DE1953152A1 - Preparations for regulating the growth of plants - Google Patents

Description

46 820. '

Applicant Fujisawa Pharmaceutical Oo. Ltd *

Preparations for regulating the growth of plants

The present invention "relates to new preparations used for Regulation of plant growth are useful. In detail, "the new invention relates to new and valuable growth! preparations that regulate plants and contain certain 5-substituted 2,4-pentadiene derivatives as an active ingredient, which are partly new connections. The present invention further relates to a new class of 5-substituted ones 2,4-pentadiene derivatives and their preparation.

In its general formulation, the present invention relates to preparations for regulating the growth of plants? which are characterized in that they contain at least one 5-substituted 2,4-pentadiene derivative as the active ingredient Formula -r

- CH

4th -2-

QQ9884 / 2215

where H ₁ for _

'τ> Κι

OH

or

stands, Rt-, Rr and R ₇ mean lower alkyl groups, R ₂ . Is hydrogen or lower alkyl, R ~ is carboxyl, lower alkoxycarbonyl, hydroxymethyl or cyano and R. is hydrogen, halogen, hydroxy, lower alkyl, lower alkoxycarbonyl or cyano,
as well as an inert carrier.

Some specific examples of the above substituents are given below:

-3-009884 / 2215

Lower alkyl is a group with 1-6 carbon atoms

(e.g. methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, etc.). ■ ν.

Lower alkoxy: a group containing 1-6 carbon atoms

(e.g. methoxy, xthoxy, propoxy, isopropoxy, Butoxy, pentoxy, hexyloxy, etc.)

Lower alkanoyl is a group with 2-7 carbon atoms

(e.g. acetyl, propyonyl, butyryl, isobutyryl, Valeryl, hexanoyl, etc.)

Halogen: chlorine, bromine, fluorine *

The 5-substituted 2,4-pentadiene derivatives generally exist from their geometric isomers, e.g., the 2-cis-4-trans and 2-trans-4-trans isomers, etc., and the compounds of the formula I according to the present invention also include these * to the 5-substituted 2,4-pentadiene derivatives Formula I above includes new compounds and known compounds.

Specific examples of 5-substituted 2,4-pentadiene derivatives of the general formula I are given below. The chemical name ^N .... »pentadiene acid ^{n stands} for the English expression" _e * .. pantadienoic acid ^w i

2t4-pentadienoic acids ₉

e.g. 3 ~ methyl-5- (1 s2-epoxy-2 _f 6 _f 6-triiE © thy! cyclohexyl) -

3-methyl-5- (1 ^ -j
trans -4-t2ranspentadienoic acid, 3-itthyl-5- (1 ^ -epoxy-a.ete cis-4 ~ tranapentadienoic acid,

Lower alkyl-5-lower alkyl ~ 5- (i ^ -
alkyIcyclohexy1) -2,4-pentadienoate,

ζ.B. Methyl 3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis-4-transpentadienoate,

. 009884/22 15 ""

BATH

Methyl-3-methyl-5- (1,2-epoxy-2,6,6-trimethy'lcyclohexyl) -2-trans-4-transpentadienoa1 ?,

Xttiyl-3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis-4-tranepentadienoate,

Ethyl 3-methyl 5- (1,2-epoxy-2, ^ ö-trimettiylcyclohexyl) -2-tran8-4-transpentadienoate,

Xthyl-3-ethyl-5- (1 ^ -epoxy ^ / Ö ^ -trimethylcyclohexyl) -2-cis-4-transpentadienoate, etc. |

3-lower alkyl-5- (1 _t 2-epoxy-2,6,6- (lower) alky! Cyclohexyl) -2,4 pentad! Enols,

e.g. 3-methyl-5- (1 ^ -epoxy ^ jojo-trimethylcyclohexyl) -2-cie-4-tranepentadienol,

3-methyl-5- (1 »2-epoxy-2,6,6-trimethylcyclohexyl) -2 · trans-4-tranapentadienol, etc .;

3-never deralkyl-5- £ i »2-epoxy-2,6,6-tri (lower) alkylcyclohexylJ-2,4-pen-tadienonitrile,

e.g. 3-methyl-5- (1 ^ -epoxy ^^ ejö-trimethylcyclohexyl) -2-cis-4-tranapentadienoneltrile,

3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-trane-4-transpentadienonitrile, etc.)

2,3HDi (lower) alkyl-5- (1,2-epoxy-2,6,6-tri (lower) alkylcyclohexy1) -2,4-pentadienoic acids,

e.g. 2t3-Diifiethyl-5- (1 »2-epoxy-2,6,6-trimethylcyclohexyl) -2-cie-4-transpentadienoic acid,

2 _# 3HDiiaetbyl-5- (1 ♦ S-epoxy ^ , 6,6-tri «ethy Icyclohexyl ) -2-trane-4-transpentadiene acid,

Lower alkyl-2 _# 3-di (lower) alkyl-5- (1 »2-epoxy-2,6 _# 6-tri i ttieder) alky! Cyclohexyl) -2,4-pentadienoates,

Q0988W2215

BATH

"" 5 "■

e.g. methyl-2,3-dimethyl-5- (1 ^ - methylcyclohexyl) -2-cis-4-transpentadienoate,

A * thy 1-2,3-dimethyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) ~ 2 ~ trans-4- ^i> transpentadienoate _i etc .;

Lower alkyl-2-cyano-3-lower-alkyl-5- (1,2-epoxy-2 »6,6-tri (lower-alkylcyclohexyl) -2,4-pentadienoate _f

ζ .B. A ^% thyl-2-cyano-3-methyl - 5- (1,2-epoxy-2,6,6-trimethylcyolohexyl) -2 ~ cis-4 ~ tran8pentaienoa1 ;,

Methyl-2 ~ cyanoQ-3-methyl - 5- (1 _t * 2-epoxy-2, 6 , b-tri methyloycloliexyl) -2-1; rans-4 - transpentaienoate,

Methyl-2-cyano-3- ± ethyl-5- (1,2-epoxy-2,6,6-trimethylcyolohexyl) »2-cis-4-transpeni; adienoai; _t etc. f

Lower alkyl-2-hydroxy-3-lower alkyl-5- (1,2-epoxy-2,6,6-tr-ime-fcliylcycloexyl) -2,4-pentadienoate,

ζ .B. Methyl 2-hydroxy-3-methyl-5- (1,2 »epoxy-2,6,6-trimethylcyclohexyl) -2-cis-4- * ranpentadienoate ,

Ethyl-2-hydroxy-3-methyl-5- (1,2-epoxy-2,6,6-trimethyl cyclohexyl) -2-trans-4-tränspeτl · fcadienoa ■ t »etc. j

Lower alkyl 5- (1,2-epoxy-2,6,6-tri (lower) alkyleyclohexyl) -2,4-pentadienoates, ■

e.g. methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cia-4-transpentadienoaii,

ethyl 5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis-4 ~ 1; ranpentadieonate,

ethyl 5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-trans-4-transpentadienoate, etc.j

2,3-di (lower) alkyl-5- (1,2-epoxy-2,6,6-tri (lower) alkylcyclohexyl) -2,4-pentadienoic acids,

009884/2215

ss.B. ' 2,3-dimethyl-5- (1,2-epoxy-2,6,6-trimethy1-cyclohexyl) -2-cis-4-transpentadienoic acid,

2 _i 5-dimethyl-5- (1,2-epoxy-2,6,6-trimethyIcyclohexyl) -E-tranB ^ -transpentadiene acid, etc.j

Lower alkyl 2,3-di (lower) alkyl-5- (1,2-epoxy-2,6,6-tri (lower) alkylcyclohexyl) -2,4-pentadienoate,

ζ.B. Methy1-2,3-dimethyl-b- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis-4-transpentadienoate,

Ethyl 2,3-dimethyl-5- (1,2-epoxy-2,6,6-trimethy1-cyclohexyl) -2-tranB-4-tranapentadienoate, etc.j

2-lower alkanoyloxy-3-lower alkyl-iJ- (1,2-epoxy-2,6,6-tri (rdeder) alky ! cyclohexyl) -2,4-pentadienoic acids,

e.g., 2-acetoxy-3-methyl-5- (1,2-epoxy-2,6,6-trimethy ! cyclohexyl) - ^ - cis ^ -transpentadienoic acid,

2-acetoxy-3-methyl-5- (1,2-epoxy-2,6,6-trimethyl-1-cyclohexyl) -2-trans-4-transpentadienoic acid etc.j

Lower alky1-2-lower alkanoyloxy-3-lower alkyl-5- (1,2-epoxy-2,6,6-tri (lower) alkyIcyclohexyl) -2,4-pentadi enoate,

e.g. methyl 2-acetoxy-3-methyl-5- (1,2-epoxy-2 _ί 6,6-trimethylcyclohexyl) -2-cis-4-transpelltadienoate,

Methyl 2-acetoxy-3-methyl-5- (1,2-6POXy ^ ₅ Oj 6-trimethy Icyclohexyl) -2-trans-4-transpentadienoat;,

Ethyl-2-acetoxy-3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis-4-transpentadiene-oat,

Ethyl 2-acetoxy-3-ethyl-5- (1 »2-epoxy-2,6,6-trimethyl-cyclohexyl) -2-trans-4- ^i- transpentadienoate, etc. j

Lower alkyl 2-hydroxy-5- (1,2-epoxy-2,6,6-tri (lower) alkylcyclohexyl) -2,4-pentadienoate%

e.g. Methy1-2-hydroxy-5- (1,2-epoxy-2,6,6-tri-

009884/2215

caö

methy lcyclohexyl) - ^ - ciB - ^ - tranepentadienoat,

A * ethyl 2-hydroxy-5- (1,2-epoxy-2,6,6-trimethylcyclohexy1) -2-trans-4-tranpentadienoate, etc.j

2-halo-3-lower alkyl-5- (1 * 2-epoxy-2 ₁ 6,6-tri (lower) alky! Cyclohexyl) -2-cisM-trans-pentadlenic acids,

e.g. 2-bromo-3-methyl-5- (i, 2-epoxy-2,6,6-trimethyl-1-cyclohexyl) -2-cie-4-tran8pentadiene acid, uew.f

Lower alkyl-2-halo-3-lower alkyl-5- (1,2-epoxy-2,6,6-tri (lower) alkylcyclohexyl) -2-ciB-4-transpentadienoate,

e.g., methyl 2-bromo-3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis-4-tranopentadienoate, etc.i

3-lower alkyl-5- (1,2-dihydroxy-2,6,6-tri (lower) alkylcyclohexyl) -2,4-pentadienoic acids,

e.g. 3-methyl-5- (1 _t 2-dihydroxy-2,6,6-trimethy1-cyclohexyl) -2-ci8-4-transpentadienoic acid,

3-methyl-5- (1,2-dihydroxy-2,6,6-trimethylcyclohexyl) -2-tran8-4-transpentadienoic acid, etc .;

Lower alkyl 1-3-lower alkyl 5- (1,2-dihydroxy-2,6,6-tri (lower) alkylcyclohexyl) -2,4-pentadienoate%

e.g. ethyl 3-methyl-5- (1,2-dihydroxy-2,6,6-trimethylcyclohexy1) -2-cis-4-transpentadienoate,

Ethyl-3Hfiethyl-5- (1,2-dihydroxy-2,6,6-trimethyl * cyclohexyl) -2-trans-4-transpentadienoate,

Ethyl-3 ^ methyl-5- (1,2-dihydroxy-2 _t 6,6-triaethyl-cycloheyl} -2-ciB-4-tranBpent; adienoate,

Ethyl-3-u * thyl-5- (t _t 2-dihydroxy-2 »6,6-trimethylcyclohexyl) -E-trans ^ -transpentadienoatt« sw. j

Honest yyiyy.fi)

6AD ORIGINAL

alkyl-2-cyclohexenyl) -2,4-pentadienoate,

B.B. Methyl 3-methyl-5- (1-hydroxy-2,6,6-trimethyl-2-cyclohexenyl) -2-cis-4-trans pentadienoate,

Methyl 3-methyl-5- (1-hydroxy-2, 6,6-trimethy1-2-cyclohexenyl) -2-trane-4-transpentadienoate, etc.{

3-lower alkyl-5- (1-hydroxy-2-methylene-6,6-di (lower) alky1-cyclohexyl) -2-, 4-pentadienoic acids,

e.g. 3-methyl-5- (1-hydroxy-2-methylene-6,6-dimethyl-1-cyclohexyl) -2-cis-4-transpentadi enoic acid,

3-Xthyl-5- (1-hydroxy-2-methylene-6,6-dimethyl / cyclohexyl ) -2-trans-4-tear pentadienoic acid, etc .;

Lower alkyl-3-lower alkyl-5- (1-hydroxy-2-methylene-6,6-di (lower) alkylcyclohexyl) -2,4-pentadi enoate,

ζ .B. Methyl 3-methyl-5- (1-hydroxy-2-methylene-6,6-dimethy / cyclohexyl) -2-cis-4-transpentadienoate,

14ethyl-3-methyl-5- (1-hydroxy -2-methylene-6,6-dimethyl ! cyclohexyl) -2-trans-4-transpentadienoate,

Xthyl-3-methyl-5- (1-hydroxy-2-methylene-6,6-dimethy ! cyclohexyl) -2-cis-4-transpentadienoate,

Ethyl 3-methyl-5- (1-hydroxy-2-methylene-6,6-dimethyl-cyclohexyl) -2-trans-4-transpentadienoate, etc. j

The 5-substituted 2,4-pentadiene derivatives of the formula I have a remarkable activity in terms of regulating the growth of plants. These activities include, inter alia, the anti-gibberellin activity, anti-auxin activity and an activity which inhibits the growth of plants. The activity in regulating plant growth includes in detail the effect of preventing germination and sprouting} the effect of causing inactivity? the effect of accelerating aging ^ the effect of accelerating bleaching? the effect that _Q

- SAD ORKSiNAi.

Accelerate color formation! the effect, the abscissa layer (, absciss layer), etc. These connections can be used as growth regulators for artificial control the growth of plants in arable and horticultural fields *

The 5-substituted 2,4-pentadiene derivatives according to the following Invention are useful for various fields of application, some typical of which are explained below:

Use as an agent for inhibiting growth ; ■

To prevent expansion in the. Height for Italian ryegrass, orchard grass, Bases, etc .;

To prevent the shooting of rice, wheat, etc. by preventing the elongation; To prevent vegetables such as cabbage, white from bursting Rapeseed, carrots, radishes, burdock, etc .; To prevent the heads of spherical ones from bursting Vegetables such as cabbage, etc .;

To prevent the fruit of grapes, cherries, apples, etc. from bursting}

To prevent overripe watermelons, melons, etc.j

To prevent growth in terms of height Vegetables such as cucumbers, tomatoes, egg plants, etc. and flowers such as oosmea, sage, chrysanthemums, cyclamen, poinsettias, Levbun, morning glory, etc .; To prevent the overgrowth of the pods of citrus fruits such as mandarins, oranges, etc .; To prevent the growth of non-bearing side shoots of vegetables such as melons, watermelons, cucumbers, Tomatoes, egg plants, etc. and fruit trees such as pears, grapes, citrus fruits, etc.

-10-

0Q 9 88 4 / 22T5

- ü ^ i "- iri - ·

Use as a means of preventing germination:

To prevent potatoes, sweet potatoes, yam, onions, chestnuts, etc. from sprouting during storage; To prevent the formation and growth of axially and igen buds on tobacco plants, especially after the Pinching off the apex or terminal buds} To prevent the formation and growth of lateral ones Buds in mulberry trees} To prevent the Ährat germination of rice, wheat, etc.

Use as defoliant;

For falling off the leaves and petioles of soybeans, Cotton, red beans, runner beans, etc. for harvest; To speed up the opening of the cotton bolls through Defoliation?.

To "fall off" the old leaves of apple or pear trees; For withering or falling off the leaves, leaf stalks and climbing stalks of potatoes, sweet potatoes, etc. for harvest

Other uses:

For deflowering or thinning the fruits of apples, peaches, tangerines, oranges, pears, etc.j To improve the storage capabilities of cereals such as rice, wheat, grain, etc. and fruits such as apples, chestnuts, as well as vegetables such as onions, yam, potatoes, sweet potatoes etc. and other seeds or crops j To prevent deformity of egg plants (tomatoes, Cucumbers or aubergines), whereby these malformations are caused by • side effects of certain agricultural methods p

To alleviate frost damage to Japanese date plum trees, Grapes, mulberries, etc.}

To alleviate transplant damage in young trees (pine, cedar, Japanese cypress, etc.)} ·· ' ■ -11-

- 11 -

To accelerate color formation in the fruits of fruit plants (Mandarins, apples, peaches, grapes, tomatoes, strawberries, etc ·);

To accelerate vernalization (vernalization) eur Control of flower bud formation in grapes, mandarins, Apples, peaches, barley, rye, wheat, etc. 5 To accelerate the formation of the female blood buds with cucumbers, tomatoes, egg plants, etc .; To induce the formation of flower buds in winds, Oosmea, sage, potmum, etc .;

To speed up the fall of fruits such as apples, Mandarins, peaches, pears, etc. or the seeds of soybeans, Beans, runner beans, pepper, etc. during harvest time.

The mentioned 5-substituted 2,4-pentadiene derivatives of the formula I can be used as plant growth regulators in the form of preparations which contain at least one of the 5-substituted 2,4-pentadiene derivatives of the formula I as an active ingredient. They can be used in the form of the separate isomers, ie as the 2-ei8-4-trans isomer or the 2-trans-4-trans isomer. Alternatively, they can be used in mixed form without the isomers being separated from one another. The effectiveness of the compounds according to the invention when used as plant growth regulators depends on the concentration used. Considerable fluctuations with regard to the effective concentrations are observed depending not only on the species, nature and structure of the plants to be treated, but also on their physiological age. Therefore, the concentration to be used should be appropriately determined depending on the intended use of the agent _f, the kind of the plant to be treated and the duration of the application. However, in Hegel an effective concentration will be in the range of 1-5000 ppm, and preferably in the range of 10-500 ppm. However, this area is not critical.

• ' ■ "--12-

009884/2215

Bie preparations for regulating the growth of plants according to of the invention can be used in a conventional manner. However, the most appropriate method should be used in each case selected depending on the intended use, the type of plant to be treated and the duration of application will. In general it can be said that when direct application to plants is desired, spraying or dusting the preparations onto the surfaces of the leaves and / or petioles of the plants or a treatment of the soil on which the plants grow "satisfactory is. If seeds, fruits, tubers, etc. are to be treated, these are to be treated with the preparation in Solution sprayed into the present in the form of a solution Dipped preparation or sprinkled with the powdered preparation. Some examples of the different. Application methods are given below.

To prevent the formation and growth of side-buds in tobacco, the preparation is applied to the surfaces of the Leaves of the plant after pinching off the terminal buds or after removing the side buds that are in the Time of application are already in place.

To prevent onions from germinating, the agent is evenly sprayed onto the leaves and stems of the onions about 2 or '5 weeks before harvest, when $ 20-30 of the onion plants are turned down. The harvested onions should advantageously be stored in a dry place at a low temperature.

To prevent potatoes from sprouting, the agent is applied to the leaves and petioles during the middle Tgils of the tuber growth period sprayed. '

To prevent the heads of cabbage from bursting, the agent is sprayed onto the outer leaves that surround the head.

. -13-

009 884/22 1 5

give when its formation is completed at around $ 70-80.

To cause fruit thinning in apple or citrus trees, the agent is applied to their flower head zone within one month after flowering.

The compounds of formula I according to the invention can be processed into various forms of preparations, for example solutions, dust, granules, tablets, wettable powders, emulsions, oily preparations, aerosols, etc., where it is mixed with various suitable excipients who the.

The form of the preparation of the preparations according to the invention can be any one known per se.

Solid preparations can be made with inert powders. Such preparations may be homogeneous powder, which are used either as such or diluted with inert solids to form dust, or suspended in a suitable liquid medium for spraying. The powders usually contain the active ingredient mixed with suitable amounts of conditioning substances. Natural clays, either absorbent such as ittapulgite or relatively poorly absorbent such as kaolin earths, diatomaceous earth, walnut shell flour, redwood flour, synthetic fine silica, calcium silicate and other inert solid carriers can be used. The active Bestanteil is generally in an amount of about 1 to about 80 wt. #, Preferably in an amount of about 1 to about 50 wt. I "of these powder preparations before. Talc, pyrophyllite, tobacco dust, volcanic ash and other dense, rapidly settling inert solids are used in the customary manner to convert the powder into dust.

The liquid preparations containing the active ingredient,

0 9 8 8 4/2215

can be prepared by mixing this with a suitable liquid medium. The active ingredient can be either in solution or in suspension in the liquid medium The constituent is generally present in these liquid preparations in an amount of about 1 to about 1% by weight, preferably from about 1 to about 100% by weight. Some of these preparations are intended to be used as such. Others should be diluted with large amounts of water.

The preparations in the form of wettable powders or liquids can also contain one or more surface-active agents such as wetting agents, dispersants or emulsifiers. Accordingly Mixtures of the above liquids with the active ingredient may contain an emulsifying agent to give a to produce emulsifiable oily preparation. The surface-active agents have the consequence that the liquid or Slightly disperse the solid state preparations in water or emulsify to give aqueous spray solutions. The surfactants that are used can be anionic, cationic and / or non-ionic Be type ..

Anionic surfactants that can be used are those corresponding to the formulas R-COOM, R-SO ^ M and R-OSO, M correspond to where M is an alkali metal atom, a Aanoniumgruppe or a substituted ammonium group and R is an organic radical containing at least one Is a group with more than 8 carbon atoms. Examples of such anionic surfactants are: (1) Soaps of fatty and / or resin acids, including dehydrated, hydrogenated and disproportionated resin soaps (e.g. sodium laurate, ammonium tearate, diethanoiammonium oil eat,

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~~ - ~ 009884/221 5

Sodium salts of disproportionated resin acids); (2) alkyl sulfonates (e.g. dodecyl sodium sulfonate, getyl potassium sulfonate) j (3) alkyl sulfates (e.g. sodium dodecyl sulfate, sodium oleyl sulfate); (4) sulfonated ethers of long and short chain aliphatic groups ( _{e.g. C 17} HjJ-OC ₂ H ₄ -SOjNa); (5) sulfonated ethers of long and short-chain aliphatic groups (e.g. _{C 17} H _{33 -OC 2} H ₄ -O-SOjNa) J (6) sulfonated alkyl esters of long-chain fatty acids ( _{e.g. C 17} HjJ-CO-OC ₂ H ₄ - SOjNa); (7) sulfonated alkyl esters of long chain fatty acids (eg ° i 7 ¹¹ Jj-CO-OC ₂ H ₄ -O-SO ₃ Na); (8) sulfonated alkyl-substituted amides of long-chain fatty acids ( _{e.g. C 17} HjJ-CO-NH-C ₂ H ₄ -SOjNa, C ₁₇ HjJ-CQ-N (CHj) -C ₂ H ₄ -SO ₅ Na) J ( 9) alkylated aryl sulfonates (e.g. isopropylnaphthalenine sodium sulfonate, dodecylbenzene sodium sulfonate) j (10) hydroaromatic sulfonates (e.g. tetrahydronaphthalene sodium sulfonate) j (11) alkyl sulfosuccinate (e.g. dioctyl sodium sulfosuccinate); (12) Arylsulfonate-formaldehyde condensation products (e.g. condensation product of formaldehyde and sodium naphthalenesulfonate).

Non-ionic surfactants that can be used are:

(1) Monoethers of polyglycols with long-chain fatty alcohols such as the reaction products of ethylene oxide or polyethylene glycol with a long-chain fatty alcohol (e.g. reaction product of ethylene oxide and oleyl alcohol); (2) Monoesters of polyglycols with long-chain fatty acids such as reaction products of ethylene oxide or polyethylene glycol with a long-chain fatty acid (eg reaction product of ethylene oxide or polyethylene glycol with oleic acid); (3) monoethers of polyglycols with alkylated phenols, such as reaction products of ethylene oxide or polyethylene glycol with an alkylphenol (for example reaction product of ethylene oxide and isopropyl phenol); (4) Polyoxy äthylenpolyoxypropyleneglykole, produced by condensation of ethylene oxide with a hydrophobic base g formed by condensation of propylene oxide with propylene glycol (e.g. H (OC, H / -) (OC ₂ H ₄ ) _n OH, where the molecular weight of (OCjHg) _m between "· · ' -16-

009884/2215

800 and 2.b00 and (OC ₂ IL) _{n is between 10 and 90 wt. # Of} the molecule, such as H (OC ₅ H ₆ ) ₂₅ _ 5O (OC ₂ H ₄ ) _8-12 0H) | (5) partial esters of polyhydric alcohols with long-chain monocarboxylic (fatty and / or resin) acids (for example glycerol monostearate, sorbitol trioleate) ; (6) Partial and complete esters of long-chain monocarboxylic (fatty and / or resin) acids with polyglycol ethers of polyhydric alcohols (eg polyoxyethylene sorbitol tristearate, polyoxyethylene sorbitol hexaoleate).

Cationic surfactants that are used can are; (1) Quaternary ammonium salts, in which one of the radicals attached to the nitrogen atom is an organic Contains group with at least 8 carbon atoms (e.g. trimethylcetylammonium iodide, laurylpyridinium chloride, Cetyldimethylbenzylammonium chloride, N-stearylbetaine) j (2) Amines, amides and diamines with an organic group containing at least 8 carbon atoms and their salts with. Acids (e.g. stearylamine hydrochloride, oleylamide, bioethylethylene oleyldiamine).

Examples of the preparation of the preparations;

Particularly practical and preferred embodiments of Preparations are described in the following examples. Parts are parts by weight.

Example 1 aqueous solution

In the compositions which are mentioned below, is a compound as an active ingredient is dissolved in water to prepare an aqueous solution. The aqueous solution is used as such:

(1) Hodium-3-methyl-5- (1 ^ -

hexyl) -2-cis-4-transpentadienoate 2 parts

Water: 1,000 parts

(2) sodium 3-methyl-5- (1 ^ -

cyclohexyl) -2-cis-4-transpentadienoate: 2 parts

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- 17.- ■■. . ■

Water 1,000 parts

• (3) Sodium-3-methyl-5- (1-hydroxy-2,6,6-trimethyl-2-

cyclohexenyl) -2 ~ cis-4-transpentadienoate: 2 parts

Water ι 1,000 parts

(4) 3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -

2-cis-4-transpentadienol: 2 parts

Water: 1,000 parts

Example 2 liquid preparation:

In the compositions mentioned below, a compound is used as an active ingredient in a solvent dissolved, and water is then added thereto to make a liquid preparation. The liquid preparation is after Dilute with water to 10-5,000 times the amount used.

(1) Methyl (or ethyl) -3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexy 1) -2-cis-4 * transpentadienoate: isopropanol: Water . ;

(2) Methyl 3-methyl-5- (1-hydroxy-2,6,6-trimethyl-2-cyclohexenyl) -2-cis-4-transpentadienoate : Isopropanol: Water:

(3) ethyl 3-methyl-5- (1-hydroxy-2-methylene-6,6-dimethylcyclohexylj ^ -cis ^ -transpentadienoat: Isopropanol: water j

(4) methyl-3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis-4-transpentadienoate s acetone: water j

(5) methyl 3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis-4-transpentadienoate : Ethanol j water:

2 Parts 20th Il 78 It 2 Parts 20th Il 78 It 2 Parts 20th Il 78 It 2 Parts 20th Il 78 η 2 Parts 10 η 88 "-18-

009884/2215

- 1B -

Example 3 emulsions?

In the compositions mentioned below, the ingredients are uniformly used to produce emulsions mixed together. The emulsions are applied 100-50,000 times as much after diluting with water.

(1) Methyl (or ethyl) -3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexylj ^ -cis ^ -transpentadienoat:

20 parts 70 "10»

20 » 70 ·· 10"

Polyoxyethylene alkyl phenyl ether

(2) Methyl 3-methyl-5- (1-hydroxy-2,6,6-trimethyl-2-cyclohexenyl) -2- ^ cis-4-transpentadienoate xylene
Polyoxyethylene alkyl phenyl ether

(3) ethyl-3-methyl-5- (1-hydroxy-2-methylene-6,6- • dimethylcyclohexylJ ^ -trans - ^ - transpenta-

dienoat

Xylene

Polyoxyethylene alkyl phenyl ether

(4) 3-methyl-5- (1 ^ -epoxy-a ^ jö 2-cis-4-transpentadienonitrile xylene
Polyoxyethylene alkyl phenyl ether

(5) Methyl (or ethyl) -3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexylj ^ -cis ^ -transpentadienoat: 20 parts xylene 70 "Toximal 500 (emulsifier consisting of Pblyoxyäthylenalkylphenyläther and calcium alkylbenzenesulfonate): 10 "

Example 4 jams:

20 parts 70 "10»

: 20 pieces: 70 "s 10"

In the compositions, which are mentioned below, the individual ingredients are evenly mixed and pulverized, to make dust. The dust is used as such. -19

009684/2215

(1) 3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis (or trans) -4-transpentadienoic acid: 1 part Talk: 999 part

(2) Sodium 3-methyl-5- (1-hydroxyl, 6,6-trimethyl-2-cyclohexenyl) -2-cis-4-tranepentadienoat: 2 part of talc: 998 ^w

(3) Methyl 3-methyl-b- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-trans-4-tranBpentadienoate : 2 Teili Talk j 99b "

Example b wettable powder

In the compositions which are mentioned below, are the individual components are crushed to produce wettable powders. The wettable powder (1 part) will, according to Dilution with water (100-10,000 parts) applied.

(1) Methyl (or ethyl) -3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexylj ^ -cis ^ -transpentadienoati 10 part «Sorpol 8048 (emulsifier containing 80 56 sodium alkylbenzenesulfonate) : 4 "

Tone s 86 "

Example 6 tablets

In the compositions which are mentioned below, the individual components are pulverized and tabletted. the Tablets (1 part) are used after dissolving in water (100-10,000 parts).

(1) methyl (or ethyl) -3-methyl-5- (i, 2-epoxy-2,6,6-trimethylcyclohexyiy - ^ - cis ^ -transpentadienoati 1 part of calcium carboxymethyl cellulose: 5 parts

Bentonite: 10 "

Tone ϊ 84 "

Example 7 granules:

In the compositions mentioned below, who-_20-

pulverized the individual components with water (10 parts) mixed and granulated in the usual way. The granules are used as such or after being dissolved in water.

. (1) Methyl (or ethyl) -3-methyl-5- (1,2-epoxy-2,6,6-

trimethylcyclohexylJ ^ -ciB ^ -transpentadienoate: 3 parts

Bentonite i 10 "

Sound: 87 "

Preparations containing active compounds other than those mentioned above are used in substantially the same manner prepared as described in the previous examples.

The preparations produced in this way can be used alone or in combination with other fungicides, nematocides, insecticides or Herbicides are applied. It is also possible to use these preparations together with fertilizers or any other to apply agents regulating the growth of plants.

The activity in terms of regulating the growth of plants of some compounds according to the invention, the correspond to the general formula I, is explained below with the aid of various experiments. The ones given in these experiments active ingredients are the following numbered compounds:

Connection no «1

Ethyl 3-methyl-5- (1,2-epoxy-2,6,6-trimethyl-cyclohexyl) -2-trans-4-transpentadienoate

Connection No. 2 .

Ethyl 3-methyl ~ 5- (1,2-epoxy-2,6,6-trimethyl-cyclohexyl) -2-cis-4-transpentadienoate

Connection No. 3

Meth; yl-3-diethyl-b- (1,2-epoxy-2,6,6-trimethy 1-cyclohexyl) -2-cis-4-transpentadjenoate P ₁

009884/2215.

Connection No. 4

3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis-4-transpentadienoic acid

Connection Kr. 5

3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-trans-4-transpentadienoic acid

Compound No. 6

Ethyl 3-methyl-ii- (1,2-dihydroxy-2,6,6-trimethylcy clonexyl) -2-cis-4-transpentadienoate

Compound No. 7

Methyl-3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) ^ -trans ^ -transpentadienoate

Compound No. 8

Methyl-3-methyl-5- (1,2-dihydroxy-2,6,6-trimethylcy clohexyl) -2-ice -4-transpentadienoate

Compound No. 9

Methyl 1-3-methyl 1- (1,2-dihydroxy-2,6,6-trimethyl-cyclohexyl) -2-trans -4-transpentadienoate

Compound No. 10

Ethy l-3-ethy 1-ί? - (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis-4-transpentadienoate

Compound No. 11

Methyl 3-methyl-5- (1-hydroxy-2,6,6-trimethyl-2-cyclohexenyl) -2-cis-4-transpentadienoate

Compound No. 12

Ethyl 3-methyl-5- (1-hydroxy-2,6,6-trimethylcy clohexyl) -2-ice -4-transpentadienoate

Compound No. 13

Ethyl-3-methyl-5- (1-hydroxy-2,6,6-trimethylcyclohexyl) -2-trans -4-transpentadienoate _2

- 0 0 9 8 8 4/2215

Compound No. 14

Ethyl 3-methyl-5- (1-hydroxy-2-methylene-6,6-dimethylcyclohexyl) -2-cis-4-tranapentadienoate

Compound No. 15

Ethyl 3-methyl-5- (i-hydroxy-2-methylene-6,6-dimethylcyclohexyl) -2-trans-4-transpentadienoate

Compound No. 16

'3-methyl-5- (1 ^ -epoxy ^ ö ^

2-trans-4-transpentadienonitrile

Compound No. 17

3-methyl-i? - (1 ^ -epoxy ^ ojo
2-cis-4-transpentadienol

Experiment 1: Rice Seedling Test

(1) 1 ml of an acetone solution of Compounds No. 1 or No. at the concentrations given below is placed in a Petri dish with a diameter of 4 x 5 cm in which a filter paper and absorbent cotton have been placed, and left to stand overnight. so that the acetone is removed. Then 5 ml of a Hoagland's nutrient solution of 1/2 concentration is added to the contents of the dish. Seven seeds of rice (Oryza sativa L., cv "Koshijiwase" germinated by 72 hr. Immersion in water of 3O ⁰ C) are placed in a dish and then for one week at 30 ⁰ C allowed to grow. During this time artificial lighting is used for 14 hours a day, while the remaining 10 hours a day are left in the dark. The total length is measured to determine the elongation ratio. The results are compiled in the table below, in which the elongation ratio (4) is expressed as the relative value based on the elongation of a control plant in an untreated area, which is taken as 100 as a basis.

-23-

009884/22 15

Concentration (ppm)

Connection No. 1.5 3. 6 12.-5 25 50

1 47.2 43.1 30.9 21.8 11.7 10.7

2 29-4 17.O 9.9 6 * 4 4.3

The composition of the Hoagland ¹ S nutrient solution used was as follows:

Calcium nitrate tetrahydrate 1,180 g / l

Ilagnesium sulfate heptahydrate 0.493 "

Potassium Nitrate O.5O6 »

Potassium dihydrogen phosphate 0.136 ^M

Perriethylene diamine tetraacetate 0.010 "

(2) Connections No. 2, 3, 4, 5, 6, 7, ö, 9 and 10 are waiting under different concentrations, which are given below, examined in the same way as in Experiment 1 in order to obtain the Effectiveness of these compounds in preventing the growth of the second leaf sheath of rice seedlings investigate. The results are compiled in the table below. Therein is the length change ratio (#) expressed as a relative value based on the change in length of the second leaf sheath of a control (untreated District), the value of which is taken as 100.

-24-

0 Q 9 8 8 W? ι 1 5

BATH ORIGINAL

Concentration (ppm)

link 1.0 1.5 3 6th 12th 25th 50 No. 0.5 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 3 70 - 79-b 71.9 63-0 45.1 0 0 4th - 101.1 100.0 98.3 85.9 81.1 80.2 5. - 88.8- 84.5 83-9 79-9 74-7 73.6 6th - 93-2 U7.2 b1 .8 85.0 76.7 70.7 7th - 91.3 92.1 92.1 ö7.6 whether .4 84.4 b - 96.1 98.2 94-2 95.8 91.3 88.7 ■ 9 94.4 91.3 81.0 78.6 56.6 _ 10

(3) Compound No. 11 becomes substantially the same Method as used in experiment (1) to determine the growth of the second leaf sheath. The result is in the named below table.

Compound Conc. No. (ppm)

Length of second leaf sheath (mm)

Relative relationship to control growth

3 .5 17.44 53. 5 11 CJN 7-98 24. 5 O no growth 0 control 32.6 100

(4) Compounds No. 12 and 13 are grounded in the same way examined as in experiment (1) to determine the growth of the total length. The result is as follows

Concentration (ppm)

1 ^ 5 3 3 6th
«MMM .2 11 .2 25th .7 50 102 .8th 104. 3 99 .5 94 .5 88 .5 83.0 109 .5 102. 96 90 85 81.2

Connection no.

12 13

(5) Compounds nos. 14 and 15 are investigated as in experiment (1) with the modification that the Petri _2ς

00 9 8 84/2215

Dish has a diameter of 6 cm, Hoagland's nutrient solution in an amount of 10 ml is used and 12 rice seeds are sown in a petri dish. The second leaf sheath becomes measured. The test results are as follows.

Concentration (ppm)

link

No. 50 25 12.5

/ second leaf sheath (mm) 0 0 0

relative ratio to control wax Vfcum (fo) 0 0 0

1.5

26.7 33.O 36.3

70.2 86.8 9.5.5

/ second leaf sheath (mm) 25.8 27.7 32.6 35.6 36.4 35.7

relative ratio to control wax

W 67.9 72.9 85.8 93.6 95.8 94.0

(6) Compounds nos. 16 and 17 are carried out as in experiment (1) checked, but with the modification that the Petri dish used has a diameter of 6 cm, Hoagland's nutrient solution in an amount of 10 ml is used and 12 rice seeds are sown in each bowl. The second leaf sheath becomes measured. The results are as follows.

Concentration (ppm)

50

link
'No. ' ^Jyj 25

/ second leaf sheath (mm) 31.7 -

12.5

• 3

1.5

relative ratio to control growth ($) 91.3 - -

^r second leaf

scabbard (mm) 16.5 23.9 27.0 3I.7 32.3 33.I

relative relationship to
Control wax
-fcum (#) 46.4 67.1 75.8 09.1 90.7 93 · Ο

009884/2215

Experiment 2: Mutual influencing of compounds according to the invention and gibberellin A,

(1) Rice seeds (Variety "Tamanishiki") are immersed in pure water, and 48 hours kept at 3O ⁰ C therein to cause germination. 2 ml of an aqueous-ethanolic solution of compound no. 2 and gibberellin A ^ in the specified concentrations are placed together with a small amount of a surface-active agent in a glass tube with a diameter of 3 cm and a height of 10 cm. A vinyl polymer mesh film is placed in the middle part of the glass tube, and germinated rice seeds are placed on it. The glass tube is closed with a polyethylene film to prevent the water from evaporating. The growth takes place for 6 days at 25 ° C. and irradiation with 300 lux. The total length and the length of the second leaf sheath of the rice seedlings are then measured. The test results are compiled in the tables below. This is the length change ratio ($) for the total length and for the length of the second leaf sheath, expressed as a relative value based on the total length or the length of the second leaf sheath of control plants (in untreated areas using water without gibberellin and compound no. 2 ), which are taken as 100.

Aspect ratio of the second Leaf sheath:

link
No. 2
(Minor) Gibberellin
ν (mol / l)
\ - io -4 10-5 4th 10 " ⁶ 2 1 10 -7 0 4th 4 x 10 " ⁶ 1Ö0 • 7 159 0 119. 7th 1 93 .6 85. 1 8 χ 10 ~ ⁷ • 375 .0 280. 5 203. 0 22nd .2 101. 0 0 456 .0 398 243. 37 .3 100.

-27-

009884/2215

link
No. 2
(Moles / 1)

27 · 1 10 -4 10 " 10 -6 953 1 52 5 0 - Aspect ratio
length: 11 .9 9 · 9 • 5 the Total- 0 9.5 Gibberellin
(Minor) 26th .0 20, 17th • 4 ΙΟ " ⁷ 1 18.9 75 .2 82, 61 .1 9. 54.5 -5 16. .5 45. .0 • 7

ΙΟ " ⁴

2 χ 10 ~ ^b
4 x 10 " ⁶

8 χ 10 " ⁷ 200.0 162.6 126.5 93.3 91.7

0 252.9 218.3 156.0 114.5 100.0

Experiment 3 Prevention of germination

(1) A filter paper is placed in a Petri dish, into which 2 ml of an acetone solution of Compound No. 2 are added. The acetone is allowed to volatilize overnight. Water is then added to obtain the desired concentration of Compound No. 2. 50 seeds of radish are placed in the Petri dish and kept ^{at 50 ° C. in a thermostat for 48 hours.} The germination ratio (fo) is given below.

Concentration (ppm)

No. 2 1.25 2.5 5 10 20th link . 16 14th 18th 10 4th control 8th?

(2) Mulberry seeds are immersed in an aqueous isopropanol solution of compound no. 3 for the period of time given below and then kept in the light in a thermostat at 30 ^° C. The ratio of germination and the time required for germination are determined. In one test, 50 seeds are used. The test results are as follows

link Treatment Concentration Ratio of ' No. type (std.) (ppm) Germination ($) * 3 (24 j 50 75 [' (100 30th (24 . 0 100

-28-

009 884/2 215

- 28 Note: Measured on the 20th day.

link

No.

Conc.
(ppm)

Treatment time (hours)

Average number of days required for germination

100

12 13

15.5 16 21

4.5

Experiment 4 Lettuce Seedling Test

(1) Lettuce seeds (Lactuca sotiva L. _f cv. "Wayahead") "are germinated in water for 24 hours. Separately, an acetone solution of Compound No. 2 is placed in a Petri dish 6 cm in diameter and Leave to stand to allow the acetone to evaporate. Then 1/2 concentration of Hoagland's nutrient solution is added. 11 of the sprouted lettuce seeds are placed in the Petri dish. 48 hours later, the lengths of the stems and roots are measured. The test results are in The figures given are the growth ratio (5 &) based on the lengths of stems and roots of control plants (not treated with the agent), which are based on 100.

Conc. Of compound no.2 (Mol / 1)

Stem growth
Root growth

10- ⁴ 37.1 74.9

2 χ 10 50.5 74.9

-5

4 x 10
59.8
8b.8

-6

8 χ 10 68.8 96.0

-7

(2) Lettuce seeds (Laetuca satira L., c.v. "Wayahead") are used in used in the same manner as in test (1) to determine the growth ratio (#) of the hypocotyl of the lettuce seedlings.

-29-

009884/2215

The results are as follows.

Concentration (mg / 1)

link

50 10 2 0.4

4 51.9 65.4 89.8 92.3

3 46.2 50.0 59.6 75.0

Test 5 Preventing Eenma minor from growing

(1) Compound No. 10 is dissolved in a 1/2 concentration Hoagland's nutrient solution containing 2 fo zucrose to give the stated concentrations. Renma minor is transplanted into the solution and then allowed to grow ^{at 25 0 O for 10 days.} The fresh weight of the fresh henma minor is then weighed. The results are summarized below. Ten pieces of Renma minor were used in each experiment. The numbers given in the table represent the average weight of the Renma minor.

Concentration Average weight (ppm) weight of the fresh

Renma minor (mg)

Compound No. 10 (1 32

> 10 18

Control 0.120

(2) Compound No., 14 is made in the same manner as in the above described test (1) investigated. The test results are as follows:

Concentration Average weight (ppm) weight of the fresh

. Renma minor (mg)

Compound No. 14 (2 37

(20 19

Control 0 126

-30-

00988A / 2215

C'5) Compound No. 17 is used in the same manner as in test (1) examined. The test result is as follows:

Concentration Average Ge

(ppm) weight of fresh Renma minor (mg)

Connection No. 17> 2 52

.20 23

Control 0 126

Experiment 6: Inhibit the germination of yam .

(1) Air tubers of yam (Dioscorea batatas) are kept at 5 ° C for 2 months and then cut in half. A filter paper is placed in a Petri dish. Then absorbent cotton soaked in 20 ml of an aqueous solution of the respective test compound of the stated concentration is placed on it. The bulbs of air are then placed in such a way that they are slightly immersed. Then they are ai for 2 weeks at 25 ^{0 C}
Determined ratio of germination.

which she keeps for 2 weeks at 25 ° C. After that, that will

Concentration germination ratio (Ppm) {}

Connection no. 11 \ ⁵ 15th (20 VJl control 0 85

(2) Compound No. 14 is tested as in Experiment (1). The test result is as follows:

Concentration germination ratio (ppm) (#)

Connection No. 14> 5 18

(50 3

Control 0 88

(3) Compound No. 17 is tested as in Experiment (1). . -31

0 G 9 8 8 4/2 2 1 5

The test result is as follows.

Concentration germination ratio (ppm) (#)

Compound No. 17 [5 31

(50 6

Control 0 öö

Experiment 7: Inhibition of sprouting of potatoes

Fresh potato tubers (variety "Danshaku") are washed well. Then the parts where the eyes are located are cut out using a drill. A filter paper and then absorbent cotton which is soaked with an aqueous solution of the test compound of the stated concentration are placed in a Petri dish. 10 pieces of the potato cuttings are placed in this bowl and left to stand at 20 ^° C. in the dark. The germination ratio (56) is determined at periodic intervals. The test result is as follows.

Concentration Ke imun gsv giving absolute rel ltnis

(ppm) compound

Mr. 11> 5

(10

5 Days 10 Days 5 1ϊ> Days 20 days 0 0 12th • 5 20th 0 5 10 15th 0 1 45 77.5

control

(2) Compound No. 14 is examined as in Test (1). The result is as follows.

Concentration germination ratio

(ppm) 5 Days 10 6th Days 15th 9 Days 20th Tagje link VJl 0 3 • 5 5 • 5 10 .0 No. 14 (20 0 15th .0 42 .0 7th .0 control 0 0 .0 .0 6b .0

(3) The compound No. 17 is tested as in test (1). That

-32-

0098.84 / 2215

Result is as follows

link
No. 17

control

Concentration (ppm)

20 0

Germination ratio

5 days 10 days 15 days 20 days 0 0 0

8.0

6.5 15.0

14-5 12.0 42.0

25-5 15.0 68.0

Experiment 8: Inhibition of the germination of ripe wheat ears

Ripe ears of wheat are cut off and sprayed well with an aqueous solution of the test compound and then air-dried. They are placed in a thermostat at 20 ^° C. in order to effect germination, including the formation of roots. During the experiment, water is sprayed onto the ears twice a day to keep them well wet. The state of germination is determined nine days after the treatment. The test results are as follows.

Conc
trati on
(ppm) total
number of
Grains
per ear number of
not ge
germinated
Grains number of
germinated
Grains relationship
of germination
(*) fioo 450 245 207 46.0 Ver
binding
No. 17 250
500 430
602 299 -
531 131
71 50.5
11.8 JOOO 468 455 15th 2.8 Con
trolls 0 511 165 546 67.7 Try S ): Seedling test

5 ml of an aqueous solution of test compound no. 5 are placed in a Petri dish with a diameter of 9 cm. Then a filter paper is put thereinto, and the number of seeds of the test plant given below is put thereinto. After the specified growing season, the length of the stems or leaves is measured. The growth ratio ($>) is expressed as a relative value, where the _3

0 9 8 8 4/2215

Growth of the control plant with the number 100 is taken as a basis. The test result is as follows.

Growth conditions

Number d. Day d. Plant-plant seeds place observation-

Concentration (ppm)

ung

part,
whose
Measured length
became

3 10 30 100

Phaseo-

hirpus

wheat
millet

Barnyard,
grass

10
10

10 *
10 *

was 7 days

mer

space

(28 ⁰ C)

Room 13th day

Stem 64.1 56.3 47.6 -

Overall 97 · 0 80.0 43-0 length

was- Day 9 JMesoco- 113.5117-5115-9 -

mer
space

j tyl-V sheets

was- 4 «day [Mesoco-

mer jtyl-

Room V sheets (28 ⁰ C)

dark- 4th day

ler

space

(28OC)

Mesoco-

tyl-

leaves

83-2 71.1 47 6 -

- 122 121 100

- 72 47 1

- 116 .114 11Ö

- 100 74 46

* means that seeds were used, the roots with a Length of about 0.1-1 cm and germs with a length of about 0.5 cm.

Experiment 10: Avena Straight-Growth Test

In a Petri dish with a diameter of 4 cm, in which a Filter paper had been placed, an Aeeton solution of the test compound is added and left to stand overnight with it the acetone evaporates. 2.5 ml of a 2% sucrose solution containing 1 mg / l indole acetic acid are added. 7 Avena coleoptile segments with a length of 5 nanometers are placed in the solution prepared in this way, from which the growing places away wordca were. Then the shell Stored in a dark place at 27 ° C for 20 hours. _ ,, _

0 0 9 8 B /> / 2 ; · 1 5

6ADOAiGINAL

The growth in length of the Avena coleoptile segments is measured. The test results show an interaction between the test compound and the indoleacetic acid the growth in length of the Avena coleoptile segments show are as follows.

Concentration (mg / 1)

No. 4th 50 5 10 6th 2_ 0
■ on Λ 0 link 3 5.67 6th • 9ö 6th • 33 7th .80 8.94 Il ^K 5.56 .04 .33 7th .00 8.94

Experiment 11: Inhibition of the growth in length of gherkin hypocotyl ,

In a beaker with a diameter of 7 cm, in the one After filter paper has been placed, 2 ml of an acetone solution of the test compound are poured. Then overnight let stand so that the acetone evaporates completely. 8 cucumber seeds are placed on top and then with 25 g of at the Air-dried fine sand covered. Then 15 ml of pure water are poured into it, and the amount that evaporates Water is replaced daily. During the experiment the seeds are continuously at 24 ° C under an irradiation of 300 lux held. The hypocotyl length is measured when the The cotyledon of the cucumber is fully developed. The test results are compiled in the table below. In it, the numbers denote the growth ratio ($) expressed as a relative value based on the hypocotyl of a Control based on 100.

. . Concentration (mg / beaker)

50 20

Connection number 3 - 'it Mr. 7

³³ B-995 * 44 61

* !! - (DimebhylaminoJ-succinic acid monoamide

10
■■ MM ** « 5 1 0.5 91 0 0 49 - 73 74 ü9 - 74 85 _ _

009884/2215
ORIGINAL

Experiment 12: Inhibition of the formation of armpit buds in tobacco

Tobacco seedlings with a total of 21 sheets are knipst, wherein 13 sheets remain · The compound no. 3 (30 g) is mixed with bb g of xylene, 10 g Sorpol 800A and 5 g of Sorpol ÜOOB, and the mixture on a water bath at 50 ⁰ C heated to make an emulsion which is diluted with water to the concentration given below before spraying onto the tobacco leaves. 2 weeks after spraying, the axillary buds formed are weighed. The test results are as follows.

Concentration of - average weight of compound no <3 formed fresh axillary (ppm) buds _ ^^

100 6.8

. 300 b.3

1000 1.2

3000 0.1

not dealt with 7.1

Experiment 13i Disappearance of the chlorophyll from the cotyledon of radishes

After the cotyledon of radishes has fully developed an aqueous solution of compound no. 3 with varying concentrations is brushed onto the cotyledon, which was excised from the lower part of the hypocotyl. The cut end is covered with a damp filter paper covered. The cotyledon is placed in a beaker, and the extent of the disappearance of chlorophyll is periodically measured Observed intervals.

009804/2216

ORJQIMAL

Conc. 1st day 2nd day 3rd day 4th day 5th day

1000 - + ++

300 - + ++

30 + ++

^M - "means green color, ^M + ⁿ pale green, '++" yellow and ^M +++ ^M yellow with wilting.

Experiment 14i acceleration of defoliation

(1) 4 red bean seedlings are cultivated in one pot. The surface of the first leaf and the petiole of these seedlings are coated with an aqueous solution of the test compound brushed with fluctuating concentrations three times at intervals over 2 days. A week after the Treatment is observed the condition of the leaves. The test results are as follows.

Conc

1000 b £ a 500 C.
■ M a 100 £ 0 a
MMB 1 CVt 3 b 3 2 b b a t) c 5 0 2 CVl CVl 5 1 1 6th - _ _ 6th 1 3 2 1 6th 1 1 7th 4th 1 4th 1 0 7th 0 0 6th _ _ _ 3 0 0 - _ _

0 0 8

^M a ^w sr number of fallen leaves "b" as number of discolored leaves "c""number of healthy leaves

(2) Red bean seedlings do well in a nutrient solution grown, - "ie the primary leaves are on both sides cut along the middle ribs, and the remaining parts are treated with an aqueous solution of the experimental, "

009884/2215

connection brushed. The seedlings are in the nutrient solution ditched. The condition of the leaves is observed. The result is as follows.

. No. 3 Conc.
(ppm) 1
a 00 ( >
£ a 300 C. a 100 C. a 0 C. No. 4th 2 b 0 2 Λ 0 2 b 0 b - Conn No. 7th 2 0 0 2 O 0 2 0 0 - - - 11 No. 9 0 0 1 0 0 1 0 0 2 - - Il control 2 1 0 2 1 0 0 0 2 - - - Il 0 0 0 0 - 2 Q

"a", "b" and "c" have the same meaning as in test (1

(3) The first interleaves ("compound" leaves) of red bean seedlings are at the bottom of the petioles cut off and then immersed in an aqueous solution of the test compound. After air drying, become put these leaves in a Petri dish to observe the change in leaf color. The results are as follows.

Concentration (ppm) ______

1000 300 100 30 0

link No. 3 Il No. 4th 11 No. 7th » No. 9 control

»-Η means green color,« · + · 'pale green, "++" yellow and "+++" yellow with withered.

Experiment 15 :

An aqueous isopropanol solution (20 ml) of compound no. 3 with the specified concentrations is applied evenly 2 or 3 times at intervals of 5 days on the leaves of tomatoes

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plants sprayed to an average height of 55-65 cm have grown and are in bloom. 40 days after the first spraying, the extent of the coloring of the fruit is observed. The result is as follows.

Number of sprayings Concentration (ppm)

10 30 100 300 2x -

3x ^v ++ ++

wn means green color, ^w + ^w weakly green, ·· ++ "pale red and" +++ "red.

Experiment 1.6:

(1) An isopropanol aqueous solution (5 ml) of Compound No. 3 in the given concentrations and then an identical solution of gibberellic acid with one concentration of 50 ppm is sprayed separately from the first solution on the leaves of Potmum, which have grown 27 days after sowing. 7 days after the spraying, the same solution of Compound No. 3 is made in the same manner as described above injected again. The total length of the plants is measured at intervals after the first spraying. The results are compiled in the following tables.

Cons. Average length (ppm) change after 18 days; (mm)

Connection No. 3

/ ΊθΟ 90.7

50 96.6

, 10 95.4

Gibberellic acid 50 118.2

Control 0 102.0

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Average daily change in length on the specified days (mm)

(ppm) 5th-7th day 7th-9th day 9th-12th day 12th-16th day 16th-23rd day

100 3 7 4.7 6.1 4.8 4.1

bO 4.8 5.9 6.0 ί? .9 4.7 _ς 0 4.4 ί> .7 6 «5 6.2 5-4 B 1) 0 9.0 9.0 8.2 6-5- 4.6

¹¹ A "= connection no. 3
^Μ Β "« Gibberellic acid

(2) An isopropanol aqueous solution (5 ml) of Compound No. 3 in the specified concentrations is applied evenly to the leaves of French marigolds (Tagetes papula L.) which have grown 18 days after sowing. 5 days after the injection, the same solution of the compound Mr. injected nochms-ls. The average growth in length The 13 days are counted from the first spray and the time (days) it takes to flower is measured in Observed intervals * The results are in the following Tables compiled.

Concentration Average change in length after (ppm) 13 days (mm)

500 '17.9

300 22.1

100 21.8

0 22.9

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008884/2215

O O O O O O O O O O O O O O O

Conc. Time required until blooming (days) (ppm) ·

35 54 35 36 37 58 59 40 41 42 43 44 45 46 47 4β 49 50 O O O

loo O

.
0

(Note: The circular mark means bloom.)

According to the method of the present invention, the 5-substituted 2,4-pentadiene derivatives of the formula. I according to the following Methods are made:

(1) Wittig reaction

(2) epoxy cleavage reaction

(3) epoxidation

(4) reduction

(5) hydrolysis

(6) dehydration

(7) Acylation of the hydroxy group

Some typical procedures for each class are detailed below «

(1) Wittig reaction

The procedure represented by the following equation falls into this category:

R ₁ - CH s CH - C s 0 +

(in*

R ₁ -CH = CH-C

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009884/2215

where R ^ and Rp each have the above meaningsj R ~ is cyano or lower alkoxycarbonyl} H ^ is hydrogen, halogen or lower alkylj and R _Q is phenyl or lower alkoxy.

Those used as the starting product for this process Some carbony compounds of the formula II are known, e.g. 4- (1,2-epoxy-2,6,6-trimethy! Cyclohexyl) -3-buten-2-one (Helvetica Chimica Acta, Volume 30 (1947), page 80) j 4- (1-Hydroxy-2,6,6-trimethy 1-2 ■ ycyclohexenylJ-S-buten ^ -one (Chemical Abstract, Volume 69, page 96916b) j 4- (1-Hydroxy-2,6,6-trimethylcyclohexyl) -3-buten-2-one (Chemical Abstract, vol. 52, pp. 199-3d). · ■

4- (1-Hydroxy-2-methylene-6,6-dimethylcyclohexyl) -3-buten-2-one is prepared by treating the aforementioned 4- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -3-buten-2-one with dilute sulfuric acid »

The other starting compounds can be made using the method disclosed in the above reference or according to other methods known per se can be produced.

The reaction is usually carried out in the absence of a solvent. Palis is required, but it can also be carried out in an inert solvent. Examples of such solvents are dimethyl sulfoxide, ether, tetrahydrofuran, dioxane, toluene, etc. It is further preferred to carry out the reaction with the exclusion of water. There is no particular limitation on the reaction temperature. However, it is usually preferred to carry out the reaction with heating to a. Carry out temperature of over 70 ⁰ C if the reaction is carried out in the absence of a solvent. If the reaction is carried out in the presence of a solvent, it is usually preferred to warm to a temperature between room temperature and the boiling point of the solvent used.

¹ -42-

0OS884 / 2215

The 5-substituted 2,4-pentadiene derivatives obtained Formula I can, if desired, by hydrolysis into the corresponding free acids are converted. Preferred hydrolysis agents are alkali metal hydroxides such as sodium hydroxide, Potassium hydroxide, etc., or inorganic acids such as sulfuric acid.

(2) Epoxy cleavage reaction:

This falls into this category due to the following formula scheme reproduced VerJäirenj

CH β CH - C

Ru

ch oh

OH

= CH - C

.f.

CH - C = C (Id)

therein R- stands for hydrogen, lower alkyl, lower alkanoyloxy or cyano and R ₂ , R ₅ , R ₅ , R ₆ and R ₇ have the same meanings as above.

The starting compound Ib is treated with an acid to produce the compounds of the formula Ic and Id. As acids, inorganic acids (eg hydrochloric _acid? Hydrobromic acid, -Perchlorsäure, sulfuric acid, etc.) and organic acids (such as benzenesulfonic acid, p-toluenesulfonic acid, acetic acid,

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009S84 / 2215

Propionic acid, trifluoroacetic acid, etc.) can be used.

The reaction is usually carried out in a solvent carried out such as methanol, ethanol, benzene, toluene, acetone, water etc. There is no particular limit for the reaction temperature. However, preferred is the reaction to be carried out at room temperature or by heating to the boiling point of the solvent used. The for Acid used in this reaction can also be used as a solvent. The ratio of through this reaction Compounds of the formulas Ic and Id formed depend on the concentration of the acid, the reaction temperature and the Reaction time.

The compounds of the formulas Ic and Id obtained can each be isolated and purified according to known methods Procedures that are commonly used. These include the Extraction with a solvent, thin layer column chromatography etc. The hydrolyzable groups (i.e. lower Alkoxycarbonyl, cyano and lower alkanoyloxy groups) the compounds of the formulas Ic and Id obtained can be converted to the corresponding carboxyl and / or hydroxyl groups are hydrolyzed.

(3) epoxidation

This falls into this category through the following formula scheme illustrated procedure

H ₂

= CH - C =

(IV)

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009884/2215

-44 f ²

CH-O

(ie)

wherein R ₂ , R 1, R ^, R ^, Rg and as above | to have.

the same meaning

ij- (2,6j5-Tri (lower) alkyl-1-cyclohexenyi) -2,4-pentadiene derivatives of the formula IV used as starting compounds are partially known, e.g. 3-methyl -!? - (2,6,6-trimethyl-1-cyclohexenyl) -2,4-pentadienoic acid and their ethyester (Helvetiea Chimica Acta, vol. 15, page 878 (1932)); Ethyl 2-hydro-3-methyl-5- (2,6,6-trimethyl-1-cyclohexene!) - 2,4-pentadienoate (Journal of the Chemical Society, Volume 42, page (1882)). You can apply dee in the quoted. Reference disclosed method or according to others per se known methods are produced.

The reaction is carried out by oxidizing the starting compound of formula IV with oxygen, ^ hydrogen peroxide or organic peroxides as oxidizing agents. Different process methods can be used depending on the type of oxidizing agent used can be applied.

In particular when using oxygen or air instead of peroxide as the oxidizing agent, it is preferred to carry out the reaction of the starting product of the formula IV with a support or a catalyst in the liquid phase or in the oase phase. Examples of such carriers are silica gel, aluminum oxide, activated carbon, diatomaceous earth, etc. Examples of the catalysts mentioned are silver, molybdenum, molybdenum oxide, sodium vanadate, silver vanadate, etc.

The pressure of the oxygen or air and the reaction temperature are chosen according to the type of catalyst.

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Otherwise, the reaction can, for example, in the case of use of hydrogen peroxide or an organic peroxide as an oxidizing agent in a solvent. Examples of solvents are ethyl acetate, chloroform, ether, hexane, etc. The hydrogen peroxide and the organic peroxide can also be used as a solvent. Examples of organic peroxides are mentioned Perbenzoic acid, m-chloroperbenzoic acid, peracetic acid, performic acid, monoperphthalic acid, monoperisophthalic acid, Pertrifluoroacetic acid, perpropionic acid, perlactic acid, methyl perhydroxide, ethyl perhydroxide, tert-butyl perhydroxide, etc. at This reaction can use a catalyst such as molybdenum powder too be used.

The 5-substituted 2,4-pentadiene derivatives obtained Formula Ie can be converted to the corresponding free acids by hydrolysis, if so desired. aside from that can then, if the symbol R. in the formula Ie a lower Alkanoyloxy group means these are hydrolyzed to the corresponding hydroxyl group simultaneously with the Hydrolysis of the lower alkoxycarbonyl group caused by the Symbol R ~ is represented in the formula Ie.

(4) reduction

In this category falls a transformation caused by the following Formulas is represented! '-

R I

- oh β oh - σ

(if)

R ₁ - CH m CH

- C

2 y CE ₂ QE

(Ig)

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009834 / 221S

wherein ß £ stands for lower alkoxycarbonyl and R ₁ , Rg and have the same meaning as above.

The starting compound of the formula If is reduced with a reducing agent to form the compound of the formula Ig.

An alkali metal aluminum hydride can be used as the reducing agent for this reduction (e.g. sodium aluminum hydride, potassium aluminum hydride, lithium aluminum hydride), or an alkali metal (e.g. Sodium, potassium) in liquid ammonia. If an alkali metal hydride is used as the reducing agent, the reaction is usually carried out in a solvent at a temperature between room temperature and the boiling point of the used solvent carried out. Examples of solvents that may be mentioned are ether, tetrahydrofuran, dioxane, η-hexane, benzene, toluene, etc.

(5) hydrolysis

Conversion according to the following formulas falls into this category

^R 2 a I R

COOH R ₁ - CH = CH - C s C "(Ii)

where R? for hydrogen, halogen, lower alkyl or hydroxy Stands and R ^, Rp and R ^ have the same meaning as above.

The reaction is carried out in such a way that the starting compound of the formula Ih hydrolyzed with a basic substance in an aqueous medium to form the compound of the formula Ii '

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009884/2215

will. Water or an aqueous organic solvent (e.g. aqueous methanol, aqueous Ethanol). Examples of the basic substances mentioned are alkali metal hydroxides (e.g. potassium hydroxide, Sodium hydroxide), alkaline earth metal hydroxides (e.g. calcium hydroxide, magnesium hydroxide), alkali metal alkoxides (e.g. sodium methoxide, sodium ethoxide, potassium methoxide, ka- " lium ethoxide), alkali metal carbonates (e.g. sodium carbonate, sodium bicarbonate, potassium carbonate), etc. Even if no particular one Limitation on the reaction temperature is required, but the reaction will usually take place at room temperature carried out.

(6) dehydration

Conversion according to the following falls into this category Form scheme:

(V)

CH - CH - C - CH

where rS stands for carboxy, lower alkoxycarbonyl or cyano, and R ₂ , R ₄ , R ₅ , R ₆ and R _{7 have} the same meaning as above,

The reaction is carried out by taking the starting compound of formula V treated with a dehydrating agent alone or in combination with a tertiary amino compound will. As a tertiary Araitt compound, for example

005884/2215

are used dimethylaniline, diethy! aniline, trimethylamine, Triethylamine, quinoline, pyridine, 2-methylpyridine, etc. As the dehydrating agent, for example, can be used Phosphorus oxychloride, phosphorus pentachloride, phosphorus oxybromide, Thionyl chloride, acetic anhydride, trifluoroacetic anhydride, N, N'-dicyclohexy! Carbodiimide, molecular sieves, etc. The reaction is usually carried out under mild conditions. The hydrousable groups (i.e. lower Alkoxycarbonyl, cyano and alkanoyloxy) of the compounds of the formula Ij obtained in this reaction can be prepared according to conventional Process to the corresponding carboxyl and / or hydroxyl groups are hydrousated.

(7) Acylation of the hydroxy group

Implementation according to the following formula falls into this category:.

R ^ R

R CH = CH-C

(Ik)

* 2 / ^R 3 CH = CH - C = C

(D

where R

_{4 stands for lower} alkanoyloxy and have the same meaning as above.

, r |, R

and

The starting compounds of the formula Ik used for this reaction can be epoxidized by a corresponding ^ _n

—4 :? "

009884 / 221-5

lower alkyl 2-hydroxy-b- (2,6,6-trimethyl-1-cyclohexenyl) -2,4-pentadienoate getting produced. One of these compounds, namely ethyl 2-hydroxy-3-methyl-5- (2,6,6-trimethy1-1-cyclohexenyl) -2,4-pentadienoate has already been described in Journal of the Chemical Society, Volume 42, page 727 (1882).

The reaction is effected by acylating the compound of formula Ia with an aliphatic carboxylic acid or an reactive derivative of acid. As reactive derivatives of carboxylic acids or the carboxyl groups of the compound of the formula Ia are, for example, acid halides, acid azides, Acid anhydrides, acid amides, etc..

To accelerate the reaction, acidic or basic catalysts or condensing agents can be used. Examples are hydrochloric acid, sulfuric acid, boron trifluoride, benzenesulfonic p-toluenesulfonic acid, hydrobromic acid, ferric chloride, aluminum chloride, zinc chloride, N, N'-dicyclohexylcarbodiimide, H-cyclohexyl-N'-morpholinoäthylcarbodiimids, N-cyclohexyl-li ^l - (4-diäthylaminocyclohexyl) carbodiimide , N, N · - diisopropylcarbodiimide, N-ithyl-N '- (3-dimethylaminopropylcarbodiimide, NjiP-carbonyldiimidazole, N, N'-carbonyldi (2-methy! Imidazo!), !!, N'-carbonyldipyrazole, P ent ame thy lenk et en-N-cyclohexylimine, diphenylketene-N-cyclohexylimine, alkoxyacethylene, i-alkoxy-i-chloroethylene, tetraalkyl phosphite, 2-ethyl-5- (N-sulfophenyl) -isoxazoliumhydr5d, -2-ethyl-7- hydroxybenzisoxazolium salt, ethyl polyphosphate, isopropyl polyphosphate, phosphorus trichloride, thionyl chloride, oxalyl chloride, strongly acidic ion exchange resins, molecular sieves, alkali metal hydroxides, - alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, etc.

The isolation, recovery and purification of the geometric isomers (e.g. 2-cis-4-trans-isomer and 2-trans-4-trans-isomer) can according to the invention according to conventional methods

009684/2215

BAD LOCATION

methods that are commonly used. These methods use the solubility of the compound in a solvent and the different solubility in Solvents, the precipitation of a compound from a solvent and the different precipitability that different affinities for different absorbents, the different separability between different Kinds of liquid phases, etc. These methods can be used alone or in combinations The sequence can be selected as desired, or the individual methods can be used repeatedly as it appears necessary. An example of the method is as follows: The reaction mixture is extracted with a solvent, and the extract is washed and dried. Then the solvent is through Distillation removed. The residue is thin layer chromatography using silica gel. The silica gel fractions that appear when exposed to a mercury lamp (Wavelength 254 mu) fluoresce are each extracted with a solvent. From the extracts the solvents are removed by distillation to give the desired compounds.

Examples of the preparation of compounds of the formula I Example 1 (Wittig reaction)

(1) A mixture of 4- (1 ^ -epoxy ^ jojo-trimethylcyclohexyl) -3-buten-2-one (750 mg) and methoxycarbonylmethylene triphenylphosphorane (1; 5 g) was ^{heated to 130-17O 0} O for 2 hours . After cooling, 10% alcoholic potassium hydroxide solution (5 ml) was added to the mixture and the alcoholic solution was allowed to stand for 72 hours. Then water was added, and the aqueous solution was washed with ether and acidified with sulfuric acid. The aqueous mixture was extracted with ether. The ether layer was washed with water and the solvent was evaporated. To the back . , ; -51- "

009884/2215 '

a small amount of benzene was added. The solution was left to stand in the refrigerator over Haclit. The precipitated crystals were collected by filtration, whereby 3-ethyl-5- (1 _f 2-epo3cy-2 _t 6 _f 6-trimettiylcyclohexyl) -2-cie-4-transpentadienoic acid, mp 146-147 ° C. was obtained. In addition, the benzene was distilled off from the filtrate, and η-hexane was added to the residue. The crystal precipitated was collected by filtration. In this manner was obtained F..105-107 ⁰ C 3-Hethyl-5- (1,2-epoxy-2,6,6-trimethyleyclohexyl) -2 trans-4-transpetadiensäure.

(2) A mixture of 4- (1, Z-3-buten-2-one (175 mg) and Methoxycarbonylmethylentriphenylphosphoran (300 mg) was heated for 2 hours at 150-180 ⁰ C. Mach cooling, the reaction mixture by thin layer chromatography using 6 plates of silica gel and using a mixture of benzene and acetic acid (97s3) as all developing solvents.

The silica gel fraction collected at an R _f value of about 0.7, which fluoresced blue on exposure to a mercury lamp of a wavelength of 254 Wfi , was extracted with ethyl acetate. The ethyl acetate layer was evaporated to give methyl 3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-trans-4-transpentadienoate (86 mg) as an oily hasse. In the same way as described above, methyl 3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis-4-transpentadienoate (61 mg) was obtained as an oil from a silica gel Fraction with an R _f value of about 0.5 was obtained. The R _f values and the IR spectra of the substances thus obtained were identified by those of ethyl-3-methyl-5- (1,2-epoxy-2,6 _} 6-trimethyl / cyclohexyl) -2-cis (and trans) -4-transpentadienoate, which had been prepared by auto-oxidation of methyl 5- (2,6,6-trimethyl-1-cyclohexenyl) -2,4-pentadienoate and each isolated in the form of the two geometric isomers. " -52-

00 9884/2215

MD ORJGiNAi

In the same way, ethyl 3-methyl-5- (1-hydroxy-2,6,6-trimethylcyclohexylj ^ -cis ^ -transpentadienoate was made produced in the form of a pale yellow oil:

I.E. spectrum? 3550, 1710, 1657, 1608, 1450, 13ö3, 124b,

1230, 1160 cm " ¹ j
UV spectrum 270 mp (is 20,000)

(3) A mixture of 4- (1-hydroxy-2,6,6-trimethyl-2-cyclohexenyl) -3-buten-2-one (500 mg) and methoxycarbonylmethylene triphenylphosphorane (1000 mg) was placed on IbO for 2 hours ⁰ O heated. The reaction mixture was dissolved in methanol. Half the amount of the obtained solution was subjected to thin layer chromatography using silica gel, using a mixture of benzene and ethyl acetate (95: 5) as all developing solvents. The silica gel collected from a top patch of the plate was extracted with ethyl acetate. The ethyl acetate was distilled off to give a pale yellow oil of methyl 3-methyl-5- (1-hydroxy-2,6,6-trimethyl-2-cyclohexenyl) -2-trans-4-transpentadienoate (90 mg) .

IR spectrum 3550, 1720, 1620 cm " ¹ .

In the same way, methyl 3-methyl-5- (1-hydroxy-2,6,6-trimethyl-2-cyclohexenyl) -2-cis-4-transpentadienoate was found as a pale yellow oil (37 mg) obtained from the silica gel collected from the lower patch on the plate.

IR spectrum 3530, 1720, Ϊ638, 16O8 cm " ¹ .

A mixture of 4- (1-hydroxy-2-methylene-6,6-dimethylcyclohexyl) -3-buten-2-one (70 mg) and ethoxycarbonylmethylene triphenylphosphorane (200 mg) were heated to 150 ° C. for 2 hours. After cooling, the reaction mixture was dissolved in η-hexane and the solution was filtered. The filtrate became the Subjected to thin layer chromatography using three plates of silica gel and containing a mixture of benzene and

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00.9884 / 2215

Ethyl acetate (9: 1) was developed. Each of the two silica gel fractions, which fluoresced blue when exposed to a queek silver lamp (wavelength 254 mp) was collected and extracted with ethyl acetate. The ethyl acetate extract obtained from the top fraction of the silica G-el plates was removed, leaving a yellowish oil (30 mg) from ethyl 5- (1-hydroxy-2-methylene-6, δ-dimethylcyclohexyl) -2-cis-4-transpentadienoate stayed behind.

In the same way, a pale yellow oil (20 mg) was obtained Ethyl-S-O-hydroxy ^ -methylene-öjö-dimethylcyclohexylJ ^ -trans-4-transpentadienoate obtained from the lower fraction of the silica gel plates.

IR spectrum
2-cis-4-trans isomer;

3520, 2930, 1710, 1635, 1602, 1450, 1380, 1240, 1160,

1050, 990, 900 cm "" ¹ ,
2-trans-4-trans isomer j ■ ·

3520, 2930, 1710, I63O, 1615, 1440, 1240, 1160, 1050,

990, 903 cm " ¹ .

In the same way crystals of methyl 3-methyl-5- (1,2-dihydroxy ^ jojö-trimethylcyclohexylj ^ -cis ^ -transpentadienoat, F. 134-136 ⁰ O and crystals of methyl-3-methyl-5- ( 1,2-dihydroxy-2,6,6-trimethylcyclohexyl) -2-trans-4-transpentadienoat obtained F. 124-126 ⁰ C.

(5) A mixture of 4- (i, 2-EpOXy ^ o, 6-trimethylcyclohexyI) -3-buten-2-one (1.0 g) and cyanomethylene triphenylphosphorane (3.0 g) was heated to 150-17O ⁰ C for 1.5 hours heated. After cooling, the reaction mixture was dissolved in η-hexane. The solution was filtered and the filtrate was evaporated. The residue was subjected to thin layer chromatography using silica gel. A mixture of benzene and ethyl acetate (93-7) was used as the developing solvent.

silver lamp (wavelength! 254 mp) fluoresced blue, were extracted with ethyl acetate. The ethyl acetate extract was concentrated by distillation to give (i, 2-epoxy-2,6,6-trimethylcyciohexyl) 2 ~ ₉ 4-pentadienonitril was obtained as an oil (190 mg) 3-Methyl-5-. The oil was separated by the same thin-layer chromatography method as described in Example 1- (4), namely into the oil from 3-methyl-5- (1 »2-epoxy 2,6,6-trimethyl / cyclohexyl) -2-cis ^ -transpentadienonitril and the oil of 3-methyl-5- (1 ^ -epoxy ^^ jß-trimethylcyclohexyl) -2-trans-4-transpentadi enoni tri1.

I.R. Spectrum

2-cis-4-trans isomer? 2250, 1635, 1588, 1450, 980 cm "" ^1, 2-trans-4-trans-isomer} 225Q, 1635, 1592, 1450, 9BO cm ^'1.

A mixture of 4- (1,2-epoxy-2,6 _S 6 -trimethy! Cyclohexyl) -3-buten-2-one (5 · 0 g) and ei-lthoxycarbonylethylidene-triphenylphosphorane (10 g) was used for one hour ^{heated to 150-16O 0} C for a long time under nitrogen atmosphere · Then ok-ltboxycarbonylethylidene triphenylphosphorane (10 g) was added and the mixture was heated to 170 ° C for 1 hour with stirring. After cooling, the reaction mixture was dissolved in η-hexane and the solution was filtered. The η-hexane was driven off from the piltrate. The residue was distilled under reduced pressure, leaving a pale yellow oil of ethyl 2,3-dimethy! -5- (1,2-epoxy-2,6,6-triffiethyley.clohexy 1) 2,4-pentadienoate, b.p. 118-122 ° C / 0.1 mmHg was obtained as a distillate.

In the same way as described above, were get the following links?

Ethyl-5 _{'(1,2-epoxy-2?} 6,6-trimethylcyclohexyl) -2,4' pentadienoatf

Ethyl 2-methyl-5- {1 _f 2-epoxy-2 »6,6-trietb: ylc2? Gloiiexyl) -2,4-pentadienoate, b.p. 105-10 ° O / O.2 imnHg.

0G3884 / 2215 io nrno original

Example 2 (epoxy cleavage reaction)

(1) A solution of ethanol (15 ml) and 20% sulfuric acid (ti ml) became ethyl 3-methyl-5- (1,2-epoxy-2,6,6-trimethy1-cyclohexyl) -2-eiB-4-transpentadienoate (300 mg) and the mixture was allowed to stand overnight. Then became water was added and the aqueous solution was extracted with ether. The ether layer was washed with water and dried. Then the solvent was removed by distillation.

The residue was recrystallized from benzene, giving crystals (100 mg) of ethyl 3-methyl-5- (1,2-dihydroxy-2,6,6-trimethylcyclohexyl) -2-cis-4-tran8pentadienoate, m.p. 116-119 ⁰ C were obtained «

I .R. Range: 3500, 3600, 166? cm ".

In the same manner as described above, the following compounds were obtained: Methyl 3-methyl-5- (1 ^ -dihydroxy ^ jöjö-trimethylcyclohexylj ^ -trans ^ -transpentadienoate, P. L4-126 ° Cj methyl-3 methyl 5- (1,2-dihydroxy-2,6,6-trimethylcyclohexyl) -2-cis-4-transpentadienoate, P. 134-136 ° Cj 3-methyl-5- (1,2-dihydroxy-2 , 6,6-trimethy Icy dohexyl) 2-cis-4-transpentadienoic acid, P. 1Üi> -156 ° C and 3-methyl-5- (1,2-dihydroxy-2,6,6-trimethyIcyclohexyl) -2- tranB-4-transpentadienoic acid, P. 213-21 b ° C.

(2) A solution of methyl 3-methyl-5- (1 _f 2-epoxy-2,6,6-trimethy lcyclohexyl) -2-trans-4-transpentadienoate (1000 mg) in ethanol (10 ml) and 20 Sulfuric acid (3 ml) was allowed to stand overnight. After the completion of the reaction, the reaction mixture was subjected to thin layer chromatography using silica gel. A mixture of benzene and ethyl acetate (9: 1) was used as the developing solvent. The fraction absorbed at the R ^ value of 0.5 was extracted with ethyl acetate. The solvent was evaporated to give a pale yellow oil of methyl 3-methyl-5- (1-hydroxy-2,6,6-trimethy1-2-cyclohexenyl) -2-trans-4-transpentadienoate. - «56-

009884/2215

>. «; ¥, Ü SAD

The R., Value (0.5) of the substance thus obtained was determined by thin layer chromatography using Methy1-3-methy1-5- (1-hydroxy-2,6, ö-trimethyl ^ -cyclohexenyl) ^ -trans ^ -transpentadienoate identified by the reaction of 4- (1-hydroxy-2,6,6-trimethyl-2-cyclohexenyl) -3-buten-2-one with methoxycarbonylmethylene triphenylphosphorane had been made.

Example 3.s (epoxidation)

(1) A solution of ethyl 3-methyl-5- (2,6,6-trimethyl-1-cyclohexenyl) -2,4-pentadienoate (5 x 0 g) in ethyl acetate (20 ml) was mixed with a sufficient amount of diatomaceous earth (trademark! Hyflo Super Gel) and allowed to stand for a week with occasional stirring. The reaction mixture was then extracted with ethyl acetate. The solvent was removed by evaporation, leaving a viscous Liquid (5-0 g) of ethyl 3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2,4-pentadienoate stayed behind.

The substance thus obtained was obtained by the following procedure identified.

This substance was subjected to silica gel column chromatography using a mixture of η-hexane and benzene as an eluting solvent to obtain the isomers (ie, the 2-cie-4-trans and 2-trans-4-trans isomers) to isolate. The two isomers thus obtained were respectively hydrolyzed with potassium hydroxide to give 3-methyl-b- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis-4-trans-pentadienoic acid, mp 145-147 ⁰ C or . 3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-trans-4-trans-pentadienoic acid, mp 107-108 ⁰ C were obtained.

(2) A solution of perbenzoic acid (2.2 g) in chloroform (28 ml) was added dropwise at ⁰ ° C. to a solution of ethyl-3-methyl-5- (2,6,6-trimethyl-i-cyclohexenyl) -2,4-pentadienoate (3.2 g) in chloroform (10 ml). The reaction mixture was left to stand overnight at 5 ^° C., then with an

009884/2216

sufficient amount of an aqueous solution of sodium carbonate and then washed with water. The solvent was removed under reduced pressure. The residue was subjected to silica gel column chromatography subjected and eluted first with hexane and then with a mixture of hexane and benzene, The ratio between benzene and hexane was gradually increased. The eluate at a ratio of hexane and benzene of 7: 3 was concentrated to give an oil of methyl-3-methyl-5- (1 »2-epoxy-2,6,6-trimethy Icy clohexyl) - 2-cis-4-transpentadienoate was obtained.

UV spectrum \ ^E 2 ° 267 mji, ί- 18,600

Max

IE spectrum: 1710, 1632, 1602 cm " ¹ '.

In addition, the fraction was concentrated at a ratio of hexane to benzene of 9: 1, leaving an oil of methyl-3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexy1) -2-trans-4 -transpentadienoat was obtained.

UV spectrum: λ ^ | ° ^{Η 26} 7 ^m | J »? = 25-670 IE spectrum: 1710, 1632, 1613 cm" ¹ .

In the same way as described in Example 2- (2), the the following connections established:

Ethyl 5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2,4-pentadienoate as an oil, by reacting ethyl 5- (2,6,6-trimethyl-1-cyclohexenyl) -2,4-pentadienoate (1g) mlt.m-chloroperbenzoic acid, (1 g) j

Ethyl 2-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2,4-pentadienoate (2.8 g) as an oil, boiling point 122-123 ° C. / 0.4 mmHg by reacting ethyl 2-methyl-5- (2,6,6-trimethyl-1-cyclohexenyl) -2,4-pentadienoate (2.8 g) with m-chloroperbenzoic acid (2.5 g);

Ethyl 2,3-dimethyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2,4-pentadienoate as a pale yellow oil, K.p. 118-122 ° C / 0.1 mmHg;

-58-

009884/2215

BAD ORlQINAU

Äth; / l-3-methyl-l-5- (1,2-epoxy-2,6, ö-trimethylcyclohexyl) 2,4-pentadienoate, bp 126-128 ^o G / 0 "2 mmHg; Ethyl 2-cyano-3-methyl-5- (1,2-epoxy-2,6,6-trimethyl-cyclohexyl) -2,4-pentadienoate as an oil; JLthy l-3-methyl-2-ace1; oxy-5- (1,2-epoxy-2,6,6-trimethy 1-cyclohexyl) -2,4-pentadienoatej

IB spectrum 1750, 1730 cm " ¹ ,

U.V. spectrum ^ AtOH 270 my j

¹ max

Xthyl 2r-hydroxy-3-methyl-5- (1,2-epoxy-2,6 »6-trimethyl-cyclohexyl) -2-cis-4-transpentadienoate, IB spectrum 3500 cm" ¹ , 1750 cm " ¹ UV Spectrum ^ AtOH 231 mus

Max

3-methyl-5- (1,2-epoxy-2,6,6-trimethyleyclohexy1) -2-cis-4-transpentadienonitrile, IB spectrum 2250, 1635, 1508, 1450, 980 cm " ¹ j

3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexy1) -2-trans-4-transpentadienonitrile, IB spectrum 2250, 1635, 1592, 1450, 980 cm "¹;

3-methyl-5- (1 »2-epoxy-2" 6,6-trimethylcyclohexy1) -2-cis-4-transpentadienol »IB spectrum 3520, 2930, 1710, 1630, 1615, 1440, 1240, 1160, 1050, 990, 903 cm " ¹ j 3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexy1) -2-trans-4-transpentadienol, IB spectrum 3520, 2930, 1710, 1630, 1615, 1440 , 1240, 1160, 1050, 990, 903 cm "¹; Methyl 2-bromo-5- (1,2-epoxy-2,6,6-trimethylcyclohexy1) -2-cis-4-transpentadienoate, IB Spectrum 1740, 1638, 1595 cm " ¹ .

Example 4s (reduction)

(1) Lithium aluminum hydride (45 mg) became ethyl 3-methyl-b- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis-4-transpentadienoate (430 mg) in tetrahydrofuran. Bas mixture was at room temperature for 6 hours and then over Left for the night. A small one became the reaction mixture

009884/2215

Amount of water and then ether given. The mixture was through a column passed over anhydrous sodium sulfate, and the ether layer was from the flowing liquid mixture severed. The ether layer was washed with water and dried. The ether was distilled off. Of the The residue was subjected to thin layer chromatography using silica gel, taking as the developing solvent a mixture of benzene and ethyl acetate (93: 7) was used. The collected silica gel fraction under a mercury lamp (wavelength: 254 mja) fluoresced blue, was extracted with ethyl acetate. The ethyl acetate was distilled off, leaving a yellowish oil (200 mg) of 3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis-4-transpentadienol was obtained.

I.R. Range: 3440, 29 (50, Ί 620, 1455, «1383, 1368, 1050,

1020, 9BO cm " ¹ .

Example 5s (hydrolysis)

(1) A 10 # ethanol solution of potassium hydroxide (2 ml) was added to ethyl 3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexy3> -2-trans-4-transpentadienoate (300 mg) given. The mixture was left standing over laughing. Then water was added, and the aqueous solution was washed with ether. The aqueous layer was acidified with dilute sulfuric acid and with Ether extracted. After the ether layer had dried, the ether was distilled off and a small amount of acetonitrile was added to the residue. The crystal precipitated was collected by filtration, whereby 100 mg of 3-methyl-5- (1,2 ~ epoxy-2,6, ö-trimethylcyclohexyl) -2-trans-4-transpentadienoic acid, P. 105-1O7 ° C.

I.R. Spectrum: 1677 cm.

In the same way, the following compounds were made in obtained crystalline form:

-60- 009884/2215

- 60 3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-- cis-4-transpentadienoic acid, P. 146-147 0 | from her

Ethyl ester;
3-methyl-5- (1,2-dihyroxy ~ 2,6,6-trimethylcyclohexyl) -2-trans-4-transpentadienoic acid, P. 213-215 C, from

their ethyl ester;
3-methyl-5- (1,2-dihydroxy-2,6,6-trimethylcyclohexyl) -2-cis-4-transpentadiene acid, m.p. 1.54-156 ⁰ C ₁ from their

Ethyl ester;
3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-trans-

4-transpentadienoic acid, P. 105-107 ⁰ CJaUS its methyl ester;
3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis-4-transpentadienoic acid, P. 146-147 ° C from their

Methyl ester;
3-methyl-5- (1,2-dihydroxy-2,6,6-trimethylcyclohexyl) -2-cis-4-transpentadienoic acid, P. 155-156 ⁰ C ^ from its

Methyl ester;
3-methyl-5- (1,2-dihydroxy-2,6,6-trimethylcy cloliexyl) -2-trans-4-trans-pentadienoic acid, P. 213-215 ⁰ C ^ from their Methylester.

Example 6: (dehydration)

(1) Phosphorus oxychloride (10 ml) was added to a solution of Von Ethyl 3-hydroxy-3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl ) -4-pentenoate (10 g) in pyridine (100 ml) was added dropwise, and the reaction mixture was poured into ice water. The watery Solution was extracted with hexane. The hexane layer was washed with dilute sulfuric acid and water and then dried. The hexane was then distilled off. The residue was distilled under reduced pressure, whereby an oil (0.9 g) of ethyl 3-methyl-5- (1,2-epoxy-2,6,6-trimethy Icy clohexyl) -2, 4-pentadienoate, K.p. 125-129 ° C / 0.1 mmHg was obtained.

(2) Thionyl chloride (30 ml) was added to a solution of ethyl

3-hydroxy-3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -4-

009384/2215

pentenoate (16 g) in pyridine (300 ml) was added ^{dropwise at -10-5 0} C, which took an hour. Then the reaction mixture was poured into ice water. The aqueous solution was extracted with hexane, and the hexane layer was washed well with dilute sulfuric acid and water and then dried . The hexane was distilled off and the residue was distilled under reduced pressure to give an oil (10 g) of ethyl-3-methyl-5 - (1,2-epoxy-2,6., 6-trimethylcyclohexyl) -2,4-pentadienoate, b.p. 126-128 ° C / 0.2 mmHg.

Example 7: (acylation)

(1) A mixture of ethyl 2-hydroxy-3-methyl-5 ~ (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2,4-pentadienoate (10 g), acetic anhydride (6 ml) and pyridine were added to 100 g for 2 hours heated. The reaction mixture was then mixed with 10 Oiger Hydrochloric acid, and the aqueous solution was extracted with ether. The ether layer was covered by a column Passed silica gel, and the effluate was distilled concentrated, leaving an oil of ethyl 2-acetoxy-3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2,4-pentadienoate stayed behind. .

IR spectrum: 1750, 1730 cm "" ¹ , UV spectrum Λ EtOH 270 mp.

Max

Claims;

00988-W2215

Claims (1)

Patent claims: 1.' Preparations for regulating the growth of plants, characterized in that they contain as active ingredient at least one 5-substituted 2,4-pentadiene derivative of the Forme1 f
R ₁ - OH = OH - 0 = 0 wherein R _{1 is} R ₁ -, Rg and R "lower alkyl groups" mean, Rg is hydrogen or lower alkyl, R _{5 is} carboxyl, _T lower alkoxycarbonyl, hydroxymethyl or cyano, and R. is hydrogen, halogen, hydroxy, lower alkyl, means lower alkanoyloxy or cyano, and contain an inert carrier. 2. Preparations according to claim 1, characterized in that they ■ as the active ingredient, alkyl 3-lower alkyl 5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2,4-pentadienoate contain. 5 · Preparations according to claims 1-2, characterized in that they contain A * ethyl-3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-is (and / or trans) -4-trans pentadienoate. -63- 009884/2215 4. Preparations according to Claims 1-2, characterized in that it as the active ingredient methyl-3-methyl-5- (1,2-epoxy-2,6,6-trimethy! .cyclohexyl) -2-ice (and / or trans) -4-transpentadiene /% nthalten. t). Preparations according to claim 1, characterized in that they as the active ingredient 3-Hethyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis (and / or trans) -4-transpentadienoic acid. · 6. Preparations according to claim 1, characterized in that they as active ingredient ethyl-3-methyl-5- (1-hydroxy-2-methylene-Gje-dimethylcyclohexylJ-cisi and / or trans) -4-transpentadienoate. 7. Preparations according to claim 1, characterized in that they contain a lower alkyl-3-methyl-5- (1,2-epoxy-2,6, e-trimethyl ^ -cyclohexenylJ ^ -cisX and / or as active ingredient trans) -4-transpentadienoate contain. 8. Preparations according to claim 7, characterized in that they are Hethyl-3-methyl-i> - (i, 2-epoxy-2,6,6-trimethyl-2-cyclohexenyl) -2-cis (and / or trans) -4-transpentadienoate. 9 · Preparations according to claim 7, characterized in that they as the active ingredient ethyl-3-methyl-b- (1,2-epoxy-2,6,6-trimethyl-2-cyclohexenyl) -2-cis (and / or trans) -4-transpentadienoate. 10. Process for the preparation of preparations for regulation the growth of plants, characterized in that one or more 5-substituted 2,4-pentadiene derivatives according to Claims .1-9 are mixed as active ingredients with one or more inert carriers. -64- 009884/221 5 11. Use of the ij-substituted 2,4-pentadiene derivatives of Formula I according to claim 1 as an active ingredient for regulating the growth of plants. 12. Method for regulating the guard tower of Pflanzan, thereby characterized in that the plants are treated with 5-substituted 2,4-pentadiene derivatives of the formula I according to Claim 1 will. 13., S-substituted 2,4-pentadiene derivatives of the formula I * - CH = CH - C where R ^{a is} OH ° ^the and Rc, Rg and R ^ are lower alkyl groups, R _{2 is} hydrogen or lower alkyl, R 1 is carboxyl, lower alkoxycarbonyl, hydroxymethyl or cyano and R _{4 is} hydrogen, halogen, hydroxy, lower alkyl, lower alkanoyloxy or cyano. 14. 3-lower alkyl-5- (1 ^ -e ciss (and / or trans) -4-transpentadienoic acids and their lower ones Alky! Ester. -65- 009884/2215 Methyl-3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) - 16. Methyl 3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-trans-4-transpentadienoate. 17. Ethyl 3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-cis-4-transpentadienoate. 18. Ethyl 3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-trans-4-transpentadienoate. 19. 3-Methyl-5- (1,2-epoxy-2,6,6-trimethyicyclohexyl) -2-cis-4-transpentadienoic acid. 20. 3-methyl-5- (1,2-epoxy-2,6,6-trimethylcyclohexyl) -2-trans-4-transpentadiene-vires . 21. Process for the preparation of 5-substituted 2,4-pentadiene derivatives the formula CH = CH - C = C wherein Rp is hydrogen or lower alkyl, R, is carboxyl, lower alkoxycarbonyl, hydroxymethyl or cyano, R. is hydrogen, halogen, lower alkyl, lower alkanoyloxy or cyano and R _{1 is} T, Rg and R _{7 are} lower alkyl groups, characterized that a compound of the formula -66- 009884/2215 -op - , Οχι = CH "CsC wherein R ₂ , R-, R., R ^, Rg and Ry have the same meaning above, is reacted with oxygen, hydrogen peroxide or an organic peroxide as an oxidizing agent. 22. Process for the preparation of 5-substituted 2,4-pentdiene derivatives the formula ι ² 4 R ₁ - CH = CH - C = CH wherein Rf is cyano or lower alkoxycarbonyl, R ^ is hydrogen, halogen or lower alkyl and R ₁ and R _{2 have} the same meaning as above, characterized in that a compound of the formula f ² R ₁ -CH = CH-C = O wherein R ₁ and R _{2 have} the same meaning as above with a compound of the formula wherein R ^ is phenyl or lower alkoxy and R and R ^ have the same meaning as above, is implemented. Q09884 / 221S 25. The method according to claims 21 or 22, characterized in that that the compound of formula OH OH- • where R? for hydrogen _{r is} lower alkyl, lower alkanoyloxy or cyano and R ₂ , R ,, R ^, Rg and have the same meaning as above, is reacted with an acid to form compounds of the formula gh - R, CH and CH = CH - C = C OH / ^E 3 »4 wherein R ₂ , R ,, R ?, Rg and R ^ have the same meaning as above. 24. The method according to claim 21, characterized in that the compound obtained der.Formel -68- O'O 9884/2215 OH = CH - C m C wherein R ^, R ₂ , R ₅ , R ₆ and R _{7 have} the same meaning as above, with an aliphatic carboxylic acid or a reactive derivative of the carboxyl group thereof to form a combining the formula CH = CH - C = A tbsp where RT stands for lower alkanoyloxy and R ₂ , R ₃ , Ur- , R / - and R _{n have} the same meaning as above, 5 ο ί
is implemented. 25. The method according to claims 21, 22 or 23, characterized in that that the compound of formula obtained R ₁ - CH = CH .- C = C. where r5 stands for lower alkoxycarbonyl and R ₁ , I and R ^ have the same meaning as above, is reacted with a reducing agent to form a compound of the formula R ₂ Ι χ CH ₂ OH R ₁ - CH = CH - C = C wherein R ₁ , R ₀ and R ^{a have} the same meaning as above ha-1 ^ 4 _69 009884/2215 - by - "ben. 26. The method according to claims 21, 22 or 23, characterized in that the compound of formula obtained L ₁ - CH = CH - C = C where R _{4 represents} hydrogen, halogen, lower alkyl or hydroxy and R ₁ , Hp and R ~ have the same meaning as above, is subjected to hydrolysis to form a compound the formula ^R 2 VCOOH R ₁ - CH ⁼ CH - C ⁼ C. where R-, Rp and R? have the same meaning as above. · 27 · Process for the preparation of 5-substituted 2,4-pentadiene derivatives of the formula ■ CH = CH - C = C ^R 4 where R ° stands for carboxyl, lower alkoxycarbonyl or cyano and R ₂ , R ^a , R ₅ , R _g and R _{7 have} the same meaning as above,
characterized in that a compound of the formula -70- 009884/2215 R, - PW C - Π - un "~ Kj = Kj wherein R ₂ , R ^, R ^, R ^, R ₆ and R _{7 have} the same meaning as above, with a tertiary amino compound and a dehydrating agent is implemented. 009864/2215