NO833296L - 28-METHYL-BRASSINOSTEROID DERIVATIVES AND AGENTS WITH PLANT REGULATORY EFFECT ON PLANTS CONTAINING THESE COMPOUNDS - Google Patents

28-METHYL-BRASSINOSTEROID DERIVATIVES AND AGENTS WITH PLANT REGULATORY EFFECT ON PLANTS CONTAINING THESE COMPOUNDS

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Publication number
NO833296L
NO833296L NO833296A NO833296A NO833296L NO 833296 L NO833296 L NO 833296L NO 833296 A NO833296 A NO 833296A NO 833296 A NO833296 A NO 833296A NO 833296 L NO833296 L NO 833296L
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Norway
Prior art keywords
oxa
ethyl
homo
cholestan
dihydroxy
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NO833296A
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Norwegian (no)
Inventor
Ulrich Kerb
Ulrich Eder
Hansjoerg Kraehmer
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Schering Ag
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Publication of NO833296L publication Critical patent/NO833296L/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J3/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by one carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J73/00—Steroids in which the cyclopenta[a]hydrophenanthrene skeleton has been modified by substitution of one or two carbon atoms by hetero atoms
    • C07J73/001—Steroids 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
    • C07J73/003—Steroids 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION 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
    • A01N49/00—Biocides, 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

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

Description

Foreliggende oppfinnelse angår nye 28-methyl-brassinosteroidderivater, fremgangsmåter for fremstilling av disse forbindelser såvel som midler med vekstregulerende virkning for planter, inneholdende disse forbindelser. The present invention relates to new 28-methyl-brassinosteroid derivatives, methods for producing these compounds as well as agents with growth-regulating action for plants, containing these compounds.

Fra pollen fra raps er det blitt isolert det plantevekstfremmende steroid - brassiribid - og strukturen er fastslått, (s. M.D. Grove et al., Nature Vol. 281, 216 The plant growth-promoting steroid - brassiribid - has been isolated from rapeseed pollen and its structure has been determined (p. M.D. Grove et al., Nature Vol. 281, 216

(1979)). Den vekstregulerende virkning.av disse forbindelser er imidlertid ikke tilfredsstillende. (1979)). However, the growth-regulating effect of these compounds is not satisfactory.

Målet med foreliggende forbindelse er å tilveie-bringe nye brassinosteroidderivater som sammenlignet med kjente konstitusjonsanaloge brassinoider utviser overlegene vekstregulerende egenskaper for planter. The aim of the present compound is to provide new brassinosteroid derivatives which, compared to known constitutionally analogous brassinoids, exhibit superior growth-regulating properties for plants.

Denne oppgave løses med et middel ifølge oppfinnel-sen hvilket er kjennetegnet ved et innhold på minst én forbindelse av generell formel This task is solved with an agent according to the invention which is characterized by a content of at least one compound of the general formula

hvori Z betegner gruppen eller R2, R 3 og<R>22er like eller forskjellige og betegner hydrogen eller en acylrest, hvorved imidlertid minst én av disse rester betegner en acylrest, eller såfremt R22betegner hydrogen eller en acylrest, kan R2og R^sammen betegne gruppen eller wherein Z denotes the group or R2, R 3 and <R>22 are the same or different and denote hydrogen or an acyl residue, whereby at least one of these residues denotes an acyl residue, or if R22 denotes hydrogen or an acyl residue, R2 and R^ together may denote the group or

hvori X betegner hydrogen, C^-C^-alkyl eller C^-C-^-alkoxy og Y betegner hydrogen, C-L-C^-alkyl, C1-C3~alkoxy eller aryl. in which X denotes hydrogen, C₁-C₁-alkyl or C₁-C₋-₄-alkoxy and Y denotes hydrogen, C-L-C₄-alkyl, C₁-C₃-₄-alkyl or aryl.

De nye forbindelser opptrer som geometriske isomerer, hvorved -0R2og -0R3 er cis 2a,3a eller cis 23,33 ori-entert og OR22og OH23utviser cis 22R, 23R konfigurasjon eller cis 22S,23S konfigurasjon. De enkelte isomerer og deres blandinger omfattes av oppfinnelsens ramme. The new compounds act as geometric isomers, whereby -0R2 and -0R3 are cis 2a,3a or cis 23,33 oriented and OR22 and OH23 exhibit cis 22R, 23R configuration or cis 22S,23S configuration. The individual isomers and their mixtures are covered by the scope of the invention.

De nye forbindelser egner seg glimrende for regu-lering av plantevekst ved forskjellige nytteplanter og over-treffer i deres virkningsspekter såvel som deres forenlighet på en overraskende måte det tidligere nevnte produkt med samme virkningsgrad. The new compounds are excellently suited for the regulation of plant growth in various beneficial plants and in their spectrum of action as well as their compatibility surprisingly exceed the previously mentioned product with the same degree of effectiveness.

De nye forbindelser fremmer den vegetative vekst av nytteplanter men kan i visse konsentrasjonsområder også virke hemmende. Ennvidere er det mulig å oppnå en viss til-vekst gjennom innvirkning på den generative fase. The new compounds promote the vegetative growth of useful plants, but in certain concentration ranges can also have an inhibitory effect. Furthermore, it is possible to achieve a certain amount of growth through impact on the generative phase.

Generelt virker substansene på membransystemet ved nytteplanter og endrer permeabiliteten for forskjellige stoffer. In general, the substances act on the membrane system of useful plants and change the permeability for different substances.

Under bestemte betingelser kan de utvise en anti-stressvirkning. Under certain conditions, they can exhibit an anti-stress effect.

Da de nye forbindelser såvel kvalitativt og kvan-titativt forårsaker forandringer av plantene såvel som forandringer i plantenes metabolisme, hører de 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 vegetative vekst av treplanter og ugress eksempelvis ved veikanter, skinneanlegg og lignende, for å hemme en for kraftig vekst, veksthemning ved korn for å unngå legde og ved bomull for å oppnå en utbytteøkning. Inhibition of the vegetative growth of tree plants and weeds, for example at roadsides, rail systems and the like, to inhibit excessively strong growth, growth inhibition in the case of cereals to avoid weeds and in the case of cotton to achieve an increase in yield.

Innvirkning på forgrening av vegetative og generative organer ved pryd- og nytteplanter for å øke blomster-mengden eller ved tobakk og tomater for å hemme sideskudd. Impact on the branching of vegetative and generative organs in ornamental and useful plants to increase the amount of flowers or in tobacco and tomatoes to inhibit side shoots.

Forbedring av fruktkvaliteten, for eksempel økning av sukkerinnholdet i sukkerrør, sukkerroer eller frukt og for å bevirke en ensartet modning av avlingen som fører til et høyere utbytte. Improving fruit quality, for example increasing the sugar content of sugar cane, sugar beet or fruit and to effect a uniform ripening of the crop leading to a higher yield.

Økning av motstandskraften overfor stress slik som for eksempel overfor klimatiske påvirkninger slik som kulde og tørke, men også overfor fytotoksiske påvirkninger av kje-mikalier. Increase in resistance to stress such as, for example, to climatic influences such as cold and drought, but also to phytotoxic effects of chemicals.

Innvirkning på latexstrømmen i gummiplanter. Impact on latex flow in rubber plants.

Dannelsen av parthenokarperfrukter, pollensterili-tet og arvepåvirkning er andre anvendelsesmuligheter. The formation of parthenocarp fruits, pollen sterility and genetic influence are other possible applications.

Kontroll av spiringen av frø eller frembringelse av knopper. Control of the germination of seeds or the production of buds.

Avløving eller påvirkning av fruktfall for å lette høstingen. Defoliation or influence of fruit drop to facilitate harvesting.

De nye forbindelser egner seg i særdeleshet for å påvirke den vegetative og generative vekst av enkelte belgfrukter slik som' for eksempel soya. The new compounds are particularly suitable for influencing the vegetative and generative growth of certain legumes such as, for example, soya.

Anvendelsesraengden utgjør alt etter anvendelses-formålet generelt 0,001 til 1 kg virkestoff/hektar, men eventuelt kan også høyere mengder anvendes. Depending on the purpose of use, the amount of application generally amounts to 0.001 to 1 kg of active substance/hectare, but possibly higher amounts can also be used.

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

Blant de nye forbindelser som utmerker seg ved den beskrevne virkning skal særlig nevnes de av den tidligere angitte generelle formel I hvori Z betegner gruppen Among the new compounds which are distinguished by the described action, those of the previously stated general formula I in which Z denotes the group

eller R2, R3 og<R>22er lik eller forskjellig og betegner hydrogen eller en acylrest, hvorved imidlertid minst én av disse rester betegner en acylrest, eller som nevnt R22betegner hydrogen eller en acylrest, kan<R>2og<R>^sammen betegne gruppene eller or R2, R3 and <R>22 are the same or different and denote hydrogen or an acyl residue, whereby however at least one of these residues denotes an acyl residue, or as mentioned R22 denotes hydrogen or an acyl residue, <R>2 and <R>^ together may denote the groups or

hvori X betegner hydrogen, C-^-C^-alkyl eller C1-C3-alkoxy og Y betegner hydrogen, C.j-C^-alkyl, Ci-C3-alkoxy eller aryl. in which X denotes hydrogen, C 1 -C 3 alkyl or C 1 -C 3 alkoxy and Y denotes hydrogen, C 1 -C 4 alkyl, C 1 -C 3 alkoxy or aryl.

Som acylrester kan nevnes formylresten, C2~C^-alkyl-CO-resten, C^-C-y-alkoxy-C-^-C^-alkyl-CO-resten og aryl-CO-resten slik som f.eks. acetoxy, methoxyacetoxy, ethoxy-acetoxy, propionyloxy, butyryloxy, valeryloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, dimethylacetoxy, diethylacetoxy, benzyloxy og fenylacetoxy. As acyl residues, mention may be made of the formyl residue, the C 2 -C 4 -alkyl-CO residue, the C 1 -C 4 -alkyl-CO residue, the C 1 -C 4 -alkyl-CO residue and the aryl CO residue such as e.g. acetoxy, methoxyacetoxy, ethoxy-acetoxy, propionyloxy, butyryloxy, valeryloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, dimethylacetoxy, diethylacetoxy, benzyloxy and phenylacetoxy.

Som C-^-C^-alkylrester kan eksempelvis nevnes methyl, ethyl, propyl, isopropyl, butyl, sek.-butyl, tert.-butyl og klormethyl; C^-C3-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-trifklorfenyl, 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. Examples of C 1 -C 4 -alkyl radicals that can be mentioned are methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl and chloromethyl; C₁-C₃-Alkoxy residues are, for example, methoxy, ethoxy and propoxy; and as aryl residues finally naphthyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,6-dichlorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,4,6-trichlorophenyl, 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, plantebeskyttelsesmidler eller pesticider tilsettes alt etter det ønskede formål.i The new compounds can either be used alone, in a mixture with each other or with other active substances. Optionally, defoliating agents, plant protection agents or pesticides can be added depending on the desired purpose.i

Såfremt en utvidelse avvirkningsspekteret tasIf an extension of the impact spectrum is taken

i betraktning, kan også andre biocider tilsettes. Som herbicid virksomme blandingspartnere egnet seg eksempelvis de virkestoffer som er angitt i 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 kan gi en synergistisk virkningsøkning med herbicidene og/eller vekstregulatorene, slik som blant annet fuktemidler, emulgatorer, løsningsmid-ler og oljeaktige tilsetningsmidler. in consideration, other biocides can also be added. As herbicidally active mixture partners, for example, the active substances indicated in Weed Abstracts, Vol. 31. 1981, under the title "List of common names and Abbreviations employed for currently used herbicides and plant growth regulators in weed abstracts", are suitable. In addition, non-phytotoxic agents can also be used which can provide a synergistic increase in effectiveness with the herbicides and/or growth regulators, such as 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 bærestoffer henholdsvis fortynningsmidler og eventuelt under tilsetning av fuktemidler, bindemidler, emulgeringsmidler og/eller dispergeringsmidler. 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 or diluents, and possibly with the addition of wetting agents, binders, emulsifiers and /or dispersants.

Egnede flytende bærere er for eksempel vann, alifatiske og aromatiske hydrocarboner slik som benzen, toluen, xylen, cyclohexanon, isoforon, dimethylsulfoxyd, dimethylformamid og mineraloljefraksjoner. Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethylsulfoxide, dimethylformamide and mineral oil fractions.

Som faste bærestoffer egner seg eksempelvis mineral-jord slik som for eksempel leirearter, silicagel, talkum, kaolin, attapulkusleire, kalkstein, kiselsyre og plantepro-dukter slik som f.eks. mel. Suitable solid carriers are, for example, mineral soil such as clay species, silica gel, talc, kaolin, attapulku clay, limestone, silicic acid and plant products such as e.g. flour.

Som overflateaktive stoffer kan eksempelvis nevnes calsiumligninsulfonat, 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 variere innen vide grenser. Eksempelvis inneholder midlet 10 til 80 vekt% virkestoff, 90 til 20 vekt% flytende eller faste bærestoffer såvel som eventuelt 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 possibly up to 20% by weight of surfactants.

Utbringelse av midlet kan skje på vanlig måte, f.eks. 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 likeledes mulig slik som påføring i form av såkalte mikrogranulater. Delivery of the agent can take place in the usual way, e.g. with water that carries in 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, such as application in the form of so-called microgranules.

For fremstilling av tilberedelser anvendes eksempelvis følgende bestanddeler: For the preparation of preparations, for example, the following ingredients are used:

A. SprøytepulverA. Spray powder

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

15 vekt% kaolin15% by weight kaolin

5 vekt% overflateaktive stoffer på basis av natrium-saltet av N-methyl-N-oleyl-taurin og calsiumsaltet av ligninsulfonsyre. 5% by weight surfactants based on the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of ligninsulfonic acid.

b) 5 0 vekt% virkestoffb) 50% by weight active ingredient

4 0 vekt% leiremineraler4 0 wt% clay minerals

5 vekt% cellebek5% by weight cell pitch

5 vekt% overflateaktive stoffer på basis av en blanding av calsiumsalter av ligninsulfonsyre med alkylfenolpolyglykolethere. 5% by weight of surfactants based on a mixture of calcium salts of ligninsulfonic acid with alkylphenol polyglycol ethers.

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% overflateaktive stoffer på basis av en blanding av" calsiumcalter av ligninsulfonsyre med alkylfenolpolyglycolethere. 5% by weight of surfactants based on a mixture of "calcium calter" of ligninsulfonic acid with alkylphenol polyglycol ether.

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

80 vekt% leire :80 wt% clay:

10 vekt% cellebek10% by weight cell pitch

5 vekt% overflateaktive stoffer på basis av et fett-syrekondensasjonsprodukt. 5% by weight of surfactants based on a fat-acid condensation product.

B. EmulsjonskonsentratB. Emulsion concentrate

20 vekt% virkestoff20% by weight active ingredient

40 vekt% xylen40% by weight xylene

35 vekt% dimethylsulfoxyd35% by weight dimethylsulfoxide

5 vekt% av en blanding av nonylfenylpolyoxyethylen eller calsiumdodecylbenzensulfonat. 5% by weight of a mixture of nonylphenylpolyoxyethylene or calcium dodecylbenzene sulphonate.

C. PastaC. Pasta

4 5 vekt% virkestoff4 5% by weight active ingredient

5 vekt% natriumaluminiumsilikat5% by weight sodium aluminum silicate

15 vekt% cetylpolyglycolether med 9 mol ethylenoxyd 15% by weight of cetyl polyglycol ether with 9 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 fomrel The new compounds can, for example, be produced by compounds of general form

omsettes med traded with

a) carboxylsyreanhydrider, eventuelt i nærvær av en katalysator, b) bortrifluorid-etherat, eventuelt løst i et organisk løsningsmiddel, c) triethylorthoeddiksyreester, eventuelt i nærvær av en katalysator, løst i et organisk løsningsmiddel, eller a) carboxylic acid anhydrides, optionally in the presence of a catalyst, b) boron trifluoride etherate, optionally dissolved in an organic solvent, c) triethyl orthoacetic acid ester, optionally in the presence of a catalyst, dissolved in an organic solvent, or

d) acetofenon i perklorsyred) acetophenone in perchloric acid

hvoretter det ønskede produkt isoleres på kjent måte. after which the desired product is isolated in a known manner.

Utgangsforbindelsen 28-methyl-brassinolid fremstilles fra stigmasterin, f.eks. som beskrevet i Steroids 39, 89 (1982). The starting compound 28-methyl-brassinolide is prepared from stigmasterin, e.g. as described in Steroids 39, 89 (1982).

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

Eksempel 1Example 1

1 g 2a,3a,22S,23S-tetrahydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on ble løst i 10 ml pyridin, ble avkjølt til 0° C og tilsatt 0,5 ml acetanhydrid og ble omrørt i 5 1/2 time ved -5 til 0° C. Deretter ble produktet utfelt i isvann, ble fraskilt, vasket med vann, tørket og kromatografert på silicagel. Etter omkrystallisering fra aceton-hexan ble det erholdt 810 mg 2a-acetoxy-3a,22A,23S-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 125° C. 1 g of 2a,3a,22S,23S-tetrahydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one was dissolved in 10 ml of pyridine, was cooled to 0° C and added 0.5 ml acetic anhydride and was stirred for 5 1/2 hours at -5 to 0° C. Then the product was precipitated in ice water, was separated, washed with water, dried and chromatographed on silica gel. After recrystallization from acetone-hexane, 810 mg of 2a-acetoxy-3a,22A,23S-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one were obtained, m.p. 125°C.

Eksempel 2Example 2

1 g 2a,3a,22S,23S-tetrahydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on ble løst i 10 ml pyridin og ble av-kjølt til 0° C og ble tilsatt 1 ml acetanhydrid og ble omrørt i 7 timer ved 0° C. Produktet ble deretter utfelt i isvann, ble fraskilt, vasket med vann og tørket. Etter kromatografi på silicagel (gradienteluering med kloroform-aceton) ble det erholdt 320 mg 2a,3a-diacetoxy-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 120° C og 536 mg 2a,22S-diacetoxy-3a,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on,sm.p. 146° C. 1 g of 2a,3a,22S,23S-tetrahydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one was dissolved in 10 ml of pyridine and was cooled to 0° C. and was added 1 ml of acetic anhydride and was stirred for 7 hours at 0° C. The product was then precipitated in ice water, separated, washed with water and dried. After chromatography on silica gel (gradient elution with chloroform-acetone), 320 mg of 2α,3α-diacetoxy-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5α-cholestan-6-one were obtained, sm. p. 120° C. and 536 mg of 2α,22S-diacetoxy-3α,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5α-cholestan-6-one, m.p. 146°C.

Eksempel 3Example 3

210 mg 2a,3a,22R,23R-tetrahydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on ble omsatt som beskrevet i Eksempel 1. Det ble etter omkrystallisering fra aceton-hexan erholdt 210 mg of 2a,3a,22R,23R-tetrahydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one was reacted as described in Example 1. After recrystallization from acetone-hexane, it was obtained

170 mg 2a-acetoxy-3a,22R,2 3R-trihydroxy-24-ethyl-7-oxa-B-homo-5a,cholestan-6-on, sm.p. 246 - 248° C. 170 mg 2a-acetoxy-3a,22R,2 3R-trihydroxy-24-ethyl-7-oxa-B-homo-5a,cholestan-6-one, m.p. 246 - 248° C.

Eksempel 4Example 4

500 mg 2a,3a,22S,23S-tetrahydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-on ble omsatt som beskrevet i Eksempel 1. Etter omkrystallisering fra methylenklorid-isopropylether ble det erholdt 385 mg 2a-aceton-3a,22S,23S-trihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-on, sm.p. 19.8 - 200° C. Eksempel 5 500 mg of 2a,3a,22S,23S-tetrahydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-one was reacted as described in Example 1. After recrystallization from methylene chloride-isopropyl ether, 385 mg were obtained 2α-aceton-3α,22S,23S-trihydroxy-24-ethyl-6-oxa-B-homo-5α-cholestan-7-one, m.p. 19.8 - 200° C. Example 5

1 g 2a,3a,22S,23S-tetrahydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-on ble omsatt og fraskilt som beskrevet i Eksempel 2. Det ble erholdt 290 mg 2a,3a-diacetoxy-22S,2 3S- dihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-on, sm.p. i. ■ 135° C og 560 mg 2a,22S-diacetoxy-3a,23S-dihydroxy-2 4-ethyl-6-oxa-B-homo-5a-cholestan-7-on, sm.p. 152° C. 1 g of 2a,3a,22S,23S-tetrahydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-one was reacted and separated as described in Example 2. 290 mg of 2a,3a- diacetoxy-22S,2 3S-dihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-one, m.p. in. ■ 135° C and 560 mg of 2a,22S-diacetoxy-3a,23S-dihydroxy-2 4-ethyl-6-oxa-B-homo-5a-cholestan-7-one, m.p. 152°C.

Eksempel 6Example 6

500 mg 23,33,22S,23S-tetrahydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on (sm.p. 182 - 183° C) ble acetylert som beskrevet i Eksempel 1. Det ble erholdt 410 mg 33~acetoxy-23/22S,2 3S-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 161 - 162° C. 500 mg of 23,33,22S,23S-tetrahydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one (m.p. 182 - 183° C) was acetylated as described in Example 1. 410 mg of 33-acetoxy-23/22S,2 3S-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one, m.p. 161 - 162° C.

Eksempel 7Example 7

300 mg 2a, 3a,22S,23S-tetrahydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on ble løst i 3 ml pyridin, ble avkjølt til 0° C og ble tilsatt 0,6 ml valeriansyreanhydrid. Blandingen ble omrørt i 10 timer ved 0° C, produktet ble utfelt i isvann, vasket med vann og tørket. Råproduktet ble kromatografert på silicagel og det erholdte..2 a-valeryloxy-3a,22S,23S-trihydroxy-24-ethyl-7-oxa-B-homo-6a-cholestan-6-on ble omkrystallisert fra aceton-hexan, sm.p. 100 - 105° C. 300 mg of 2a,3a,22S,23S-tetrahydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one was dissolved in 3 ml of pyridine, was cooled to 0° C and was added 0.6 ml valerian anhydride. The mixture was stirred for 10 hours at 0° C., the product was precipitated in ice water, washed with water and dried. The crude product was chromatographed on silica gel and the obtained ..2 a-valeryloxy-3a,22S,23S-trihydroxy-24-ethyl-7-oxa-B-homo-6a-cholestan-6-one was recrystallized from acetone-hexane, sm .p. 100 - 105° C.

På analog måte ble fremstilt: 2a-heptanoyloxy-3a,22R,23R-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 85 - 87° C. In an analogous manner was prepared: 2a-heptanoyloxy-3a,22R,23R-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one, m.p. 85 - 87° C.

2a-dimethylacetoxy-3a,22S,2 3S-trihydroxy-2 4-ethyl-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 121 - 122,5° C. 2α-dimethylacetoxy-3α,22S,2 3S-trihydroxy-2 4-ethyl-7-oxa-B-homo-5α-cholestan-6-one, m.p. 121 - 122.5° C.

2a-butyryloxy-3a,22S,23S-trihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-on,sn-p. 92 - 94° C. 2α-butyryloxy-3α,22S,23S-trihydroxy-24-ethyl-6-oxa-B-homo-5α-cholestan-7-one,sn-p. 92 - 94° C.

2a-diethylacetoxy-3a-22S,23S-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 113 - 115° C. 2α-diethylacetoxy-3α-22S,23S-trihydroxy-24-ethyl-7-oxa-B-homo-5α-cholestan-6-one, m.p. 113 - 115° C.

Eksempel 8Example 8

300 mg 2a,3a,22S,23S-tetrahydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on ble løst i 3 ml pyridin, ble avkjølt til 0° C og ble tilsatt 1 ml valeriansyreanhydrid. Blandingen ble omrørt i 20 timer ved 0° C, produktet ble utfelt i isvann, vasket med vann og tørket. Etter kromatografi på silicagel (gradienteluering med kloroform-aceton) ble det erholdt 120 mg 2a,3a-divaleryloxy-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 109 - 111° C og 160 mg 2a,22S-divaleryloxy-3a,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 128,5 - 130° C. 300 mg of 2a,3a,22S,23S-tetrahydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one was dissolved in 3 ml of pyridine, cooled to 0° C and 1 ml of valeric anhydride was added . The mixture was stirred for 20 hours at 0° C., the product was precipitated in ice water, washed with water and dried. After chromatography on silica gel (gradient elution with chloroform-acetone), 120 mg of 2a,3a-divaleryloxy-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one were obtained, sm. p. 109 - 111° C and 160 mg of 2a,22S-divaleryloxy-3a,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one, m.p. 128.5 - 130° C.

På analog måte ble fremstilt: 2a,3a-dihexanoyloxy-22S,2 3S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 88 - 90° C. In an analogous manner was prepared: 2a,3a-dihexanoyloxy-22S,2 3S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one, m.p. 88 - 90° C.

2a,22S-dihexannyloxy-3a,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 117 - 120° C. 2α,22S-dihexanyloxy-3α,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5α-cholestan-6-one, m.p. 117 - 120° C.

Eksempel 9Example 9

500 mg 2a,3a,22R,23R-tetrahydroxy-24-ethyl-7-oxa-B-homo-5a-choletan-6-on ble løst i 5 ml pyridin, ble avkjølt til 0° C og tilsatt 0,3 ml ethoxyeddiksyreanhydrid og ble omrørt i 6 timer ved -5 til 0° C. Etter opparbeidelse og isolering som beskrevet i Eksempel 1, ble det erholdt 310 mg 2a-ethoxyacetoxy-3a,22R,23R-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 182 - 185° C. 500 mg of 2a,3a,22R,23R-tetrahydroxy-24-ethyl-7-oxa-B-homo-5a-choletan-6-one was dissolved in 5 ml of pyridine, was cooled to 0° C and added 0.3 ml ethoxyacetic anhydride and was stirred for 6 hours at -5 to 0° C. After work-up and isolation as described in Example 1, 310 mg of 2a-ethoxyacetoxy-3a,22R,23R-trihydroxy-24-ethyl-7-oxa- B-homo-5a-cholestan-6-one, m.p. 182 - 185° C.

Eksempel 10Example 10

1 g 2a, 3a,22S,2 3S-tetr.ahydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on ble i 100 ml tetrahydrofuran og 100 ml aceton tilsatt 0,5 ml bortrifluorid-etherat og ble omrørt i 30 minutter ved -5 til 0° C. Etter tilsetning av 1 ml pyridin ble løsningen inndampet i vakuum, produktet ble utfelt med vann, fraskilt og vasket med vann. Etter omkrystallisering fra aceton ble det erholdt 731 mg 2a,3a-isopropyliden-dioxy-22S,23S-dihydroxy-2 4-ethyl-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 198 - 201° C. 1 g of 2a,3a,22S,2 3S-tetr.ahydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one was added to 100 ml of tetrahydrofuran and 100 ml of acetone and 0.5 ml of boron trifluoride etherate and was stirred for 30 minutes at -5 to 0° C. After addition of 1 ml of pyridine, the solution was evaporated in vacuo, the product was precipitated with water, separated and washed with water. After recrystallization from acetone, 731 mg of 2α,3α-isopropylidene-dioxy-22S,23S-dihydroxy-2 4-ethyl-7-oxa-B-homo-5α-cholestan-6-one were obtained, m.p. 198 - 201°C.

På analog måte ble fremstilt: 2a,3a-isopropylidendioxy-22S,2 3S-dihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-on, sm.p. 211 - 213° C. In an analogous manner was prepared: 2a,3a-isopropylidenedioxy-22S,2 3S-dihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-one, m.p. 211 - 213° C.

23,33-isopropylidendioxy-22S ,:23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 189 - 191° C. 23,33-isopropylidenedioxy-22S,:23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one, m.p. 189 - 191° C.

Eksempel 11Example 11

1 g 2a,3a,22S,23S-tetrahydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on ble i 100 ml benzen tilsatt 1,5 ml triethylorthoeddiksyreester og 5 mg p-toluensulfonsyre, og ble omrørt i 30 minutter ved romtemperatur. Etter tilsetning av 2 dråper pyridin ble løsningen inndampet i vakuum, ble fortynnet med methylenklorid, vasket med vann og inndampet. Råproduktet ble triturert med isopropylether og det ble erholdt 72 0 mg amorft 2a,3a-(1-ethoxyethylendioxy)-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on som en diastereomer blanding. 1 g of 2a,3a,22S,23S-tetrahydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one was added to 100 ml of benzene, 1.5 ml of triethylorthoacetic acid ester and 5 mg of p-toluenesulfonic acid, and was stirred for 30 minutes at room temperature. After adding 2 drops of pyridine, the solution was evaporated in vacuo, diluted with methylene chloride, washed with water and evaporated. The crude product was triturated with isopropyl ether and 720 mg of amorphous 2α,3α-(1-ethoxyethylenedioxy)-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5α-cholestan-6-one was obtained as a diastereomeric mixture.

På analog måte ble fremstilt: 2a,3a-(1-ethoxy-propylidendioxy)-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, amorft 2a,3a-(1-methoxy-methylendioxy)-22R,23R-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 96 - 99° C. 2 3,33-(1-ethoxy-ethylendioxy)-22S,2 3S-dihydroxy-2 4-ethyl-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 84 - 87° C. In an analogous manner was prepared: 2a,3a-(1-ethoxy-propylidenedioxy)-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one, amorphous 2a,3a-( 1-methoxy-methylenedioxy)-22R,23R-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one, m.p. 96 - 99° C. 2 3,33-(1-ethoxy-ethylenedioxy)-22S,2 3S-dihydroxy-2 4-ethyl-7-oxa-B-homo-5a-cholestan-6-one, m.p. . 84 - 87° C.

Eksempel 12Example 12

200 mg 2a,3a,22S,23S-tetrahydroxy-24-ethyl-7-oxa-.B-homo-5a-cholestan-6-on ble i 2 ml acetofenon tilsatt 0,01 ml 72 %-ig perklorsyre og ble omrørt i 16 timer ved romtemperatur. Deretter ble 0,1 ml pyridin tilsatt og blandingen ble kromatografert på silicagel. Ved gradienteluering med 200 mg of 2a,3a,22S,23S-tetrahydroxy-24-ethyl-7-oxa-.B-homo-5a-cholestan-6-one was added to 2 ml of acetophenone with 0.01 ml of 72% perchloric acid and was stirred for 16 hours at room temperature. Then 0.1 ml of pyridine was added and the mixture was chromatographed on silica gel. By gradient elution with

toluen-eddikester ble det erholdt 120 mg amorft 2a,3a-(l-methyl-l-fenyl-methylendioxy)-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on som en diastereomer blanding. toluene-acetic ester, 120 mg of amorphous 2α,3α-(1-methyl-1-phenyl-methylenedioxy)-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5α-cholestan-6-one were obtained as a diastereomeric mixture.

På analog måte ble fremstilt: 2a,3a-(1-methyl-l-fenyl-methylendioxy)-22S,2 3S-dihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-on In an analogous manner was prepared: 2a,3a-(1-methyl-1-phenyl-methylenedioxy)-22S,2 3S-dihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-one

Eksempel 13Example 13

200 mg 2a,3a-22S,2 3S-tetrahydroxy-2 4-ethyl-6-oxa-B-hbmo-5a-cholestan-7-on ble i 7 ml diethylcarbonat og 2 ml tetrahydrofuran oppvarmet i 2 1/2 rime til 13 0° C (badtempe-ratur) etter tilsetning av 15 mg natriummethylat. Etter avkjøling ble blandingen nøy.tralisert med eddiksyre og inndampet i vakuum.. Residuet ble løst i kloroform-aceton, ble filtrert over silicagel og filtratet ble inndampet. Ved omkrystallisering fra aceton-hexan ble det erholdt 155 mg 2a,3a-carbonyldioxy-22S,23S-dihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-on. sm.p. 242,5 - 244° C. 200 mg of 2a,3a-22S,2 3S-tetrahydroxy-2 4-ethyl-6-oxa-B-hbmo-5a-cholestan-7-one was heated in 7 ml of diethylcarbonate and 2 ml of tetrahydrofuran for 2 1/2 rime to 13 0° C (bath temperature) after adding 15 mg of sodium methylate. After cooling, the mixture was neutralized with acetic acid and evaporated in vacuo. The residue was dissolved in chloroform-acetone, filtered over silica gel and the filtrate was evaporated. By recrystallization from acetone-hexane, 155 mg of 2α,3α-carbonyldioxy-22S,23S-dihydroxy-24-ethyl-6-oxa-B-homo-5α-cholestan-7-one were obtained. sm.p. 242.5 - 244° C.

På analog måte ble fremstilt: 2a,3a-carbonyldioxy-22R,23R-dihydroxy-24-ethyl-6-oxa-B-homo-5a-jcholestan-7-on, sm.p. 216 - 217° C. In an analogous manner was prepared: 2α,3α-carbonyldioxy-22R,23R-dihydroxy-24-ethyl-6-oxa-B-homo-5α-jcholestan-7-one, m.p. 216 - 217° C.

Eksempel 14Example 14

200 mg 2a,3a,22S,23S-tetrahydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-on ble løst i 4 ml tetrahydrofuran, 1 ml benzaldehyd ble tilsatt, blandingen ble avkjølt til -15° C og 0,2 ml av en perklorsyreløsning (fremstilt fra 0,5 ml 70 %-ig perklorsyre i 1,5 ral tetrahydrofuran) ble tilsatt. Blandingen ble omrørt i 15 minutter ved -15° C, ble nøytra-lisert med pyridin, ble fortynnet med kloroform og kromatografert over silicagel. Med kloroform-aceton (1:1) ble det erholdt 153 mg amorft 2a,3a-benzylidendioxy-22S,23S-dihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-on. 200 mg of 2a,3a,22S,23S-tetrahydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-one was dissolved in 4 ml of tetrahydrofuran, 1 ml of benzaldehyde was added, the mixture was cooled to -15 ° C and 0.2 ml of a perchloric acid solution (prepared from 0.5 ml of 70% perchloric acid in 1.5 ral of tetrahydrofuran) was added. The mixture was stirred for 15 minutes at -15°C, neutralized with pyridine, diluted with chloroform and chromatographed over silica gel. With chloroform-acetone (1:1) 153 mg of amorphous 2a,3a-benzylidenedioxy-22S,23S-dihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-one were obtained.

På analog måte ble fremstilt: 2a,3a-benzylidendioxy-22R,23R-dihydroxy-24-ethyl-7-oxa-B-homo-5 a-chole s tan-6-on In an analogous manner was prepared: 2a,3a-benzylidenedioxy-22R,23R-dihydroxy-24-ethyl-7-oxa-B-homo-5a-chole s tan-6-one

2a,3a-benzylidendioxy-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-choletan-6-on . 2α,3α-benzylidenedioxy-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5α-choletan-6-one.

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, tetraklor-carbon, 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, carbon tetrachloride, aromatic hydrocarbons such as such as benzene, toluene and xylene, ethers such as diethylether, 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 15Example 15

Vekstøkning av buskbønner.Growth of bush beans.

Buskbønner av sorten "Pinto" ble dyrket i klima-kammer ved 25° C under innvirkning av lys med en høy andel av intensitet i området på 660 nm og en svært lav andel i området 730 nm. Bush beans of the variety "Pinto" were grown in climate chambers at 25° C 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 2 0 yg av forbindelsene som skulle prøves, løst i et løsningsmiddel og påført det utviklende andre internodium. 3 dager etter påføring ble lengden av internodiene målt og den prosentuelle forlengelse i sammenligning med kontrollen ble nedtegnet. After 6 days of culture, 10 and 20 µg of the compounds to be tested were dissolved in a solvent and applied to the developing second internode. 3 days after application, the length of the internodes was measured and the percentage elongation compared to the control was recorded.

Tabellen inneholder resultatene fra disse forsøk. The table contains the results from these experiments.

Resultatene viser at de nye forbindelser under de angitte prøvebetingelser bevirket en mer intensiv strekking enn sammenligningsmidlet og kontrollen. The results show that the new compounds under the specified test conditions caused a more intensive stretching than the comparator and the control.

Sammenligningsmidlet forårsaket ennvidere bare en mer eller mindre sterk økning av tykkelsesveksten hvilket delvis til og med førte til en sammenpresning av internodiene. Furthermore, the comparator only caused a more or less strong increase in thickness growth, which in part even led to a compression of the internodes.

Eksempel 16Example 16

Veksthemning ved agurker.Growth retardation in cucumbers.

Agurkfrø ble under veksthusbetingelser bragt til spirer i vandige emulsjoner av de forbindelser som skulle prøves i en konsentrasjon av 0,01 vekt%. Cucumber seeds were germinated under greenhouse conditions in aqueous emulsions of the compounds to be tested at a concentration of 0.01% by weight.

Etter 6 dager ble lengden av røttene og skuddene målt. After 6 days, the length of the roots and shoots was measured.

Tabellen inneholder den prosentvise hemning av veksten i dager etter konsentrasjonsområdet. The table contains the percentage inhibition of growth in days by concentration range.

De nye forbindelser virker ved de angitte forsøks-betingelser tydelig veksthemmende. The new compounds have a clear growth inhibitory effect under the stated test conditions.

Claims (8)

1. 28-methyl-brassinolidderivater av generell formel 1. 28-methyl-brassinolide derivatives of general formula hvori Z betegner gruppen in which Z denotes the group eller or R2f R3 og R22 er !ik eller forskjellig og betegner hydrogen eller en acylrest, hvorved imidlertid minst én av disse rester betegner en acylrest, eller såfremt R22 betegner hydrogen eller en acylrest, kan R2 og R^ sammen betegne gruppen R2f R3 and R22 are the same or different and denote hydrogen or an acyl residue, whereby at least one of these residues denotes an acyl residue, or if R22 denotes hydrogen or an acyl residue, R2 and R^ together can denote the group eller or hvori Z betegner hydrogen, C-^ -C^ -alkyl eller C-^ -C^ -alkoxy og Y betegner hydrogen, C-^ -C^ -alkyl, C-^ -C^ -alkoxy eller aryl.wherein Z represents hydrogen, C1-3 -C1 -alkyl or C1-3 -C1 -alkyl and Y represents hydrogen, C1 -C3 -alkyl, C1 -C3 -alkyl or aryl. 2. 28-methyl-brassinolidr-derivater ifølge krav 1, karakterisert ved at Z betegner gruppen 2. 28-methyl-brassinolide derivatives according to claim 1, characterized in that Z denotes the group eller or R2 , <R>3 og R22 er like eller forskjellige og betegner en acylrest fra gruppen bestående av en formylrest, C2 -C7 -alkyl-CO-rest, C2 -C-7 -alkoxy-C1 -C3 -alkyl-CO-rest eller aryl-CO-rest, hvormed imidlertid minst én av disse rester betegner en slik acylrest, eller såfremt R22 betegner hydrogen eller en slik acylrest, kan R2 og R2 sammen betegne gruppen R2 , <R>3 and R22 are equal or different and denote an acyl residue from the group consisting of a formyl residue, C2 -C7 -alkyl-CO residue, C2 -C-7 -alkyl-C1 -C3 -alkyl-CO residue or aryl-CO residue, with however at least one of these residues denotes such an acyl residue, or if R22 denotes hydrogen or such an acyl residue, R2 and R2 can together denote the group eller hvori X betegner hydrogen, C^- C^-alkyl .eller C^ -C^ -alkoxy og Y betegner hydrogen, C^-C^-alkyl, Cj^ -C^-alkoxy eller aryl.or 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. 3. 2 8-methyl-brassinolidderivater ifølge krav 1, karakterisert ved at disse er 2a-acetoxy-3a,22S,23S-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, eller 2a,22S-diacetoxy-3a,2 3S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, ;eller 2a-acetoxy-3a,22R,23R-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, eller 2a-acetoxy-3a,22S,23S-trihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-6-on, eller 2a,22S-diacetoxy-3a,23S-dihydroxy-2 4-ethyl-6-oxa-B-homo-5a-cholestan-7-on, eller3. 2 8-methyl-brassinolide derivatives according to claim 1, characterized in that these are 2a-acetoxy-3a,22S,23S-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one, or 2a,22S-diacetoxy-3a,2 3S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one, ;or 2a-acetoxy-3a,22R,23R-trihydroxy-24-ethyl -7-oxa-B-homo-5a-cholestan-6-one, or 2a-acetoxy-3a,22S,23S-trihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-6-one, or 2a,22S-diacetoxy-3a,23S-dihydroxy-2 4-ethyl-6-oxa-B-homo-5a-cholestan-7-one, or 3 a-acetoxy-2 3,2 2S,2 3S-trihydroxy-2 4-ethyl-7-oxa-B-homo-5a-cholestan-6-on, eller 2a-valeryloxy-3a,22S,23S-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, eller 2a-heptanoyloxy-3a,22R,23R-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, eller 2a-dimethylacetoxy-3a,22S,23S-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, eller 2a-butyryloxy-3a,22S,23S-trihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-on, eller 2a-diethylacetoxy-3a,22S,23S-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, eller 2a,3a-divaleryloxy-22S,2 3S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, eller 2a,22S-divaleryloxy-3a-2 3S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, eller 2a-ethoxyacetoxy-3a,22R,23R-trihydroxy-24-ethyl-7-oxa-B-homo-5a-choletan-6-on, eller 2a,3a-isopropylidendioxy-22S,23S-dihydroxy-2 4-ethyl-7-oxa-B-homo-5a-cholestan-6-on, eller 2a,3a-isopropylidendioxy-22S,23S-dihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-on, eller 23/ 33~ isopropylidendioxy-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, eller 2a,3a-(1-ethoxy-ethylendioxy)-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, eller 2a,3a-(1-ethoxy-propylidendioxy)-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, eller 2a,3a-(1-methoxy-methylendioxy)-22R,23R-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, eller 23,33-(1-ethoxy-ethylendioxy)-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, eller 2a,3a-]1-methyl-l-fenyl-methylendioxy)-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, eller 2a,3a-(1-methyl-l-fenyl-methylendioxy)-22S,23S-24-ethyl-6-oxa-B-homo-5a-cholestan-7-on, eller 2a,3a-carbonyldioxy-22S,23S-dihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-on, eller 2a,3a-carbonyldioxy-22R,23R-dihydroxy-24-ethyl-6-oxa-B-homo-5a-choletan-7-on, eller 2a,3a-benzylidendioxy-22S,2 3S-dihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-on, eller 2a,3a-benzylidendioxy-22R,23R-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on, eller 2a,3a-benzylidendioxy-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on , eller 2a,3a-dihexanoyloxy-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cnolestanr6-on, eller 2a,22S-dihexanoyloxy-3a,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-on.3 a-acetoxy-2 3,2 2S,2 3S-trihydroxy-2 4-ethyl-7-oxa-B-homo-5a-cholestan-6-one, or 2a-valeryloxy-3a,22S,23S-trihydroxy- 24-ethyl-7-oxa-B-homo-5a-cholestan-6-one, or 2a-heptanoyloxy-3a,22R,23R-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6 -one, or 2a-dimethylacetoxy-3a,22S,23S-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one, or 2a-butyryloxy-3a,22S,23S-trihydroxy-24 -ethyl-6-oxa-B-homo-5a-cholestan-7-one, or 2a-diethylacetoxy-3a,22S,23S-trihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6- on, or 2a,3a-divaleryloxy-22S,2 3S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one, or 2a,22S-divaleryloxy-3a-2 3S-dihydroxy- 24-ethyl-7-oxa-B-homo-5a-cholestan-6-one, or 2a-ethoxyacetoxy-3a,22R,23R-trihydroxy-24-ethyl-7-oxa-B-homo-5a-choletan-6 -one, or 2a,3a-isopropylidenedioxy-22S,23S-dihydroxy-2 4-ethyl-7-oxa-B-homo-5a-cholestan-6-one, or 2a,3a-isopropylidenedioxy-22S,23S-dihydroxy- 24-ethyl-6-oxa-B-homo-5a-cholestan-7-one, or 23/ 33~ isopropylidenedioxy-22S,23S-dihydroxy-24-ethyl -7-oxa-B-homo-5a-cholestan-6-one, or 2a,3a-(1-ethoxy-ethylenedioxy)-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one, or 2a,3a-(1-ethoxy-propylidenedioxy) -22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one, or 2a,3a-(1-methoxy-methylenedioxy)-22R,23R-dihydroxy-24-ethyl- 7-oxa-B-homo-5a-cholestan-6-one, or 23,33-(1-ethoxy-ethylenedioxy)-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestane -6-one, or 2a,3a-]1-methyl-1-phenyl-methylenedioxy)-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one, or 2a ,3a-(1-methyl-1-phenyl-methylenedioxy)-22S,23S-24-ethyl-6-oxa-B-homo-5a-cholestan-7-one, or 2a,3a-carbonyldioxy-22S,23S- dihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-one, or 2a,3a-carbonyldioxy-22R,23R-dihydroxy-24-ethyl-6-oxa-B-homo-5a-choletane -7-one, or 2a,3a-benzylidenedioxy-22S,2 3S-dihydroxy-24-ethyl-6-oxa-B-homo-5a-cholestan-7-one, or 2a,3a-benzylidenedioxy-22R,23R- dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholestan-6-one, or 2a,3a-benzylidenedioxy-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholesta n-6-one , or 2a,3a-dihexanoyloxy-22S,23S-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cnolestanr6-one, or 2a,22S-dihexanoyloxy-3a,23S-dihydroxy- 24-ethyl-7-oxa-B-homo-5a-cholestan-6-one. 4. Fremgangsmåte for fremstilling av 2 8-methyl-brassinolidderivater ifølge krav 1-3, karakterisert ved at forbindelser av generell formel 4. Process for the production of 2 8-methyl-brassinolide derivatives according to claims 1-3, characterized in that compounds of the general formula omsettes med a) carboxylsyreanhydrider, eventuelt i nærvær av en katalysator, b) bortrifluorid-etherat, eventuelt løst i et organisk løsningsmiddel, c) triethylorthoeddiksyreester, eventuelt i nærvær av en katalysator, oppløst i et organisk løsningsmiddel, d) acetofenon i perklorsyre eller e) diethylcarbonat og katalytiske mengder natriummethylat, og at det ønskede produkt isoleres på i og for seg kjent måte.traded with a) carboxylic acid anhydrides, possibly in the presence of a catalyst, b) boron trifluoride etherate, optionally dissolved in an organic solvent, c) triethyl orthoacetic acid ester, optionally in the presence of a catalyst, dissolved in an organic solvent, d) acetophenone in perchloric acid or e) diethylcarbonate and catalytic amounts of sodium methylate, and that the desired product is isolated in a manner known per se. 5. Middel med vekstregulerende virkning for planter, karakterisert ved at det inneholder minst én forbindelse ifølge krav 1-3.5. Agent with a growth-regulating effect for plants, characterized in that it contains 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 innvirkning av den vegetative og generative vekst av belgfrukter, i særdeleshet soye.7. Means according to claims 5 and 6, for influencing the vegetative and generative growth of legumes, in particular soybeans. 8. Middel med vekstregulerende virkning for planter ifølge krav 5, fremstilt ettex fremgangsmåten ifølge krav 4.8. Agent with a growth-regulating effect for plants according to claim 5, produced according to the method according to claim 4.
NO833296A 1982-09-15 1983-09-14 28-METHYL-BRASSINOSTEROID DERIVATIVES AND AGENTS WITH PLANT REGULATORY EFFECT ON PLANTS CONTAINING THESE COMPOUNDS NO833296L (en)

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