JPS5955887A - Brassinosteroid derivative, manufacture and plant growth regulant drug - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel prascinosteroid receptor, a method for producing the same, and a drug containing the compound that has a growth-regulating effect on plants.

Brassinolide, a steroid that promotes plant growth, was isolated from the pollen of Brassica napus and its structure was elucidated.
(See Vol. 281, p. 216 (1979)). However, the growth-regulating effect of this compound is insufficient, and the problem of the present invention is to obtain a new brassinosteroid conductor that has superior growth-controlling properties compared to the commonly used Brassinolide similar to Mizozo. be.

This problem has been solved in the present invention by the general formula I [wherein R17 represents a B□10-7 /l/*-l group or +-i C8-C1o-alkenyl thread,
However, R2 and R13 are independently "C1 each represents hydrogen or an acyl group, or together, X is hydrogen,
cl-c, -J'ruki/l/ group or C1-42
Represents a 3-flukoxy group, Y is hydrogen, CI, C, -
The problem is solved by a drug containing at least one compound (representing an alkoxy group, a C1-, C,-alkoxy group, or an aryl group).

The compounds according to the invention occur as geometric isomers, where:
-0R2 and -0R3 are cis2α, 3α or cis2
β, '5β. Both individual isomers and mixtures thereof belong to the target substances of the present invention.

The compounds according to the invention are eminently suitable for regulating plant growth in various cultivated plants and exceed the products of the same direction of action mentioned at the outset in their spectrum of action and in their tolerability.

The compounds according to the invention are capable of promoting the productive growth of cultivated plants, but can also be inhibited within a certain concentration range. Furthermore, by influencing the developmental stage, a certain increase in yield can be achieved.

In general, this substance acts on the membrane system in cultivated plants, changing its permeability to various substances a).

This material Jt can also exert anti-stress effects under certain conditions.

The compounds according to the invention also cause qualitative and quantitative changes in plants.
1. Since it does not cause changes in the metabolism of products, it can be placed in the classification of plant growth regulation 1jj8rII, which has better IJ ability for the following uses.

13. Suppression of reproductive growth of woody and herbaceous plants on roadsides, rail facilities, etc. to prevent sticky and overgrown growth. Growth control is used to prevent grains from collapsing or breaking, and growth control is used to increase yield (ig) in cotton.

? +'A ZtTi1tIncreases flower buds in plants and cultivated plants. Improved quality, such as increased sugar content in sugar cane, sugar beet or fruits and constant ripening of the crop to increase yield.

Increased resistance to the effects of stress, weather conditions such as cold and dryness, and also to the 4R toxic effects of chemicals.

Effects on latex fluids in rubber trees.

This strain is used to affect parthenocarpic fruit formation, pollen sterility and sex.

λIM node for regulation of seed germination or flower bud germination.

Impact of leaf or fruit fall to facilitate harvesting.

The compounds according to the invention are particularly suitable for influencing the reproductive and developmental growth of some legumes, such as soybean.

The amount used is for each purpose of use (active substance 0.001 from C).
~1 kg/%, and optionally even more convenient doses can be used.

The timing of use is determined by the purpose of use and the prevailing conditions.

Among the compounds according to the invention, in particular in the general formula 1 R17 is 2-methyl-henomen-6-yl, 2-methyl-6-nitylhept-4-en-6-yl, 2.3-
dimethyl-hepler 4-nin-6-yl, 2-methyl-
5-ethyl-heptan-6-yl or 2,6-dimethyl-heptan-6-yl, 2 is a group 0, R7 and R5 are independent, and each is a primary hydrogen or formyl group. , C2<two-alkyl-00- group, C2<, .-alkoxy-01-,03-alkyl-
Represents a CO- group or an aryl-00- group (where X & yo hydrogen atom, (represents 11-C4-alkyl or C1-03-alkoxy, Y is hydrogen, 01-04-alkyl, C□-C3- Compounds representing alkoxy or aryl are the most important in this effect.

08<,. -alkyl&andhiG3-13□0-alkenylno, (for example, 2-methyl-heptane-6
-yl, 2-methyl-6-nityl-hezo-4-en-6-yl, 2.39-methyl-heftu-4-en-6-yl, 2-methyl-5-ethyl-helanotan-6-yl and 2.3-yl. Dimethyl-hep, tan-6-yl can be suppressed, and the acyl crystals include formyl group, 02-,O,-alkyl-CO- group, [32-+0-alkoxy[]1
-J33-alkyl-(]〇- group and aryl-CO-
The radicals may be, for example, acetoxy, methoxyacetoxy, ethoxyacetoxy, propionyloxy, butyryloxy, valeryloxy, pentanoyloxy, hexanoyloxy, henoctuyloxy, dimethylacetoyl, dimethylacetoyl, benzoyloxy and phenylacetoxy.

Examples of Cl, C4-alkyl groups include methyl, ethyl, zorobyl, inpropyl, butyl, Bea-butyl,
Tert-butyl and chloromethyl can be represented by a): C1-, a, -alkoxy groups are, for example, methoxy, ethoxy and fluoroboxy; near-aryl groups include naphthyl, phenyl, 2-chlorophenyl, 3-10
ruphenyl, 4-chlorophenyl, 2.6-dichlorophenyl 1.2.4-7 chlorphenyl, 5.4-dichlorphenyl, 2.4.6-)'J dichlorophenyl, 4-
Bromphenyl, 2.4-cyfromphenyl, 2.6-
cyfuromphenyl, 2,4.6-) IJ -y” r
1 Muphenyl, 2-fluorophenyl, Ro-fluorophenyl, 11-fluorophenyl, 2,4-dinolorphenyl 1.2-mer-y-phenyl, 3-/tylphenyl, 4-methylphenyl, 6 .4-dimethylphenyl, 2-methoxyphenyl, 6-methoxyphenyl, 4-
Methoxyphenyl % 514-di, dl=dimethylenephenyl, 2-diphenyl, phenoxyphenyl, 2-nitrophenyl and 3-nitrophenyl can be given.

Book 46 Ming U (Yoro compounds are single and mutually mixed, 5!
ki and other agents 4. Can be used with 't.

Depending on the use, leaf shavings, plant infestation agents, or anticides can be added depending on the purpose.

Other biocides can also be added if desired to widen the spectrum of action. Weed Abstracts (Weed Ahshr)
Acts), Volume 61, 1981 with the title "List of Common Names and Applications Employed for Calendarly Used Herbisizers and Plant Growth Regulators in Weed"・Abstracts (L
j,et of common names
aM Abbreviation semployed
for currθntly used herhl
cldeean(lplantgrOWthrFIgl
, tla, t(1rFlinWf'1Qrlabstr
Suitable are the active substances listed in ``Acts''. In addition, they can be used synergistically with herbicides and/or growth regulators. , emulsifiers, solvents and oily additives can be used.

The active substances according to the invention or the mixtures thereof can be prepared in the form of a liquid and/or solid carrier or diluent and optionally with the addition of wetting agents, adhesives, emulsifying agents and/or dispersing agents, for example powders, dusting agents. It is advantageous to use them in the form of granules, solutions, emulsions or suspensions.

Suitable liquid phases for Ml are, for example, water, aliphatic and aromatic hydrocarbons such as penzole, doluol, quidyol, cyclohexanone, isophorone, dimethyl sulfoxide, dimethyl formamide, and also mineral oil fractions.

Suitable solids 111 are mineral earths such as tonesil, silica flour, talc, kaolin, attack clay, limestone, silicic acid and 41 products such as grain flour.

Surface-active substances include, for example, calcium ligninsulfonate, polyoxyethylene-alkylphenol ether, naphthalenesulfonate phe-1 and tit 4%.
Penzole sulfonic acid and its salts.

The amount of each active substance in the dosage forms can be varied within a wide range. For example, the medicament may contain about 10 to 80 parts by weight of active substance, 90 to 20 parts by weight of liquid or solid carrier, and optionally up to 20 parts by weight of surface-active material.

Spraying of this drug is carried out in a conventional manner, for example by spraying a carrier
Water is preferably used to achieve a spray volume of about 100 to 1000//ha. Applying this drug in the so-called low volume or ultra-low volume method is the FIJ-like VCnJ ability when applied in the form of so-called microgranules.

For example, the following ingredients are used to make the N11 agent.

8. Powder for dispersion a) Active substance 80% Kaolin 15% surfactant (based on sodium salt of N-methyl-N-ole 5% Ilutaurine and calcium hydroxide of IJ Kuninsulfonic acid) b ) Active substance 50 weight clay mineral 40 weight @% cell pitch
F41t% elevation/concave active agent (based on a mixture of lignin sulfonic acid, 5% calcium by weight, and alkylphenol 11t' glycol ether) C) Agent η 2o% by weight clay ()
7 Shimono 70 Heavy Bone% Cell Pinch
5-layered surface active agent (5 weight range of lignin sulfonic acid) 7-weight alkyl phenol 1 (based on a mixture with lyglycol ether) d) Effect on surface quality 5 weight% tone sil 80% cell pitch
10j Static I surfactant (Based on fatty acid 1 compound product, 5-fold f1:%) B Breast wound? For shrinkage fti*? (20% by weight Kijirol 40% I dimethyl sulfoxide 35% by weight Nonylphenyl polyoxyethylene 5116 5" mixture of calcium sulfonate C Paste active substance 45% by weight Sodium aluminum silicate 5% by weight Ethylene oxide 15] f amount 1 chilli IJ ri 1
7 Coal Edel Spindle Oil 2% ethylene glycol 107fdif water
23 Parts The novel compound of the present invention is, for example, a compound of the general formula [wherein R17 represents the above].
Osmium 1 was converted to I At using butyl hydroperoxide or N-methyl-morpholine-IJ-oxidide.
．． or 1-t, f
(1 liter of p-acid water) Add 1 ounce of vinegar and iodine to the solution ゛C-
Compounds of the formula [in the formula, [+2] and '17 G represent the above] can be treated with a peracid to produce the desired compound. .

For the preparation of the compound of the general formula (1), sterine, fl-cholesterin, stigmasterin, pseudocysterin or β-sitosterin is used as a starting material and converted into the 2-6-kedosteroid of the general formula (2) by a method known per se. (Holy,
(See Vol. 49, No. 1581 Sada C1966).

R formula Ill (1) The reaction to 2α,3α-cis-glycol was carried out in a manner similar to the known method, using 80% t-butyl hydroperoxide (Q and (K, B).

1 by 5harplGs s, TAO8 Volume 98, 1
986 (1976)) or using N-methyl-morpholine-N-oxyP (V+Van Rheen
Tetrahe+1rOn Lett, No. 19
76, p. 1976), osmium tetroxide catalyzed hydroxylation is carried out.

-ff 2β,6β-cis-glycols of formula IV or derivatives thereof are obtained by Pre'vo reaction with silver acetate and iodine in aqueous acetic acid.

The production of B+M lactone of general formula ■ is general 2■ and 6 of ■.
- Kedosteroids are prepared using peracids such as trifluorperacetic acid, formic acid, bermaleic acid, etc.
tion). “2” in the side chain
Compounds with a 2/C23 double bond are obtained from Ic by brominating this double bond before lactonization.

The double bond reacts with the zinc in acetic acid by Bayer-Villiger oxidation.

The present invention will now be described in detail with reference to examples.

Example 1 a) Dissolve 24-B-x thyl-5α-cholester-2゜22-dien-6-one 3-569 in 60□' of t-butanol, add 41□' of 20% tetraethylammonium hydroxide solution, Cooled to 0 °C and diluted with 80% t;-butyl hydroperoxide 12WLl and osminium tetroxide solution (Oθ04 25Qmg, t-butanol 49.7
5 mf, and 80 t-butyl hydroperoxide 0
-25m/manufactured from) add 6mA. The reaction solution is stirred at room temperature for 6 hours, poured into 5% sodium bisulfite solution and extracted with acetic ester. The extract is washed with water, dried over sodium sulfate and concentrated. 2α after recrystallization from methylene chloride-methanol.

2.6 g of 6α-dihydroxy-24-8-ethyl-5α-cholest-22-en-6-one are obtained. Melting point:
234.5-235.5°c0b) 2α,6α-dihydroxy-24-day-ethyl-5α-choleslar22-
Dissolve 2.2g of nin-6-one in 15ml of pyridine, add 8 parts of acetic anhydride and 220 parts of 4-dimethylaminopyridine.
Add m9 and leave at 20°C for 17 hours. Afterwards precipitation in ice water, the product was filtered off with suction, washed and dried.

C) 2.6 g of crude diacetate in 601 ml of ether and 0.28 bromine in 50 ml of glacial acetic acid! / and stir at room temperature for 10 minutes. For working up, dilute with ether, wash neutral with water and concentrate in vacuo. In this way, coarse 2α, 6α
3.2 g of -diacetoxy-22,23-dibromo-24-ethyl-5α-cholestan-6-one are obtained.

d) 60% hydrogen peroxide in 28ml of methylene chloride/1.
5. The mA is suspended, cooled to -10°C and 27.72 d of trifluoroacetic anhydride are slowly added dropwise so that the internal temperature does not rise above +-10'C. Subsequently, 2α,6α-diacetoxy- in methylene chloride 25d
Add 6.2y of 22,23-dibromo-24-ethyl-5α-cholestan-6-one and stir for 40 minutes at room temperature.

It is subsequently diluted with methylene chloride, washed successively with water, aqueous sodium carbonate solution and water, dried and concentrated in vacuo. The residue is heated in 100 m/l of acetic acid with 5 g of zinc powder for 1 hour on a steam bath. Filter off the zinc, dilute with methylene chloride, wash neutral with water and concentrate. Chromatography on silica del (gradient doluol/acetic ester) and delivery from acetone/hexane resulted in 2α,3α-diacetoxy-24-ethyl-7
-Oxa-B-homo-5α-cholestu-22-ene-6
-on, 11 points 221-225℃ 1.5g and 2
α,3α-diacetoxy-24-ethyl-6-oxa-
B-homo-5α-choleslar 22-nin-huon, melting point 202-204"0 510 ml/ is obtained.

Example 2 a) 6.2 g of silver acetate and 1.9 iodine in a solution of 2 g of 24-ethyl-5α-cholesnow 2.22-dien-6-one in 270 ml of ice fm'li & 6.7 l of water
g) Add r and heat at 45°C for 173 hours with stirring. After separating the silver salt and washing with chloroform, the filtrate is diluted with chloroform, washed with water, sodium thiosulfate and water, dried and concentrated. 2β-acetoxy-6β-hydroxy-24-ethyl-5α-choleslar 22-nin-6- after crystallization from acetone/hexane
On'1.2. ! 7 is obtained. , melting point 192-194
℃.

b) △ as described in Example I Q) and 1 a)
After bromination of the 22-double bond, Bayer-Villiger obturation and zinc reduction, the crude product is chromatographed on silica gel.

After recrystallization from hexane/ether by gradient elution with chloroform/acetone, mp 151-1
2β-acetoxy-6β-hydroxy-24 at 53 °C
-ethyl-7-oxa-B-homo-5α-choleslar 2
Yield of 2-nin-6-one, melting point 175-1
2β-acetoxy-6β-hydroxy-24 at 76°C
-ethyl-6-oxa-B-homo-5α-choleslar 2
2-nin-huon is obtained in a yield of 1(:l).

Example 5 a) 2β-acetoxy-3β-hydroxy-24-ethyl-7-oxa-B- in methanol 5 Q rn/i
Homo-5α-choleslar 22-nin-6-one 2.2g
500 m of potassium hydroxide in 1 ornl of methanol
Add y and stir at room temperature for 60 minutes. Acidified with acetic acid,
Precipitate in ice water, filter with suction, wash and dry.

After crystallization from chloroform-ether, melting point 211
1.7 g of 2β,6β-dihydroxy-24-ethyl-7-oxer B-homo 5α-cholest-22-en-6-one are obtained at ~213°C.

b) 2β,3β-dihydroxy-24-ethyl-7
-Oxa-B-homo-5α-=Res22-:r-7
-6-one 500 mg at 110 mg in Biricif 4 mA
Cool to 0C, add acetic anhydride Q, 5mA, and stir at -5 to 0C for 6.5 hours. After precipitation in ice water, the product is filtered off with suction, washed, dried and then recrystallized from acetone/hexane.

3β-acetoxy-2β-hydroxy-24-ethyl-7-oxa-B-homo-5α- with melting point 182-184°C
Kolesler 22-nin-6-one 41 (I+9 is obtained).

Example 4 2α,5α-dihydroxy-7-oxer B-homo5
α-cholestan-6-one 1! ! Wobirijin 10rn
1 ml of acetic anhydride, cooled to 0 ”O
Add. Stir at 0-5°C for 5 hours, pour into ice water,
Aspirate (jtM), wash and dry. After crystallization of P+ from pentane, 2α with melting point 165.5-167 °C
-acetoxy-3α-hyproxy, 7-oxerB-
950 ~ of homo-5α-cholestan-6-one are obtained.

Preparation of starting materials: a) 5α-choleslar 2-nin-6-one 25,F
was dissolved in 1401 tetrahydrofuran, 14 g of N-methylmorpholine-N-oxide, 25 Tnl of water and t
-Add 501 butanol and 5Qm tetrahydrofuran
A solution of 2501 v of osmium tetroxide in l is added under stirring. The reaction solution is stirred at room temperature for 177 hours in the absence of light. Subsequently, 50 ml of 2N sulfuric acid and 1 g of sodium sulfide
The product was precipitated in ice water 71 added with
Wash with water, dissolve in chloroform and concentrate the solution in vacuo. This crude product (60 g) was mixed with pyridine i4
After adding 7Qmi of acetic anhydride and 6g of 4-dimethylaminopyridine, the mixture is left at room temperature for 16 hours.

After precipitation in water, the product is filtered off with suction, washed with water, dried and then chromatographed on silica gel. After recrystallization from ethanol, melting point 150.0 ~
151.5” 2α of O.

3α-diacetoxy-5α-cholestan-6-one with a yield of 75% and a melting point of 185.5-185°C.
-Diacetoxy-5α-cholestan-6-mene in yield of 1
Get it for 5%.

b) 26 mA of 50% hydrogen peroxide was suspended in methylene chloride and cooled to -10°C to form trifluoroacetic anhydride.
611 is slowly added dropwise so that the internal temperature does not exceed 10°C. Subsequently, 2 g of 2α,3α-diacetoxyl 5α-cholestane-6-off 2 g in 160 l of methylene chloride are added and stirred for 40 minutes at room temperature. For work-up, it is diluted with methylene chloride, washed successively with water, sodium carbonate solution and water and concentrated in vacuo. Chromatography on a silica shell and recrystallization from acetone/hexane resulted in a 2α
, 3α-diacetoxy7-oxer B-homo-5α-
Cholestan-6-one has a yield range of 81% and a melting point of 245% to 2%.
-2α,3α-diacetoxy-6-okiner B at 47°C
- Up to 6.2 liters of homo-5α-cholestan-7-one are obtained.

C) 28.3 g of 2α,6α-diacetoxy-7-oxa-B-homo-5α-cholestan-6-one are dissolved in 5QQ m/i of methanol and 150+7
! The solution of potassium hydroxide 11' in the solution is stirred at room temperature for 30 minutes. Then, it was acidified with acetic acid and precipitated in ice water.
The product is filtered with suction, washed with water and dried. After recrystallization from acetone/pentane, melting point 168-1
2α,3α-zohydroxy-7-oxer B- at 40°C
Homo-5α-cholestan-6-one 22.4.9 (9
Section 5) is obtained.

Example 5 a) 2α as described in Example 4 C).

6α-Diacetoxy-6-oxer B-homo-5α-cholesmen-7-one 1.111 is saponified.

2α,3α-dihydroxy-6-oxa-B-homo-5α-cholestan-7-one 785rn9 is obtained with a melting point of 216.5-218°C.

b) 2α,6α-dihydroxy 6-oxer B-
Homo-5α-cholestan-7-one 250■? Dissolved in Linf 2M, cooled to -10°C and diluted with 0.2 acetic anhydride.
4. Add heat and stir at -5°C to 0°C for 4 hours. After precipitation in ice water, the product was filtered off with suction, washed and dried and then recrystallized from acetone/hexane. Melting point 199
2α-acetoquine-6α-hydroxy-6 at ~201°C
-Oxa-B-homo-5α-cholestan-7-one 21
0 ■ is obtained.

Example 6 2α,5α-dihydroxy-24-methyl-6-oxa-B-homo-5α-choleslar 22-nin-huon 6
00Ing is acetylated as described in Example 5b) VC. 2α-acetoxy-3α with melting point 175-174°C
-Hydroxy-24-methyl-6-oxa-B-homo-
5α-Koresler 22-Ninh Huong 515”F/”
can get.

Preparation of Yamamoto Material: 24-May-ru-5α-cholest-2,22-syn-6-one is prepared from Prassicasterin by known methods and reacted exactly as described in Example 1.

Example 7 2β,6β-dihydroxy-7-okipoo-B-homo5α-cholestan-6-one 11 in acetone 100ml
and tetrahydrofuran 100%, cooled to 0°C, and diluted with boron trifluoride ether lead compound h/IJIJ, 5 ml.
and stirred at 0-5°C for 60 minutes. After adding pyridine, 1. Recrystallize from methylene chloride/isopropyl ether stone. Melting point 216-217
．． 2β,6β-inpropylidenedioxy-7-oxa-B-ho,mo5α-cholestan-6-one 73
1~ is obtained.

Similarly, the following is obtained: 2α,5α-ingropylidenedioxy-7-oxer B-homo-5α-cholestan-6-one, melting point: 216
~217℃.

2α,6α-Inzolobylidenedioxy-24-ethyl-7-oxa-B-homo-5α-choleslar 22-nin-6-one, melting point = 157-158°C.

Example 8 2α,5α-dihydroxy-7-oxa-B-homo-5
α-Cholestan-6-one 900g pyridine 10w
Dissolve in Ll and cool to 0°.

Mix with 8 ml of anhydrous valerian C'fR1 and incubate at 0-5℃ for 10 minutes.
Stir for an hour. After work-up as described in Example 4, 2α-valeryloxy-3α-hydroxy-7-oxa-B-homo-5α-choles, tan-6-
On 950m9 is obtained.

Example 9 2α,6α-diacetoxy-24 as described in Example 6
-ethyl-7-oxa-B-homo-5α-choleslar 2
2-Nin-6-one is dissolved (1) and partially acetylated. 2α-acetoxy-3α-
hirroxy24-ethyl-7-oxa-B-homo-5
α-Colemen-22-en/-6-one is obtained in a yield of over 70%.

Example 10 2α,3α-zohydroxy-7-oxer B-homo-5
α-cholestan-6-one 900~ in pyridine IQml
Add ethoxyacetic acid and hydrate 1a and stir at 0-5°C for 5 hours. Treat as described in Example 4 and 7 and reconstitute from acetone/hexane. 2α-Ethoxyacetoxy 3α-hydroxy-7-oxa-B-homo-5α with a melting point of 172-173°C after crystallization
- Cholestan-6-one 72 o da is obtained.

Example 11 2α,3α-dihydroxy-24-ethyl-7-oxa-B-homo-5α-choleslar 22-nin-6-one 3
Q[11v anhydride 7 with phenyl acid 6 in pyridine 3d
Incubate for 10 hours at 0-5°C with 80 ml of water.

After work-up and ex-crystallization from acetone/hexane, 2α-phenylacetoxy-3 has a melting point of 185-186 °C.
α-hydroxy-24-ethyl-7-oxa-B-homo-5α-choleslar 22-nin-6-one 210In9
is obtained.

Example 12 2α,roα-dihydroxy-7-oxa~B-homo5
α-cholestan-6-one 500 ~ Penzol 5Qt
Add 0.75+ g of triethyl melt acetate in nl, add 51 ng of t,p-)luolsulfonic acid.

The solution was stirred at room temperature for 20 minutes and then pyridine 3tvI6
is added and contracted by θ in vacuum. Dissolve the remainder in methylene chloride, wash with water, dry over sulfuric acid,
Shrink.

Thus, 2α, 5α-(1-
Ethoxy-ethylenedioxy)-7-oxa-B-homo-5α-cholestan-6-one 605 rw is obtained.

1i14J) K L, -C The following is produced: 2
rt, 3α-(1-ethoxy-ethylenedio=V
-6-oxa-B-homo-5α-cholesmen-
7-on, M/Difficulty: 122-124°C.

2α, 6α-(1-ethoxy-progylidenedioxy)
-7-okiri-B-homo5α-cholestane-6-
On, waking Q point: 115-118°C.

2α, 3α-(1-methoxymethylene/dioxy)-2
4-Ethyl-7-oxa-B-homo-5α-choleslar 22-nin-6-one, 1 = 96-98°C.

2β,3//-(1-ethoxyethylenesoaoxy)
-24-ethyl-7-oxa-B-homo-5α-choleslar 22-nin-6-one, FA'lt point: 126-1
25℃.

Example 15 2α,5α-dihydroxy-7-oxa-B-homo-5
α~cholestan-6-one 500~ in tetrahydrofuran 5 Hl with acetophenone i, 5 ml. and 9.1 ml of boron trifluoride ether complex compound, and 3
Heat for an hour. Pull LM.

J't, filtrate in 2, pyridine 1m/! and e-contract in the air. After rubbing with hexane -77, kc, the noncipitated form 2'' + 5α-(1-methyl-1-
phenyl-methylenedioxy)-7-oxer B-homo 5α-cholestan-6-one 465 P9 has a melting point of 13
It is recorded as a mixture of diastereomers at a temperature of 0.5 to 132°C.

Example 14 2α,6α-dihydroxy-7-oxer B-homo5
Dissolve 500 m9 of α-cholestan-6-one in 151 diethyl carbonate and ? Heat until it makes a ringing sound, and after distilling off diethyl carbonate 2ve, sodium methylate! sOmy
Add. DI/distill from the reaction solution over 3 minutes. After cooling, add 0.15 m/g of glacial acetic acid and evaporate f1 in vacuo.
Shrink. The residue is recrystallized from acetone/hexane. In this way, 7450 my of 2α,6α-carbonyldioxy-7-oxa-B-homo-5α-cholestane-6-1 with a melting point of 205.5-205°C is obtained.

In the same way, the following is prepared: Nα,3α-carbonyldioxy-24-ethyl-7-oxa-B-homo-5α-choleslar 22-nin-6-one, 2β, melting point 193-195°C , 3β-carbonyldioxy-7-ogidu-13-
Homo5α-cholestan-6-one, FA'l! Points: 2
12-214℃.

Example 15 2α,3α-dihydroxy-7-oxa-B-homo-5
α-cholestan-6-one 300FS' dissolved in benzaldehyde 2x, 70% 0% Velchlor, 02m/
; and stirred at room temperature for 2 hours. Next, neutralize the mushroom solution with pyridine.

Dilute with hexane and chromatograph on silica gel. Hexane/+III; acid ester (6:
4) 258 m9 of 2α,3α-benzylidenedioxy-7-oxa-B-homo-5α-cholestan-6-one are eluted and recrystallized from ether/pentane. Fkl1
Point: 137-169°C.

Similarly, the following is prepared: 2α,6α-penzylidenezooxy-6-mexar B-
Homo-5α-cholestan-7-one, 6 points: 179-1
800C 2β,3β-benzylidenedioxy-6-oxa-B-
Homo-5α-cholestane-6-ono, melting point: 129-1
．． ! +1'00 2β, 3. Turbenzylidenedioxy-7-oxa-B
-Homo-5α-cholestan-6-one, melting point: 153~
155°C.

The compounds according to the invention are generally colorless, odorless, crystalline substances that are soluble in water, to some extent soluble in aliphatic hydrocarbons such as petroleum ether, hexane, pentane and cyclohexane, chloroform, halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, aromatic hydrocarbons such as penzole, doluol and quidyol, ethers such as diethyl ether, tetrahydrofuran and dioxane, carboxylic acid nitriles such as acetonitrile, acetone C7 7. Ketones such as methanol and emenol. C-type: T-type, dimethylformamide) '1. Sulfoxides such as dimethyl sulfoxide in the order C.

Example 1 (υK) of v) The properties of the first starch syrup 111j f) of the two compounds will be explained in detail.

Ifsu 16 Ink vine 7, c L, growth promotion in Kami 11+1 “Pinto” vine 1f Air beans, H
i, 'J k, indoors at 25°C, humidity 90%, 6
4111 of 60 nm, and 7
, 'S Onm , with a non-76' low part.

60 songs 4 - 1 station cultivated, test compounds 10 and 2
011g into the 7th agent and grow the second part KJlf t#sa・1:ru.

Both use 5 [I Y*)' Measure the distance between JiI and examine the 1K Hi rate compared to the control.

Record this result in the Buddha table.

Promotion rate Compound according to the invention 2α-acetoxy6α-hydroxy-B-homo-7-oxa-5α-cholestan-6-one 292
1252α,6α-carbonyldioxy-B-pomo7-ochinar5α-cholethl-6-one 190 30
42α-acetoxy-6α-hydroxy-B-homo-6-oxa-5α-cholestan-huone 162
1252α,6α-(1-ethoxy-ethylenedioxy)-13-homo-7-oxa-5α-cholestan-6-one 165 1622α,3
α-(1-Methyl-1-phenyl-methylenedioxy)-B-homo-7-oxa-5α-cholesta/-6-one 152
342 ratio II
(3-Indolyl)-Butyric Acid 5138 Control 100 100 ftK showed that the compounds according to the invention had a stronger impact on the described test conditions -F than the comparative cross-agent and the control.

On the other hand, is there a lot of metaplasia? It acts strongly only on the growth of the thick skin, leading to the reduction of the 1st part to the 1st part.

Example 17 Imitation of root growth in Mung beans (Aungbohnen) Six beans are germinated under warm conditions in an aqueous suspension of the test compound at a concentration ranging from 0.01 wt.

After 6 days, determine the root length of the germinated JTfj plants.

The experimental results are expressed in percentages in the table below.

2α-acetoxy-6 (χ-hydroxy-B-homo7
-Oquinar 5α-cholestan-6-one
1802α,6α-carbonyldioxy-B-homo-7-oxa-5α-cholestane-6-
on 160
2α-acetoxy-6α-hydroxy-B-homo-6-
Oxa-5α-cholestane-huon
1602α, 3α-(1-ethoxy-
ethylenedioxy)-B-homo-7-oxa-5α-cholestan-6-one 20
02α, 3α-(1-methyl-1-phenyl-methylenedioxy)-B-homo-7-oxa-5α-cholestan-6-one 150 ratio 1·, gibberellic acid (GA3) 80 control 100 cases 18 Cultivation (1 [(Increase in object resistance a14) The cultivated plants listed in +19 are treated with an aqueous emulsion of the test compound 1 or its ?i1 compound. One week after the treatment, the treatment results are shown as O~ Divided into 10 stages.

o=iod destruction, 10=no damage This allows the compounds of the present invention to have a Z) high 1 relative to known weed killers.
Eighty-four! t: It was found that it gives tr'+ property (;j.

Procedural amendment (voluntary) 1. Indication of the case Patent Application No. 130371 of 1982 2. Name of the invention 3. Relationship with the person making the amendment Patent applicant name Schering Akchengesellschaft 4
, Claims column and Detailed explanation of the invention column 7 of the sub-agent's specification Contents of amendment (1) The scope of claims will be amended as shown in the attached sheet.

(2) [and...] on page 14, line 13 of the specification
``in ...'' is amended to ``and in their compatibility.''

(3) ro, ool on page 16, line 13...
..., and "r O, OO is 1 to 1 kg/ha," is corrected.

(4) On page 19, line 14 of the same, [single and mutually mixed] is amended to "single and mutually mixed."

(5) At the end of page 26 of the same page, replace "obtainable." with "obtainable (
(See He1v, Vol. 49, p. 1581 (1966)). ” he corrected.

(6) “Truffle hyperaceteric intoxication” on page 27, lines 2-3.
is corrected to "trifluoroperacetic acid".

(7) Correct "r24-s-ethyl-" on page 27, line 13 to "24S-ethyl."

(8) r-24-s-ethyl on page 28, line 6.”
is corrected to "r-248-ethyl".

(9) “Jihi 10ki 7-24-” on page 28, line 9 of the same
8-'' is corrected to [JIHI PRO ROXY 248-J.

(10) Change “up to 6.2%” on page 35, line 5 of the same to “
6.2%”.

(11) Change “promotion rate” in the first line of page 46 to “promotion rate (%)”.
)” is corrected.

θ2) “Mung beans (Mur +
g-bohnen) J as ``mu/gu beans (Mungbo)
hnen.

Phaseolus Aureus ) J and correct.

(13) Change “promotion rate” in line 4 of page 48 to “promotion rate (%)”.
)” is corrected.

(“To treat.” in line 7 of page 49 of 141 is corrected to “to treat the soil.”)

・(15) “2-Cα, α,
α−” is corrected to “2−(α, α, α−”).

2. Claims 1-- General formula I [wherein R17 is a C8-C1o-alkyl group or a C8-C1o-alkyl group]
Represents C1o-alkenyl group, Z is group 0
0 R3 independently represent hydrogen or an acyl group, or together ＼ /C=0 or >c / X <wherein, or hydrogen,
C1-C4-alkyl group or C1-C3-alkoxy group, Y is hydrogen, 01-C4-alkyl group, C1-C4-alkyl group,
C3-alkoxy group or aryl group).

”-R17 is 2-methyl-heptan-6-yl, 2-methyl-3-ethylhezoen-6-yl, 2
, 3-,) methyl-hezo-en-6-yl, 2
-methyl-3-ethyl-heptan-6-yl or 2.3
-) methyl-heptane-6-yl, 2 represents R3 independently, and each represents hydrogen or formyl group, 02-c7-alkyl-CO- group, 02-C7-
Alkoxy-01-C3-represents an alkyl-CO- group or an aryl-CO- group, or together with a group C-
0 or ゝc/X/ / \Y (where, or hydrogen, 01-C4-alkyl group or 01
~C3-alkoxy group, Y is hydrogen, 01-C4
2. The brannosteroid derivative according to claim 1, which represents a -alkyl group, an 01-C5-alkoxy group, or an aryl group.

3. The compound according to claim 1, which is 2α,3α-diacetoxy-24-ethyl-7-oxa-B-homo-5α-choleslar-22-nin-6-one.

Cattle, 2α,3α-diacetoxy-24-ethyl-6-
The compound according to claim 1, which is Oxer B-homo-5α-choleslar 22-nin-huon.

5.2β-acetoxy-3β-hydroxy-24-ethyl-7-oxa-B-homo-5α-choleslar 22-nin-6-4% of the compound according to claim 1.

62β-acetoxy-3β-hydroxy-24-ethyl-6-oxa-B-homo-5α-choleslar 22-nin-huontheal The compound according to claim 1.

7. The compound according to claim 1, which is 3β-acetoxy-2β-hydroxy-24-ethyl-7-oxa-B-homo-5α-choleso-22-en-6-onte.

8. The compound according to claim 1, which is 2α-acetoxy-3α-hydroxy-7-, oxa-B-homo-5α-cholestan-〇-one.

9. The compound according to claim 1, which is 2α-acetoxy-3α-hydroquine-6-oxa-B-homo-5α-cholestan-7-one.

10.2α-acetoxy-3α-hyproxy24-methyl-6-oxa-B-homoδα-cholestu22-
The compound according to claim 1, in which the percentage of S is % of en-7-one.

11. The compound according to claim 1, which is 2β,3β-isozolobylidenedioxy-7,oxa-B-homo-5α-cholestan-6-one.

12. The compound according to claim 1, which is 2α,3α-isozolobylidenedioxy-7-ox+-B-homo-5α-cholestan-6-one.

13,2α,3α-inzolobylidenedioxy-24-
Ethyl-7-oxa-B-pomo5α-cholesnow 22
-en-6-onetheal% Compound according to claim 1.

14, 2α-noS leliruoki/-δα-hydroxy-
The compound according to claim 1, which is 7-oxa-B-homo-5α-cholestan-6-one.

152.alpha.-acetoquine-3.alpha.-hydroxy/-24-ethyl-7-oxer B-homo 5.alpha.-cholest-22-en-6-ontheal% Compound according to claim 1.

16, 2α-ethoxyacetoxy-3α-hydroxy/
The compound according to claim 1, which is -7-ogycer B-homo5α-cholestan-6-one.

172α-phenylacetoxy-3α-hydroxy/-2
The compound according to claim 1, which is 4-ethyl-7-oxa-B-homo-5α-cholesno-22-en-6-one.

18, 2α, 3α-(l-ethoxy-ethylenedioquine)-7-oxa-B-homo-5α-cholestane-6-
The compound according to claim 1, which is

19.2α, 3α-(1-ethoxy-ethylene dioxy7
)-6-oxerB-homo5α-cholestan-7-one.

20.2α,3α-(1-ethoxy-propylidenedioxy)-7-oxa-B-homo-5α-cholestane-6
The compound according to claim 1, which is -one.

21.2α,3α-(1-Methoxy-methylenedioxy)-24-ethyl-7-oxerB-homo5α-choles-22-en-6-one Claim 1
Compounds described in Section.

22.2β, 3β-(1-Ethoxy-ethylenedioxy)-24-ethyl-7-oxa-B-homo-5α-cholesurar 22-nin-6-one Claim 1
Compounds described in Section.

23. The compound according to claim 1, containing 6% of 2α,3α-(1-methyl-1-phenyl-methylenedioxy)-7-oxa-B-homo-5α-cholestan-6-one.

24. The compound according to claim 1, which is 2α,3α-carponyldioxy/-7-ogily B-homo-5α-cholestan-6-one.

The compound according to claim 1, which is 252α,3α-carzenyldioxy-24-ef-7-t-B-homo-5α-choleslar-22-nin-6-one.

262β,3β-carbonyldioxy-7-oxa-B
-Homo-5α-cholestan-6-one, the compound according to claim 1 272α,3α-benzylidenedioxy-7-oxy(t-B-homo-5α-cholestan-6-one) A compound according to claim 1.

28. The compound according to claim 1, which is 2α,3α-benzylidenedioxy-6-oxa-B-homo-5α-cholestan-7-one.

29.2β,3β-inzylidenedioxy-6-oct
The compound according to claim 1, which is -B-homo-5α-cholestan-7-one.

30. The compound according to claim 1, which is 2β,3β-benzylidenedioxy-7-oxa-B-homo-5α-cholestan-6-one.

31, General formula I [wherein R47 is a 08-C4°-alkyl group or a C8-
C1o-alkenyl group, Z and R3 each independently represent hydrogen or an acyl group,
or - together with c=o or)(X (where,
X represents hydrogen, C1-Y C4-alkyl group or 01-C3-alcokyne group, Y represents hydrogen, 01-C4-alkyl group, C1-C3-
In order to produce a brassinosterite derivative of the general formula (1) (representing an alkoxy group or an aryl group), a compound of the general formula or using 19-methyl-morpholine-N-oxide to prepare a compound of onumium tetroxide-catalyzed hydroquine It IJ [wherein R17 represents the above], or -. Silver acetate and iodine are reacted to form a compound of the general formula [wherein R2 and R17 represent the above], and these are treated with peracid to form the desired compound. Method for producing nosteroid derivatives.

32 General formula ■ [In the formula, R17 is a C8-C1o-alkyl group or a C8-
Cl0-alkenyl group, Z represents R3 independently, each represents hydrogen or an aryl group, or - together, C-0 or >07X (wherein X is hydrogen, 01 ~C4-alkyl group or 01-C3-alkoxy group, Y is hydrogen, C1-C4-alkyl group, C
1-C5-alkoxy group or aryl group)] A drug having a plant growth regulating action, characterized in that it contains at least one brassinosteroid derivative.

33. The drug according to claim 32, mixed with a carrier substance and/or an auxiliary agent.

34. The agent according to claim 32 or 33, which affects the reproductive and developmental growth of leguminous plants, especially soybean.

61

Claims (1)

[Claims] 1 General formula 1 [In the formula, R□7 is a C8~(Co□0-alkyl group or Cρ
~C10-alkenyl group, 2 is a group -(j-0-
OH2-Make-o-e-(represents 3H2-, R
2111 00 and R3&U independent, each with water g.
or represents an acyl group, or consists of ゛C, &''/
C20 or C(d) (where K is hydrogen, 01~C
4-alkylno, (or C1-0, -alkoxy group, Y4 engineering hydrogen, C1-C4-alkyl group, C1-C
3,-representing an alkoxy group or an aryl group]. 2, a□7 is 2-methyl-heptan-6-yl. 2-Methyl-6-nityl-heptu-4-en-6-yl, 2,5-dimethyl-heptu-4-nin-6-yl, 2
-methyl-3-ethyl-heptan-6-yl or 2.5
-dimeguruhebutan-6-yl, 2 is 0 0R
2 and R3 are independent, and each represents Jt hydrogen or formyl group, (12-Q fualkyl-CO- group,
(!2~07'-7/l/Nia xy-(31903-alkyl-CC+-, IA or aryl-C〇-
represents a group or together with the group C20 or / represents a group (where X is hydrogen, 01-C4-alkyl group or 01-C3-alkoxy group, and Y is hydrogen; ,
C]~C3-alkyl group, 00~C3-alkoxy group or LJ aryl group 4-) IF, ll, correction h
i1 □ Desired A11] The Plassinus j°loid derivative described in item 1 below. The compound according to claim 1, which is 62α,6α-diacetoxy-24-ethyl-7-ogycerB-homo5α-choles-22-en-6-one. 4.2α, 3α-diacetoxy-24-nityl-6-oxer B-homo-5α-choleslar 22-nin-huon %f + range of requirements Item 1 Item 11 That compound, 5, 2β-acetoxy-6β-bitroxy- 24-Ethyl-7-oxa-B-homo-5α-choleslar 22-
Nin-6-onthea7: A compound according to claim 1. 6,2I-acetoxy-6I-hydroxy-24-ethyl-6-oxerB-bomo-5α-choles-22-yune-7-onte, I) Le/iKf The compound according to claim 1. 7.5p-acetoxy-2β-hydroxy-24-ethyl-7-oxa-B-homo-5α-choleslar 22-nin-6-ontheal The compound according to claim 1. 8. The compound according to claim m1 which is 2α-acetoxy-3α-hydroxy-7-oxa-B-homo-5α-cholestan-6-one. 92α-acetoxy-6α-hydroxy-6-oxa-
The compound according to claim 1, which is B-homo-5α-cholestan-7-one. 10.2α-acetoxy-6α-hydroxy-24-methyl-6-ochinar B-homo 5α-cholestu22-
Compound I according to claim 1, which is en-7-one. 11. The compound according to claim 1, which is 2β,6β-inzolobylidenedioxy-7-oxa-b-homo-5α-cholestan-6-one. 122α, 3α-inzolobylidenedioxy-7-oxutrohomo-5a-cholestan-6-one
[Yen Allowance M Required Range The chemical compound (compound) described in item 1. 16.2α,6α-inpropylidenedioxy-24-
Ethyl-7-oxa-B-homo-5α-choleslar 22
-nin-6-onte J') f1 of Le special 6'1° revision 1 request
1. A compound according to item 1, box 1. 14, 2α-valeryloxy-5α-hydroxy-7-
1. The compound according to item 1, which is occhyli[deg.]-B-homo5[alpha]-cholestan-6-one. 15, 2α-acetoxy-6α-hydroxy-24-ethyl-7-ogyser B-homo 5α-choles-22-
en-6-ontheall'f'jrt'l'+jl"
The compound described in Section 1 of Section 21 of Section 21 of 1. 16.2α-ethoxyacetoxy-3α-hydroxy-
7-Ogily B-homo 5α-cholestan-6-mene. 17.2α-phenyl 6α-hydroxy-
The compound according to claim 1, which is 24-ethyl-7-oxer B-homo5α-cholest-22-en-6-one. 18. The compound according to Claim 1J+81 which is 2α,3α-(1-ethoxy-ethylenedioxy)-7-oxa-B-homo-5α-cholestan-6-one. 19. The compound according to claim 11, which is 2α,6α-(1-ethoxy-ethylenedioxy)-6-oxa-B-homo-5α-cholestan-7-one. 20,2α,3α-(1-ethoxy-propylidenedioxy)-7-oxer B-homo 5α-cholestane-6
-Claim No. 1.0 that is on! Compounds described. 21.2α, 3α-(1-Methoxymebu-rensoxy)-24-ethyl-7-oyacer B-homo5α-choles-22-ene-6-one deru, i) '1'UI
S occurrence for T'l'ifi''I 14) 1 Compounds commonly described.
Small mo 5α-Koresu two 2 noen-6-on'
F'j H1ilI! A compound according to item 281 of the desired scope. 25.2α, 6α-(1-methyl-1-phenyl-methylenedioxy)-7-oxa-B-ho and 15α-cholestan-6-one, the compound described in item 1 of the patent ftII claim . 24. The compound according to claim 1, which is 5α-cholestan-6-one. 2r-), 2α,5α-carbonyldioxy-24-
Ejiru 7-Okizer B-Homo-5α-Koresler 22
-nin-6-one The compound according to claim 1 JJi. 262β,6β-carbonyldioxy-7-ogycer B
-Homo-5α-cholestan-6-one. 272 (and 3α-benzylidenedioxy-7-oxythi-13-homo-5α-cholestan-6-one). 28,2α,6α-benzylidenedioxy-6- Oki・
The compound according to claim 1, which is S-B-homo-5 (χ-cholestan-7-one). The compound described in item 1 of the scope of the Patented Patent I, which is 3U, 2β, 3β-benozylidene-sioquine-7=oxerB-homo-5α-cholestan-6-one.
11. The compound according to item 1. 61, General formula ■ tt, o H [In the formula, 1 (□7 is a C8-C0°-alkyl group or C
8~C□. -represents an alkenyl group, 2 is 0
0 representation, R
2 and R3 are each independently hydrogen or an acyl group, or
, -alkyl group or C1-]]3-alkoxy I, ,Y is hydrogen%C1<4-alkyl group, 01-C,-
In order to produce a prascinosteroid derivative of the alkoxy group or aryl group represented by '1), a compound of the general formula
osmium tetroxide-catalyzed hydroxylation using butyl hydroperoxide or using N-methyl-sulfoline-N-oxide to give a compound of the general formula (1), where R1 is as defined above; or The compound of the general formula (2) is reacted with silver acetate and iodine in an aqueous acetic acid solution to form a compound of the general formula (2) (wherein R2 and R1 represent the above), and these are treated with peracid to form the desired compound. A method for producing a brassinosteroid conductor, which is characterized by forming it into a compound. '52. General Formula ■ [In the formula, R17 is C3-JOo. -alkyl group or 08
~C: represents a to--ylkenyl group, 2 is OO, L, f<2 and R3 are independent, and each represents hydrogen or an acyl group, or \ /X - together group /C =0 or a\, (where X is hydrogen,
represents a C1-C4-alkyl group or a 01-03-alkoxy group, Y is hydrogen, O,-, O4-alkyl group, C1
1. An agent for plant growth IA1A1, characterized in that it contains at least one prascinosteroid derivative (representing -b-alkoxy group or aryl group). 36. The drug according to claim 32, mixed with a carrier substance and/or an auxiliary agent. 34. Agents according to claims 52 and 63 which influence the reproductive and developmental growth of leguminous plants, in particular soybeans.