LU85002A1 - BRASSINOSTEROID DERIVATIVES, METHOD FOR PRODUCING THESE COMPOUNDS AND THEIR CONTAINING AGENTS WITH GROWTH REGULATORY EFFECT FOR PLANTS - Google Patents

Description

SCHERING AG

-5- Commercial Recnäsdiutz

T

!, ^ The invention relates to new brassinosteroid derivatives, method j; for the preparation of these compounds and f ji compositions containing them with growth-regulating action for plants.

i i j A plant growth-promoting steroid - brassinolide - was isolated from the rape pollen and the structure clarified (see M.D. Grove et al., Nature Vol. 28l, 2l6 (1979))

However, the growth regulatory effect of this compound is not satisfactory.

15

The object of the present invention is to develop new brassinasteroid derivatives with growth-regulating properties for plants which are superior to the known constitutionally analogous brassinolide.

20th

According to the invention, this object is achieved by an agent which is characterized by a content of at least one compound of the general formula =

ί · H

30 5. in the R17 a Cg-C ^ alkyl radical or a Cg-C ^ alkenyl radical and Z the groups - C - 0 - CH. - or - 0 - Ç - CH -, I! 2 λ o o represent, R and R are either different and each Vaaser! 2 3 .Λ substance or an acyl residue y ά. or together the groups - 0 or ___ 'Va y 2 / \ Board: Dr. Herbert AsmisOr.Christian BruhnHans-Jürgen Hamann Poatanedirift: SCHERING AG - D-10OQ Berlin βPoetfadi «β 11 t Dr. Heinz HannieKarl Otto Mlttelstenscfieid Dr. Horst jokes! =. ο .., - λ. ". _______________

SCHERiNG AG

”6“ Commercial real estate chut? t ^ mean in which X is hydrogen, C1-C ^ -alkyl or C1-C ^ -alkoxy and! _. Y represents hydrogen, C ^ C ^ alkyl, C ^ C ^ alkoxy or aryl j.

* ’The connections according to the invention occur as geometric

Isomers on, where -OR ^ un <^ cis 2α, 3a or cis 2ß, 3ß are oriented. The individual isomers and their mixtures also belong to the subject of the invention.

The compounds according to the invention are extremely suitable

To regulate plant growth in various crops and surprisingly outperform the above-mentioned product with the same direction of action in terms of its spectrum of activity and its tolerability.

20th

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

In general, the substances act on the membrane system in crop plants and change its permeability for * 20 different substances.

“Under certain conditions, they can have an anti-stress effect.

- 25 Since the compounds according to the invention cause both qualitative and quantitative changes in plants and also changes in the metabolism of plants, they are to be classified in the class of plant growth regulators which are distinguished by the following possible uses.

ko 1 ls \ -7- 1 4 - Board: Dr. Herbert AsmiaDr. Christian Bruhn · Hins-Jürgen Hamann Oestansehrift: SCHERING AG · 0-1000 Barfin «5 - Postfadl 850311 J? Dr. Heinz hannseKarl Otto Mittelstensdwehr Qr. Horst Witrai ____ ... . _ ......... ... - i

SCHERINGAG

-7 ~ Commercial: Recjrfxsdiuör f 1 '5 Inhibition of vegetative growth in woody and herbaceous ’J plants, for example on roadsides, railroad tracks and on ·.

i; in order to prevent excessive growth. Inhibition of growth, i '* in the case of cereals to prevent storage or folding, \ in the case of cotton to increase the yield.

^ 10

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

15

Improvement in fruit quality, for example an increase in the sugar content of sugar cane, sugar beet or fruit and a more uniform ripeness of the crop, which leads to higher yields.

20 «

Increased resistance to stress, for example! against climatic influences such as cold and drought, but also against phyto-toxic influences of chemicals.

25 '

Influencing the latex flow in rubber plants.

Education of parthenocarpic fruits, pollen sterility and gender interference are also possible applications.

ii 30

Control the germination of seeds or buds.

Defoliation or influencing the fall of fruit to facilitate harvesting.

'35

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

i Λ - Board: Or. Herbert Asmis - Dr. Christian Brunn Hans-Jürgen Hamann. Postal address: SCHERING AG D-1000 Berlin 65Pestfar * «5 0311 i Z * Dr. Heinz HannsaKarl Otto. rv uor «· Witrei _ .... ___

SCHERING AG

-8- Commercial legal protection f 5 Depending on the application, the application rates are generally from 0.001 to 1 kg of active ingredient / ha; if necessary, higher application rates can also be used.

I ** 4 * The application time depends on the application goal and 1 i o yj the climatic conditions.

4 | Of the compounds according to the invention, the action described is particularly notable in those in which, in the general formula I 15.

R 2-methyl-heptan-6-yl, 2-methyl-3-ethyl-hept-4-en-6-yl, 2,3-dimethyl-hept-4-en-6-yl, 2-methyl-3 -ethyl-heptan- 6-yl or 2,3-dimethyl-heptan-6-yl and Z represent the groups -Ç-0-CH - or -0-Ç-CH-, 20 | 2 T 2 0 0 R and R_ are either different and each is hydrogen: 2 3 or a formyl radical, a C ^ -C ^ alkyl-CO radical, one: "L _CL-C" alkoxy-C -C alkyl -CO radical or an aryl-CO radical 25 / "- rC - or together denote the groups r __ \: v-“ V CaO or ^ --- \ γ, in which; X is hydrogen, C.- C, alkyl or CC alkoxy and = 30 1 '1 3 Y represent hydrogen, C1-C ^ alkyl, C ^ C alkoxy or aryl.

Examples of Al3 Cg-C ^ Q-alkyl and alkenyl radicals are 2-methyl-heptan-6-yl, 2-methyl-3-ethyl-hept-4 ~ en-6-yl, 2,3-di- 25 raethyl_hept-4-en-6-yl, 2-methyl-3-ethyl-heptan-6-yl and 2,3-dimethyl-heptan-6-yl; Acyl radicals can mean the formyl radical, a Co-C_-alkyl-C0 radical, a C -C_-alkoxy-C -C.-alkyl-CO radical and an aryl-CO radical, such as acetoxy, methoxy-acetoxy , Ethoxyacetoxy, Propionyloxy, Butyryloxy, Valeryloxy, 40 Pentanoyloxy, Hexanoyloxy, Heptanoyloxy, Diraethylacetoxy, Diethy cn § / acetoxy, Benzoyloxy and Phenylacetoxy.

! - lr \ '51 - · //. Board: Or. H.rbert Asmia - Dr. Christian Brunn - Hans-Jürgen Hamann Postal address: SCHEHINQ AQ - D-10C0 Berlin 95Poetfactl 95 0311 3? 1V rte U «> H« U ..... ΛΙ *. ft- n._A 14 «: * __ i

SCHERING AG

-9- Commercial Itechtnchutz> j -3 Examples of C -C.-alkyl radicals include methyl, r 1 d ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl and

Chloromethyl; C 1 -C 4 alkoxy radicals are, for example, methoxy, ethoxy and propoxy; Finally, aryl residues include naphthyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chloro-“phenyl, 2,6-dichlorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,4,6 -Trichlorphenyl, 4-bromophenyl, 2,4-dibromophenyl, 2,6-dibromophenyl, 2,4,6-tribromophenyl, 2-fluorophenyl, 3-fluorophenyl

Iyl, 4-fluorophenyl, 2,4-difluorophenyl, 2-methylphenyl, 3 “methyl- ^ phenyl, 4-methylphenyl, 3,4-dimethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 3,4-dioxymethylenephenyl , 2-phenoxyphenyl, 3-phenoxyphenyl, 2-nitrophenyl and 3-nitro-phenyl.

The compounds of the invention can be used either alone, in a mixture with one another or with other active ingredients. If necessary, defoliation, plant protection or pest control agents can be added, depending on the desired ^ "Zwëi ^ '^.' 25 -

If it is intended to broaden the spectrum of activity, other biocides can also be added. For example, those active ingredients which are listed in Weed Abstracts, Vol. 31> 1981 »un- * 2o ter ^ em" List of common names and Abbreviations employed for currently used herbicidefes and plant growth regulators in weed abstracts "are suitable as herbicidally active mixture partners . In addition, non-phytotoxic agents can also be used which can result in a synergistic increase in activity with herbicides and / or growth regulators, such as, inter alia, wetting agents, emulsifiers, solvents and oily additives.

, -10- - / a I · 2 lv ΠΊ '°, r' H * rbert Asmis Dr Christian Bruhn · hans-Jürgen Hamann Postal address: SCHERING AG · D-1000 Seriin «- Posttecn 6S0311« ti Df. Hemz Hannse ♦ Kan Otto Mittelstenscnetd · Dr rtorst Wttze! «, _ ^ Ä _ ï v / üi.nwai HIXBI Po * t« rft <* rtr-> inntn - n «riin.W» «f Rankleitrwhl 1fln ΊΟΓΜίΙ

SCHERING AG

Commercial legal protection r 5 The active compounds according to the invention or mixtures thereof are expedient in the form of preparations, such as powders, scattering agents, granules, solutions, emulsions or suspensions, IV with the addition of liquid and / or solid carriers ώ or diluents and, if appropriate, 1 - Wetting agents, adhesives, emulsifiers and / or dispersants, applied to.

Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, such as benzene, 1 ^ toluene, xylene, cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide and mineral oil fractions.

Mineral earths, for example Tonsil, silica gel, talc, kaolin, Attaclay, limestone, silicic acid and vegetable products, for example flours, are suitable as solid carriers.

^ irTöl> surfactants include, for example: ^ alcaumligninsulfonat, polyoxyethylene alkylphenol ether, - Na |> itthalinsulfonic acids and their salts, phenolsulfonic acids 25 dnd "their salts, formaldehyde condensates, fatty alcohol sulfates and substituted benzenesulfonic acids and their salts.

The proportion of the active ingredient (s) in the various preparations can vary within wide limits.

: 30. O.

For example, the agents contain about 10 to 40 percent by weight of active ingredient, about 90 to 20 percent by weight of liquid or solid carriers and optionally up to 20 percent by weight of surface-active substances.

35

The agents can be applied in a customary manner, for example using water as a carrier in spray liquor amounts of about 100 to 1000 liters / ha. The use of the agents in the so-called low-volume or ultra-low-volume process is just as possible as their application in the form of so-called microco S granules. -11- f ’j / - ^ Head: Dr. Herbert Asmis - Or. Christian Bruhn Hans-Jürgen Hamann Postal address: SCHERING AG - D-1000 Berlin «5 · PO Box es © 11 l Z L- Dr. Heinz Hannse - Kar! Otto Mitteistenscneid - Dr. Horst jokes! Qm ... «! · - 'Ι / βΑ.Β · O. af i. Itf.ae Λ Λ 4 rt__1.1 · 1__. _ I. -μ .a.

0 / Ή_ * Γ “rv *. »/ * ·" _ 1 ± _ oühbnii \ α / \ c:

Commercial R * chii * chirtx t 5 For example, the following ingredients are used to prepare the preparations: ^ i. A. wettable powder v a) 80 percent by weight of active ingredient 15 percent by weight of kaolin M 5 percent by weight of surface-active substances based on i the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of lignin sulfonic acid.

15 b) 50 weight percent active ingredient 4θ weight percent clay minerals 5 weight percent cell pitch 5 weight percent surfactants on the 20th

Based on a mixture of the calcium salt of lignin sulfonic acid with alkylphenol polyglycol ether.

20% by weight of active ingredient I "" 3ΡΞ503 70% by weight of clay minerals '25. ·; 5% by weight of cell pitch .- - 5% by weight of surfactants on the

Base of a mixture of the calcium salt of lignin sulfonic acid with alkylphenol polyglycol ethane.

30 d) 5% by weight of active ingredient 80% by weight of Tonsil 10% by weight of cell pitch 5% by weight of surfactants based on a fatty acid condensation product.

'35 I- k9 -12- i / "(y Board of Directors: Or. Herbert Asmis - Dr. Christian Bruhn Hans-Jürgen Hamann Postal address: SCHERING AG · D-1000 Berlin 65. Postfacn SS 0311 2 Or. Heinz Hannse. Karl Otto Mittelstenscfteid · Herst Witz ·· _________ _______ _____ _______ _ .. w 41

; SCHEHN3 AG

Industrial property rights t t ï t 5 B. Emulsion concentrate 20% by weight of active ingredient il * ko% by weight xylene il 35% by weight dimethyl sulfoxide I * 5% by weight mixture of nonylphenylpolyoxyethylene or calcium dodecylbenzenesulfonate.

C. Paste 15 k5 percent by weight of active ingredient 5 percent by weight sodium aluminum silicate 15 percent by weight cetyl polyglycol ether with 8 moles of ethylene oxide 2 percent by weight spindle oil 20 10 percent by weight polyethylene glycol 23 parts of water.

"^ JJ ^^ new compounds according to the invention can be prepared, for example, by using compounds of the general formula 25... _

30 1 Γ J

H

35 by osmium tetroxide-catalyzed hydroxylation with t-butyl hydroperoxide or with N-methyl-morpholine-N-oxide to give compounds of the general formula ko I / “/ l / 'vàtstànà: Dr. Herbert Asmis - Dr. Christian Bruftn - Hans-Jürgen Hamann Postal address: SCHEHING AG D-1000 Berlin S £ · PO Box 65 β 11 | Z / Or. Heinz HannseKarl Otto Mitteistenscheid-Dr. Horst Witzei Postschecx account: Berün-West 1175-101. Bank code ιοηΐΜΐη

SCHcRiNG AG

-13- Gcrtrèlicher

T

5 l17 HO 1 “10

H

reacted, or to which silver acetate and iodine in aqueous acetic acid to form compounds of general formula 15

rA

—1 IV

20 i

ho ^ mV

- 0 H __ ...............

can act. Which are treated with peracids to form the 25 desired process products, in which R ^ andÆ ^ have the meaning given above.

To prepare the compounds of the formula I, sterols, such as cholesterol, stigmasterol, brassica; 20 sterol or β-sitosterol, and converts them in a known manner to the ^ -6 — ketosteriods of the formula XI.

(In Helv. ^ 9, 1581 (1966)).

The further conversion to 2a, 3oC "" cis-glycols of the formula III 2 ^ is based on known methods, namely the osmium tetroxide-catalyzed hydroxylations with 80 tigers of t-butyl hydroperoxide (KB Sharpless JACS 98, 1986 (19 / 6)) or with N-methyl-morpholine-N-oxide (V.van Rheen, Tetrahedron Lett.

1976, 1973).

, 210 -1¾.

S j ~ .//Voriland: Or.Herbert AsmisDr. Christian Bruhn - Hans-Jürgen Hamann Postal address: SCHEHING AG · 0-1000 Berlin 85 · Postfach 850311 2 l, 0r. Mm HannseKarl Otto M.tte.s.enscneid Dr. Horst Witzei Postschedc account: Berün-West iws-iot. Bank details 100 looto

SCHERING AG

Commercial · «· Legal protection y 2 The 2ß, 3ß-cis-glycols or their derivatives of the formula IV are obtained by a Prevost reaction with silver acetate and iodine in aqueous acetic acid (4: 9, lpßl (1966)).

at the.

- The B-ring lactones of the formula I are prepared “^ by Baeyer-Villiger oxidation with peracids such as trifluoroperacetic acid, performic acid, permaleic acid etc. of the 6-keto-steroids of the formula Illund IV. For compounds with a C. double bond in the side chain must be in front of the lactonization

«J

; rang this double bond to be protected by bromination.

15

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

The following exemplary embodiments explain the preparation 20 of the compounds according to the invention, -25 ---- '30 "35

II 4oA

l Board: Qr. Herbert Asmis Dr. Christian BruhnHans-Jürgen Hamann Postal address: SCHSSING AG0-1000 Berlin iSPostfadt iS 0311 z Dr. Heinz Hannse Karl Otto MitteistensaieidOr.Horst Witzei a.r.in.w.MiTt.m

SCHERÎNG AG

- 15 "G * werkÎich # r legal protection 5 EXAMPLE 1 r [a) 3.56 g of 24 S ethyl-5a-cholesta-2,22-dien-6-one were dissolved in i * 60 ml of t'-butanol, 4 ml 20? 6 tetraethylammonium -jj "hydroxide solution added, cooled to 0 ° C and with 12 ml of I - 80 tigers of t-butyl hydroperoxide and with 6 ml of an osmium il tetroxide solution (prepared from 250 mg OsO ^, ^ 9.75 ml I t-butanol and 0.25 ml of 8.0% t-butyl hydroperoxide) were added.

The reaction solution was stirred for 6 hours at room temperature, poured into 5/6 sodium hydrogen sulfite solution and extracted with ethyl acetate. The extract was washed with water, dried over sodium sulfate and evaporated.

After recrystallization from methylene chloride-methanol, 2.3 g of 2α, 3a-dihydroxy-24 S-ethyl-5a-cholest-22-en-6-one are obtained.

20, o

Pp 234.5-235.5 C.

: è. b) 2.2 g of 2a, 3a-dihydroxy-24 S ethyl-5 «-cholest-22-en-6-one t were dissolved in 15 ml of pyridine, with 8 ml of acetic anhydride and j - 220 mg.; 4-dimethylaminopyridine were added and the mixture was left for 17 hours at 25 ° to 20 ° C. It was then dropped into ice water, the product was filtered off, washed and dried.

c) 2.6 g of crude diacetate in 30 ml of ether and 30 ml of ice were mixed with 0.28 ml of bromine and stirred for a further 10 minutes at room temperature. For working up, the mixture was diluted with ether, washed neutral with water and evaporated in vacuo. 3.2 g of crude 2a, 3a "0iacetoxy-22,23-dibromo-24-ethyl-5a-choiestan-6-one are thus obtained.

35 d) 4.5 ml of 30 “4ig hydrogen peroxide were suspended in 28 ml of methylene chloride, cooled to -10 ° C. and 27.7 ml of trifluoroacetic anhydride were slowly added dropwise so that the internal temperature did not rise above - * - 10OC. Then 3.2 g of 2α, 3a-oiacetoxy-22,23-dibromo-24-ethyl-5a- * 7 r s / choiestan-o-on, -l6- ^ fj / board: Or. Herbert Asmis Dr. Christian SruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin «PO Box« £ 311 ± 4 z./ Dr. Heinz Hannse Kan Otto MittelstenschaidOr. Horst Witzei n

i. SCHERINGAG

1—16— Legal protection r 3 dissolved in 25 “1 methylene chloride, added and kO minutes stirred at room temperature. The mixture was then diluted with methylene chloride and washed in succession with water, 5-6 iS sodium carbonate solution and with water, dried and concentrated in vacuo. The residue was dissolved in 100 ml of 10

Acetic acid with 5 S zinc dust heated on the steam bath for 1 hour. The zinc was filtered off, diluted with methylene chloride and washed neutral with water and evaporated.

After chromatography on silica gel (gradient elution toluene-ethyl acetate) and crystallization from acetone-hexane, 15 1.5 g of 2α, 3a-diacetoxy-2 ^ -ethyl-7-oxa-B-homo-5a-cholest-22-6- on, m.p .: 221-223 ° C and 310 mg 2a, 3α-diacetoxy-24-ethyl-6-oxa-B-homo-5tt-cholest-22-en-7-one, m.p .: 202-204 ° C.

20 - · ... ..... .. - -: · · '-: -. -. - - -.- - - - - ---- ... -, - ... ". .- -.— 7 ---'— 30 35 -17- 1 V \ c / »orstanaiDr. Herbert AsmisDr. Christian Bruhn Hans-Jürgen Hamann Postal address: SCHERING AG0-1000 Berlin 65 - P.O.Box 65 0311 2 Dr. Heinz HannseKarl Otto Mitte! Stensche> d - Dr. Horst Witzei postal check account r Rsrlin-W.st R.n.l.itr.h «in mn-m

SCHEKNG AG

-17 ~ Commercial «· Right κτ.ιτίζ> ί; [j 5 EXAMPLE 2 i; Ü I; _ a) 3.2 g of silver acetate and 1 , 9 g of iodine and stirring 3 10, o

Heated to k.3 C for 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-15 3ß-hydroxy-2 ^ -ethyl-5a-cholest-22-en-6-one is obtained.

Mp .: 192-19 ^ ° C.

22 b) After bromination of the A double bond, Baeyer-Villiger oxidation and zinc reduction, as described in Examples 1c) and 1d) 20, the crude product is chromatographed on silica gel. Gradient elution with chloroform-acetone vt gives pach recrystallization from hexane ether in - 75:% yield 2ß-acetoxy-3ß-hydroxy-2 ^ aäihyl-7-. ^ .- oxa - B-homo-5Q: - cholest-22-en-6-one, mp: 15i-153 ° c 25

And in 10% yield 2ß-Ace toxy ^ ß-hydroxy ^^ - ethyl-Arb-Oxa-B-homo-Sa-choles t-22-en-7-one, m.p .: 175 “176 ° C.

30th

"• UL

= 35 - / ° -18-? // \ -Ï / L / Board: Or, Herbert AsmiaOr.Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65Postbox 650311 3 / Dr. Heinz HannsaKarl Otto Mitteistenscfteid Dr. Horst Witzei.

SCHERING AG

- 1g- Industrial property protection 5 EXAMPLE 3> a) 2.2 g 2ß-acetoxy-3ß-hydroxy-24-ethyl-7-oxa-B-homo-5a-; * cholest-22-en-6-one were mixed in 50 ml of methanol with a solution of 500 mg of potassium hydroxide in 10 ml of methanol [1 Π 10 and stirred for 30 minutes at room temperature. It was acidified with acetic acid, precipitated in ice water, off! sucked, washed and dried. After crystallization from chloroform ether, 1.7 g of 2β, 3ß-dihydroxy-24-ethyl-7-oxa-B-homo-5cr-cholest-22-en-6-one, 15 p.p .: 211-213 ° C.

b) 500 mg 2β, 3ßrDihydroxy-24-ethyl-7-oxa-B-homo-5o: -cholest - 22-en-6-one were cooled to -10 ° C in k ml pyridine, 20 with 0.5 ml of acetic anhydride are added and the mixture is stirred at -5 to -0 ° C. for 3> 5 hours. After precipitating in ice water, suctioning off the product, washing and drying, the product was recrystallized from acetone • -: ....... hexane. 410 mg of 3β-acetoxy- "'.r 2ß-hydroxy-24-ethyl-7-oxa-B-homo-5oc-choies t-22-en-6-one, 25" Z1: Mpp *: l82 -l84 ° C.

; 30 35 -19- 2 = a - L · I -! . · Board: Dr. Herbert Asmis Dr. Christian Brunn Hans-Jürgen Hamann Postal address: SCHERING AG 0-1000 Berlin 65Postfacft 65 0311! Z Πρ H * in? Hann «* · Karl ÖHn Ιυ <ι *» Α («1οη« ι · * η®ιΗ. Pif · Mnrtf Wifral - ... _

SCHERING AG

”9“ Intellectual Property Law ► t Î r \ ς EXAMPLE 4 È ^ ---— r 1 g 2α, 3a-Dihydroxy-7-oxa-B-horao-5a-choj £ stan -6-one were | v dissolved in 10 ml pyridine, cooled to 0 ° C and with 1 ml acetane! hydride added. The mixture was stirred for 5 hours at 0-5 ° C., poured into ice water, suction filtered, washed and dried

net. After recrystallization from pentane, 95 ° mS is obtained

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

Mp: 165.5-167 ° C.

15 Preparation of the starting material: a) _ 25 g of 5a-cholest-2-en-6-one were dissolved in 140 ml of tetrahydrofuran, mixed with 14 g of N-methylmorpholine-N-oxide, 25 ml of water and 50 ml of t-butanol and a solution of 25 mg of osmium tetroxide in 50 ml of tetrahydrofuran was added with stirring.

The reaction solution was stirred at room temperature for 17 hours with the exclusion of light. Then it was precipitated in 7 l of ice-water, which had been mixed with 50 ml of 2N sulfuric acid and 1 g of sodium sulfide, the product was filtered off with suction, washed with water: aI, dissolved in chloroform and the solution was evaporated in a vacuum of 25 lbs Crude product (30 g) was dissolved in 140 ml of pyridine and, after the addition of 70 ml of acetic anhydride and 3 S '4-dimethylaminopyridine, left to stand for 16 hours at room temperature After water precipitation, suction filtration of the product, washing with water and drying, chromatography was carried out on silica gel after recrystallization from ethanol in 75% 1 yield the 2a, 3oc-diacetoxy-5 <z-cholestan-6-one,

Mp .: 150.0-151.5 ° C and 15% da 2ß, 3ß-diacetoxy-5cc-cholestan-6-one, m.p .: 183.5 - 185 ° C.

35 b2. 26 ml of 30% hydrogen peroxide were suspended in methylene chloride, cooled to -10 ° C. and 16 ml of trifluoroacetic anhydride were slowly added dropwise so that the internal temperature did not rise above + 10 ° C. Then 27.2 g of 2α, 3oc-diacetoxy-5a-cholestan-6-one, in ΐ6θ ml methylene chloride 1 J / Λ -20- - L 'ß 2 Board: Dr. Heroert AsmisDr. Christian Brunn Hans-Jürgen Hamann Postal address: SCHERING AG 0-1000 Berlin SS - P.O.Box 65 0311 3 9 i Dr Heiri7 Hannen - KsrI Drin Mitfal «; ran ^ f-noirl. Dr Unre, u / i, vai _ _ .... - ......... _

SCHERING AG

• ΠΟ

Commercial legal protection r l 5 dissolved, added and stirred for 40 minutes at room temperature. J For working up, the mixture was diluted with methylene chloride and washed successively with water, 5% sodium carbonate solution and with water and concentrated in vacuo. After chromatography on silica gel and recrystallization from acetone-hexane, the 2a, 3a-diacetoxy-7-oxa-B-homo-5a-cholestan-6-one is obtained in 8l% yield, mp: l83 -184 ° C. and to 6.2% the 2a, 3oc-diacetoxy-6-oxa-B-horao-5a-choles tan-7-one,

Mp .: 245-247 ° C.

15 c) 28.3 g of 2α, 3a-diacetoxy-7-oxa-B-homo-5a-cholestan-6-one were dissolved in 500 ml of methanol and after adding a solution of 14 g of potassium hydroxide in 150 ml of methanol for 30 minutes Room temperature stirred. The mixture 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-pentane, 22.4 g (95%) of 2a, 3a-dihydroxy

_xa-B-homo-5ct-cholestan-6-one, mp. : 138-l40 ° C

'>: · ^ · ·>. -....

25 -: 3o 35 -21- ±, / Board: Or. Herbert Asmis - Dr. Christian Brunn - Hans-Jürgen Hamann Postal address: SCHERING AGQ-1C00 Beriin 65Pcstfadi 650311

SCHERING AG

'e9 le

Commercial law school »5 EXAMPLE 5 a) 1.1 g of 2α, 3a-diacetoxy-6-oxa-B-homo-5a-cholestan-7-one were saponified as described in Example 4 c).

This gives 7 ^ 5 mg of 2a, 3a-dihydroxy-6-oxa-B-homo-5a-cholestan-7-one with a melting point of 2l6.5-2l8 ° C.

b) 250 mg of 2a, 3a-dihydroxy-6-oxa-B-homo-5cr-choiestan-7 ~ one were dissolved in 2 ml of pyridine, cooled to -10 ° C, treated with 15 0.24 ml of acetic anhydride and 4 hours stirred at -5 to 0 ° C. After precipitation in ice water, suction filtration of the product, washing and drying, the product was recrystallized from acetone-hexane. 210 mg of 2a-acetoxy-3a-hydroxy-6-oxa-B-homo-5a-cholestan-7-one are obtained, mp: 199-201 ° C.

20 - 'T' ’." · Ϊ́Γ - · - · ~ r'r. '': R- / r 25 ...

; 3o 35 40 / ___v m v— \ -22-

Board: Dr. Herbert AsmisDr Christian Bruhn Hans-Jürgen Hamann Postal address: SCHHSING A6 D-1000 Berlin 65 - Postfach 650311 t

/ SCHfchlNG AG

• J -22- Intellectual Property Law 5 EXAMPLE 6 [600 mg 2a, 3ct-Dihydroxy-2zi: -methyl-6-oxa-B-homo-5o: -cholest-; '* 22-en-7-one were acetylated as in Example 5 b).

5 ^ 5 mg of 2a-acetoxy-3a-hydroxy-24-methyl-6-oxa - "10 B-homo-5 <2-choiest-22-en-7-one, mp: 173-17 ^ ° C.

Production of the starting material: 15

The 2k-methyl-5cr-cholesta-2,22-dien-6-one was prepared from brassicasterin using a known method and this was reacted as described in Example 1.

20 25 · ^: î 30 35 -23- J | ^ Management 'Πγ Worherf Àsmm - ör. Christian Rrnnn Han * -.! I »rnAo Mamsrin Prt« fan «r * trtft- ζΛΗΡΠίΜΛ Art. Π.1000 Rarfin fiC. Powtfaei SS0311 5 EXAMPLE 7 i iU-i til / * tw * “23“ Commercial Rechiasd-.jtc jjd; -j 1 g 2ß, 3ß “Dihydroxy-7-oxa-B-homo-5c-cholestan-6-one 1 'î 45, · Ο

Π dissolved in 100 ml acetone and 100 ml tetrahydrofuran, to 0 C

y "cooled, mixed with 0.5 ml of boron trifluoride etherate and stirred for 30 g ^ minutes at 0 to 5 ° C. After the addition of 1 ml of pyridine I", the mixture was concentrated in vacuo and recrystallized from methylene chloride-isopropyl ether. 731 mg of 2β, 3ß-isopropylidene-dioxy-7-oxa-B-homo-5a-cholestan-6-one are obtained, mp: 2-16-217 ° C · 15

The following were prepared analogously: 2a, 3a-isopropylidenedioxy-7-oxa-B-homo-5a-cholestan-6-one

Mp: 2-16-217 ° C

2a, 3a-isopropylidenedioxy-24-ethyl-7-oxa-B-homo-5a-cholest-20 22-en-6-one, m.p .: 157-158 ° C

i 25 '.

: 3o 35 -2k- ko / i Ï »^ Board: Or. Herbert Asmis Dr. Christian Bruhn Hans-Jurgen Hamann Postal address: SCHHSING AG0-1000 Berlin 65Pox 65 0311

SCHERING AG

_0 ^ _ Commercial legal protection! 5 EXAMPLE 8! 1'900 mg of 2a, 3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-one {O. · · Λ

• were dissolved in 10 ml of pyridine, cooled to 0 C, mixed with 1.8 ml of J ^ valeric anhydride and 10 hours at 0 to 5 ° C

I stirred. After working up, as described in Example k, I 950 mg 2a-Va ryloxy-3a-hydroxy-7-oxa-B-homo-5a i are obtained cholestan-6-one, m.p .: 92 - 9 ^ ° C »15 20 - - -çi: ..

25 sis; - - - - · - - -.

; 30 35 -25- i »1¾ ^ Board: Dr. Herbert AsmisDr. Christian Brunn Hans-Jürgen hamann Postal address: SCHERING AG · 0-1000 Berlin S5 · Postfach 65 0311 5 EXAMPLE 9

SCHERING: /, G

“2 5 - Commercial Rcefcirsshuia 2α, 3a-diacetoxy-24-ethyl-7-oxa-B-homo-5α-cholest-22-en-6-one * were saponified and partially acetylated, as in Example 3.

The 2a-acetoxy-3-hydroxy-10 24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one is obtained in 70% yield, mp: 158 ° -60 ° C.

15 2 °. . -Τ..ΓΕ _____.

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; 30 35 -26- kof 1 f ^ ~ '' _ Board: Dr. Herbert Asmis Dr. Christian 3ruhn Hans-Jürgen Hamann Postal address: SCHERING AG D-100ö Berlin 65Postbox 55 0311

SCHERING AG

Commercial Rechiischuh! 5 EXAMPLE 10 Ί —-——, | , 900 mg 2a, 3a-dihydroxy-7-oxa-B-homo-5ci-cholestan-6-one! * were dissolved in 10 ml pyridine, cooled to 0 ° C, with 1 ml! 5.

[j w added ethoxyacetic anhydride and 5 hours at 0 to | ^ 5 ° C stirred. After working up, as described in Example 4, and recrystallization from acetone-hexane, one obtains! 720 mg 2a-thoxyacetoxy-3Œ-hydroxy-7-oxa-B-homo-5Œ “cholestan- 6-one, mp .: 172-173 ° C * 15 20 ----- -_ ·, γ_- -: ····· u 25 '-l' I 30 35 -27- 40 /! 1 ir \.

y? ·. Ι Board: Or. Herbert Asmis · Or. Christian Brunn - Hans-Jürgen Hamann Postal address: SCHE3ING AG · 0-1000 Berlin 65 - Pestfacn 65 0311

SCHEftiNG AG

- “2 (- Commercial law» di utz 5 EXAMPLE 11 300 mg 2a, 3a-dihydroxy-2zi-ethyl-7-oxa-B-homo-5s-cholest-22-en-6-one were mixed in 3 ml pyridine 70 mg of phenylacetic anhydride were stirred for 10 hours at 0 to 5 ° C. After working up and recrystallization from acetone-hexane, 210 mg of 2a-phenylacetoxy-3a-hydroxy-24-ethyl-7-oxa-B-homo-5a- cholest-22-en-6-one, m.p .: 185 -86 ° C.

15 20 25: - "" 7 3 ° 35 -28-

2 IU

I ** - “Board: Or. Herbert Asmis · Dr. Christian Bruhn Hans-Jürgen Hamann Postanscfirift: SCHERING AG0-iCOO 3erim 65Pox 85 8511

SCHERING AG

"28- Commercial Rechiîîchuti i 5 EXAMPLE 12 500 mg 2 <z, 3a" Dihydroxy-7-oxa-B-homo-pce-choiestan-6-one '* were mixed with 0.75 ml of triethyl orthoacetic acid ester in 50 ml of benzene and 5 mg of p-toluenesulfonic acid were added. i0 The solution is stirred for 20 minutes at room temperature, mixed with 3 drops of pyridine and evaporated in vacuo. The residue is dissolved in methylene chloride, washed with water, dried over sodium sulfate and evaporated. This gives 6θ5-mg 2α, 3a- (1-ethoxy-ethylenedioxy) -7-oxa-B-homo-5 <x-cholestan-6-one, mp; 150-154 ° C.

The following were produced analogously:

2a, 3a- (1-ethoxyethylenedioxy) -6-oxa-B-homo-5a-cholestan-7-one 20 m.p .: 122-124 ° C

2a, 3a- (1-ethoxypropylidenedioxy) -7-oxa-B-homo-5a-cholestan

I 6-on, mp .: 115-il8 ° C

* ... r 2a] 3a- (1-methoxy-methylenedioxy) -24-ethyl-7-oxa-B-homo-5a- • ^ _cdolest-22-en-6-one, mp: 96-98 ° C.

2ß, 3ß- (1-ethoxy-ethylenediaoxy) -24-ethyl-7-oxa-B-homo-5a-chol'est-22-en-6-one, m.p .: 123-125 ° C

; 30 35 40 /? -29-! _ Board: Dr. Herbert AsmisDr. Christian 8ruhn Hans-Jürgen Hamann Postal address: SCHERING AG D-'COO Benin 6SPostbox $ 5 0311 R? ftr Ηβιητ Ulonrtea. / srl ΛΜη UiffalciAnema · «« _ ΓΛ. Un »» uriwni _

SCHERING AG

Industrial legal protection 5 EXAMPLE 13 500 mg 2ct, 3ct-dihydroxy-7-oxa-B-homo-5a: -cholestan-6-one Λ were dissolved in 5 ml tetrahydrofuran with 1.5 ml acetophenone and 0.1 ml boron trifluoride Etherate added and heated under reflux for 3 hours. The mixture was then concentrated in vacuo, 1 ml of pyridine was added and the mixture was evaporated in a high vacuum.

After trituration with hexane, 465 mg of amorphous 2a, 3a- (1-methyl-1-phenyl-methylenedioxy) -7-oxa-B-homo-5a-cholestan-6-one is obtained as a diastereomeric mixture of mp: 130.5 -132 ° C.

• 15 20: 25 ";; 30 ii 35 -30-. ¥> I / ί / ^ ·» Board: Dr. Herbert Asmis Dr. Christian Brunn - Hans-Jürgen Hamann Postal address: SCHEPING AG · D-1000 Benin 65 · Postfach 65 0311 5 EXAMPLE ik c Γ 'ut K fr> a ^

Ouï it — t iiiXO./ r, w.

Commercial law: 5OO mg of 2a, 3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-one * were dissolved in 15 ml of diethyl carbonate, heated to boiling ~ and after distilling off 2 ml of diethyl carbonate 30 mg of sodium methylate were added. A few ml were distilled off from the reaction solution 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-rexan. This gives ^ 50 mg of 2a, 3a-carbonyldioxy-7-oxa-B-homo-5a- "^ cholestan-6-one of mp .; 203i5-205 ° C.

The following were produced analogously:

2a, 3a-carbonyldioxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-20 en-6-one, m.p .: 193-195 ° C

2ßÖ £ rCarbonyldioxy-7-oxa-B-homo-5a-choies tan-6-one

’" 1 m.p .: 212-21¾ ° C

25 BC ’7" ·: :: ”" "" '30 35 / -31- kcf m h i

^ / Board: Dr. Herbert AsmisDr. Christian Sruhn * Hans-Jürgen Hamann Postal address: SCHERING AG - D-1G00 Benin 65 * Postfach 65 03 TI

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SCHERING AG

"21- Intellectual Property Law 5 EXAMPLE 15 • $ 1 | 300 rag 2a, 3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-one dissolve in 2 ml benzaldehyde, 0.02 ml 70% chlorine; 1 ? j-J acid added and stirred for 2 hours at room temperature.

M The solution was then neutralized with pyridine,

! I.

diluted with hexane and chromatographed on silica gel.

258 mg of 2a, 3a-benzylidene-dioxy-7-oxa-B-homo-5a-cholestan-6-one were eluted with hexane-ethyl acetate (6: 4) and tun-crystallized from ether-pentane.

15 mp: 137-139 ° C

The following were prepared analogously: 2a, 3oc “benzylidenedioxy-6-oxa-B-homo-5ût-cholestan-7-one, 20 m.p .: 179-180 ° C ~ 2ß i'3ß-Benzvlidenedioxy-6-oxa-B-homo -5c: -choles tan-7-one,; - mp: 129-131 c q _ 2ß, 3ß-benzylidenedioxy-7-oxa-B-homo-5ot-cholestan-6-one,. :: u.Fp .: 153-155 c

V

30 35 7 ~ 32 "^ w Board: Or. Heroert Asmis Or. Christian Bruhn Hans-Jürcen Hamann Postal address: SCHERING AG · O-'CCO Berlin 65 PO Box 65 0311

SCHERING AG

Commercial legal protection 5 The compounds according to the invention are generally crystalline, colorless and odorless substances which are sparingly soluble in water and conditionally soluble in aliphatic ^ *. Hydrocarbons such as petroleum ether, hexane, pentane and cyclo- .j. i hexane, readily soluble in halogenated hydrocarbons; f 10 such as chloroform, methylene chloride, carbon tetrachloride, I aromatic hydrocarbons such as benzene, toluene and: | Xylene, ether, such as diethyl ether, tetrahydrofuran and dioxane J carboxylic acid nitriles such as acetonitrile, ketones such as acetone,

Alcohols such as methanol and ethanol, carboxamides such as * 5 dimethylformamide and sulfoxides such as dimethyl sulfoxide.

The following examples explain the possible uses of the compounds according to the invention which took place in the form of the preparations listed above.

20 λ.Ί · '.

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: 3o 35 -33- i 1 y; Board: Dr. Herbert Asmis - Dr. Christian BruhnHans-Jürgen Hamann Postal address: SCHEHING AG D-1000 Berlin 65 - Postfacn 650311: Z ftr Uaιλτ l — l.nrtf. . h ^ arl Λιϊλ MitteietAne.HisiH _ r ^ r · Urseet \ A /*.&! . _ - __. .

5 EXAMPLE 16

SCHERING AG

Intellectual Property

Promoting growth in bush beans

Bush beans of the "Pinto" variety were grown in climate chamber 10 at 25 ° C and 90% humidity under the influence of light with a high proportion of intensity in the range of 660 nm and a very low proportion in the range of 730 nm.

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

The extension of the internodes was measured 3 days after the application and the percentage elongation compared to the control was determined.

The table contains the results of this experiment.

25 "- ~ --- ·

Compounds according to the invention Percentage promotion - · -10 ug_50 ug 2a-acetoxy-3a-hydroxy-B-homo-7-o: xa- 5a-choiestan-6-one 292 125 "Γ -λ 2a, 3e-carbonyldioxy-B-homo -7-oxa- 3,5a-cholestan-6-one 190 304 c 2a-acetoxy-3a-hydroxy-B-homo-6-oxa- 5a-cholestan-7-one 162 125 2a, 3a- (1-ethoxy -ethylenedioxy) -B-homo-7-oxa-5a-cholestan-6-one 165 162 25 2a, 3 "- (1-methyl-1-phenyl-methylenedioxy) - B-homo-7-oxa-5a-cholestan -6-on 152 3 ^ 2

COMPARATIVE

2a, 3a, 22S, 23S-tetrahydroxy-24-ethyl-B-homo-7-oxa-5a-cholestan-6-one 89 114 4- (3-indolyl) -butyric acid 51 3 & ψ control 100 100 i / rev - -34-. ? Board: Qr. Heroert AsmisDr. Christian 8ruhnHans-Jürgen Hamann Postal address: SCHERING AG D-1000 Berlin 65Postbox 65 0311

SCHERING AG

'-3 ^ - Commercial legal protection »5 The results show that the compounds according to the invention cause a more intensive stretching than the comparative means and the control * under the specified test conditions.

: * 10 The comparison means, on the other hand, only cause a more or less strong promotion of thickness growth! which in some cases even led to a compression of the internodes.

. 15 20 25. '· ·; 30 ~ 35 4® ’35 · I / 1 / ^ w ’Board: Dr. Herbert Asmis Dr. Christian Brunn Hans-Jürgen Hamann Postal address: 3CHEHING A3 D-1CC0 3ernn 65Posrtaoi 65 0311 Z Dr. Heinz Hannse Karl Ctto Mittelstenscheid - Dr. Horst Witzei __ "v__3 ... ι.". Ι.ι <"η <ι> ι <ιι SCHERING /: 3 *" 35 "Commercial law shoes 5 EXAMPLE 17

Stimulation of root growth in mung beans

V

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

J 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 according to the invention Percentage promotion 2a-acetoxy-3c-hydroxy-B-homo-7-oxa- 5a-cholestan-6-one 180a, 3ct-carbonyldioxy-B-homo-7 "oxa- 5a-cholestan-6 -on ΐ6θ 2a-acetoxy-3a-hydroxy-B-homo-6-oxa-25 5ct-cholestan-7-one. l6o 2a, 3a- (1-ethoxy-ethylenedioxy) -B-homo-7-oxa-5a-cholestan-6-one 200 2a, triple (1-methyl-1-phenyl-methylenedioxy) -B-homo- 7-oxa-3a-choles tan-o-on 150

COMPARATIVE

"30 i Gibberellic acid (GA) 80 * 3

Check 100 3 35! * # \ ». Board: Dr. Herbert Asmis - Or. Christian Brunn Hans-jürgen Hamann Postal address: SCHHHING AG 0-1000 Benin 55 »Postfach 55 0311

Df. Heinz HannseKarl Otto Miîteistenscneid * Dr. Horst Witzei s ** te / - * »orv_Krtnm · Qeriin.w *« r SamriPffraM inn * rvnn 5 EXAMPLE 18

SCHERING AC

_ 36- Commercial calculation

Increase in the resistance of crops] w i j: j * The crops listed in the table were in! 1 -. - I - 10 pre-emergence processes with aqueous emulsions to be tested - 1 the compounds or their mixture treated. One week 1 after the treatment, the treatment result was rated according to the scheme 0 to 10, in which 0 = 100% destruction and 10 = no damage.

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Claims (6)

5 PATENT CLAIMS - 1. Brassinosteroid derivatives of the general formula R; o. i "XT ^ i 15 3: H in the R" _ a CQ-C alkyl radical or a C - C. alkenyl radical 17 o 10 o 10 20 ^ Z the groups - C - 0 - CH - or - 0 - C - CH_ -, II 2 I 2. 0 0 .- represent, 2 ^ - and R ^ are either different and each represent hydrogen or an acyl radical or together are the groups = 0 or.-C, in which X is hydrogen, C.-C.-alkyl or C -C alkoxy and -30 1 'i 1 JY hydrogen, C ^ C ^ alkyl, Cj-C ^ alkoxy or aryl ^ represent. 2. Brassinosteroid derivatives according to claim 1, wherein rj 5 - R 2-methyl-heptan-6-yl, 2-methyl-3-ethyl-hept ~% -en-6-yl »2,3-dimethyl-hept- ^ -en-6-yl, 2-methyl-3-ethyl-heptan- 6-yl or 2,3-dimethyl-heptan-6-yl and Z the groups, -C-0-CH „- or -0- Ç-CH - represent, kO η 2 5 2 I ο o -2- c —'Vöi'yand: Df.Herbert Asmis Or. Christian Bruhn - Hans-Jürgen Hamann postal address: SCHEHING AG - 0-1000 Berlin ββ - Pntfedi es 0311 i I Dr. Heinz HannseKarl Otto Mitte.stenscneKlOr. Horst Witzet Postscftedc account: Berlin-West 1175-101. BanMeitzatW 10010010 £ Chairman of the Supervisory Board: Or. Eduard v. Dickxoppen Berlin Commerzoan * AQ. Berlin. Account number. 10S TQQS üQ_ Bemuectzxni iqd am m SCHERING AG “2- Geuerölisner Rechtssdurtz 5 and are either different and each hydrogen or a formyl residue, a C -C -Alky.l-CO residue, one! «L C ^ -C ^ alkoxy-C ^ -C ^ alkyl-CO radical or an aryl-CO radical i Ir 'or together the groups v ~ in ^ \ ^ X iU C = 0 or in the - X is hydrogen, C ^ -C ^ alkyl or C ^ -C ^ alkoxy and Y is hydrogen, C ^ -C ^ alkyl, C ^ -C ^ alkoxy or aryl - 15. 3. 2a, 3a-diacetoxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one. 4. 2a, 3a-diacetoxy-24-ethyl-6-oxa-B-homo-5a-cholest-22-en-7-one. 5. 2ß-acetoxy-3ß-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-20 en-6-one. 6. 2β-acetoxy-3ß-hydroxy-24-ethyl-6-oxa-B-homo-5a-cholest-22-en-7-one. J i7 "vX; 3ß-acetoxy-2ß-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-; . ... · i 'en-6-one. SW; A2a-acetoxy-3a-hydroxy-7-oxa-B-homô-5a-choiestan-6-one, 25 "9; 2a-acetoxy-3a-hydroxy-6-oxa-B-homo-5a-cholestan-7- on ·· 10. 2a-acetoxy-3a-hydroxy-24-methyl-6-oxa-B-homo-5cr-cholest-22- - .. - en-7-one. 11. 2ß, 3ß-isopropylidenedioxy-7 -oxa-B-homo-5a-cholestan-6-one. 12. 2a, 3a-isopropylidenedioxy-7-oxa-B-homo-5a-choiestan-6-one. y 30 13. 2α, 3a-isopropylidenedioxy-24 -ethyl-7-oxa-B-homo-5c-cholest- Γ 22-en-6-one. ·> 14. 2a-vairyloxy-3a-hydroxy-7-oxa-B-homo-5cc-cholestan-6- on. 15. 2a-Acetoxy-3a-bydroxy-24-ethyl-7-oxa-B-homo-5a-choiest-22-en-6-one. 16. 2a-Ethoxyacetoxy-3a-hydroxy-7-oxa- B-homo-5ct-cholestan-6-one. 17. 2a-Phenylacetoxy-3a-hydroxy-24-ethyl-7-oxa-B-homo-5c: -eholest-22-ën-6-one. 18. 2α , 3ο- (1-ethoxy-ethylenedioxy) -7oxa-B-homo-5a-choiestan-6-one. 19. 2a, 3a- (1-ethoxy-ethylenedioxy) -6-oxa-B-homo-5a-cholestan -7-one. 20. 2a, 3a- (1-Athoxy-propylidendioxy) -7-oxa-B-homo-5a-cholestan- ψ 6-one · - L ^ -3- i H Board: Or. Herbert Asrms - Dr. Christian Bruhn - Hans-Jürgen Hamann Poatansdmft : SCHEFUMG AG * 0-1000 Sertin 65. PO Box «s ttJH 1? / Dr. Heinz Hannse · Karl Otto Mitteistenscneid · Or. Horst Wittel o „_. ". ... ". _ _ _ SCHERING AG -3 “Commercial legal protection t 5 21. 2α, 3a- (1-methoxy-methylenedioxy) -24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one . 22. 2ß, 3ß- (1-ethoxy-ethylenedioxy) -24-ethyl-7-oxa-B ~ homo-5ci-holest-22-en-6-one. -k · T 23 · 2α, 3a- (1-methyl-1-phenyl-raethylenedioxy) -7-oxa-B-homo-5a- j ^ cholestan-6-one. I ^ 24. 2a, 3a ”carbonyldioxy-7 ~ oxa-B-homo-3a-cholestan-6-one. .1 j 25.2a, 3a-carbonyldioxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-I en-6-one. j 26. 2ß, 3ß-Carbonyldioxy-7-oxa-B-homo-5a-cholestaii-6-oii. 27. 2a, 3a-Benzylidendioxy-7-oxa-B-homo-5a - cholestan-6-one. ^ 5 28. 2a, 3a-Benzylidendioxy-6-oxa-B-homo-5a-cholestan-7-one. 29 · 2ß, 3ß-benzylidendioxy-6-oxa-B-homo-5a-cholestan-7-one. 30. 2ß, 3ß-Benzylidendioxy-7-oxa-B-homo-5a-cholestan-6-one. 31. A process for the preparation of brassinosteroid derivatives 20 according to claims 1 to 30 ', characterized in that I compounds of the general formula * -17- 25 - 11 Ei H 30 by osmium tetroxide-catalyzed hydroxylation with t-butyl hydroperoxide or with N -Methyl-morpholine-N-oxide to compounds of the general formula * 17 35 J XII Z 0, f ° H p - / 0 j! w board? Or. Heröert Asmis 0r_ Christian Brunn Η9η «..: Ί> Α« η Hamdnn 8 ^. ··> η · <4 «.ί» »· ft ^ uesiur: Λ / t. runma. «;. · <e. SCHERING AC: * * Commercial legal ut. r 5, or to which silver acetate and iodine in aqueous acetic acid to form compounds of the general formula::> 1? 10th 1 R2o_. | ^ | AsJ- IV. - 0 H, 15 act, which are treated with peracids to form the desired process products, wherein R and R have the meaning given above. 1 f ^ 20 32 · Agent with growth regulating action for plants, characterized by a content of at least one compound according to Claims 1 to 30 · 33. Agents with growth regulatory effect for plants 25 according to claim 32 in a mixture with carriers and / or auxiliary substances. 3½. Agent according to claims 32 and 33 for influencing the vegetative and generative growth in legumes, especially 30 soy. 35, growth regulating agent for plants according to claim 32, prepared by the method according to claim 31 · ~ 35. IU.U.U «^ ζή m T P -5 Board: Or. Herbert Asmis - Dr. Christian Brunn Hans-Jürgen Hamann Postal address: SCHERING AG. 0-1000 BeHin «5. PO Box «0311 f3 2 Or. Heinz Hannsa · Karl Otto Mittelstenscneid · Or. Horst Witzei. o.-ü- ui .... ·. · ». * ,, _ Pcstscnecfc account: Berlin-West 1175-101. Sankletteihl 100 lûoifl