DD213347A5 - BRASSINOSTEROID DERIVATIVES WITH GROWTH REGULATORY EFFECT ON PLANTS - Google Patents

Abstract

The invention relates to agents having growth-regulatory activity for plants containing novel brassino-steroid derivatives d. general formula in which R deep 17 is a C deep 8-C deep 10-alkyl radical or a C deep 8 -C deep 10-alkenyl radical and Z the groups -CO-CH deep 2- or -OC-CH deep 2- , R deep 2 and R deep 3 are either different and are each hydrogen or an acyl radical or together the groups C = O or C is high X deep Y, in the hydrogen, C deep 1-C deep 4-alkyl or C deep 1- C is lower alkoxy and y is hydrogen, C is deep 1-C "4" -alkyl, C is deep C "1" C "3" -alkoxy or C is C "1" C "deep" -alkoxy or aryl, in admixture with carriers and / or adjuvants ,

Description

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field of use the invention

The invention relates to an agent with growth-regulatory action for plants.

The agent according to the invention is used in agriculture, for example for influencing vegetative and generative growth in legumes, in particular soybeans.

Characteristic of the known technical solutions

Compounds with growth-regulatory effects are already known and have in some cases even been put into practice *

From the pollen of oilseed rape, a steroid - the brassinolide * promoting plant growth - was isolated and the structure elucidated (see M _# D ₀ Grove et al **, Nature VoI * 281 »216 (1979)) However, the growth-regulatory effect of this combination is not satisfactory.

Object of the invention

The aim of the invention is the provision of new agents with strong growth-regulatory effect *

Explanation of the essence of the invention

It is an object of the present invention to provide novel brassinosteroid derivatives having growth-regulatory properties superior to brassinolide, a known constitutional analogue.

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developing plants for plants,

This object is achieved by an agent which is characterized by a content of at least one compound of the general formula

17

in the

a C ₃ -C _1Q ~ alkyl radical or a C _Q * »C ₀ ~ alkenyl radical

the groups

CH ₂ -

or

«- 0 - C - CH il 0

represent ^

and R are either different and each is hydrogen or an acyl radical

or together the groups ^ C = O or ^ C

mean »in the

X is hydrogen * Q, -C -alkyl or C ~ C_-alkoxy and

Y is hydrogen, C 1 -C 4 -alkyl, C ₃ -C ₃ -alkyl or aryl

show *

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The compounds of the invention occur as geometric isomers, wherein -OR ₂ and <-0R ice 2 & c ^ 3ä <: or ice 2ß, 3ß are oriented »The individual isomers and their mixtures are also part of the subject invention *

The compounds according to the invention are outstandingly suitable for regulating plant growth in various cultivated plants and, in their spectrum of activity and in their compatibility, surprisingly exceed the product of the same direction of action mentioned at the outset.

The compounds according to the invention are able to promote the vegetative growth of crop plants, but also to inhibit them in certain areas of concentration. In addition, it is possible to achieve certain additional yields by influencing the regenerative phase.

In general, the substances act on the membrane system in crops and change its permeability to various substances,

Under certain conditions they can develop an anti-stress effect *

Since compounds of the invention both qualitative and quantitative changes in plants and change gen cause in the metabolism of plants, they are classified in the class of plant growth regulators ,; which are characterized by the following applications.

-H-

Inhibition of vegetative growth in woody and herbaceous plants, for example, on roadsides, railroad tracks and others, to prevent too much growth. Growth inhibition in cereals, to prevent storage or buckling, in Baumvollen to increase yield.

Influencing the branching of vegetative and generative organs in ornamental and crop plants to increase the flower bud or tobacco and tomato to inhibit side shoots.

Improving fruit quality, for example increasing the sugar content of sugar cane, sugar beet or fruit and ensuring a more even ripeness of the crop resulting in higher yields.

Increasing the resistance to stress, for example against climatic influences, such as cold and dryness, but also against the phybotoxic effects of chemicals.

Influence of latex flow in rubber plants.

Training of parthenocarp fruits, male sterility and sex influence are also possible applications.

Control germination of seeds or budding buds.

Defoliation or influence of the fruit case for harvest relief.

The compounds according to the invention are particularly suitable for influencing vegetative and generative growth in some legumes, such as, for example, soya.

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The application rates are, depending on the application target in general from 0.001 to 1 kg of active ingredient / ha ,. if necessary, higher application rates can also be used ·

The application time depends on the application target and the climatic conditions *

Of the compounds according to the invention are characterized by the action described in particular those from> in which in the above-mentioned general formula I.

R 2-methyl-heptan-6-yl 2-methyl-3-ethyl-hept-4-en-6-yl, 2,3-dimethyl-hept-4 -ene-6-yl, 2 Methyl-3-yl-heptane-6-yl or 2-3-dimethyl-heptan-6-yl and

Z the groups

C-CWCH ₀ * or -0-C-CH ₀ -, 0 0

R ₀ and R "are either different and in each case hydrogen or a formyl radical, a C ₀ -C ₇ -alkyl-CO radical * a C ₂ -C_ -alkoxy" -. C ₁ -C ₃ -alkyl-C0 radical or an aryl = »CO radical

or together the groups

J ^ C = 0 or ^. C

mean * in the

X is hydrogen, "C <-C" is alkyl or C ₃ = C "is alkoxy and Y is hydrogen, C ₂ -C 4, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or aryl»

As C - C.gwAlkyl "alkenyl and 6" may be mentioned, for example, 2-methyl "heptan ~ yl _f 2-methyl-3-ethyl ~ hept" 4 ~ en-6-y! _t . 2

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methyl-hept * -4-en'-6-yl _a 2-methyl-L-3-ethyl-heptane ~ 6-yl and 2,3-dimethyl-heptane ~ 6-yl; Acyl radicals may denote the fortyl radical, a C ₂ -C _ alkyl-C0 radical, _f . a C ₂ JC ₇ -alkoxy ^ C ₁ -C ~ alkyl CO radical and an aryl-CO * radical, such as acetoxy> methoxyacetoxy _s ethoxyacetoxy * propionyloxy, butyryl »oxy, valeryloxy," pentanoyloxy _# hexanoyloxy "heptanoyloxy , üimethylacetoxyv diethylacetoxy, benzoyloxy and phenylacetoxy *

-J-

Examples of C.sub.C, -alkyl radicals which may be mentioned are methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl and chloromethyl; C -C alkoxy radicals are, for example, methoxy, ethoxy and propoxy; Finally, aryl radicals are naphthyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 1-phenyl, 2, 6-dichlorophenyl, 2, 3-dichlorophenyl, 3-phenyl-dichlorophenyl, 2-hydroxybenzene, 6-trichlorophenyl, Bromophenyl, 2, ^ -dibromophenyl, 2,6-dibromophenyl, 2, k , 6-tribro-mphenyl, 2-fluorophenyl, 3-fluorophenyl, ^ -fluorophenyl, 2, ^ -difluorophenyl, 2-methylphenyl, 3-methylphenyl, ^ t-methylphenyl, 3-yl-dimethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, ^ i-methoxyphenyl, 3 > ^ i-dioxymethylenephenyl, 2-phenoxyphenyl, 3-phenoxyphenyl, 2-nitrophenyl and 3-nitrophenyl.

The compounds of the present invention may be used alone, in admixture with each other or with other active ingredients, and defoliants, pesticides or pesticides may be added as appropriate depending on the desired purpose.

If propagation of the activity spectrum is intended, other 3iocides may also be added. For example, as herbicidally effective mixing partners, those active compounds which are described in Veed Abstracts, Vol. 31, 1981, are suitable.

., Q. is entitled "List of Common Names and Abbreviations employed for currently used herbicides and plant growth regulators in weed abstracts". In addition, it is also possible to use non-phytotoxic agents which can give a synergistic increase in activity with herbicides and / or vehicle regulators, such as, inter alia, wetting agents, emulsifiers, solvents and oily additives.

The active compounds according to the invention or mixtures thereof are expediently used in the form of preparations, such as powders, scattering agents, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers or diluents and optionally of wetting agents, tackifiers, emulsifiers. and / or dispersing aids.

Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethylsulfoxide. Dimethylformamide, further mineral oil fractions.

Suitable solid carriers are mineral earths, for example tonsil, silica gel, talc, kaolin, attaclay, limestone, silicic acid and vegetable products, for example flours "

Surfactants include, for example, calcium lignosulfonate, polyoxyethylene alkylphenol ethers, naphthalenesulfonic acids and their salts, phenolsulfonic acids

and their salts, formaldehyde condensates, fatty alcohol sulfates and substituted benzenesulfonic acids and their salts.

The proportion of or of the active ingredient (s) in the various preparations can vary within wide tolerances (!. 30

For example, the compositions contain about 10 to 80 percent by weight of active compound, about 90 to 20 percent by weight of liquid or solid carriers and optionally up to 20 percent by weight of surface-active substances.

The application of the funds can be done in the usual way,

for example, with water as carrier in Spritzbrühmengen of about 100 to 1000 liters / ha. An application of the funds in the so-called low-volume or ultra-low-volume method is just; _o as possible as their application in the form of so-called microgranules. _

For the preparation of the preparations, for example, the following components are used:

A · Spray powder

a) 80 weight percent active ingredient weight percent kaolin weight percent surfactants based on the sodium salt of N-methyl-N-oleyl-taurine and

the calcium salt of lignosulfonic acid. 15

b) 50% by weight of active ingredient

^ iO weight percent clay minerals weight percent cell pitch weight percent surfactants on the

Base of a mixture of the calcium salt of lignin

sulfonic acid with alkylphenol polyglycol ethers.

c) 20% by weight of active ingredient

Weight percent clay minerals

Percent by weight Zellpech Weight Percent surfactants based on a mixture of the calcium salt of Ligninsulf onsäure with AlkylphenolpolyglycoläthaTn.

d) 5% by weight of active ingredient

δθ weight percent tonsil weight percent cell pitch weight percent surfactants based on a fatty acid condensation product.

-ICl-

^ B. Emulsions concentrate

20% by weight of active ingredient% 0% by weight of xylene 35% by weight of dimethyl sulfoxide

5 weight percent mixture of nonylphenylpolyoxyethylene or calcium dodecylbenzenesulfonate.

C. Paste

^ 5% by weight of active ingredient 5% by weight of sodium aluminum silicate

15% by weight of cetyl polyglycol ether with 8 moles of ethylene

o acid

2 percent by weight spindle oil

Gewichtsο weight percent polyethylene glycol 23 parts water.

The novel compounds according to the invention can be prepared, for example, by adding compounds of the general _formula I

- ⁾ by Osmiuffltetroxid-catalyzed hydroxylation with t-butyl hydroperoxide or with N-methyl-morpholine-N-oxide to compounds of the general formula

III

or to which silver acetate and iodine in aqueous acetic acid are added to give compounds of general formula 1

IV

which are treated with peracids to form the desired process products, wherein R ^ y and ^R 2 have ^{the meaning given to ODen} .

For the preparation of the compounds of the formula I, sterols, such as cholesterol, stigmasterol, brassicasterine or β-sitosterol, are used and these are added in a manner known per se to the Δ. "" -6-Ke termiodenioden the formula II mn. (In-HeIv.k3_ , 1581 (1966)).

The further conversion to 2a, 3a-cis-glycols of the formula III is carried out in accordance with known methods, namely the osmium tetroxide catalyzed hydroxylations with 80 tigers 1: »butyl hydroperoxide (KB Sharpless JACS _9_8, 19-86 (1976)) or with N-methyl-morpholine-N-oxide (V.van Rheen, Tetrahedron Lett., 1976, 1973).

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The glycols or their derivatives of the formula IV are obtained by reaction with silver acetate and water in aqueous acetic acid (HeIV * 49, 1581 (1966)).

The preparation of the B-ring lactones of formula I is carried out by Baeyer-Villiger "* oxidation with peracids such as trifluoroperacetic acid, performic acid" permaleic acid, etc., the 6 "keto steroids of formula III and IV * For compounds with a C_ ₂ " C _2; The double bond in the side chain must be protected by bromination before the lactonization of this double bond.

After the Baeyer-Villiger oxidation, the double bond can be regenerated with zinc in acetic acid.

AusfQhrunqsbeispiel

The invention will be explained in more detail below with reference to some examples.

The following examples illustrate the preparation of the compounds according to the invention »

11-

EXAMPLE 1

a) 3.56 g of 2k S ethyl-5o: -chole3ta-2,22-dien-6-one were dissolved in 60 ml of t'butanol, k ml of 20% tetraethylammonium hydroxide solution was added, cooled to 0 ° C and treated with 12 ml of 80 tiger t-butylhydric peroxide and 6 ml of an osmiurate tetroxide solution (prepared from 250 mg OsO.sub.4, 49.75 t-butanol and 0.25 ml 8.0% t-3-butylhydroperoxide). The reaction solution was stirred at room temperature for 6 hours, in 5% poured in sodium bisulfite solution and extracted with ethyl acetate. The extract was washed with water, dried over sodium sulfate and evaporated. Recrystallization from methylene chloride-methanol gives 2.3 g of 2z. , 3a-dihydroxy- 2k S-ethyl-5a-cholest-22-en-6-one

 Mp .: 23 ^, 5-235.5 ° C

b) 2.2 g of 2a, 3a-dihydroxy-2 S k pyridine ethyl-5a-cholest-22-en-6-one in 15 ml, added with 8 ml of acetic anhydride and 220 mg of 4-D ijae t hy 1 amino pyridine and 17 hours at

* ~ ο

20 C left. It was then precipitated in ice water, the product was filtered off with suction, washed and dried.

c) 2.6 g of crude diacetate was dissolved in 30 ml of ether and 30 ml of ice ^ _n with 0.28 mL acetic 3ro; .versetzt s and stirred for 10 minutes at room temperature. For work-up, it was diluted with ether, washed neutral with water and evaporated in vacuo. This gives 3.2 g of crude 2a, 3a-diacetoxy-22,23-dibromo-24-ethyl-5 <2-choles tan-6-one.

d) k, 5 ml of 30% hydrogen peroxide were suspended in 28 ml of methylene chloride, cooled to -10 ° C and 27.7 nl of trichlorethylene.

fluoroacetic anhydride slowly added dropwise so that the internal temperature did not rise above * 10 C. Then I ^ q, 3 * 2 g 2a, 3c ~ diacetoxy-22, 23-dibromo-24-ethyl-5 <2-choles tan-6-οη,

254 773 -3.

dissolved in 25 ¹ ^ l of methylene chloride, added and stirred for k minutes at room temperature. It was then diluted with methylene chloride and washed successively with water, 5% sodium carbonate solution and with water, dried and concentrated in vacuo. The residue was heated in 100 ml of acetic acid with 5 S zinc dust on the steam bath for 1 hour. It was filtered off from the zinc, diluted with methylene chloride and washed neutral with water and evaporated. After chromatography on silica gel (Qradientenelution toluene-ethyl acetate) and crystallization from acetone hexane to obtain, 1, 5 g of 2a, 3a-diacetoxy-2 ^/ i-ethyl-7-oxa-B-horno-5a-cholest-22-6- on, m.p .: 221-223 ° C and 310 mg of 2a, 3 <2-diacetoxy-24-ethyl-6-oxa-B-homo-5a-cholest-22-en-7-one, m.p .: 202- 204 ⁰ C.

EXAMPLE 2

a) To a solution of 2 g of 24-ethyl-3a-cholesta-2,22-dien-6-one in 270 ml of glacial acetic acid and 3) 7 ml of water were added 3.2 g of silver acetate and 1.9 g of iodine and under Stirring heated to 45 C for 3 hours. After filtering off the silver salts, washing with chloroform, the filtrate is diluted with chloroform and washed with water, sodium thiosulfate and water, dried and concentrated. After crystallization from acetone-hexane, 1.2 g of 2β-acetoxy-3β-hydroxy-24-ethyl-5 <2-cholest-22-en-6-one. ~ - - mp: °

22 b) After bromination of the ε ·, double bond, Baeyer-Villiger oxidation and zinc reduction, as described in Example Ic) and Id), the crude product is chromatographed on silica gel. By gradient elution with chloroform-acetone is obtained after recrystallization from hexane ether in 75% yield, the 2ß-acetoxy-3ß-hydroxy-24 * Äih-yl-7-oxa-B-homo-5ot-cholest-22-en-6 -on, mp: 151-153 ° C and in 10% yield 2β-acetoxy-3β-hydroxy-24-ethyl-6-oxa-Bh.omo-5 <2-choles t-22-en-7 on, m.p .; °

EXAMPLE 3

a) 2.2 s 2ß-acetoxy-3.beta.-hydroxy-2 ^z i-ethyl-7-oxa-B-homo-5 were <2-cholest-22-en-6-one in 50 ml of methanol with a solution of 500 mg of potassium hydroxide in 10 ml of methanol and stirred for 30 minutes at room temperature. It was acidified with acetic acid, precipitated in ice water, filtered off with suction, washed and dried. After crystallization from chloroform-ether, 1.7 g of 2β, 3β 2 -äthyl-7-oxa-B-hoπJO-5 <z-cholest-22-en-6-one, m.p .: 211-213 ° C. ,

b) 500 mg of diethyl-7-oxa-B-homo-5a-cholest-22-ene-6-one, 3β-dihydroxy-2-pyridine, were cooled to -10 ° C. in 1 ml of pyridine, containing 0 '5 ml of acetic anhydride' and stirred for 3> 5 hours at -5 to -0 C stirred. After precipitating in ice-water, suctioning off the product, washing and drying, it was recrystallized from acetone-hexane. One obtains 10 mg of 3β-aceto-2-ε5c-2β-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one,: 182-184 ° C.

EXAMPLE k

2α, 3cc-dihydroxy-7-oxa-B-homo-5cc-chotetan-6-one

dissolved in 10 ml of pyridine, cooled to 0 C and treated with 1 ml of acetic anhydride. The mixture was stirred for 5 hours at 0-5 C, poured into ice water, filtered off with suction, washed and dried. After recrystallization from pentane, 950 mg of 2α-acetoxy-32-hydroxy-7-oxa-B-homo-5a-choles-tan-6-one, mp: 165.5-167 ° C., are obtained.

Preparation of the starting material:

a) 25 S 5cc-Cholest-2-en-6-one were dissolved in I ² 10 ml of tetrahydrofuran, with lk g of N-methylmorpholine N-oxide, 25 ml of water and 50 ml of t-butanol and added with stirring, a solution of 25 om osmium tetroxide in 50 ml of tetrahydrofuran.

The reaction solution was stirred at room temperature for 17 hours with exclusion of light. Then in 7 1 of ice water, which was treated with 50 ml of 2N sulfuric acid and 1 g of sodium sulfide, precipitated, the product was filtered off with suction, washed with water, dissolved in chloroform and the solution was evaporated in vacuo. Da3 crude product (30 g) was dissolved in ΐΛθ ml of pyridine and after addition of 70 ml of acetic anhydride and 3 S ^ i-dimethylaminopyridine allowed to stand for 16 hours at room temperature. After water precipitation, suctioning off the product, washing with water and drying, chromatography on silica gel was carried out.

Obtained after Umkrx3tallisation from ethanol in 75% yield, the 2a, 3oc-diacetoxy-5a: ~ cholestan-6-one, mp.: 150.0-151.5 ^o C and to 15 Yo the 2ß, 3ß-diacetoxy 5ccolestan-6-one, m.p .: 183.5 - 85 ° C.

26 ml of 30% hydrogen peroxide were suspended in methylene chloride, cooled to -10 ° C. and 161 ml of trifluoroacetic anhydride were slowly added dropwise so that the internal temperature did not rise above +10 ° C. Subsequently, 27.2 g of 2a, 3 <2-diacetoxy-5'3-cholestan-6-one, in 160 ml of methylene chloride

2 54 7 7-3-3:

The reaction mixture was diluted with methylene chloride and washed successively with water, 5% sodium carbonate solution and with water and concentrated in vacuo in 8l% yield, the 2a, 3a-diacetoxy-7-oxa-B-homo-5a-cholestan-6-one, mp.: l83-l84 C and to 6.2 % the 2a, 3a-diacetoxy ~ 6- oxa-B-homo-5a-cholestan-7-one, m.p .:

c) 28.3 g of 2a , 3a-diacetoxy-7-oxa-B-homo-5 ^| 2-Cholestan-6-one were dissolved in 500 ml of methanol and stirred after addition of a solution of 1Λ g of potassium hydroxide in 150 ml of methanol for 30 minutes at room temperature. It was then acidified with acetic acid, precipitated in ice water, the product was filtered off with suction, washed with water and dried. After recrystallization from acetone-penxan, 22.5 g of (95%) 2z, 3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-one, m.p .: 138-1AO C, are obtained

EXAMPLE 5

a) 1.1 g of 2a, 3a-diacetoxy-6-oxa-B-homo-5a-cholestan-7-one were saponified as described in Example k c). This gives 785 mg of 2a, 3a-dihydroxy-6-oxa-B-homo-5acholestan-7-one, mp. 2l6.5-218 ° C.

b) 25Ο mg of 2a, 3a-dihydroxy-6-oxa-B-homo-5a-cholestan-7-oπ were dissolved in 2 ml of pyridine, cooled to -10 ° C, mixed with 0.2 ^ i ml of acetic anhydride and ^ Stirred at -5 to 0 C for hours. After precipitation in ice-water, filtration with suction of the product, washing and drying, the mixture was recrystallized from acetone-hexane. 210 mg of 2a-acetoxy-3a-hydroxy-6-oxa-B-homo-5'-chloroestan-7-one are obtained, mp: 199-2O1 ° C.

773 -3

PARTY 6

600 mg 2α, 3c-dihydroxy-2 ^z i-methyl-6-oxa-B-homo-5c: cholest-22-en-7-one were, as in Example 5 b), acetylated

Obtained 515 mg of 2a-acetoxy-3 ^{<2-hydroxy-24-methyl-6} * oxa - B-homo-5a-cholest-22-en-7-one, mp .: 173 ^ ⁰

Preparation of the starting material:

From Brassicastrin was prepared by known method, the 24-methyl-5a-cholesta-2,22-dien-6-one and this, as described in Example 1, implemented.

EXAMPLE 7

1 g of 2β, 3β-dihydroxy-7-oxa-B-homo-5a-cholestan-6-one was dissolved in 100 ml of acetone and. Dissolved 100 ml of tetrahydrofuran, cooled to ^{0 0} C, treated with 0.5 ml boron trifluoride etherate and stirred at 0 to 5 C for 30 minutes. After addition of 1 ml of pyridine was concentrated in vacuo and recrystallized from methylene chloride-isopropyl ether. This gives 731 mg of 2β, 3β-isopropylidenedioxy-7-oxa-B-homo-52-cholestan-6-one, mp: 216-217 ° C.

Analog were produced:

2a , 3 <2-isopropylidenedioxy-7-oxa-B-homo-5c-brolestan-6-one

Mp: 2l6-217 ° C

2a, 3a-isopropylidenedioxy-24-ethyl-7-oxa-3-homo-5o-chloro-22-ene-6-one, m.p .: 157-158 ° C

4 7 7 3-3! · -

EXAMPLE 8

900 mg of 2α, 3c: -dihydroxy-7-oxa-B-homo-5cc-cholestan-6-one were dissolved in 10 ml of pyridine, - - cooled to 0 ° C, treated with 1.8 ml of valeric anhydride and 10 hours at 0 to 5 C stirred. After work-up, as described in Example. **, 950 mg of 2a-Va-ryloxy-3a-hydroxy-7-oxa-B-homo-5'-cholestan-6-one, mp.: 92 - 9 ^ ⁰ C.

EXAMPLE 9

2a , 3 <2-diacetoxy-2 ^<: i-ethyl-7-oxa-B-homo-5 <2-choles t-22-en-6-one were saponified and partially acetylated as in Example 3t. In 70% yield to obtain the 2-acetoxy-3α-hydrσxy-2 ^£ ^ -ethyl-7-oxa-B-homo-5α-choies t-22-en-6-one, mp .: 158 ° l6O C.

EXAMPLE 10

900 mg of 2a, 3c-dihydroxy-7-oxa-B-homo-5a; -cholestan-6-one were dissolved in 10 ml of pyridine, cooled to 0 ° C, treated with 1 ml of Athoxyessigsäureanhydrid and 5 hours at 0 to 5 C. touched. After work-up, as described in Example 4, and recrystallization from acetone-kexane, 720 mg of 2a-Xthoxyacetoxy-3a-hydroxy-7-oxa-B-hotno-5c: -cholestane-S-OIi ₁ mp.: 172-173 ° C.

EXAMPLE 11

3OO mg 2a, 3a-dihydroxy-2 ^z i-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one in 3 ml of pyridine with 780 mg of phenylacetic anhydride for 10 hours at 0 to 5 ° C touched. After working up and recrystallization from acetone-hexane gives 210 mg of 2-phenylacetoxy-3-hydroxy-2 ^z i-ethyl-7-oxa ~ B-homo-5o: cholest-22-en-6-one, mp .: l85-l86 ° C.

7? S -

EXAMPLE 12

500 mg. 2α, 3 <2-Dihydroxy-7-oxa-B-homo-5c: -cholestan-6-one were added in 50 ml of benzene with 0.75 ml Triäthylorthoessigsäureester and added 5 mg.p-toluenesulfonic acid

 The solution is stirred for 20 minutes at room temperature, treated with 3 drops of pyridine and evaporated in vacuo. The residue is dissolved in methylene chloride, washed with water, dried over sodium sulphate and evaporated to give 6O5 mg of 2a, 3a (1-ethoxy-ethylenedioxy) -7-oxa-B-homo 5a-cholestan-6. on, mp .: 15015 ^

Analog were produced:

2a, 3a- (1-ethoxy-ethylenedioxy) -6-oxa-B-homo-5a-cholestan-7-one

Mp: 122-12 ° C

2a, 3a- (1-ethoxy-propylidendioxy) -y-oxa-B-homo-Sa-cholestan-6-one. Mp: 115-118 ° C

2a, 3a- (1-Methoxy-methylenedioxy) -2-ethyl-7-oxa-B-homo-5-aol-22-ene-6-one, m.p .: 96-93 ° C

2SS, 3ß- (1-ethoxy-äthylendiaoxy) -2 ^z i-ethyl-7-oxa-3-homo-5acholest-22-en-6-one, mp .: 123-125 ° C

EXAMPLE 13

500 mg of 2a, 3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-one were added in 5 ml of tetrahydrofuran with 1.5 ml of acetophenone and 0.1 ml of boron trifluoride atherate and heated under reflux for 3 hours. It was then concentrated under reduced pressure, 1 ml of pyridine added and concentrated by evaporation in a high vacuum

 Trituration with hexane gives ^ i65 mg of amorphous 2a, 3a (1-methyl-1-phenylmethylenedioxy) -7-oxa-B-homo-5-ateolestan-6-one as a diastereomeric mixture of mp. 13O, 5- 132 ° C

2S4J73-3 -3H

EXAMPLE lk

500 mg of 2α, 3a-dihydroxy-7-oxa-B-homo-5cr-cholestan-6-one were dissolved in 15 ml of diethyl carbonate, heated to boiling and after distilling off. To 2 ml of diethyl carbonate was added 30 mg of sodium methylate. From the reaction solution, several ml was distilled off over 3 minutes. After cooling, 0.15 ml of glacial acetic acid are added and the mixture is evaporated in vacuo. The residue is recrystallized from acetone-hexane. This gives 50 mg of 2a, 3'-carbonyldioxy-7-oxa-B-homo-5acholestan-6-one, mp. 2O3.5-2O5 ° C.

Analog were produced:

2a, 3 <z-carbonyldioxy-2 ^ -ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one, m.p .: 193-195 ° C

2β, 3β-Carbonyldioxy-7-oxa-B-homo-5cr-cholestan-6-one EXAMPLE 15 ^FP * ^{: 212-2ΐΛ}

300 mg of 2a, 3a-dihydroxy-7-oxa-B-homo-5o: -cholestan-6-one are dissolved in 2 ml of benzaldehyde, 0.02 ml of 70% perchloric acid added and stirred for 2 hours at room temperature. The solution was then neutralized with pyridine, diluted with hexane and chromatographed on silica gel. Using hexane-ethyl acetate (6: 4), 253 mg of 2a, 3a-benzylidenedioxy-7-oxa-B-homo-5 <2-cholestan-6-one were eluted and recrystallized from ether-pentane

 Mp: 137-139 ° C

Analog were produced:

2a, 3a-Benzylidendioxy-6-oxa-B-homo-5a-cholestan-7-one,

Mp .: 179-18Ο C

'ß, 3ß-Benz-vedidenedioxy-6-oxa-B-homo-5a: -cholestane-7-cn,

Mp .: I29-I3I C

2ß, 3ß-Benzylidendioxyr-7-oxa-B-homo-5a-cholestan-6-one,

Mp .: 153-155 C

The compounds of the invention are generally crystalline dyes and odorless substances which are sparingly soluble in water, conditionally soluble in aliphatic hydrocarbons such as petroleum ether, hexane, pentane and cyclohexane, readily soluble in halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane, carbonitriles such as acetonitrile, ketones such as acetone, alcohols such as methanol and ethanol, carboxylic acid amides such as dimethylformamide and sulfides such as dimethyl sulfoxide.

The following examples illustrate the applications of the compounds of the invention »in the form of

The preparations listed above were made. 20

254 773 -3

EXAMPLE Ιβ

Vachstumsförderung with bush beans

Bush beans of the variety "Pinto" were grown in the climatic chamber at 25 C and 90% humidity under the influence of light with a high intensity of intensity in the range of 66Onm and a very low fraction in the range of 730 in.

After 6 days of culture, 10 and 20 μg of the compounds to be tested were dissolved in solvents applied to the developing second internode.

Three days after the application, the extension of the inter nodals was measured and the percentage elongation was determined in comparison to the control.

The table contains the results of this experiment.

Compounds of the invention Percentage promotion 10 μg 50 μg

2a-Ac, oxy-3α-hydroxy-B-homo-7-oxa-5 cc-cholestan-6-one

2a, 3 <2-carbonyldioxy-B-homo-7-oxa-5a-cholestan-6-one -

2a-acetoxy-3a-hydroxy-B-homo-6-oxa-5 <2-cholestan-7-one

2a, 3 "- (1-ethoxy-ethylenedioxy) -B-homo-7-oxa-5a-cholesan-6-one

2a, 3 <2- (1-methyl-1-phenyl-methylenedioxy) B-homo-7-oxa-5a-cholestan-6-one

COMPARISON MEDIUM

2α, 3c, 22S, 23S-T9-tetrahydroxy-24-ethyl-B-homo-7-oxa-5a-choles tan-6-oo-4- (3-indolyl) -butyric acid control

292 125 190 304 162 125 165 162 152 342 89 114 51 100 100

The findings show that the compounds according to the invention under the stated Prüxbedingungen effect a more intense stretching than the comparison means and the control.

773-3:

In contrast, the comparison means cause only a more or less strong promotion of the thickness growth • which in some cases even led to a compression of the internodes.

EXAMPLE 17

Stimulation of root wax turns on mung beans

Mung beans were germinated under greenhouse conditions in aqueous emulsions of the compounds to be tested at a concentration of 0.01% by weight

After 6 days, the root length of the germinated plants was determined.

The table contains the results of the experiment in the form of percentages.

Compounds of the Invention Percentage Funding

2 a-acetoxy-3α-hydroxy-B-homo-7-oxy

5a-cholestan-p-one 188

2cr, 3 <2-carbonyldioxy-B-homo-7-oxa-5a-cholestan-6-one ΐβθ

2a-acetoxy-3 <z-hydroxy-B-homo-6-oxa-5a-cholestan-7-one ΐ6θ

2a , 3ct- (1-ethoxy-ethylenedioxy) -3-homo-7-oxa-5a-cholestan-6-one 200

2a , 3 * 2- (1-methyl-1-phenyl-methylenedioxy) -

B homo-7-oxa-5 <2- cholestane-6-one 150

VEPVGLE MEANS

Gibberallic acid (GA) 80

Control 100

254773-3 -35-

BEI5PIEL 18

Increase the resistance of crops

The crops listed in the table were pre-emergence treated with aqueous emulsions of the compounds to be tested or their mixture. One week after the treatment, the treatment result was scored according to the scheme 0 to 10, in which 0 = 100% destruction and 10 = no damage.

Dose components in kg of tomato cucumber wheat soybean corn turnip

2α-acetoxy- yes -

hydroxy-B-homo-

7-oxa-5ot-CHO

leatan-6-one I 0.02 10 10 <10 10 10 10

Ί-chloro-5-methyl-amino-2-Ca, a, atrifluoro-m-tolyl) pyridazine- J-one

(Norflurazon) II 0.3 '* 3 5 9 3 5

3.0 1 1 1 Λ 2 1

I + II 0.3 + 0.02 8 7 10 10 9 7 1 + II 3.0 + 0.02 6 5 8 ίο 7 7

Control - 10 10 10 10 10 10

It can be seen that the compound according to the invention gives the plants a higher resistance to the known herbicide,

Claims (1)

Erfindunqsran claim 1 * Agent with Vfachstumsregulatorischer effect for plants, characterized by a content of at least one Brassinosteroid ~ derivative of the general formula 17 in the R "_ a C _o « C. _n «alkyl radical or a C _Q « C. _n- alkenyl JL / O XU O XU rest and
Z the groups CH- or -0 C ~ 0 Il show * and R 'are either different and each is hydrogen or an acyl radical or together the groups ^ C = 0 or ^ C ^ " mean * in the Represents ^ C «alkyl or C ₁ -C -alkoxy and Y is hydrogen> C ^ C-alkyl" C ₁ -C ₃ -alkoxy or aryl »in admixture with carriers and / or auxiliary sst - X is hydrogen ^ C. ₁₁ open" Means according to point.x> characterized in that it is used to influence the vegetative and generative growth in legumes, especially soya.