GB1469135A - Alkenals and process for producing alkenals - Google Patents

Alkenals and process for producing alkenals

Info

Publication number
GB1469135A
GB1469135A GB3208374A GB3208374A GB1469135A GB 1469135 A GB1469135 A GB 1469135A GB 3208374 A GB3208374 A GB 3208374A GB 3208374 A GB3208374 A GB 3208374A GB 1469135 A GB1469135 A GB 1469135A
Authority
GB
United Kingdom
Prior art keywords
alkylidene
trans
reacting
alkenal
alkyl
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.)
Expired
Application number
GB3208374A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
International Flavors and Fragrances Inc
Original Assignee
International Flavors and Fragrances Inc
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 US383580A external-priority patent/US3929919A/en
Priority claimed from US05/383,578 external-priority patent/US3970701A/en
Application filed by International Flavors and Fragrances Inc filed Critical International Flavors and Fragrances Inc
Publication of GB1469135A publication Critical patent/GB1469135A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0007—Aliphatic compounds
    • C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20—Synthetic spices, flavouring agents or condiments
    • A23L27/202—Aliphatic compounds
    • A23L27/2024—Aliphatic compounds having oxygen as the only hetero atom
    • 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
    • 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
    • C07C45/004—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with organometalhalides
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
    • 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
    • C07C45/515—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 acetalised, ketalised hemi-acetalised, or hemi-ketalised 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
    • C07C45/62—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 hydrogenation of carbon-to-carbon double or triple 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
    • C07C45/61—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
    • C07C45/63—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 introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • 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
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/222—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon triple bonds as unsaturation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/24—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing halogen
    • 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
    • C07C49/255—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Nutrition Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

1469135 Unsaturated aldehydes INTERNATIONAL FLAVORS & FRAGRANCES Inc 19 July 1974 [30 July 1973 (2)] 32083/74 Heading C2C [Also in Divisions A2 and A5] The invention comprises 2-alkylidene-3-alkenals of formula wherein one of R 1 and R 2 is H and the other is CH 3 and one of R 3 and R 4 is H and the other is C 2 - or C 4 -alkyl and a method of preparing compounds of the above Formula I in which R 1 is C 1-4 alkyl, R 2 is H and one of R 3 and R 4 is C 1-4 alkyl and the other is H, which comprises the steps of (1) reacting an aliphatic alpha-betaunsaturated aldehyde with a halogen to provide the corresponding alpha-halo alkenal where X is halogen; either (i) reacting the said alpha-halo alkenal with an alkyl magnesium halide Grignard reagent, hydrolysing the resulting product to form a hydroxyhaloalkene, and dehydrating the resulting hydroxyhaloalkene to form an alkylidene trans-alkene halide or (ii) reacting the said alpha-halo aldehyde derivative with a tri-substituted alkylidene phosphorane or an alkylidene phosphorus triamide to provide a mixture of alkylidene cis-alkene halide and alkylidene trans-alkene halide; (3) either (i) treating either the mixture of said alkylidene alkene halide isomers or said alkylidene trans-alkene halide with a metal such as magnesium thereby forming an organo-metallic compound where M is MgX and reacting the said organometallic compound so formed with a trialkyl orthoformate (to yield an acetal which is then hydrolysed with acid to yield the desired alkylidene-trans-alkenal or (ii) reacting the mixture of alkylidene alkene halide isomers with an alkyl alkali metal to form a second organometallic reagent (mixture of isomers) of the above formula where M is Li, Na or K and then reacting said organo-metallic reagent with a dialkyl formamide followed by acid hydrolysis forming a mixture of 2-alkylidene-3-cis-alkenal and alkylidene-3-trans-alkenal or (iii) physically separating the alkylidene cis-alkene halide from the alkylidene trans-alkene halide and then reacting each isomer independently with an alkyl alkali metal to form a second organo-metallic reagent and then reacting each of said second organo-metallic reagents with a dialkyl formamide, followed by acid hydrolysis forming, separately, an alkylidene-trans-alkenal and an alkylidene-cis-alkenal, where M is MgX, Li, Na or K and X is halogen. 2-Alkylidene-3-alkenals of the above Formula I, including 2-ciscompounds in R 2 is C 1-4 alkyl and R 1 is H may also be prepared by the processes of Specification 1,468,073. Trans - 2 - ethylidene - cis - 3 - hexenal is also obtained from concentrated orange juice by extraction with ether followed by gas-liquid chromatography. Intermediate compounds isolated in examples of the above-described process are α-chloro- and α - bromo - crotonaldehyde, 3 - chloro - 4 - hydroxy- 2-heptene, 3-bromo- and 3-chloro-2,4-heptadiene. The alkylidene-alkenals are used to modify organoleptic properties, e.g. in foodstuffs, beverages, tobacco and perfumes.
GB3208374A 1973-07-30 1974-07-19 Alkenals and process for producing alkenals Expired GB1469135A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US383580A US3929919A (en) 1973-07-30 1973-07-30 Process for producing alkylidene alkene halides
US05/383,578 US3970701A (en) 1973-07-30 1973-07-30 Lower alkenals

Publications (1)

Publication Number Publication Date
GB1469135A true GB1469135A (en) 1977-03-30

Family

ID=27010233

Family Applications (1)

Application Number Title Priority Date Filing Date
GB3208374A Expired GB1469135A (en) 1973-07-30 1974-07-19 Alkenals and process for producing alkenals

Country Status (3)

Country Link
DE (1) DE2433199A1 (en)
FR (1) FR2245599B3 (en)
GB (1) GB1469135A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1336345A1 (en) * 2000-11-06 2003-08-20 Japan Tobacco Inc. Perfume compositions for deodorizing tobacco, tobacco deodorizing agents and cigarette and tobacco packages with little side smoke flow odor
WO2004016105A1 (en) * 2002-08-19 2004-02-26 Givaudan Sa Improvements in or related to organic compounds

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4107217A (en) * 1973-07-30 1978-08-15 International Flavors & Fragrances Inc. Acetals of conjugated alkenals

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1336345A1 (en) * 2000-11-06 2003-08-20 Japan Tobacco Inc. Perfume compositions for deodorizing tobacco, tobacco deodorizing agents and cigarette and tobacco packages with little side smoke flow odor
EP1336345A4 (en) * 2000-11-06 2006-01-18 Japan Tobacco Inc Perfume compositions for deodorizing tobacco, tobacco deodorizing agents and cigarette and tobacco packages with little side smoke flow odor
US7481891B2 (en) 2000-11-06 2009-01-27 Japan Tobacco Inc. Cigarette wrapper consisting of mandarin orange essential oil
WO2004016105A1 (en) * 2002-08-19 2004-02-26 Givaudan Sa Improvements in or related to organic compounds

Also Published As

Publication number Publication date
FR2245599B3 (en) 1977-06-03
DE2433199A1 (en) 1975-02-20
FR2245599A1 (en) 1975-04-25
AU7054874A (en) 1976-01-08

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PS Patent sealed
PCNP Patent ceased through non-payment of renewal fee