CN101747366B - Method for oxidizing conjugate unsaturated enol - Google Patents
Method for oxidizing conjugate unsaturated enol Download PDFInfo
- Publication number
- CN101747366B CN101747366B CN2008102403054A CN200810240305A CN101747366B CN 101747366 B CN101747366 B CN 101747366B CN 2008102403054 A CN2008102403054 A CN 2008102403054A CN 200810240305 A CN200810240305 A CN 200810240305A CN 101747366 B CN101747366 B CN 101747366B
- Authority
- CN
- China
- Prior art keywords
- tempo
- unsaturated
- conjugation
- compound
- conjugate
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The invention relates to a method for oxidizing conjugate unsaturated enol into conjugate unsaturated ketene, which comprises the following steps: mixing a reactant conjugate unsaturated enol and catalyst 4-R-TEMPO/cuprous chloride; adjusting the pH value of a reaction system to between 3 and 6.5 by acid; and under the action of O2, oxidizing the conjugate unsaturated enol into corresponding conjugate unsaturated ketene. The method has the advantages of high yield of a target product, simple operation and low cost, avoids damaging a conjugated double bond and can guarantee the chirality required by the product.
Description
Technical field:
The present invention relates to a kind of method for oxidation of conjugate unsaturated enol.The compound oxidation that is specifically related to contain conjugate unsaturated enol is the compound method of conjugation ethylenic unsaturation ketone compound.
Background technology:
At pharmacy and some chemical field, often need the conjugate unsaturated enol compounds be oxidized to corresponding conjugation ethylenic unsaturation ketone compound.But because the unstable of this compounds is easy to simultaneously its pair key destroyed in oxidation.In addition, the chirality of product can't guarantee.As in the process of reduction synthesis of vitamin d class conjugate unsaturated enol, producing a part of unwanted chirality conjugate unsaturated enol, cause product cost high.
Someone uses chromium trioxide pyridinium salt oxidation style, and effect is relatively poor.
WO03/106412 discloses and a kind of unwanted chirality conjugate unsaturated enol has been converted into the method for required product through two-step reaction, its method complicated operation, and the time is long, and the chirality of product can't guarantee.
Therefore, the selective oxidation of conjugate unsaturated enol is the important topic that needs exploration and research.Most critical be: need find a kind of conjugated double bond of neither destroying, it is required in the catalyzer of property to guarantee to obtain product again.
Summary of the invention:
The purpose of this invention is to provide a kind of compound oxidation that will contain conjugate unsaturated enol is the method for corresponding ketenes; This method reaction conditions is gentle; Do not destroy conjugated double bond, possess the conjugation ethylene linkage, and can guarantee to obtain the required chirality of product in the oxidation continued.
Method for oxidation provided by the invention is:
In reactor drum, add solvent, catalyzer 4-R-TEMPO/ cuprous chloride successively, be adjusted to 3～6.5, add reactant again, feed O with sour pH value with reaction system
2, reactant is oxidized into the unsaturated ketenes of corresponding conjugation;
Said R is selected from hydroxyl, carbonyl or hydrogen; TEMPO representes 2,2,6,6-tetramethyl piperidine-1-oxyradical;
The mol ratio of 4-R-TEMPO and cuprous chloride consumption is 1: 0.5～2;
The reactant conjugate unsaturated enol should be looked the particular case of different compounds with catalyzer mole proportioning and decide, and common molar ratio scope is: the consumption of catalyzer 4-R-TEMPO is 0.1～10% (w/w) of reactant conjugate unsaturated enol charging capacity.
Said acid is organic acid or mineral acid, and preferred organic acid is like oxalic acid.
Low reaction speed is slow more more because of temperature of reaction, and the required reaction times is also long more.Consider temperature condition and speed of response factor, therefore preferably be controlled at 0 ℃～30 ℃ and carry out.Reaction times is confirmed with HPLC detection reaction terminal point.
Reaction solvent should be selected for use according to the situation of different compounds, like available methylene dichloride, and N.N N, sherwood oil, organic solvents such as ETHYLE ACETATE.
When there was chiral carbon atom in the described conjugate unsaturated enol compound of present method, no matter its configuration was R or S, and all available present method is carried out oxidation, and title product content all can reach 70～95%, and yield can reach more than 70%.
When containing in the conjugate unsaturated enol compound when not hoping oxidized one or more hydroxyl, available hydroxyl protecting group well known to those skilled in the art is protection in advance.For example, blocking group can be trimethyl silicon based, siloyl group such as tertiary butyl dimethyl-is silica-based.Slough the protection base with ordinary method again after the oxidizing reaction.
Under the situation that a plurality of hydroxyls that need protection are arranged, can select identical hydroxy-protective group for use, also can use different hydroxy-protective groups.
Conjugate unsaturated enol compound of the present invention can be a vitamin d compounds; In an instance that provides in the present invention; The conjugate unsaturated enol compound is a formula II compound, and the unsaturated ketenes of oxidation products conjugation is following compound of Formula I: the oxidizing reaction formula is:
In the formula:
R
1, R
2It is respectively hydroxyl protecting group;
R
3, R
4Be selected from hydrogen or methylene radical;
R
5Be selected from the alkyl of 1～6 carbon atom, the naphthenic base of 3～6 carbon atoms;
R
1, R
2Can be identical hydroxy-protective group, also can be different hydroxy-protective groups; Blocking group can be trimethyl silicon based, siloyl group such as tertiary butyl dimethyl-is silica-based.
R
3, R
4Difference, one is hydrogen, another is exactly methylene radical, promptly works as R
3When being Wasserstoffatoms, R
4Be that methylene radical and methylene radical are connected with two keys with the parent ring; And work as R
3When being methylene radical and methylene radical with the parent ring with two strong connection, R
4Be then to be Wasserstoffatoms.
Use present method preparation I compound, no matter the configuration of No. 24 carbon atoms of formula II compound is R or S, and title product content all can reach 70～95%, and yield can reach more than 70%.The preparation method of formula II compound sees Tetrahedron Vol.43 No20pp.4609 to 4619.
Method reaction conditions of the present invention is gentle, and the target product yield of gained is high, and is with low cost, simple and safe operation, and the catalyzer raw material is easy to get.Neither destroy conjugated double bond, can guarantee to obtain the required chirality of product again.
Embodiment:
For making this area professional and technical personnel understand the present invention more all sidedly, will combine embodiment that method of the present invention is detailed for example below, but not limit the present invention in any way.In fact, other many conjugate unsaturated enol compounds all can adopt method of the present invention to carry out oxidation, and do not destroy its conjugated double bond.
Resulting product all adopts the HPLC method to detect detecting instrument: LC-10ATVP in following examples; Testing conditions is following:
Chromatographic column: Lichrospher Si 4.6*250mm 5um
Detect wavelength: 270nm
Moving phase: normal hexane: ETHYLE ACETATE (88: 12)
Flow velocity: 2.0ml/min
Sample size: 20 μ l
Temperature: 25 ℃
Embodiment 1 [1S, 1 ' E, 3R, 5Z, 7E, 20R)-9,10-open loop courage steroid-20-(3 '-sec.-propyl-3 '-carbonyl-1 '-propylene)-1,3-two (trimethylsiloxy group)-5,7,10 (19)-triolefins] preparation
In reactor drum, add 2.5L DMF successively, 10gTEMPO, 6g CuCl adds oxalic acid and regulates pH to 6, under 0-5 ℃; Drip conjugate unsaturated enol compound [1S, 1 ' E, 3R, 5Z; 7E, 20R)-9,10-open loop courage steroid-20-(3 '-sec.-propyl-3 '-hydroxyl-1 '-propylene)-1,3-two (trimethylsiloxy group)-5; 7,10 (19)-triolefins] (24 (S) content is that 84.1%, 24 (R) content is 15.9%) 111.4g (0.200mol) 200ml sherwood oil, feed O simultaneously
2(50-60ml/min) stirring reaction.The HPLC detection reaction finishes, to going in the 1L frozen water 2L Petroleum ether extraction 3 times; United extraction liquid is used 1L10%NaHCO respectively
3, the 1L water washing, anhydrous magnesium sulfate drying 0.5h.Filter, concentrated mother liquor obtains the unsaturated ketenes title compound of conjugation, be light yellow oil 102.5g (0.160mol), and yield 80.0%, the HPLC detection level is 75.9%.
Embodiment 2 [1S, 1 ' E, 3R, 5Z, 7E, 20R)-9,10-open loop courage steroid-20-(3 '-sec.-propyl-3 '-carbonyl-1 '-propylene)-1,3-two (trimethylsiloxy group)-5,7,10 (19)-triolefins] preparation
In reactor drum, add 2.5L DMF successively, 1.1g 4-hydroxyl-TEMPO, 646mg CuCl adds oxalic acid and regulates pH to 4, under 0-5 ℃; Drip conjugate unsaturated enol compound [1S, 1 ' E, 3R, 5Z; 7E, 20R)-9,10-open loop courage steroid-20-(3 '-sec.-propyl-3 '-hydroxyl-1 '-propylene)-1,3-two (trimethylsiloxy group)-5; 7,10 (19)-triolefins] (24 (S) content is that 84.1%, 24 (R) content is 15.9%) 111.4g (0.200mol) 200ml sherwood oil, feed O simultaneously
2(50-60ml/min) stirring reaction.The HPLC detection reaction finishes, to going in the 1L frozen water 2L Petroleum ether extraction 3 times; United extraction liquid is used 1L10%NaHCO3,1L water washing respectively, anhydrous magnesium sulfate drying 0.5h.Filter, concentrated mother liquor obtains the unsaturated ketenes title compound of conjugation, be light yellow oil 100.5g (0.157mol), and yield 78.5%, the HPLC detection level is 76.8%.
Embodiment 3 [(1S, 1 ' E, 3R, 5Z, 7E, 20R)-9,10-open loop courage steroid-20-(3 '-cyclohexyl-3 '-carbonyl-1 '-propylene)-1,3-two (tertiary butyl dimethyl Si base)-5,7,10 (19)-triolefins] preparation
In reactor drum, add 2.5L DMF successively, 6.54g 4-carbonyl-TEMPO, 2g CuCl adds oxalic acid and regulates pH to 3, under 0-5 ℃; Drip conjugate unsaturated enol compound [1S, 1 ' E, 3R, 5Z; 7E, 20R)-9,10-open loop courage steroid-20-(3 '-cyclohexyl-3 '-hydroxyl-1 '-propylene)-1,3-two (tertiary butyl dimethyl Si base)-5; 7,10 (19)-triolefins] (24 (S) content is that 77.4%, 24 (R) content is 22.6%) 136.6g (0.200mol) 200ml sherwood oil, feed O simultaneously
2(50-60ml/min) stirring reaction.The HPLC detection reaction finishes, to going in the 1L frozen water 2L Petroleum ether extraction 3 times; United extraction liquid is used 1L10%NaHCO3,1L water washing respectively, anhydrous magnesium sulfate drying 0.5h.Filter, concentrated mother liquor obtains the unsaturated ketenes title compound of conjugation, be light yellow oil 111.5g (0.174mol), and yield 87.0%, the HPLC detection level is 74.6%.
Embodiment 4 [(1S, 1 ' E, 3R, 5Z, 7E, 20R)-9,10-open loop courage steroid-20-(3 '-cyclohexyl-3 '-carbonyl-1 '-propylene)-1,3-two (tertiary butyl dimethyl Si base)-5,7,10 (19)-triolefins] preparation
In reactor drum, add 2.5L DMF successively, 5g TEMPO, 5g CuCl adds oxalic acid and regulates pH to 7, under 0-5 ℃; Drip conjugate unsaturated enol compound [1S, 1 ' E, 3R, 5Z; 7E, 20R)-9,10-open loop courage steroid-20-(3 '-cyclohexyl-3 '-hydroxyl-1 '-propylene)-1,3-two (tertiary butyl dimethyl Si base)-5; 7,10 (19)-triolefins] (24 (S) content is that 77.4%, 24 (R) content is 22.6%) 136.6g (0.200mol) 200ml sherwood oil, feed O simultaneously
2(50-60ml/min) stirring reaction.The HPLC detection reaction finishes, to going in the 1L frozen water 2L Petroleum ether extraction 3 times; United extraction liquid is used 1L10%NaHCO3,1L water washing respectively, anhydrous magnesium sulfate drying 0.5h.Filter, concentrated mother liquor obtains the unsaturated ketenes title compound of conjugation, be light yellow oil 108g (0.169mol), and yield 84.5%, the HPLC detection level is 73.6%.
Embodiment 5 [(1S, 1 ' E, 3R, 5Z, 7E, 20R)-9,10-open loop courage steroid-20-(3 '-cyclohexyl-3 '-carbonyl-1 '-propylene)-1,3-two (tertiary butyl dimethyl Si base)-5,7,10 (19)-triolefins] preparation
In reactor, add 2.5L DMF successively, 10g 4-hydroxyl-TEMPO, 4.6g CuCl adds oxalic acid and regulates pH to 6, under 0-5 ℃; Drip conjugate unsaturated enol compound [1S, 1 ' E, 3R, 5Z; 7E, 20R)-9,10-open loop courage steroid-20-(3 '-cyclohexyl-3 '-hydroxyl-1 '-propylene)-1,3-two (tertiary butyl dimethyl Si base)-5; 7,10 (19)-triolefins] (24 (S) content is that 77.4%, 24 (R) content is 22.6%) 136.6g (0.200mol) 200ml benzinum, feed O simultaneously
2(50-60ml/min) stirring reaction.The HPLC detection reaction finishes, to going in the 1L frozen water 2L Petroleum ether extraction 3 times; United extraction liquid is used 1L10%NaHCO3,1L water washing respectively, anhydrous magnesium sulfate drying 0.5h.Filter, concentrated mother liquor obtains the unsaturated ketenes title compound of conjugation, be light yellow oil 106 (0.166mol), and yield 83.0%, the HPLC detection level is 75.1%.
Embodiment 6 [(1S, 1 ' E, 3R, 5Z, 7E, 20R)-9,10-open loop courage steroid-20-(3 '-cyclohexyl-3 '-carbonyl-1 '-propylene)-1,3-two (tertiary butyl dimethyl Si base)-5,7,10 (19)-triolefins] preparation
In reactor drum, add 2.5L DMF successively, 3.4g 4-carbonyl-TEMPO, 2.4g CuCl adds oxalic acid and regulates pH to 5,5-10 ℃; Drip conjugate unsaturated enol compound [1S, 1 ' E, 3R, 5Z; 7E, 20R)-9,10-open loop courage steroid-20-(3 '-cyclohexyl-3 '-hydroxyl-1 '-propylene)-1,3-two (tertiary butyl dimethyl Si base)-5; 7,10 (19)-triolefins] (24 (S) content is that 77.4%, 24 (R) content is 22.6%) 136.6g (0.200mol) 200ml sherwood oil, feed O simultaneously
2(50-60ml/min) stirring reaction.The HPLC detection reaction finishes, to going in the 1L frozen water 2L Petroleum ether extraction 3 times; United extraction liquid is used 1L10%NaHCO3,1L water washing respectively, anhydrous magnesium sulfate drying 0.5h.Filter, concentrated mother liquor obtains the unsaturated ketenes title compound of conjugation, be light yellow oil 104.5g (0.164mol), and yield 82.0%, the HPLC detection level is 76.2%.
Embodiment 7 [1S, 1 ' E, 3R, 5E, 7E, 20R)-9,10-open loop courage steroid-20-(3 '-cyclopropyl-3 '-carbonyl-1 '-propylene)-1,3-two (trimethylsiloxy group)-5,7,10 (19)-triolefins] preparation
In reactor drum, add 2.5L DMF successively, 6g TEMPO, 3.8g CuCl adds oxalic acid and regulates pH to 6, under 0-5 ℃; Drip conjugate unsaturated enol compound [1S, 1 ' E, 3R, 5Z; 7E, 20R)-9,10-open loop courage steroid-20-(3 '-cyclopropyl-3 '-hydroxyl-1 '-propylene)-1,3-two (trimethylsiloxy group)-5; 7,10 (19)-triolefins] (24 (S) content is that 19.1%, 24 (R) content is 80.9%) 111.4g (0.200mol)/200ml sherwood oil, feed O simultaneously
2(50-60ml/min) stirring reaction.The HPLC detection reaction finishes, to going in the 1L frozen water 2L Petroleum ether extraction 3 times; United extraction liquid is used 1L10%NaHCO3,1L water washing respectively, anhydrous magnesium sulfate drying 0.5h.Filter, concentrated mother liquor obtains the unsaturated ketenes title compound of conjugation, be light yellow oil 115g (0.180mol), and yield 90.0%, the HPLC detection level is 78.3%.
Embodiment 8 [1S, 1 ' E, 3R, 5E, 7E, 20R)-9,10-open loop courage steroid-20-(3 '-cyclopropyl-3 '-carbonyl-1 '-propylene)-1,3-two (trimethylsiloxy group)-5,7,10 (19)-triolefins] preparation
In reactor, add 2.5L DMF successively, 4.1g4-hydroxyl-TEMPO, 2.5g CuCl adds oxalic acid and regulates pH to 3, under 5-10 ℃; Drip conjugate unsaturated enol compound [1S, 1 ' E, 3R, 5Z; 7E, 20R)-9,10-open loop courage steroid-20-(3 '-cyclopropyl-3 '-hydroxyl-1 '-propylene)-1,3-two (trimethylsiloxy group)-5; 7,10 (19)-triolefins] (24 (S) content is that 19.1%, 24 (R) content is 80.9%) 111.4g (0.200mol)/200ml benzinum, feed O simultaneously
2(50-60ml/min) stirring reaction.The HPLC detection reaction finishes, to going in the 1L frozen water 2L Petroleum ether extraction 3 times; United extraction liquid is used 1L10%NaHCO3,1L water washing respectively, anhydrous magnesium sulfate drying 0.5h.Filter, concentrated mother liquor obtains the unsaturated ketenes title compound of conjugation, be light yellow oil 110g (0.172mol), and yield 86.0%, the HPLC detection level is 78.5%.
Embodiment 9 [1S, 1 ' E, 3R, 5E, 7E, 20R)-9,10-open loop courage steroid-20-(3 '-cyclopropyl-3 '-carbonyl-1 '-propylene)-1,3-two (tertiary butyl dimethyl Si base)-5,7,10 (19)-triolefins] preparation
In reactor drum, add 2.5L DMF successively, 7.2g TEMPO, 4.1g CuCl adds oxalic acid and regulates pH to 6, under 0-5 ℃; Drip conjugate unsaturated enol compound [1S, 1 ' E, 3R, 5Z; 7E, 20R)-9,10-open loop courage steroid-20-(3 '-cyclopropyl-3 '-hydroxyl-1 '-propylene)-1,3-two (tertiary butyl dimethyl Si base)-5; 7,10 (19)-triolefins] (24 (S) content is that 18.3%, 24 (R) content is 81.7%) 128.2g (0.200mol)/200ml sherwood oil, feed O simultaneously
2(50-60ml/min) stirring reaction.The HPLC detection reaction finishes, to going in the 1L frozen water 2L Petroleum ether extraction 3 times; United extraction liquid is used 1L10%NaHCO3,1L water washing respectively, anhydrous magnesium sulfate drying 0.5h.Filter, concentrated mother liquor obtains the unsaturated ketenes title compound of conjugation, be light yellow oil 107.5g (0.168mol), and yield 84.0%, the HPLC detection level is 77.8%.
Embodiment 10 [1S, 1 ' E, 3R, 5E, 7E, 20R)-9,10-open loop courage steroid-20-(3 '-cyclopropyl-3 '-carbonyl-1 '-propylene)-1,3-two (tertiary butyl dimethyl Si base)-5,7,10 (19)-triolefins] preparation
In reactor drum, add 2.5L DMF successively, 2.5g 4-carbonyl-TEMPO, 1.8g CuCl adds oxalic acid and regulates pH to 7, under 0-5 ℃; Drip conjugate unsaturated enol compound [1S, 1 ' E, 3R, 5Z; 7E, 20R)-9,10-open loop courage steroid-20-(3 '-cyclopropyl-3 '-hydroxyl-1 '-propylene)-1,3-two (tertiary butyl dimethyl Si base)-5; 7,10 (19)-triolefins] (24 (S) content is that 18.3%, 24 (R) content is 81.7%) 128.2g (0.200mol)/200ml sherwood oil, feed O simultaneously
2(50-60ml/min) stirring reaction.The HPLC detection reaction finishes, to going in the 1L frozen water 2L Petroleum ether extraction 3 times; United extraction liquid is used 1L10%NaHCO3,1L water washing respectively, anhydrous magnesium sulfate drying 0.5h.Filter, concentrated mother liquor obtains the unsaturated ketenes title compound of conjugation, be light yellow oil 105.5g (0.165mol), and yield 82.3%, the HPLC detection level is 75.7%.
Claims (4)
1. conjugate unsaturated enol is oxidized to the method for the unsaturated ketenes of conjugation in the thing D compounds of will supporting one's family; In reactor drum, add solvent, catalyzer 4-R-TEMPO/ cuprous chloride successively; Be adjusted to 3～6.5 with sour pH value, add reactant again, feed O reaction system
2, reactant is oxidized into the unsaturated ketenes of corresponding conjugation;
Said R is selected from hydroxyl, carbonyl or hydrogen; TEMPO representes 2,2,6,6-tetramethyl piperidine-1-oxyradical;
The mol ratio of 4-R-TEMPO and cuprous chloride consumption is 1: 0.5～2;
The consumption of catalyzer 4-R-TEMPO is 0.1%～10% (w/w) of reactant conjugate unsaturated enol charging capacity;
Said acid is organic acid or mineral acid;
The said thing D compounds of supporting one's family is a formula II compound, and the unsaturated ketenes of oxidation products conjugation is a formula I compound:
Among formula II and the formula I:
R
1, R
2Be respectively hydroxyl protecting group, hydroxyl protecting group can be identical or different;
R
3, R
4Be selected from hydrogen or methylene radical, and R
3, R
4Inequality;
R
5Be selected from the alkyl of 1～6 carbon atom, the naphthenic base of 3～6 carbon atoms.
2. the described method of claim 1, said acid is oxalic acid.
3. claim 1 or 2 described methods, said hydroxyl protecting group be selected from trimethyl silicon based or tertiary butyl dimethyl-silica-based.
4.4-R-TEMPO/ cuprous chloride is as the purposes that conjugate unsaturated enol in the described formula II compound of claim 1 is oxidized to the catalyzer of the unsaturated ketenes of conjugation, wherein:
R is selected from hydroxyl, carbonyl or hydrogen;
TEMPO representes 2,2,6,6-tetramethyl piperidine-1-oxyradical;
The mol ratio of said 4-R-TEMPO and cuprous chloride consumption is 1: 0.5～2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102403054A CN101747366B (en) | 2008-12-18 | 2008-12-18 | Method for oxidizing conjugate unsaturated enol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102403054A CN101747366B (en) | 2008-12-18 | 2008-12-18 | Method for oxidizing conjugate unsaturated enol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101747366A CN101747366A (en) | 2010-06-23 |
| CN101747366B true CN101747366B (en) | 2012-06-27 |
Family
ID=42475041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102403054A Active CN101747366B (en) | 2008-12-18 | 2008-12-18 | Method for oxidizing conjugate unsaturated enol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101747366B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5118866A (en) * | 1987-02-24 | 1992-06-02 | Basf Aktiengesellschaft | Preparation of polyene aldehydes |
| US5136103A (en) * | 1991-09-30 | 1992-08-04 | Shell Oil Company | Process for the preparation of ketones |
-
2008
- 2008-12-18 CN CN2008102403054A patent/CN101747366B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5118866A (en) * | 1987-02-24 | 1992-06-02 | Basf Aktiengesellschaft | Preparation of polyene aldehydes |
| US5136103A (en) * | 1991-09-30 | 1992-08-04 | Shell Oil Company | Process for the preparation of ketones |
Non-Patent Citations (5)
| Title |
|---|
| 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》.1984,第106卷3375-3376. * |
| M.F.Semmelhack et al..Oxidation of Alcohols to Aldehydes with Oxygen and Cupric Ion |
| Roger A. Sheldon,et al.Organocatalytic Oxidations Mediated by Nitroxyl Radicals.《Advanced Synthesis Catalysis》.2004,第346卷1051-1071. * |
| Zhenkun Ma,et al..Organic Oxoammonium Salts. 3. A New Convenient Method for the Oxidation of Alcohols to Aldehydes and Ketones.《Journal of Organic Chemistry》.1991,第56卷6110-6114. * |
| 杨贯羽等.氮氧自由基TEMPO：选择氧化醇的高效有机小分子催化剂.《化学进展》.2007,第19卷(第11期),1727-1735. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101747366A (en) | 2010-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1770088B1 (en) | Process for preparing 5-methyl-2-furfural | |
| WO2006028756A3 (en) | Optimized liquid-phase oxidation | |
| WO2006028771A3 (en) | Optimized liquid-phase oxidation | |
| Hartley et al. | Metal π-allyl chemistry III. The preparation of π-allylpalladium complexes from palladium (II) salts | |
| WO2006028767A8 (en) | Optimized liquid-phase oxidation in a bubble column reactor | |
| EP1059290B1 (en) | Process for producing canthaxanthin | |
| CN101747366B (en) | Method for oxidizing conjugate unsaturated enol | |
| FI89161C (en) | FREQUENCY REARING FOR ALKETOFETERING | |
| US4269781A (en) | Dimeric carbonylation of 1,3-butadiene | |
| Lacroix et al. | Chemically Modified β‐Cyclodextrins as Supramolecular Carriers in the Biphasic Palladium‐Catalyzed Cleavage of Allylic Carbonates: Activity Enhancement and Substrate‐Selective Catalysis | |
| IE51526B1 (en) | Process for the manufacture of beta-hydroxybutyric acid and its oligocondensates | |
| EP1747211B1 (en) | Process for preparing unsaturated lactones | |
| EP0375463B1 (en) | Process for recovering lactic acid from solutions which contain it | |
| WO2006028752A3 (en) | Optimized liquid-phase oxidation | |
| Breslow et al. | Approaches to “push-pull” stabilized cyclobutadienes1 | |
| WO2006028816A8 (en) | Optimized liquid-phase oxidation | |
| Wang et al. | Polyoxometalates supporting cyclopendienylzirconium CpZrXW11O39n-: A new kind of olefin polymerization catalyst | |
| US3766212A (en) | Process for the preparation of epsilon-caprolactone | |
| EP2240479B1 (en) | Novel nitrogen-containing organic compounds that can be used as precursor of a catalytic composition | |
| Kotha et al. | Allylation of caged diketones via fragmentation methodology | |
| CH643226A5 (en) | PROCESS FOR THE MANUFACTURE OF CARBONYL COMPOUNDS BY OXIDATION OF OLEFINIC COMPOUNDS. | |
| JP3413296B2 (en) | Method for producing highly chlorinated paraffins | |
| CN101265225B (en) | Method for oxidizing unsaturated conjugated enol | |
| WO2006028766A8 (en) | Optimized liquid-phase oxidation | |
| Wallace et al. | The Base-Catalyzed Autoxidation of Hydrocarbons in Diphenyl Sulfoxide1 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CHONGQING HUAPONT PHARMACEUTICAL CO., LTD. Free format text: FORMER OWNER: HUABANG PHARMACEUTICAL CO., LTD., CHONGQING Effective date: 20130217 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20130217 Address after: 401121 Chongqing, Yubei District and the number of stars Avenue, No. 69 Patentee after: Chongqing Huapont Pharm. Co., Ltd. Address before: 401121 Chongqing, Yubei District and the number of stars Avenue, No. 69 Patentee before: Huabang Pharmaceutical Co., Ltd., Chongqing |