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• • 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
  • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
  • C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms
• • 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
  • C07C403/06—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 singly-bound oxygen atoms
  • C07C403/10—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 singly-bound oxygen atoms by etherified hydroxy 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
  • C07C45/61—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
  • C07C47/00—Compounds having —CHO groups
  • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
• • 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
  • C07C47/105—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing rings
  • C07C47/11—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing rings monocyclic
• • 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
  • C07C47/19—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing hydroxy groups
• • 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
  • C07C47/198—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing ether groups, groups, groups, or groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
  • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
  • C07D317/24—Radicals substituted by singly bound oxygen or sulfur atoms esterified
• • 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
• • 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
  • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
• • 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

Definitions

• hydrocarbon residues which, in Formula I, are depicted by the symbol R are saturated aliphatic hydrocanbon residues having from 1 to 16 carbon atoms and unsaturated aliphatic hydrocarbon residues having from 2 to 16 carbon atoms.
• R represents alkyl and alkenyl groups, of the type mentioned heretofore, having oxygen-containing substituents.
• R represents a hydrocarbon residue having free, esterified and etherified hydroxy groups, oxo groups or free or esten'fied carboxyl groups.
• the esterified hydroxy groups include, for example, acyloxy groups, the acyl residue of which is derived from a lower aliphatic or aromatic carboxylic acid, such as, formic acid, acetic acid, propionic acid, butyric acid, etc. or benzoic acid.
• the etherified hydroxy groups include, for example, lower alkoxy groups, such as, methoxy, ethoxy, propoxy, isoprop-oxy, etc. radicals; or aryloxy groups, such as a phenoxy radical.
• esterified carboxyl groups there can be mentioned carbalkoxy groups, the alkyl component of which is derived from a lower alkanol, such as, methanol, ethanol, propanol, etc.
• Additional examples of the groups represented by the symbol R in Formula I are aromatic or araliphatic residues, such as, phenyl, benzyl, phenethyl, etc. radicals, as well as derivatives of such radicals having oxygen-containing substituents.
• the latter derivatives include aromatic and araliphatic residues which contain free, etherified or esterified hydroxy groups or free or esterified carboxyl groups.
• R which appears in Formula I represents an alkyl group having from 1 to 8 carbon atoms, such as, ethyl, propyl, butyl, pentyl, hexyl, etc.
• a preferred group of compounds of the invention contain, however, a methyl group as the R substituent.
• R which 3,381,039 Patented Apr. 30, 1968 "ice appears in Formula I represents a hydrogen atom or an alkyl group having, for example, from 1 to 3 canbon atoms, such as, an ethyl or propyl radical.
• the preferred compounds of the invention contain a methyl group as the R alkyl substituent.
• R Representative of the lower hydrocarbon residues which, in Formula I, are represented by the symbol R are alkyl, cycloalkyl, aryl, and aralkyl groups having from 1 to 8 carbon atoms, such as, methyl, ethyl, propyl, cyclohexyl, allyl, pentyl, phenyl, benzyl, etc. radicals.
• R and R of Formula I when taken together, represent a ring structure, such as a S-member or a 6-member carbocyclic radical.
• R and R taken together represent a tetramethylene or pentamethylene group.
• the starting aldehydes of Formula I are, in a first step of the process, either acetalized to produce an p-unsaturated acetal of the following formula:
• R2 1113 lit-i 1 5 R1C CCH2OHCII-OR5 II or hydrogenated to yield an aldehyde having the following formula:
• R2 l a I'M Pn-CH-CH-CHr-CH-CHO III
• the acetals of Formula II are hydrogenated or the aldehydes of Formula III are acetalized to yield a compound having the formula 1
• the symbols R R and R have the same meaning as in Formula I.
• the symbol R which appears in Formulas II and IV represents a lower alkyl group, e.g., an alkyl group having from 1 to 6 carbon atoms or a lower alkenyl group, e.g. an alkenyl group having from 2 to 6 carbon atoms; taken together, the two symbols R represent a lower alkylene group.
• the preferred compounds of Formula IV contain as the R substituents, lower alkyl groups, such as, methyl, ethyl, propyl, butyl, etc. groups.
• the lower alkylene group which is represented by the symbols R and R includes ethylene, trimethylene, tetramethylene, etc. radicals.
• Acetalization of the aldehydes of Formula I or Formula III is effected in a known manner.
• the acetalization is carried Out in the presence of hydrogen ions, with the separation of the water which forms.
• the requisite hydrogen ion concentration can be provided, for example, :by the use of acid catalysts, such as, anhydrous mineral acids; p-toluene sulphonic acid; cation exchangers, such as, phenol-resin sulphonic acids; ammonium chloride; zinc chloride; pyridine hydrochloride; sodium hydrogen sulphate; ferric chloride, boron trifiuoride etherate; etc.
• the water which is formed during the course of the reaction, can be removed from the reaction mixture by azeotropic distillation or by the addition of a waterbinding agent, such as, an orthosilicic acid ester, an orthoformic acid ester, 2,2-dirnethoxy-propane or dimethyl sulphite.
• a waterbinding agent such as, an orthosilicic acid ester, an orthoformic acid ester, 2,2-dirnethoxy-propane or dimethyl sulphite.
• Acetalization which is effected by the reaction by the aldehyde of Formula I or III with an alcohol, especially a lower molecular weight primary alcohol, in admixture with orthoformic acid ethyl ester, has been found to be a convenient preparative step.
• any catalyst which is normally used for the selective hydrogenation of the olefin :bond of carbonylcontaining olefins Suitable for use as the catalyst are, for example, palladium and Raney nickel.
• the 'y,6-unsaturated aldehydes of Formula I are converted to the aldehydes of Formula 111 which are saturated'in the 'y,6-position.
• the hydrogenation reaction is continued until such time as a calculated theoretical amount of hydrogen has been absorbed by the reaction mixture. If desired, this quantity of hydrogen used may be sufiicient to hydrogenate also any other olefinic bonds, present in the aldehyde.
• acetone is used as a solvent for the reaction and a finely divided palladium oxide-palladium hydroxide mixture on carbon is used as the catalyst.
• Hydrogenation of the acetals of Formula II is readily effected. Since it is Well known that an acetal group is quite resistant to the reaction of the reducing agents, there can be used as the hydrogenation catalyst, in addition to palladium and Raney nickel, catalysts which are less selective in their activity. In all other respects, the hydrogenation of an acetal compound of Formula II can be effected in the conventional manner, at atmospheric pressure or higher.
• R has the same meaning as in Formula I and R represents a lower alkyl group.
• This reaction is effected with the splitting off of one mole of the alcohol represented by the formula R OH, in which the symbol R has the same meaning as in Formula VI.
• novel compounds of Formulas II, III and IV have valuable and particularly useful properties. Because of their fine and, at times, unusual fragrance, the compounds are useful as odorants in the preparation of perfumes and other scented preparations. In general, the compounds are characterized by a natural flowery note. The acetals of Formulas II and IV are especially useful for the perfuming of soap and other cosmetic preparations.
• EXAMPLE 2 A mixture of 112 grams of 5-methyl-4-hexen-1-al, 62 grams of ethylene glycol and 0.2 gram of p-toluenesulphonic acid was distilled atSO mm. in a 100 C.-bath. A.
• EXAIVIPLE 5 63 grams of 2,5 L dimethyl 4 hexen 1 a1 were mixed with 650 ml. of n-propyl alcohol and 75 grams of orthoformic acid ethyl ester. The reaction was initiated by the addition of 1.5 ml. of boron trifluoride etherate. After two hours, 300 ml. of the reaction was evaporated off in a 120 C.-bath, following which the portion of the reaction mixture remaining was neutralized with 3 ml. of triethylamine. A fore-run was thereafter separated at 13 mm. in a 100 C.-bath.
• 1,1-di-n-propoxy- 2,5 dimethyl 4 hexene was distilled ofi using to C.-bath.
• EXAMPLE 6 63 grams of 2,5-dimethyl-4-hexen-1-al were mixed with 700 m1. of n-butanol and 75 grams of orthoformic acid ethyl ester. Thereafter, 1.5 ml. of boron trifiuoride etherate was added to the mixture and it was allowed to stand for a period of two hours, during which time the temperature thereof rose, exothermically, to 33 C. A 350 ml. of a fore-run was then distilled off in a 70 C.-bath at 13 mm. That portion of the reaction mixture which remained behind was thereafter neutralized with 3 ml. of triethylamine.
• a mixture of 126 grams of 2,5 dimethyl 4 hexen 1 al, 62 grams of ethylene glycol and 0.18 gram of ptoluene sulphonic acid was first prepared. Water was distilled from this mixture at 50 mm. in a 100 C.-bath. Thereafter, the bath-temperature was increased to 130 C. and the 1,1 ethylenedioxy 2,5 dimethyl 4 hexene which was thus formed, was distilled off. The compound had a boiling point of 120 C. at 50 mm. and lz :1.453l. It had a fruit-like green odor with a fine cacao-like side-note.
• EXAMPLE 9 38 grams or" 4-cyclohexylidene-l-butanal in 23 grams of ethanol and 38 grams of orthoformic acid ethyl ester were treated with 0.8 ml. of boron u'iliuoride etherate. The desired aeetalization reaction proceeded, exothermically, up to a temperature of 57 C. The 1,1-diethoxy-4- cyclohexylidene-butane, which was thus formed was obtained by distillation in high vacuum. The compound, having a boiling point of 87 C. at 0.08 mm. and iz 1.4602, had an original fresh-flowery odor.
• EXAMPLE 15 45 grams of 5,9-dimethyl-4,8-decadien-l-al in 220 ml. of acetone were hydrogenated by the procedure described in Example 14. About 11 liters of hydrogen were taken up. Pure 5,9-dimethyl-l-decanal was ohtained after the usual working up and distillation in high vacuum. The compound, boiling at 55 C. at 0.06 mm. and 12 1.4348, had a typical aldehydic long lasting odor with a new and interesting note.

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• 1963
  • 1963-07-18 CH CH895463A patent/CH422204A/de unknown
• 1964
  • 1964-05-15 DE DEH52690A patent/DE1235284B/de active Pending
  • 1964-06-04 NL NL6406295A patent/NL6406295A/xx unknown
  • 1964-07-07 US US380927A patent/US3381039A/en not_active Expired - Lifetime
  • 1964-07-16 BE BE650657D patent/BE650657A/xx unknown
  • 1964-07-17 ES ES0302225A patent/ES302225A1/es not_active Expired
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• 1967
  • 1967-12-06 US US688378A patent/US3428694A/en not_active Expired - Lifetime

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