DE2313505C3 - 2,3-Dihydrobenzofuran derivatives, processes for their preparation and pesticides containing these compounds - Google Patents

Description

R ₄ AICIEI "O

Rs Rh R7

(IV)

in which R _{1 is} a hydrogen atom or a methyl or ethyl group, R ₃ and R _{4 are} a methyl, ethyl or propyl group, R ₂ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R _{10 are} a hydrogen atom or a methyl group , A is a hydrogen atom, a methyl or ethyl group, a methoxy or ethyl group or the allyloxy group and B is a hydrogen atom or A and B together form an additional bond or an oxygen bridge, C and D are a hydrogen atom or together an additional bond, E and F are a hydrogen atom or together an additional bond and η denotes the number I or 2.

2. 6 - [(6 ', 7'-epoxy-3'-ethyl-7'-methyl-2'-nonenyI) -oxy] -2,3-dihydrobene: zofuran.

3. 6 - [(7'-ethoxy-3 ', 7'-dimethyl-2'-octenyl) -oxy] -2,3-dihydrobenzofunin.

4. Process for the preparation of 2,3-dihydrobenzofuran derivatives of the general form specified in claim 1;!, characterized in that that one in a known manner

a) a compound of the general formula in which R ₁₁ denotes a methyl or ethyl group or an allyl group and Z has the meaning given in formula II.

5. Pesticides, characterized in that there are one or more 2,3-dihydrobenzofuran derivatives of the general formula I given in claim 1 and an inert carrier material.

The invention relates to 2,3-dihydrobenzofuran derivatives of the general formula

R ₄ AIC | Έ I ^H O R ₅ R ₆ R ₇

R ₄ A

(II)

wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , IJlL ₆ , R ₇ , A, B, C, D, E, F and η have the meaning given in claim I, and Z is the chlorine or bromine Iodine atom, a methylsulfonyloxy or a p-toluenesulfonyloxy group means, 'with a compound of the general formula

(HI)

wherein R ₈ , R ₉ and R _{10 have the} meaning given in claim and M is an alkali or alkaline earth metal, or

b) a corresponding compound of the formula I given in claim 1, wherein at least one of the symbol pairs A uiid B, C and D or E and F together mean an additional bond, hydrogenated, or

c) a corresponding compound of Fontnel I specified in claim I, in which A and B together represent an additional bond, epoxidized at this double bond, or in which R _{1 is} a hydrogen atom or a methyl or ethyl group, R ₃ and R _{4 are} methyl -, ethyl or propyl group, R ₂ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R _{10 are} a hydrogen atom or a methyl group, A is a hydrogen atom, a methyl or ethyl group, a methoxy or ethoxy group or the allyloxy group and B is a hydrogen atom or A and B together are an additional bond or an oxygen bridge, C and D are a hydrogen atom or together are an additional bond, E and F are a hydrogen atom or together are an additional bond and η is the number 1 or 2, and a process for their preparation and pesticides containing these compounds.

Preferred compounds of the formula I are those in which R ₈ , R ₉ and R _{10 represent} a hydrogen atom.

The compounds of the formula I according to the invention are suitable for combating pests. In contrast to most of the pesticides known to date, which are used as contact and Food poisons that kill, paralyze or drive away animals take effect the compounds according to the invention Formula I into the hormonal system of the animal organism. In the case of insects, for example, the Conversion to the imago, the laying of viable eggs and the development of laid eggs normal eggs disturbed. The generation sequence is interrupted and the animals become indirect killed. For vertebrates, the substances of formula I are

practically non-toxic. Their toxicity is over mg / kg of body weight and, moreover, they will easily degraded. The risk of an accumulation is therefore excluded. The compounds of the formula I can therefore be used safely for combating pests in animals, plants and supplies can be used.

The compounds according to the invention are particularly suitable for controlling invertebrates, preferably of arthropods and nematodes, especially of aecarines, orthopteres, leafids, psocoids, Thysanopteroids, Hemiptera, Hymenoptera, Choleoptera, Diptera, Lepiribptera and Neuroptera. Examples of such pests are the following:

Metatetranychus (red citrus spider mite), Tettanychus spp. (common spider mite), Anthonomus grandis (cotton beetle), Chilo suppressalis (Asian rice borer), Diatraea saccharalis
Heliothis spp. (Cotton boll worm), Pyrausta nubilalis (European corn borer), Carpocapsa pomonella (codling moth), Ceratitis capitata (Mediterranean fruit fly), Aonidiella aurantii (red Californian scale insect), Aphis gossypii (cotton aphid), Myzus persicae (peach aphid), Locusta nigrigria . (Rice flour beetle), Sitophilus spp. (Grain beetle),
Ephestia kühniella (flour moth), Plodia interpunctella (dried fruit moth), Aedes spp. (Mosquitoes),

Calculation:

Anopheles spp. (Malaria mosquito), Musca domestica (house flies :), Stomoxys calcitrans (Stallfiiege [Wadenstecher]) Blattella germanica (cockroach), Cochliomyia hominivorax (screwworm).

In general, an active ingredient concentration of 10 ~ ³ to 10 ~ ^ft g / cm ^{3 is} sufficient to ensure the intended effect.

In comparative experiments, the effect of some compounds according to the invention was compared with known ones Substances with the same properties were tested; the following two tests I and II were carried out for this purpose accomplished.

Attempt I.

Tenebrio test

methodology

Filter paper discs (60 cm ² ) are moistened with an active ingredient solution containing the compound to be tested (preferably acetone as solvent) of a defined concentration. 10 freshly skinned pupae (0-24 hours old) are each placed on a roundel and kept in plastic dishes at 25 ° C and 60% relative humidity until the adult animals hatch. Untreated (UC) and roundels treated only with acetone (AC) are used After 10 days, the results are given in% reduction in reproductive adult animals in comparison with the controls.

Fertile adult animals (AC + UC) - fertile adult animals (treated) 10 - fertile adult animals (treated

100 =% reduction.

Result:

100% igc

Effect in

Dose l <r * g / cm ²

1.Standard: methyl-! 0,11-epoxy-

3, Il -di methy 1-7-eth y 1-

2,6-tridecadienoate χ = 5

2nd standard: Prop-2-ynyl-3,7-ll-tri-

methyl-dodeca-

2,4-dienoate χ = 5.5

6 - [(3 ', 7'-dimethyl-2', 6'-octadienyl) -oxy] -2,3-dihydrobenzo-

furan (example 1) χ - 6

6 - [(6 \ T-epoxy-y, T-dimethyl- 2'-octenyl) M) xy] -2,3-dihydro-

benzofuran (example 2) χ - 8

6 - [(6 ', 7'-epoxy-3', 6 ', 7'-trimethyl-2'-octenyl) -oxy] -2,3-dihydro-

benzofuran (Example 2 b) χ = 7.5

6 - [(6 ', 7'-epoxy-3'-ethyl-7'-methyl-2'-nonenyl) -oxy] -2,3-dihydro-

benzofuran (example 2c) ,, χ = 8.5 6 «,

6 - [(3 ', 7', 7'-trimethyl-2 ', 4'-octadienyI) -oxy] -2,3-dihydrobenzofuran (Example 3) χ = 6

100% igc effect in a dose of 10 "g / cm ²

6 - [(7'-methoxy-3 ', 7'-dimethyloctyl) -oxy] -2,3-dihydrobenzo-

furan (example 4) χ = 6

6 - [(7'-ethoxy-3 ', 7'-dimethyl-2'-octenyl) -oxy] -2,3-dihydro-

benzofuran (example 8) χ = 9

6 - [(6 ', 7'-epoxy-7'-ethyl-3'-methyl-2'-nonenyl) -oxy] -2,3-dihydro-

benzofuran (example 2g) χ = 7.5

6 - [(6 ', 7'-Epoxy-3', 7'-dimethyl-2'-nonenyl) -oxy] -2,3-dihydro-3-methylbenzofuran (Example 2e) χ = 7.5 6- [ (6 ', 7'-epoxy-3', 7'-dimethylnonyl) -oxy] -2,3-dihydro-3-methyl-

benzofuran (Example 6 b) χ - 1

6 - [(6 ', 7'-epoxy-3-, 7'-dimethyl-2'-nonenyl) -oxy] -2,3-dihydro-2-methylbemzofuran (Example 2d) χ = 8 6 - [(6 ', 7'-epoxy-3', 7 ', 9'-trimethyl-2'-decenyl) -oxy] -2,3-dihydro-

benzofuran (Example 20 χ = 6.5

6 - [(7'-ethoxy-3 ', 7'-dimethyloctyl) -oxy] -2,3-dihydro-3-methylbenzo-

furan (example 7) χ = 6.5

iOOVoige effect in dose 10 "Ίΐ cnr

6 - [(7'-ethoxy-3 ', 7'-dimethyloctyl) -oxy] -2,3-dihydrobenzofuran

(Example 7a) χ = 7.5

6 - [(7'-methoxy-3 ', 7'-dimethyloctyl) -oxy] -2,3-dihydro-2-methyl-

benzofuran (Example 4 a) χ =

6 - [(6 ', 7'-epoxy-7'-ethyl-3'-methy1-2'-nonenyl) -oxy] -2,3-dihydro-2-methylbenzofuran (Example 2h) χ =

The standard 1. is that from J. Econ. Entomol. 61 (1968), p. 866, well known effective preparation.

Standard 2. is known from a prospectus from Zoecon, USA.

Attempt Il

Aedes test (morphogenetic)
methodology

0.2 ml of an active ingredient solution containing the compound to be tested (preferably with acetone al Solvent), which has a defined concentration of active ingredient, are mixed with 20 ml of tap water mixed. 10 larvae, which are in the last larval stage, are in the treated water given and kept in test tubes at 25 "C and 60 ° / l relative humidity until the adult Animals have hatched. The test tubes contain small bits of dog biscuits and are single-sided Cotton plug closed. Untreated (UC and water treated with acetone (AC) only) are used as a control. The results are expressed as the% reduction in adult animals compared to the controller expressed. Counting takes place after 14 to 21 days

Calculation:

Result:

% adult animals (UC + AC) -% adult animals (treated) 100 -% adult animals (treated) 100 =% reduction.

IOOVoige

Effect in

Dose 10 "* g / cm ²

Standard: methyl-10,11-epoxy-

3, ll-dimethyl-7-ethyI-

2,6-tridecadienoate χ =

Standard: Prop-2-ynyl-3,7, l 1-tri-

methyl-dodeca-

2,4-dienoate χ = 5.5

6 - [(6 ', 7'-epoxy-3', 7'-dimethyl) -2'-octenyl) -oxy] -2,3-dihydro-

benzofuran (example 2) χ = 7, j

6 - [(3 ', 7'-dimethyl-2', 6'-nonadienyl) -oxy] -2,3-dihydrobenzo-

furan (example la) χ = 6.5

6 - [(6 ', 7'-epoxy-3', 7'-dimethyl-2'-nonenyl) -oxy] -2,3-dihydro-

benzofuran (Example 2 a) χ = 7.5

6 - [(6 ', 7'-epoxy-3 \ 6', 7'-trimethyl-2'-octenyl) -oxy] -2,3-dihydro-

benzofuran (example 2 b) χ =

6 - [(6 ', 7'-epoxy-3', 7'-dimelhylnonyl) -oxy] -2,3-dihydrobenzo-

furan (Example 6) χ = 6.5

6 - [(6 ', 7'-epoxy-7'-ethyl-3'-methyl-2'-nonenyl) -oxy] -2,3-dihydro-

benzofuran (example 2g) χ = 7.5

6 - [(6 ', 7'-Epoxy-3', 7'-dimethyl-2'-nonenyl) -oxy] -2,3-dihydro-3-methylbenzofuran (Example 2e) χ = 6.5 6- [ (6 ', 7'-Epoxy-3'i7'-dimethyl-2'-nonenyi) -oxy] -2,3-dihydro-2-methylbenzofuran (Example 2d) χ = 8.5 1 (X)% activity in dose 10 " ^Λ g / cm

6 - [(7'-methoxy-3 ', 7'-dimethyloctyl) -oxy] -2,3-dihydro-2-methyl-

benzofuran (Example 4 a) χ = 6.5

6 - [(6 ', 7'-epoxy-7'-ethy] -3'-methyl-2'-nonenyl) -oxy] -2,3-dihydro-2-methylbenzofuran (Example 2h) χ = 7.5

The experiments show that the tested compounds according to the invention have a considerable effect are safer than the known substances.

The further tests also show the advantageous effect of some of the inventive Links.

45 rice flour beetle test

20 mature rice flour beetles (Tribolium castaneum) were brought into contact with wheat flour in plastic cages for 5 days. This wheat flour is soaked in acetone with a solution of 10 g of the substance to be tested per gram of wheat flour. After 5 days, the beetles are removed and the plastic cages at 29 ° C and 75-80% relative Luftfeuchtig held wedge until the F ₁ generation hatched used as controls analogous experiments with untreated! and wheat flour treated with acetone. The results are given as a percentage reduction in the F 1 generation compared to the controls

do give. The calculation is based on the following equation chung:

R H ki "-

Fi "G ^{enerat 'on} (AC + UC) -F, generation (treated) F, -Gcneration (AC + UC)

AC = mean value from control stitching with acetone treated wheat flour. fJC = mean value from control tests with unbundled wheat flour.

Tested connection

Dose 1 (T *

% Reduction in F, generation

6 - [(7'-ethoxy-3 ', 7'-dimethyl-2'-octenyl) -oxy] -2,3-dihydrobenzofuran (Example 8)

4 5 6 7 8

K) U

100

97

41

16

Phytotoxicity test

Cotton plants and tomato plants are left to drain with a 0.4% of the relevant Test compound containing solution by means of a Spray gun sprayed. After spraying, the plants are placed in a climatic cabin at 25 ° C and 70% relative humidity incubated. After 48 hours the leaves will be regarding any burns occurred and necroses rated, based on the percentage of leaf mass destroyed or attacked on the total leaf mass. Tests without the test substance are used as controls each carried. The solution containing 0.4% test substance is prepared by diluting the following specified concentrate with the calculated amount of water. The concentrate has the following composition:

Polyoxyethylated vegetable oil 12%

Monoglycerides of low molecular weight saturated coconut fatty acids 13%

2-ethylhexyl-2-cyano-3,3-diphenyl-

acrylate 5%

Fractionated triglyceride from coconut oil, which is soluble in ethanol 20%

Test substance 50%

Active subscription

Burns and necroses

cotton

6 - [(6 ', 7'-epoxy-3 \ 7'-dimethyl-0 1

2'-nonenyl) oxy] -2,3-dihydro-

ΐΑ, ιι ^ υιυιαυ \ uvupiui £. <\)

6 - [(6 ', 7'-epoxy-3'-ethyI-7'-methyl-0 0

2'-nonenyl) oxy] -2,3-dihydro-

henzofuran (example 2c)

The pesticides according to the invention can be in the form of concentrates, granules or used together with carriers as sprays, aerosols or powders. For certain Purposes it can be beneficial. Emulsions, suspensions or solutions together with emulsifying or Use wetting agents. As solid carriers come z. B. in question: chalk, talc, bentonite, Kaolin, diatomaceous earth, silica, fuller's earth, lime, gypsum, powder and flours made from organic waste products Etc.

In general, you can use the invention

Formulate pesticides according to the method described e.g. B. in Farm Chemicals, Volume 128, Page 52 and following are described. The pesticides according to the invention can s also contain other additives such as emulsifiers or masking agents.

For example, concentrates of the invention are suitable for storage and transport Pesticides with a content of ίο 40-80% of the active ingredient of the formula I. These concentrates can be used with the same or different carrier materials up to the Concentrations suitable for practical use should be diluted. A ready-to-use one For example, spray preferably contains a concentration of active ingredient from 0.01-0.5%. The active ingredient concentration can, however, also be smaller or larger being.

The pesticides according to the invention are used against the pests according to the usual methods Methods used, e.g. B. through contact or ingestion with food.

The 2,3-dihydrobenzofuran derivatives of formula 1 are produced by, in a manner known per se:

a) a compound of the general formula

R ₄ A

wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , A, B, C, D, E, F and η are as defined above and Z is a chlorine, bromine or iodine atom , means a methylsulfonyloxy or a p-toluenesulfonyloxy group, with a compound of the general formula

Tomatoes MO

(Hl)

wherein R ₈ , R ₉ and R ₁₀ are as defined above and M is an alkali metal or alkaline earth metal, or

b) a corresponding connection of the ones given above Formula I. wherein at least one of the pairs of symbols A and B, C and D or E and F together mean an additional bond, hydrogenated, or

c) a corresponding compound of the above Formula I, in which A and B together are one

do additional bond mean on this double bond epoxidized, or

d) a corresponding compound of the above Formula I, in which at least A and B together represent an additional bond, with water

fi.s or methanol or ethanol in the presence of Reacts acid or a mercury salt, one obtained in the latter case, corresponding Organic mercury compound reduced and a

si

corresponding obtained hydroxy compound with a compound of the formula

R ₁₁ -Ζ

(IV)

in which R _n denotes a methyl or ethyl group or the allyl group and Z has the meaning given in the above formula II.

The implementation according to method a) with z. B. a corresponding halide or a tosylate ι ο of the formula II is carried out in an inert organic solvent, preferably in dimethylformamide, dioxane, Hexamethylphösphorsäuretriarhidi tetrahydrofuran or in a combination of two or more of these solvents. The corresponding 6-oxy compound of the formula III is expediently employed, specifically in the presence of an alkali metal or alkaline earth metal, preferably in the presence of sodium or a corresponding hydride or amide, preferably sodium hydride or sodium imide. The corresponding phenolate is formed from the 6-oxy compound. Suitably, the reaction between -20 ⁰ C and the boiling temperature of the reaction mixture is performed. It is preferred to work at room temperature, especially in the event that Z in formula II represents a bromine atom.

In method b), the hydrogenation with catalytically excited hydrogen in an inert organic solvents such as ethyl acetate or methanol in one between the space and the temperature range lying around the boiling point of the solvent, at normal or increased Pressure. The catalysts are, for. B. Raney nickel or a noble metal such as platinum or palladium, are suitable.

The epoxidation to be carried out according to method c) of the corresponding compounds of the formula I is expediently carried out in such a way that the compound in question is in an inert solvent, especially in a halogenated hydrocarbon such as methylene chloride or chloroform, dissolves and at 0 "C to room temperature with an organic peracid, e.g. with Perbenzoic acid, m-chloroperbenzoic acid or perphthalic acid, or that one treats the relevant Compound suspended in water and treated with such an amount of an inert solvent, e.g. B. mixed with dioxane, tetrahydrofuran or 1,2-dimethoxyethane that a homogeneous, concentrated Solution is formed and N-bromosuccinimide is added in portions to this solution at Q'C to room temperature enters. The resulting bromohydrin is then by the action of alkalis, in particular of Sodium methylate in methanol converted smoothly into the corresponding epoxide.

In the further process variant d), a corresponding compound of the formula I in which A and B together represent an additional bond, reacted with water or methanol or ethanol. This reaction takes place in the presence of an acid, preferably a mineral acid such as sulfuric acid. The solvent is expediently an inert organic solvent, preferably tetrahydrofuran, used. The reaction can be carried out between OC and the reflux temperature of the reaction mixture, preferably between 0 and 40.degree will. Compounds of the formula I are obtained in which A is hydroxy or methoxy or Means ethoxy group. That is particularly preferred in J. Am. Chem. Soc. 91, p. 5646 (1969) Proceedings. This process consists in the reaction of such an unsaturated compound with water or the corresponding alcohol and a mercury salt, then reduced without isolating the mercury-containing intermediate product will. Suitable mercuric salts are mercuric acetate and other acrylates, mercuric nitrate, and mercuric trifluoroacetate and mercury halides. Suitable reducing agents are, for. B. alkali metal borohydrides, hydrazine and sodium amalgam. In the event that the terminal double bond of a corresponding compound formally water is attached, one obtains a hydroxy compound of the formula I in which A is the hydroxy group. Such a hydroxy compound is then etherified with a compound of the formula IV. This etherification takes place in the same way as above for the reaction of a compound of formula II with a compound of formula III described.

Some of the compounds of the formula II to be used as starting materials are known. she can be made from compounds of the general formula

B CHO

(V)

m of R ₃ , R ₄ , R ₅ , A and B have the meaning given in the formula II, by means of known synthesis methods such as the Wittig, Horner and / or Grignard reaction and an enol ether condensation via the corresponding alcohol, the then with z. B. thionyl chloride, phosphorus tribromide or tosyl chloride or mesyl chloride is implemented.

Furthermore, the compounds of the general formula II can also be selected from the compounds of the general formula

(VI)

in which R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , a, B, C and D have the meaning given in formula II, are obtained by using simple reactions known per se to form them corresponding alcohol and prepared from this the halide or tosylate in question of the general formula II.

The compounds of formula I fall in the production, provided that the side chain is unsaturated, as a cis / trans isomer mixture. The isomer mixture can in the usual way, for. B. by fractional Distillation or preparative gas chromatography, separated into the corresponding isomers will. Furthermore, the starting compounds of the formula II can also be used, provided they are used as a mixture of isomers present, in the usual way, e.g. B. by fractional distillation or chromatography will.

example 1

A mixture of 27.7 g of 6-hydroxy-2,3-dihydrobenzofuran, 52.1 g of geranyl bromide and 41.4 g of anhydrous, powdered potash in 200 ml of methyl ethyl ketone are refluxed for 70 hours with stirring. The cooled reaction mixture is filtered, the filtered potash is washed with acetone and the filtrate is evaporated. Chromatography on silica gel with a hexane ι ο ether mixture (4: 1) gives a yield of 67% pure 6 - [(3 ', 7' - dimethyl - 2 ', 6' - octadienyl) oxy] - 2,3-dihydrobenzofuran of b.p. 0.001 130 "C; nJT: 1.5414 .

In an analogous manner, the following compounds are obtained when using the corresponding starting materials:

a) From 1 - bromo - 3,7 - dimethyl - 2,6 - nonadiene and 6 - hydroxy - 2,3 - dihydrobenzofuran the 6 - [(3 ', 7' - dimethyl - 2 ', 6' - nonadienyl) - oxy] -2,3-dihydrobenzofuran, bp 0.002138 "C; n?: 1.5382.

b) From 1 - bromo - 3,6,7 - trimethyl - 2,6 - octadiene and 6 - hydroxy - 2,3 - dihydrobenzofuran the 6 - [(3 ', 6', 7 '- trimethyl - 2 \ 6' octadienyl) oxy] -2,3-dihydrobenzofuran with a boiling point of 0.001 124-126 ° C; n'S: 1.5412.

c) From 1 - bromo - 3 - ethyl - 7 - methyl - 2,6 - nonadiene and 6 - hydroxy - 2,3 - dihydrobenzofuran, the 6 - [(3'-ethyl-7'-methyl-2 ', 6 '-nonadienyl) -oxy] -2,3-dihydrobenzofuran of boiling point 0.001 132-134 ° C; nf: 1.5346.

d) From 1-bromo-3,7-dimethyl-2,6-nonadiene and

6 - Hydroxy - 2 - methyl - 2,3 - dihydrobenzofuran 6 - [(3 ', 7'-Dimethyl-2', 6'-nonadienyl) -oxy] -2-methyl-2,3-dihydrobenzofuran of bp. 0.001 approx. 145 ° C; n'S: 1.5286.

e) From 1-bromo-3,7-dimethyl-2,6-nonadiene and

6 - Hydroxy - 3 - methyl - 2,3 - dihydrobenzofuran 6- [(3 ', 7' - dimethyl - 2 ', 6' - nonadienyl) - oxy] -3-methyl-2,3-dihydrobenzofuran b.p. 0.001 147 ° C; nff: 1.5312.

From 1 - bromo - 3,7,9 - trimethyl - 2,6 - decadiene and 6 - hydroxy - 2,3 - dihydrobenzofuran the 6 - [(3 ', 7', 9 '- trimethyl - 2', 6 '- decadienyl) - oxy] -2,3-dihydrobenzofuran with a boiling point of 0.03 112 ^r; C (spherical tube); ηV: 1.5271.

g) From 1-bromo-3,7,7-trimethyl-2-octene (prepared using 3,7,7-trimethyl-1-octen-3-ol according to the procedure described in Example 5 for the starting material) and 6 - hydroxy - 2,3 - dihydrobenzofuran 2,3-dihydro-6 - [(3 ', 7', 7'-trimethyl-2'-octenyl) -oxy] -benzofuran of boiling point 0.04 95 ' C (spherical tube); n% ⁵ : 1.5177.

Example 2

g of 6 - [(377'-dimethyl -2 ', 6'-octadienyl) -oxy] -?, 3-dihydrobenzofuran are dissolved in 180 ml of methylene chloride and, with stirring and ice-cooling, at) -5 "C 14.3 g 80% M-chloroperbenzoic acid is added in portions and the mixture is stirred for a further 2 hours while cooling with ice. The reaction mixture is initially diluted with 360 ml of ether and washed successively with ice-cold 1N sodium hydroxide solution and water. The organic phase is dried over sodium sulphate and evaporated. By chromatography on silica gel with a hexane-ether mixture (7: 3) becomes pure 6 - [(6 ', 7'-epoxy-3', 7'-dimethyl-2 '- octenyl) - oxy] - 2,3 - dihydrobenzofuran with a b.p. 0.001 approx. 150 "C; nf: 1.5346 obtained (yield 76%).

In an analogous manner, the following compounds are obtained when using the corresponding starting materials:

a) From 6 - [(3 ', 7'-dimethyl-2', 6'-nonadienyl) -oxy] -2,3 - dihydrobenzofuran the 6 - [(6 ', 7' - epoxy- yT - dimethyl - 2 '- nonenyl) - oxy] - 2,3 - dihydrobenzofuran of boiling point 0.001 approx. 150 "C;nl": 1.5324.

b) From 6 - [(3 ', 6', 7 '- trimethyl - 2 \ 6' - octadienyl) oxy] - 2,3 - dihydrobenzofuran the 6 - [(6 ', 7' - epoxy - 3 ', 6 ', 7' - trimethyl - 2 '- octenyl) - oxy] -2,3 - dihydrobenzofuran with a boiling point of 0.001 approx. 150 ° C .; I. 62-64 ^r 'C.

c) From 6 - [(3'-ethyl-7'-methyI-2 ', 6'-nonadienyl) -oxy] -2,3-dihydrobenzofuran the 6 - [(6', 7'-epoxy - 3 '- . -T- methyl ethyl -T- nonenyl) - oxy] -2,3-dihydrobenzofuran, bp 0.001 150 "C;n'S: 1.5287.

d) From 6 - [(3 ', 7'-dimethyl-2 \ 6'-nonadienyl) -oxy] -2-methyl-2,3-dihydrobenzofuran the 6 - [(6', 7'-epoxy-3 ' , 7'-dimethyl-2'-nonenyI) -oxy] -2-methyl-2,3-dihydrobenzofuran of boiling point 0.001 approx. 150 "C;n'S: 1.5286.

e) From 6 - [(3 ', 7'-dimethyl-2', 6'-nonadienyl) -oxy] -3-methyl-2,3-dihydrobenzofuran the 6 - [(6 ', 7'-epoxy-3 ', 7'-dimethyl-2'-nonenyl) -oxy] -3-methyl-2,3-dihydrobenzofuran of bp 0.001 approx. 160-165 "C;n'S: 1.5261.

From 6 - [(3 ', 7', 9 '- trimethyl - 2', 6 '- decadienyl) -oxy] -2,3-dihydrobenzofuran the 6 - [(6', 7'-epoxy-3 ', 7 ', 9'-trimethyl-2'-decenyl) -oxy] -2,3-dihydrobenzofuran of boiling point 0.3 140 "C (Kugelrohr); nl ³ : 1.5219.

g) From 6 - [(7'-ethyl-3'-methyI-2 ', 6'-nonadienyl) -oxy] -2,3-dihydrobenzofuran the 6 - [(6'J'-epoxy -T- ethyl - 3 '- methyl - 2' - nonenyl) - oxy] -2,3-dihydrobenzofuran, «0 °: 1.5273.

h) From 6 - [(7'-ethyl-3'-methyI-2 ', 6'-nonadienyI) -oxy] - 2,3 - dihydro - 2 - methyl benzo furan the 6 - [(6', 7 '-Epoxy-7'-ethyl-3'-methyl-2'-nonenyl) -oxy] - 2,3 - dihydro - 2 - methylbenzofuran with a boiling point of 0.01 128 ° C (Kugelrohr); ηϊ: 1.5201.

Example 3

mg of 55 percent sodium hydride dispersion are washed three times with absolute tetrahydrofuran under nitrogen and then covered with 5 ml of absolute tetrahydrofuran. It is then cooled to O'C and a solution of 0.85 g of 6-hydroxy-2,3-dihydrobenzofuran in 10 ml of absolute tetrahydrofuran is added dropwise with stirring. The mixture is stirred for 1 hour at room temperature, again cooled to 0 ^° C. and 1.22 g of l-bromine ^ JJ-trimethyl ^^ - octadiene, dissolved in 10 ml of absolute tetrahydrofuran, are added. Then it is diluted with 10 ml of absolute hexamethylphosphoric acid triamide, the ice bath is removed and the mixture is stirred for hours. It is then poured onto ice water and extracted three times with ether. The combined ether extracts are then washed with water and saturated sodium chloride solution, ee-

dries and evaporated. Chromatography on silica gel with a hexane-ether mixture (98: 2) gives pure 6 - [(3 ^/ , 7 ', 7'-trimethyl-2', 4'-octadienyl) - oxy] - 2,3 - dihydrobenzofuran, which distilled 0.02 130 ⁰ C in a Kugelrohr at Kp.. n _'D °: 1.5438. (Yield 30%).

The 1-bromo-3,7,7-trimethyl-2,4-octadiene used as the starting material above has been manufactured as follows:

23.75 g of copper (iodide) iodide are placed in a dry reaction vessel and the apparatus is flushed with argon. Then 125 ml of absolute ether are added and the suspension is cooled to -40 ° C. Then allowed under stirring 100 ml of 2 molar solution of methyllithium in ether at -40 to -30 ° C shrink, and then dropwise during 30 minutes at about - 30 ⁰ C a solution of 9.3 g of 6-methyl-3,5-heptadien- 2-one in 75 ml of absolute ether too. The mixture is then allowed to warm to -5 ° C. over the course of an hour, while stirring, the whole is then poured into an ice-cold aqueous ammonium chloride solution, stirred well and filtered through CeIHt. The organic phase is separated off and the aqueous phase is re-extracted once with ether. The organic phase and the ether extract are combined, then washed with saturated sodium chloride solution, dried over sodium sulfate and freed from the solvent at 30 ° C. on a rotary evaporator. The residue is dissolved in 100 ml of acetone, with 2 ml of conc. Hydrochloric acid is added and the mixture is left to stand at room temperature for 24 hours. The mixture is then poured into ice-cold 10 percent soda solution, extracted exhaustively with ether, the combined extracts washed neutral with saturated sodium chloride solution, dried over sodium sulfate and evaporated at 30 ° C. on a rotary evaporator. Chromatography on silica gel with a hexane-ether mixture (92.5: 7.5) gives pure 6,6-dimethyl-3-hepten-2-one, which distills nl ° in a bulb tube at bp 10-60 ° C : 1.4460.

6.0 g of the above 6,6-dimethyl-3-hepten-2-one, 15.0 g of carbethoxymethylene triphenylphosphorane and 2.5 g of benzoic acid are dissolved in 90 ml of absolute benzene and refluxed for 65 hours. The cooled down The reaction mixture is poured onto 75 ml of ice water and 15 ml of 2N sodium hydroxide solution and the benzene layer severed. The aqueous phase is extracted twice with ether and the extracts with the Benzene layer combined and first with 1 / O percent potassium bicarbonate solution, then three times with water and then washed once with saturated sodium chloride solution, dried over sodium sulfate and evaporated. The residue is taken up with a little hexane and filtered. The filtrate is on Kleselgel chromatographicrt with a hexane-ether mixture (9: 1). 3,7,7-Trimethyl-2,4-octadienoic acid ethylsler is obtained as a mixture of isomers, which distills in a Kugclrohr at boiling point 0.05, 65 ° C; / iff: 1.4855.

A solution of 4.2 g of the above 3,7,7-trimelhyl-2,4-octadienic acid ethyl acetate in 90 ml of absolute ether is slowly mixed with a suspension of 0.75 g of lithium aluminum hydride in 45 ml of absolute ether are added. The reaction mixture is allowed to warm to room temperature within 2 hours and is then decomposed in the cold by the dropwise addition of 60 ml of 10% ammonium chloride solution is extracted with ether and the combined ether solutions washed with saturated sodium chloride solution, dried over sodium sulfate and evaporated to give 3,7,7-trimethyl-2,4-octadien-1-ol, which is purified by distillation the compound is obtained with a boiling point of 0.03, 60 "C; «?: 1.4790.
A solution of 1.5 g of the above obtained

ίο 3,7,7-trimethyl-2,4-octadien-1-ol in 15 ml of ether is added ^{dropwise at -20 0} C with 1.20 g of phosphorus tribromide. The temperature is allowed to rise to 0 ° C. within 30 minutes and the whole is then poured onto 30 ml of ice water. It is then extracted three times with ether, the combined extracts washed successively with water, 10 percent potassium bicarbonate solution, semi-saturated and saturated sodium chloride solution and dried over sodium sulfate After removing the solvent under reduced pressure in the cold, 1-bromo-3,7,7-trimethyl-2,4-octadiene is obtained, which shows a spot in the thin-layer chromatogram (R _f = 0.63, hexane-ethyl acetate 4: 1) The compound is used without further purification for the reaction described in paragraph 1 of this example.

Example 4

0.875 g of 55 percent sodium hydride dispersion are washed three times with absolute tetrahydrofuran under nitrogen and then covered with 10 ml of absolute tetrahydrofuran. The mixture is cooled to O ' ^J C and a solution of 2.27 g of 6-hydroxy-2,3-dihydrobenzofuran in 12 ml of absolute tetrahydrofuran is added dropwise over the course of 15 minutes. The mixture is then stirred for 1 hour at room temperature before it is again cooled to 0 ° C. and 5.5 g of 3,7 - dimethyl - 7 - methoxy - octyl p-toluenesulfonate dissolved in 12 ml of absolute tetrahydrofuran are added dropwise over the course of 15 minutes. Then it is diluted with 12 ml of absolute hexamethylphosphoric triamide, the ice bath is removed and the mixture is stirred at room temperature overnight. The whole is then poured into ice water and extracted three times with ether. The combined ether extracts are washed successively with water and twice with saturated sodium chloride solution, dried over sodium sulfate and evaporated. Chromatography on silica gel with a hexane-ether mixture (9: 1) gives pure 6 - [(3 ', 7' - dimethyl -T- methoxy - octyl) - oxy] - 2,3 - di-

hydrobenzofuran, which distills in the Kugelrohr at boiling point 0.0Z 150 ° C, ng ¹ : 1.5086 (yield 69%).

In an analogous manner, when using the corresponding starting materials, the following compounds are obtained:

a) From 7 - melhoxy - 3,7 - dimethyloclyl - ρ - toluenesulfonate and 6-hydroxy-2,3-dihydro-2-methylbenzofuran 6 - [(7'-methoxy-3 ', 7'-dimelhyloctyl) - oxy] - 2,3 - dihydro - 2 - methylbenzofuran

ίκ> of bp 0.01, 116 ^J C (Kugelrohr); n ?: 1.5011.

b) From 3.7 - Dimeihyi - 6 - octenyi - ρ - toiuolsulfonal {nV: 1.5022; made from citronellol by a Grignard reaction with methyl magnesium iodide, followed by a reaction with

ρ - toluene sulfochloride) and 6 - hydroxy - 2,3 - dihydrobenzofuran 6 - [(3 ', 7'-dimethyl-6'-octynyl) -oxy] -2,3-dihydrobenzofuran of bp 0.001, 126-128 ° C »?" · 1 wi

c) From 3,7-dimethyl-6-octenyl-p-toluenesulfondt and 6 - hydroxy - 3 - methyl - 2.3 - dihydrobenzofuran the 6 - [(3 ', 7'-dimethyl-6'-octenyl) -oxy] - 3-methyl-2,3-dihydrobenzofuran, bp 0.14. 130 C ( spherical tube): ηΐ: 1.5150.

The 3,7-dimethyl-7-methoxy-octyl-para-toluene sulfonate used as the starting material above has been manufactured as follows:

A suspension of 7.6 g of lithium aluminum hydride in 500 ml of absolute ether is added with ice cooling 93.2 g of 7-methoxycitronellal dissolved in 200 ml added dropwise to absolute ether. The mixture is then stirred for 30 minutes and then decomposed in the Cold by adding 100 ml of aqueous ammonium chloride solution. The resulting pulp is through Cellite filtered, the filtrate once with saturated ammonium chloride solution and saturated sodium chloride solution washed, dried over sodium sulfate and evaporated. The residue is at 0.1 torr distilled. Pure 3,7-dimethyl-7-methoxy-1-ctanol is obtained b.p. 0.1, 87 ° C; n ?: 1.4456.

3.76 g of the above SJ-dimethyl ^ -methoxy-1-oclanol are dissolved in 20 ml of anhydrous pyridine and with stirring and ice cooling with 4.2 g of p-toluenesulfochloride offset. The reaction solution is then left to stand at 5 ° C. overnight, and then poured then on ice water and extracted three times with ether. The combined extracts are sequentially with cold 2N hydrochloric acid solution, water and washed twice with saturated sodium chloride solution, over sodium sulfate-potassium carbonate dried and evaporated at reduced pressure, finally at 0.05 torr. SJ-Dimethyl ^ -methoxy-octyl-p-toluenesulphonate is obtained. »Ι ?: 1.4927.

Example 5

10.9 g of 6-hydroxy-2,3-dihydrobenzofuran become dissolved in 80 ml of anhydrous dimethylformamide and with stirring and ice cooling at 0-3 ° C. with 5.3 g freshly powdered potassium hydroxide added. The mixture is stirred at 0 ° C. for 1 hour under a nitrogen atmosphere and then a solution of 19.6 g of i-bromo-7-ethyl-3-methyl-2,6-nonadiene is added dropwise within one hour in 10 ml of absolute tetrahydrofuran. The mixture is then stirred for 2 hours at 0 ° C. and then for 2 hours Room temperature, whereupon the reaction mixture is added to a mixture of 100 ml of 10% sodium hydroxide solution and pour 100 ml of ice water. One now extracts three times with pentane, washes the combined extracts in sequence with 10% sodium hydroxide solution, water and saturated saline solution, dried over sodium sulfate and evaporated. By chromatography Kieselgcl with a hexane-ether mixture (19: 1) gives pure 6 - [(7'-EthyU3'-methyl-2 ', 6'-nonä- * dicnylj-oxy] -2.3-dihydrobenzofuran, which distills in a bulb tube at b.p. 0.02 132 C; ii ?: 1.5350 (Yield 63%).

The 1-bromo-7-ethyl-3-methyl-2,6-nonadicn used as the starting material above has been manufactured as follows:

18.2 g 7 - ethyl - 3 - methyl - 1,6 - nonadicn - 3 - oil. HM) ml of hexane and 1 ml of anhydrous pyridine are cooled to -15 ° C. and a solution of 4 ml of phosphorus trinromide in 50 ml of hexane is added ^{dropwise over a period of 1 1/2 hours, the reaction temperature being kept between -15 and -IOC.} The reaction mixture is stirred for 90 minutes while slowly warming to room temperature. The mixture is then poured into 50 ml of ice water, the organic phase is separated off and washed once with 20 ml of 10% sodium carbonate solution, 50 ml of saturated sodium chloride solution and 50 ml of saturated sodium chloride solution, dried over sodium sulphate and evaporated under reduced pressure Pressure a. You get

further purification for the conversion described above is used.

Example 6

1.0 g of 6 - [(6 ', 7'-epoxy-3', 7'-dimethyl-2'-nonenyl) -oxy] -2,3-dihydrobenzofuran are dissolved in 25 ml of ethyl acetate and in the presence of 50 mg Platinum oxide until the theoretical amount has been absorbed Hydrogenated hydrogen. The catalyst is then filtered off and evaporated. By chromatography the residue on silica gel with a hexane-ether mixture (19: 1) gives pure 6 - [(6 ', 7'-epoxy - 3 ', 7' - dimethylnonyl) - oxy] - 2,3 - dihydrobenzofuran of n?: 1.5118 (yield 50%).

In an analogous manner, one obtains when using the appropriate Starting materials the following compounds:

a) From 6 - [(6 ', 7'-epoxy-3', 7 ', 9'-trimethyl-2'-decynyl) -oxy] -2,3-dihydrobenzofuran the 6 - [(6 ', 7'-epoxy - 3', 7 ', 9' - trimethyldecyl) - oxy] - 2,3 - dihydrobenzofuran with a boiling point of 0.03 140 C (Kugelrohr);

ii ?: 1.5083.

b) From 6 - [(6 ', 7'-epoxy-3', 7'-dimethyl-2'-noncnyl) -oxy] - 3 - methyl - 2,3 - dihydrobenzofuran das 6 - [(6 ', 7' - epoxy - 3 ', 7' - dimethylnonyl) - oxy] -3-methyl-2,3-dihydrobenzofuran from bp 0.001

• ^s approx. 165 "C;n'g: 1.5108.

c) From 6 - [(3 ', 7'-Dimethyl-6'-oclenyl) -oxy] -2,3-dihydrobenzofuran 6 - [(3 ', 7'-Dimcthyloctyl) -oxy] - 2,3-dihydrobenzofuran of bp 0, (M) I 116-117 ° C; 11? ': 1.5102.

Be is ρ i e 1 7

A suspension of 3.81 g of mercury acetal in 30 ml of absolute alcohol is left at room temperature slowly a solution of 3.48 g of 6 - [(3 ', 7'-diethyl - 6' - octenyl) - oxy] -3r methyl - 2,3 - dihydrobenzofuran in 15 ml of absolute alcohol. Then it is stirred for 1 hour at room temperature, then cools by means of an ice bath and leaves first

so 12.8 ml of 10% sodium hydroxide solution and then 0.24 g of sodium borohydride Add drops to 12.8 ml of 10% sodium hydroxide solution. The mixture is stirred for 30 minutes at room temperature, now filtered through cellite, the aqueous phase saturates with common salt and extracted this with pentane. The combined extracts are washed with saline washed neutral, dried over sodium sulfate and dampened. By Chrorriatographic on silica gel one obtains pure 6 - [(7'-Älhoxy-3 \ 7'-dimetliyloctyl ^ oxy] - 3 - methyl - 2,3 - dihydrobenzofuran, the

(»0 distilled in a bulb tube at boiling point 0.01 132" C; ■ «#: · 1.4976 (yield 25%).

In an analogous manner, when using 6 - f (3 ', 7' - dimethyl - 6 '- octenyl) - oxy] - 2.3 - dihydl'oben is obtained zo furan

a) the 6 - [(7'-ethoxy-3'.7'-dimcthyloctyl) -OXj] -2.3-dihyuroben7ofur «ui of b.p. 0.01 132; CV (Kugclrohr): "ii? F: 1.5018.

Example 8

875 mg of 55% sodium hydride dispersion are washed three times with absolute tetrahydrofuran and then covered with K) ml of absolute tetrahydrofuran. A solution of 2.72 g of 6-hydroxy-2,3-dihydrobenzofuran in 12 ml of absolute tetrahydrofuran is then added to the dispersion at OC and with stirring. The mixture is stirred while warming to room temperature for 1 hour, then cooled again to O'C and a solution of 1 -Biom ^ -ethoxy ^ J-dimethyl ^ -octene in 12 ml of absolute tetrahydrofuran is added dropwise. Then 12 ml of the purest hexamethylphosphoric triamide are added to the mixture, the ice bath is removed and the mixture is stirred for 3 hours. For work-up, the whole thing is poured onto ice water and extracted three times with ether. The combined extracts are washed with water and saturated sodium chloride solution, dried over sodium sulfate and evaporated. Chromatography of the residue on silica gel with a hexane-ether mixture (19: 1) gives pure 6 - [(7'-ethoxy - 3 ', 7' - dimethyl - 2 '- octenyl) - oxy] - 2,3 - Dihydrobenzofuran, which distills in the Kugelrohr at boiling point 0.05 150 ° C; n? ¹ : 1.5172 (yield 43.5%).

The 1-bromo-7-ethoxy-3,7-dimethyl-2-octene used as the starting material above is like has been produced as follows:

30 ml conc. Sulfuric acid is slowly added dropwise to 460 ml of absolute alcohol at -5 to 0 C. 126 g of methylheptenone are then added to the solution while slowly warming to 20 ° C. The mixture is stirred for 24 hours at room temperature, then poured into 750 ml of water and the oily mixture is separated. The aqueous phase is washed four times with 75 ml of benzene each time extracted and the extracts combined with the oily layer. The organic phase is washed twice with water and twice with saturated sodium chloride solution, dried over sodium sulfate. The solvent is first removed by distillation under reduced pressure, and then pure 6-ethoxy-6- is obtained. methyl-2-heptanone of bp 1086-88'C;n'i: 1.4287.

16.4 g of 55% sodium hydride dispersion are washed three times with hexane and covered with 200 ml of dimethylformamide. Is then added dropwise under nitrogen for 2 ¹ I ₂ hours a solution of 8415 Diäthylphosphonoessigsäureäthylester in 400 ml of dimethylformamide, while the temperature rises slightly After the addition stirring is continued for I hour at room temperature, and the M: - ski-jig then slowly treated with a Solution of 43 g des

s 6-ethoxy-6-methyl-2-heptanons obtained above in 400 ml of dimethylformamide. The mixture is then stirred overnight at room temperature and then for a further 5 hours at 55 'C. The reaction mixture is then poured into 250 ml of ice water and mixed three times with

ίο ether extracted. The combined ether extracts become Washed twice with water and then once with saturated sodium chloride solution, over sodium sulfate dried and evaporated under reduced pressure. Pure ones are obtained by distilling the residue

Ethyl 7-ethoxy-3,7-dimethyl-2-octenoate with a boiling point of 0.03 83-85 ° C .; / i ?: i, 4572.

From the 7-ethoxy-3,7-dimethyl-2-octenoic acid ethyiester obtained above is obtained by means of lithium aluminum hydride according to the method in Example 3 in the case of

Starting material described process the 7-ethoxy-3,7-dimethyl-2-octene-l-o! of b.p. 0.02 77-78 "C; η if: 1.4584.

The above 7-ethoxy-3,7-dimethyl-2-octenl-ol is converted into 1-bromo-7-ethoxy-3,7-dimethyl-2-octcn by reaction with phosphorus tribromide according to the method described in Example 3 for the starting material , _'D n °: 1.4862 obtained.

Example 9

ίο An ice-cold solution of 6.0 g of 6 - [(3 ', 7'-dimethyl-2', 6 ' - nonadienyl) - oxy] - 2,3 - dihydrobenzofuran in 40 ml of absolute methanol is added dropwise with stirring a solution of 6.7 g of mercury acetate in 100 ml of methanol is added. Then you stir

vs 2 hours at room temperature, whereupon you at Cooling with an ice bath, first 23 ml of 10% sodium hydroxide solution and then 0.4 g of sodium borohydride in 23 ml of 10% sodium hydroxide solution are added. The mixture is stirred for 20 minutes at room temperature, filtered through cellite,

saturate the filtrate with common salt and extract three times with ether. The combined extracts are washed neutral with sodium chloride solution, dried over sodium sulfate and evaporated. Chromatography of the residue on silica gel with a hexane-Essigester mixture 19: 1 there is obtained pure 6 - [(7 '- methoxy - 3', 7 '- dimethyl -T- nonenyl) - oxy] -2,3 - dihydrobenzofuran, which distills in the Kugelrohr at bp 0.03 125 ° C; «?: 1.5236 (yield 16%).

Claims (1)

Patent claims: 1. 2,3 - Dihydrobenzofuran derivatives of the general formula (I) ίο d) a corresponding compound of the formula I given in claim 1, wherein at least A and B together represent an additional bond, with water or methanol or ethanol in the presence of acid or a mercury salt, one in the latter Trap obtained, corresponding organic mercury compound reduced and a corresponding obtained hydroxy compound with a compound of the formula