WO1999052849A1 - Oxidation process using tempo - Google Patents
Oxidation process using tempo Download PDFInfo
- Publication number
- WO1999052849A1 WO1999052849A1 PCT/US1999/007466 US9907466W WO9952849A1 WO 1999052849 A1 WO1999052849 A1 WO 1999052849A1 US 9907466 W US9907466 W US 9907466W WO 9952849 A1 WO9952849 A1 WO 9952849A1
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- WO
- WIPO (PCT)
- Prior art keywords
- recited
- substituted
- unsubstituted
- cycloalkyl
- alkyl
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/29—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with halogen-containing compounds which may be formed in situ
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
Definitions
- Oxidation is one of the most fundamental transformations in organic synthesis and there are numerous methods reported in the literature. (Hudlicky, M. "Oxidations In Organic Chemistry", ACS Monograph No. 186 American Chemical Society Washington D.C. (1990).) However, relatively few methods exist for the oxidation of primary alcohols to the corresponding carboxylic acids. The most commonly used ones are CrO 3 /H 2 SO 4 (Bowden; Heilbron; Jones; Weedon J. Chem. Soc, 1946, 39; Bowers; H.; Jones; L. J. Chem. Soc, 1953, 2548; Millar, J. G.; Oehlschlager, A. C; Wong, J. W. J. Org.
- the present invention relates to an oxidation using sodium chlorite in the presence of a catalytic amount of TEMPO and sodium hypochlorite which converts a primary alcohol to a carboxylic acid.
- This oxidation method avoids the disposal issues associated with running a Jones oxidation (CrO 3 /H 2 SO 4 ) reaction, as well as reducing the epimerization of any ⁇ -chiral centers and is a one step procedure.
- the present invention reduces this problem.
- the present invention discloses a process for preparing a compound of Formula I:
- R! is ! a) H, b) Ci-Cs alkyl, c) C2-C8 alkynyl, d) C3-C7 cycloalkyl, e) aryl, ) heteroaryl, or g) heterocyclyl;
- Ci-Cs alkyl, C2-C8 alkynyl, or C3-C8 cycloalkyl are unsubstituted or substituted with one, two or three substituents selected from the group consisting of: OH,
- CO2R 4 Br, Cl, F, I, CF3, Ci-Cs alkoxy, C3-C8 cycloalkyl, aryl, heteroaryl, heterocyclyl, and CO(CH2)nCH3,
- aryl is defined as phenyl or naphthyl , which is unsubstituted or substituted with one, two or three substituents selected from the group consisting of: OH, CO2R 4 , Br, Cl, F, I, CF3, Ci-Cs alkoxy, Ci-Cs alkyl, C2-C8 alkynyl, or C3-C8 cycloalkyl, CO(CH2)nCH3, or when aryl is substituted on adjacent carbons they can form a 5- or 6-membered fused ring having one, two or three heteroatoms selected from O, N, and S, this ring is unsubstituted or substituted on carbon or nitrogen with one, two or three substituents selected from the group consisting of: OH, CO2R 4 , Br, Cl, F, I, CF3, Ci-Cs alkoxy, Ci-Cs alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cyclo
- heteroaryl is defined as a 5- or 6-membered aromatic ring containing 1, 2 or 3 heteroatoms selected from O, N and S , which is unsubstituted or substituted with one, two or three substituents selected from the group consisting of: OH, CO2R 4 , Br, Cl, F, I, CF3, Ci-Cs alkoxy, Ci-Cs alkyl, C2-C8 alkynyl, C3-C8 cycloalkyl, CO(CH2) n CH3, and additionally the 5- or 6-membered aromatic ring can be benzofused and unsubstituted or substituted with one, two or three substituents as described above;
- heterocyclyl is defined as a 5- or 6-membered, non-aromatic ring containing 1, 2 or 3 heteroatoms selected from O, N and S , which may contain one or two double bonds and which is unsubstituted or substituted with one, two or three substituents selected from the group consisting of: OH, CO2R 4 , Br, Cl, F, I, CF3, Ci-Cs alkoxy, Ci-Cs alkyl, C2-C8 alkynyl, or C3-C8 cycloalkyl, CO(CH2) n CH3, and additionally the 5- or 6-membered ring can be benzofused and unsubstituted or substituted with one, two or three substituents as described above;
- n 0 to 5;
- t 0, 1 or 2;
- R 4 is: H, or Ci-Cs alkyl
- Rl is a) H, b) Ci-Cs alkyl, c) C2-C8 alkynyl, d) C3-C7 cycloalkyl, e) aryl, f) heteroaryl, or g) heterocyclyl;
- Ci-Cs alkyl, C2-C8 alkynyl, or C3-C8 cycloalkyl are unsubstituted or substituted with one, two or three substituents selected from the group consisting of: OH, CO2R 4 , Br, Cl, F, I, CF3, Ci-Cs alkoxy, C3-C8 cycloalkyl, aryl, heteroaryl, heterocyclyl, and CO(CH2)nCH3,
- aryl is defined as phenyl or naphthyl , which is unsubstituted or - substituted with one, two or three substituents selected from the group consisting of: OH, CO2R 4 , Br, Cl, F, I, CF3, Ci-Cs alkoxy, Ci-Cs alkyl, C2-C8 alkynyl, or C3-C8 cycloalkyl, CO(CH2)nCH3, or when aryl is substituted on adjacent carbons they can form a 5- or 6-membered fused ring having one, two or three heteroatoms selected from O, N, and S, this ring is unsubstituted or substituted on carbon or nitrogen with one, two or three substituents selected from the group consisting of: OH, CO2R 4 , Br, Cl, F, I, CF3, Ci-Cs alkoxy, Ci-Cs alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8
- heteroaryl is defined as a 5- or 6-membered aromatic ring containing 1, 2 or 3 heteroatoms selected from O, N and S , which is unsubstituted or substituted with one, two or three substituents selected from the group consisting of: OH, CO2R 4 , Br, Cl, F, I, CF3, C1-C8 alkoxy, Ci-Cs alkyl, C2-C8 alkynyl, C3-C8 cycloalkyl, CO(CH2) n CH3, and additionally the 5- or 6-membered aromatic ring can be benzofused and unsubstituted or substituted with one, two or three substituents as described above;
- heterocyclyl is defined as a 5- or 6-membered, non-aromatic ring containing 1, 2 or 3 heteroatoms selected from O, N and S , which may contain one or two double bonds and which is unsubstituted or substituted with one, two or three substituents selected from the group consisting of: OH, CO2R 4 , Br, Cl, F, I, CF3, C1-C8 alkoxy, Ci-Cs alkyl, C2-C8 alkynyl, C3-C8 cycloalkyl, CO(CH2) n CH3, and additionally the 5- or 6-membered ring can be benzofused and unsubstituted or substituted with one, two or three substituents as described above;
- n 0 to 5;
- t 0, 1 or 2;
- R 4 is: H, or Ci-Cs alkyl
- the solvent is selected from the group consisting of: acetonitrile, tetrahydrofuran, acetone, tertiary C 4 -C 8 -alcohol, diethyl ether, DME (dimethyl ether), diglyme, triglyme, MTBE (methyl t-butyl ether), toluene, benzene, hexane, pentane, dioxane, dichloromethane, chloroform, carbon tetrachloride, or a mixture of said solvents.
- the solvent is selected from the group consisting of: acetonitrile, tetrahydrofuran, acetone, tertiary C 4 -C 8 -alcohol, diethyl ether, DME (dimethyl ether), diglyme, triglyme, MTBE (methyl t-butyl ether), toluene, benzene, hexane, pentan
- the phosphate buffer comprises an aqueous mixture of NaOH, KOH, NaH 2 PO 4 , KH 2 PO 4 , Na 2 HPO 4 , and j HPO ⁇ sufficient to maintain a pH of about 4.0 to about 8.0, and preferably a pH of about 6.5 to about 7.0.
- TEMPO 2,2,6,6- tetramethyl-1-piperidinyloxy, free radical
- reaction temperature is about 0°C to about 50°C, and preferably about 35°C to about 40°C.
- reaction time is up to about 24 hours, and preferably between about 2 and about 4 hours.
- alkyl substituents recited above denote straight and branched chain hydrocarbons of the length specified such as methyl, ethyl, isopropyl, isobutyl, tert-butyl, neopentyl, isopentyl, etc.
- Cycloalkyl denotes rings composed of 3 to 8 methylene groups, each of which may be substituted or unsubstituted with other hydrocarbon substituents, and include for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and 4-methylcyclohexyl.
- the alkoxy substituent represents an alkyl group as described above attached through an oxygen bridge.
- the aryl substituent represents phenyl and 1-naphthyl or 2- naphthyl, including aryls substituted with a 5- or 6-membered fused ring, such as an unsubstituted and substituted methylenedioxy, oxazolyl, imidazolyl, or thiazolyl ring.
- the heteroaryl substituent represents a carbazolyl, furanyl, thienyl, pyrrolyl, isothiazolyl, imidazolyl, isoxazolyl, thiazolyl, oxazolyl, pyrazolyl, pyrazinyl, pyridyl, pyrimidyl, purinyl.
- the heterocyclyl substituent represents, oxazolidinyl, thiazolidinyl, thiazolidinyl, oxadiazolyl, or thiadiazolyl.
- Each of the above substituents can be either — unsubstituted or substituted as defined within the description.
- the reaction was then optimized regard to further reduce the chlorination and enhance the safety for scale up.
- the reaction was faster at lower pH, but it was accompanied by increased chlorination. It was slower at lower temperature as expected, but surprisingly, the chlorination level appeared to be slightly elevated.
- Increasing the amount of TEMPO and bleach increased the reaction rate, but the TEMPO NaClO ratio should be >2 to reduce the chances of chlorination.
- the bleach was added slowly and simultaneously with NaClO 2 to the batch at 35 °C to prevent build up of the oxidant and the risk of a run away reaction. It should be noted that mixing of bleach and NaClO 2 prior to the addition is not advised since some toxic and potentially explosive chlorine dioxide (ClO 2 ) may be generated.
- reaction mixture is cooled to 15°C and carefully quenched into a cold (10 °C) saturated ammonium chloride solution (150 mL) while maintaining the temperature ⁇ 25°C.
- Ethyl acetate (500 mL) is added and the layers are separated. The organic layer is washed with water (100 mL) and then transfered to a 1L round bottom flask equipped for distillation. The solution was concentrated and charged with fresh ethyl acetate. This is repeated until a solution with a volume of 200 mL has KF ⁇ 200 ⁇ g/mL. The solvent is then switched to DMF to give the final volume of 200 mL with a KF ⁇ 200 ⁇ g/mL.
- the addition funnel is charged with water (400 mL) which is added dropwise to the reaction mixture over a period of 30 min. while maintaining the temperture ⁇ 15°C.
- the temperature is controlled by 16
- the benzyl chloride is isolated by filtration. The cake is washed with (1:1) DMF:H 2 O (lOOmL) and then water (200 mL). The solid is dried in vacuo to give 93 g of the benzyl chloride( 94% yield, 96 A%).
- Methoxypropene (140 mL) is charged to an addition funnel and added over 30 minutes at a temperature of 50°C.
- reaction slurry is aged for 1-2 hours at 50°C. HPLC assay at this point shows ⁇ 0.5A% of the amide remaining. The amide is not removed in the isolation so it is important to push the reaction to completion.
- the reaction slurry is cooled to 0-5°C and quenched by addition of 5% aqueous sodium carbonate solution (1 L) and heptane (1 L). The layers are stirred and separated and the organic is washed with water (300 mL).
- HPLC assay at this point shows the acetonide in >98A% and >90% yield.
- the acetonide/THF/heptane solution is filtered into a 2 L round bottom flask and the solution is distilled to a final volume of 700mL.
- Heptane (1L) is added and the solution is distilled to a final volume of 700mL.
- the distillation is done under partial vacuum at ⁇ 50°C.
- NMR assay at this point shows ⁇ 2 mol% THF.
- the solution is allowed to cool and is seeded with acetonide at 35-40°C.
- the thick slurry is aged for 1 hour at ambient temperature then cooled to 0-5°C and aged for 1 hour.
- the slurry is filtered and the cake is washed with cold heptane (200 mL) and air dried to yield acetonide as a crystalline white solid (141.1 g, 85% yield, 99.6 A%).
- a THF solution (2L, KF ⁇ 200 ⁇ g/mL) of the acetonide (252 g) and the benzyl chloride (255 g) is cooled to -10°C.
- Lithium bis(trimethylsilyl)amide (1.45 L) is added dropwise over 5 h at 0-2°C.
- the mixture is then aged for 1.5 h and assayed by HPLC.
- the reaction is quenched by adding aqueous saturated ammonium chloride solution (1 L).
- the initial addition of the ammonium chloride should be slow in order to control the foaming. The rate can be increased when the foaming subsides.
- the quenched reaction is then transfered into a mixture of aqueous ammonium chloride (1.5 L), water (0.5 L), and ethyl acetate (3 L). The mixture is then agitated for 15 min and the layers are separated. The organic layer is washed with water (1 L) and brine (0.5 L). The ethyl acetate solution is concentrated to a low volume and solvent switched to 1,4-dioxane. The dioxane solution is adjusted to a final volume of 1.8 L. The dioxane solution of the coupled product is charged to a
- the mixture is cooled to 20°C and MTBE (3 L) is added. The mixture is agitated for 15 min and the layers are separated. The organic layer is washed with water (1 L).
- the MTBE solution of the crude acid is extracted with 0.6 M sodium hydroxide (2 L).
- the aqueous solution of the sodium salt of the acid is combined with MTBE (2.5 L) and cooled to 10°C.
- the two phase mixture is acidified with 5.4 M sulfuric acid (250 mL), agitated for 15 min, settled and the layers separated.
- the MTBE solution of the acid is washed with water (0.5 L).
- the MTBE solution of the acid is dried by distilation and then solvent switched to THF.
- the final volume of the THF is 2 L with a KF ⁇ 250 ⁇ g/mL.
- THF solution (2 L) of the acid is added to the sodium borohydride slurry over 1 h while maintaining the temperature at 20-25°C.
- reaction is controlled with a cooling bath and by carefully monitoring the addition rate. A nitrogen sweep and proper venting of the hydrogen is also important.
- the mixture is aged for 30 min at 20-25 °C.
- Boron trifluoride etherate (152 g) is added over 1 h at 30-35 °C. The addition produces a delayed exotherm and should be carefully monitored in order to control the reaction temperature.
- the resulting milky white slurry is aged for 1 h at 30 °C and sampled for HPLC assay.
- reaction mixture is cooled to 15 °C and carefully quenched in a cold (10°C) ammonium chloride solution (1.5 L) while maintaing the temperature at 25 °C.
- the rate of hydrogen evolution is controlled by the rate of the addition of the mixture into the ammonium chloride.
- the quenched mixture is distilled in vacuo to remove the
- the aqueous layer is extracted with MTBE (1.5 L) and the organic layer is dried by flushing with additional MTBE.
- the MTBE solution is then solvent switched to hexanes and adjusted to a volume of 350 mL and seeded.
- the slurry is aged for 2 h at 20 °C and then cooled to 0-5 °C aged for 1 h and filtered.
- the cake is washed with cold hexanes (200 mL).
- the solid is dried under a nitrogen sweep.
- the isolated solid (164 g) is > 99A% by HPLC and > 99%ee. 20
- the acid was prepared following the general procedure recited in Example 1.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002327890A CA2327890A1 (en) | 1998-04-09 | 1999-04-05 | Oxidation process using tempo |
JP2000543412A JP2002511440A (en) | 1998-04-09 | 1999-04-05 | Oxidation method using TEMPO |
EP99916376A EP1070039A1 (en) | 1998-04-09 | 1999-04-05 | Oxidation process using tempo |
AU34711/99A AU748207B2 (en) | 1998-04-09 | 1999-04-05 | Oxidation process using tempo |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US8120298P | 1998-04-09 | 1998-04-09 | |
US60/081,202 | 1998-04-09 | ||
GB9810188.4 | 1998-05-13 | ||
GBGB9810188.4A GB9810188D0 (en) | 1998-05-13 | 1998-05-13 | Oxidation process using TEMPO |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999052849A1 true WO1999052849A1 (en) | 1999-10-21 |
Family
ID=26313666
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/007466 WO1999052849A1 (en) | 1998-04-09 | 1999-04-05 | Oxidation process using tempo |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1070039A1 (en) |
JP (1) | JP2002511440A (en) |
AU (1) | AU748207B2 (en) |
CA (1) | CA2327890A1 (en) |
WO (1) | WO1999052849A1 (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001034657A1 (en) * | 1999-11-08 | 2001-05-17 | Sca Hygiene Products Zeist B.V. | Process of oxidising primary alcohols |
JP2002371044A (en) * | 2001-04-11 | 2002-12-26 | Ajinomoto Co Inc | METHOD FOR MANUFACTURING beta-AMINO-alpha-HYDROXYCARBOXYLIC ACID |
WO2003016278A1 (en) * | 2001-08-21 | 2003-02-27 | Fujisawa Pharmaceutical Co., Ltd. | Process for preparation of piperidin-2-ylacetic acid |
WO2003037867A1 (en) * | 2001-11-02 | 2003-05-08 | Apotex Inc. | Processes for the manufacturing of 3-hydroxy-n,1,6-trialkyl-4-oxo-1,4-dihydropyridine-2-carboxamide |
EP1336599A1 (en) * | 2002-02-15 | 2003-08-20 | Consortium für elektrochemische Industrie GmbH | Process for the preparation of alkynoic acids and alkynoic acid esters via oxidation of alkynols |
DE10244633B3 (en) * | 2002-09-25 | 2004-02-26 | Consortium für elektrochemische Industrie GmbH | Preparation of alkynoic acid, e.g. propiolic or acetylenedicarboxylic acid, used in synthesis, e.g. cycloaddition or nucleophilic addition, by alkaline oxidation in presence of nitroxyl involves adding alkynol and hypohalite during reaction |
WO2005103060A1 (en) * | 2004-04-21 | 2005-11-03 | Wacker Chemie Ag | Method for the production of organosilicon compounds comprising carboxy radicals |
WO2013078172A1 (en) * | 2011-11-23 | 2013-05-30 | The United States Of America As Represented By The Secretary Of The Navy | Tempo-mediated glycoconjugation of an immunogenic composition against campylobacter jejuni |
US8809580B2 (en) | 2009-10-23 | 2014-08-19 | 3M Innovative Properties Company | Methods of preparing fluorinated carboxylic acids and their salts |
CN104557579A (en) * | 2014-12-09 | 2015-04-29 | 杭州海尔希畜牧科技有限公司 | Method for preparing betaine |
WO2023151894A1 (en) | 2022-02-11 | 2023-08-17 | Henkel Ag & Co. Kgaa | Process for the synthesis of alpha-methylene-gamma-butyrolactone |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5274764B2 (en) * | 2006-11-08 | 2013-08-28 | 広栄化学工業株式会社 | Process for producing N-substituted-formylpolymethyleneimine |
AU2008330684B8 (en) * | 2007-11-26 | 2014-01-23 | The University Of Tokyo | Cellulose nanofiber, production method of same and cellulose nanofiber dispersion |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US5631366A (en) * | 1995-01-12 | 1997-05-20 | Hoffmann-La Roche Inc. | Process for making 3-formylcephem derivatives |
-
1999
- 1999-04-05 AU AU34711/99A patent/AU748207B2/en not_active Ceased
- 1999-04-05 WO PCT/US1999/007466 patent/WO1999052849A1/en not_active Application Discontinuation
- 1999-04-05 JP JP2000543412A patent/JP2002511440A/en not_active Withdrawn
- 1999-04-05 CA CA002327890A patent/CA2327890A1/en not_active Abandoned
- 1999-04-05 EP EP99916376A patent/EP1070039A1/en not_active Withdrawn
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US5631366A (en) * | 1995-01-12 | 1997-05-20 | Hoffmann-La Roche Inc. | Process for making 3-formylcephem derivatives |
Non-Patent Citations (3)
Title |
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ANELLI P. L., ET AL.: "FAST AND SELECTIVE OXIDATION OF PRIMARY ALCOHOLS TO ALDEHYDES OR TOCARBOXYLIC ACIDS AND OF SECONDARY ALCOHOLS TO KETONES MEDIATED BY OXOAMMONIUM SALTS UNDER TWO-PHASE CONDITIONS.", THE JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY, US, vol. 52., no. 12., 12 June 1987 (1987-06-12), US, pages 2559 - 2562., XP000567759, ISSN: 0022-3263, DOI: 10.1021/jo00388a038 * |
DALCANALE E., ET AL.: "SELECTIVE OXIDATION OF ALDEHYDES TO CARBOXYLIC ACIDS WITH SODIUM CHLORITE-HYDROGEN PEROXIDE.", THE JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY, US, vol. 51., no. 04., 1 January 1986 (1986-01-01), US, pages 567 - 571., XP002921361, ISSN: 0022-3263, DOI: 10.1021/jo00354a037 * |
NOOY DE A. E. J., BESEMER A. C., BEKKUM VAN H.: "ON THE USE OF STABLE ORGANIC NITROXYL RADICALS FOR THE OXIDATION OFPRIMARY AND SECONDARY ALCOHOLS.", SYNTHESIS, GEORG THIEME VERLAG, STUTTGART, DE., 1 October 1996 (1996-10-01), STUTTGART, DE., pages 1153 - 1174., XP002072173, ISSN: 0039-7881, DOI: 10.1055/s-1996-4369 * |
Cited By (17)
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---|---|---|---|---|
WO2001034657A1 (en) * | 1999-11-08 | 2001-05-17 | Sca Hygiene Products Zeist B.V. | Process of oxidising primary alcohols |
US6770755B1 (en) | 1999-11-08 | 2004-08-03 | Sca Hygiene Products Zeist B.V. | Process of oxidizing primary alcohols |
JP2002371044A (en) * | 2001-04-11 | 2002-12-26 | Ajinomoto Co Inc | METHOD FOR MANUFACTURING beta-AMINO-alpha-HYDROXYCARBOXYLIC ACID |
WO2003016278A1 (en) * | 2001-08-21 | 2003-02-27 | Fujisawa Pharmaceutical Co., Ltd. | Process for preparation of piperidin-2-ylacetic acid |
WO2003037867A1 (en) * | 2001-11-02 | 2003-05-08 | Apotex Inc. | Processes for the manufacturing of 3-hydroxy-n,1,6-trialkyl-4-oxo-1,4-dihydropyridine-2-carboxamide |
EP1336599A1 (en) * | 2002-02-15 | 2003-08-20 | Consortium für elektrochemische Industrie GmbH | Process for the preparation of alkynoic acids and alkynoic acid esters via oxidation of alkynols |
DE10206619A1 (en) * | 2002-02-15 | 2003-10-09 | Consortium Elektrochem Ind | Process for the preparation of alkyne carboxylic acids and alkyne carboxylic acid alkali alcohol esters by oxidation of alkyne alcohols |
DE10206619B4 (en) * | 2002-02-15 | 2004-03-25 | Consortium für elektrochemische Industrie GmbH | Process for the preparation of alkyne carboxylic acids and alkyne carboxylic acid alkali alcohol esters by oxidation of alkyne alcohols |
EP1403240A1 (en) * | 2002-09-25 | 2004-03-31 | Consortium für elektrochemische Industrie GmbH | Process for the preparation of acetylenic carboxylic acids by oxidation of acetylenic alcohols |
DE10244633B3 (en) * | 2002-09-25 | 2004-02-26 | Consortium für elektrochemische Industrie GmbH | Preparation of alkynoic acid, e.g. propiolic or acetylenedicarboxylic acid, used in synthesis, e.g. cycloaddition or nucleophilic addition, by alkaline oxidation in presence of nitroxyl involves adding alkynol and hypohalite during reaction |
US7173149B2 (en) | 2002-09-25 | 2007-02-06 | Consortium für elektrochemische Industrie GmbH | Process for preparing alkynecarboxylic acids by oxidation of alkyne alcohols |
WO2005103060A1 (en) * | 2004-04-21 | 2005-11-03 | Wacker Chemie Ag | Method for the production of organosilicon compounds comprising carboxy radicals |
US7902392B2 (en) | 2004-04-21 | 2011-03-08 | Wacker Chemie Ag | Method for the production of organosilicon compounds comprising carboxy radicals |
US8809580B2 (en) | 2009-10-23 | 2014-08-19 | 3M Innovative Properties Company | Methods of preparing fluorinated carboxylic acids and their salts |
WO2013078172A1 (en) * | 2011-11-23 | 2013-05-30 | The United States Of America As Represented By The Secretary Of The Navy | Tempo-mediated glycoconjugation of an immunogenic composition against campylobacter jejuni |
CN104557579A (en) * | 2014-12-09 | 2015-04-29 | 杭州海尔希畜牧科技有限公司 | Method for preparing betaine |
WO2023151894A1 (en) | 2022-02-11 | 2023-08-17 | Henkel Ag & Co. Kgaa | Process for the synthesis of alpha-methylene-gamma-butyrolactone |
Also Published As
Publication number | Publication date |
---|---|
AU748207B2 (en) | 2002-05-30 |
EP1070039A1 (en) | 2001-01-24 |
AU3471199A (en) | 1999-11-01 |
JP2002511440A (en) | 2002-04-16 |
CA2327890A1 (en) | 1999-10-21 |
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