JPH0421696A - Novel steroid compound and carcinostatic agent - Google Patents

Abstract

NEW MATERIAL:The compound of formula (R1 is H, OH or acetyloxy; R2 and R5 are OH or acetyloxy; R3 and R7 are methyl; R4, R6 and R8 are H or OH; R3 and R4 may together form terminal methylene; R7 and R8 may together form terminal methylene; R5 and R6 may together form epoxy; R5 may together with 27-carbon atom form pyran ring; R5 may together with 25-carbon atom form furan ring). EXAMPLE:3-0-acetyl-2,20,22,25-tetradeoxy-22,23-epoxy-24-hydroxymakiste rone A. USE:Carcinostatic agent. PREPARATION:The objective compound is produced by extracting CHOREI (dried sclerotium of Polyporus umbellatus belonging to family Polyporaceae) with a water-soluble solvent (e.g. water and methanol) and fractionating and purifying the extract by chromatography.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to novel compounds and anticancer agents.

More specifically, the invention relates to the general formula [wherein R is hydrogen, a hydroxyl group or an acetyloxy group, R2 and R5 are a hydroxyl group or an acetyloxy group, R and R1 are methyl, R4, R6 and R8
is hydrogen or hydroxyl group. however.

a) R and R4 may form a terminal methylene.

b) Rt and R may form a terminal methylene.

e) Epoxy may be formed with R and R5.1゜d)
Rs and carbon 27 may form a pyran ring.

e) R and carbon 25 may form a furan ring)
.

] and - maximum.

[In the formula, R1 is hydrogen or a hydroxyl group or an acetyloxy group, R2 and R5 are a hydroxyl group or an acetyloxy group, R and R1 are methyl, and R4, R5 and R1
is hydrogen or hydroxyl group. However, a) R□ and R1 may form a terminal methylene.

b) R and R8 may form a terminal methylene.

e) R and R5 may form an epoxy.

d) Rf and carbon 27 may form a pyran ring.

e) Rs and carbon 25 may form a furan ring.

The present invention relates to an anticancer agent containing a compound represented by the following as an active ingredient.

[Background technology]

In recent years, cancer has become the leading cause of death among Japanese people, and the same trend has been observed in the developed countries of the world, making cancer control a fervent desire of humankind. Currently, surgical treatment, radiation therapy, and drug therapy are mainly used to treat cancer. In drug treatment, chemotherapeutic agents and immunotherapeutic agents are mainly used. Known chemotherapeutic agents include mitomycin C, pleomycin, 5-fluorouracil, doxorubicin, methotrexate, cyclophosphamide, and vincristine, but all of them cause serious side effects, such as bone marrow damage.

It is associated with gastrointestinal disorders, liver disorders, kidney disorders, etc.

In addition, as immunotherapeutic agents, protein polysaccharides and the like isolated from plants of the Arunococcaceae family have been known, but in recent years, it has been reported that they are not sufficiently effective.

As described above, the current situation is that no definitive anticancer drug has been found in terms of anticancer activity and safety.

[Disclosure of the invention]

The present inventors have conducted various studies from various angles with the theme of cancer control, and have discovered that the compound according to the present invention has anticancer activity and has a wide safety margin. The present invention is based on this knowledge. Therefore, the present invention provides a novel compound represented by (1) above, and further provides an anticancer agent containing the compound represented by (II) above as an active ingredient. .

The compound represented by the above-mentioned 2〇) and formula (II) according to the present invention is derived from Polyporaceae [Polyporaceae].
ae) Choreimaitake (b〃μ±肚umbella
The extract obtained by extracting the dried sclerotia of S. tus with water and a water-soluble solvent such as methanol is separated using a chloroform-methanol-based solvent using various chromatography techniques, such as silica gel chromatography. It can be obtained by fractionation and purification, and further, various derivatives can be obtained by treating the obtained compound using an acetylation reaction, etc., which is commonly adopted in chemical reactions. For the above acetylation, any chemical means normally employed to convert a hydroxyl group present in a chemical structure into an acetyloxy group (acetate ester) can be used. For example, a suitable solvent may be used. The unacetylated form of the compound according to the present invention is reacted with an acetylating agent such as acetic anhydride in the solvent to carry out the acetylation, and an organic solvent such as ether is removed from the reaction product. The compound according to the present invention can be obtained by extracting the target compound using silica gel column chromatography, separating and purifying it using silica gel column chromatography, and recrystallizing it from an appropriate solvent such as methanol.

Examples of manufacturing the compounds according to the present invention are listed below. The physical property values and analytical data of the compounds obtained in each example are listed after the example. In addition, the pharmacological action, toxicity, and other information regarding the compounds are listed in Tables 1 and 2 below.

[Example 1] 100 kg of Porphyra sativa was extracted with 100 OA of 30% ethanol, and the extract was concentrated to dryness under reduced pressure. The residue was suspended in 4Q water and extracted three times with 12Q ether. After washing the extract twice with 200% of IN sodium carbonate, the ether layer was concentrated to dryness under reduced pressure. The residue was subjected to silica gel column chromatography (Kiesel Gel 60), and chloroform/
Elute with 93 ml of methanol and 4 υ with chloroform/methanol (90:10). The eluate was concentrated to dryness under reduced pressure and subjected to silica gel column chromatography, eluting with chloroform/ethanol (90:10) and chloroform/ethanol (89:11).

The eluate was concentrated to dryness under reduced pressure, and the residue was separated and purified by liquid chromatography under the conditions shown below to obtain 25-deoxymaxterone A and 25-deoxy-24 (2 g
) Separate both portions of dehydromaxisterone A. By recrystallizing both parts from methanol, 25-
Obtain 350 mg of deoxymaxisterone A and 350 mg of 25-deoxy=24(28)dehydromaxisterone A. Liquid chromatography conditions Column: Inatosil ODS ha (22,2X 25
0mm) Mobile phase: water/tetrahydrofuran/methanol (49:21:30) Detection wavelength: 245nNote 1) Confirmed by silica gel thin layer chromatography, developing solvent (chloroform/methanol = 1
0:1) [Example 2] 25-deoxymaxisterone A11 obtained in Example 1
Add pyridine 10- and acetic anhydride 2- to 6 mg and leave at room temperature for 1 hour. After the reaction is complete, add water 30- and extract 4 times with ethyl acetate 50-. Next, combine the ethyl acetate layers. , and concentrated to dryness under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 3 mg of chloropho-22-tri0-acetyl-25-deoxymaxerone A and 2,3-di-0-acetyl-25-deoxymaxerone A +4+ag. Next, J+, to 2,22-, was prepared with chloroform/methanol 98:2.
Di-0-acetyl-25-deoxymaxisterone A 8
Obtain 11 g. Furthermore, chloroform methanol (9
It was eluted at 6:4 and the Li ratio was 47. from 2-0-acetyl-
62 mg of 25-deoxymaxisterone A is obtained.

Note 1) Confirm by silica gel thin layer chromatography. Developing solvent (chloroform/methanol = 1
0:1) [Example 3] Pyridine 10- and acid anhydride @2- were added to 63 mg of 25-deoxy-24(28)dehydromaxterone A obtained in Example 1, and the mixture was left at room temperature for 3 hours. After the completion of the reaction, 30% of water was added, and the mixture was extracted 4 times with 50% of dithyl acetate.

Next, the ethyl acetate layers are combined and concentrated to dryness under reduced pressure.

The residue was subjected to silica gel column chromatography.
2. From 2,3.22-tree〇-acetyl-25-
Deoxy-24(28) dehydromaxisterone A 11
mg and 2,3-di-0-acetyl-25-deoxy-
8 mg of 24(28) dehydromaxisterone A is obtained.

Next, chloroform methanol-JLt (98:2 T
: Sarel 4+17'l") 2,22-G0-
7 cetyl-25-deoxy-24(28)dehydromaxisterone A14B is obtained. Furthermore, chloroform/methanol (96:4 image 11. to 2-〇-
Obtain 18 mg of acetyl-25 deoxy-24 (2 g) dehydromaxisterone A.

Note 1) Confirm using silica gel thin layer chromatography using developing solvent (chloroform/methanol = 1
0:1) [Example 4] 100 kg of Porphyra sativa was extracted with 30% ethanol at 1000Ω, and the extract was concentrated to dryness under reduced pressure. The residue was suspended in 4Q water and extracted three times with 12Q ether. After washing the extract twice with IN sodium carbonate 200, the ether layer was concentrated to dryness under reduced pressure. The residue was subjected to silica gel column chromatography (Kiesel Gel 60) and eluted with chloroform methanol (purified with 93 nia, 1., chloroform/methanol (90:10). The eluate was concentrated to dryness under reduced pressure and purified with silica gel. Subjected to column chromatography and purified with chloroform/ethanol (90:10), 1
．． , eluted with chloroform/ethanol (89:11).

The eluate was concentrated to dryness under reduced pressure, and the residue was separated and purified by liquid chromatography under the conditions shown below.
5-dideoxy-22,23-epoxymaxisterone A
Collect the fraction. By recrystallizing both obtained components from methanol, 22.25-dideoxy-22,2
26 mg of 3-epoxymaxisterone A is obtained.

Liquid chromatography conditions Column: Inertsil OD55μm (22,2X250
mm) Mobile phase: water, tetrahydrofuran, methanol (
49:21:30) Detection wavelength: 245 nm Note 1) Perform while checking with silica gel thin layer chromatography. Developing solvent (chloroform/methanol = 1
0:1) [Example 5] 22.25-dideoxy-22,2 obtained in Example 4
Pyridine 10- and acetic anhydride 2- are added to 20 mg of 3-epoxymaxisterone A, and the mixture is left at room temperature for 1 hour.

After the reaction was completed, 30% of water was added, and the solution was diluted with 50% of ethyl acetate.
Next, the ethyl acetate layers were combined and concentrated to dryness under reduced pressure. The residue was subjected to silica gel column chromatography and diluted with chloroform/methanol 99:1 to 1 ml.
11 is 47. from 2,3-di-O-acetyl22.2
5-dideoxy-22,23-epoxymaxisterone A
Obtain 5 mg. Furthermore, chloroform methanol 96
:4) Image produced in 43. 15 mg of 2-〇-acetyl-22.25-dideoxy-22,23-epoxymaxisterone A is obtained.

Note 1) Confirm using silica gel thin layer chromatography using developing solvent (chloroform/methanol = 1
0:1) [Example 6] 100 kg of Porphyra sativa was extracted with 1000 A of 30% ethanol, and the extract was concentrated to dryness under reduced pressure. The residue is suspended in 4K of water and extracted three times with 11 of ether. After washing the extract twice with 200% of IN sodium carbonate, the ether layer was concentrated to dryness under reduced pressure. The residue was subjected to silica gel column chromatography (Kiesel Gel 60), and chloroform/
Elute with methanol 95:5, 11, and chloroform/methanol (93 nia). The eluate was concentrated to dryness under reduced pressure, subjected to alumina column chromatography, and purified with chloroform/methanol (95:5).
．． Elute with chloroform/methanol (80:20). The eluate is concentrated to dryness under reduced pressure. The residue was subjected to silica gel column chromatography (Kiesel Gel 60) and eluted with n-hexane/ethanol 4:1.
1. ．． 20゜22.25-trideoxy-22,23-
A fraction of epoximaxisterone A is obtained. By recrystallizing the obtained fraction from methanol, 20,22.2
5-trideoxy-22°23-epoxymaxisterone A 22+og is obtained.

Note 1) Confirm by silica gel thin layer chromatography. Developing solvent (chloroform/methanol=]
O: 1) [Example 7] 20,22.25-trideoxy- obtained in Example 6
22゜23-Epoxymaxisterone A 15B with pyridine 10- and anhydrous vinegar I! Add 1iZ- and leave at room temperature for 1 hour. After the reaction is completed, 30° of water is added, and the mixture is extracted four times with 5° of ethyl acetate. Next, the ethyl acetate layers were combined and soaked under reduced pressure 1 to solidify. The residue was subjected to silica gel column chromatography using chloroform/methanol 99%
:11 loss a l,, chloroform methanol 98.
5: 1.5 engineering, tttl, 61 standing J+1 to 2,3-
Di-O-acetyl-20,22゜25-trideoxy-
3 mg of 22,23-epoxymaxisterone A is obtained. Furthermore, 2-〇-acetyl-20,22.25 was dissolved in chloroform/methanol (96:4).
Trideoxy-22,23-epoxymaxisterone A
Get Lowg.

Note 1) Confirm using silica gel thin layer chromatography using developing solvent (chloroform/methanol = 1
0:1) [Example 8] 100 kg of Porphyra sativa was extracted with 1000 Q of 30% ethanol, and the extract was concentrated to dryness under reduced pressure. The residue was suspended in 4Ω of water and extracted three times with ether 12Q. Inject the extract
After washing twice with 200 g of sodium carbonate, the ether layer was concentrated to dryness under reduced pressure. The residue was subjected to silica gel column chromatography (Kiesel Gel 60) and eluted with chloroform/methanol 95:5 (40:40) and chloroform/methanol (93 nia). The eluate was concentrated to dryness under reduced pressure and subjected to alumina column chromatography.
Elute with chloroform/methanol (95:5) and chloroform/methanol (80:20).

The eluate is concentrated to dryness under reduced pressure. The residue was subjected to silica gel column chromatography (Kiesel Gel 60).

Elute with n-hexane/ethanol (4:1) 411
．． 20°25-dideoxy-maxisterone A and 20.
A mixed fraction of 25-dideoxy-24(28)dehydromaxisterone A is obtained. Both obtained fractions were concentrated to dryness under reduced pressure, and the residue was separated and purified by liquid chromatography under the conditions shown below to obtain 20.25-dideoxy-maxterone A and 20.25-dideoxy-24(28) dehydro. A fraction of Maxisterone A is collected. By recrystallizing each of the obtained fractions from methanol, 20
g2:)-dideoxy-maxisterone A 15mg
and 20.25-dideoxy-24(28)dehydromaxisterone A15+ag are obtained.

Liquid chromatography conditions Column: Inertsil ODS 5sm (22,2X 2
50++v+) Mobile phase: water/tetrahydrofuran/methanol (49:21:30) Detection wavelength: 245nm Note 1) Performed while confirming by silica gel thin layer chromatography, developing solvent (chloroform/methanol = 1
0:1) [Example 9] To 10+++ g of 20.25-dideoxy-maxisterone A obtained in Example 8, 10-pyridine and 2-2 acetic anhydrides were added.
- and leave it for 1 hour at room temperature.After the reaction is complete, add 3 parts of water.
Then, the ethyl acetate layers were combined and concentrated to dryness under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 2,3.22-tri-acetyl-20.25-dideoxy-maxisterone A1 and 2,3-diO-acetyl-20.25-dideoxy-maxterone A2I.
Get og. Next, chloroform methanol (98:
2) Fraction eluted in ``1'' to 2,22-di-O-acetyl-20.25-dideoxy-maxisterone A 2
Get mg. Furthermore, chloroform methanol 96:
Will be done in 4, 1. to 2-0-acetyl-20
, 5 mg of 25-dideoxy-maxisterone A is obtained.

Note 1) Confirm using silica gel thin layer chromatography using developing solvent (chloroform/methanol = 1
0:1) [Example 10] 20.25-dideoxy-maxisterone A of Example 9
10 mg of 20.25-dideoxy-24(28)dehydromaxisterone A obtained in Example 8 instead of 10 inches
2, 3.
22-tri-〇-acetyl-20.25-dideoxy-24(28) dehydromaxisterone A 1 mg, 2,
3-di-O-acetyl-20.25-dideoxy-24
(28) Dehydromaxisterone A 2B, 2,22-
Di-0-acetyl-20,25-dideoxy-24(2
8) Obtain 2 mg of dehydromaxisterone A and 2-0-acetel-20.25-dideoxy-24(28) dehydromaxisterone A 5B. [Example 11] Extract 100 kg of Pigrum annua with 1000 Q of 30% ethanol. The liquid was concentrated to dryness under reduced pressure. Make the residue into 4Ω of water!
'Turn it cloudy and extract 3 times with ether 12Ω. 1 extract
After washing twice with N' sodium carbonate 200, the ether layer was concentrated to dryness under reduced pressure. The residue was subjected to silica gel force column chromatography (Kiesel Gel 60), and chloroform/methanol (90:10 Jゎ, chloroform/methanol) was applied.
Elute with methanol (80:20). The eluate was concentrated to dryness under reduced pressure and subjected to silica gel column chromatography.
Elute with chloroform/ethanol (+15:15), and concentrate the eluate to dryness. By recrystallizing the residue from methanol, 24-methyl-5β-cholesto-7
50 mg of 20-dien-2β, 3β, 14α, 22α-tetraol-6-one are obtained.

[Example 12] 24-methyl-5β-cholesto 7 obtained in Example 11
．． 20-diene-2β, 3β, 14α, 22α-tetraol-6one 30B with 10 pyridine and anhydrous vinegar @2
- and leave it at room temperature for 1 hour 8 After the reaction, add 3 parts of water.
Add 0- and extract 4 times with 50 ethyl acetate. Next, the ethyl acetate layers are combined and concentrated to dryness under reduced pressure. The residue was subjected to silica gel column chromatography.1. 2,3.22-tri-acetyl-2 from L chloroform-methanol (99:1), fraction eluted with chloroform-methanol (98,5:1.5)
4-methyl-5β-cholesto-7,20-diene-2β
, 3β, 14α, 22α-tetraol-6-one 31
1g and 2,3-di-O-acetyl-24-methyl-5
β-Cholest-7,20-diene-2β, 3β, 14α
, 22-di0-acetyl-24-methyl-5β-cholesto-7, 20 diene - 2β, 3β, 1
4α,22Ct-tetraol-6-one 6m& is obtained. Furthermore, from fraction 11. eluted with chloroform/methanol (96:4), 2-0-acetyl-24-methyl-5β-cholesto-7,20-diene-2β,3β,1
4α,22α-tetraol-6-one 15B is obtained.

Note 1) Confirm using silica gel thin layer chromatography using developing solvent (chloroform/methanol = 1
0:1) [Example 13] 100 kg of Porphyra sativa was extracted with 1000 fl of 30% ethanol, and the extract was concentrated to dryness under reduced pressure. The residue was suspended in 4Q of water and extracted three times with 12ρ of ether. Extract I
After washing twice with 200 ml of N sodium carbonate, the ether layer was concentrated to dryness under reduced pressure. The residue was subjected to silica gel column chromatography (Kiesel Gel 60) and purified with chloroform/methanol 95:5. , chloroform
Elute with methanol (93 near). The eluate was concentrated to dryness under reduced pressure, subjected to silica gel column chromatography, and eluted with cyclohexane/ethanol (4:1).
1. do.

After concentrating the eluate to dryness, it was subjected to 0DS)I column chromatography, washed with 55% methanol, both fractions eluted with 60% methanol were concentrated to dryness, and recrystallization from methanol was repeated. , 22.25- )-lysooxy-22,27-epoxy-23-hydroxymaxterone A 16B is obtained.

Note 1) Confirm using silica gel thin layer chromatography using developing solvent (chloroform/methanol = 1
0:1) [Example 14] Pyridine 10- and acetic anhydride 2- were added to 15 mg of 2,22.25-trideoxy-22゜27-epoxy 23-hydroxymaxterone A obtained in Example 13, and the mixture was heated to room temperature. After the reaction is completed, add 30 g of water and extract 4 times with 50 g of ethyl acetate.Next, the ethyl acetate layers are combined and concentrated to dryness under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 4 mg of chloroform-di-acetyl-2,22,25-trideoxy-22,27-eboxy-23-hydroxymaxterone A. Next, chloroform-methanol (98 : 4 mg of 3-0-acetyl-2,22,25-trideoxy-22,27-nivoxy-23-hydroxymaxisterone A and 2
3-0-acetyl-2,22,25-1-lysooxy-
22,27-Eboxy 23-hydroxymaxisterone A 4B is obtained.

Note 1) Confirm by silica gel thin layer chromatography. Developing solvent (chloroform/methanol = 1
0:1) [Example 15] 100 kg of Porphyra annua was extracted with 1000 ρ of 30% ethanol, and the extract was concentrated to dryness under reduced pressure. The residue was suspended in 4Q water and extracted three times with 12Q ether. After washing the extract twice with 200 ml of IN thorium carbonate, the ether layer was concentrated to dryness under reduced pressure. The residue was subjected to silica gel column chromatography (Kiesel Gel 60), and chloroform/
Elute with methanol (95:5, 41) and chloroform/methanol (93, nia). The eluate was concentrated to dryness under reduced pressure, subjected to silica gel column chromatography, and extracted with cyclohexane/ethanol 4:1. do.

After concentrating the eluate to dryness, it was subjected to 0DSH column chromatography, which had been washed sequentially with methanol and water in advance, and was washed with 50% methanol and 60% methanol≦.
From the two fractions extracted, 45 ml of 2,22,25-trideoxy-22,23-epoxy-24-hydroxymaxterone A and 2,22,25-)-lysooxy-22,25-epoxy-23-hydroxy were obtained. Maxisterone A 9B is obtained. Furthermore, it is extracted with ox methanol. 15B of 2.20.22.25-tetradeoxy-22,23-epoxy-24-hydroxymaxisterone A and 27 ml of 2,25-dideoxymaxisterone A are obtained from both the components.

Note 1) Confirm by silica gel thin layer chromatography. Developing solvent (chloroform/methanol = 1
0:1) [Example 16] Pyridine 2- and anhydrous vinegar wi 2- were added to 5 mg of 2,22.25-trideoxy-22,23-epoxy-24-hydroxymaxterone A obtained in Example 15,
After leaving the reaction for 1 hour at room temperature, add 30 m9 of water.
Then, the ethyl acetate layers were combined and concentrated to dryness under reduced pressure. The residue was subjected to silica gel column chromatography.2. 1. With chloroform/methanol 99:1). ], chloroform methanol (98:2 fraction 17.Gara 3
-0-acetyl-2,22,25-)-lysooxy-2
2,23-epoxy-24-hydroxymaxisterone A
Obtain 4 Hog.

Note 1) Confirm by silica gel thin layer chromatography. Developing solvent (chloroform/methanol = 1
0:1) [Example 17] Pyridine 10- and acetic anhydride 2- were added to 6 g of 2,22,25-trideoxy-22,25-epoxy-23-hydroxymaxterone 8 obtained in Example 15. After the reaction is complete, add 30% of water and extract 4 times with 50% of ethyl acetate.Next, the ethyl acetate layers are combined and concentrated to dryness under reduced pressure. The residue was subjected to silica gel column chromatography.1. 42. Chloroform/methanol 99:1. From the resulting fraction, 3g of 23-di-0-acetyl-2,22,25-)-lysooxy-22,25-epoxy-23-hydroxymaxisterone A6 was obtained.

Furthermore, 3-0-acetyl-2,22,
2 g of 25-trideoxy-22,25-epoxy-23-hydroxymaxterone A and 2 mg of 23-0-acetyl-2,22,25-trideoxy-22°25-epoxy-23-hydroxymaxterone A are obtained.

Note 1) Confirm using silica gel thin layer chromatography using developing solvent (chloroform/methanol = 1
0:1) [Example 18] Pyridine 10- and acetic anhydride 2- were added to 15 mg of 2,25-dideoxymaxisterone A obtained in Example 15, and the mixture was left at room temperature for 1 hour. After completion of the reaction, water was added. Then, the ethyl acetate layers were combined and concentrated to dryness under reduced pressure. The residue was subjected to silica gel column chromatography, and 3,22
3 mg of -di-0-acetyl-2,25-dideoxymaxterone A is obtained. Furthermore, 3-0-acetyl-2?25-dideoxymaxisterone A 51I was obtained from fraction 11. eluted with chloroform/methanol (98:2).
g and 22-0-acetyl-2,25-dideoxymaxterone A 5B are obtained.

Note 1) Confirm using silica gel thin layer chromatography using developing solvent (chloroform/methanol = 1
0:1) [Example 19] Pyridine 2- and acetic anhydride 2- were added to the 2,20,22.25-tetradeoxy-22,23-epoxy-24-hydroxymaxterone A5 block obtained in Example 15. After the reaction is complete, add 30% of water and extract 4 times with 50% of ethyl acetate.Next, the ethyl acetate layers are combined and concentrated to dryness under reduced pressure. The residue was subjected to silica gel column chromatography.1. Chloroform-2.20,22.25-tetradeoxy-22,
23-epoxy-24-hydroxymaxisterone A 5
Get mg.

Note 1) Confirm using silica gel thin layer chromatography using developing solvent (chloroform/methanol = 1
0:1) Physical property values and analytical data of the compound according to the present invention are shown.

(1) Physical properties and analytical data of 25-deoxymaxterone A 1) Properties and solubility Colorless and odorless needle-shaped crystals with a melting point of 290-295°C, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, and hexane. , 1 for chloroform, benzene, and ether! soluble and insoluble in water.

Sarcolasky reaction, Liberman-Perchert reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3350.1
The maximum absorption is shown at 650 c+++-''.

3) Ultraviolet absorption spectrum (ethanol) analysis EtOl
(4) H1 nuclear magnetic resonance spectrum (d,-pyridine) analysis showing the following signal: 6.28 (18, doublet.

4.24 (IH, - double line) 4.18 (IH, double line.

3.93 (1) 1. Double line.

3.61 (IH, multiple g) (δ+　PPm)・ J=2.5Hz) (H in 7th place) (3rd place H) J=11Hz) (2nd place H) J=9.5Hz) (22nd H) (9th H) 1.58 (3L 1.45 (IH.

1.25 (3) 1゜ 1.09 (3H.

0.88 (3H.

single line) multiplet) single layer NIA) single line) Double line.

0.87 (3H, double line.

(H of methyl group at position 21) (H of methyl group at position 25) (H of methyl group at position 18) (H of methyl group at position 19) 6.3Hz) (H of methyl group at position 19) J: 6 .3Hz) (H of the methyl group at positions 26 and 27) (H of the methyl group at the 28th position) (d, -pyridine) 0.76 (3H, doublet, J: 6.8Hz) 5)"
C nuclear magnetic resonance spectroscopy showing the following signal (δ+ PPl11) *202.3
8 (C of carbonyl group at position 6) 165.28.12
1.06 (C derived from double bond at position 7 and 8) 83.7
3 (14th place C) 76.51 (20th place C) 74.30 (22nd place C) 67.80, 67.77 (2nd and 3rd place C) 24.
37.21.28.21.22.17.79.16.0
8.15.76 (C of methyl group) 6) Mass spectrum analysis m/z 517 (M+K)”, 502
(MAN a )", 479 (M+1)" (2) Physical properties and analytical data of 2-0-acetel-25-deoxymaxterone A 1) Properties and solubility Colorless amorphous powder, ethanol, methanol.

Soluble in dimethyl sulfoxide, pyridine, chloroform, and ether, sparingly soluble in hexane and benzene, and insoluble in water.

2) Infrared absorption spectrum (KBr) analysis 3350.1
It shows an absorption maximum at 725.1650 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis tOH 4) H' nuclear magnetic resonance spectrum (d&-pyridine) analysis Showing the following signal (δ+ PP@) s5.24 (I
H, multiplet) (H in 2nd place) 4.32 (1)1. - double line) (H at 3rd position) 3.93 (LH, double line, J=9.9Hz) (H at 22nd position) 1.95 (
3H, - heavy line) (H of methyl group derived from acetoxyl group) 5) 13C nuclear magnetic resonance spectrum (dS-pyridine) analysis The following signal is shown (δr ppm).

170.50 (C of carbonyl group derived from acetoxyl group) 74.65 (C of 22nd position) 72.74 (C of 2nd position) 65.31 (C of 3rd position) 21.50 (Methyl group derived from acetoxyl group) C)
6) Mass spectrum analysis m/z 520 (M') (3) Physical properties and analytical data of 2.22-di-O-acetyl-25-deoxymaxterone A 1) Properties and solubility Colorless melting point 139-141.5 Needle crystals at °C, ethanol, methanol, dimethyl sulfoxide, pyridine,
Soluble in chloroform and ether, sparingly soluble in hexane and benzene, and insoluble in water.

2) Infrared absorption spectrum (KBr) analysis 3350.1
It shows an absorption maximum at 725.1650 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis tOH 4) H1 nuclear magnetic resonance spectroscopy (ds-pyridine) analysis minutes The following signal is shown (δ+PPm).

5.52 (IH, double line + J = 9.23Hz)
(H at position 22) 5.25 (IH + multiplet) (H at position 2) 4.33 (IH, - multiplet) (H at position 3) 5
)”C nuclear magnetic resonance spectrum (d,-pyridine) analysis shows the following signal (δr PPI”).

77.89 (C at position 22) 72.74 (C at position 2) 65.31 (C at position 3) 6) Mass spectrum analysis m/z 562 (M+) (4) 2.3-di-O-acetyl Physical properties and analytical data of 25-deoxymaxterone A 1) Properties and solubility Colorless needle-like crystals with a melting point of 149.5-151°C, containing nitanol, methanol, dimethyl sulfoxide, and pyridine.

Soluble in chloroform and ether, sparingly soluble in hexane and benzene, and insoluble in water.

2) Infrared absorption spectrum (KBr) analysis 3350.1
It shows an absorption maximum at 725.1650 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis 4) H Nuclear magnetic resonance spectrum (dS-pyridine) showing signal of separation (δ+ pp@L 5.51 (LH, - double line) (H at 3rd position) 5 .3
2 (LH, multiplet) (H in 2nd place) 3.93 (
LH, double, J=9.9Hz) (H in 22nd position)
D) 1) (Nuclear magnetic resonance spectrum (d,-pyridine) analysis showing the following signal (δr PPIH)-(C at position 22)
) (C at position 2) 67.91 (C at position 3) 69.37 74.64 6) Mass spectrum analysis m/z 562 (M”) (5)2,3.22-), Li-O Acetyl -25- Physical properties and analytical data of deoxymaxisterone A 1)
Properties and solubility Colorless needle-like crystals with a melting point of 122-126.5°C, soluble in ethanol, methanol, dimethyl sulfoxide, pyrnodine, chloroform, and ether, sparingly soluble in hexane and benzene, and insoluble in water. It is.

2) Infrared absorption spectrum (KBr) analysis 3350, 1
It shows an absorption maximum at 725.1650 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis λ (
log t ) nm = 241 (4,02) tOH 4) H1 nuclear magnetic resonance spectrum (dS-pyridine) analysis shows the following signals (δ+ ppm).

5.52 (IH, double line, J=9.23Hz)
(H at position 22) 5.51 (IH, - double line) (
H in 3rd place) 5.33 (IH, multiplet) (H in 2nd place) 5
) ifC nuclear magnetic resonance spectrum (dS-pyridine) analysis shows the following signal (δy PP”).

77.86 (C at position 22) 69.37 (C at position 2) 67.90 (C at position 3) 6) Mass spectrum analysis m/z 604 (M') (C) 2B-deoxy-24 (28 ) Deoxymaxterone A 1) Properties and Solubility Colorless and odorless needle-shaped crystals with a melting point of 250-254°C, soluble in ethanol, methanol, dimethyl sulfoxide, and pyridine, and sparingly soluble in hexane, chloroform, benzene, and ether. , insoluble in water.

Sarkolasky reaction, Liberman-Birchiard reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3350, 1
It shows an absorption maximum at 650 cm-1.

3) Ultraviolet absorption spectrum (ethanol) analysis tOH H1 nuclear magnetic resonance spectroscopy (d5-pyridine) analysis The following signal is shown (δr　PP'').

6.28 (IH, double line, J=2.2Hz) (H in 7th position) 4.25 (IH.

4.19 (IL 4.05 (IH.

3.61 (LH.

1.60 (3H.

1.24 (3H.

(H at position 3) (H at position 2) (H at position 22) (H at position 9) (H at methyl group at position 21) (H at methyl group at position 18) Singlet) Double line, J =11.4Hz) doublet, J:9.8Hz) multiplet) singlet) singlet) 1.09 (3H, - doublet) (H of methyl group at position 19)
1.05 (3H, double line, J: 6.78Hz)
(H of methyl group at position 26) 1.03 (3H, double line, J-6, 78Hz)
(H of methyl group at position 27) 2.62 (1)1. double line, J:14.511z)
(H at position 23) 2.30 (1B, double doublet, J = 14.5. j: 10.3Hz) (H at position 23
) 2.42 (IH, septet, j=6.78Hz)
(H at position 25) 5) 13C nuclear magnetic resonance spectrum (d
S-pyridine) analysis shows the following signals (δ+ppm).

203.45 (C of carbonyl group at position 6)]66.
06. ! 21.69 (C derived from the double bond at positions 7 and 8) 154.36.108.68 (C derived from the double bond at positions 24 and 28) 84.16 (C at position 14) 76.72 (20th place C) 75.38 (22nd place C) 68.12.68.07 (2nd and 3rd place C) 24.
45.22.09.21.84.21.54.17.8
9 (C of methyl group) 6) Mass spectrometry analysis m/z 515 (M K)', 499 (
M1N a )', 477 (M+1)" (7) 2-0-acetyl-25-deoxy-24 (28
) Physical properties and analytical data of dehydromaxisterone A 1) Properties and solubility Colorless needle-like crystals with a melting point of 205-209°C, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, nityl, /\xane, Slightly soluble in benzene and insoluble in water.

2) Infrared absorption spectrum (KBr) analysis 3474.1
The maximum absorption is shown at 715.1659 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis tOH 4) H1 nuclear magnetic resonance spectrum (dS-pyridine) analysis The following signals are shown (δ, PPm).

5.25 (IH, multiplet) (H in 2nd place) 4
．． 33 (1)1. - double line) (H in 3rd place)
4.06 (IH, double line, J410Hz) (2
H at position 2) 1.96 (3H, - heavy line) (H of methyl group derived from acetoxyl group) D) 12C nuclear magnetic resonance spectrum (ds-pyridine) analysis The following signal is shown (δy ppm).

170.50 (C of carbonyl group derived from acetoxyl group) 75.44 (C of 22nd position) 72.74 (C of 2nd position) 65.31 (C of 3rd position) 21.65 (Methyl group derived from acetoxyl group) C)
6) Mass spectrum analysis m/z 51g (M”) (8) 2.22-diO-acetyl-25-deoxy-
24 (28) Physical properties and analytical data of dehydromaxterone A 1) Properties and solubility Colorless needle-like crystals with a melting point of 213-215°C, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, and ether. Slightly soluble in hexane and benzene, and insoluble in water.

2) Infrared absorption spectrum (KBr) analysis 3506.1
The maximum absorption is shown at 725.1719.1657 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis shows the following signal (δr PPII) s5.59 (
LH, double line, J=9.24Hz) (22nd H
)5.24 (IH, double line, J=10.22Hz)
(H in 2nd position) 4.34 (IH, - double line)
(H at position 3)”c nuclear magnetic resonance spectrum (d,-pyridine) Analysis shows the following signal (δl PP@) @77.50
(22nd position (7)C) 72.57 (2nd position C) 65.11 (3rd position C) 6) Mass spectrum analysis m/z 560 (M”) (9) 2.3-di○-acetyl 25-deoxy 24
(28) Physical properties and analytical data of dehydromaxisterone A 1) Properties and solubility Colorless amorphous powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroborum, and ether, and li-soluble in hexane and benzene. 2 and is insoluble in water.

2) Infrared absorption spectrum (KBr) analysis 3412, 1
It shows an absorption maximum at 744.1665 cm-1.

3) Ultraviolet absorption spectrum (ethanol) analysis tOH H1 nuclear magnetic resonance spectrum (dS-pyridine) analysis showing the following signal (δ+ PPII) *5.52 (
LH, - heavy line) (H at 3rd position) 5.34 (L
H, double line, J=11.9Hz) (H in 2nd place)4.
06 (IH, double line, J=9.2Hz) (22
H)s)X3c nuclear magnetic resonance spectroscopy (ds-pyridine) analysis shows the following signal (δ+ PPII)
) 2nd position C) 67.90 (3rd position C) 69.37 75.42 6) Mass spectrum analysis m/z 560 (M”) (10)2,3.22-)-LeO-acetyl 25-
Physical properties and analytical data of deoxy-24(28) dehydromaxterone A 1) Properties and solubility Colorless needle-like crystals with a melting point of 103-105°C. Soluble, sparingly soluble in hexane, insoluble in water.

2) Infrared absorption spectrum (KBr) analysis 3500.1
The absorption maximum is shown at 744.1663 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis Eto)
Analysis of t4nH'' nuclear magnetic resonance spectrum (d,-pyridine) shows the following signals (δ+ ppm).

5.58 (IH, double line, J=9.2Hz) (
22nd place H) 5.51 (1) 1. - heavy line)
(H in 3rd place) 5.33 (IH, double line, J=11
．． 9Hz) (H at position 2)s)"c Nuclear magnetic resonance spectrum (d,-pyridine) analysis showing the following signal (δy PPII) * (C at position 22)
) (C at position 2) 67.90 (C at position 3) 69.37 77.68 6) Mass spectrum analysis m/z 602 (M+) (11) 22.25-dideoxy-22,23-divoximer Physical properties and analytical data of Kisterone A 1) Properties and solubility Colorless needle-shaped crystals with a melting point of 250 to 252°C, soluble in ethanol, methanol, dimethyl sulfoxide, and pyridine, and soluble in hexane, chloroform, benzene, and ether.
soluble and insoluble in water, positive in Sarcolaskill reaction, Lieberman-Birchard reaction, and Chugaev reaction.

2) Infrared absorption spectrum (KBr) analysis 3296.1
644.1263.880.800 The extremely thick absorption is shown at c+n-'.

3) Ultraviolet absorption spectrum (ethanol) analysis tOH 4) H1 nuclear magnetic resonance spectrum (dS analysis) Showing the following signal (δ+ ppm) 6.24 (I
H, double line, J=2.2Hz) (H in 7th position)4.
28 (IH, multiplet) (3rd position H) pyridine) min 4.19 (LH, doublet, j = 10.21 (z)
(2nd H) 3.62 (IH, multiplet) (
9th H) 3.04 (IH, double line, J=2.4H
z) (H at 22nd position) 2.97 (IH, double doublet, J=7.6.2.4Hz) (H at 23rd position) 1.61 (IH, multiplet) (25th position H) 1.54
(3H, - double line) (H of methyl group at position 21) 1.19
(IH, double quartet, J=7.6.6.8Hz) (
H at position 24) 1.16 (3H, - double line) (H at methyl group at position 18)
1.09 (3H, - double line) (H of methyl group at position 19)
1.01 (3H, double line, J=6.8Hz) (
H of methyl group at position 26) 0.95 (3H, doublet, 6.8Hz) (2
H of methyl group at position 7) 0.91 (3)1. double line, J=6.8Hz)
(H of methyl group at position 28) 5)"C nuclear magnetic resonance spectrum (dS-pyridine) analysis shows the following signal (between δt and PP).

203.40 (C of carbonyl group at position 6) 165.
93 (8th place C) 121.72 (7th place c) 84.02 (14th place c) 71.98 (20th place C) 66.18 (22nd place C) 58.14 (23rd place C) C) 6) Mass spectrum analysis m/z 477 (M+1)” Physical properties and analytical data of 2-○-acetyl-22゜25-dibuoxy-22,23-epoxymaxisterone A 1) Properties and solubility Colorless powder , ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, and ether, Nr@ in hexane, benzene, and insoluble in water.

2) Infrared absorption spectrum (KB r) analysis 3350.
The maximum absorption is shown at 1725.1650 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis shows the following signal (δ+ PPII)-5,24(I
H, double line, J: 10Hz) (H in 2nd place) 4.3
3 (1)1. Multiplet) (H in 3rd place) 1.
95 (3H, - heavy line) (H of methyl group derived from acetoxyl group) 5) "C nuclear magnetic resonance spectrum (d, -pyridine) analysis shows the following signal (δr PPIm) -170,60
(C of carbonyl group of acetoxyl group) 72.80
(C at position 2) 65.30 (C at position 3) 21.53 (C at methyl group of acetoxyl group) 6)
Mass spectrum analysis m/z 518 (M+) (13) Physical properties and analytical data of 2.3-di○-acetyl-22.25-dideoxy-22,23-epoxymaxisterone A 1) Properties and solubility Colorless powder It is soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, benzene, and ether, sparingly soluble in hexane, and insoluble in water.

2) Infrared absorption spectrum (KBr) analysis 3380.1
The maximum absorption is shown at 745.1664 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis λ (
logf) EtOH n = 241 (4,00) H1 nuclear magnetic resonance spectrum (dS-pyridine) Analysis shows the following signal (δp PPIII) s5.55
(IH, multiplet) (H in 3rd position) 5.35 (
1)1. Double line, J=10Hz) (H in 2nd place)5
)11C nuclear magnetic resonance spectrum (dS-pyridine) analysis shows the following signal (δ+ pp+m).

69.40 (C at position 2) 67.88 (C at position 3) 6) Mass spectrum analysis m/z 560 (M4) (14) 20,22.25-trideoxy-22゜23
- Physical properties and analytical data of dipoximaxisterone A l) Properties and solubility A colorless and odorless prismatic crystal with a melting point of 232 to 235°C,
Soluble in ethanol, methanol, dimethyl sulfoxide, and pyridine, sparingly soluble in hexane, chloroform, benzene, and ether, and insoluble in water.

Sarkolasky reaction, Liberman-Birchiard reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3296.1
The maximum absorption is shown at 644.907.880 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis tOH 4) H1 nuclear magnetic resonance spectrum (d,-pyridine) analysis Showing the following signal (δ+ PPI”) *6.23 (
IH, double line, J = 2.2) (H at 7th position) 4.26 (IH, - double line) (H at 3rd position) 4.18 (LH, double line, , T = 10.2 )
(H in 2nd place) 3.59 (IH, multiplet) (9
H) 2.67 (IH, double line, J=6.92H
z) (H at 22nd position) 2.54 (IH, double doublet, J=6.92.2.40Hz) (H at 23rd position) 1.09 (3H, - doublet) (19th position H of the methyl group of
1.07 (3H, double line, J=6.92Hz) (2
H of methyl group at position 1) 1.01 (3H, doublet, J=6.59Hz) (2
H of the methyl group at position 6) 0.94 (31 (, doublet, J = 7.92Hz) (
H of methyl group at position 27) 0.91 (3)1. Double line, J=6.92Hz) (
H of methyl group at position 28) 0.72 (31(, -17km) <0 at position 18)
Mef group (7)H)5)0C nuclear magnetic resonance spectrum (d
S-pyridine) analysis shows the following signal (δ+PP■).

203.42 (C of carbonyl group at position 6) 165.
41 (8th place C) 121.64 (7th place C) 83.63 (14th place C) 67.96 (2nd and 3rd place C) 64.04 (22nd place C) 59.90 ( 23rd place C) 24.42.20.50. 16.59. 15.90
．． 15.90. 13.82 (C of methyl group) 6) Mass spectrum analysis m/z 461 (M+1)” (15) Physical properties of 2-○-acetyl-20.22.25-1-lithioquine-22,23-epoximaxisterone A Values and analytical data 1) Properties and solubility Colorless amorphous powder, ethanol, methanol.

Soluble in dimethyl sulfoxide, pyridine, chloroform, and ether, sparingly soluble in hexane and benzene, and insoluble in water.

2) Infrared absorption spectrum (KBr) analysis 3350, 1
It shows an absorption maximum at 725.1650 cm-'.

UV absorption spectrum (ethanol) analysis tOH 4) H1 nuclear magnetic resonance spectrum (mu-pyridine) analysis The following signal is shown (δ+ppm).

5.23 (LH, double line, J=10.2Hz) (
2nd place H) 4.32 (1) 1. - heavy line) (H at position 3) 1.96 (3H, - heavy line) (H of methyl group derived from acetoxyl group) s)! ffc nuclear magnetic resonance spectrum (d,-pyridine)
Analysis shows the following signal (δ+ PPII) s170.50
(C of carbonyl group derived from acetoxyl group) 72.79 (C of 2nd position) 65.25 (C of 3rd position) 21.50 (C of methyl group derived from acetoxyl group)
6) Mass spectrum analysis m/z 502 (M”) (16) 2.3-di-O-acetyl-20,22°25
-trideoxy-22,23-divoximaxisterone A
Physical properties and analytical data 1) Properties and solubility It is a colorless powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, benzene, and ether, slightly soluble in hexane, and insoluble in water.

2) Infrared absorption spectrum (KBr) analysis 3375.1
The maximum absorption is shown at 743.1665 c1'.

3) Ultraviolet absorption spectrum (ethanol) analysis The following signal is shown (δl ppm).

5.56 (IH, - double line) (H in 3rd position) 5.37
(IH, doublet, J: 10.0)lz) (H at 2nd position) 5)''1C nuclear magnetic resonance spectrum (ds-pyridine) analysis Shows the following signal (δ+ ppm).

69.35 (C at 2nd position) 67.90 (C at 3rd position) 6) Mass spectrum analysis m/z 544 (M”) (17) Physical property values and analytical data of 20,25-dideoxy-maxisterone A 1) Properties and solubility Colorless prismatic crystals with a melting point of 251-252°C, soluble in ethanol, methanol, dimethyl sulfoxide, and pyridine, sparingly soluble in hexane, chloroform, benzene, and ether, and insoluble in water. reaction, Liberman-Birchiard reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KB r) analysis 3338.
The maximum absorption is shown at 1649 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis tOH 4) H1 nuclear magnetic resonance spectrum (d,-pyridine) analysis indicates the next signal 6.24 (LH, double line.

4.21 (1) 1. - heavy line) 4.11 (LH, multiplet) 4.11 (IH, multiplex) 3.57 (IH, multiple line) 1.30 (3) 1. - heavy line) 1.28 (3) 1. Double line.

1.22 (3) 1. Double line.

1.15 (3H, double line.

(δr ppm) - J=2.5t(z) (H at position 7) (H at position 3) (H at position 2) (H at position 22) (H at position 9) (H at position 19) H) J=6.92Hz) (H of methyl group at position 21) J=6.59Hz) (H of methyl group at position 26) J=7.92Hz) (H of methyl group at position 27) 1.12 (3H, double line, J=6.92)1z)
(H of methyl group at position 28) 0.93 (3)1. - double line) (H of methyl group at position 18
)s)! 3c nuclear magnetic resonance spectrum (d,-pyridine)
Analysis shows the following signal (δy PPII) *203.71
(C of carbonyl group at position 6) 165.85 (8
C at position 121.68 (C at position 7) 83.90 (C at position 14) 70.87 (C at position 22) Mass spectrum analysis m/z 463 (M+1)” (1,8)2-〇 - Physical properties and analytical data of acetyl-20.25-dideoxymaxisterone A 1) Properties and solubility Colorless powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, and ether, and sparingly soluble in hexane and benzene. and is insoluble in water.

2) Infrared absorption spectrum (KBr) analysis 3340.1
It shows an absorption maximum at 725.1650 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis 5.25 showing the following signals (1) 1. multiplet) 4.33 (LH, - multiplet) 3.90 (LH, multiplet) 1.95 (3H, - multiplet) (δ+ PP resin) e (H at 2nd position) (H at 3rd position) (H at position 22) (H of methyl group derived from acetoxyl group) s) 18c nuclear magnetic resonance spectrum (aS-pyridine) analysis Showing the following signal (δy PP”) s170.50 (
C)72.75 of carbonyl group derived from acetoxyl group
(C at position 2) 70.88 (C at position 22) 65.50 (C at position 3) 21.49 (C of methyl group derived from acetoxyl group) 6
) Mass spectrum analysis m/z 504 (M”) (19) Physical properties and analytical data of 2,22-di○-acetyl-20.25-dideoxymaxterone A 1) Properties and solubility Colorless powder, ethanol, Soluble in methanol, dimethyl sulfoxide, pyridine, chloroform, and ether, sparingly soluble in hexane and benzene, and insoluble in water.

2) Infrared absorption spectrum (KBr) analysis 3345.1
The maximum absorption is shown at 725°1719°1650 cm-''.

UV absorption spectrum (ethanol) analysis analysis indicates the next signal 5.40 (LH, Multiplex II) 5.25 (IH, multiple line) 4.33 (IH, - heavy + 1ri (δr　PP”).

(H at position 22) (H at position 2) (H at position 3) 5) "C nuclear magnetic resonance spectrum (dS-pyridine) analysis shows the following signal (δr PP")・73.00
(C at position 22) 72.76 (C at position 2) 65.49 (C at position 3) 6) Mass spectrum analysis m/z 546 (M”) (20) 2,3-di○-acetyl 20. Physical properties and analytical data of 25-dideoxymaxerone A 1) Properties and solubility A colorless powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, and ether, slightly soluble in hexane and benzene, and slightly soluble in water. It is insoluble in

2) Infrared absorption spectrum (KBr) analysis 3412, 1
The maximum absorption is shown at 745.1665 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis tOH 4) H1 nuclear magnetic resonance spectrum (dS-pyridine) analysis The following signal is shown (δ+ppm).

5.50 (LH, - double line) (H in 3rd position) 5.32
(1)1. Multiplet) (H at position 2) 3.90 (IH, multiplet) (H at position 22) s) 13c Nuclear magnetic resonance spectrum (d, -pyridine) analysis Showing the following signal (δy PP”) #72 .74
(C at position 2) 70.87 (C at position 22) 65.31 (C at position 3) 6) Mass spectrum analysis m/z 546 (M”) (21)2,3.22-)-Lee○ - Acetyl-20゜25-dideoxymaxterone A physical properties and analytical data 1) Properties and solubility Colorless powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, benzene, and ether, and difficult to dissolve in hexane. soluble and insoluble in water.

2) Infrared absorption spectrum (KBr) analysis 3500, 1
The maximum absorption is shown at 744.1663 c+w-”.

3) Ultraviolet absorption spectrum (ethanol) analysis tOH 4) H'' nuclear magnetic resonance spectrum (d,-pyridine) analysis indicates the next signal 5.50 (IH, - double line) 5.40 (1) 1. Multiplex 1m 5.32 (1) 1. multiplet) (δ+ PP vote)・ (3rd place H) (H in 22nd place) (2nd place H) '3C nuclear magnetic resonance spectrum (d,-pyridine) analysis The following signal is shown (δ+PP”).

73.00 69.38 67.95 (C at position 22) (C at position 2) (C at position 3) 6) Mass spectrum analysis m/z 588 (M”) (22) 20.25-dideoxy-24 (28) Physical properties and analytical data of dehydromaxisterone A 1) Properties and solubility Colorless prismatic crystals with a melting point of 251-252°C, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, hexane, chloroform, benzene. , sparingly soluble in ether and insoluble in water. Shows positive results in Salkowski reaction, Liberman-Birchayard reaction, and Chugaev reaction.

2) Infrared absorption spectrum (KBr) analysis 3340.1
It shows an absorption maximum at 650 cm-1.

3) Ultraviolet absorption spectrum (ethanol) analysis The following signal is shown (δr ppm).

6.24 (1)1. Double line, j=2.5Hz) (7
position H) 4.21 4.11 4.11 3.57 1.30 1.28 (IH2 (IH9 (IH2 (IH5 (3H2 (3H9 single M) multiplet) multiplet) multiplet) singlet) 2 Heavy line.

(H at position 3) (H at position 2) (H at position 22) (H at position 9) (H at methyl group at position 19) J=6.92Hz) (H at methyl group at position 21) 1. 15 (3)! , double line, 7.92Hz) (
H of methyl group at position 26) 1.12 (3H, doublet, J=6.92Hz) (
H of methyl group at position 27) 0.93 (3H, - double line) (H of methyl group at position 18)
5) 11C nuclear magnetic resonance spectrum (d,-pyridine) analysis shows the following signal (δ+ ppgo).

203.71 (C of carbonyl group at position 6) 165.
74 (8th place C) 121.72 (7th place C) 154J5 (26th place C) 108.66 (28th place C) 83.90 (14th place C) 71.72 (22nd place C) 6) Mass spectrum analysis m/z 461 (M+1)” (23) 2-0-acetyl-20,25-dideoxy-
24 (28) Physical properties and analytical data of dehydromaxterone A 1) Properties and solubility Colorless amorphous powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, and ether, and soluble in hexane and benzene. It is a flute and is insoluble in water. Sarcolasky reaction, Liberman-Birchiard reaction, and Chuganiv reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3340, 1
It shows an absorption maximum at 725.1650 cm''.

3) Ultraviolet absorption spectrum (ethanol) analysis 4) Signal of H nuclear magnetic resonance spectrum (dS-pyridine) separation is shown (δ+ ppm).

5.25 (IH, multiplet) (2nd place H) 4.33 (
IH, -heavy, I) (H in 3rd position) 4.11 (1)
1. Multiplet) (H at position 22) 1.95 (31 (, - doublet) (H at methyl group of acetoxyl group) 5) 13C nuclear magnetic resonance spectrum (d, -pyridine) analysis shows the following signal (δ+ PPM).

170.50 (C of carbonyl group of acetoxyl group
)72.75 (C at position 2) 71.72 (C at position 22) 65.50 (C at position 3) 21.49 (C at methyl group of acetoxyl group) 6)
Mass spectrum analysis m/z 502 (M)” (24) Physical properties and analytical data for 2.22-di○-acetyl-20.25-dideoxy-24(28) dehydromaxterone 1) Properties and solubility Colorless Amorphous powder, nitanol, methanol.

It is soluble in dimethyl sulfoxide, pyridine, chloroform, and nityl, 113 in hexane and benzene, and insoluble in water. Shows positive results in Sarnilaski reaction, Liberman-Birchiard reaction, and Tiniganif reaction.

2) Infrared absorption spectrum (KBr) analysis 3345, 1
The maximum absorption is shown at 725.1719.1630 cm-''.

3) Analysis of ultraviolet absorption spectrum using ethanol The following signal is shown (δ* ppm).

5.40 (LH, multiplet) (H at 22nd position) 5.25
(LH, multiplet) (H at 2nd position) t33 (LH, - multiplet) (H at 3rd position) 1.98 (3H, -multiplet V methyl group of acetoxyl group 1.97 (3H, -multiplet) Line) J of H) 5) 11C nuclear magnetic resonance spectrum (dS-pyridine) analysis shows the following signals (δ, PPm).

73.84 (C at position 22) 72.67 (C at position 2) 65.10 (C at position 3) 6) Mass spectrum analysis m/z 544 (M) 10 (25) 2.3-diO- Physical properties and analytical data of acetyl-20,25-dideoxy-24(2B) dehydromaxterone A 1) Properties and solubility Colorless amorphous powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, hexane, Slightly soluble in chloroform, benzene, and ether, and insoluble in water. Sarkolasky reaction, Liberman-Birchiard reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3412, 1
The maximum absorption is shown at 744.1665 am-1.

3) Ultraviolet absorption spectrum (ethanol) analysis tOH 4) H1 nuclear magnetic resonance spectrum (dS-pyridine) analysis The following signals are shown (δ, ppm).

5.48 (IH, - double line) (H in 3rd position) 5.26
(1)1. multiplet) (2nd place H) 4.12 (LH,
Multiplet) (H at position 22) 5) 13C nuclear magnetic resonance spectrum (mu-pyridine) analysis shows the following signal (δl PPII) @ 170.23
J 71.72 (C at position 22) 69.47 (C at position 2) 68.02 (C at position 3) 6) Mass spectrum analysis m/z 544 (M)” (26)2,3.22- Tory〇-acetyl-20゜2
Physical properties and analytical data of 5-dihydroxy-24(28) dehydromaxterone A 1) Properties and solubility Colorless amorphous powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, benzene, and ether. It is sparingly soluble in hexane and insoluble in water. Sarkolasky reaction, Liberman-Birchiard reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3500, 1
The absorption maximum is shown at 744.1663 CD-''.

UV absorption spectrum (ethanol) analysis analysis Shows the following signal (δ.

ppm)・ 5.40 (LH2 multiplet) (H in 22nd place) 5.48 (LH2 single line) (3rd place H) 5.26 (LH9 multiplet) (2nd place H) “C nuclear magnetic resonance spectrum (dS-pyridine) analysis Shows the following signal (δ.

ppm) - 73,84 (C at position 22) 69.47 (C at position 2) 68.02 (C at position 3) 6) Mass spectrum analysis m/z 586 (M)" (27) 24-methyl- 5β-Cholest-7,2°-diene-2β,3β,14α,22α-tetraol-6-
Physical properties and analytical data of 1) Properties and solubility Colorless and odorless needle-like crystals with a melting point of 250-254°C, soluble in ethanol, methanol, dimethyl sulfoxide, and pyridine, and sparingly soluble in hexane, chloroform, benzene, and ether. and is insoluble in water.

Sarkolasky reaction, Liberman-Birchiard reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3350.1
It shows an absorption maximum at 650 cm-''.

3) Shows the signal of the ultraviolet absorption spectrum (ethanol) analysis method (δr ppm).

6.27 (LH, double line, J: 2.3Hz) (H at 7th position) 4.49 4.23 4.14 3.82 3.60 1.05 (1) 1° (IHl (LH9 ( LH9 (LH2 (31(.

Triple line.

single line) Double line.

Multiplet) Multiplet) Singlet) (H at position 22) (H at position 3) (H at position 2) (H at position 17) (H at position 9) (H of methyl group at position 19) J: 10.9Hz) j=6.6Hz) 0.84 (3+1.-double line) (H of the methyl group at the 18th position
)5)! 30 nuclear magnetic resonance spectrum (d,-pyridine)
Analysis shows the following signal (δ+ PP”) a203.63
(C of carbonyl group at position 6) 165.94 (C of position 8) 154.09 (C of position 20) 121.59 (C of position 7) 111.59 (C of position 21) 84.11 (14 C) 74.31 (22nd (7) C) 24.50. 20.57. 17.71. 17.6
4. 16.11 (C of methyl group) 6) Mass spectrometry analysis m/z 461 (M+1)' (28) 2-○-acetyl-24-methyl-5β cholest-7,20-diene-2β, 3β, 14α.

Physical properties and analytical data of 22α-tetraol-6-one 1) Properties and solubility Colorless amorphous powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, and ether, and sparingly soluble in hexane and benzene. and is insoluble in water.

2) Infrared absorption spectrum (KBr) analysis 3340, 1
It shows an absorption maximum at 725.1650 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis tOH 4) H1 nuclear magnetic resonance spectrum (aS-pyridine) analysis The following signal is shown (δ+PP hazy).

5.20 (IH, double line, J: 10.9Hz)
(H in 2nd position) 4.31 (IH, - double line)
(H in 3rd place) 4.49 (IH, triple line, J=6
．． 6Hz)) (H at position 22) 1.96 (3H,
- heavy line) (H of methyl group derived from acetoxyl group) 5) CI magnetic resonance spectrum (dS-pyridine) analysis The following signal is shown (δr ppm).

170.50 (C of carbonyl group derived from acetoxyl group) 74.37 (C of 22nd position) 72.78 (C of 2nd position) 65.40 (C of 3rd position) 21.65 (Methyl group derived from acetoxyl group) C)
6) Mass spectrum analysis m/z 502 (M”) (2g) 2.22-di○-acetyl-24-methyl-
5β-cholesto-7,20-diene-2β,3β.

Physical properties and analytical data of 14α,22α-tetraol-6-one 1) Properties and solubility Colorless amorphous powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, and ether, and soluble in hexane and benzene. It is sparingly soluble and insoluble in water.

2) Infrared absorption spectrum (KBr) analysis 3506.1
The maximum absorption is shown at 725.1719.1657 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis plate showing the following signal (δ* PPm) * 6.03 (L
H, triple line, J=6.6Hz) (H at position 22)5
．． 20 (IH, double line, J=10.9Hz) (2
H) 4.31 (1)1. - heavy line) (
3rd position H) 5) ”CvAEiHK resonance spectrum (
d, -HiJSin) analysis showing the following signal (δl r'P”)*(C at position 22
) (C at position 2) 65.40 (C at position 3) 72.78 76.43 6) Mass spectrum analysis m/z 544 (M+) (30) 2.3-di○-acetyl-24-methyl 5β
-Cholest-7,20-diene-2β,3β.

Physical properties and analytical data of 14α,22α-tetraol-6-one 1) Properties and solubility Colorless amorphous powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, and ether, and soluble in hexane and benzene. It is sparingly soluble and insoluble in water.

2) Infrared absorption spectrum (KBr) analysis 3350.1
The absorption maximum is shown at 744.1665 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis plate The following signals are shown (δ, PPm).

5.50 (IH, - double line) (H in 3rd position) 5.29
(1)1. Double line, J: 10.9Hz) 4.50
(IH, triplet, J=6.6Hz) (H at position 2) (H at position 22) s)X)c Nuclear magnetic resonance spectrum (dS-pyridine) analysis shows the following signal (δl PPII) @74 .37
(C at position 22) 69.41 (C at position 2) 68.00 (C at position 3) 6) Mass spectrum analysis m/z 544 (M”) (31)2,3.22-)-Lee O -acetyl-24-
Methyl-5β-cholesto-7,20-diene-2β.

Physical properties and analytical data of 3β, 14α, 22α-tetraol-6-one 1) Properties and solubility Colorless amorphous powder containing ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, benzene,
Soluble in ether, slightly soluble in hexane, and insoluble in water.

2) Infrared absorption spectrum (KBr) analysis 3500.1
The absorption maximum is shown at 744.1663 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis The following signal is shown (δ+PPIH).

6.03 (IH, triple line, J=6.6Hz)
(H at position 22) 5.50 (1B, - double line) (H at position 3) 5.29 (IH, double line, J: 10.9Hz
) (H at the 2nd position) "c Nuclear magnetic resonance spectrum (d, -pyridine) Analysis shows the following signal (δy PPII) *76.43
(C at position 22) 69.41 (C at position 2) 68.00 (C at position 3) 6) Mass spectrum analysis m/z 586 (M') (32) 2,22,25 hlysooxy-22, 27
= Physical properties and analytical data of epoxy-23-hydroxymaxisterone A 1) Properties and solubility Colorless amorphous powder in ethanol and methanol.

Soluble in dimethyl sulfoxide, pyridine, hexane,
Slightly soluble in chloroform, benzene, and ether, and insoluble in water. Sarkolasky reaction, Liberman-Birchiard reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3350.1
It shows an absorption maximum at 650 cm-'.

3) Ultraviolet absorption spectrum (ethanol) analysis indicates the next signal 6.26 (LH, double line.

4.14 (IH, - double line) 3.89 (2)1. multiplet) 3.56 (IH, multiplet) (δ+PP addition) J=2.5Hz) (H at 7th position) (H at 3rd position) (H at 22nd and 23rd positions) (H at 9th position) 2.98 (11 (, triple line, J=9.0Hz)
(H at position 17) 1.71 (3H, -double line) (H at methyl group at position 21) 1.28 (3) 1. Double line, J=6
．． 27Hz) (H of methyl group at position 28) 1.24 (3H, - double line) (H of methyl group at position 18)
1.06 (3)1. - double line) (H of methyl group at position 19)
)0.89 (3H, double line, J=6.6Hz)
(H of the methyl group at position 26) s) 13c Nuclear magnetic resonance spectrum (dS-pyridine) analysis The following signal is shown (δ+ ppm).

203.48 (C of carbonyl group at position 6) 166.
96 (8th place C) 121.49 (7th place C) 87.31 (23rd place C) 84.55 (14th place C) 79.64 (22nd place C) 77.10 (20th place C) C) 74.65 (C at position 27) 64.20 (C at position 3) 6) Mass spectrum analysis m/z 476 (M)” (33) 3-0-7 cetyl-2.22.25-trideoxy- Physical properties and analytical data of 22,27-Eboxy 23-Hydroxymaxterone A 1) Properties and solubility Colorless amorphous powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, hexane, chloroform, benzene, It is soluble in ether and insoluble in water.Shows positive results in Sarcolasky reaction, Lieberman-Perchert reaction, and Chugaev reaction.

2) Infrared absorption spectrum (KBr) analysis 3340, 1
It shows an absorption maximum at 725.1650 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis tOH 4) H1 nuclear magnetic resonance spectrum (d,-pyridine) Shows the signal of separation (δt PP).

5.33 (LH, - double line) (H in 3rd position) 3.8
9 (2H, multiplet) (H at 22nd and 23rd positions) 2.02
(3)! , - heavy line) (H of the methyl group of the acetoxyl group) s) 13c nuclear magnetic resonance spectrum (d, -pyridine) analysis showing the following signal (δ* PPII) e170.23
(C of carbonyl group of acetoxyl group) 87.31
(C at position 23) 66.80 (C at position 3) 20.95 (C at methyl group of acetoxyl group) 6)
Mass spectrum analysis m/z 51g (M)'' (34) Physical properties and analytical data of 23-0-acetyl-2,22,25-1-lysooxy-22,27-diboxy-23-hydroxymaxterone A 1) Properties and solubility Colorless amorphous powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, and ether, sparingly soluble in hexane and benzene, and insoluble in water. Sarcolasky reaction, Liberman Birchiard reaction and Chugaev reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3506, 1
The maximum absorption is shown at 719.1657 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis shows the following signal (δr PP”) *5.43 (I
H, multiplet) (H at position 23) 4.14 (IH, - doublet) (H at position 3) 2.07 (3H, -multiplet) (H of methyl group of acetoxyl group) 5)"C Nuclear magnetic resonance spectroscopy (dS-pyridine) analysis shows the following signals (δ, PPm).

170.50 (C of carbonyl group of acetoxyl group
) 89.37 (C at position 23) 64.20 (C at position 3) 22.25 (C of methyl group of acetoxyl group) 6)
Mass spectrum analysis m/z 518 (M)” (35) 3,23-di○-acetyl-2,22°25
Physical properties and analytical data of -trideoxy-22,27-epoxy-23-hydroxymaxterone A 1) Properties and solubility Colorless amorphous powder, containing ethanol, methanol, dimethyl sulfoxide, pyridine, and chloroform.

Soluble in benzene and ether, sparingly soluble in hexane,
Insoluble in water. Sarcolaski reaction, Liberman
Birchiard reaction and Chugaev reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3500, 1
It shows an absorption maximum at 744.1663 cm-1.

3) Ultraviolet absorption spectrum (ethanol) analysis Shows the following signal (δ.

pp dust)- 5,43 (IH.

multiplet) (23rd place H) 5.33 (IH.

single line) (3rd place H) ``c nuclear magnetic resonance spectrum (dS-pyridine) analysis Shows the following signal (δ.

pp+m)・89.37 (C at position 23) 66.80 (C at position 3) Mass spectrum analysis m/z 560 (M)” (36) 2,22.25-trideoxy-22゜23-
Physical properties and analytical data of epoxy-24-hydroxymaxterone A 1) Properties and solubility Colorless amorphous powder, containing ethanol, methanol, dimethyl sulfoxide, pyridine, and chloroform.

Soluble in ether, sparingly soluble in benzene, hexane, and water. Sarkolasky reaction, Liberman-Birchiard reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3400, 1
650.880. The absorption maximum is shown at ``Boo cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis tOH 4) H1 nuclear magnetic resonance spectrum (d,-pyridine) analysis The following signal is shown (δ+ppm).

6.24 (IH, double line, J:2.5)1z)
(H in 7th position) 4.14 (IH, - double line)
(H in 3rd place) 3.74 (IH, double line, J=2.5
Hz) (H at position 22) 3.56 3.32 3.07 1.60 1.40 (IH2 (IH2 (IH2 (3H2 (3H)

multiplet) Double line.

Triple line.

Singlet) Singlet) (H at position 9) J=2.5Hz) (H at position 23) J=9Hz) (H at position 17) (H at methyl group at position 21) (H at methyl group at position 2H) H) 5) 12 C nuclear magnetic resonance spectrum (d,-pyridine) analysis shows the following signals (δ+ ppm).

203.20 (C of carbonyl group at position 6) 166.
32 (8th place C) 121.47 (7th place C) 84.13 (14th place C) n, 9B (20th place C) 71.45 (24th place C) 64.05 (3rd place C) C) 62.70 (22nd place C) 60.1B (23rd place C) 24.31. 24.31. 22.49. 21.9
0. 17.79. 17.67 (C of methyl group) 6) Mass spectrum analysis m/z 477 (M+1)” (37) 3-'O-acetyl-2,22,25-trideoxy-22,23-epoxy-24-hydroxymaxisterone Physical properties and analytical data of A 1) Properties and solubility Colorless amorphous powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform ether, and benzene, slightly soluble in hexane, and insoluble in water. .Sarkolasky reaction, Liberman-Perchard reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3350, 1
The maximum absorption is shown at 725.1650 cm-”, 3)
Ultraviolet absorption spectrum (ethanol) analysis tOH 4) H1 nuclear magnetic resonance spectrum (d,-pyridine) analysis showing the following signal (δy PPII)-5,34(I
H, - double line) (H at position 3) 2.02 (3H, - double line) (H at methyl group of acetoxyl group) S)! IC nuclear magnetic resonance spectrum (dS-pyridine) analysis shows the following signals (δt ppm).

170.25 (C of carbonyl derived from acetoxyl group) 66.65 (C of 3rd position) 20.94 (C of methyl derived from acetoxyl group) 6
) Mass spectrum analysis m/z 520 (M)+ (38)2,22.25-trideoxy-22°25-
Physical properties and analytical data of epoxy-23-hydroxymaxterone A 1) Properties and solubility Colorless amorphous powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, ether, benzene, hexane, water It is poorly soluble in Sarcolasky reaction, Liberman-Perchard reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3350, 1
It shows an absorption maximum at 650 cm-'.

3) Ultraviolet absorption spectrum (ethanol) analysis tOH 4) H1 nuclear magnetic resonance spectrum (d,-pyridine) analysis indicates the next signal 6.21 (LH, double line.

4.16 (1) 1. Double line.

4.12 (LH, - double line) 4.02 (IH, triple line.

3.48 (IH, multiple line) 1.35 (3H, - weight! 1.18 (3H, double line.

1.16 (3H, double line.

(δr PPII) @ J = 2.5Hz) (H at 7th position) J = 8Hz) (H at 23rd position) (H at 3rd position) J = 8H2) (H at 22nd position) (H at 9th position) ( H of methyl group at position 27) J = 7) + 2) (H of methyl group at position 28) J = 7Hz) (H of methyl group at position 21) 1.15 (3H, - double line) (H of methyl group at position 26) Methyl group H)
1.04 (3H, -jig) (H of the methyl group at the 19th position) 0.72 (3H, - heavy line) (H of the methyl group at the 18th position) 5) 13c nuclear magnetic resonance spectrum (d, -pyridine) analysis Showing the following signal (δ+ PP11) -203,20
(C of carbonyl group at position 6) 166.27 (C at position 8) 121.35 (C at position 7) 84.60 (C at position 23) 84.07 (C at position 14) 80.32 (25 C) 77.15 (C in 22nd place) 64.17 (C in 3rd place) 27.18.25.54.24.48.15.73.1
3.50.12.80 (C of methyl group) 6) Mass spectrum analysis m/z 461 (M+1)4 (39) 3-0-acetyl-2,22,25-trideoxy-22,25-epoxy-23 -Physical properties and analytical data of Hydroxymaxisterone A 1) Properties and solubility Colorless amorphous powder, soluble in ethanol, methanol, dimethylsulfate, phoxite, pyridine, chloroform, ether, and benzene, and sparingly soluble in hexane. Insoluble in water. Sarkolasky reaction, Liberman-Birchiard reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KB r) analysis 3350,
shows absorption maximum at 1725.1650 cm-1, 3
) Ultraviolet absorption spectrum (ethanol) analysis shows the following signal (δ+ ppm).

5.35 (11 (, - double line) (H in 3rd place) 2.02
(3H, - heavy line) (H of methyl group of acetoxyl group) 5) 12c nuclear magnetic resonance spectrum (dS-pyridine) analysis shows the following signal (δt ppw+) *170.25
(C of carbonyl derived from acetoxyl group) 66.6
4 (C at position 3) 20.93 (C of methyl derived from acetoxyl group) 6
) Mass spectrum analysis m/z 504 (M)” (40) Physical properties and analytical data of 23-○-acetyl-2,22.25-)-lysooxy-22,25-diboxy-23-hydroxymaxterone A 1) Properties and solubility Colorless amorphous powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, and ether, and sparingly soluble in hexane, benzene, and water.Sarkolasky reaction, Liberman-Birchiard reaction, and Chugaev The reaction shows positive.

2) Infrared absorption spectrum (KBr) analysis 3400, 1
It shows an absorption maximum at 720.1655 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis λ (
logi) nm=241(3,89)tOH 4) H1 nuclear magnetic resonance spectrum (d,-pyridine) analysis shows the following signal (δy PI”Im)*5.56
(IH, double line, J=8Hz) (H in 23rd position) 4
．． 12 (IH, - double line) (H in 3rd position) 2.07 (
3H, - heavy line) (H of methyl group of acetoxyl group) 5)'' 3C nuclear magnetic resonance spectrum (d, -pyridine) analysis shows the following signal (δy PPM) ++170.50
(C of carbonyl derived from acetoxyl group) 86.7
0 (C at position 23) 64.17 (C at position 3) 22.25 (C of methyl derived from acetoxyl group) 6
) Mass spectrum analysis m/z 504 (M)' (41) 3.23-di-O-acetyl-2,22°25
Physical properties and analytical data of -trideoxy-22,25-epoxy-23-hydroxymaxterone A 1) Properties and solubility A colorless amorphous powder that can be easily dissolved in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, ether, and benzene. Soluble, sparingly soluble in hexane and insoluble in water. Sarkolasky reaction, Liberman-Birchiard reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KB r) analysis 3500,
The maximum absorption is shown at 1744.1663 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis shows the following signal (δ+ PP4) *5.56 (I
H, double line, J=8Hz) (H at position 23) 5.3
5 (IH, - heavy line) (H at position 3) 5) 11c nuclear magnetic resonance spectrum (d, -pyridine) analysis showing the following signal (δ+ PP@) a86.70
(C at position 23) 66.64 (C at position 3) 6) Mass spectrum analysis m/z 548 (M)” (42) 2,20,22,25-tetradeoxy-22
, 23-diboxy-24-hydroxymaxterone A physical properties and analytical data 1) Properties and solubility Colorless amorphous powder, ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform.

Soluble in ether, sparingly soluble in benzene, hexane, and water. Sarkolasky reaction, Liberman-Birchiard reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3400, 1
The maximum absorption is shown at 650.880.800 cm-1.

3) Ultraviolet absorption spectrum (ethanol) analysis The following signal is shown (δy ppm).

6.22 (IH, double line, J: 2.5Hz)
(7th place H) 4.15 (1) 1. - heavy line)
(3rd place H) 3.55 (1)1. multiple layers
(H in 9th position) 3.27 (IH, double double line, J=8.2 Hz) (H in 22nd position) 2.90
(1)1. Double line, J=2Hz) (23
H at position) 1.38 (3H, - double line) (H at methyl group at position 28) 1.06 (3H, - double line) (H at methyl group at position 19) 0.73 (3H, - heavy line) Line) (H of the methyl group at position 18) 5)"C nuclear magnetic resonance spectrum (d, ~pyridine) analysis shows the following signal (δ+ PP-).

203.25 (C of carbonyl group at position 6) 165.
97 (8th place C) 121.35 (7th place C) 83.90 (14th place C) 71.57 (24th place C) 64.11 (3rd place C) 61.94 (22nd place C) C) 60.41 (23rd place C) 24.42.22.31.17.79.17.79.1
6.79.16.03 (C of methyl group) 6) Mass spectrum analysis m/z 461 (M+1)” (43) 3-0-acetyl-2,20,22°25-tetradeoxy-22,23- Physical properties and analytical data of epoxy-24-hydroxymaxisterone A 1) Properties and solubility Colorless amorphous powder, ethanol, methanol.

Soluble in dimethyl sulfoxide, pyridine, chloroform, ether, and benzene, sparingly soluble in hexane, and insoluble in water. Sarkolasky reaction, Liberman-Birchiard reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3340, 1
It shows an absorption maximum at 725.1650 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis The following signal is shown (δr　PP−).

5.35 (IH, - double line) (H in 3rd position) 2.02
(3H, - heavy line) (H of methyl group of acetoxyl group) 5) 13C nuclear magnetic resonance spectrum (d, -pyridine) analysis The following signal is shown (δr ppm).

170.25 (C of carbonyl derived from acetoxyl group) 66.71 (C of 3rd position) 20.94 (C of methyl derived from acetoxyl group) 6
) Mass spectrum analysis m/z 504 (M)+ (44)2. ．． Physical properties and analytical data of 25-dideoxymaxterone A 1) Properties and solubility Colorless non-crystalline powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, and ether, and hardly soluble in benzene, hexane, and water. It is melting. Sarcolasky reaction, Liberman-Perchard reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3350, 1
The maximum absorption is shown at 650 cm-1.

3) Ultraviolet absorption spectrum (ethanol) analysis tOH 4) H1 nuclear magnetic resonance spectrum (dS-pyridine) analysis Showing the following signal (δr PPII) *6.27 (
LH, double line.

4.14 (IH, - double line) 3.93 (LH, double line.

3.57 (1M, multiplet) 1.60 (3H, -multiplet) 1.25 (3H, -multiplet) 1.06 (3H, -multiplet) J=2.5Hz) (H at 7th position ) (H at position 3) J: 10Hz)) (H at position 22) (H at position 9) (H at methyl group at position 21) (H at methyl group at position 18) (H at methyl group at position 19) ) s) l) c Nuclear magnetic resonance spectrum (d,-pyridine) analysis showing the following signals (δ+ ppm).

203.31 (C of carbonyl group at position 6) 166.
56 (8th place C) 121.47 (7th place C) 84.31 (14th place C) 76.91 (20th place C) 74.56 (22nd place C) 64.11 (3rd place C) C) 24.42, 21.43, 21.42, 17.97, 1
6.03, 15.79 (C of methyl group) 6) Mass spectrum analysis m/z 463 (M+1)' (45) Physical properties and analytical data of 3-○-acetyl-2.25-dideoxymaxterone A 1) Properties and solubility Colorless amorphous powder, soluble in ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, ether, and benzene, sparingly soluble in hexane, and insoluble in water. Sarkolasky reaction, Liberman-Birchiard reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3350, 1
It shows an absorption maximum at 725.1650 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis 4) H1
Nuclear magnetic resonance spectroscopy (dS-pyridine) analysis shows the following signals (δ+ ppm).

5.34 (IH, - double line) (H in 3rd position) 3
．． 94 (1)1. Double line, J: 10Hz) (22
H at position 2.02 (3H, - heavy line) (H at methyl group of acetoxyl group) 5) "C nuclear magnetic resonance spectrum (d, -pyridine) analysis shows the following signal (δ+ PP") e170. 24
(C of carbonyl derived from acetoxyl group) 74.55
(C at position 22) 66.71 (C at position 3) 20.93 (C of methyl derived from acetoxyl group) 6
) Mass spectrum analysis m/z 506 (M)” (46) Physical properties and analytical data of 22-0-acetyl-2,25-dideoxymaxisterone A l) Properties and solubility Colorless amorphous powder, ethanol It is soluble in methanol, dimethyl sulfoxide, pyridine, chloroform, ether, and benzene, slightly soluble in hexane, and insoluble in water.Shows positive results in Sarcolasky reaction, Lieberman-Perchard reaction, and Chugaev reaction.

2) Infrared absorption spectrum (KBr) analysis 3400, 1
It shows an absorption maximum at 720.1655 cm-''.

3) Ultraviolet absorption spectrum (ethanol) analysis shows the following signal (δt PPII) @5.43 (
1)1. Double line, J:1ot(z) (H at position 22) 4.15 (IH, - double line) (3
H) 1.99 (3H, - heavy line) (H of methyl group of acetoxyl group) 5)"C nuclear magnetic resonance spectrum (ds-pyridine) analysis shows the following signal (δy PPII) a170.50
(C of carbonyl derived from acetoxyl group) 76.6
7 (C at position 22) 64.12 (C at position 3) 22.25 (C of methyl derived from acetoxyl group) 6
) Mass spectrum analysis m/z 506 (M)” (47) Physical properties and analytical data of 3.22-di-O-acetyl-2.25-dideoxymaxterone A 1) Properties and solubility Colorless amorphous powder , ethanol, methanol, dimethyl sulfoxide, pyridine, chloroform, ether, benzene, hexane, and insoluble in water.

Sarkolasky reaction, Liberman-Birchiard reaction, and Chugaev reaction are positive.

2) Infrared absorption spectrum (KBr) analysis 3505, 1
The maximum absorption is shown at 725.17191657 cm-'.

3) Ultraviolet absorption spectrum (ethanol) analysis tOH H1 nuclear magnetic resonance spectrum (d,-pyridine) minutes Shows the following signal (δ.

ppm)・ 5.44 (IH9 Double line.

J=1041z) (H in 22nd place) 5.35 (IHL - heavy line) (3rd place H) s)! 3c nuclear magnetic resonance spectrum (d,-pyridine) analysis Shows the following signal (δ.

ppm).

76.65 (C at position 22) 66.71 (C at position 3) Mass spectrometry analysis m/z 550 (M)” Experimental examples regarding the pharmacological action and toxicity of the compound according to the present invention are shown.

[Experimental Example 1] L1210 leukemia cells (hereinafter referred to as L121) were used as cancer cells.
0) was used. Cell Glosser-H (manufactured by Meguro Institute) was used as the medium, and 11210 cells were grown 8X in this medium.
It was prepared at 10' cells/ml and used in the experiment. After adding various concentrations of the test drug to the prepared cell suspension and culturing, for 3 days,
The number of viable cells on the 5th and 7th day was counted using the trypan blue staining method, and the growth inhibition rate of the test drug against L]210 cells was determined from the number of viable cells in the control group and the drug administration group. ,. Shown as a value. The test drug was dissolved in dimethyl sulfoxide, and only dimethyl sulfoxide was added to the control group.

As shown in Table 1, it was revealed that the compound according to the present invention exhibits an inhibitory effect on L12]0 cell proliferation.

[Experiment Example 2] (Toxicity) Std+ddY male mice were used in the experiment.

After intravenous administration of the test drug, the number of deaths for 72 hours is calculated from L.
LD based on the itchfield-Wilcoxon method
, oM was calculated.

The results are shown in Table 2.

As shown in Table 2, the compound according to the present invention was
No deaths were observed at a dose of 1.

As described above, it has been revealed that the compound according to the present invention has a cancer cell growth suppressive effect.

Table 1 Liu Koma IC6゜, 44-9 (95!Muf-) 3 days
5th day 7th day Maxisterone A 3rd day 5th day 7th day Table 10 Sell) Test drug Maxisterone A Maxisterone A rA.

IC, o, dv&, (95'IaaRk world) 3 days, 5 days, 7 days Table 2 (Substitute Todeoxymaxterone A 2+ Acetyl 1Lp-'HrDeoxymaxisterone A2.
22-di÷acetyl) L/-25-deoxymaxterone A2.3-di÷acetyl/l, -25-deoxymaxterone A2.3.22-tree can acetyl side todeoxymaxterone A dideoxy (24) 28 Dehydromaxisterone A2+acetyl)L/-25-deoxy(24)28
Dehydromaxisterone A2.22-di÷acetino Ll-
25-deoxy<24>28 dehydromaxisterone A 10<10<10<10<10<10<10<10< 2.3-di÷acetyl/l/-25-deoxy (24) 2
8 Dehydromaxisterone A 10〈 22.25-dideoxy-22,23-epoxymaxisterone A20, 22.25-trideoxy-22,Z
3-epoxymaxisterone A20.25-dideoxymaxisterone A20,'! :r-dideoxy-24(28
)-Dehydromaxisterone A10 < 10 < 10 < 10 < Table 2 Toxicity (#!ki) Test drug 2.25-Dideoxymaxterone A LD. , -hl 10< The clinical dosage of the anticancer agent according to the present invention is 1 to 1oOOIII for adults as the active ingredient! , /day is preferred. The formulation of the present invention is prepared for use in a conventional manner with any necessary pharmaceutical carriers or excipients.

Tablets, powders, granules, capsules, etc. for oral administration are prepared using conventional excipients such as calcium carbonate, magnesium carbonate, calcium phosphate, and corn.

It may contain potato starch, sugar, lactose, talc, magnesium stearate, gum arabic, etc. The tablets may be coated by known methods.
Oral liquid preparations may be aqueous or oily suspensions, solutions, syrups, elixirs, and the like.

Injectable preparations are preferably in the form of a solution according to the invention and may also contain formulation agents such as suspending, stabilizing or dispersing agents, sterile distilled water, essential oils such as peanut oil, etc. , corn oil or a non-aqueous solvent, polyethylene glycol, polypropylene glycol, etc. 1. For rectal administration, it is provided in the form of a suppository composition and is well known in the art as a pharmaceutical carrier 2. For example, it may contain polyethylene glycol, lanolin, coconut oil, etc.

For topical application, it may be provided in the form of ointment or plaster compositions.

Pharmaceutical carriers 2 well known in the art, such as petrolatum, paraffin, hydrated lanolin, plastibase, parent petrolatum, macrogol, wax, resin.

It may contain MH thyranone, rubber, etc.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [In the formula, R_1 is hydrogen, a hydroxyl group, or an acetyloxy group, and R_2 and R_5 are a hydroxyl group or an acetyloxy group. , R_3 and R_7 are methyl, R_4,
R_6 and R_8 are hydrogen or hydroxyl groups. However, a) R_3 and R_4 may form a terminal methylene. b) R_7 and R_8 may form a terminal methylene. c) R_5 and R_6 may form an epoxy. d) R_5 and carbon 27 may form a pyran ring. e) R_5 and carbon 25 may form a furan ring. ] A compound represented by 2. General formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [In the formula, R_1 is hydrogen or a hydroxyl group or an acetyloxy group, R_2 and R_5 are a hydroxyl group or an acetyloxy group, and R_3 and R_7 are methyl, R_4,
R_6 and R_8 are hydrogen or hydroxyl groups. However, a) R_3 and R_4 may form a terminal methylene. b) R_7 and R_8 may form a terminal methylene. c) R_5 and R_6 may form an epoxy. d) R_5 and carbon 27 may form a pyran ring. e) R_5 and carbon 25 may form a furan ring. An anticancer agent containing a compound represented by ] as an active ingredient.