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
  • C11B9/0019—Aliphatic compounds containing oxygen as the only heteroatom carbocylic acids; Salts or esters thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
  • C07C17/363—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms by elimination of carboxyl 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
  • C07C45/511—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
  • 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
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
  • C07C51/295—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with inorganic bases, e.g. by alkali fusion
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
  • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
  • C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl 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
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
  • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
  • C07C51/38—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by decarboxylation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
  • C07C53/15—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing halogen
  • C07C53/19—Acids containing three or more carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
  • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
  • C07C57/03—Monocarboxylic acids

Definitions

• the invention relates to new oxygenated derivatives of acyclic olefins which have interesting olfactive and fixative properties and are, therefore, useful and used as fragrances and fixatives in the preparation of perfumes and perfumed products. Furthermore, the invention relates to methods for the manufacture of the said new derivatives.
• the compounds of this invention correspond to the general formula wherein a double bond is located in one of the positions indicated by the dotted lines and wherein R represents a COOH or CH OH group and n stands for the integer l or 2.
• the compounds of Formula I exist both in the cis and trans configurations.
• the acids and alcohols represented by Formula I have been found to possess interesting odours of a surprisingly high intensity exceeding substantially the average odoriferous power of many of the common known fragrances. When added to mixtures of other odoriferous ingredients, the new compounds also exert a fixing action on these mixtures.
• the compounds I develop powdery and somewhat fatty, very natural odour notes and can be used as odoriferous ingredients, fixatives or modifiers in the preparation of perfumes and perfumed products.
• perfumes includes undiluted perfume concentrates, perfume compositions diluted with solvents, such as ethyl alcohol, essential oils, and fragrant mixtures which are not finished perfumes but are used as modifiers in the preparation of finished perfumes.
• perfumed products includes soaps, detergents, cosmetic products such as creams, milks, hair lotions, toilet waters, deodorants and the like, and more generally all goods in which fragrances are incorporated in order to make them more attractive.
• the proportions in which the new compounds of Formula I are used vary within wide limits depending on the particular odoriferous effects to be achieved and the type of fragrant material to be obtained. Due to their unusually high odoriferous power the acids and alcohols of Formula I can be used in extremely low concentrations, for instance of the order of about 0.05 to 0.5% of the total weight of a perfume concentrate. In certain cases it is possible to obtain noticeable odoriferous effects with proportions even lower than 0.05%, e.g., in diluted perfumes. However, higher concentrations of the new fragrances can be used, e.g., about 0.5 to 5% of the weight of a composition, when special odoriferous effects are desired.
• the new fragrances can also be used in the preparation of artificial essential oils such as Cassie oil.
• the new compounds I when added in small proportions, e.g. 0.05 to 0.5% to perfume compositions, prothe basic and final note of the perfumes. Moreover, the compositions, impart to the latter a more natural odoriferous character.
• the odoriferous properties of the acids and alcohols of Formula I are similar in kind, they can be used either individually or as mixtures of two or more of them. Furthermore, since the cis and trans isomers of each of the compounds of Formula I have very similar olfactive properties it is generally advantageous to use a mixture of the two geometrical forms instead of one or the other isomer of the selected compound. Moreover, except for particular cases, the proportion of each of the geometrical isomers in the said binary mixtures has no substantial influence on the desired odour note and, consequently, it is generally more economical to use the cistrans-mixtures directly resulting from the syntheses without previously separating the cis-and trans-forms.
• a process for the preparation of compounds I with trans-configuration comprises (a) saponifying and partially hydrogenating esters of formula r'ce containing two conjugated double bonds in two of the positions indicated by the dotted lines and wherein R represents an aliphatic radical comprising from 1 to 4 carbon atoms and n stands for the integer 1 or 2, in order to obtain the compounds I wherein R is COOH, then (b) subsequently reducing the carboxylic groups of the partially hydrogenated products to obtain the compounds I wherein R is a methylol group.
• the starting material 11 used in the process described thereabove can be prepared by known methods [see for instance Tetrahedron 22, 293 (1966); J. Prakt. Chemie 284, 50 (1960); Chem. Rev. 61, 607 (1961)] according to the following reaction scheme:
• a process for the preparation of the trans compound of formula comprises oxidising 3-methyl-4-decen-1-al by means of an oxidising agent.
• Oxidising agents commonly used for oxidising aldehydes to the corresponding carboxylic acids can be used.
• the oxidation is preferably carried out by means of silver nitrate in aqueous alkaline solution.
• the 3-methyl-4-decen-1-al used as a starting substance in the above process can conveniently be prepared by condensing crotonaldehyde with n-amylmagnesium bromide under Grignard reaction conditions and refluxing the resulting 2-nonen-4-ol with ethyl vinyl ether in the presence of mercuric acetate.
• the method described above is summarised in the following scheme:
• a process for the preparation of those compounds of Formula I which have the double bond in the 3-position and have cis configuration comprises (a) condensing the magnesium derivative of cis-Z-bromo-Z-nonene with ethylene oxide under usual Grignard reaction conditions and (b) oxidising the resulting cis-3-methyl-3-decen-l-ol to cis-3-methyl-3-decenoic acid by means of an oxidising agent.
• the oxidation is preferably carried out by means of CrO (Jones reagent) although any other method normally used for oxidising unsaturated primary alcohols to the corresponding carboxylic acids can also be used.
• a process for the preparation of those compounds of Formula I which contain a double bond in the 4-position and have cis-configuration comprises (a) partially hydrogenating 3-methyl-4- decynoic acid in the presence of a poisoned hydrogenation catalyst to the corresponding olefinic acid and (b) subsequently reducing the COOH group of the olefinic acid to the corresponding methylol group.
• the above partial hydrogenation can be carried out in the presence, for
• 3-methyl-4-decynoic acid which is used as the starting substance in the above mentioned process can be prepared by known methods [see J. Chem. Soc. p. 39 (1946); I. Am. Chem. Soc. H, 1242 (1949)], e.g. according to the following reaction scheme:
• EXAMPLE 1 A perfume composition having a Cassie-like odour was prepared by mixing the following ingredients:
• EXAMPLE 2 A perfume composition of the floral type was prepared Benzyl salicylate 3 Methylnonyl acetaldehyde at 1 1 Dodecanal at 10% 1 0.5 Undecylenic aldehyde at 10% 1 1.5 Isojasmone at 10% 1 1.5 Cardamom at 1% 1 3 Santalol 1.5 Vetyveryl acetate 4.5 Exaltolide at 10% 1 (pentadecanolide) 1.5 Natural degreased civet at 10% 1 3 4 tert.Butyl 3,5 dinitro 2,6 dimethylacetophenone 6 Orange blossom abs. at 10% 1 2 Rose absolute 1 Bulgarian rose oil 1 Jasmin absolute 2 Vanillin at 1% 1 3 1 In die'thyl phthail ate.
• EXAMPLE 3 A composition of the floral-chypre type was prepared by mixing the following ingredients:
• EXAMPLE 4 (a) Preparation of a mixture of methyl 3-methyl- 2,4- decadien-l-oate and methyl 3-methyl-3,5-decad1enl-oate A laboratory vessel was equipped with a reflux condenser and a dropping funnel containing a mixture of 81 g. of methyl 3-methyl-4-bromocrotonate and 52 g. of trimethyl phosphite. A fraction of ml. of this mixture was poured into the vessel and heated to 90, at which temperature the reaction started. The heat source was removed, and the remainder of the liquid was introduced at such a rate that the reaction proceeded at 90 to 110. A temperature of 120 was maintained for an additional 1% hours, then distillation yielded 56.4 g.
• NMR spectrum 1.97 p.p.m., 3H (vinylic methyl); 3.06 p.p.m., 2H (protons at C-2). (3) 50% of methyl 3-methyl-2,4-decadienoate, trans-structure of the double bond at C2.
• NMR spectrum 2.25 p.p.m., 3H (vinylic methyl). The above mixture was thus composed of a total of 85% of methyl 3-methyl-2,4-decadienoate (mixture of cis and trans) and of 15% of 3,5- diene ester.
• This product contained the following fractions (separated according to usual methods): (1) 80% of 3-methyl-3-decenol of trans-configuration the NMR spectrum of which was as follows: 0.88 p.p. m., 3H, T.; 1.28 p.p.m., 8H, s.
• EXAMPLE 6 (a) Preparation of 3-n0nyn-2-ol 215 g. of ethyl bromide were added dropwise at reflux temperature to a suspension of 48.6 g. of activated Mg in 500 ml. of anhydrous ether. Heating was continued for 1 hour, then it was allowed to stand overnight at 20".
• the alkaline fraction (main aqueous mixture plus alkaline washing fractions) were acidified with 10% HCl and extracted with ether. The extract was treated as usual and concentrated. Before the final distillation, the residue was steam-distilled for a few minutes in order to remove some remaining volatile impurities. The final distillation of the residue gave 217.5 g. (32%) of trans-3-methyl-4- decenoic acid, B.P. 84-86/0.0001 torr.
• a process for the preparation of trans-3-methyl-4- decenoic acid which comprises oxidising 3-methyl-4- decen-l-al by means of an agent eifective for oxidizing the unsaturated aldehyde to the corresponding acid.
• Process according to claim 4 which comprises using silver nitrate in aqueous alkaline solution as an oxidising agent.
• Process for the preparation of ciscompounds of formula wherein R represents a COOH group which comprises (a) condensing the magnesium derivative of cis-2- bromo-Z-nonene with ethylene oxide and (b) oxidizing the resulting cis-3-methyl-3-decen-l-ol to the corresponding cis-3-methyl-3-decenoic acid by means of an oxidizing agent effective for oxidizing unsaturated primary alcohols to the corresponding carboxylic acids.
• Process according to claim 6 which comprises performing (a) under usual Grignard reaction conditions and (b) using CrO (Jones reagent) as an oxidising agent.

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

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• 1968
  • 1968-01-17 CH CH79268A patent/CH491192A/fr not_active IP Right Cessation
• 1969
  • 1969-01-15 GB GB2400/69A patent/GB1211512A/en not_active Expired
  • 1969-01-16 DE DE19691902074 patent/DE1902074A1/de active Pending
  • 1969-01-16 NL NL6900769A patent/NL6900769A/xx unknown
  • 1969-01-16 US US791770*A patent/US3579550A/en not_active Expired - Lifetime
  • 1969-01-17 FR FR6900774A patent/FR2000344A1/fr not_active Withdrawn

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