GB756896A - Polyene dialdehydes and process for the manufacture thereof - Google Patents

Polyene dialdehydes and process for the manufacture thereof

Info

Publication number
GB756896A
GB756896A GB20138/54A GB2013854A GB756896A GB 756896 A GB756896 A GB 756896A GB 20138/54 A GB20138/54 A GB 20138/54A GB 2013854 A GB2013854 A GB 2013854A GB 756896 A GB756896 A GB 756896A
Authority
GB
United Kingdom
Prior art keywords
acid
ine
ester
water
diol
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
GB20138/54A
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.)
Roche Products Ltd
Original Assignee
Roche Products Ltd
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
Application filed by Roche Products Ltd filed Critical Roche Products Ltd
Publication of GB756896A publication Critical patent/GB756896A/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/30—Compounds having groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/30—Compounds having groups
    • C07C43/303—Compounds having groups having acetal carbon atoms bound to acyclic carbon 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
    • C07C45/51—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
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen

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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

The invention comprises 4,9-dimethyldodecatetraene - (2, 4, 8, 10) - ine - (6) - diol - (1, 12) and 4,9 - dimethyl - dodecapentaene - (2,4,6,8,10) - diol-(1,12). The novel compounds are prepared by acetalizing 2,7-dimethyloctadien-(2,6)-ine-(4) - diol - (1,8) or 2,7 - dimethyloctatriene-(2,4,6)-diol-(1,8), for example by reaction with an ortho-ester, such as methyl, ethyl or butyl orthoformate, in the presence of an acid agent, e.g. p-toluene-sulphonic acid, phosphoric acid, boron trifluoride etherate, zinc chloride, ammonium chloride or ammonium nitrate, condensing the resulting diacetal with 2 molecular proportions of a vinyl ether in the presence of a condensing agent, such as boron trifluoride etherate, aluminium chloride, ferric chloride or tin tetrachloride, preferably at a temperature between 25 DEG and 60 DEG C., and treating the product with an acid to hydrolyse the acetal groups and eliminate alcohol. The hydrolysis may be effected using, for example, p-toluenesulphonic acid, acetic, propionic, oxalic, sulphuric or phosphoric acid, zinc chloride or sodium hydrogen sulphate. It is advantageous to exclude oxygen during hydrolysis and to remove the alcohol continuously. A water-miscible solvent, such as dioxane, tetrahydrofurane or ethylene glycol dimethyl ether, may be added to the hydrolysis mixture. Any triple bond in the product may be reduced to a double bond by treating with one mole. of hydrogen in the presence of a palladium-lead catalyst. In an example, 2,7-dimethyl-octadien-(2,6)ine-(4)-dial-(1,8) is reacted with ethylorthoformate in the presence of ammonium nitrate, the resulting acetal is condensed with ethyl-vinyl-ether with the aid of boron trifluoride etherate, and the product is dissolved in dioxane and hydrolysed by boiling with phosphoric acid under an atmosphere of nitrogen; the reaction mixture is poured in water to separate 4,9-dimethyldodecatetraen - (2,4,8,10) - ine - (6) - dial - (1,12). The novel compounds may be condensed with 2 mols. of a -bromopropionic acid ester with subsequent elimination of water and hydrolysis to give dehydrocrocetin or crocetin. The novel compounds may be acetalized followed by condensation of the resulting acetals with propenyl ether and treatment with acid to give dehydrocrocetin dialdehyde and crocetin dialdehyde. The latter are treated with bromo-acetic ester and water is eliminated to produce dehydrobixin ester and bixin ester. Alternatively, they may be acetalized, condensed with vinyl ether and treated with acid to convert them to dehydro-bixin dialdehyde and bixin dialdehyde. These compounds may be condensed with 2-methyl-6-bromoheptene-(2) to give, after eliminating water, dehydrolycopene and lycopene. The initial 2,7-dimethyloctadien-(2,6)-ine-(4)-dial-(1,8) may be obtained as described in Specification 744,890 and may be hydrogenated to the corresponding triene compound in the presence of a palladium/lead catalyst.
GB20138/54A 1953-07-10 1954-07-09 Polyene dialdehydes and process for the manufacture thereof Expired GB756896A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH756896X 1953-07-10

Publications (1)

Publication Number Publication Date
GB756896A true GB756896A (en) 1956-09-12

Family

ID=4534350

Family Applications (1)

Application Number Title Priority Date Filing Date
GB20138/54A Expired GB756896A (en) 1953-07-10 1954-07-09 Polyene dialdehydes and process for the manufacture thereof

Country Status (1)

Country Link
GB (1) GB756896A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5107030A (en) * 1991-03-04 1992-04-21 Loyola University Of Chicago Method of making 2,7-dimethyl-2,4,6-octatrienedial and derivatives thereof
EP3103352A1 (en) 2015-06-12 2016-12-14 DSM IP Assets B.V. Acid stable beverages comprising bixin
WO2016198570A1 (en) 2015-06-12 2016-12-15 Dsm Ip Assets B.V. New natural color for edible coatings
WO2016198569A1 (en) 2015-06-12 2016-12-15 Dsm Ip Assets B.V. New orange color for edible coatings

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5107030A (en) * 1991-03-04 1992-04-21 Loyola University Of Chicago Method of making 2,7-dimethyl-2,4,6-octatrienedial and derivatives thereof
WO1992015544A1 (en) * 1991-03-04 1992-09-17 Loyola University Of Chicago Method of making 2,7-dimethyl-2,4,6-octatrienedial and derivatives thereof
EP3103352A1 (en) 2015-06-12 2016-12-14 DSM IP Assets B.V. Acid stable beverages comprising bixin
WO2016198570A1 (en) 2015-06-12 2016-12-15 Dsm Ip Assets B.V. New natural color for edible coatings
WO2016198567A1 (en) 2015-06-12 2016-12-15 Dsm Ip Assets B.V. Acid stable beverages comprising bixin
WO2016198569A1 (en) 2015-06-12 2016-12-15 Dsm Ip Assets B.V. New orange color for edible coatings

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