CN1146457A - Method for preparation of progestol by degradation of steroidal saponin - Google Patents
Method for preparation of progestol by degradation of steroidal saponin Download PDFInfo
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- CN1146457A CN1146457A CN 96116304 CN96116304A CN1146457A CN 1146457 A CN1146457 A CN 1146457A CN 96116304 CN96116304 CN 96116304 CN 96116304 A CN96116304 A CN 96116304A CN 1146457 A CN1146457 A CN 1146457A
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Abstract
The present invention relates to a method degrading steroid sapogenin into pregnanediol compound and its application. Said method uses peroxyorganic acid to make steroid sapogenin oxidate in polar solvent under the condition of room temp., adds reducing agent to reduce excess oxidant and makes alkali or/and alcohol liquor back flow so as to obtain its products, i.e. pregnanediol with three chiral carbons of C16, C17 and C20 and (R)-Y-methyl valerolactone or 1-chloro-2-(R)-methyl-methyl valerate. The pregnanediol can be taken as counter-performance of propgesterone which is an important intermediate for synthesizing steroidal medicines, and (R)-Y-methyl valerolactone and 1-chloro-2-(R)-methyl-methyl valerate can be used as basic raw material for synthesizing chirality-containing methyl side chain compounds, such as chiral liquid crystal and insect pheromone, etc.
Description
The present invention relates to a kind of degradation of steroid sapogenin becomes the method for pregnane compound, promptly becomes method of pregnen alcohol and uses thereof by the oxidative degradation to steroid sapogenines.
Steroid sapogenines is to make various steroid drugs important chemical material as diosgenin, sisalagenin, zhimusaponin unit, american aloe sapogenin and analogue thereof always.Utilize steroid sapogenines synthesizing steroid medicine, at first need steroid sapogenin degradation is become pregnant steroid or androstane.Common degradation method, be Marker, R.E.et al J.Am.Chem.Soc.1947, disclosed in autoclave in 69,2167, steroid sapogenines and diacetyl oxide are heated to 200 ℃ are cracked into false steroid sapogenines, through chromic anhydride oxidation and elimination reaction, by obtaining corresponding Progesterone behind the above three-step reaction, total yield is approximately 60% again, for example, the degraded of sisalagenin.Reaction formula is as follows:
Although after this chemists constantly improve the method that the degradation of steroid sapogenin becomes Progesterone, Micovic, I.V.et al Synthesis 1,990 591 and hereinreferrences, but be in the conversion of reaction reagent top, and do not do the change of essence on the reactions steps.In common and the improved method, the consumption that still exists diacetyl oxide in the DeR process of High Temperature High Pressure is big, and to the deep-etching of conversion unit, reaction conditions is abominable; Problems such as environmental pollution that the use of chromic anhydride brought in oxidation reaction process and reaction total yield are low.For a long time, these problems are perplexing people always.Chemists are also seeking a kind of approach of solution always.
We find a kind of simple and effective synthetic method in the research of carrying out the steroid sapogenines resource rational utilization.Purpose of the present invention just provides a kind of reaction conditions gentleness, and reactions steps is easy, and reaction yield height does not have the degradation of steroid sapogenin of environmental pollution to become the method for pregnen alcohol and the purposes of gained pregnen alcohol.
Degradation method of the present invention is exactly under 0-25 ℃ condition, fresh peroxide organic acid is added drop-wise in the polar solvent that has dissolved steroid sapogenines, the mol ratio of peroxide organic acid and steroid sapogenines is 1-2: 1, after dropwising, at room temperature, reacted completely until steroid sapogenines in stirring reaction 20-50 hour; Drip the peroxide organic acid of saturated reductive agent aqueous solution decomposing excessive then.After polar solvent and acid are removed in decompression, add alkali and/or alcohol solution backflow 1-5 hour.Add the neutralization of 10% hydrochloric acid again, alcohol is removed in decompression, filters, and obtains the pregnen alcohol crude product, gets the pregnen alcohol of product-colourless needle crystal with polar solvent and/or alcoholic solvent recrystallization, and yield is 90-96%; Filtrate gets product (R)-γ-methylpent lactone through acid treatment; Through sulfur oxychloride and methyl alcohol handle product 1-chloro-2-(R)-methyl-methyl valerate, reaction formula is as follows:
Wherein the peroxide organic acid comprises trifluoro Peracetic Acid, Peracetic Acid, benzoyl hydroperoxide, metachloroperbenzoic acid, adjacent formic acid benzoyl hydroperoxide; Steroid sapogenines comprises diosgenin, sisalagenin, zhimusaponin unit, american aloe sapogenin and their analogue.Polar solvent can be methylene dichloride, chloroform, tetrahydrofuran (THF) etc.Reductive agent comprises sodium bisulfite, pyrosulphite hydrogen sodium etc.; Alcohol is alcohols such as methyl alcohol, ethanol, propyl alcohol; Alkali is sodium hydroxide, potassium hydroxide, salt of wormwood, yellow soda ash etc.
This law products therefrom pregnen alcohol can be considered the peer-to-peer of Progesterone, because pregnen alcohol has three chiral carbon: C than Progesterone more
16, C
17, C
20With the synthetic C of pregnen alcohol
16, C
20, especially have a C
18The steroidal compounds that replaces will be than synthetic more simple and convenient from Progesterone.This is to have C because of synthesizing from Progesterone
18During substituent steroidal compounds, need at first the Progesterone Stereoselective is reduced into to have C
20The chirality pregnen alcohol utilizes C then
20Hydroxyl is transformed C
18Methyl; At synthetic C
20During the steroidal compounds of the different alkyl group side chains of bit strip, also need pregnant steroid-Δ
16-20-ketone transforms into pregnant steroid-Δ through three-step reaction
17-16-ketone.
Another product (R)-γ-methylpent lactone of this law gained and 1-chloro-2-(R)-methyl-methyl valerate then can become the compound of synthesis of chiral methyl chains, as the important source material of chiral liquid crystal, insect pheromone etc.
Method of the present invention and purposes compared with prior art, it is the reaction conditions gentleness not only, i.e. reaction at room temperature, reactions steps is few, reaction yield is high, promptly greater than 90% yield; Reaction cost is low, does not have the sorrow of environmental pollution because boiling points such as the trifluoroacetic acid, acetate that are produced in the reaction low, be easy to reclaim, actual consumption only is hydrogen peroxide.And operation is easy, does not need special conversion unit.And the product pregnen alcohol can be considered the peer-to-peer of the important intermediate Progesterone of synthesizing steroid medicine, because it has C16, C17, three chiral carbon of C20, the transformation that is more conducive to steroidal C18 is connected alkyl substituent with C20, and synthetic C18, C16 and C20 have the steroid drugs and the steroidal molecule of different substituents.Product (R)-γ-methylpent lactone and 1-chloro-2-(R)-methyl-methyl valerate are the important source material of synthesis of chiral methyl chains compound.
Following examples help to understand the present invention, but are not limited to the present invention.
Embodiment 1
Put 6 milliliters of (40mmol) trifluoroacetic anhydride (TFAA)s in 20 milliliters of methylene dichloride, (50-90%, 40mmol), after being added dropwise to complete, reaction solution continues stirring and got the trifluoro peracetic acid soln in 30 minutes to drip hydrogen peroxide lentamente at 0 ℃.Keep temperature of reaction at 0-25 ℃, the trifluoro peracetic acid soln that drips prepared fresh is in methylene dichloride 80 ml solns of sisalagenin (Tigogenin) acetic ester 9.2 grams (20mmol); After being added dropwise to complete, at room temperature stirring reaction reacted completely until steroid sapogenines in 30 hours.Drip the trifluoro Peracetic Acid of saturated aqueous solution of sodium bisulfite decomposing excessive.Methylene dichloride and trifluoroacetic acid are removed in decompression, add 80 ml methanol and 20 milliliters of 4N aqueous sodium hydroxide solutions, reflux 1.5 hours, and with the neutralization of 10% hydrochloric acid, methyl alcohol is removed in decompression then, filter collect 63 β more than restraining, 16 β, the pregnant steroid triol of 20R-.Yield is 95%, gets colourless needle crystal with methylene dichloride, recrystallizing methanol again.3 β, 16 β, the pregnant steroid triol of 20R-:
Fusing point: 240-241.8 ℃ [α]
D 25: 24 (c=0.35, CHCl
3)
1HNMR (300MHz, CHCl
3): 4.13 (1H, dq, J=9.8,6.2Hz, 20-H), 4.48 (1H, ddd, J=7.7,7.7and5.5HZ, 16-H), 3.59 (1H, m, 3-H), 1.32 (3H, d, J=6.2HZ, 21-H), 0.87 (3H, s, 19-H), 0.82 (3-H, s, 18-H) ppm.MS (EI) m/e:337 (M+1)
+, 320,318,300,303,285,275,259,246,232,215.IR (KBr) ν: 3300 (OH) cm
-1. ultimate analysis C
21H
36O
31/2H
2O:
Calculated value: C 73.00, H 10.75
Measured value: C 73.67, H 10.72
Embodiment 2
6.9 gram metachloroperbenzoic acids (40mmol) are dissolved in the 20ml methylene dichloride, keep temperature of reaction, slowly be added drop-wise in methylene dichloride 80 ml solns of zhimusaponin unit (Sarsasapogenin) acetic ester 9.2 grams (20mmol) at 0-25 ℃; After being added dropwise to complete, at room temperature stirring reaction reacted completely until steroid sapogenines in 50 hours.Drip the metachloroperbenzoic acid of saturated pyrosulphite hydrogen sodium water solution decomposing excessive.Methylene dichloride is removed in decompression, add in the yellow soda ash and m-chlorobenzoic acid after, add 80 ml methanol and 20 milliliters of 4N aqueous sodium hydroxide solutions, refluxed 5 hours, with the neutralization of 10% hydrochloric acid, methyl alcohol is removed in decompression then, filtration collect 3 above β of 6 grams, 16 β, 20R-(5 β)-pregnant steroid triol.Yield is 90%, gets colourless needle crystal with methylene dichloride, recrystallizing methanol again.3 β, 16 β, 20R-(5 β)-pregnant steroid triol:
1HNMR (300MHz, CHCl
3): 4.13 (1H, dq, J=9.8,6.2Hz, 20-H), 4.48 (1H, ddd, J=7.7,7.7and5.5HZ, 16-H), 3.59 (1H, m, 3-H), 1.32 (3H, d, J=6.2HZ, 21-H), 0.87 (3H, s, 19-H), 0.82 (3-H, s, 18-H) ppm.MS (EI) m/e:337 (M+1)
+, 320 (M-O), 318 (M-H
2O), 285,275.IR(KBr)ν：3300，1035，2900，1440，1370cm
-1。Ultimate analysis C
21H
36O
3:
Calculated value: C 73.98, H 10.75
Measured value: C 73.90, H 10.70
Embodiment 3
Put 6 milliliters of (40mmol) trifluoroacetic anhydride (TFAA)s in 20 milliliters of chloroforms, (50-90%, 40mmol), after being added dropwise to complete, reaction solution continues stirring and got the trifluoro peracetic acid soln in 30 minutes to drip hydrogen peroxide lentamente at 0 ℃.Keep temperature of reaction at 0-25 ℃, the trifluoro peracetic acid soln that drips prepared fresh is in chloroform 80 ml solns of (10)-dihydro-american aloe sapogenin 9.5 grams (20mmol); After being added dropwise to complete, at room temperature stirring reaction reacted completely until steroid sapogenines in 25 hours.Drip the trifluoro Peracetic Acid of saturated aqueous solution of sodium bisulfite decomposing excessive.Chloroform and trifluoroacetic acid are removed in decompression, add 20 milliliters of 4N aqueous sodium hydroxide solutions, refluxed 1.5 hours, then with the neutralization of 10% hydrochloric acid, filter collect 63 β more than restraining, 12 β, 16 β, the pregnant steroid tetrol of 20R-.Yield is 95%, gets colourless needle crystal with chloroform, recrystallizing methanol again.3 β, 12 β, 16 β, the pregnant steroid tetrol of 20R-:
1HNMR (300MHz, CHCl
3): 4.17 (1H, dq, J=4.4,6.4Hz, 20-H), 4.34 (1H, m, 16-H), 3.32 (1H, m, 3-H), 3.07 (1H, m, 12-H), 1.27 (3H, d, J=6.5HZ, 21-H), 0.86 (3H, s, 19-H), 0.72 (3-H, s, 18-H) ppm.MS (EI) m/e:334 (M-H
2O), 316 (334-H
2O), 301 (316-CH
3), 283,273,43,55.IR (KCl) ν: 3290,2950,1470,1370,1080cm
-1. ultimate analysis C
21H
36O
4:
Calculated value: C 71.55, H 10.29
Measured value: C 71.49, H 10.33
Embodiment 4
Put 6 milliliters of (40mmol) trifluoroacetic anhydride (TFAA)s in 20 milliliters of tetrahydrofuran (THF)s, (50-90%, 40mmol), after being added dropwise to complete, reaction solution continues stirring and got the trifluoro peracetic acid soln in 30 minutes to drip hydrogen peroxide lentamente at 0 ℃.Keep temperature of reaction at 0-25 ℃, the trifluoro peracetic acid soln that drips prepared fresh is in tetrahydrofuran (THF) 80 ml solns of diosgenin (Diosgenin) acetic ester 10.8 grams (20mmol); After being added dropwise to complete, at room temperature stirring reaction reacted completely until steroid sapogenines in 45 hours.Drip the trifluoro Peracetic Acid of saturated aqueous solution of sodium bisulfite decomposing excessive.Tetrahydrofuran (THF) and trifluoroacetic acid are removed in decompression, add 80 ml methanol and 20 milliliters of 4N potassium hydroxide aqueous solutions, room temperature reaction 3 hours, with the neutralization of 10% hydrochloric acid, methyl alcohol is removed in decompression then, filter collect 6 grams above 5, (6)-(α)-and epoxy-3 β, 16 β, the pregnant steroid triol of 20R-.Yield is 90%, gets colourless needle crystal with methylene dichloride, recrystallizing methanol again.5, (6)-(α)-epoxy-3 β, 16 β, the pregnant steroid triol of 20R-:
1HNMR (300MHz, CHCl
3): 4.41 (1H, m, 16-H), 4.09 (1H, m, 20-H), 3.54 (1H, m, 6-H), 3.78 (1H, m, 3-H), 1.32 (3H, d, J=6.2HZ, 21-H), 0.86 (3H, s, 19-H), 0.80 (1H, s, 18-H) ppm.MS (EI) m/e:351 (M+1)
+, 350 (M
+), 332 (M-H
2O), 317 (332-CH
3), 43,55.IR (KCl) ν: 3350,1040,2900,1440,1380cm
-1. ultimate analysis C
21H
34O
4:
Calculated value: C 71.96, H 9.78
Measured value: C 72.25, H 9.41
Embodiment 5
Put 3.8 milliliters of (40mmol) diacetyl oxides in 20 milliliters of methylene dichloride, (50-90%, 40mmol), after being added dropwise to complete, reaction solution continues stirring and got peracetic acid soln in 30 minutes to drip hydrogen peroxide lentamente at 0 ℃.Keep temperature of reaction at 0-25 ℃, the peracetic acid soln that drips prepared fresh is in methylene dichloride 80 ml solns of 6-oxo sisalagenin 8.9 grams (20mmol); After being added dropwise to complete, at room temperature stirring reaction reacted completely until steroid sapogenines in 50 hours.Drip the Peracetic Acid of saturated aqueous solution of sodium bisulfite decomposing excessive.Methylene dichloride and acetate are removed in decompression, add 80 ml methanol and 20 milliliters of 4N aqueous sodium hydroxide solutions, reflux 5 hours, with the neutralization of 10% hydrochloric acid, methyl alcohol is removed in decompression then, filter collect above 6-oxo-beta-Gao-7-oxa--2 α of gram, 3 α, 16 β, the pregnant steroid tetrol of 20R-.Yield is 92%, gets colourless needle crystal with methylene dichloride, recrystallizing methanol again.6-oxo-beta-Gao-7-oxa--2 α, 3 α, 16 β, the pregnant steroid tetrol of 20R-:
1HNMR (300MHz, CHCl
3): 4.51 (1H, m, 16-H), 4.14 (1H, m, 20-H), 4.05 (2H, m, 7-H), 5.80 (1H, m, 3-H), 4.32 (1H, m, 2-H), 1.28 (3H, d, J=6.3HZ, 21-H), 0.88 (3H, s, 19-H), 0.81 (3-H, s, 18-H) ppm.MS (EI) m/e:381 (M+1), 380 (M
+), 362 (M-H
2O), 334 (362-H
2O), 319 (334-CH
3) .IR (KBr) ν: 3300,2900,1720,1440,1200cm
-1. ultimate analysis C
21H
34O
6:
Calculated value: C 66.29, H 8.48
Measured value: C 65.90, H 8.18
Embodiment 6
The 6.9 adjacent chloroperoxybenzoic acids of gram (40mmol) are dissolved in the 20ml methylene dichloride, keep temperature of reaction, drip adjacent chloroperoxybenzoic acid solution lentamente in methylene dichloride 80 ml solns of 6 Alpha-hydroxy sisalagenins, 8.6 grams (20mmol) at 0-25 ℃; After being added dropwise to complete, at room temperature stirring reaction reacted completely until steroid sapogenines in 50 hours.Drip the adjacent chloroperoxybenzoic acid of saturated pyrosulphite hydrogen sodium water solution decomposing excessive.Methylene dichloride is removed in decompression, add in the yellow soda ash and 0-chloro-benzoic acid after, add 80 ml methanol and 20 milliliters of 4N aqueous sodium hydroxide solutions, refluxed 1.5 hours, with the neutralization of 10% hydrochloric acid, methyl alcohol is removed in decompression then, filter collect 3 above β of 6 grams, 6 α, 16 β, the pregnant steroid tetrol of 20R-.Yield is 90%, gets colourless needle crystal with methylene dichloride, recrystallizing methanol again.3 β, 6 α, 16 β, the pregnant steroid tetrol of 20R-:
1HNMR (300MHz, CHCl
3): 4.49 (1H, m, 20-H), 4.10 (1H, m, 16-H), 3.62 (1H, m, 3-H), 3.14 (1H, m, 6-H), 1.29 (3H, d, J=6.4HZ, 21-H), 0.91 (3H, s, 19-H), 0.83 (3-H, s, 18-H) ppm.MS (EI) m/e:334 (M-H
2O), 316 (334-H
2O), 301 (316-CH
3), 283,55,97.IR(KCl)ν：3350，2900，1440，1050cm
-1。Ultimate analysis C
21H
36O
4:
Calculated value: C 71.55, H 10.29
Measured value: C 71.20, H 10.44
Embodiment 7
Put 6 milliliters of (40mmol) trifluoroacetic anhydride (TFAA)s in 20 milliliters of methylene dichloride, (50-90%, 40mmol), after being added dropwise to complete, reaction solution continues stirring and got the trifluoro peracetic acid soln in 30 minutes to drip hydrogen peroxide lentamente at 0 ℃.Keep temperature of reaction at 0-25 ℃, drip the trifluoro peracetic acid soln to 5 of prepared fresh, in methylene dichloride 80 ml solns of 6-dibromo sisalagenin 11.5 grams (20mmol); After being added dropwise to complete, at room temperature stirring reaction reacted completely until steroid sapogenines in 30 hours.Drip the trifluoro Peracetic Acid of saturated aqueous solution of sodium bisulfite decomposing excessive.Filter products therefrom through debromination, methylene dichloride and trifluoroacetic acid are removed in decompression, add 80 ml methanol and 20 milliliters of 4N aqueous sodium hydroxide solutions, reflux 1.5 hours, with the neutralization of 10% hydrochloric acid, methyl alcohol is removed in decompression then, final 3 above β of 6 grams, 16 β, 20R-5, (6)-pregnene triol.Yield is 90%, gets colourless needle crystal with methylene dichloride, recrystallizing methanol again.3 β, 16 β, 20R-5, (6)-pregnene triol:
1HNMR (300MHz, CHCl
3): 4.50 (1H, m, 20-H), 4.11 (1H, m, 16-H), 3.65 (1H, m, 3-H), 5.38 (1H, m, 6-H), 1.33 (3H, d, J=6.2HZ, 21-H), 0.88 (3H, s, 19-H), 0.79 (3-H, s, 18-H) ppm.MS (EI) m/e:334 (M
+), 316 (M
+-H
2O), 301 (316-CH
3), 283,44,55.IR (KCl) ν: 3350,2850,1600,1440,1380cm
-1. ultimate analysis C
21H
34O
3:
Calculated value: C 75.86, H 9.70
Measured value: C 76.14, H 9.65
Filtrate is handled through hcl acidifying and is all obtained about 0.90 gram (R)-γ-methylpent lactone of product equally among the above embodiment 1-7, and wherein embodiment 2 acidifying products therefroms are enantiomers of (R)-γ-methylpent lactone, and yield is 40-50%.(R)-γ-methylpent lactone:
[α]
D 20:+16.1 (C 0.95, CHCl
3)
1HNMR (300MHz, CHCl
3): 0.94 (3H, d, J=6.6HZ, 4-CH
3), 1.41-1.54 (1H, m, 3-H), 1.86-2.04 (m, 2H, 3-H, 4-H), 2.39-2.63 (2H, m, 2-H), 3.85 (m, 1H, 5-H), 4.22-4.28 (m, 1H, 5-H) .MS (EI) m/e:115 (M
++ 1), 114 (M
+), 99 (M
+-CH
3), 84,69,42.IR (film) ν: 2900,1720,1470,1180cm
-1. ultimate analysis C
6H
10O
2:
Calculated value: C 63.12, H 8.94
Measured value: C 62.77, H 9.01
Filtrate among the embodiment 1-7 is handled through sulfur oxychloride, methyl alcohol and is all obtained about 1.64 gram 1-chloro-2-(R)-methyl-methyl valerates equally, and yield is 50-60%.1-chloro-2-(R)-methyl-methyl valerate:
1HNMR (300MHz, CHCl
3): 3.67 (3H, s, OCH
3), 3.46 (2H, d, J=2.7HZ ,-CH
2Cl), 2.36 (2H, m ,-COCH
2-), 1.84 (2H, m ,-CH
2CH-), 1.57 (1H, m ,-CH
2CH-), 1.02 (3H, d, J=7.7HZ ,-CHCH
3-) .MS (EI) m/e:165 (M
++ 1), 149 (M
+-CH
3), 131 (149-H
2O), 87,69,55.IR (film) ν C
7H
13O
2Cl:2800,1760,1440,1200cm
-1. ultimate analysis
Calculated value: C 51.20, H 7.99
Measured value: C 51.61, H 8.11
Claims (12)
1. a degradation of steroid sapogenin becomes the method for pregnen alcohol, be by degraded to steroid sapogenines, it is characterized in that under 0-25 ℃ condition, in polar solvent, the peroxide organic acid is added drop-wise in the steroid sapogenines solution, peroxide organic acid and steroid sapogenines mol ratio are 1-2: 1, after being added dropwise to complete, reacted completely until steroid sapogenines in stirring reaction 20-50 hour, after dripping reductant solution decomposing excessive peroxide organic acid again, pressure reducing and steaming polar solvent and acid added alkali and/or alcoholic solution and reflux, after return time 1-10 hour, acid neutralization with 10%, pressure reducing and steaming alcohol, filter the product pregnen alcohol, yield is 90-96%.
2. press the method for the described synthetic pregnen alcohol of claim 1, it is characterized in that described reaction filtrate gets (R)-γ-methylpent lactone through sour acidification, yield is 40-70%, handles to such an extent that 1-chloro-2-(R)-methyl-methyl valerate yield is 50-60% through sulfur oxychloride and methyl alcohol.
3. by the method for claim 1 and 2 described synthetic pregnen alcohols, it is characterized in that described peroxide organic acid comprises trifluoro Peracetic Acid, Peracetic Acid, benzoyl hydroperoxide, metachloroperbenzoic acid, adjacent formic acid benzoyl hydroperoxide.
4. by the method for the described synthetic pregnen alcohol of claim 3, it is characterized in that described steroid sapogenines comprises diosgenin, sisalagenin, zhimusaponin unit, american aloe sapogenin and their analogue.
5. by the method for claim 1 and 2 described synthetic pregnen alcohols, it is characterized in that described polar solvent comprises methylene dichloride, chloroform, tetrahydrofuran (THF) etc.
6. by the method for claim 1 and 2 described synthetic pregnen alcohols, it is characterized in that described reductive agent comprises sodium bisulfite, pyrosulphite hydrogen sodium etc.
7. by the method for claim 1 and 2 described synthetic pregnen alcohols, it is characterized in that described alcohol comprises methyl alcohol, ethanol, propyl alcohol etc.
8. by the method for claim 1 and 2 described synthetic pregnen alcohols, it is characterized in that described alkali is sodium hydroxide, potassium hydroxide, salt of wormwood, yellow soda ash etc.
9. the purposes of the method for the synthetic pregnen alcohol of degradation of steroid sapogenin is characterized in that described product pregnen alcohol can be considered the peer-to-peer of Progesterone, and pregnen alcohol has three chiral carbon: C than Progesterone more
16, C
17, C
20
10. by the method purposes of the described synthetic pregnen alcohol of claim 9, it is characterized in that described product pregnen alcohol is to be used for synthetic C
18, C
16And C
20Steroid drugs and steroidal molecule with different substituents.
11., it is characterized in that described product (R)-γ-methylpent lactone and 1-chloro-2-(R)-methyl-methyl valerate are to be used for the synthetic chirality methyl side chain compound that contains by the method purposes of the described synthetic pregnen alcohol of claim 9.
12. the method purposes by the described synthetic pregnen alcohol of claim 11 is characterized in that the described chirality methyl side chain compound that contains is chiral liquid crystal, insect pheromone etc.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100548965C (en) * | 2004-12-21 | 2009-10-14 | 中国科学院上海有机化学研究所 | ω-the hydroxy-acid derivative of band chirality methyl side chain |
| CN102134193A (en) * | 2011-01-07 | 2011-07-27 | 中国科学院上海有机化学研究所 | Method for synthesizing (4R, 2E)-4-methyl-2-alkenyl valerate compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1221563C (en) * | 2003-07-16 | 2005-10-05 | 中国科学院上海有机化学研究所 | Cleaning production technique of 16-dehydro pregnenetrolone and its same kind compound |
| CN1962680B (en) * | 2006-12-01 | 2010-05-12 | 中国科学院上海有机化学研究所 | 20-hydroxy-16 alpha- bromo-steroid compound, synthesis method and its uses |
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| CN1068121A (en) * | 1992-01-20 | 1993-01-20 | 广西南宁制药企业集团公司 | The process for extracting of Tigogenin |
| CN1033754C (en) * | 1993-05-31 | 1997-01-08 | 上海第二医科大学 | Medicine with regulating effect on beta adrenergic receptor and M-cholinergic receptor and preparation thereof |
| CN1061988C (en) * | 1994-05-03 | 2001-02-14 | 厦门同安皂素厂 | Method for extracting diosgenin from Dioscorea plant |
| CN1055930C (en) * | 1994-10-08 | 2000-08-30 | 中国科学院上海有机化学研究所 | Steroalkenol polyfluohydrocarbyl sulfonate compound and its deriv., use and preparing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100548965C (en) * | 2004-12-21 | 2009-10-14 | 中国科学院上海有机化学研究所 | ω-the hydroxy-acid derivative of band chirality methyl side chain |
| CN102134193A (en) * | 2011-01-07 | 2011-07-27 | 中国科学院上海有机化学研究所 | Method for synthesizing (4R, 2E)-4-methyl-2-alkenyl valerate compound |
| CN102134193B (en) * | 2011-01-07 | 2013-05-01 | 中国科学院上海有机化学研究所 | Method for synthesizing (4R, 2E)-4-methyl-2-alkenyl valerate compound |
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| CN1061985C (en) | 2001-02-14 |
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