mixture stirred for 2 hrs. at 20-25 ⁰ C and 70 ⁰ to ansehliessend C heated. The mixture is cooled for 2 hours, poured into water and extracted with ether. The organic phase is washed with saturated sodium chloride solution, dried with sodium sulfate and evaporated. The residue is distilled at rjrnm Hg, whereby β-isopentyloxy-butyric acid isopentyl ester of bp. 127-129 ° / l is obtained as a colorless oil.
Analysis: ^C i4 ^H 28 ° 3 Kol weight:

boron. C 68.8 # H $ 11.5

found 68.5 # 11.2 %

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ΊiJ> S (0.03 mol) of ß-isopentyloxy-butyric acid-isopentyl ester, dissolved in 20 ml of benzene ornaments in the course of 10 min. At 20 ⁰ C to a solution of 6.1 g (0.06 mol) of sodium bis (2-methoxy-ethoxy) -alurniniuradihydrld was added dropwise to 20 ml of benzene. The mixture is heated to Rückflussteraperatur, after 1 ⁼ h. Cooled proz 10 with 4o ml. Sodium hydroxide solution is added and the mixture is extracted with benzene. The Eenzollö'sung is washed with saturated sodium chloride solution, evaporated and the residue is distilled. The 3-isopentyloxy-l-butanol boils at 100-101 ° / 13 mm,

Analysis: ^C q ^H 20 ° 2 - Molecular weight: l6o, 3

calc. C 67.5 1 * "H 12.6 %

found 67.5 1>. 12.9 %

The following compound of the general formula IVa (Example 86) can also be prepared analogously to Example 85, but using 3,3-dimethylallyl alcohol instead of isopentanol:
Example 86: 3 ^ (3-Kethyl-2-butenyloxy) -1-butanol

Sdp. 145-150 ° / 50mm

Analysis: ^c q ^H 18 ° 2 'Molecular weight: 158.2

ber ^ C 63.3 % H 11.4 %

found 67.9 56 "11.4 ^

Example 87: 5; isopropoxy-3-r: iethylpentanol

To an ethanoligchen llatriumäthylat solution, made from 9 * ^ 5 g of sodium and 200 ml of absolute ethanol are under Nitrogen and stirring at 50 ° C within 15 kin, 67.7 g (0.423 Mvol) diafchyl malonate was added dropwise, followed by 80.0 g (0.4l0 mol) 2-Bvo: a-4-isopropoxybutane, ir.i course of ', iitors 15 min. The mixture is refluxed for 24 hours.

309848/1188

boils, -then neutralized with glacial acetic acid and distilled freed from the main amount of ethanol. The ether extract of the with The residue treated with ice water is made more saturated with water Washed saline solution, dried over sodium sulfate and im ' Evaporated in vacuo. The resulting crude 2-CarbaethQv: y-5-isopropoxy-3-methyl-n-valeric acid ethyl ester can be converted to acid without further purification. In chromatography of 24.8 g of residue with hexane-ethyl acetate (9: 1) on 750 g of silica gel the pure ester is obtained as a colorless oil.

Analysis: ^C 14 ^H 2 ^ ^Of i Molecular Weight: 274.4

calcd. C 61.3 ^, H 9.6 <f>

found ■ 61.0 pounds 9.5 ίο

110 g of crude 2-carbaethoxy-5-isopropoxy-3-methyl-n-valeric acid ethyl ester are converted into 180 g of 50 ~ pros over the course of 15 minutes with stirring at 60 °. KOH (1.6o mol) was added dropwise and the mixture was refluxed for 2 hours. After adding 100 ml of water, the ethanol formed during the hydrolysis is distilled off at normal pressure. The acidified at 10 ⁰ C with 250 ml of 6 Ν.Schwefelsäure stirring residue is extracted with ether., The ether extract solution of sodium chloride Lc-washed with a little water and with saturated, dried over sodium sulfate and evaporated. The crude surückbleibene Diearbonsäure is stirred for 1 h decarboxylation. At 190 ⁰ C and the product then destilliert- in vacuo Here, the 5-isopropoxy-3-methyl-nvaleriansäure as a colorless gel, bp. 89-9I ⁰ / O, lrr, m received.

Analysis: ^C Q ^H 18- ° 3 Col weight: 174.23

calc. C 62.0 ^ H 10.4 Jg 0 27.5 # '. found '62.0 % 10.4 # 27.6 fo

A solution of 19.8 g (0.114 mol) of 5-isopropoxy-5-diethyl-n-va- _: leric acid in 120 ml of absolute benzene is in the course of a

309848/1188

130-3711,

Hrs. To 96 ml (0.3 * 12 mol) of 70 percent. Sodium Ms- (2-methoxy-ethoxy) aluminum dihydride in 220 ml of absolute benzene. The mixture is refluxed for 2 hours, ^{cooled to IG 0} C, acidified with 2N sulfuric acid while stirring and extracted with ether. The extract is washed with a little water and with saturated sodium chloride solution, dried over sodium sulfate and evaporated. When the residue is chromatographed with hexane / ethyl acetate (9: 1) on βθθ g silica gel, 5-isopropoxy-3-methylpentanol is obtained as a colorless oil.

Analysis:

ber.
found

^C 9 ^H 20 ° 2

C 67.5 67.3

H 12.6 <fo 12.7 %

Molecular weight: 160.3

0 £ 20.0 20.2 fo

In a manner analogous to that described for Example 87, can also produce the following compounds of the general formula IVa (examples: 88-91):

Example 88: 5

C. 10 ^H 22 ° 2 11 ^H 24 ° 2 H $ 12.7
12.5 % Bp 86-89 ° 5-butox2 / -3-methylpentanol 10 ^H 22 ° 2 . H 12.7 #
$ 12.7 > ■ 68-70 ° / 0.1 mm Analysis: C. $ 68.9
$ 68.7 70.2 #
$ 71.0 (3 ~ pentyloxy] Molecular weight: $ 68.9
68.6 % ' Molecular weight: 174.3 ber.
found 3-methyl-5- 0 $ 18.4
17.9 pounds C. 0 I8j4 $
$ 18.4 Example 89: ) pentanol C. C. H 12.8 %
12.9 ίο Bp 87-89 ° / 0.02 mm Analysis: C. Molecular weight: 188.3 ber.
found 0 17.0 Ji
15.5 ίο Example 90: / 0.03 mm Analysis: 174.3 ber.
found

309846/1188

Example 91: 3-Kethyl-5; (2 ^ ge ^ tyJ.oxy) -pentanol -

Bp. 74-76 ° / 1.5mm Analysis: O ₁₁ Hp ₂₁ Op Col weight: 183.5

calcd. C 70.2 % H 12.8 % 0 17.0

■ ^ r: 69.8 £ 12.7 si 16.9

Beis piel _92: 5-Isopropoxypentanol

190 g (1.80 mol) of 1,5-pentanediol are mixed with 56.0 ml of 10 N sodium hydroxide solution (0.56 mol) in 50O ml of benzene for 16 hours at reflux cooked and at the same time all water removed from the system by means of a water separator. After the benzene has been distilled off v / earth 45 g (0.56 mol) isopropylbrorcid added and the equipment Stirred at 60 ° for 12 hours. The one created by filtration in front The reaction product freed from sodium bromide is distilled in vacuo. A fraction of the ßdp is obtained. 127-l4o ° / I9mrn, which one half consists of the sought-after 5-isopropoxypentanol, the other half of 1,5-pentanediol. The chromatography of this A mixture of 700 g of silica gel with hexane-ethyl acetate (7: 5) gives 5-isopropoxypentanol as a colorless oil.

Analysis: ^C 8 ^H 18 ° 2 Molecular weight: 146.2

calc. C 65.7 ^c / o H 12.4 % 0.21.9 #

göf. 65.6 <fo 12.2 ^ 21.7 #

Example 93: 5

Is produced analogously to Example 92 , sdp. 62-65 ° / 0.06 mm Analysis: C ₉ H ₂₉ O ₂ Molecular weight: 160.3

berv C 67.5% H 12.6% O 20.0 % found. 67, β% 12.6% 20.1 %

309846/1188

- 59 - 130-3711

Example 94

To a suspension of 11.6 g (0.264 mol) of 55 percent sodium hydride dispersion in 400 ml of absolute toluene 41.5 g (0.40 hol) of 1,5-pentanediol are added with stirring at 25 ° dripped. The equipment is> for 5 hours. boiled under reflux, then cooled to room temperature, mixed with 40.0 g (0.264 mol) of 1-brorapentane and stirred for a further 18 hours at reflux temperature. The reaction mixture is cooled and with 100 ml Water added. The organic phase is separated off in a separating funnel to remove the excess 1,5-pentanediol washed twice with water, over Sodium sulfate "dried and evaporated. The residue is distilled at 16 mm, whereby 5 ~ pentyloxy-pentanol, bp 129-132 ° / 16 mm

can be obtained as a gas-chromatographically uniform, colorless oil.

Analysis: ^c io ^H 22- ° 2 molecular weight: 174.3

calc. C 68.9% H 12.7%

68.9% 12.6%

In a manner analogous to that described in Example 92, the following compounds of the general formula IVa (Example 95-98).

Example 95: 10-isopropoxydecanol

Analysis: ^C 13 ^H 28 ° 2 Molecular weight: 2l6, * l

calc. C 72.2 £ H 13.0 #

72.0 % 13.1 yrs

309846/1188

130-3711

Example 96 :

6-isopropoxyhexanol

Analysis:

ber.

Example 97:

Analysis:

ber .

Example 98 :

C 67.5 % 67.4 %

4-isopropoxybutanol

^C 7 ^H 16 ° 2

C 63.6 63.7

Mo1weight: l6o,

H $ 12.6 12.6 %

Bp. 90 ° / 30mm molecular weight: 132.2

12.2 % 12.2 %

3-isopropoxypropanol

Analysis:

ber .

C 61.0

Molecular weight: 118.2

H 11.9 11.3

In a manner analogous to that described in Example 94, can also the following compounds of the general formula IVa (Examples 99-13) can be prepared.

Example 99:

Bp 129-131 ° / 16 mm

309846/1188

- 61 - 130-3711

Example 100 : 5- (2-Methy_l-buty_lox; £) _- p_entanol bp. 127-129 ° / 15 mm

Example 101; 5-Isogent ^ loxYgentanol b.p. 51-52 ° / 0.02 mm

Example 102;

The synthesis is carried out in an autoclave at 120 °.

Bp. 145 - 150 ° / 15 ram

Analysis: ^c io ^H 22 ° 2 molecular weight: 174.3

calc. C 68.9% H 12.7% _ 69.2% 12.5%

Example 103; §I ^ Si ^ 22Y22tB22i

The synthesis is carried out in an autoclave at 120 °.

137-140 ° / 16 mm

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- 62 - 130-3711

Example 104:

12.0 g (0.25 mol) 50% percent. Sodium hydride dispersion in mineral oil are freed from mineral oil with hexane and 150 ml of absolute 1,2-diir.ethoxyethane layered. The resulting suspension is stirred at 5-10 in the course of 90 minutes. a solution of 35.4 g (0.3 Hol) 2,5-hexanediol added in 60 ml of absolute 1,2-dimethoxyethane.

After stirring for two hours at 50, the 10 ° dissolved mixture 24.2 g (0.2 mol) of AHyI bromide added dropwise in 40 ml of dry 1,2-dimethoxyethane. The mixture is slowly warmed to 60 and stirred at this temperature for 16 hours.

After this time the reaction mixture is on Room temperature cooled. Räch addition of 200 ml each Ether and water are stirred vigorously for 15 minutes and the organic phase in a separating funnel severed. The ether extract is saturated with Washed brine, dried over Iodium sulfate and evaporated. ,. The residue is determined by chromatography purified on silica gel with hexane-ethyl acetate (2: 1), wherein 5-allyloxy-2-hexanol

as uniform, colorless according to gas chromatography Gel can be obtained .. ·

= 1.4423 bp. 62-63 ° / 0.75 mm

Analysis: - ' ^c g ^H ₁₈ ° 2 times weight: 158.2

her Λ G 68.3 % H 11.5 # O 20.2 & found . 68.4 ^ 11.1 ^ 20.3? ^

309846/1 188

- 63 - 130-3711

Example 105

9.43 g (0.08 KoI) 1,6-hexanediol in 180 ml absolute 1,2-diisethoxyethane are stirred with stirring at room temperature in the course of 10 min. 3.12 g (0.104 mol) 80 percent. Sodium hydride dispersion in Oil added in portions. The resulting suspension is stirred for 2 hours at 60 °, then cooled to 0 and in the course of 25 min. with a solution of 17.2 g (0.08 mol) Piperonyl bromide in 80 ml of absolute 1,2-dimethoxyethane offset. This mixture is stirred for 65 hours at room temperature. The reaction mixture is heated to 60 minutes with 8.2 g of pyridine heated, then cooled, mixed with 50 ml V / water and extracted with ether. The organic extracts with water, twice with 6-K sulfuric acid, twice with \ iasser and with saturated saline solution washed ", dried over sodium sulfate and evaporated. Distillation of the residue supplies a fraction of bp 155-166 ° / 0.1 mm, from which in the chromatography 500 g keel gel with hexane-ethyl acetate (4: l) 1,6 ~ dipiperonyloxyhexane, as well as gas chromatography ch uniform 6-piperonyloxyhexanol as

colorless oil can be obtained.

= 1.5192
Analysis: ^C 14 ^H 20 ° 4 Molecular weight: 252.3

calc. C 66.6 $> H 8.0 $ 0 25.4 ? ° 66.7 fo. 8.1 i> 25.8 %

30S3iS / 1188

13O-? 711

Example 106

To 1.50 g (0.0076 mol) in 20 ml abs .. citronellyl methanol is added under stirring at 0 - 5 ⁰ C over 15 min a solution of 3.56 g (0.0121 mol) of mercuric acetate in 50th ml abs. Methanol was added dropwise and the mixture was stirred at 0-5 ° C. for a further 30 minutes. Then 2.97 g (0.053 mol) of potassium hydroxide in 20 ml of methanol are added, followed by 0.232 g (0.556 l mol) of sodium borohydride in portions. The reaction mixture is stirred for 4 hours at room temperature, the mercury formed is decanted off, 120 ml of water / water are added and the mixture is concentrated to 100 ml in vacuo. The product is extracted with ether, the extract is washed with saturated sodium chloride solution, dried with sodium sulfate and evaporated.

Chromatography of the residue on 70 g of silica gel with hexane-ethyl acetate (95: 5 to 9: 1) gives 7-methoxy-3> 7-dimethyloctanol as a colorless oil. "-,.

_{n =}

analysis
ber.

iefT

^σ ιι ^Η ₂ 4 ° 2

C 70.2 % 70.0 %

H 12.8 12.8

Formula Weight: 188.3 $ 17.0

The compounds of general formula VIII can, for example can be represented as follows:

309846/1188

- 65 - 13G-371I

Example 107; 5- (5; 3rompentyloxy) -l _i 3-b3nzodioxole

For the suspension of, 0.550 g (0.0080 mol) 55 percent. Sodium hydride dispersion - freed from the oil by washing with absolute tetrahydrofuran - in 10 ml of absolute tetrahydrofuran, 2.0 g (0.15 mol) of 3,4-methylenedioxyphenol in 10 ml of abs. Tetrahydrofuran is added dropwise and the mixture is stirred for 30 minutes at 20 ° C. and then for 1 hour at 60 ° C. After cooling to 0-5 ° C., 5.1 g (0.0222 mol) of 1,5-dibromopentane are successively added in 20 ml of abs. tetrahydrofuran and 5 ml of hexamethylphosphoric triamide was added and l6 hours cooked. under reflux in an oil bath at 90 ⁰ C.

The reaction product is cooled, poured onto ice and extracted with ether. The organic phase is washed with cold 1 N sodium hydroxide solution, water, 2 N sulfuric acid, water and saturated sodium chloride solution, dried over sodium sulfate and evaporated. Chromatography of the residue on g of silica gel with hexane-ethyl acetate (96: 4) gives pure 5- (5-brompentyloxy) 1,3-benzodioxole. A sample recrystallized from hexane ether has a melting point of 40 - 41 ° C.

Analysis: ^C i2 ^H 15 ^Br ° 3 molecular weight: 287.2

calc. C 50.2 # H 5.3 $ Br 27.8 $ έ found. 50.3 % 5.3 £ 27.9 #

Example go ; ί * ΐί5ΐ5 £ 2ϊ £? ^η ί; ϊ3: 2 & 1ΐΜΒ *} 2?} ¥ .ϊ

5.10 g (0.03 mol) of 4-hydroxy-biphenyl are stirred in 50 ml of 1,2 dimethoxyethane for 20 minutes at 20 ° C. with 1.68 g (0.03 mol) of potassium hydroxide, then with 6.90 g (0.03 mol) 1,5-dibromopentane were added and the mixture was refluxed for 16 hours. To the reaction product water is added and extracted with ether, the extract is washed with 2 N sulfuric acid and saturated sodium chloride solution,

309848/1111

. ■ '■ -.- 66 - 130-3711

dried with sodium sulfate and evaporated. The residue is purified by chromatography on 400 g of silica gel with hexane- ethyl acetate (99.5: 0.5 to 70:30). 4- (5-Brompentyloxy) -blphenyl is obtained, which can be recrystallized from hexane ether. Mp. 50 - 51 ⁰ C.

Analysis: C, ₇ H _1Q Br0 Molecular weight: 319.2

calcd. C 64.0 % H 6.0 % Br 25.0 # found. 63.8 % $ 6.1> $ 24.6

The same approach can also be carried out with 0.075 moles of potassium carbonate in Acetone (instead of 0.03 mol KOH in dimethoxyethane) carried out will. ·

The compounds of the general formula VII can according to can be obtained from the following production example:

Example 109:

In a solution, cooled to 0 °, of 16.2 g (0.1 mol) isosafrole 14.6 g (0.4 mol) of hydrogen chloride are passed into 50 ml of ether. The slightly yellow solution will Left to stand for 20 hours at 0 ° and then evaporated under reduced pressure. The crude ct-ethylpiperonyl chloride accrues as a brown oil and is used without purification.

3Q9846 / 1188

Claims (6)

R ₁ -YC- (CH ₂ ) _v C- (CH ₂ ) _z -XR ₆ I. wherein R- is a short-chain or optionally branched alkyl radical with 1 to 11 carbon atoms, a low-chain cdsr branched, mono- or polyunsaturated, non-cyclic hydrocarbon grate with 5 to 11 carbon atoms, a cycloalkyl radical or a cycloalkyl radical substituted with a lower alkyl group with 5 to J denotes ring carbon atoms and R_, R ", R and R _r independently of one another for hydrogen or a straight-chain or optionally branched alkyl radical with 1 to 6 carbon atoms and w and ζ for 0 or a number from 1 to 8 are with the proviso that the sum w + ζ should mean a number from 1 to 8 and Y for oxygen or sulfur, X for oxygen, sulfur, an -OCH ₂ -, -SCH ₂ -. -OCHR-- or ~ SCHR - group, v7obeherein R_ denotes a straight-chain or optionally branched alkyl radical having 1 to 4 carbon atoms and in which R, an aromatic radical Ar,: ο .1 ■ ^oäer exnen aromatic
rest 309846/1188 - 68 - 130-3711 means in which U represents a lower alkyl, alkenyl, phenyl, lower alkoxy, lower alkenyloxy, formyl, lower alkylcarbonyl, lower alkoxycarbonyl, mono- or di-lower alkyl substituted carbamoyl, lower alkoxyrnethylen, lower alkylthio or a cyano group or chlorine or bromine and R _R and R independently of one another represent hydrogen or a lower alkyl group and W. stands for a nitro group and the individual substituents U; can be different from each other and in which m stands for 0.1 or 2, η for 0.1, 2 or 3 and the sum m + η for a number from 1 to 5, ρ for 1 or 2 and q for 0, 1 or 2 with the proviso that R_ should only stand for a straight-chain or optionally branched alkyl radical with 1 to 6 carbon atoms if X stands for -OCHR ₇ or -SCHR--, or if X stands for -OCH ₃ - or -SCH- - stands and R _g at the same time has the meaning .Ar., and / or ifz. ^ is a number from 1 to 4 and at the same time the sum w + ζ means a number from 1 to 4, characterized in that one a) a compound of the general formula II ? 2 v
R ₁ -YC- (CH ₂ ) _w C- (CH ₂ ) _z -Q ₁ . ■ II wherein R ₁ , R ₀ , R -, ^ .., R _n . and Y as well as w and ζ the above be-1 2 j5 4 5 Signed meanings and Q-j for chlorine, bromine or a tosyl radical, with a compound of general formula III ■ ₆ III 309846/1188 - 69 -. 130-3711 where Rg and X have the meanings given above, and M _{1 stands} for hydrogen , sodium or potassium with the proviso that if M _{1 stands} for hydrogen, the reaction is preferably carried out in the presence of an acid-binding agent, or b) if X in general formula I is oxygen and ζ is an integer from 1 to 8 /
one. Compound of the general formula IYa ■ '? 2 ^R 4. R ₁ -YC- (CH ₂ ) _w C- (CH ₂ ) _z ~ OH IVa wherein R, R *, R. ,, R ,,., R _c and Y sov / w ie the above bezeichne- 1 2 5 Ί 5
have ten meanings and ζ for an integer of 1 to 8 stands with a compound of the general formula IHa wherein R / - has the meaning given above with bicyclohexyl carbodiimide as the condensing agent, or
c) if in the general formula I w + ζ for ¹ 2 to 8 and Y for oxygen are a compound of
general formula Va. HOR ₁ '"Va wherein R _{1 has} the meanings indicated above, by addition to the compound of the general formula VI ^ j,); ^ - (CH ₂ ) _a -XR ₆ » ^R 5 3ote4 «/ part - 70 - 130-3711 wherein , B., R, Rj ,,, Rp. , R-, X, and w and ζ have the meanings given above, or d) if the radical X in the compounds of the general formula I is -OCH ₂ -, -SCH ₂ -, -OCHR ₇ - or -SCHR ₇ , a compound of the general formula IV R ₂ R ₄ R -YC- (CH) C- (CH ₀ ) ZM ₀ IV χ ι λ W ₁ Z Z R ₃ R ₅ where R ,, R ₂ , R_, R., R ₅ as well as w and ζ have the meanings given above and % represents oxygen or sulfur and M _{2 represents} hydrogen, sodium or potassium with a compound of the general formula VII Q ₂ CHR ₆ R ₁₀ VII where R _{fi has} the meaning given above, R-.q is hydrogen or R ₇ and Q _{2 is} chlorine or bromine with the proviso that, if M ₂ in the general formula IV is hydrogen, the reaction is carried out in the presence of an acid acceptor, or e) if the substituent R ₃ in the general formula I is hydrogen, a compound of the general formula VIII h ^R 5 - 71-130-3711 v / orin IU, R ^, R, R ^, X and w and ζ have the meanings given above and Q _{3 represents} chlorine, bromine or a tosyl radical
with the compound of the general formula V M YR ₁
3 1 V wherein R ₁ and Y have the meanings given above and M _{3 is} hydrogen, sodium or potassium, with the addition that, if M _{3 is} hydrogen, the reaction is carried out in the presence of an acid acceptor, or f) if in the general formula I the substituents fc R ^ for Is hydrogen, a compound of the general formula IX ' ) ^ C- (CHg) ₂ -XR ₆ IX '«5 where R_-, R ,,, R, .- * R, -, χ and Y, as well as w and ζ the above j r ^ i O Have signed meanings, and M _{4 stands} for hydrogen, sodium or potassium, with the proviso that, if M stands for hydrogen, the reaction is carried out in the presence of an acid acceptor, with a compound of the general formula X where Q _{4 stands} for chlorine, bromine or a tosyl radical and R a straight-chain or optionally branched px'imary or secondary alkyl radical with 1 to 11 carbon atoms, a straight-chain or branched, single or 309846/1188 - 72 - 130-3711 polyunsaturated noncyclic primary or secondary hydrocarbon radical with ~ j> up to 11 carbon atoms, a cycloalkyl radical or a cycloalkyl radical with 5 to γ ring carbon atoms substituted with a lower alkyl group, with the proviso that the radical Q should be bonded to a primary or secondary carbon atom , is implemented. 2. Compounds of the general formula I R ₁ -YC- (CH ₂ ) _W C- (CH ₂ ) _Z -XR ₆ I. R ₃ R ₅ wherein R _{1 is} a straight-chain or optionally branched alkyl radical with 1 to 11 carbon atoms, a "straight-chain or branched, mono- or polyunsaturated, non-cyclic hydrocarbon group with J to 11 carbon atoms, a cycloalkyl radical or one with a lower one Alkyl group-substituted cycloalkyl radical with 5 Ms 7 Pangköhlenstofi'storr and R ₀ , R-, R. and R _r independently of one another for hydrogen or a straight-chain or optionally branched alkyl radical with 1 to 6 carbon atoms and w and ζ for 0 or a number stand from 1 to 8 with the proviso that the sum w + ζ should mean a number from 1 to 8 and Y for oxygen or sulfur, X for oxygen, sulfur, a -OCH ₀ -, -SCH ₀ -. -OCHR- or -SCRR - group, where R "denotes a straight-chain or optionally branched alkyl radical with 1 to 4 carbon atoms and in which R, - is an aromatic radical Ar ₁ : D J- 309846/1188 - 73 - 130-3711 an aro- inatic ^ Residue Ar ₂ : ^u _q means where U is a lower alkyl / alkenyl, phenyl, lower alkoxy / lower alkenyloxy, formyl, lower alkylcarbonyl, lower alkoxycarbonyl, mono- or di-lower alkyl substituted carbamoyl, lower alkoxymethylene, lower alkylthio or a cyano group or Is chlorine or bromine and R1 and FL independently of one another are hydrogen or a lower alkyl group and W stands for a nitro group and the individual substituents U. . · Can be different among themselves and where m stands for 0,1 or 2, η stands for 0,1 2 or 3 and the sum m + η is to stand for a number from 1 to 5, ρ for 1 or 2 and g for 0, 1 or 2 with the proviso that R_ should only stand for a straight-chain or optionally branched alkyl radical with 1 to 6 carbon atoms _{if X stands for -CCHR 7} or -SCHR ₇ -, or if X stands for -OCK ₂ - or - SCH ₂ -is and R _ß at the same time the meaning Ar _? and / or ifz is a number from 1 to 4 and at the same time the sum w + ζ is a number from 1 to 4. 309846/1188 '.. - ⁷⁴ - 130-3711 3.5 ~ (5-Isopropoxy-3-methyl-pentyloxy) -1 _J 3-t> enzodioxole. 4. 5- (5-sec-Butoxy-3-methyl-pentyloxy) -1,3-kenzodioxole. 5. 5- [3-methyl-5- (3-pentyloxy) -pentyloxy-3-1,3-benzodioxole, 6. - 5- (5 ~ isopropoxy-pentyloxy) -l _i 5 "t> enzodloxol. 7. 5- (6-Isopropoxy-hexyloxy) -l _/ 3 ~ t ⁾ enzodioxole. 8. 1- (5-Isopropoxy-pentyloxy) -4- (methylthio) -benzene. 9. ^ - (5-Isopropoxy-pentyloxy) -biphenyl. 10. (5-Isoproppxypentyl) piperonyl ether. 11. 5- (3-Isopentyloxy-butoxy) -1, 3-t> enzodioxole. 12. 4- (3-Isopentyloxy-butoxy) -benzoic acid methyl ester. 13. (6-Isopropoxy-hexyl) -a-ethylpiperonyl ether 14. (7-Methoxy-3,7-dimethyloctyl) -a-ethylpiperonyl ether 3098U / 1188 - 75 - 130-3711 15. 1-Ethyl-4- (6-isLopropoxy-hexyloxy) -benzene 16. 1-Bromo-4- (5-isopropoxy-pentyloxy) -benzene 17. (6-Isopropoxy-hexyl) -piperonyl ether 18. (5-pentyloxypentyl) piperonyl ether 19. 1-Ethyl-4- [5- (2-pentyloxy) pentyloxy] benzene 20. 1-Ethyl-4- (6-butoxy-hexyloxy) -benzene 21. 5- [3-Methyl ~ 2-butenyloxy) butoxy] -1,3-benzodioxole 22. Agents for combating insects and acarines, characterized in that they contain one or more Compounds of general formula I according to claim 1 contain as active ingredient. 23. Agent for combating insects and acarines, characterized in that it contains 5 * - (5-isopropoxy-3-methyl-pentyloxy) -l, 3-benzodioxole contains as an active ingredient. 24. Agent for combating insects and acarines, characterized in that it contains 5 ~ (5-sec-butoxy-3-methyl-pentyloxy) -1,3-benzodioxole. contains as an active ingredient. 25. Agent for combating insects and acarines, characterized in that it contains 5- [3-methyl-5- (3-pentyloxy) pentyloxy] -1,3-benzodioxole contains as an active ingredient. 309846/1188 - 76-130-3711 26. Agent for combating insects and acarines, characterized in that it is 5- (5-isopropoxy-pentyloxy) -1,3-benzodioxole contains as an active ingredient. 27. Agent for combating insects and acarines, characterized in that it is 5- (6-isopropoxy-hexyloxy) -l, 3-benzodioxole contains as an active ingredient. 28. Agent for combating insects and acarines, characterized in that it contains 1- (5-isopropoxy-pentyloxy) -4- (methylthio) -benzene contains as an active ingredient. 29. Agent for combating insects and acarines, characterized in that it is 4- (5-isopropoxy-pentyloxy) -biphenyl contains as an active ingredient. 30. Means for combating insects and acarines, thereby characterized in that it is (5-isopropoxypentyl) piperonyl ether contains as active substance. "3-1 · Means of combating insects and acarines, thereby characterized in that it is 5- (3-isopentyloxy-butoxy) -1,3-benzodioxole contains as an active ingredient. 32. Means for combating insects and acarines, thereby characterized in that it contains 4- (3-isopentyloxy-butoxy) -benzoic acid methyl ester as active ingredient. 309 8 46/1188 - 77 - 13C-37I1 33. Agent for combating insects and acarines, characterized in that it is (6-isopropoxy-hexyl) -cc-äthylpiperonyläther contains as active ingredient. 34, means for combating insects and acarines, characterized in that it is n-methoxy-S ^ -dimethyl -ct-ethyl-piperonyl ether contains as active ingredient. Agent for combating insects and acarines, characterized in that it contains l-ethyl-4- (6-isopropoxy-hexyloxy) -benzene contains as an active ingredient. 3g _m agent for combating insects and acarines, characterized in that it contains l-bromo-4- (5-isopropaxy-pentyloxy) benzene as an active ingredient. 37 _m agent for combating insects and acarines, characterized in that it contains (6-isopropoxy-hexyl) piperonyl ether as an active ingredient. 38. Means for combating insects and acarines, thereby characterized in that it is (5-pentyloxy-pentyl) piperonyl ether contains as an active ingredient. 39. Means for combating insects and acarines, thereby characterized in that it contains l-ethyl-4- [5- (2-pentyloxy) - -pentyloxy] -benzene as an active ingredient. 309848/1188 130-3711 40. Means for combating insects and acarines, characterized in that it is l-ethyl-4- (6-butoxy-hexyloxy) -benzene contains as an active ingredient. 41. Means for combating insects and acarines, characterized in that it is 5- [3-methyl-2-butenyloxy) butoxy] -1, 3-benzodioxole contains as an active ingredient. 3700 / HT / RS 6th 0 9 8 4 6/1 188