WO2006119745A2 - Verfahren zur herstellung von olefinen aus carbonylverbindungen - Google Patents
Verfahren zur herstellung von olefinen aus carbonylverbindungen Download PDFInfo
- Publication number
- WO2006119745A2 WO2006119745A2 PCT/DE2006/000796 DE2006000796W WO2006119745A2 WO 2006119745 A2 WO2006119745 A2 WO 2006119745A2 DE 2006000796 W DE2006000796 W DE 2006000796W WO 2006119745 A2 WO2006119745 A2 WO 2006119745A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mmol
- substituted
- alkyl
- reaction
- aryl
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the present invention relates to a process for the preparation of olefins from carbonyl compounds.
- reaction by-products represent a significant problem in large-scale production, since these compounds must be separated from the desired product and then disposed of or reprocessed. Furthermore, it is disadvantageous for large-scale production that in the Horner-Wadsworth-Emmons reaction stoichiometric amounts of a base and in many cases also air- and moisture-sensitive compounds such as n-BuLi, LDA or NaH must be used.
- the stereoselectivity is usually lower than in the Wittig or Homer-Wadsworth-Emmons reaction, and both the desired ⁇ , ⁇ -unsaturated and the undesired ⁇ , ⁇ -unsaturated esters or acids and their mixtures are isolated when enolizable Carbonyl compounds are used.
- ⁇ , ⁇ -unsaturated and the undesired ⁇ , ⁇ -unsaturated esters or acids and their mixtures are isolated when enolizable Carbonyl compounds are used.
- the present invention is a process for the preparation of ⁇ , ß-unsaturated compounds having the general formula I.
- R 1 and R 2 may be the same or different and represent hydrogen, substituted or unsubstituted alkyl or substituted or unsubstituted aryl,
- R 3 is hydrogen, substituted or unsubstituted alkyl or substituted or unsubstituted ares, or a functional group such as OR 4 , NR 5 R 6 , SR 7 , where R 4 , R 5 , R 6 and R 7 may be customary substituents, in particular alkyl and / or aryl groups, or halogen,
- EWG an electron-withdrawing functional group such as CO 2 H, CO 2 R 8 , CONR 9 R 10 ,
- the process according to the invention is a catalytic reaction, which typically takes place at or below room temperature, without any special requirements, such as inert gas, moisture exclusion, heat, etc.
- the only by-products are CO 2 and water.
- alkyl as used herein means a linear, branched or cyclic hydrocarbon radical usually having from 1 to 30, preferably from 1 to 24 carbon atoms and more preferably from 1 to 6 carbon atoms, such as methyl, ethyl, n -propyl, isopropyl, n -butyl, isobutyl , t-butyl, octyl, decyl, etc., but also cycloalkyl groups such as cyclopentyl, cyclohexyl, etc.
- the hydrocarbon radicals have 1 to 18, in particular 1 to 12 carbon atoms.
- aromatic ring systems having 5 to 30 carbon atoms and optionally heteroatoms such as N, O, S, P, Si, used in the ring, wherein the rings single or multiple ring systems, for. B. may be fused ring systems or single bonds or multiple bonds bonded together rings.
- aromatic rings are phenyl, naphthyl, biphenyl, diphenyl ether, diphenylamine, benzophenone and the like.
- Substituted aryl groups have one or more substituents.
- heteroalkyl groups are alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated aminoalkyl and the like.
- heteroaryl substituents are pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1, 2,4-triazolyl, tetrazolyl, and the like.
- heteroatom-containing alicyclic groups pyrrolidino, morpholino, piperazino, piperidino, etc. may be mentioned.
- substituents which may have the abovementioned groups, OH, F, Cl, Br, J, CN, NO 2 , NO, SO 2 , SO 3 -, amino, -COOH, -COO (C r C 6 alkyl ), Mono- and di- (C 1 -C 24 -alkyl) -substituted amino, mono- and di (C 5 -C 2 o-aryl) -substituted amino, imino, which in turn may be substituted, eg dC 6 - Alkyl, aryl, and phenyl.
- the cyclic radicals may also contain C 1 -C 6 -alkyl groups as substituents.
- the process according to the invention is carried out in the presence of an amine as catalyst.
- amines primary, secondary and tertiary amines can be used, with cyclic amines such as DBU, DBN, DABCO, pyridine, piperidine, imidazole and their derivatives, and aniline and its derivatives and mixtures of amines are preferred.
- Dimethylaminopyridines, such as 4-dimethylaminopyridine (DMAP) have proven to be particularly suitable.
- the amine acts as a catalyst and is preferably used in the process according to the invention in an amount of from 0.1 to 15 mol%, in particular from 5 to 10 mol%, based on the amount of the compound of the formula II or III.
- the process according to the invention has the advantage that the reaction can be carried out under mild reaction conditions.
- the reaction temperature may be from O to 3O 0 C, preferably from 10 to 25 ° C. It is not necessary to carry out the reaction under inert gas atmosphere or moisture exclusion.
- the process is carried out in an organic solvent.
- Suitable solvents are those which do not adversely affect the reaction, such as pentane, hexane, heptane, octane, petroleum ether, toluene, xylene, Ethyl acetate, tetrahydrofuran, diethyl ether, methyl-Fe / F-butyl ether, 1,4-dioxane, methylene chloride, chloroform, carbon tetrachloride, dimethylformamide, sulfolane, 1,2-dichloroethane.
- reaction time is shortened substantially on addition of piperidine (17 mg, 0.2 mmol).
- the entire reaction mixture was briefly cooled (about 10 0 C) and the piperidine was added dropwise, then stirring was continued at room temperature.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Hydrogenated Pyridines (AREA)
- Furan Compounds (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/913,706 US20090012320A1 (en) | 2005-05-10 | 2006-05-09 | Method for the Production of Olefins from Carbonyl Compounds |
JP2008510398A JP2008540464A (ja) | 2005-05-10 | 2006-05-09 | カルボニル化合物からオレフィンを製造する方法 |
EP06742316A EP1879848A2 (de) | 2005-05-10 | 2006-05-09 | Verfahren zur herstellung von olefinen aus carbonylverbindungen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005022361A DE102005022361A1 (de) | 2005-05-10 | 2005-05-10 | Verfahren zur Herstellung von Olefinen aus Carbonylverbindungen |
DE102005022361.3 | 2005-05-10 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2006119745A2 true WO2006119745A2 (de) | 2006-11-16 |
WO2006119745A3 WO2006119745A3 (de) | 2007-01-04 |
Family
ID=37055949
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE2006/000796 WO2006119745A2 (de) | 2005-05-10 | 2006-05-09 | Verfahren zur herstellung von olefinen aus carbonylverbindungen |
Country Status (6)
Country | Link |
---|---|
US (1) | US20090012320A1 (de) |
EP (1) | EP1879848A2 (de) |
JP (1) | JP2008540464A (de) |
CN (1) | CN101193850A (de) |
DE (1) | DE102005022361A1 (de) |
WO (1) | WO2006119745A2 (de) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62281840A (ja) * | 1986-05-29 | 1987-12-07 | Otsuka Pharmaceut Co Ltd | 桂皮酸誘導体の製造方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100395308B1 (ko) * | 2001-04-17 | 2003-08-21 | 한국과학기술연구원 | 페룰릭산 이합체 및 그의 약학적 허용 염, 그 제조방법 및치매 치료를 위한 그의 용도 |
US7247649B2 (en) * | 2003-08-13 | 2007-07-24 | Hoffmann-La Roche Inc. | Oxazoles, their manufacture and use as pharmaceutical agents |
-
2005
- 2005-05-10 DE DE102005022361A patent/DE102005022361A1/de not_active Withdrawn
-
2006
- 2006-05-09 EP EP06742316A patent/EP1879848A2/de not_active Withdrawn
- 2006-05-09 WO PCT/DE2006/000796 patent/WO2006119745A2/de not_active Application Discontinuation
- 2006-05-09 CN CNA2006800158057A patent/CN101193850A/zh active Pending
- 2006-05-09 US US11/913,706 patent/US20090012320A1/en not_active Abandoned
- 2006-05-09 JP JP2008510398A patent/JP2008540464A/ja not_active Withdrawn
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62281840A (ja) * | 1986-05-29 | 1987-12-07 | Otsuka Pharmaceut Co Ltd | 桂皮酸誘導体の製造方法 |
Non-Patent Citations (9)
Title |
---|
A. VENKAT NARSAIAH ET AL.: "An Eco-friendly Synthesis of electrophilic Alkenes Catalyzed by Dimethylaminopyridine Under Solvent-free Conditions" SYNTHETIC COMMUNICATIONS, Bd. 34, Nr. 16, 2004, Seiten 2893-2901, XP009073472 * |
DATABASE BEILSTEIN BEILSTEIN INSTITUTE FOR ORGANIC CHEMISTRY, FRANKFURT-MAIN, DE; XP002402407 Database accession no. Reaction ID 5337012 & P. DELL'ORCO ET AL.: ANAL. CHEM., Bd. 71, Nr. 22, 1999, Seiten 5165-5170, * |
J. GUYOT, A.KERGOMARD: "Cinétique et Mécanisme de la Réaction de Knoevenagel dans le Benzène-2" TETRAHEDRON, Bd. 39, Nr. 7, 1983, Seiten 1167-1179, XP002402401 * |
J. RODRIGUEZ, B. WAEGELL: "An Efficient One-Pot Preparation of 2,4-Pentadienoic Esters from .alpha., .beta.-Unsaturated" SYNTHSIS, 7, 1988, Seiten 534-535, XP002402399 * |
J. S. NEW ET AL.: "The Thieno[3,2-c]pyridine and Furo[3,2-c]pyridine Rings: New Pharmacophors with Potential Antipsychotic Activity" JOURNAL OF MEDICINAL CHEMISTRY, Bd. 32, Nr. 6, 1989, Seiten 1147-1156, XP002402402 * |
LIST, BENJAMIN ET AL: "A Practical, efficient, and atom economic alternative to the Wittig and Horner-Wadsworth-Emmons reactions for the synthesis of (E)-.alpha.,.beta.-unsaturated esters from aldehydes" TETRAHEDRON, Bd. 62, Nr. 2-3, 2006, Seiten 476-482, XP002402404 * |
N. RAGOUSSIS, V. RAGOUSSIS: "Improvement on the synthesis of (E)-alk-3-enoic acid" J. CHEM. SOC., PERKIN TRANS 1,, 1998, Seiten 3529-3533, XP002402403 * |
PATENT ABSTRACTS OF JAPAN Bd. 012, Nr. 172 (C-497), 21. Mai 1988 (1988-05-21) -& JP 62 281840 A (OTSUKA PHARMACEUT CO LTD), 7. Dezember 1987 (1987-12-07) * |
YAMANAKA, HIROSHI ET AL: "Influence of heteroaromatic amines on Knoevenagel condensation" HETEROCYCLES, Bd. 20, Nr. 8, 1983, Seiten 1541-1544, XP009073484 * |
Also Published As
Publication number | Publication date |
---|---|
EP1879848A2 (de) | 2008-01-23 |
WO2006119745A3 (de) | 2007-01-04 |
DE102005022361A1 (de) | 2006-11-23 |
JP2008540464A (ja) | 2008-11-20 |
US20090012320A1 (en) | 2009-01-08 |
CN101193850A (zh) | 2008-06-04 |
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