WO1995016698A1 - Conversion of bisnoralcohol to bisnoraldehyde - Google Patents

Conversion of bisnoralcohol to bisnoraldehyde Download PDF

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Publication number
WO1995016698A1
WO1995016698A1 PCT/US1994/012196 US9412196W WO9516698A1 WO 1995016698 A1 WO1995016698 A1 WO 1995016698A1 US 9412196 W US9412196 W US 9412196W WO 9516698 A1 WO9516698 A1 WO 9516698A1
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Prior art keywords
bisnoraldehyde
production
mole percent
hydroxy
catalytic amount
Prior art date
Application number
PCT/US1994/012196
Other languages
French (fr)
Inventor
Bradley Dee Hewitt
Original Assignee
The Upjohn Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to RU96115126A priority Critical patent/RU2131437C1/en
Priority to DE69415345T priority patent/DE69415345T2/en
Priority to HU9601672A priority patent/HU220871B1/en
Priority to NZ275951A priority patent/NZ275951A/en
Priority to SI9430227T priority patent/SI0734392T1/en
Priority to ES95900414T priority patent/ES2124990T3/en
Priority to PL94314965A priority patent/PL181212B1/en
Priority to SK761-96A priority patent/SK281716B6/en
Application filed by The Upjohn Company filed Critical The Upjohn Company
Priority to EP95900414A priority patent/EP0734392B1/en
Priority to US08/809,719 priority patent/US6608220B1/en
Priority to AU81244/94A priority patent/AU693126B2/en
Priority to DK95900414T priority patent/DK0734392T3/en
Priority to CA002175906A priority patent/CA2175906C/en
Priority to JP51674695A priority patent/JP3778927B2/en
Publication of WO1995016698A1 publication Critical patent/WO1995016698A1/en
Priority to NO962524A priority patent/NO306163B1/en
Priority to FI962480A priority patent/FI115914B/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane

Definitions

  • the present invention is a process for the conversion of bisnoralcohol (I) to bisnoraldehyde (II) which is a known intermediate in the synthesis of progesterone.
  • J. Org. Chem., 52, 2559 (1987) discloses TEMPO and 4-Methoxy-TEMPO catalyzed, two-phase oxidation of primary alcohols and secondary alcohols to aldehydes and ketones, respectively, using potassium bromide and 0.35 M sodium hypochlorite buffered to Ph 8.5 with sodium bicarbonate.
  • J. Org. Chem., 56, 6110 (1991) discloses the use of stoichiometric amounts of oxammonium salts, generated by treatment of TEMPO or 4-acetylamino-TEMPO with organic sulfonic acids, for the selective oxidation of primary or secondary alcohols to aldehydes or ketones, respectively.
  • J. Am. Chem. Soc, 106, 3374 (1984) discloses the use of TEMPO or 4- hydroxy-TEMPO to catalyze the oxidation of primary or secondary alcohols to aldehydes or ketones, respectively, by oxygen and copper (II) salts.
  • US Patent 5,136,102 discloses the use of TEMPO or 4-substituted TEMPO derivatives and a bromide containing salt to catalyze the oxidation of secondary alcohols to ketones with nitric acid and oxygen.
  • US Patent 5,155,278 discloses the use of TEMPO or 4-substituted TEMPO derivatives to catalyze the oxidation of primary alcohols to aldehydes with nitric acid and oxygen.
  • US Patent 5,155,279 discloses the use of TEMPO or 4-substituted TEMPO derivatives to catalyze the selective oxidation of primary alcohols to aldehydes with nitric acid in the absence of oxygen.
  • US Patent 5,155,280 discloses the use of TEMPO or 4-substituted TEMPO derivatives and an alkali metal nitrosodisulfonate salt to catalyze the selective oxidation of primary alcohols to aldehydes with oxygen in the absence of nitric acid.
  • Japanese patent J5 6152498 discloses the oxidation of bisnoralcohol to bisnoraldehyde using dimethyl sulfide and N-chlorosuccinimde or chlorine.
  • step (2) (2) contacting the mixture of step (1) with a stoichiometric amount of hypochlorite.
  • Bisnoraldehyde (II) is known to be useful as an intermediate in the synthesis of progesterone and hydrocortisone, see J. Am. Chem. Soc, 74, 5933 (1952).
  • the present invention is practiced by (1) forming a mixture of bisnoralcohol (I), a catalytic amount of 4-hydroxy TEMPO in a pH range of about 8.5 to about 10.5 and in a temperature range of about - 10° to about 15°, and (2) contacting the mixture of step (1) with a stoichiometric amount of hypochlorite. It is preferred to perform the reaction in the presence of bromide, preferably a catalytic amount of the bromide. The mixture can be cooled at any point prior to the addition of the hypochlorite.
  • Operable amounts of the 4-hydroxy-TEMPO are from about 0.025 mole percent to about 15 mole percent; it is preferred that the amount of the 4-hydroxy- TEMPO be from about 0.025 mole percent to about 2.5 mole percent.
  • Operable amounts of the bromide are from about 5 mole percent to about 25 mole percent; it is preferred that the amount of bromide be from about 10 mole percent to about 15 mole percent.
  • the pH is preferably regulated by the use of bicarbonate. Operable amounts of bicarbonate are from about 5 mole percent to about 30 mole percent; it is preferred that the amount of bicarbonate be from about 10 mole percent to about 20 mole percent.
  • the cation of the bromide or bicarbonate is not important as long as it is soluble; preferred cation are sodium, potassium and lithium, more preferably sodium or potassium.
  • Operable solvents include dichloroethane, toluene, ethyl acetate, methyl tert-butyl ether, dichloromethane, o-dichlorobenzene chlorobenzene and chloroform; it is preferred that the solvent be methylene chloride. While the operable solvents are organic water immiscible solvents, a small amount of water is operable and even preferred as is known to those skilled in the art. In addition, the hypochlorite is added as an aqueous mixture.
  • reaction temperature be in the range of about - 5° to about 5°. It is preferred that the hypochlorite is added over a period of from about 1 hr to about 6 hr. It is preferred that the amount of hypochlorite be from about 95 mole percent to about 120 mole percent.
  • Operable quenching agents include bisulfite, thiosulfate, dimethylsulfide, trimethylphosphate and triethylphosphate; it is preferred that the quenching agent be sodium or potassium thiosulfate.
  • the process of the present invention can be practiced in either batch mode or continuous mode as is known to those skilled in the art.
  • the reaction mixture is worked up by methods well known to those skilled in the art.
  • the bisnoraldehyde (II) can be transformed to progesterone by known methods, see J. C. S. Chem. Comm., 314 (1969) and Tet. Lett., 985 (1969).
  • 4-hydroxy-TEMPO refers to 4-hydroxy-2,2,6,6-tetramethylpiperidine-l-oxyl.
  • TEMPO refers to 2,2,6,6-tetramethylpiperidine-l-oxyl.
  • TEMPO A mixture of bisnoralcohol (I, 4 g), 4-hydroxy-2,2,6,6-tetramethylpiperidine-l- oxyl (4-hydroxy- TEMPO, 10 mg), potassium bromide (133 mg), sodium bicarbonate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Steroid Compounds (AREA)

Abstract

The present invention is a process for the conversion of bisnoralcohol (I) to bisnoraldehyde (II) which is a known intermediate in the synthesis of progesterone.

Description

CONVERSION OF BISNORALCOHOL TO BISNORALDEHYDE BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a process for the conversion of bisnoralcohol (I) to bisnoraldehyde (II) which is a known intermediate in the synthesis of progesterone.
2. Description of the Related Art The oxidation of bisnoralcohol (I) to bisnoraldehyde (II) is a well known process.
4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-l-oxyl) is known, see Synthesis, 190-202 and 401-414 (1971).
J. Org. Chem., 52, 2559 (1987) discloses TEMPO and 4-Methoxy-TEMPO catalyzed, two-phase oxidation of primary alcohols and secondary alcohols to aldehydes and ketones, respectively, using potassium bromide and 0.35 M sodium hypochlorite buffered to Ph 8.5 with sodium bicarbonate. J. Org. Chem., 56, 6110 (1991) discloses the use of stoichiometric amounts of oxammonium salts, generated by treatment of TEMPO or 4-acetylamino-TEMPO with organic sulfonic acids, for the selective oxidation of primary or secondary alcohols to aldehydes or ketones, respectively.
J. Am. Chem. Soc, 106, 3374 (1984) discloses the use of TEMPO or 4- hydroxy-TEMPO to catalyze the oxidation of primary or secondary alcohols to aldehydes or ketones, respectively, by oxygen and copper (II) salts.
US Patent 5,136,102 discloses the use of TEMPO or 4-substituted TEMPO derivatives and a bromide containing salt to catalyze the oxidation of secondary alcohols to ketones with nitric acid and oxygen. US Patent 5,155,278 discloses the use of TEMPO or 4-substituted TEMPO derivatives to catalyze the oxidation of primary alcohols to aldehydes with nitric acid and oxygen.
US Patent 5,155,279 discloses the use of TEMPO or 4-substituted TEMPO derivatives to catalyze the selective oxidation of primary alcohols to aldehydes with nitric acid in the absence of oxygen.
US Patent 5,155,280 discloses the use of TEMPO or 4-substituted TEMPO derivatives and an alkali metal nitrosodisulfonate salt to catalyze the selective oxidation of primary alcohols to aldehydes with oxygen in the absence of nitric acid. Japanese patent J5 6152498 discloses the oxidation of bisnoralcohol to bisnoraldehyde using dimethyl sulfide and N-chlorosuccinimde or chlorine. SUMMARY OF INVENTION Disclosed is a process for the production bisnoraldehyde (II)
Figure imgf000004_0001
which comprises:
(1) forming a mixture of (a) bisnoralcohol (I)
Figure imgf000004_0002
(b) a catalytic amount of 4-hydroxy-2,2,6,6-tetramethylpiperidine-l- oxyl in a pH range of about 8.5 to about 10.5 in a temperature range of about - 10° to about 15°, and
(2) contacting the mixture of step (1) with a stoichiometric amount of hypochlorite.
DETAILED DESCRIPTION OF THE INVENTION
Bisnoraldehyde (II) is known to be useful as an intermediate in the synthesis of progesterone and hydrocortisone, see J. Am. Chem. Soc, 74, 5933 (1952).
The present invention is practiced by (1) forming a mixture of bisnoralcohol (I), a catalytic amount of 4-hydroxy TEMPO in a pH range of about 8.5 to about 10.5 and in a temperature range of about - 10° to about 15°, and (2) contacting the mixture of step (1) with a stoichiometric amount of hypochlorite. It is preferred to perform the reaction in the presence of bromide, preferably a catalytic amount of the bromide. The mixture can be cooled at any point prior to the addition of the hypochlorite.
Operable amounts of the 4-hydroxy-TEMPO are from about 0.025 mole percent to about 15 mole percent; it is preferred that the amount of the 4-hydroxy- TEMPO be from about 0.025 mole percent to about 2.5 mole percent. Operable amounts of the bromide are from about 5 mole percent to about 25 mole percent; it is preferred that the amount of bromide be from about 10 mole percent to about 15 mole percent. The pH is preferably regulated by the use of bicarbonate. Operable amounts of bicarbonate are from about 5 mole percent to about 30 mole percent; it is preferred that the amount of bicarbonate be from about 10 mole percent to about 20 mole percent. The cation of the bromide or bicarbonate is not important as long as it is soluble; preferred cation are sodium, potassium and lithium, more preferably sodium or potassium. Operable solvents include dichloroethane, toluene, ethyl acetate, methyl tert-butyl ether, dichloromethane, o-dichlorobenzene chlorobenzene and chloroform; it is preferred that the solvent be methylene chloride. While the operable solvents are organic water immiscible solvents, a small amount of water is operable and even preferred as is known to those skilled in the art. In addition, the hypochlorite is added as an aqueous mixture. It is preferred that the reaction temperature be in the range of about - 5° to about 5°. It is preferred that the hypochlorite is added over a period of from about 1 hr to about 6 hr. It is preferred that the amount of hypochlorite be from about 95 mole percent to about 120 mole percent. Following step (2) it is preferred to quench the reaction mixture. Operable quenching agents include bisulfite, thiosulfate, dimethylsulfide, trimethylphosphate and triethylphosphate; it is preferred that the quenching agent be sodium or potassium thiosulfate.
The process of the present invention can be practiced in either batch mode or continuous mode as is known to those skilled in the art.
The reaction mixture is worked up by methods well known to those skilled in the art. The bisnoraldehyde (II) can be transformed to progesterone by known methods, see J. C. S. Chem. Comm., 314 (1969) and Tet. Lett., 985 (1969).
DEFINITIONS AND CONVENTIONS The definitions and explanations below are for the terms as used throughout this entire document including both the specification and the claims. DEFINITIONS
All temperatures are in degrees Centigrade.
4-hydroxy-TEMPO refers to 4-hydroxy-2,2,6,6-tetramethylpiperidine-l-oxyl. TEMPO refers to 2,2,6,6-tetramethylpiperidine-l-oxyl.
EXAMPLES Without further elaboration, it is believed that one skilled in the art can, using the preceding description, practice the present invention to its fullest extent. The following detailed examples describe how to prepare the various compounds and/or perform the various processes of the invention and are to be construed as merely illustrative, and not limitations of the preceding disclosure in any way whatsoever. Those skilled in the art will promptly recognize appropriate variations from the procedures both as to reactants and as to reaction conditions and techniques.
EXAMPLE 1 Bisnoralcohol (I) to Bisnoraldehyde (II) at 1° with 4-Hydroxy-
TEMPO A mixture of bisnoralcohol (I, 4 g), 4-hydroxy-2,2,6,6-tetramethylpiperidine-l- oxyl (4-hydroxy- TEMPO, 10 mg), potassium bromide (133 mg), sodium bicarbonate
(133 mg), dichloromethane (14 ml) and water (2.2 ml) are cooled to 1°. While maintaining this temperature, aqueous sodium hypochlorite (14%, 6.3 ml) is added over a five hr period. The reaction is complete and aqueous sodium thiosulfate is added, the two phases were separated, and the bisnoraldehyde product is crystallized by replacing the dichloromethane with heptane to give the title compound, mp = 153-154°; NMR (CDClg) 9.56, 5.73, 2.2-2.5, 1.2-2.1, 1.20, 1.10, 0.79 δ; [α]D 22 = + 83.4° (methylene chloride, c = 1).
EXAMPLE 2 Bisnoralcohol (I) to Bisnoraldehyde (II) at 10° with 4-
Hydroxy-TEMPO Following the general procedure of EXAMPLE 1 and making non-critical variations the process of EXAMPLE 1 is repeated at 10° and the title compound is obtained.
EXAMPLE 3 Bisnoralcohol (I) to Bisnoraldehyde (II) at -10° with 4-Hydroxy-
TEMPO Following the general procedure of EXAMPLE 1 and making non-critical variations the process of EXAMPLE 1 is repeated at -10° and the title compound is obtained.
EXAMPLE 4 Bisnoralcohol (I) to Bisnoraldehyde (II) at 1° with 4-Hydroxy-
TEMPO Following the general procedure of EXAMPLE 1 and making non-critical variations the process of EXAMPLE 1 is repeated using 500 mg of 4-hydroxy-
TEMPO and the title compound is obtained.
EXAMPLE 5 Bisnoralcohol (I) to Bisnoraldehyde (II) at 1° with 4-Hydroxy-
TEMPO Following the general procedure of EXAMPLE 1 and making non-critical variations the process of EXAMPLE 1 is repeated using 5 mg of 4-hydroxy-TEMPO and the title compound is obtained.
EXAMPLE 6 Bisnoralcohol (I) to Bisnoraldehyde (II) with 4-oxo-TEMPO
A mixture of bisnoralcohol (I, 6.6 g), 4-oxo-2,2,6,6-tetramethylpiperidine-l- oxyl (18 mg), dichloromethane (30 ml), sodium bicarbonate (180 mg), potassium bromide (238 mg) and water (5 ml) is cooled to 1°. Then aqueous sodium hypochlorite (14.6 %, 11.4 ml) is added to the mixture over a 15 min period. The reaction produced the title compound but in only a 7% conversion of bisnoralcohol with 58% selectivity for bisnoraldehyde.
CHART A
Figure imgf000008_0001
10
Figure imgf000008_0002
25
30

Claims

CLAIMS 1. A process for the production bisnoraldehyde (II)
Figure imgf000009_0001
which comprises: (1) forming a mixture of
(a) bisnoralcohol (I)
Figure imgf000009_0002
(b) a catalytic amount of 4-hydroxy-2,2,6,6-tetramethylpiperidine-l- oxyl in a pH range of about 8.5 to about 10.5 in a temperature range of about - 10° to about 15°, and
(2) contacting the mixture of step (1) with a stoichiometric amount of hypochlorite.
2. A process for the production of bisnoraldehyde (II) according to claim 1 which is performed in the presence of a catalytic amount of bromide.
3. A process for the production of bisnoraldehyde (II) according to claim 1 where the catalytic amount of the 4-hydroxy-2,2,6,6-tetramethylpiperidine-l-oxyl is from about 0.025 mole percent to about 15 mole percent.
4. A process for the production of bisnoraldehyde (II) according to claim 3 where the catalytic amount of the 4-hydroxy-2,2,6,6-tetramethylpiperidine-l-oxyl is from about 0.025 mole percent to about 2.5 mole percent.
5. A process for the production of bisnoraldehyde (II) according to claim 2 where the catalytic amount of bromide is from about 5 mole percent to about 25 mole percent.
6. A process for the production of bisnoraldehyde (II) according to claim 5 where the catalytic amount of bromide is from about 10 mole percent to about 15 mole percent.
7. A process for the production of bisnoraldehyde (II) according to claim 1 where the pH is regulated by the presence of bicarbonate.
8. A process for the production of bisnoraldehyde (II) according to claim 7 where the amount of bicarbonate is from about 5 mole percent to about 30 mole percent.
9. A process for the production of bisnoraldehyde (II) according to claim 8 where the amount of bicarbonate is from about 10 mole percent to about 20 mole percent.
10. A process for the production of bisnoraldehyde (II) according to claim 1 which is performed in the presence of a solvent selected from the group consisting of dichloroethane, toluene, ethyl acetate, methyl tert-butyl ether, dichloromethane, o- dichlorobenzene chlorobenzene and chloroform.
11. A process for the production of bisnoraldehyde (II) according to claim 10 where the solvent is methylene chloride.
12. A process for the production of bisnoraldehyde (II) according to claim 1 where the temperature is range is from about -5 to about 5°.
13. A process for the production of bisnoraldehyde (II) according to claim 1 where amount of hypochlorite is from about 95 mole percent to about 120 mole percent.
14. A process for the production of bisnoraldehyde (II) according to claim 1 where the bisnoralcohol (I), the catalytic amount of 4-hydroxy-2,2,6,6- tetramethylpiperidine-1-oxyl, the catalytic amount of bromide and bicarbonate are all mixed together prior to cooling to about - 10° to about 15°.
15. A process for the production of bisnoraldehyde (II) according to claim 1 where the reaction mixture of step (2) is quenched.
16. A process for the production of bisnoraldehyde (II) according to claim 1 where the reaction mixture of step (2) is quenched with a quenching agent selected from the group consisting of bisulfite, thiosulfate, dimethylsulfide, trimethylphosphate and triethylphosphate.
17. A process for the production of bisnoraldehyde (II) according to claim 16 where the quenching agent is sodium or potassium thiosulfate.
18. A process for the production of bisnoraldehyde (II) according to claim 1 which is performed in a non-continuous or batch method.
19. A process for the production of bisnoraldehyde (II) according to claim 1 which is performed in a continuous method.
PCT/US1994/012196 1993-12-17 1994-10-27 Conversion of bisnoralcohol to bisnoraldehyde WO1995016698A1 (en)

Priority Applications (16)

Application Number Priority Date Filing Date Title
EP95900414A EP0734392B1 (en) 1993-12-17 1994-10-27 Conversion of bisnoralcohol to bisnoraldehyde
DE69415345T DE69415345T2 (en) 1993-12-17 1994-10-27 METHOD FOR PRODUCING BISNORALDEHYDES FROM BISNORAL ALCOHOL
US08/809,719 US6608220B1 (en) 1994-10-27 1994-10-27 Conversion of bisnoralcohol to bisnoraldehyde
SI9430227T SI0734392T1 (en) 1993-12-17 1994-10-27 Conversion of bisnoralcohol to bisnoraldehyde
ES95900414T ES2124990T3 (en) 1993-12-17 1994-10-27 CONVERSION OF BISNORALCOHOL IN BISNORALDEHIDO.
PL94314965A PL181212B1 (en) 1993-12-17 1994-10-27 Method of transforming bisnoralcohol into bisnoraldehyde
SK761-96A SK281716B6 (en) 1993-12-17 1994-10-27 Method for producing bisnoraldehyde
RU96115126A RU2131437C1 (en) 1993-12-17 1994-10-27 Method of preparing bisnoraldehyde
HU9601672A HU220871B1 (en) 1993-12-17 1994-10-27 Process for oxidizing of 20-hydroxymethyl-pregn-4-en-3-on into 20-formyl-pregn-4-en-3-on
NZ275951A NZ275951A (en) 1993-12-17 1994-10-27 Bisnoraldehyde production from bisnoralcohol
AU81244/94A AU693126B2 (en) 1993-12-17 1994-10-27 Conversion of bisnoralcohol to bisnoraldehyde
DK95900414T DK0734392T3 (en) 1993-12-17 1994-10-27 Conversion of bisnoral alcohol to bisnoraldehyde
CA002175906A CA2175906C (en) 1993-12-17 1994-10-27 Conversion of bisnoralcohol to bisnoraldehyde
JP51674695A JP3778927B2 (en) 1993-12-17 1994-10-27 Conversion of bisnor alcohol to bisnoraldehyde
NO962524A NO306163B1 (en) 1993-12-17 1996-06-14 Conversion of bisnoral alcohol to bisnoraldehyde
FI962480A FI115914B (en) 1993-12-17 1996-06-14 Conversion of bisnoral alcohol to bisnoraldehyde

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US16896193A 1993-12-17 1993-12-17
US08/168,961 1993-12-17

Publications (1)

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WO1995016698A1 true WO1995016698A1 (en) 1995-06-22

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EP (1) EP0734392B1 (en)
JP (1) JP3778927B2 (en)
KR (1) KR100355516B1 (en)
CN (1) CN1057094C (en)
AT (1) ATE174601T1 (en)
AU (1) AU693126B2 (en)
CA (1) CA2175906C (en)
CZ (1) CZ284649B6 (en)
DE (1) DE69415345T2 (en)
DK (1) DK0734392T3 (en)
ES (1) ES2124990T3 (en)
FI (1) FI115914B (en)
HU (1) HU220871B1 (en)
NO (1) NO306163B1 (en)
NZ (1) NZ275951A (en)
PL (1) PL181212B1 (en)
RU (1) RU2131437C1 (en)
SK (1) SK281716B6 (en)
WO (1) WO1995016698A1 (en)

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* Cited by examiner, † Cited by third party
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EP1302456B1 (en) 2001-10-11 2004-01-02 Consortium für elektrochemische Industrie GmbH Process for oxidation of alcohols catalysed by nitroxyl compounds
DE10156138A1 (en) * 2001-10-11 2003-04-30 Consortium Elektrochem Ind Process for the oxidation of alcohols to aldehydes and ketones with catalysis by nitroxyl compounds
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CN104109183A (en) * 2014-07-04 2014-10-22 湖北葛店人福药业有限责任公司 New technique for synthesizing progesterone
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56152498A (en) * 1980-04-24 1981-11-26 Mitsubishi Chem Ind Ltd Production of steroid aldehyde
DE4236887A1 (en) * 1992-10-31 1994-05-05 Huels Chemische Werke Ag New 3-(4-methylphenyl(-2-(ar)alkylpropanal cpds. - prepn. from 3-(4-methylphenyl)-2-(ar)alkylpropan-1-ol cpds. and used in perfumes
JPH06211827A (en) * 1993-01-14 1994-08-02 Nippon Soda Co Ltd Production of aldehydes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56152498A (en) * 1980-04-24 1981-11-26 Mitsubishi Chem Ind Ltd Production of steroid aldehyde
DE4236887A1 (en) * 1992-10-31 1994-05-05 Huels Chemische Werke Ag New 3-(4-methylphenyl(-2-(ar)alkylpropanal cpds. - prepn. from 3-(4-methylphenyl)-2-(ar)alkylpropan-1-ol cpds. and used in perfumes
JPH06211827A (en) * 1993-01-14 1994-08-02 Nippon Soda Co Ltd Production of aldehydes

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 122, no. 1, 2 January 1995, Columbus, Ohio, US; abstract no. 9868, J. SUZUKI: "Preparation of Ether-Bond Containing Aldehydes" page 1099; column 2; *
DATABASE WPI Section Ch Week 8202, Derwent World Patents Index; Class B01, AN 82-03202E *
I. NITTA ET AL: "The Synthesis of the Corticoid Side-Chain. II. A New Synthesis of 17-alpha,21-Dihydroxypregna-1,4-diene-3,20-dione 21-Acetate from 21-Hydroxy-20-methylpregna-1,4-dien-3,20-dione", BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN., vol. 58, no. 3, 1985, TOKYO JP, pages 1081 - 1082 *
M. F. SEMMELHACK ET AL: "Oxidation of Alcohols to Aldehydes with Oxygen and Cupric Ion, Mediated by Nitrosonium Ion", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY., vol. 106, no. 11, 30 May 1984 (1984-05-30), GASTON, PA US, pages 3374 - 3376 *
P. N. ANELLI ET AL: "Fast and Selective Oxidation of Primary Alcohols to Aldehydes or to Carboxylic Acids and of Secondary Alcohols to Ketones Mediated by Oxoammonium salts under Two-Phase Conditions", JOURNAL OF ORGANIC CHEMISTRY., vol. 52, no. 12, 12 June 1987 (1987-06-12), EASTON US, pages 2559 - 2562 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107164286A (en) * 2017-07-12 2017-09-15 湖北共同生物科技有限公司 A kind of microbial strains and its selection and application
CN107164286B (en) * 2017-07-12 2021-01-08 湖北共同生物科技有限公司 Microbial strain and breeding method and application thereof

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EP0734392A1 (en) 1996-10-02
RU2131437C1 (en) 1999-06-10
SK281716B6 (en) 2001-07-10
NO306163B1 (en) 1999-09-27
AU8124494A (en) 1995-07-03
JP3778927B2 (en) 2006-05-24
PL314965A1 (en) 1996-09-30
AU693126B2 (en) 1998-06-25
CA2175906A1 (en) 1995-06-22
NO962524L (en) 1996-06-14
FI962480A0 (en) 1996-06-14
ES2124990T3 (en) 1999-02-16
NZ275951A (en) 1997-12-19
ATE174601T1 (en) 1999-01-15
HU220871B1 (en) 2002-06-29
JPH09506613A (en) 1997-06-30
SK76196A3 (en) 1996-11-06
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FI115914B (en) 2005-08-15
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PL181212B1 (en) 2001-06-29
CA2175906C (en) 2005-04-05
DE69415345D1 (en) 1999-01-28
CN1137800A (en) 1996-12-11
HU9601672D0 (en) 1996-08-28
DK0734392T3 (en) 1999-08-23
CZ284649B6 (en) 1999-01-13
CN1057094C (en) 2000-10-04
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EP0734392B1 (en) 1998-12-16
NO962524D0 (en) 1996-06-14
HUT74942A (en) 1997-03-28

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