WO2008092655A1 - Procédé d'élaboration de diènones - Google Patents

Procédé d'élaboration de diènones Download PDF

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Publication number
WO2008092655A1
WO2008092655A1 PCT/EP2008/000709 EP2008000709W WO2008092655A1 WO 2008092655 A1 WO2008092655 A1 WO 2008092655A1 EP 2008000709 W EP2008000709 W EP 2008000709W WO 2008092655 A1 WO2008092655 A1 WO 2008092655A1
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WO
WIPO (PCT)
Prior art keywords
methyl
dien
compound
formulas
octa
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PCT/EP2008/000709
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English (en)
Inventor
Werner Bonrath
Original Assignee
Dsm Ip Assets B.V.
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 claimed from EP07001946A external-priority patent/EP1953134A1/fr
Application filed by Dsm Ip Assets B.V. filed Critical Dsm Ip Assets B.V.
Priority to EP08707406A priority Critical patent/EP2109597A1/fr
Publication of WO2008092655A1 publication Critical patent/WO2008092655A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/15—Unsaturated ethers containing only non-aromatic carbon-to-carbon double bonds
    • 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
    • C07C45/511—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 involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/513—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 involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/203—Unsaturated compounds containing keto groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation

Definitions

  • the present invention relates to a process for preparing dienones and intermediates useful in preparing dienones.
  • Dienones in particular 6-methyl-octa-3,5-dien-2-one, 6-methyl-octa-4,5-dien-2-one, 7- methyl-nona-5,6-dien-3-one, 3,6-dimethyl-octa-4,5-dien-2-one, 7-methyl-nona-4,6-dien-3- one and 3,6-dimethyl-octa-3,5-dien-2-one are interesting compounds for the flavour and fragrances industry.
  • Processes for the synthesis of dienones are known, which are based on pyrolysis of tertiary-acetylenic carbinyl acetoacetates.
  • US 741 ,047 discloses a process for the production of a doubly unsaturated ketone which comprises pyrolysing a tertiary acetylenic carbinyl acetonate in the presence of an acidic catalyst.
  • the acetoacetates are prepared by the reaction of the corresponding carbinols with diketene.
  • DE 1 078 112 discloses a process for the preparation of dienones, wherein esters from the general formula of tertiary acetylenic carbinyl acetoacetates are pyrolized, wherein the pyrolysis is conducted in the presence of lower aluminium trialcoholates and a lower fatty acid.
  • dienones (2), (A) and (B) can be synthesized in excellent yield (based on (2) alone or the sum of (A) + (B)) and purity, in particular as the high temperatures as needed for pyrolysis have not to be applied. Further it has been found that dienones (C) and (D) can be advantageously synthesized from dienones (A) and (B) according to the following scheme 2:
  • the present invention relates to a process for the preparation of a compound of the formulas Ma or Mb
  • R 1 and R 2 are defined as above and R 6 is a hydroxy protecting group.
  • R 1 , R 2 , R 3 and R 4 each branched or nonbranched alkyl, branched or nonbranched cyclo-alkyl, branched or nonbranched alkenyl, branched or nonbranched cyclo-alkenyl, or aryl group, which can optionally be substituted, can be present.
  • the hydrocarbon moiety is a straight, branched or cyclic C r C 16 alkyl or a straight, branched or cyclic C 2 -C 16 alkenyl or a C 6 -C 16 aryl, such as phenyl or naphthyl, which aryl may optionally be substituted by an C 1 -C 6 alkyl group.
  • R 1 , R 2 , R 3 and R 4 are independently a hydrogen, a C 1 -C 6 alkyl, or a C 2 -C 6 alkenyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertbutyl, n-pentyl and n-hexyl.
  • R 1 is hydrogen, methyl or ethyl, in particular hydrogen or methyl
  • R 2 is hydrogen, methyl or ethyl, in particular hydrogen or methyl
  • R 3 is hydrogen or methyl, in particular methyl
  • R 4 is methyl, ethyl or n-propyl, in particular ethyl.
  • residues R 2 is H or C 1 -C 6 alkyl, in particular C 2 -C 6 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertbutyl, n-pentyl and n-hexyl, and R 1 is H or methyl.
  • residues R 3 and R 4 are different hydrocarbon moieties and the double bond including the carbon atom R 3 and R 4 are attached to is preferably in E-configuration. Most preferably, R 3 is methyl and R 4 is ethyl.
  • the present application also comprises embodiments wherein residues R 1 and R 2 are equal. In this case the compounds of formulas Na and Hb are equal. Therefore the mixture of the compounds of formulas Ma and Hb only comprises more than one compound if residues R 1 and R 2 are different.
  • R 1 is hydrogen and R 2 is methyl.
  • R 5 is hydrogen and R 6 is a hydroxy protecting group.
  • protecting groups for the protected hydroxy group usual protecting groups known to the person skilled in the art may be used. Suitable protecting groups are exemplified in WO 03/044011 , the content of which is incorporated by references herein.
  • a preferred protecting group for R 6 is a methyl group.
  • R 1 is hydrogen
  • R 2 is a methyl group
  • R 6 is a Ci-C 4 alkyl group (e.g. methyl, ethyl, propyl or butyl).
  • the reaction of the compound of the formula III with the compound of the formula IV of the process of the present invention can be carried out in any usual solvent, which preferably provides sufficient solubility to the starting materials used, e.g. C 3 to C 12 hydrocarbons.
  • the reaction of the compound of the formula III with the compound of the formula IV of the process of the present invention is preferably carried out without additional solvents.
  • the reaction can be carried out under acid catalysis.
  • suitable acid any preferably strong acid, preferably a Br ⁇ nsted acid, pKgi-4,5 can be used, preferably a strong inorganic acid, e.g. phosphoric acid or sulphur-VI containing acid, e.g.
  • the reaction is preferably carried out in a temperature range of 90 0 C to 200 0 C, more preferably 100 0 C to 150°C, in particular at about 105 0 C, depending on the specific starting materials used.
  • the reaction can be carried out under inert atmosphere (e.g. argon atmosphere) and is preferably carried out under increased atmospheric pressure, e.g. in a pressure range of 1 - 20 bar absolute, in particular 1 ,5 to 5 bar absolute.
  • the process of the present invention preferably further comprises the step of isomerising a compound of formulas Ma or Hb
  • the isomerisation reactions for the preparation of a compound of formulas Ia or Ib or a mixture thereof can be carried out in any suitable solvent, e.g. water, alcohol, such as methanol or ethanol, or esters such as ethylacetate.
  • the preferred solvent is methanol.
  • the isomerisation reactions are catalyzed by an alkaline compound.
  • suitable alkaline compound hydroxide containing compounds such as NaOH, KOH or similar can be used, preferably NaOH is used.
  • the isomerisation is carried out in the absence of alcohol as solvent.
  • the isomerisation can be carried out with alkaline compound in water.
  • the isomerisation reactions are preferably carried out in a temperature range of -15°C to +15°C, e.g. at about O 0 C.
  • the isomerisation reactions can be carried out under inert atmosphere, such as argon atmosphere.
  • the products i.e. the compounds of the formulas Ia 1 Ib or a mixture thereof, can be purified according to methods known in the art, preferably the compounds of the formulas Ia, Ib or a mixture thereof are extracted from the raw reaction product with an organic solvent, e.g. methyltertbutylether (MTBE).
  • MTBE methyltertbutylether
  • the product can be further purified, e.g. by distillation.
  • the compounds of formulas Ha, lib or mixtures thereof are obtained as described above and isomerised to obtain compounds of formulas Ia, Ib or mixtures thereof.
  • the compounds of formulas Ma, lib or mixtures thereof can be purified before the isomerisation reactions to obtain the compounds of formulas Ia, Ib or mixtures thereof are conducted.
  • the compounds of formula Ha and Hb or mixtures thereof are isomerised to obtain compounds of formulas Ia, Ib or mixtures thereof without prior purification, i.e. the raw product from the process of the present invention to prepare the compounds of formulas Ha, Nb or mixtures thereof is subjected to an isomerisation reaction as described above to obtain the corresponding compounds of formulas Ia, Ib or mixtures thereof.
  • the isomerisation reaction for the preparation of a compound of formula Ia or Ib is carried out such that the compounds of formulas Ha, Hb or mixtures thereof are prepared as described above and the compound of formula Ha or the compound of formula lib are separated and/or purified, before isomerisation to the corresponding compound of formula Ia or Ib 1 respectively.
  • Useful separation and purification methods are known to the person skilled in the art, such as chromatographic separation and purification methods.
  • mixtures of compounds of formulas Ha and lib which are preferably obtained as described above, are isomerised to obtain a mixture of compounds of formulas Ia and Ib.
  • R 1 is hydrogen
  • R 2 is hydrogen or methyl
  • R 3 is methyl
  • R 4 is ethyl
  • the compound of the formula Ma is 6-methyl-octa-4,5-dien-2-one (2) or 3,6-dimethyl-octa-4,5-dien-2-one (A)
  • the compound of formula Hb is 7-methyl-nona-5,6-dien-3-one
  • the compound of the formula Ia is 6-methyl-octa-3,5-dien-2-one (1) or 3,6-methyl-octa-3,5-dien-2-one (C)
  • the compound of the formula Ib is 7-methyl-nona-4,6-dien-3-one (D).
  • dienones in particular 6-methyl-octa- 4,5-dien-2-one (2), 3,6-dimethyl-octa-4,5-dien-2-one (A), 7-methyl-nona-5,6-dien-3-one (B), 6-methyl-octa-3,5-dien-2-one (1), 3,6-dimethyl-octa-3,5-dien-2-one (C) and 7-methyl-nona- 4,6-dien-3-one (D), can be advantageously obtained in excellent yields and in excellent purity.
  • the yield may be at least 90%, preferably it is at least 92%, more preferably at least 95%, e.g. 95%-99%, most preferably more than 95%.
  • the present invention further relates to the compound of formula V
  • R 1 , R 2 , R 3 and R 4 are defined as above.
  • the compounds of formula V are useful in the preparation of dienones, in particular compounds of the formulas Ha, lib, and mixtures thereof, and compounds of the formulas Ia, Ib, and mixtures thereof.
  • the compound of formula V wherein R 1 is hydrogen, R 2 is hydrogen or methyl, R 3 is methyl and R 4 is ethyl is useful in the preparation of 6-methyl-octa-4,5-dien-2-one (2), 3,6-dimethyl- octa-4,5-dien-2-one (A), 7-methyl-nona-5,6-dien-3-one (B), 6-methyl-octa-3,5-dien-2-one (1), 3,6-dimethyl-octa-3,5-dien-2-one (C) and 7-methyl-nona-4,6-dien-3-one (D).
  • the present invention further relates to the compound of formula Ia
  • R 1 , R 2 , R 3 and R 4 are defined as above, with the proviso that R 1 and R 2 are not both hydrogen.
  • the compounds of formula Ia can be prepared according to the process as described above.
  • the compounds of formula Ia are compounds C and D or E/Z isomers thereof.
  • Each process of the present invention can further comprise one or more steps of separation or enrichment of enantiomers, e.g. steps of racemic separation.
  • steps of separation or enrichment of enantiomers are known in the art.
  • the stereoconfiguration of reducts, intermediates and products is chosen such that when used in processes for the present invention, the intermediates and products resulting from said processes show the stereoconfiguration suitable for the preparation of 6- methyl-octa-4,5-dien-2-one, 6-methyl-octa-3,5-dien-2-one, 3,6-dimethyl-octa-4,5-dien-2- one, 7-methyl-nona-5,6-dien-3-one, 3,6-dimethyl-octa-3,5-dien-2-one and 7-methyl-nona- 4,6-dien-3-one.
  • the shaker frequency was set to 250 min "1 , the reaction temperature was 105 0 C, the reaction time was 120 minutes (incl. 15 minutes heating-up)
  • the jacket temperature (Tj) was first set to 60 0 C and then within 30 minutes slowly increased (intense reflux) up to 70 0 C. Within 8 hours the internal temperature increased from 50 0 C up to 70 0 C. During the 12 hour after reaction time the color of the reaction mixture turned from light yellow to amber. The reaction mixture was actively cooled down to room temperature. For the work-up 2 liters of MTBE were added to the reaction mixture and then extracted 3 times with 500 ml water deionized (total 1.5 liters). The MTBE is necessary to separate the phases, because the water is soluble in 2,2-dimethoxypropane (DMP). The water phase was not re-extracted with MTBE (results in a one phase system).
  • DMP 2,2-dimethoxypropane
  • the organic phase was dried with Na 2 SO 4 , filtered and concentrated under vacuum at 40°C and 10 mbar.
  • the crude product was distilled in a 2 liter two-necked round-bottomed flask with an oil bath, magnetic stirrer, PT 100, 30 cm Vigreux-column, Liebig-condenser, two-way fraction-separator, cold trap, membrane vacuum-pump.
  • the first product fraction was taken at TJ 74 - 75 0 C 1 internal temperature (T,) 64 - 66°C, distillate temperature (head) (T H ) 59 - 60 0 C and 8 mbar.
  • the stirrer is a stainless steel four-propeller with a speed range from 0 to 1200 rpm, from Flender ATB-Loher, number EAFY63/2B-7/N12 (0.25 kW).
  • the sampling was done via a stainless steel capillary and a thin spiraled stainless steel tube connected to the sampling flask.
  • the reactor is also connected to a safety and a data control system.
  • the low-boilers were evaporated at Tj 40 ° and down to 10 mbar.
  • the residue was solved in 50 ml MTBE and extracted once with 2.9 g water deionized. After separation the water phase was re-extracted with 10 ml MTBE.
  • the united organic phases were dried with Na 2 SO 4 , filtered and concentrated under vacuum at 40 0 C and down to 10 mbar.
  • the crude product was distilled bulb-to-bulb under vacuum.
  • the product fraction was taken at Tj up to 105 0 C and 9 mbar.
  • Example 5 mixture of 3,6-dimethyl-octa ⁇ 4,5-dien-2-one (A) and 7-methyl-nona-5,6- dien-3-one (B)
  • the crude product was purified by distillation.
  • a and B The structure of A and B was characterized by GC MS, IR, elementary analyses, and 1 H-, and 13 C-NMR spectroscopy.
  • Example 6 Mixture of 3,6-dimethyl-octa-3,5-dien-2-one (C) and 7-methyl-nona-4,6- dien-3-one (D)
  • the residue was solved in 1 liter tert-butyl methyl ether (TBME), extracted 3 times with 100 ml of deionized. water, the water layers were extracted with 200 ml tert-butyl methyl ether and the combined organic layers were dried with Na 2 SO 4 , filtered, and the solvent was evaporated at 40°C (20 mbar).
  • the crude product was purified by distillation. Head temperature 77 - 93°C, pressure 10 mbar (internal temperature 87 - 93°C).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne des procédés d'élaboration de diènones et les intermédiaires pour ce procédé.
PCT/EP2008/000709 2007-01-30 2008-01-30 Procédé d'élaboration de diènones WO2008092655A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08707406A EP2109597A1 (fr) 2007-01-30 2008-01-30 Procede d'elaboration de dienones

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP07001946A EP1953134A1 (fr) 2007-01-30 2007-01-30 Procédé pour la préparation des diénones
EP07001946.8 2007-01-30
EP07010782.6 2007-05-31
EP07010782 2007-05-31

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WO2008092655A1 true WO2008092655A1 (fr) 2008-08-07

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011131607A1 (fr) 2010-04-19 2011-10-27 Dsm Ip Assets B.V. Isomérisation de β-céto-allènes
WO2018108606A1 (fr) 2016-12-12 2018-06-21 Dsm Ip Assets B.V. Procédé de fabrication de 6,10-diméthylundécan-2-one, d'isophytol, d'alpha-tocophérol (acétate) et d'autres intermédiaires de celui-ci
CN109534977A (zh) * 2018-12-12 2019-03-29 万华化学集团股份有限公司 一种由炔丙醇合成α,γ-不饱和二烯酮的方法及用于该方法的催化剂
WO2020140414A1 (fr) * 2019-01-02 2020-07-09 浙江新和成股份有限公司 Procédé de préparation de cétone insaturée

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DE1078112B (de) 1956-06-27 1960-03-24 Hoffmann La Roche Verfahren zur Herstellung von diolefinisch-ungesaettigten Ketonen
GB865478A (en) * 1958-08-01 1961-04-19 Hoffmann La Roche A process for the manufacture of unsaturated ketones
US3632860A (en) * 1964-02-25 1972-01-04 Hoffmann La Roche Acetylenic ketals
GB1422518A (en) * 1972-03-27 1976-01-28 Ayerst Mckenna & Harrison 11-deoxyprostaglandin derivatives and process therefor
US4005147A (en) * 1971-10-13 1977-01-25 Badische Anilin- & Soda-Fabrik Aktiengesellschaft Production of α,β-unsaturated ketones
US4169109A (en) * 1978-08-10 1979-09-25 International Flavors & Fragrances Inc. Process for preparing ketones using zinc acetate condensation catalysts, products produced thereby and organoleptic uses of same
US4523042A (en) * 1983-07-29 1985-06-11 Usv Pharmaceutical Derivatives of alpha-alkyl polyolefinic carboxylic acid useful in the treatment of psoriasis
US6184420B1 (en) * 1997-09-10 2001-02-06 Basf Aktiengesellschaft Preparation of unsaturated ketones
WO2004041764A1 (fr) * 2002-11-07 2004-05-21 Basf Aktiengesellschaft Procede pour produire en continu des ionones et pseudoionones

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GB741047A (en) 1952-04-15 1955-11-23 Distillers Co Yeast Ltd Unsaturated ketones
DE1078112B (de) 1956-06-27 1960-03-24 Hoffmann La Roche Verfahren zur Herstellung von diolefinisch-ungesaettigten Ketonen
GB865478A (en) * 1958-08-01 1961-04-19 Hoffmann La Roche A process for the manufacture of unsaturated ketones
US3632860A (en) * 1964-02-25 1972-01-04 Hoffmann La Roche Acetylenic ketals
US4005147A (en) * 1971-10-13 1977-01-25 Badische Anilin- & Soda-Fabrik Aktiengesellschaft Production of α,β-unsaturated ketones
GB1422518A (en) * 1972-03-27 1976-01-28 Ayerst Mckenna & Harrison 11-deoxyprostaglandin derivatives and process therefor
US4169109A (en) * 1978-08-10 1979-09-25 International Flavors & Fragrances Inc. Process for preparing ketones using zinc acetate condensation catalysts, products produced thereby and organoleptic uses of same
US4523042A (en) * 1983-07-29 1985-06-11 Usv Pharmaceutical Derivatives of alpha-alkyl polyolefinic carboxylic acid useful in the treatment of psoriasis
US6184420B1 (en) * 1997-09-10 2001-02-06 Basf Aktiengesellschaft Preparation of unsaturated ketones
WO2004041764A1 (fr) * 2002-11-07 2004-05-21 Basf Aktiengesellschaft Procede pour produire en continu des ionones et pseudoionones

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011131607A1 (fr) 2010-04-19 2011-10-27 Dsm Ip Assets B.V. Isomérisation de β-céto-allènes
CN102858730A (zh) * 2010-04-19 2013-01-02 帝斯曼知识产权资产管理有限公司 β-酮-联烯的异构化
US8802898B2 (en) 2010-04-19 2014-08-12 Dsm Ip Assets B.V. Isomerization of β-keto-allenes
CN102858730B (zh) * 2010-04-19 2015-02-11 帝斯曼知识产权资产管理有限公司 β-酮-联烯的异构化
KR101811465B1 (ko) 2010-04-19 2017-12-26 디에스엠 아이피 어셋츠 비.브이. β-케토-알렌의 이성질화
WO2018108606A1 (fr) 2016-12-12 2018-06-21 Dsm Ip Assets B.V. Procédé de fabrication de 6,10-diméthylundécan-2-one, d'isophytol, d'alpha-tocophérol (acétate) et d'autres intermédiaires de celui-ci
CN109534977A (zh) * 2018-12-12 2019-03-29 万华化学集团股份有限公司 一种由炔丙醇合成α,γ-不饱和二烯酮的方法及用于该方法的催化剂
CN109534977B (zh) * 2018-12-12 2022-04-22 万华化学集团股份有限公司 一种由炔丙醇合成α，γ-不饱和二烯酮的方法及用于该方法的催化剂
WO2020140414A1 (fr) * 2019-01-02 2020-07-09 浙江新和成股份有限公司 Procédé de préparation de cétone insaturée

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