WO2004041764A1 - Kontinuierliches verfahren zur herstellung von pseudojononen und jononen - Google Patents
Kontinuierliches verfahren zur herstellung von pseudojononen und jononen Download PDFInfo
- Publication number
- WO2004041764A1 WO2004041764A1 PCT/EP2003/011926 EP0311926W WO2004041764A1 WO 2004041764 A1 WO2004041764 A1 WO 2004041764A1 EP 0311926 W EP0311926 W EP 0311926W WO 2004041764 A1 WO2004041764 A1 WO 2004041764A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ketone
- reaction
- aldehyde
- reaction mixture
- formula
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
- C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
-
- 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
-
- 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
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Definitions
- the present invention relates to a continuous process for the production of pseudo-ionons and their subsequent subsequent cyclization to form ions.
- the process for the preparation of compounds such as 6-methylhepta-3,5-dien-2-one, pseudojonon, methylpseudojonone, dimethylpseudojonone, pseudoiron, methylpseudoiron and dimethylpseudoiron and their cyclization products ⁇ -, ⁇ - and ⁇ -ionone, ⁇ is preferred -, ß- and ⁇ -methyljonone (N-form, iso-form or mixtures) and homologues. These substances are of great economic importance as fragrances and fragrance intermediates.
- Pseudojonon itself is also an important intermediate for the production of vitamins E and A and carotenoids.
- ß-Jonon is an important intermediate for the production of vitamin A and carotenoids.
- PL 147748 describes a process for the production of jons by condensation of citral and acetone on basic ion exchangers at 56 ° C. Thereafter, acetone and citral are stirred discontinuously in a flask with the catalyst for 5 hours.
- the disadvantage of this process is the very low space-time yields.
- DE-A 33 19430 teaches the preparation of higher ketones by condensing methyl ketones and unsaturated aldehydes over mixed metal catalysts in the presence of hydrogen at 100 to 280 ° C. and 10 to 60 bar in a tubular reactor.
- a process for the production of pseudo-ionones by reacting citral with acetone using LiOH as a catalyst is described in US 4,874,900.
- the reaction is then carried out batchwise or continuously at temperatures from -20 to 240 ° C.
- the pressure is adjusted so that the reaction mixture remains in the liquid phase at the appropriate temperature.
- the reactants are stirred in a vessel and the catalyst is filtered off after the reaction has ended, while in the continuous mode of operation the premixed reactants are pumped through a column filled with catalyst.
- the reaction mixture is neutralized with CO 2 after the end of the reaction and the excess ketone is distilled off.
- this process with a molar ratio of acetone to citral of 20 yields of 89.5% citral are achieved. These low yields are unsatisfactory for an industrial process.
- DE-A 31 14071 describes a process for the preparation of pseudonones by reacting an aldehyde with an excess of a ketone at elevated temperature. Numerous methods are also known in the prior art for the subsequent cyclization of pseudo-ionons to ionons. It is known, for example, that the cyclization of pseudo-ionone with acids, such as concentrated sulfuric acid or phosphoric acid, gives mixtures of ⁇ - and ⁇ -ions. The ratio of the amounts in which these compounds are formed is strongly dependent on the conditions under which the reaction takes place.
- the object of the present invention was to develop a process for the production of pseudo-jons and a subsequent subsequent cyclization to the corresponding jons, which requires fewer starting materials in comparison to the prior art and produces more product per starting material.
- R 2 , R 3 are hydrogen, CH 3 or C 2 H 5 , R 4 , R 5 are hydrogen or CH 3 ,
- R 1 , R 2 and R 3 have the meanings given above, in the presence of water and alkali metal hydroxide at elevated temperature in a homogeneous solution, which is characterized in that
- the homogeneous reaction mixture is then passed through a reactor at a temperature which is 10 to 120 ° C. above the boiling point of the lowest-boiling component and a vapor pressure p of 10 6 to 10 7 Pa and has a residence time of 2 allows up to 300 minutes
- the process according to the invention is preferably used for the preparation of 6-methylhepta-3,5-dien-2-one, pseudojonon, methylpseudojonon, dimethylpseudojonon, pseudoiron, methylpseudoiron and dimethylpseudoiron and their isomers.
- the aldehydes used according to the invention are preferably citral, citronellal and 2,6-dimethyloctanal, but also any straight-chain or branched saturated or unsaturated aldehyde having 1 to 10 carbon atoms, and preferably acetone, 2-butanone, or 2 or 3 as ketones - Pentanon used.
- An aqueous alkali is an aqueous solution of potassium hydroxide, sodium hydroxide or lithium hydroxide, but preferably sodium hydroxide solution.
- concentration of the alkali metal hydroxide used is between 0.005 and 50% by weight, preferably between 1 and 15% by weight.
- the isomers are understood to mean all possible positional isomers or double bond isomers of the pseudojonones or jones.
- aqueous alkali lye is added to the homogeneous mixture of the starting materials aldehyde, ketone and water at 10 to 120 ° C., preferably at temperatures below 50 ° C., as to dissolve homogeneously after thorough mixing.
- Any water and alkali hydroxide that separate out are separated off before the homogeneous reaction mixture, while avoiding backmixing, at a temperature which is 10 to 120 ° C. above the boiling point of the lowest-boiling component and a pressure p of 10 6 to 10 7 Pa, where p the vapor pressure of the reaction mixture at the reaction temperature is passed through a reactor which allows a residence time of 2 to 300 minutes, preferably 5 to 30 minutes.
- the reaction mixture is cooled by flashing, a part of the excess ketone can be evaporated and returned to the recycle, the ketone is then removed from the reaction mixture with steam in countercurrent, the steam containing enough evaporable acid that the catalyst base is neutralized and a pH Value from 4 to 9.
- the crude product is then dried and freed from excess aldehyde and secondary components via a rectification column, preferably via a dividing wall column, as disclosed, for example, in DE-A 3302525 or in EP-A 804 951.
- Another object of the invention is a continuous process for the preparation of jons of the general formulas (IV), (V) and (VI) and their isomers, which is characterized in that the pseudo-jons obtained by the process according to the invention are used as jons of the general Formulas (IV) - (V!)
- alkali metal hydroxide solution is metered in, which extracts water from the reaction mixture and dissolves the required amount of alkali metal hydroxide into the reaction mixture.
- the reaction is carried out with a 5 to 50-fold, preferably with a 20 to 25-fold molar excess of ketone in order to achieve an optimal yield with respect to the aldehyde used.
- the unreacted portion of ketone is separated off after the reaction zone at a pressure of 10 7 to 10 9 mPa abS and fed back to the fresh ketone for synthesis.
- the water content of the aldehyde-ketone mixture is also of particular importance. This obviously determines the amount of alkali hydroxide which can be homogeneously dissolved in the aldehyde-ketone mixture.
- the water content of the aldehyde-ketone mixture should be between 1 and 15% by weight.
- the amount of alkali metal hydroxide in turn determines the rate of conversion, but also influences the rate of undesired by-products. This is in line with the fact that the removal of excess liquor before the reactor is advantageous. In contrast to the prior art, this means that no further alkali metal hydroxide is dissolved in the reaction mixture towards the end of the reaction due to the increase in the water content, which promotes the formation of by-products in this phase. The latter plays an important role especially with sensitive unsaturated aldehydes such as citral and lowers the yield.
- the water is advantageously introduced into the process via the proportion of the ketone component which is generated by the steam stripping of the reaction mixture after the reactor. It is of economic importance that the excess ketone can be separated with little technical and energy expenditure, since a complex drying before recycling is unnecessary.
- an anhydrous mixture of aldehyde and ketone can be used and the required water (about 1 to 15% by weight) can be mixed in, using a very dilute alkali hydroxide solution.
- a mixture of aldehyde and ketone with a very high water content can be used if a concentrated alkali hydroxide solution is added.
- a lower mixing temperature is required to avoid the uncontrolled start of the reaction.
- the consumption of alkali hydroxide increases, since this only partially passes into the organic phase. It partially extracts water from the aldehyde-ketone mixture and has to be separated and disposed of.
- the homogeneous reaction solution is heated under autogenous pressure in a tubular reactor, the reaction temperature being set at a given residence time such that the conversion of the aldehyde component is 60 to 98%, preferably 85 to 95%, the unreacted aldehyde being separated off and introduced into the reaction is returned.
- the tubular reactor is dimensioned such that the average residence time is between 2 and 300 minutes, preferably between 5 and 30 minutes, in such a way that there is as far as possible no backmixing. Higher conversions require a disproportionate increase in the reaction temperature, which favors by-product formation. Lower conversions enable a lower reaction temperature, which suppresses the by-product rate, but increases the recycle currents ketone and aldehyde and thus the energy requirement of the process.
- the use of column packings ensures that no significant quantities of other products are produced at the top of the column in addition to ketone and water, the return flow to the column advantageously being set such that the ketone can be drawn off with the desired amount of water.
- the amount of acid is advantageously dimensioned such that the pH value of 4 to 9 which is most favorable for further workup is established at this point.
- the crude product is dried by heating it and spraying it into a flash container which is kept under reduced pressure. From there it is transferred to a rectification column in which the unsaturated ketone is cleaned of impurities under reduced pressure and the unreacted aldehyde is separated off and fed back from there.
- the recycling is advantageously carried out in a dividing wall column as described in EP-A 804 951, where there are preferably 2 side draws in order to obtain both main fractions (product and aldehyde) in sufficient purity in one step.
- the mixture of pseudo-ionones obtained is reacted with high-percentage, ie about 50 to about 98% sulfuric acid in the presence of a diluent which is inert under the reaction conditions, advantageously as described in DE 196 19 557.
- cyclization temperatures of ⁇ 20 ° C. and a sulfuric acid concentration of ⁇ 90% are advantageous if a residence time of> 10 seconds is maintained between cyclization and hydrolysis.
- the reaction mixture from the tubular reactor is expanded to normal pressure. Approx. 2000 l / h acetone distill off, the product solution cooling to approx. 60 ° C. The remaining acetone is then freed in countercurrent with about 700 kg / h of steam. So much acetic acid is added to the steam that the sodium hydroxide solution is neutralized in the mixture and the running, aqueous mixture has a pH of 4-5. The acetone is returned to the process.
- aqueous phase After the aqueous phase has been separated off, it is dried at about 100 ° C. and about 50 mbar and purified by distillation in a dividing wall column with 2 side draws. About 400 kg / h pseudo-ionon with a purity of 98% are obtained at the lower side draw (area% GLC, total of all isomers!). Approx. 26 kg / h of citral (sum of all isomers) accumulate at the upper side discharge, which are continuously returned to the process.
- the reaction mixture from the tubular reactor is expanded to normal pressure. During this process, approx. 1000 l / h of 2-butanone distill off *, the product solution cooling to approx. 75 ° C. The remaining 2-butanone is then freed in countercurrent with about 550 kg / h of steam. So much acetic acid is added to the steam that the sodium hydroxide solution is neutralized in the mixture and the running, aqueous mixture has a pH of 4-5. The 2-butanone is returned to the process.
- aqueous phase After the aqueous phase has been separated off, it is dried at about 100 ° C. and about 50 mbar and purified by distillation in a dividing wall column with 2 side draws. Approx. 100 kg / h of methyl pseudo-ionone with a purity of 98% are obtained at the lower side hood (area% GLC, total of all isomers!). About 20 kg / h of citral (total of all isomers) accumulates at the upper side discharge, which are continuously returned to the process.
- the reaction mixture from the tubular reactor is expanded to normal pressure. About 1000 l / h of 2-butanone distill off, the product solution cooling to about 75 ° C. The remaining 2-butanone is then freed in countercurrent with about 550 kg / h of steam. Sufficient acetic acid is added to the steam so that the sodium hydroxide solution is neutralized in the mixture and the aqueous mixture which runs off has a pH of 4-5. Excess 2-butanone is returned to the process.
- aqueous phase After the aqueous phase has been separated off, it is dried at about 100 ° C. and about 50 mbar and purified by distillation in a dividing wall column with 2 side draws. Approx. 100 kg / h of methyl pseudo-ionone with a purity of 98% are obtained at the lower side draw (area% GLC, total of all isomers). About 25 kg / h of citral (total of all isomers) accumulates at the upper side discharge, which are continuously returned to the process.
- aqueous phase After the aqueous phase has been separated off, it is dried at about 50 mbar and 100 ° C. and cleaned in a dividing wall column with 2 side draws. In the main run (side draw 1), approximately 120 l / h of methyl ionone with a ⁇ -n-methyl pseudo ionone content between 80 and 90% are obtained.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003285305A AU2003285305A1 (en) | 2002-11-07 | 2003-10-28 | Continuous process for producing pseudoionones and ionones |
US10/533,969 US7141698B2 (en) | 2002-11-07 | 2003-10-28 | Continuous process for producing pseudoionones and ionones |
DE50308134T DE50308134D1 (de) | 2002-11-07 | 2003-10-28 | Kontinuierliches verfahren zur herstellung von pseudojononen und jononen |
CA002505094A CA2505094A1 (en) | 2002-11-07 | 2003-10-28 | Continuous process for producing pseudoionones and ionones |
EP03778290A EP1562885B1 (de) | 2002-11-07 | 2003-10-28 | Kontinuierliches verfahren zur herstellung von pseudojononen und jononen |
JP2004548796A JP4727228B2 (ja) | 2002-11-07 | 2003-10-28 | プソイドイオノンおよびイオノンの連続的製造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10252259 | 2002-11-07 | ||
DE10252259.6 | 2002-11-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004041764A1 true WO2004041764A1 (de) | 2004-05-21 |
Family
ID=32308508
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2003/011926 WO2004041764A1 (de) | 2002-11-07 | 2003-10-28 | Kontinuierliches verfahren zur herstellung von pseudojononen und jononen |
Country Status (9)
Country | Link |
---|---|
US (1) | US7141698B2 (de) |
EP (1) | EP1562885B1 (de) |
JP (1) | JP4727228B2 (de) |
CN (1) | CN1310863C (de) |
AT (1) | ATE372315T1 (de) |
AU (1) | AU2003285305A1 (de) |
CA (1) | CA2505094A1 (de) |
DE (1) | DE50308134D1 (de) |
WO (1) | WO2004041764A1 (de) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008092655A1 (en) * | 2007-01-30 | 2008-08-07 | Dsm Ip Assets B.V. | Process for preparing dienones |
EP1997796A1 (de) * | 2007-06-01 | 2008-12-03 | DSMIP Assets B.V. | Aldolkondensationsreaktion und Katalysator dafür |
CN106045831A (zh) * | 2016-06-08 | 2016-10-26 | 万华化学集团股份有限公司 | 一种假性甲基紫罗兰酮的绿色合成方法 |
WO2020099452A1 (en) | 2018-11-13 | 2020-05-22 | Basf Se | Process of making pseudoionone and hydroxy pseudoionone in aqueous mixtures comprising citral and acetone, comprising adding first and second amounts of hydroxide |
WO2020099461A1 (en) | 2018-11-13 | 2020-05-22 | Basf Se | Apparatus for and process of making pseudoionone and hydroxy pseudoionone |
WO2022104581A1 (zh) * | 2020-11-18 | 2022-05-27 | 厦门金达威维生素有限公司 | 一种假性紫罗兰酮的连续合成方法 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1921058A1 (de) * | 2006-11-10 | 2008-05-14 | DSMIP Assets B.V. | Verfahren zur Herstellung von Jononen, Vitamin A, Vitamin A Derivaten, Carotin und Carotinoiden |
CN101781182B (zh) * | 2010-01-15 | 2012-09-05 | 绍兴文理学院 | 一种联合制备β-紫罗兰酮的制备方法 |
CN101781183B (zh) * | 2010-01-15 | 2012-08-22 | 绍兴文理学院 | β-紫罗兰酮的制备方法 |
WO2012057894A1 (en) | 2010-10-26 | 2012-05-03 | Quinnova Pharmaceuticals, Inc. | Econazole composition and methods of treatment therewith |
GB201208566D0 (en) | 2012-05-16 | 2012-06-27 | Givaudan Sa | Organic compounds |
CN103044223B (zh) * | 2012-12-28 | 2015-04-15 | 安徽丰原发酵技术工程研究有限公司 | 一种连续性制备维生素a中间体假性紫罗兰酮的方法 |
CN106673980A (zh) * | 2016-12-24 | 2017-05-17 | 上海弗鲁克科技发展有限公司 | 一种用微通道连续生产β—紫罗兰酮的装置和方法 |
JP2022528610A (ja) | 2019-04-15 | 2022-06-15 | ディーエスエム アイピー アセッツ ビー.ブイ. | 環化によるポリエンからのビタミンa誘導体の合成のための中間体の調製方法 |
CN111825538B (zh) * | 2020-07-13 | 2022-08-05 | 万华化学集团股份有限公司 | 一种连续化生产假性紫罗兰酮的方法 |
CN111909017A (zh) * | 2020-08-06 | 2020-11-10 | 上海应用技术大学 | 一种提高反应速率及转化率的假性紫罗兰酮制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3480677A (en) * | 1963-08-08 | 1969-11-25 | Rhodia | Novel ionone |
SU704938A1 (ru) * | 1978-05-29 | 1979-12-25 | Всесоюзный научно-исследовательский институт синтетических и натуральных душистых веществ | Способ получени псевдоионона |
EP0062291A1 (de) * | 1981-04-08 | 1982-10-13 | BASF Aktiengesellschaft | Verbessertes Verfahren zur Herstellung mehrfach ungesättigter Ketone |
EP0295361A2 (de) * | 1987-06-16 | 1988-12-21 | Union Camp Corporation | Herstellung von Pseudoiononen |
WO1997043254A1 (de) * | 1996-05-14 | 1997-11-20 | Basf Aktiengesellschaft | VERBESSERTES VERFAHREN ZUR HERSTELLUNG ON JONONEN, INSBESONDERE VON β-IONON |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3840601A (en) * | 1972-02-07 | 1974-10-08 | Rhodia | Process for preparation of methyl ionones |
DE3302525A1 (de) | 1983-01-26 | 1984-07-26 | Basf Ag, 6700 Ludwigshafen | Destillationskolonne zur destillativen zerlegung eines aus mehreren fraktionen bestehenden zulaufproduktes |
DE3319430A1 (de) | 1983-05-28 | 1984-11-29 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von ketonen |
DE19617210A1 (de) | 1996-04-30 | 1997-11-06 | Basf Ag | Trennwandkolonne zur kontinuierlichen destillativen Zerlegung von Mehrstoffgemischen |
-
2003
- 2003-10-28 AU AU2003285305A patent/AU2003285305A1/en not_active Abandoned
- 2003-10-28 EP EP03778290A patent/EP1562885B1/de not_active Expired - Lifetime
- 2003-10-28 AT AT03778290T patent/ATE372315T1/de not_active IP Right Cessation
- 2003-10-28 WO PCT/EP2003/011926 patent/WO2004041764A1/de active IP Right Grant
- 2003-10-28 US US10/533,969 patent/US7141698B2/en not_active Expired - Lifetime
- 2003-10-28 CN CNB2003801028095A patent/CN1310863C/zh not_active Expired - Lifetime
- 2003-10-28 DE DE50308134T patent/DE50308134D1/de not_active Expired - Lifetime
- 2003-10-28 CA CA002505094A patent/CA2505094A1/en not_active Abandoned
- 2003-10-28 JP JP2004548796A patent/JP4727228B2/ja not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3480677A (en) * | 1963-08-08 | 1969-11-25 | Rhodia | Novel ionone |
SU704938A1 (ru) * | 1978-05-29 | 1979-12-25 | Всесоюзный научно-исследовательский институт синтетических и натуральных душистых веществ | Способ получени псевдоионона |
EP0062291A1 (de) * | 1981-04-08 | 1982-10-13 | BASF Aktiengesellschaft | Verbessertes Verfahren zur Herstellung mehrfach ungesättigter Ketone |
EP0295361A2 (de) * | 1987-06-16 | 1988-12-21 | Union Camp Corporation | Herstellung von Pseudoiononen |
WO1997043254A1 (de) * | 1996-05-14 | 1997-11-20 | Basf Aktiengesellschaft | VERBESSERTES VERFAHREN ZUR HERSTELLUNG ON JONONEN, INSBESONDERE VON β-IONON |
Non-Patent Citations (1)
Title |
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DATABASE WPI Section Ch Week 198032, Derwent World Patents Index; Class B05, AN 1980-56547C, XP002267975 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008092655A1 (en) * | 2007-01-30 | 2008-08-07 | Dsm Ip Assets B.V. | Process for preparing dienones |
EP1997796A1 (de) * | 2007-06-01 | 2008-12-03 | DSMIP Assets B.V. | Aldolkondensationsreaktion und Katalysator dafür |
WO2008145350A1 (en) * | 2007-06-01 | 2008-12-04 | Dsm Ip Assets B.V. | Aldol condensation reaction and catalyst therefore |
CN106045831A (zh) * | 2016-06-08 | 2016-10-26 | 万华化学集团股份有限公司 | 一种假性甲基紫罗兰酮的绿色合成方法 |
WO2020099452A1 (en) | 2018-11-13 | 2020-05-22 | Basf Se | Process of making pseudoionone and hydroxy pseudoionone in aqueous mixtures comprising citral and acetone, comprising adding first and second amounts of hydroxide |
WO2020099461A1 (en) | 2018-11-13 | 2020-05-22 | Basf Se | Apparatus for and process of making pseudoionone and hydroxy pseudoionone |
WO2022104581A1 (zh) * | 2020-11-18 | 2022-05-27 | 厦门金达威维生素有限公司 | 一种假性紫罗兰酮的连续合成方法 |
Also Published As
Publication number | Publication date |
---|---|
DE50308134D1 (de) | 2007-10-18 |
ATE372315T1 (de) | 2007-09-15 |
EP1562885B1 (de) | 2007-09-05 |
CA2505094A1 (en) | 2004-05-21 |
US20060014984A1 (en) | 2006-01-19 |
CN1711232A (zh) | 2005-12-21 |
CN1310863C (zh) | 2007-04-18 |
EP1562885A1 (de) | 2005-08-17 |
JP2006505597A (ja) | 2006-02-16 |
US7141698B2 (en) | 2006-11-28 |
JP4727228B2 (ja) | 2011-07-20 |
AU2003285305A1 (en) | 2004-06-07 |
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