NO833295L - BRASSINOSTEROID DERIVATIVES AND AGENTS FOR PLANT REGULATORY EFFECT ON PLANTS CONTAINING THESE COMPOUNDS - Google Patents

BRASSINOSTEROID DERIVATIVES AND AGENTS FOR PLANT REGULATORY EFFECT ON PLANTS CONTAINING THESE COMPOUNDS

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Publication number
NO833295L
NO833295L NO833295A NO833295A NO833295L NO 833295 L NO833295 L NO 833295L NO 833295 A NO833295 A NO 833295A NO 833295 A NO833295 A NO 833295A NO 833295 L NO833295 L NO 833295L
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Norway
Prior art keywords
oxa
homo
cholestan
ethyl
cholest
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NO833295A
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Norwegian (no)
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Ulrich Kerb
Ulrich Eder
Hansjoerg Kraehmer
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Schering Ag
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Publication of NO833295L publication Critical patent/NO833295L/en

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07JSTEROIDS
    • C07J3/00Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by one carbon atom
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N49/00Biocides, pest repellants or attractants, or plant growth regulators, containing compounds containing the group, wherein m+n>=1, both X together may also mean —Y— or a direct carbon-to-carbon bond, and the carbon atoms marked with an asterisk are not part of any ring system other than that which may be formed by the atoms X, the carbon atoms in square brackets being part of any acyclic or cyclic structure, or the group, wherein A means a carbon atom or Y, n>=0, and not more than one of these carbon atoms being a member of the same ring system, e.g. juvenile insect hormones or mimics thereof
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07JSTEROIDS
    • C07J73/00Steroids in which the cyclopenta[a]hydrophenanthrene skeleton has been modified by substitution of one or two carbon atoms by hetero atoms
    • C07J73/001Steroids in which the cyclopenta[a]hydrophenanthrene skeleton has been modified by substitution of one or two carbon atoms by hetero atoms by one hetero atom
    • C07J73/003Steroids in which the cyclopenta[a]hydrophenanthrene skeleton has been modified by substitution of one or two carbon atoms by hetero atoms by one hetero atom by oxygen as hetero atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07JSTEROIDS
    • C07J9/00Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Insects & Arthropods (AREA)
  • Agronomy & Crop Science (AREA)
  • Steroid Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Description

Foreliggende oppfinnelse angår nye brassino-steroidderivater, fremgangsmåte for. fremstilling av disse forbindelser såvel som midler med vekstregulerende virkning for planter inneholdende disse forbindelser. The present invention relates to new brassino-steroid derivatives, method for. production of these compounds as well as agents with growth-regulating action for plants containing these compounds.

Fra pollen fra raps ble et plantevekstfremmende steroid - brassinolid - isolert og strukturen ble klarlagt (s. M.D. Grove et al., Nature Vol. 281, 216 (1979)). Den vekstregulerende virkning av denne forbindelse er imidlertid ikke tilfredsstillende. From rapeseed pollen, a plant growth-promoting steroid - brassinolide - was isolated and its structure elucidated (p. M.D. Grove et al., Nature Vol. 281, 216 (1979)). However, the growth-regulating effect of this compound is not satisfactory.

Målet med foreliggende oppfinnelse er å tilveie-bringe nye brassinosteroidderivater som sammenlignet med det kjente konstitusjonsanaloge brassinolid utviser overlegne vekstregulerende egenskaper for planter. The aim of the present invention is to provide new brassinosteroid derivatives which, compared to the known constitutional analogue brassinolide, exhibit superior growth-regulating properties for plants.

Dette mål løses ifølge oppfinnelsen med et middel som er kjennetegnet ved at det inneholder minst én forbindelse av generell formel According to the invention, this objective is solved with an agent which is characterized by the fact that it contains at least one compound of the general formula

hvori R^~ j betegner en Cg-C-^<-a>lkylrest eller en Cg-<C>1Q<->alkenylrest og in which R^~j denotes a Cg-C-^<-a>alkyl radical or a Cg-<C>1Q<->alkenyl radical and

Z betegner gruppen - C - 0 - CH9 - eller - 0 - C - CH9 -,Z denotes the group - C - 0 - CH9 - or - 0 - C - CH9 -,

ii ^ ii z 0 0 ii ^ ii z 0 0

1*2 og R^er enten forskjellig og betegner hydrogen eller en acylrest, eller betegner sammen gruppen 1*2 and R^ are either different and denote hydrogen or an acyl residue, or together denote the group

eller or

hvori X betegner vannstoff, where X denotes hydrogen,

C^-C^-alkyl eller Cj^-C^-alkoxy og Y betegner vannstoff, C^-C^-alkyl, C^-C-j-alkoxy eller aryl. C₁-C₁-alkyl or C₁-C₁- alkoxy and Y denotes hydrogen, C₁-C₁-alkyl, C₁-C₁-j- alkoxy or aryl.

De nye forbindelser opptrer som geometriske isomerer, hvoved -0R2 og -OR^er cis 2a,3a eller cis 23,33-orientert. De enkelte isomerer og deres blandinger faller innen oppfinnelsens ramme. The new compounds act as geometric isomers, whereby -OR2 and -OR2 are cis 2a,3a or cis 23,33-oriented. The individual isomers and their mixtures fall within the scope of the invention.

De nye forbindelser egneri.seg fremragende til regulering av plantevekst av forskjellige nytteplanter og overgår i deres virkningsspekter såvel som i deres forenlig-het på en overraskende måte det tidligere angitte produkt med samme virkningsretning. The new compounds are excellently suitable for regulating plant growth of various useful plants and surpass in their spectrum of action as well as in their compatibility in a surprising way the previously indicated product with the same direction of action.

De nye forbindelser øker den vegetative vekst av nytteplanter, men kan i visse konsentrasjonsområder også hemme denne.Envidere er det mulig å oppnå en viss tilvekst på grunn av innvirkning på den generative fase. The new compounds increase the vegetative growth of useful plants, but in certain concentration ranges can also inhibit this. Furthermore, it is possible to achieve a certain increase due to an impact on the generative phase.

Generelt virker substansene på membransysternet i nytteplanter og endrer dets permeabilitet for forskjellige stoffer. In general, the substances act on the membrane system in useful plants and change its permeability to different substances.

Under bestemte betingelser kan de også gi en anti-strekkvirkning. Under certain conditions, they can also provide an anti-stretch effect.

Da de nye forbindelser såvel kvalitativt som kvantitativt forårsaker endringer på plantene samt også forandringer i plantenes metabolisme, hører de inn under klassen av plantevekstregulatorer som utviser.følgende anvendelsesmuligheter. As the new compounds both qualitatively and quantitatively cause changes in the plants as well as changes in the plants' metabolism, they belong to the class of plant growth regulators which exhibit the following application possibilities.

Hemning av den vegative vekst av treaktige planter og ugress eksempelvis ved veikanter, skinneanlegg og lig-nende, for å unngå en for kraftig vekst. Veksthemning av korn for å unngå legde, og av bomull for å øke utbyttet. Inhibition of the vegetative growth of woody plants and weeds, for example at roadsides, rail installations and the like, to avoid excessive growth. Growth retardation of cereals to avoid late blight, and of cotton to increase yield.

Innvirkning på forgreningen av vegativ.e og generative organer i pryd-^og nytteplanter for å øke blomsterpro-duksjon eller i tobakk og.tomater for å hemme sideskudd. Effect on the branching of vegetative and generative organs in ornamental and useful plants to increase flower production or in tobacco and tomatoes to inhibit side shoots.

Forbedring av fruktkvaliteten, for eksempel en økning i sukkerinnholdet i sukkerrør, sukkerroer eller ved frukt og oppnå en samtidig modning av avlingen som fører til et høyere utbytte. Improving the quality of the fruit, for example an increase in the sugar content of sugar cane, sugar beet or fruit and achieving a simultaneous ripening of the crop leading to a higher yield.

Økning av motstandskraften overfor stress, slik som f.eks. overfor klimåtiske påvirkninger slik som kulde og tørke, men også overfor fytotoksiske påvirkninger av kjemikalier. Increasing resistance to stress, such as e.g. to climatic influences such as cold and drought, but also to phytotoxic effects of chemicals.

Påvirkning av latexstrømmen i gummiplanter. Influence of latex flow in rubber plants.

Dannelse av parthenokarpe frukter, pollensterilitet og arvelighetspåvirkning er andre anvendelsesmuligheter. Formation of parthenocarpic fruits, pollen sterility and influence of heredity are other application possibilities.

Kontroll av spiring av frø eller dannelse av knop-per. Control of seed germination or bud formation.

Avløving eller bivirkning på fruktfall for åDefoliation or adverse effect on fruit drop to

lette innhøstningen.ease the harvest.

De nye forbindelser egner seg særlig til å påvirke den vegetative og generative vekst av enkelte belgfrukter slik som f.eks. soya. The new compounds are particularly suitable for influencing the vegetative and generative growth of certain legumes such as e.g. soy.

Anvendelsesmengdene utgjør alt etter anvendelsesmålet generelt 0,001 til 1 kg virkestoff/ha, men eventuelt kan også større mengder anvendes. Depending on the application target, the application amounts generally amount to 0.001 to 1 kg of active substance/ha, but possibly larger amounts can also be used.

Anvendelsestiden retter seg etter anvendelsesmålet og de klimatiske betingelser. The period of use depends on the purpose of use and the climatic conditions.

Blant de nye forbindelser som utmerkear.' seg ved den beskrevne virkning er særlig slike av generell formel I hvori R,., betegner 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 eller 2,3-dimethyl-heptan-6-yl og Among the new connections that stand out.' themselves by the described effect are particularly those of general formula I in which R,., denotes 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 betegner gruppen Z denotes the group

eller R2og R^er enten forskjellig og betegner hydrogen eller en formylrest, en C2-C7-alkyl-CO-rest, en C-j-C-^-alkoxy-C-^-C-j-alkyl-CO-rest eller en aryl-CO-rest eller betegner sammen gruppen eller or R 2 and R 3 are either different and denote hydrogen or a formyl residue, a C 2 -C 7 -alkyl-CO residue, a C 1 -C 4 -alkyl-CO residue or an aryl CO residue or collectively denotes the group or

hvori X betegner hydrogen, C-^-C^-alkyl eller C-^-C^-alkoxy og Y betegner hydrogen, Ci~C4-alkyl, C-^-C-j-alkoxy eller aryl. in which X denotes hydrogen, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy and Y denotes hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkyl or aryl.

Som Cg-C^Q-alkyl- og alkenylrester kan eksempelvis nevnes 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 og 2,3-dimethyl-heptan-6-yl; arylrester kan bety formylrest, Examples of Cg-C^Q-alkyl and alkenyl residues that can be mentioned are 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 and 2,3-dimethyl-heptan-6-yl; aryl residues can mean formyl residues,

en<C>2<-C>7-alkyl-CG—rest, en C2-C7-alkoxy-C1-C3-alkyl-CO-rest og en aryl-CO-rest, slik som f.eks. acétoxy, methoxyacetoxy, ethoxyacetoxy, propionyloxy, butyryloxy, valeryloxy, pentanoyl-oxy, hexanoyloxy, heptanoyloxy, dimethylacetoxy, diethyl-acetoxy, benzoyloxy og fenylacetoxy. a<C>2<-C>7-alkyl-CG—residue, a C2-C7-alkoxy-C1-C3-alkyl-CO-residue and an aryl-CO-residue, such as e.g. acetoxy, methoxyacetoxy, ethoxyacetoxy, propionyloxy, butyryloxy, valeryloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, dimethylacetoxy, diethylacetoxy, benzoyloxy and phenylacetoxy.

Som C^-C^-alkylrester kan eksempelvis nevnesFor example, C1-C3-alkyl radicals can be mentioned

methyl, ethyl, propyl, isopropyl, butyl, sek.butyl, tert.-butyl og klormethyl; Ci-C^-alkoxyrester er eksempelvis methoxy, ethoxy og propoxy; og som arylrester kan endelig nevnes nafthyl, fenyl, 2-klorfenyl, 3-klorfenyl, 4-klorfenyl, 2,6-diklorfenyl, 2,4-diklorfenyl, 3,4-diklorfenyl, 2,4,6-tri-klorfenyl, 4-bromfenyl-2,4-dibromfenyl, 2,6-dibromfenyl, 2,4,6-tribromfenyl,.2-fluorfenyl, 3-fluorfenyl, 4-fluorfenyl, 2,4-difluorfenyl, 2-methylfenyl, 3-methylfenyl, 4-methylfenyl, 3,4-dimethylfenyl, 2-methoxyfenyl, 3-methoxyfenyl, 4-methoxyfenyl, 3,4-dioxymethylenfenyl, 2-fenoxyfenyl, 3-fenoxyfenyl, 2-nitrofenyl og 3-nitrofenyl. methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl and chloromethyl; C 1 -C 4 -Alkoxy residues are, for example, methoxy, ethoxy and propoxy; and finally naphthyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,6-dichlorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,4,6-tri-chlorophenyl, 4-bromophenyl-2,4-dibromophenyl, 2,6-dibromophenyl, 2,4,6-tribromophenyl,.2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 2-methylphenyl, 3-methylphenyl , 4-methylphenyl, 3,4-dimethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 3,4-dioxymethylenephenyl, 2-phenoxyphenyl, 3-phenoxyphenyl, 2-nitrophenyl and 3-nitrophenyl.

De nye forbindelser kan enten anvendes alene, i blanding med hverandre eller med andre virkestoffer. Eventuelt kan bladfjernende midler, bladbeskyttelsesmidler eller pesticider tilsettes alt etter det ønskede formål. The new compounds can either be used alone, in a mixture with each other or with other active substances. Optionally, defoliating agents, leaf protection agents or pesticides can be added depending on the desired purpose.

Såfremt en utvidelse av virkningsspekteret.taes i betraktning kan også andre biocider tilsettes. Som herbicid virksomme'blandingspartnere egner seg eksempelvis de virkestoffer som er angitt i Weed Abstracts, Vol. 31, 1981, If an extension of the spectrum of action is taken into account, other biocides can also be added. Suitable as herbicidally active 'mixing partners' are, for example, the active substances indicated in Weed Abstracts, Vol. 31, 1981,

under titelen "List of common names and Abbreviations employed for currently used herbicides and plant growth regulators in weed abstracts". I tillegg kan også ikke fytotoksiske midler anvendes som med herbicidene og/eller vekstregulatorene kan gi en synergistisk virkningsøkning, under the title "List of common names and Abbreviations employed for currently used herbicides and plant growth regulators in weed abstracts". In addition, phytotoxic agents cannot be used which with the herbicides and/or growth regulators can give a synergistic increase in effectiveness,

slik som blant annet fuktemidler, emulgatorer, løsningsmid-ler og oljeaktige tilsetningsstoffer. such as, among other things, wetting agents, emulsifiers, solvents and oily additives.

Hensiktsmessig anvendes de nye virkestoffer eller deres blandinger i form.av tilberedelser slik som pulvere, strømidler, granulater, løsninger, emulsjoner eller suspen-sjoner, under tilsetning av flytende og/eller faste bærer-stoffer, henholdsvis fortynningsmidler, og eventuelt under tilsetning av fuktemidler, bindemidler, emulgeringsmidler og/eller dispergeringshjelpemidler. Appropriately, the new active substances or their mixtures are used in the form of preparations such as powders, flow agents, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers, respectively diluents, and possibly with the addition of wetting agents , binders, emulsifiers and/or dispersing aids.

Egnede flytende bærere er f.eks. vann, alifatiskeSuitable liquid carriers are e.g. water, aliphatic

og aromatiske hydrocarboner slik som benzen, toluen, xylen, cyclohexanon, isoforon, dimethylsulfoxyd, dimethylformamid og mineraloljefraksjoner. and aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethylsulfoxide, dimethylformamide and mineral oil fractions.

Som faste bærestoffer egner seg mineraljord slik som f.eks. leirearter, silicagel, talkum, kaolin, attapulkus-leire, kalkstein, kieselsyre og planteprodukter, slik som f.eks. mel. Mineral soil such as e.g. clay species, silica gel, talc, kaolin, attapulkus clay, limestone, silicic acid and plant products, such as e.g. flour.

Som overflateaktive stoffer kan eksempelvis nevnes calciumligninsulfonat, polyoxyethylen-alkylfenolether, nafthalinsulfonsyrer og deres salter, fenolsulfonsyrer og deres salter, formaldehydkondensater, fettalkoholsulfater såvel som substituerte benzensulfonsyrer og deres salter. Examples of surfactants include calcium lignin sulfonate, polyoxyethylene alkyl phenol ether, naphthalene sulfonic acids and their salts, phenol sulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates as well as substituted benzene sulfonic acids and their salts.

Andelen av virkestoffet i de forskjellige tilberedelser kan varierer innen vide grenser. Eksempelvis inneholder midlet 10 til 80 vekt% virkestoff, 90 til 20 vekt% flytende eller faste bærestoffer såvel som opp til 20 vekt% overflateaktive stoffer. The proportion of the active substance in the different preparations can vary within wide limits. For example, the agent contains 10 to 80% by weight of active ingredient, 90 to 20% by weight of liquid or solid carriers as well as up to 20% by weight of surfactants.

Utbringelse av midlet kan skje på vanlig måte, eksempelvis med vann som bærer i sprøytemengder på fra 100 til 1000 liter/ha. En anvendelse av midlet i den såkalte low-volume eller ultra-low-volume-metoden er også mulig såvel som anvendelse i form av såkalte mikrogranulater. Application of the agent can be carried out in the usual way, for example with water carrying spray quantities of from 100 to 1000 litres/ha. Application of the agent in the so-called low-volume or ultra-low-volume method is also possible, as well as application in the form of so-called microgranules.

For fremstilling av tilberedelsene kan eksempelvis følgende bestanddeler anvendes: For the preparation of the preparations, for example, the following ingredients can be used:

A.<g>prøytepulver A.<g>spraying powder

a) 80 vekt% virkestoffa) 80% by weight active substance

15 vekt% kaolin15% by weight kaolin

5 vekt% overflateaktivt stoff på basis av natrium-saltet av N-methyl-N-oleyl-taurin og calciumsaltet av ligninsulfonsyre. 5% by weight surfactant based on the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of ligninsulfonic acid.

b) 50 vekt% virkestoffb) 50% by weight active ingredient

40 vekt% leiremineraler40 wt% clay minerals

5 vekt% cellebek5% by weight cell pitch

.5 vekt% overflateaktivt stoff på basis av fen blanding . av_calciumsalter av ligninsulfonsyre med alkylfenol-polyglykolether. .5% by weight surface-active substance on the basis of fen mixture. of_calcium salts of ligninsulfonic acid with alkylphenol-polyglycol ether.

c) 2 0 vekt% virkestoffc) 20% by weight active ingredient

70 vekt% leiremineraler70% by weight clay minerals

5 vekt% cellebek5% by weight cell pitch

5 vekt% overflateaktivt stoff på basis av en blanding av calciumsalter av ligninsulfonsyre med alkyl-fenolpolyglycolether. 5% by weight surfactant on the basis of a mixture of calcium salts of ligninsulfonic acid with alkyl-phenol polyglycol ether.

d) 5 vekt% virkestoffd) 5% by weight active ingredient

80 vekt% leirearter80% by weight clay species

10 vekt% cellebek10% by weight cell pitch

5 vekt% overflateaktivt stoff på basis av et fett-syrekondensasjonsprodukt. 5% by weight surfactant based on a fatty acid condensation product.

B. EmulsjonskonsentratB. Emulsion concentrate

20 vekt% virkestoff20% by weight active ingredient

4 0 vekt% xylen40% by weight xylene

35 vekt% dimethylsulfoxyd.-35% by weight dimethylsulfoxyd.-

5 vekt% av en blanding av nonylfenylpolyethylen eller calciumdodecylbenzensulfonat. 5% by weight of a mixture of nonylphenyl polyethylene or calcium dodecylbenzene sulphonate.

C. PastaC. Pasta

45 vekt% virkestoff45% by weight active ingredient

5 vekt% natriumaluminiumsilicat5% by weight sodium aluminum silicate

15 vekt% cetylpolyglycolether med 8 mol ethylenoxyd 15% by weight of cetyl polyglycol ether with 8 mol of ethylene oxide

2 vekt% spindelolje2% by weight spindle oil

10 vekt% polyethylenglycol10 wt% polyethylene glycol

23 deler vann.23 parts water.

De nye forbindelser kan eksempelvis fremstilles ved at forbindelser av generell formel The new compounds can, for example, be prepared by compounds of the general formula

omsettes ved osmiumtetroxyd-katalysert hydroxylering med t-butylhydroperoxyd eller med N-methyl-morfolin-N-oxyd til forbindelser av generell formel eller innvirkes av sølvacetat og jod i vandig eddiksyre under dannelse av forbindelser av generell formel reacted by osmium tetroxide-catalyzed hydroxylation with t-butyl hydroperoxide or with N-methyl-morpholine-N-oxide to compounds of general formula or acted upon by silver acetate and iodine in aqueous acetic acid to form compounds of general formula

som behandles med persyrer under dannelse av de ønskede fremgangsmåteprodukter hvori R, -, og R2har de ovenfor angitte betydninger. which is treated with peracids to form the desired process products in which R, -, and R2 have the meanings indicated above.

For fremstilling av forbindelsene av formel I utgår man fra steriner slik som cholesterin, stigmasterin, brassicasterin eller p-sitosterin, og omsetter disse på i og for seg kjent måte til A 2-6-ketosteroider av formel II For the preparation of the compounds of formula I, one starts from sterols such as cholesterin, stigmasterin, brassicasterin or p-sitosterin, and converts these in a manner known per se to A 2-6-ketosteroids of formula II

(In Heiv. 49, 1581 (1966)). (In Heiv. 49, 1581 (1966)).

Den videre omsetning til 2a,3a-cis-glycoler av formel III skjer etter kjente metoder, nemlig osmiumtetroxyd-katalysert hydroxylering med 80 %-ig t-butylhydroperoxyd (K.B. Sharpless JACS 98, 1986 (1976)) eller med N-methyl-morfolin-N-oxyd (V.van Rheen, Tetrahedron Lett. 1976, 1973). The further reaction to 2a,3a-cis-glycols of formula III takes place according to known methods, namely osmium tetroxide-catalyzed hydroxylation with 80% t-butyl hydroperoxide (K.B. Sharpless JACS 98, 1986 (1976)) or with N-methyl-morpholine -N-oxide (V. van Rheen, Tetrahedron Lett. 1976, 1973).

Til 23,3&-cis-glycolene eller deres derivater av formel IV kommer man via Prevost-reaksjonen med sølvacetat og jod i vandig eddiksyre (49, 1581 (1966)). The 23,3&-cis-glycols or their derivatives of formula IV are obtained via the Prevost reaction with silver acetate and iodine in aqueous acetic acid (49, 1581 (1966)).

Fremstilling av B-ringlactonet av formel I skjer ved Baeyer-Villiger-oxydasjon med persyrer slik som trifluor- pereddiksyre, permaursyre, permaleinsyre, etc. av 6-keto-steroidet av formel III og IV. Med forbindelser med en C22~C23~dobbeltbinding i sidekjeden må denne dobbeltbinding beskyttes ved bromering før lactoniseringen. Production of the B-ring lactone of formula I takes place by Baeyer-Villiger oxidation with peracids such as trifluoroperacetic acid, permauric acid, permaleic acid, etc. of the 6-keto steroid of formulas III and IV. With compounds with a C22~C23~ double bond in the side chain, this double bond must be protected by bromination before lactonization.

Etter Baeyer-Villiger-oxydasjonen kan dobbeltbindingen regenereres med sink i eddiksyre. After the Baeyer-Villiger oxidation, the double bond can be regenerated with zinc in acetic acid.

De etterfølgende eksempler illustrerer fremstil-lingen av de nye forbindelser. The following examples illustrate the preparation of the new compounds.

Eksempel 1Example 1

a) 3,56 g 24 S ethyl-5a-cholesta-2,22-dien-6-on ble løst i 6 0 ml t-butanol, 4 ml 20 %-ig tetraethylammoniumhydroxyd-løsning ble tilsatt, blandingen ble avkjølt til 0° C og ble tilsatt 12 ml 80 %-ig t-butylhydroperoxyd og 6 ml a) 3.56 g of 24 S ethyl-5a-cholesta-2,22-dien-6-one was dissolved in 60 ml of t-butanol, 4 ml of 20% tetraethylammonium hydroxide solution was added, the mixture was cooled to 0 ° C and 12 ml of 80% t-butyl hydroperoxide and 6 ml were added

av en osraiumtetroxydløsning (fremstilt fra 250 mg OsO^, 49,75 ml t-butanol og 0,25 ml 80. %-ig t-butylhydroperoxyd) . Reaksjonsløsningen ble omrørt i 6 timer ved romtemperatur, ble helt over i 5 %-ig natriumhydrogensulfitt-løsning og ble ekstrahert med eddikester. Ekstraktet ble vasket med vann, tørket over natriumsulfat og ble inndampet. Etter omkrystallisering fra methylenklorid-methanol ble det erholdt 2,3 g 2a,3a-dihydroxy-24-S-ethyl-5a-cholest-22-en-6-on. of an osraium tetroxide solution (prepared from 250 mg of OsO^, 49.75 ml of t-butanol and 0.25 ml of 80% t-butyl hydroperoxide). The reaction solution was stirred for 6 hours at room temperature, poured into 5% sodium hydrogen sulphite 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,3α-dihydroxy-24-S-ethyl-5α-cholest-22-en-6-one was obtained.

Sm.p. 234,5 - 235,5° C. Sm.p. 234.5 - 235.5° C.

b) 2,2 g 2a,3a-dihydroxy-24-S-ethyl-5a-cholest-22-en-6-on ble løst i 15 ml- pyridin, ble tilsatt 8 ml acetanhydrid b) 2.2 g of 2a,3a-dihydroxy-24-S-ethyl-5a-cholest-22-en-6-one was dissolved in 15 ml of pyridine, 8 ml of acetic anhydride was added

og 22 0 mg 4-dimethylaminopyridin og fikk stå i 17 timer ved 20° C. Deretter ble produktet utfelt i isvann, ble and 220 mg of 4-dimethylaminopyridine and allowed to stand for 17 hours at 20° C. The product was then precipitated in ice water,

fraskilt, vasket.og tørket.separated, washed.and dried.

c) 2,6 g urent diacetat ble i 30 ml ether. og 30 ml iseddik tilsatt 0,28 ml brom og ble omrørt i 10 minutter ved c) 2.6 g of impure diacetate was dissolved in 30 ml of ether. and 30 ml of glacial acetic acid added with 0.28 ml of bromine and was stirred for 10 minutes at

romtemperatur. For opparbeidelsen ble blandingen fortynnet med ether, vasket nøytral med vann og ble inndampet i vakuum. Det ble erholdt 3,2 g urent 2a,3a-diacetoxy-22,2 3-dibrom-24-ethyl-5a-cholestan-6-on. room temperature. For the work-up, the mixture was diluted with ether, washed neutral with water and evaporated in vacuo. 3.2 g of impure 2a,3a-diacetoxy-22,2-3-dibromo-24-ethyl-5a-cholestan-6-one were obtained.

d) 4,5 ml 30 %-ig hydrogenperoxyd ble suspendert i 28 ml methylenklorid, ble avkjølt til -10° C og ble langsomt d) 4.5 ml of 30% hydrogen peroxide was suspended in 28 ml of methylene chloride, was cooled to -10° C and slowly

dråpevis tilsatt 27,7 ml trifluoreddiksyreanhydrid slik at temperaturen ikke oversteg +10° C. Deretter ble 27.7 ml of trifluoroacetic anhydride were added dropwise so that the temperature did not exceed +10° C. Then

3,2 g 2a,3a-diacetoxy-22,23-dibrom-24-ethyl-5a-cholestan-6-on løst i 25 ml methylenklorid tilsatt, og blandingen ble omrørt i 40 minutter ved romtemperatur. Reaksjonsblandingen ble deretter fortynnet med methylenklorid og vasket med vann, 5 %-ig natriumcarbonatløsning og med vann, ble tørket og inndampet i vakuum. Residuet ble i 100 ml eddiksyre oppvarmet med 5 g sinks.tøv i 1 time på dampbad. Sink/ble frafiltrert og blandingen ble fortynnet med methylenklori.d og vasket nøytral med vann og inndampet. Etter kromatografi.på silicagel (gradient-elueringrtoluen-eddikester) og krystallisering fra aceton-hexan ble det erholdt 1,5 g 2a,3a-diacetoxy-24-ethyl-7-oxa-B-horao-5a-cholest-22-6-on, sm.p. 221 - 223°C og 310 mg ,2a,3a-diacetoxy-24-ethyl-6-oxa-B-homo-5a-cholest-22-en-7-on, sm.p. 202 - 204° C. 3.2 g of 2a,3a-diacetoxy-22,23-dibromo-24-ethyl-5a-cholestan-6-one dissolved in 25 ml of methylene chloride was added, and the mixture was stirred for 40 minutes at room temperature. The reaction mixture was then diluted with methylene chloride and washed with water, 5% sodium carbonate solution and with water, was dried and evaporated in vacuo. The residue was heated in 100 ml of acetic acid with 5 g of zinc dust for 1 hour on a steam bath. Zinc was filtered off and the mixture was diluted with methylene chloride and washed neutral with water and evaporated. After chromatography on silica gel (gradient-elution-toluene-acetic ester) and crystallization from acetone-hexane, 1.5 g of 2a,3a-diacetoxy-24-ethyl-7-oxa-B-horao-5a-cholest-22-6 was obtained -on, sm.p. 221 - 223°C and 310 mg of ,2a,3a-diacetoxy-24-ethyl-6-oxa-B-homo-5a-cholest-22-en-7-one, m.p. 202 - 204°C.

Eksempel 2Example 2

a) Til en løsning av 2 g 24-ethyl-5a-cholesta-2,22-dien-6-on i 270 ml iseddik og 3,7 ml vann ble tilsatt 3,2 g a) To a solution of 2 g of 24-ethyl-5a-cholesta-2,22-dien-6-one in 270 ml of glacial acetic acid and 3.7 ml of water was added 3.2 g

sølvacetat og 1,9 g jod, og blandingen ble oppvarmet til 4 5° C under omrøring i 3 timer. Etter avfiltrering av silver acetate and 1.9 g of iodine, and the mixture was heated to 45°C with stirring for 3 hours. After filtering off

sølvsaltet, vasking med kloroform ble filtratet fortynnet med kloroform og ble vasket med vann, natriumthiosulfat og vann, ble tørket og inndampet. Etter krystallisering fra aceton-hexan ble det erholdt.1,2 g 23-acetoxy-33-hydroxy-2 4-ethyl-5a-cholest-22-en-6-on. the silver salt, washing with chloroform, the filtrate was diluted with chloroform and was washed with water, sodium thiosulfate and water, was dried and evaporated. After crystallization from acetone-hexane, 1.2 g of 23-acetoxy-33-hydroxy-2 4-ethyl-5a-cholest-22-en-6-one was obtained.

Sm.p. 192 - 194° C. Sm.p. 192 - 194° C.

b) Etter bromering av A 22-dobbeltbindingen, Baeyer-Villiger-oxydasjon og sinkreduksjon slik som beskrevet i Eksempel b) After bromination of the A 22 double bond, Baeyer-Villiger oxidation and zinc reduction as described in Example

lc) og ld) ble råproduktet kromatografert på silicagel. lc) and ld) the crude product was chromatographed on silica gel.

Ved hjelp av gradienteluering med kloroform-aceton ble det etter omkrystallisering fra hexan-ether erholdt.i 75 %-ig utbytte 23-acetoxy-33-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-on, sm.p. 151 - 153° C og i 10 %-ig utbytte 23-acetoxy-33_hydroxy-24-ethyl-6-oxa-B-homo-5a-cholest-22-en-7-on, sm.p. 175 - 176° C. Using gradient elution with chloroform-acetone, after recrystallization from hexane-ether, 23-acetoxy-33-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22- en-6-one, m.p. 151 - 153° C and in 10% yield 23-acetoxy-33_hydroxy-24-ethyl-6-oxa-B-homo-5a-cholest-22-en-7-one, m.p. 175 - 176° C.

Eksempel 3Example 3

a) 2,2 g 23-acetoxy-33-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-on ble i 50 ml methanol tilsatt en løs- ning av 500 mg kaliumhydroxyd i 10 ml methanol, og blandingen ble omrørt i 30 minutter ved romtemperatur. Blandingen ble surgjort med eddiksyre, produktet ble utfelt i isvann, fraskilt, vasket og tørket. Etter krystallisering fra kloroform-ether ble det erholdt 1,7 g 23,33-dihydroxy-2 4-ethyl-7-oxa-B-homo-5a-cholest-22-en-6 -on. a) 2.2 g of 23-acetoxy-33-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one was added to 50 ml of methanol to a solution of 500 mg potassium hydroxide in 10 ml of methanol, and the mixture was stirred for 30 minutes at room temperature. The mixture was acidified with acetic acid, the product was precipitated in ice water, separated, washed and dried. After crystallization from chloroform-ether, 1.7 g of 23,33-dihydroxy-2 4-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one was obtained.

Sm.p. 211 - 213° C. Sm.p. 211 - 213° C.

b) 500 mg .23/33-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22- en-6-on ble i 4 ml pyridin avkjølt til -10° C tilsatt b) 500 mg of .23/33-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one was added in 4 ml of pyridine cooled to -10° C

0,5 ml acetanhydrid og blandingen ble omrørt i 3,5 time ved -5 til fl°.C. Etter utfelling med isvann, separering av produktet, vasking og tørking ble dette omkrystallisert fra aceton-hexan. Det ble erholdt. 410. mg 33acetoxy-23- hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-on. 0.5 ml of acetic anhydride and the mixture was stirred for 3.5 hours at -5 to fl°. After precipitation with ice water, separation of the product, washing and drying, this was recrystallized from acetone-hexane. It was obtained. 410. mg 33-acetoxy-23-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one.

Sm.p. 182 - 184° C. Sm.p. 182 - 184° C.

Eksempel 4Example 4

1 g 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-on ble løst i 10 ml pyridin, ble avkjølt til 0° C og ble tilsatt 1 ml acetanhydrid. Blandingen ble omrørt i 5 timer ved 0 - 5° C, ble helt over i isvann, produktet ble fraskilt, vasket og tørket. Etter omkrystallisering fra pentan ble det erholdt 950 mg 2a-acetoxy-3a-hydroxy-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 165,5 - 167° C. 1 g of 2α,3α-dihydroxy-7-oxa-B-homo-5α-cholestan-6-one was dissolved in 10 ml of pyridine, cooled to 0° C. and 1 ml of acetic anhydride was added. The mixture was stirred for 5 hours at 0 - 5° C, poured into ice water, the product was separated, washed and dried. After recrystallization from pentane, 950 mg of 2α-acetoxy-3α-hydroxy-7-oxa-B-homo-5α-cholestan-6-one, m.p. 165.5 - 167° C.

Fremstilling av utgangsmaterialer:Preparation of starting materials:

a) 25 g 5a-cholest-2-en-6-on ble løst i 140 ml tetrahydrofuran, ble tilsatt 14 g N-methylmorfolin-N-oxyd, 25 ml a) 25 g of 5α-cholest-2-en-6-one was dissolved in 140 ml of tetrahydrofuran, 14 g of N-methylmorpholine-N-oxide, 25 ml

vann og 50 ml t-butanol og under omrøring en løsning avwater and 50 ml of t-butanol and, while stirring, a solution of

250 mg.osmiumtetroxyd i 50 ml tetrahydrofuran. Reaksjons-løsningen ble omrørt i 17 timer ved romtemperatur under ute-lukkelse av lys. Deretter ble produktet utfelt i 7 liter isvann som var blitt- tilsatt 50 ml 2N svovelsyre og 1 g natriumsulfid, produktet ble fraskilt, vasket med vann, ble oppløst i kloroform og løsningen ble inndampet i vakuum. Råproduktet (30 g). ble løst i 140 ml pyridin, og etter tilsetning av 70 ml acetanhydrid og 3 g 4-dimethylaminopyridin fikk blandingen stå i 16 timer ved romtemperatur. Etter vannutfelling, separering av produktet, vasking med vann og 250 mg osmium tetroxyd in 50 ml tetrahydrofuran. The reaction solution was stirred for 17 hours at room temperature under exclusion of light. The product was then precipitated in 7 liters of ice water to which 50 ml of 2N sulfuric acid and 1 g of sodium sulphide had been added, the product was separated, washed with water, dissolved in chloroform and the solution evaporated in vacuo. The raw product (30 g). was dissolved in 140 ml of pyridine, and after adding 70 ml of acetic anhydride and 3 g of 4-dimethylaminopyridine, the mixture was allowed to stand for 16 hours at room temperature. After water precipitation, separation of the product, washing with water and

tørking ble dette kromatografert på silicagel. Etter omkrystallisering fra ethanol ble det i 75 %-ig utbytte erholdt 2a,3a-diacetoxy-5a-cholestan-6-on, sm.p. 150,0 - drying, this was chromatographed on silica gel. After recrystallization from ethanol, 2a,3a-diacetoxy-5a-cholestan-6-one was obtained in 75% yield, m.p. 150.0 -

151,5° C og i 15 % utbytte 23,3&-diacetoxy-5a-cholestan-6-on, sm.p. 183,5 - 185° C. b) 26 ml 30 %-ig hydrogenperoxyd ble. suspendert i methylenklorid, ble avkjølt til -10° C hvorpå 161 ml trifluoreddiksyreanhydrid langsomt ble dråpevis tilsatt .slik at temperaturen ikke oversteg +10° C. • Deretter ble 2 7,2 g 2a,3a-diacetoxy-5a-cholestan-6-on i 160 ml methylenklorid tilsatt og blandingen ble omrørt i 40 minutter ved romtemperatur. For opparbeidelse ble reaksjonsblandingen fortynnet med methylenklorid og vasket med vann, 5 %-ig natriumcarbo-natløsning og med vann og ble inndampet i vakuum. Etter kromatografi på silicagel og omkrystallisering fra aceton-hexan ble det i 81 % utbytte erholdt 2a,3a-diacetoxy-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 183 - 184° C og i 6,2 % utbytte 2a,3a-diacetoxy-6-oxa-B-homp-5a-cholestan-7-on, 151.5° C and in 15% yield 23,3β-diacetoxy-5α-cholestan-6-one, m.p. 183.5 - 185° C. b) 26 ml of 30% hydrogen peroxide was. suspended in methylene chloride, was cooled to -10° C, whereupon 161 ml of trifluoroacetic anhydride was slowly added dropwise, so that the temperature did not exceed +10° C. • Then 2 7.2 g of 2a,3a-diacetoxy-5a-cholestane-6- on in 160 ml of methylene chloride added and the mixture was stirred for 40 minutes at room temperature. For work-up, the reaction mixture was diluted with methylene chloride and washed with water, 5% sodium carbonate solution and with water and was evaporated in vacuo. After chromatography on silica gel and recrystallization from acetone-hexane, 2a,3a-diacetoxy-7-oxa-B-homo-5a-cholestan-6-one was obtained in 81% yield, m.p. 183 - 184° C and in 6.2% yield 2a,3a-diacetoxy-6-oxa-B-homp-5a-cholestan-7-one,

sm.p. 245 - 247° C. sm.p. 245 - 247° C.

c) 28,3 g 2a,3a-diacetoxy-7-oxa-B-homo-5a-cholestan-6-on ble løst i 500 ml methanol og etter tilsetning av en c) 28.3 g of 2a,3a-diacetoxy-7-oxa-B-homo-5a-cholestan-6-one was dissolved in 500 ml of methanol and after the addition of a

løsning av 14 g kaliumhydroxyd i 150 ml methanol ble blandingen omrørt i 30 minutter ved romtemperatur. Reaksjons-løsningen ble deretter surgjort med eddiksyre, ble utfelt med isvann, produktet ble fraskilt, vasket med vann og tørket. Etter omkrystallisering fra aceton-pentan ble det erholdt 22,4 g (95 %) 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 138 - 140° C. solution of 14 g of potassium hydroxide in 150 ml of methanol, the mixture was stirred for 30 minutes at room temperature. The reaction solution was then acidified with acetic acid, precipitated with ice water, the product was separated, washed with water and dried. After recrystallization from acetone-pentane, 22.4 g (95%) of 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-one were obtained, m.p. 138 - 140° C.

Eksempel 5Example 5

a) 1,1 g 2a,3a-diacetoxy-6-oxa-B-homo-5a-cholestan-7-oh ble som beskrevet i Eksempel 4c) forsåpet. Det ble a) 1.1 g of 2a,3a-diacetoxy-6-oxa-B-homo-5a-cholestan-7-oh was saponified as described in Example 4c). It was

erholdt 785 mg 2a,3a-dihydroxy-6-oxa-B-homo-5a-chole-stan-7-on med sm.p. 216,5 - 218° C. obtained 785 mg of 2a,3a-dihydroxy-6-oxa-B-homo-5a-chole-stan-7-one with m.p. 216.5 - 218° C.

b) 25 0 mg 2a,3a-dihydroxy-6-oxa-B-homo-5a-cholestan-7-orT ble løst i 2 ml pyridin, ble avkjølt til -10° C, ble b) 250 mg of 2a,3a-dihydroxy-6-oxa-B-homo-5a-cholestan-7-orT was dissolved in 2 ml of pyridine, was cooled to -10° C, was

tilsatt 0,24 ml acetanhydrid og ble omrøtt i 4 timer ved added 0.24 ml of acetic anhydride and was stirred for 4 hours at

-5 til 0° C. Etter utfelling med isvann, separering av produktet, vasking og tørking ble dette omkrystallisert -5 to 0° C. After precipitation with ice water, separation of the product, washing and drying, this was recrystallized

fra aceton-hexan. Det ble erholdt 210 mg 2a-acetoxy-3a-hydroxy-6-oxa-B-homo-'5a-cholestan-7-on, sm.p. 199 - from acetone-hexane. 210 mg of 2a-acetoxy-3a-hydroxy-6-oxa-B-homo-'5a-cholestan-7-one were obtained, m.p. 199 -

201° C. 201°C.

Eksempel 6Example 6

600 mg 2a,3a-dihydroxy-24-methyl-6-oxa-B-homo-5a-cholest-22-en-7-on ble acetylert som beskrevet i Eksempel 5 b). Det ble erholdt 515 mg 2a-acetoxy-3a-hydroxy-24-methyl-6-oxa-B-homo-5a-cholest-22-en-7-on, sm.p. 173 - 174°C. Fremstilling av utgangsmaterialer: Fra brassicasterin ble etter kjente metoder 24-methyl-5a-cholesta-2/22^.dien-6-on fremstilt, og dette ble omsatt som beskrevet i Eksempel 1. 600 mg of 2a,3a-dihydroxy-24-methyl-6-oxa-B-homo-5a-cholest-22-en-7-one was acetylated as described in Example 5 b). 515 mg of 2α-acetoxy-3α-hydroxy-24-methyl-6-oxa-B-homo-5α-cholest-22-en-7-one were obtained, m.p. 173 - 174°C. Preparation of starting materials: 24-methyl-5a-cholesta-2/22^.dien-6-one was prepared from brassicasterin according to known methods, and this was reacted as described in Example 1.

Eksempel 7Example 7

1 g 2(3,3f}-dihydroxy-7-oxa-B-homo-5a-cholestan-6-on ble løst i 100 ml aceton og 100 ml tetrahydrofuran, ble avkjølt til 0° C, ble tilsatt 0,5 ml bortrifluorid-etherat og ble omrørt i 30.minutter ved 0 til 5° C. Etter tilsetning av 1 ml pyridin ble blandingen inndampet i. vakuum og produktet ble omkrystallisert fra methylenklorid-isopropylether. 1 g of 2(3,3f}-dihydroxy-7-oxa-B-homo-5a-cholestan-6-one was dissolved in 100 ml of acetone and 100 ml of tetrahydrofuran, was cooled to 0° C, was added 0.5 ml boron trifluoride etherate and was stirred for 30 minutes at 0 to 5° C. After addition of 1 ml of pyridine, the mixture was evaporated in vacuo and the product was recrystallized from methylene chloride-isopropyl ether.

Det ble erholdt 731 mg 23,33-isopropylidendioxy-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 216 - 217° C. 731 mg of 23,33-isopropylidenedioxy-7-oxa-B-homo-5a-cholestan-6-one were obtained, m.p. 216 - 217° C.

På analog måte.ble fremstilt: In an analogous way.was produced:

2a,3a-isopropylidendioxy-7-oxa-B-homo-5a-cholestan-6-on,2a,3a-isopropylidenedioxy-7-oxa-B-homo-5a-cholestan-6-one,

sm.p. 216 - 217° C. sm.p. 216 - 217° C.

2a,3a-isopropylidendioxy-2 4-ethyl-7-oxa-B-homo-5a-cholestan-22-en-6-on, sm.p. 157 - 158° C. 2α,3α-isopropylidenedioxy-2 4-ethyl-7-oxa-B-homo-5α-cholestan-22-en-6-one, m.p. 157 - 158° C.

Eksempel 8Example 8

900 mg 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-on ble løst i 10 ml pyridin, ble avkjølt til 0° C, ble tilsatt 1,8 ml valeriansyreanhydrid og ble omrørt i 10 timer ved 0 til 5° C. Etter opparbeidelse som teskrevet i Eksempel 4 ble det erholdt 950 mg 2a-valeryloxy-3a-hydroxy-7-oxa-B-homo-5a-cholestan-6-on,sm.p. 92 - 94° C. 900 mg of 2α,3α-dihydroxy-7-oxa-B-homo-5α-cholestan-6-one was dissolved in 10 ml of pyridine, cooled to 0° C, 1.8 ml of valeric anhydride was added and stirred for 10 hours at 0 to 5° C. After work-up as described in Example 4, 950 mg of 2a-valeryloxy-3a-hydroxy-7-oxa-B-homo-5a-cholestan-6-one, m.p. 92 - 94° C.

Eksempel 9Example 9

2a,3a-diacetoxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-on ble forsåpet som beskrevet i Eksempel 3 og ble partielt acetylert. Det ble i 70 %-ig utbytte erholdt 2a-acetoxy-3a-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-on, sm.p. 158 - 160° C. 2α,3α-diacetoxy-24-ethyl-7-oxa-B-homo-5α-cholest-22-en-6-one was saponified as described in Example 3 and was partially acetylated. 2α-acetoxy-3α-hydroxy-24-ethyl-7-oxa-B-homo-5α-cholest-22-en-6-one was obtained in 70% yield, m.p. 158 - 160° C.

Eksempel 10Example 10

900 mg 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-on ble løst i 10 ml pyridin, ble avkjølt til 0° C, ble tilsatt 1 ml ethoxyeddiksyreanhydrid og ble omrørt i 5 timer ved 0 — 5° C. Etter opparbeidelse som beskrevet i Eksempel 4 ble" det etter omkrystallisering. fra aceton-hexan erholdt 720 mg 2a-e±hoxyacetoxy-3a-hydroxy-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 172 - 173° C. 900 mg of 2α,3α-dihydroxy-7-oxa-B-homo-5α-cholestan-6-one was dissolved in 10 ml of pyridine, cooled to 0° C, 1 ml of ethoxyacetic anhydride was added and stirred for 5 hours at 0 — 5° C. After working up as described in Example 4, after recrystallization from acetone-hexane, 720 mg of 2a-e±hoxyacetoxy-3a-hydroxy-7-oxa-B-homo-5a-cholestan-6-one were obtained , mp 172 - 173° C.

Eksempel 11Example 11

300 mg 2a,3a-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-on ble i 3 ml pyridin omrørt med 780 mg fenyleddiksyreanhydrid i 10 timer ved 0 - 5° C. Etter opparbeidelse og omkrystallisering fra aceton-hexan.ble det erholdt 210 mg 2a-fenylacetoxy-3a-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-ren-6-on, sm.p- 185 - 186° C. 300 mg of 2a,3a-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one was stirred in 3 ml of pyridine with 780 mg of phenylacetic anhydride for 10 hours at 0 - 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-ren-6-one were obtained, m.p. - 185 - 186° C.

Eksempel 12Example 12

500 mg 2a, 3a-dihydroxy-7-oxa-B-homio-5a-cholestan-6-on ble i 50 ml benzen tilsatt 0,75 ml triethylorthoeddiksyre-ester og 5 mg p-toluensulfonsyre. Løsningen ble omrørt i 20 minutter ved romtemperatur, ble tilsatt 3 dråper pyridin og ble inndampet i vakuum. Residuet ble løst i methylenklorid, ble vasket med vann, tørket over natriumsulfat og inndampet. Det ble erholdt 605 mg 2a,3a-(1-ethoxy-ethylendioxy)-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 150 - 154° C. 500 mg of 2a, 3a-dihydroxy-7-oxa-B-homio-5a-cholestan-6-one was added to 50 ml of benzene, 0.75 ml of triethyl orthoacetic acid ester and 5 mg of p-toluenesulfonic acid. The solution was stirred for 20 minutes at room temperature, 3 drops of pyridine were added and evaporated in vacuo. The residue was dissolved in methylene chloride, washed with water, dried over sodium sulfate and evaporated. 605 mg of 2a,3a-(1-ethoxy-ethylenedioxy)-7-oxa-B-homo-5a-cholestan-6-one were obtained, m.p. 150 - 154° C.

På analog måte ble fremstilt: 2a,3a-(1-ethoxy-ethylendioxy)-6-oxa-B-homo-5a-cholestan-7-on In an analogous manner was prepared: 2a,3a-(1-ethoxy-ethylenedioxy)-6-oxa-B-homo-5a-cholestan-7-one

sm.p. 122 - 124° C, sm.p. 122 - 124° C,

2a,3a-(1-ethoxy-propylidendioxy)-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 115 - 118° C, 22,3a- (1-methoxy-methylendioxy)-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-on, sm.p. 123 - 125° C. 2α,3α-(1-ethoxy-propylidenedioxy)-7-oxa-B-homo-5α-cholestan-6-one, m.p. 115 - 118° C, 22,3a-(1-methoxy-methylenedioxy)-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one, m.p. 123 - 125° C.

Eksempel 13Example 13

500 mg 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-on ble i 5 ml tetrahydrofuran tilsatt 1,5 ml acetofenon og 0,1 ml bortrifluorid-etherat og ble oppvarmet i 3 timer til tilbakeløpskokning. Deretter ble løsningen inndampet i vakuum, 1 ml pyridin ble tilsatt, og løsningen ble inndampet i høyvakuum. Etter triturering med hexan ble det erholdt 500 mg of 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-one was added to 5 ml of tetrahydrofuran, 1.5 ml of acetophenone and 0.1 ml of boron trifluoride etherate and heated for 3 hours to reflux . Then the solution was evaporated in vacuo, 1 ml of pyridine was added, and the solution was evaporated in high vacuum. After trituration with hexane, it was obtained

465 mg amorft 2a,3a-(1-methyl-l-fenyl-methylendioxy)-7-oxa-B-homo-5a-cholestan-6-on som diastereoraer blanding med smeltepunkt 130,5 - 132° C. 465 mg of amorphous 2a,3a-(1-methyl-1-phenyl-methylenedioxy)-7-oxa-B-homo-5a-cholestan-6-one as diastereomeric mixture with melting point 130.5 - 132° C.

Eksempel 14Example 14

500 mg 2a,3a-dihydroxy-7-oxa-B-horao-5a-cholestan-6-on ble løst i 15 ml diethylcarbonat, ble oppvarmet til kokning og etter avdestillering av 2 ml diethylcarbonat ble 30 mg natriummethylat tilsatt. Fra reaksjonsløsningen ble noen ml avdestillert i løpet av 3 minutter. Etter avkjøling ble reaksjonsløsningen tilsatt 0,15 ml iseddik og ble inndampet i vakuum. Residuet ble omkrystallisert fra aceton-hexan. Det ble erholdt 450 mg 2a,3a-carbonyldioxy-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 203,5 - 205° C. 500 mg of 2a,3a-dihydroxy-7-oxa-B-horao-5a-cholestan-6-one was dissolved in 15 ml of diethyl carbonate, heated to boiling and after distilling off 2 ml of diethyl carbonate, 30 mg of sodium methylate was added. A few ml were distilled from the reaction solution within 3 minutes. After cooling, 0.15 ml of glacial acetic acid was added to the reaction solution and evaporated in vacuo. The residue was recrystallized from acetone-hexane. 450 mg of 2a,3a-carbonyldioxy-7-oxa-B-homo-5a-cholestan-6-one were obtained, m.p. 203.5 - 205° C.

På analog måte ble fremstilt: 2a,3a-carbonyldioxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-on, sm.p. 193 - 195° C In an analogous manner was prepared: 2a,3a-carbonyldioxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one, m.p. 193 - 195° C

23,33-carbonyldioxy-7-oxa-B-homo-5a-cholestan-6-on,23,33-carbonyldioxy-7-oxa-B-homo-5a-cholestan-6-one,

sm.p. 212 - 214° C sm.p. 212 - 214° C

Eksempel 15Example 15

300 mg 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-on ble løst i 2 ml benzaldehyd, 0,02 ml 70 %-ig perklor-syre ble tilsatt og blandingen ble omrørt i 2 timer ved romtemperatur. Deretter ble løsningen nøytralisert med pyridin, ble fortynnet med hexan og kromatografert over silicagel. Med hexan-eddikester (6:4) ble det eluert 258 mg 2a, 3a-benzylidendioxy-7-oxa-B-homo-5a-cholestan-6-on som ble omkrystallisert fra ether-pentan. Sm.p. 137 - 139° C. 300 mg of 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-one was dissolved in 2 ml of benzaldehyde, 0.02 ml of 70% perchloric acid was added and the mixture was stirred for 2 hours at room temperature. The solution was then neutralized with pyridine, diluted with hexane and chromatographed over silica gel. With hexane-acetic ester (6:4) 258 mg of 2a,3a-benzylidenedioxy-7-oxa-B-homo-5a-cholestan-6-one were eluted, which was recrystallized from ether-pentane. Sm.p. 137 - 139° C.

På analog måte ble fremstilt: In an analogous way, the following was produced:

2a,3a-benzylidendioxy-6-oxa-B-homo-5a-cholestan-7-on,2a,3a-benzylidenedioxy-6-oxa-B-homo-5a-cholestan-7-one,

sm.p. 179 - 180° C, sm.p. 179 - 180° C,

23/33-benzylidendioxy-6-oxa-B-homo-5a-cholestan-7-on, 23/33-benzylidenedioxy-6-oxa-B-homo-5a-cholestan-7-one,

sm.p. 129 - 131° C sm.p. 129 - 131° C

23,33-benzylidendioxy-7-oxa-B-homo-5a-cholestan-6-on-23,33-benzylidenedioxy-7-oxa-B-homo-5a-cholestan-6-one-

sm.p. 153 - 155° C sm.p. 153 - 155° C

De nye forbindelser utgjør krystallinske farve- og luktløse substanser som er tungt løselige i vann, betinget løselige i alifatiske hydrocarboner slik som petrolether, hexan, pentan og cyclohexan, godt løselige i halogenerte hydrocarboner slik som kloroform, methylenklorid, tetra-klorcarbon, aromatiske hydrocarboner slik som benzen, toluen og xylen, ethere slik som diethylether, tetrahydrofuran og dioxan, carboxylsyrenitriler slik som acetonitril,. ketoner slik som aceton, alkoholer slik som methanol og ethanol, carboxylsyreamider slik som dimethylformamid og sulfoxyder slik som dimethylsulfoxyd. The new compounds are crystalline, colorless and odorless substances that are poorly soluble in water, conditionally soluble in aliphatic hydrocarbons such as petroleum ether, hexane, pentane and cyclohexane, well soluble in halogenated hydrocarbons such as chloroform, methylene chloride, tetrachlorocarbon, aromatic hydrocarbons such as such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane, carboxylic acid nitriles such as acetonitrile,. ketones such as acetone, alcohols such as methanol and ethanol, carboxylic acid amides such as dimethylformamide and sulfoxides such as dimethylsulfoxyd.

De etterfølgende eksempler illustrerer anvendelses-mulighetene for de nye forbindelser, i form av de tidligere angitte tilberedelser. The following examples illustrate the application possibilities for the new compounds, in the form of the previously indicated preparations.

Eksempel 16Example 16

Vekstøkning av buskbønner.Growth of bush beans.

Buskbønner av sorten "Pinto" ble dyrket i klima-kammer ved 25° C og 90 % luftfuktighet under innvirkning av lys med en høy andel av intensitet i. området.660 nm og en meget lav andel i området 730 nm. Bush beans of the variety "Pinto" were grown in climate chambers 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.

Etter 6 dagers dyrkning ble 10 og 20 mikrogram av de forbindelser som skulle prøves, oppløst i løsningsmidlet, og påført på det utviklende andre internodium. 3 dager etter påføring ble økningen av internodiene målt og den prosentuelle forlengelse bestemt i sammenligning med kontrollen. After 6 days of cultivation, 10 and 20 micrograms of the compounds to be tested were dissolved in the solvent and applied to the developing second internode. 3 days after application, the increase of the internodes was measured and the percentage elongation determined in comparison with the control.

Tabellen inneholder resultatene av disse forsøk. The table contains the results of these experiments.

Resultatene viser at de nye forbindelser under de angitte prøvebetingelser"utviser en mer intensiv strekning enn sammenligningsmidlet og kontrollen. The results show that the new compounds under the specified test conditions exhibit a more intensive stretch than the comparator and the control.

Sammenligningsmidlet forårsaker ennvidere bare en mer eller mindre sterk økning av tykkelsesveksten, hvilket til og med delvis fører til en sammenpresning av internodiene. The comparator further only causes a more or less strong increase in thickness growth, which even partially leads to a compression of the internodes.

Eksempel 17Example 17

Stimulering av rotvekst ved mungbønner.Stimulation of root growth in mung beans.

Mungbønner ble under veksthusbetingelser bragt til spiring i vandige emulsjoner av de forbindelser som skulle prøves i en konsentrasjon på 0,01 vekt%. Under greenhouse conditions, mung beans were germinated in aqueous emulsions of the compounds to be tested in a concentration of 0.01% by weight.

Etter 6 dager ble rotlengden av de spirede planter bestemt. After 6 days, the root length of the germinated plants was determined.

Tabellen inneholder resultatene av disse forsøk i form av prosentangivelser. The table contains the results of these trials in the form of percentages.

Eksempel 18 Example 18

Økning av motstandskraften i nytteplanter.Increasing the resilience of useful plants.

De i tabellen angitte nytteplanter ble ved pre-emergensmetoden behandlet med vandige emulsjoner av de forbindelser som skulle prøves eller deres blandinger. En uke etter behandlingen ble behandlingsresultatet vurdert etter et skjema.fra 0 til 10, hvori 0 = 100 %-ig tilintetgjørelse og 10 = ingen beskadigelse. The useful plants indicated in the table were treated by the pre-emergence method with aqueous emulsions of the compounds to be tested or their mixtures. One week after the treatment, the treatment result was assessed according to a form from 0 to 10, where 0 = 100% destruction and 10 = no damage.

Det fremgår at de nye forbindelser gir plantene en høyere motstandskraft enn det kjente herbicid. It appears that the new compounds give the plants a higher resistance than the known herbicide.

Claims (8)

1. Brassinosteroid-derivater av generell formel 1. Brassinosteroid derivatives of general formula hvoriin which <R>^7 be tegner en Cg-C^ g-alkylrest eller en Cg-C^Q -alkenylrést og Z betegner gruppen <R>^7 be denotes a Cg-C^g-alkyl residue or a Cg-C^Q-alkenyl residue and Z denotes the group eller or R2 og R^ er enten forskjellige og betegner, hydrogen eller en acylrest, eller betegner sammen gruppen R 2 and R 1 are either different and denote hydrogen or an acyl residue, or together denote the group eller or hvori X betegner hydrogen, C-^ -C^ -alkyl eller C-^-C-^-alkoxy og Y betegner hydrogen, C^ -C^ -alkyl, C^ -C^ -alkoxy eller aryl.in which X denotes hydrogen, C-^-C^-alkyl or C-^-C-^-alkoxy and Y denotes hydrogen, C₁ -C₁ -alkyl, C₁ -C₂ -alkyloxy or aryl. 2. Brassinosteroid-derivater ifølge krav 1, karakterisert ved at R17 er 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 eller 2,3-dimethyl-heptan- S-yl og Z er gruppen 2. Brassinosteroid derivatives according to claim 1, characterized in that R17 is 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- S-yl and Z are the group eller or R2 og R^ er enten forskjellige og betegner hydrogen eller en formylrest, C2~<C>7 -alkyl-CO-rest, C2 -C7 -alkoxy-C1 -C3 -alkyl-CO-rest eller en aryl-CO-rest, eller betegner sammen gruppen R2 and R^ are either different and denote hydrogen or a formyl residue, C2~<C>7 -alkyl-CO-residue, C2-C7 -alkyl-C1-C3 -alkyl-CO-residue or an aryl-CO-residue, or together denote the group eller or hvori X betegner hydrogen, C-j^-C^-alkyl eller C-^-C-j-alkoxy og Y betegner hydrogen, C-^ C^ -alkyl, c^ -C^ -alkoxy eller aryl.where X denotes hydrogen, C 1 -C 4 -alkyl or C 1 -C 1 -alkyl and Y denotes hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or aryl. 3. Brassinosteroid-derivater ifølge krav 1, karakterisert ved at disse er 2a,3a-diacetoxy-2 4-ethyl-7-oxa-B-homo-5a-cholest-2 2-en-6-on, 2a, 3a-diacetoxy-2 4-ethyl-6-oxa-B-hoino-5a-cholest-22-en-7-on, 23-acetoxy-33-hydroxy-2 4-ethyl-7-oxa-B-homo-5a-cholest-22- en-7-on, 33-acétoxy-33-hydroxy-2 4-ethyl-6-oxa-B-homo-5a-cholest-22- en-7-on, 33-acetoxy-23-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22- en-6-on, 2a-acetoxy-3a-hydroxy-7-oxa-B-homo-5a-cholestan-6-on, 2a-acetoxy-3a-hydroxy-6-oxa-B-homo-5a-cholestan-7-on, 2a-acétoxy-3a-hydroxy-24-methyl-6-oxa-B-homo-5a-cholest-22- en-7-on, 23-33-isopropylidendioxy-7-oxa-B-homo-5a-cholestan-6-on, 2a,3a-isopropylidendioxy-7-oxa-B-homo-5a-cholestan-6-on, 2a, 3a-isopropylidendioxy-24-ethyl-7-oxa-3-horno-5a-cholest- 22-en-6-on, 2a-valeryloxy-3a-hydroxy-7-oxa-B-homo-5a-cholestan-6-on, 2a-acetoxy-3a-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22- en-6-on, 2a-ethoxyacetoxy-3a-hydroxy-7-oxa-B-homo-5a-cholestan-6-on, 2a-fenylacetoxy-3a-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest- 22-en-6-on, 2a,3a-(1-ethoxy-éthylendioxy)-7-oxa-B-homo-5a-cholestan-6-on, 2a,3a-(1-ethoxy-ethylendioxy)-6-oxa-B-homo-5a-cholestan-7-on, 2a,3a-(1-ethoxy-propylidendioxy)-7-oxa-B-homo-5a-cholestan- 2-on, 2a,3a-(l-methoxy-methylendioxy)-24-ethyl-7-oxa-B-homo-5a- cholest-22-en-6-on, 23,23-(1-ethoxy-ethylendioxy)-24-ethyl-7-oxa-B-homo-5a- cholest-22-en-6-on, 2a,3a-(1-methyl-l-fenyl-methylendioxy)-7-oxa-B-homo-5a- cholestan-6-on, -2a,3a-carbonyldioxy-7-oxa-B-homo-5a-cholestan-6-on, 2a,3a-carbonyldioxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-on, 23r 33-carbonyldioxy-7-oxa-B-horao-5a-cholestan-6-on, 2a, 3a-benzylidendioxy-7-oxa-B-homo-5a-cholestan-6-on, 2a,3a-benzylidendioxy-6-oxa-B-homo-5a-cholestan-7-on,3. Brassinosteroid derivatives according to claim 1, characterized in that these are 2a,3a-diacetoxy-2 4-ethyl-7-oxa-B-homo-5a-cholest-2 2-en-6-one, 2a, 3a- diacetoxy-2 4-ethyl-6-oxa-B-hoino-5a-cholest-22-en-7-one, 23-acetoxy-33-hydroxy-2 4-ethyl-7-oxa-B-homo-5a- cholest-22- one-7-one, 33-acetoxy-33-hydroxy-2 4-ethyl-6-oxa-B-homo-5a-cholest-22- one-7-one, 33-acetoxy-23-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22- one-6-one, 2a-acetoxy-3a-hydroxy-7-oxa-B-homo-5a-cholestan-6-one, 2a-acetoxy-3a-hydroxy-6-oxa-B-homo-5a-cholestan-7-one, 2a- acetoxy-3a-hydroxy-24-methyl-6-oxa-B-homo-5a-cholest-22- one-7-one, 23-33-isopropylidenedioxy-7-oxa-B-homo-5a-cholestan-6-one, 2a,3a-isopropylidenedioxy-7-oxa-B-homo-5a-cholestan-6-one, 2a,3a-isopropylidenedioxy- 24-ethyl-7-oxa-3-horno-5a-cholest- 22-a-6-on, 2a-valeryloxy-3a-hydroxy-7-oxa-B-homo-5a-cholestan-6-one, 2a-acetoxy-3a-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22- one-6-one, 2a-ethoxyacetoxy-3a-hydroxy-7-oxa-B-homo-5a-cholestan-6-one, 2a-phenylacetoxy-3a-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest- 22-a-6-on, 2a,3a-(1-ethoxy-ethylenedioxy)-7-oxa-B-homo-5a-cholestan-6-one, 2a,3a-(1-ethoxy-ethylenedioxy)-6-oxa-B-homo-5a- cholestan-7-one, 2a,3a-(1-ethoxy-propylidenedioxy)-7-oxa-B-homo-5a-cholestan- 2-on, 2a,3a-(1-methoxy-methylenedioxy)-24-ethyl-7-oxa-B-homo-5a- cholest-22-en-6-on, 23,23-(1-ethoxy-ethylenedioxy)-24-ethyl-7-oxa-B-homo-5a- cholest-22-en-6-on, 2a,3a-(1-methyl-1-phenyl-methylenedioxy)-7-oxa-B-homo-5a- cholestane-6-one, -2a,3a-carbonyldioxy-7-oxa-B-homo-5a-cholestan-6-one, 2a,3a-carbonyldioxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6 -on, 23r 33-carbonyldioxy-7-oxa-B-horao-5a-cholestan-6-one, 2a,3a-benzylidenedioxy-7-oxa-B-homo-5a-cholestan-6-one, 2a,3a-benzylidenedioxy-6 -oxa-B-homo-5a-cholestan-7-one, 23/3 3-ben zylidendioxy-6-oxa-B-homo-5 a-chole s tan-7-on, 23,33-benzylidendioxy-7-oxa-B-homo-5a-cholestan-6-on.23/3 3-benzylidenedioxy-6-oxa-B-homo-5 a-chole s tan-7-one, 23,33-benzylidenedioxy-7-oxa-B-homo-5a-cholestan-6-one. 4. Fremgangsmåte for fremstilling av brassinosteroid-derivater ifølge krav 1-3, karakterisert ved at forbindelser av generell formel. 4. Process for the production of brassinosteroid derivatives according to claims 1-3, characterized in that compounds of general formula. omsettes ved osmiumtetroxyd-katalysert hydroxylering med t-butylhydroperoxyd eller med N-methyl-morfolin-N-oxyd til forbindelser av generell formel is reacted by osmium tetroxide-catalyzed hydroxylation with t-butyl hydroperoxide or with N-methyl-morpholine-N-oxide to compounds of the general formula eller innvirkes med sølvacetat og jod i vandig eddiksyre under dannelse av forbindelser av generell formel som behandles med persyrer under dannelse av. de ønskede fremgangsmåteprodukter hvori R. _ og R2 har de ovenfor angitte betydninger.or reacted with silver acetate and iodine in aqueous acetic acid to form compounds of general formula which are treated with peracids to form the desired process products in which R. and R.sub.2 have the meanings given above. 5. Middel med vekstregulerende virkning for planter, karakterisert ved at de inneholder minst én forbindelse ifølge krav 1-3.5. Agent with growth-regulating effect for plants, characterized in that they contain at least one compound according to claims 1-3. 6. Middel med vekstregulerende virkning for planter ifølge krav 5, i blanding med bærer- og/eller hjelpestoffer.6. Agent with growth-regulating effect for plants according to claim 5, in a mixture with carrier and/or auxiliary substances. 7. Middel ifølge krav 5 og 6 for påvirkning av den vegetative og generative vekst av belgfrukter, i særdeleshet soya.7. Means according to claims 5 and 6 for influencing the vegetative and generative growth of legumes, in particular soya. 8. Middel med vekstregulerende virkning for planter ifølge krav 5, fremstilt ved fremgangsmåten ifølge krav 4.8. Agent with growth-regulating effect for plants according to claim 5, produced by the method according to claim 4.
NO833295A 1982-09-15 1983-09-14 BRASSINOSTEROID DERIVATIVES AND AGENTS FOR PLANT REGULATORY EFFECT ON PLANTS CONTAINING THESE COMPOUNDS NO833295L (en)

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IT8322861A1 (en) 1985-03-13
FI833252A0 (en) 1983-09-12
ES8404696A1 (en) 1984-05-16
DD213347A5 (en) 1984-09-12
BE897758A (en) 1984-03-14
ZA836872B (en) 1984-05-30
DK417783D0 (en) 1983-09-14
FR2532941A1 (en) 1984-03-16
AU1861283A (en) 1984-03-22
IL69701A0 (en) 1983-12-30
BR8304545A (en) 1984-04-24
PT77257A (en) 1983-09-01
GR78759B (en) 1984-10-02
DE3234605A1 (en) 1984-03-22
GB2127021A (en) 1984-04-04
PL243719A1 (en) 1984-07-30
ZW19683A1 (en) 1983-12-21
PT77257B (en) 1986-02-04
DK417783A (en) 1984-03-16
FI833252A (en) 1984-03-16
SE8304841D0 (en) 1983-09-09
LU85002A1 (en) 1984-03-16
NL8302425A (en) 1984-04-02
GB8324347D0 (en) 1983-10-12
IT8322861A0 (en) 1983-09-13
KR840005736A (en) 1984-11-16
SE8304841L (en) 1984-03-16

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