US3381039A - 1, 1-diethoxy-4-cyclohexylidene butane - Google Patents
1, 1-diethoxy-4-cyclohexylidene butane Download PDFInfo
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- 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
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- 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
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- 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
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- 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
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- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- C11B9/00—Essential oils; Perfumes
- C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
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- 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.
Description
United States Patent 3,381,039 1,1-l)IETHGXYA-CYCLOHEXYLIDENE BUTANE Roman Marbet, Riehen, Switzerland, assignor to Holiniann-La Roche Inc., Nutley, N.J., a corporation of New Jersey N0 Drawing. Filed July 7, 1964, Ser. No. 380,927 Claims priority, application Switzerland, July 18, 1963, 8,954/63 1 Claim. (Cl. 260-611) This invention relates, in general, to a novel class of compounds and to a process for producing same. More particularly, the invention relates to novel derivatives of vat-unsaturated aldehydes and to methods for producing such derivatives.
The compounds of this invention are derivatives produced by the acetalization and/or catalytic hydrogenation of 'y,5-unsaturated aldeyhdes having the general formula R1( 3=( JCH2-CHCHO I in which R represents a hydrocarbon residue or an oxygen-containing hydrocarbon residue; R represents a lower alkyl group; and wherein R and R taken together, represent a carbocyclic radical; R represents a hydrogen atom .or a lower alkyl group and R represents a hydrogen atom or a lower hydrocarbon residue.
Representative of the 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. In a preferred embodiment of the invention, the symbol R represents an alkyl or alkenyl group having a straight or branched chain, such as, a methyl, ethyl, propyl, isopropyl, butyl, isobutyl group or a group having the formula II c =CH-CH OBI 3 LC r- J" in which It presents an integer from 1 to 3, and wherein the broken line represents an optional double bond.
Additionally, the symbol R as it appears in Formula I, represents alkyl and alkenyl groups, of the type mentioned heretofore, having oxygen-containing substituents. Thus, for example, 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. As examples of 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.
The symbol 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. The symbol 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. However, the preferred compounds of the invention contain a methyl group as the R alkyl substituent.
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.
Additionally, R and R of Formula I, when taken together, represent a ring structure, such as a S-member or a 6-member carbocyclic radical. For example, R and R taken together, represent a tetramethylene or pentamethylene group.
In the practice of this invention, 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 In a subsequent step of the process, the acetals of Formula II are hydrogenated or the aldehydes of Formula III are acetalized to yield a compound having the formula 1| R3 R4 0R5 R;-CH(JIICH2OHCHOR5 Iv In Formulas II, III and IV, 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. In general, 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. 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. In producing a di methyl acetal or a dipropyl acetal, it has been found advisable to use an excess of the alcohol reactant, that is, methanol or propanol respectively, in an excess amount to avoid the formation of the diethyl acetal. Thus, for example, in the preparation of a dimethyl acetal or dipropyl acetal, it is preferred to use a large excess'of alcoho1, namely, from about 10 to about 20 moles of alcohol per mole of aldehyde. Acetalization of the aldehyde using a glycol, particularly using ethylene glycol, is effected quite readily, even in the absence of a waterbinding agent.
In the hydrogenation step of the present process, one can use 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. Using such a catalyst, 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. In a preferred preparative method, 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.
The aldehydes of Formula I, which are used in the starting material in the practice of this invention, can be prepared by the acid-catalyzed reaction of a tertiary allyl alcohol of the formula R2 Rs 6 l R1lo=orr2 OH V in which the symbols R R and R have the same meaning as in Formula I,
with an aldehyde enol ether of the formula t Y HC=CHOR&
in which 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.
The 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.
For a fuller understanding of the nature and objects of this invention, reference may be had to the following examples which are given merely as illustrations of the in vention and are not to be construed in a limiting sense.
EXAMPLE 1 A solution of 140 mg. of p-toluenesulphonic acid in 280 ml. of methanol was added to a mixture of 28 grams of -methyl-4-hexen-1-al and 37 grams of ort'hoformic acid ethyl ester. The reaction was exothermic, the tem-. perature of'the reaction mixture reaching 33 C. After standing for a period of two hours, the reaction mixture was treated with 1.4 grams of sodium acetate and concentrated in a 50 C.-bath at 35 mm. Distillation of the residue, in vacuo, yielded 1, -dimethoxy-5-methyl-4-hexene, boiling point at 89 C. at 35 mm; 15 -14294. The compound has a characteristic fruit-like green odor.
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.
major portion of water present thereinwas thus removed. Thereafter, the pressure was reduced to '12 mm.- and there was thus obtained 1,1-ethylenedioxy-5-methyl-4- hexene [=1 (l,3-dioxo1an-2 yl) 4-methyl-3-pentene] as a colorless oil which was purified by repeated distillation. This compound had a boiling point at C. at 12 mm.; n =1.4512. The compound had an odor resembling 5- methyl-l-hexanal, but much finer.
EXAMPLE 3 63 grams of 2,5 dimethyl-4-hexen-l-al were mixed with 640 ml. of methanol, 75 grams of orthoformic acid ethyl ester and 1.5 ml. of boron trifluoride etherate. After 30 minutes the mixture was treated with 3 ml. of triethylamine and a fore-run was first distilled off at 13 mm. in a 50 C.-bath. Thereafter, there was obtained from a C.-bath, 1,1 dimethoxy 2,5 dimethyl 4 hexene which was purified by redistillation. This compound, boil ing point at 77 C. at 13 mm. and n =1.4343, had a harsh, fruit-like green odor.
EXAMPLE 4 63 grams of 2,5 dimethyl 4 hexen 1 al were mixed with 46 grams of ethanol, 75 grams of orthoformic acid ethyl ester and 1.7 ml. of boron trifluoride etherate. The temperature of the reaction mixture rose, exothermically, to 60 C. After two hours, the mixture was neutralized with 3.4 ml. of triethylamine and a fore-run was first distilled off at 14 mm. in a 50 C.-bath. Thereafter, 1,1 diethoxy 2,5 dimethyl 4 hexene was distilled off in a C.-bath. The compound, boiling point at 92 C. at 14 mm. and n =1.4321, had an odor similar to that of l,1-dimethoxy-2,5-dimethyl-4-hexene, but distinctly finer.
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. Subsequently, 1,1-di-n-propoxy- 2,5 dimethyl 4 hexene was distilled ofi using to C.-bath. The compound, thus obtained, had a 'boiling point of 113 to 114 C. at 13 mm. and n =1.4358. It had an odor which was finer and more flowery than 1,1-diethoxy-2,5-dimethyl-4-hexene.
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 second fore-run was separated off in a 100 C.- bath at 13 mm. and, subsequently, 1,1-di-n-butoxy-2,5- dimethyl-4-hexene was distilled off in high vacuum. That compound, which had a boiling point at 70 C. at 0.015 mm. and n =1.4392, had a fresh-flowery, faint odor.
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 8 A mixture of 180 g. of 5,9 dimethyl 4,8 decadien- 1 al, 62 "rams of ethylene glycol and 0.25 gram of ptoluenesulphonic acid was distilled, first in a 120 C.- bath at 13 mm. and then in high vacuum. There was thus obtained 1,1 ethylenedioxy 5,9 dimethyl 4,8-decadiene, boiling point at 91 C. at 0.02 mm. and ;1 =1.4738. This compound had a pleasant mellow odor, reminiscent of that of 5,9 dimethyl 4,8 decadiene 1 al, but is significantly finer and milder.
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 10 56 grams of 2 -pentyl 5 isobutyl4-hexen-1-al in 23 grams of ethanol and 38 grams of orthoformic acid ethyl ester were treated with 1 ml. of boron trifluoride etherate and worked up after 2 hours. There was thus obtained, 1,l-diethoxy-2-pentyl-5-isobutyl-4hexene, boiling point at 98 C. at 0.08 mm. and n =1.4452, having a faintly fatty odor.
EXAMPLE 11 A mixture of 46 grams of 5-methyl-7-acetoxy-4-heptenl-al, 15.5 grams of ethylene glycol and 60 mg. of p-toluene sulphonic acid was maintained at 13 mm. in a 120 C. bath. Thereafter, the 1,1-ethylenedioxy-5-methyl-7-acetoxy-4-hepten, which was thus formed, was recovered by distillation in high vacuum. The compound, having a boiling point of 92 C. at 0.05 mm. and n =1.4628, had a faint, fresh odor.
EXAMPLE 12 42.5 grams of 5,9-dimethyl-9-methoxy-4-decen l-al in grams of ethanol and grams of orthoformic acid ethyl ester were treated with 1 ml. of boron trifluoride etherate and worked up after a period of about two hours. There was, thus obtained,l,1-diethoxy- 5,9 dime'thyl-9- methoxy-4-decene, boiling point at 105 C. at 0.07 mm. and n =1.4476, having a smoky, faintly flowery-fatty odor.
EXAMPLE 13 lation. The compound, boiling point at 84 C. at mm. and n =1.4104, had a strong, fruitlike odor.
EXAMPLE 14 31.5 grams of 2,5-dimethyl-4-hexen-l-al were dissolved in 150 ml. of acetone, treated with 3.1 g. of a palladiumcarbon catalyst, identical to that described in Example 13, and the mixture was shaken in a hydrogen atmosphere. Approximately 2.5 liters of hydrogen were taken up within one hour. Thereafter, an additional 3.1 grams of palladium-carbon catalyst were added to the mixture, under an atmosphere of nitrogen gas, and the hydrogenation was continued for a period of 8 hours. During that time an additional 3 liters of hydrogen were taken up. There was, thus obtained, 2,5-dimethyl-1-hexanal, boiling point at 47 C. at 13 mm. and n =1.4142, having a fine and fruit-like 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.
EXAMPLE 16 38 grams of 4-cyclohexylidene-l-butanal in 200 ml. of acetone were hydrogenated, two times, using 3.8 grams of palladium-carbon catalyst, by the method described in Example 14. About 5.5 liters of hydrogen were taken up. The desired 5-cyclohexyl-1-butanal was obtained as a colorless oil after the usual working up and distillation in high vacuum. The compound, having a boiling point at 55 C. at 0.15 mm. and n =1.4595, had a complex odor which was fruit-like green and faintly alde-hydic.
EXAMPLE 17 25 grams of 5,9-dimethyl-9-hydroxy-4-decen-l-al in 150 ml. of acetone were hydrogenated in the presence of 2.5 grams of 5 percent palladium-carbon catalyst as described in Example 13. About 3 liters of hydrogen were taken up. There was thus obtained 5,9-dimethyl-9-hydroxy-l-decanal as a colorless oil after the usual working up and disstillation in high vacuum. The compound had a boiling point at 99 C. at 0.04 mm. and n ==1.4573 and a faint, but pleasant, fresh-flowery odor.
EMMPLE 18 26.5 grams of 5,9-dimethyl-9-methoxy-4-decen-l-al in 150 ml. of acetone were hydrogenated in the presence of 2.6 grams of 5 percent palladium-carbon catalyst, as described in Example 13. About 3 liters of hydrogen were taken up. After the customary working up, there was obtained 5,9-dimethyl-9-methoxy-l-decanal, boiling point at 78 C. at 0.03 mm. and n =1.4442. The compound had a fine and flowery odor.
EXAMPLE 19 (a) 32 grams of 2,5-dimethyl-1-hexanal, produced as described in Example 14, were worked up by the method of Example 1 with 37 grams of orthoformic acid ethyl ester, 280 m1. of methanol and mg. of p-toluene sulphonic acid. There was thus obtained, l,l-dimethoxy-2,5- dimethyl-hexane, boiling point at 72 C. at 13 mm. and n =1.4l54, having a flowery, slightly fruit-like green odor.
(b) The same compound was obtained by the hydrogenation of 1,1-dimethoxy-2,5-dimethyl-4-hexene by the process described in Example 13. The starting 1,1-dimethoxy-2,5-dimethyl-4-hexene was produced as described in FOREIGN PATENTS Exampl? 960,003 6/1964 Great Britain.
I clam.
1. 1,l-diethoXy-4-cyclohexy1idcue-butane. OTHER REFERENCES References Cited 5 Hill et al.: Journal of the American Chemical Soc., UNITED STATES PATENTS 74 (1952) 166-167 2,816,117 12/1957 CaWley 260 4 ALEX MAZEL, Primary Examiner.
2,852,563 9/1958 Hagemeyer et al. 260601 2 9 2 534 11 19 0 Montagna fit 1 26Q 6()] 10 J. H. TURNIPSEED, Assistant Examiner.
Claims (1)
1. 1,1-DIETHOXY-4-CYCLOHEXYLIDENE-BUTANE.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US775915A US3584010A (en) | 1964-07-07 | 1968-11-14 | 1,1-ethylenedioxy-5-9-dimethyl-4,8-decadiene |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH895463A CH422204A (en) | 1963-07-18 | 1963-07-18 | Fragrances |
Publications (1)
Publication Number | Publication Date |
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US3381039A true US3381039A (en) | 1968-04-30 |
Family
ID=4346691
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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US380927A Expired - Lifetime US3381039A (en) | 1963-07-18 | 1964-07-07 | 1, 1-diethoxy-4-cyclohexylidene butane |
US688378A Expired - Lifetime US3428694A (en) | 1963-07-18 | 1967-12-06 | 1,1-dialkoxy substituted alkenes |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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US688378A Expired - Lifetime US3428694A (en) | 1963-07-18 | 1967-12-06 | 1,1-dialkoxy substituted alkenes |
Country Status (9)
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US (2) | US3381039A (en) |
BE (1) | BE650657A (en) |
CH (1) | CH422204A (en) |
DE (1) | DE1235284B (en) |
DK (1) | DK110021C (en) |
ES (1) | ES302225A1 (en) |
GB (3) | GB1025047A (en) |
NL (1) | NL6406295A (en) |
SE (1) | SE316161B (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3896150A (en) * | 1971-09-02 | 1975-07-22 | Basf Ag | 2,6,10-trimethyldodeca-2,6,11-trien-10-ol-1-al-2,6-dimethyl-2,6-undecadien-10-on-1-al and their acetals and processes for their production |
US4191842A (en) * | 1975-01-27 | 1980-03-04 | Hoffmann-La Roche Inc. | Protected alcohols |
US4657926A (en) * | 1983-05-25 | 1987-04-14 | National Research Development Corporation | Behavior modifying compounds |
US5136061A (en) * | 1990-06-14 | 1992-08-04 | Asahi Denka Kogyo K.K. | Optically active pentane derivatives and intermediates thereof, and process for manufacturing same |
US5243096A (en) * | 1990-06-14 | 1993-09-07 | Asahi Denka Kogyo K.K. | Optically active pentane derivatives and intermediates thereof, and process for manufacturing same |
US10450532B2 (en) | 2014-12-09 | 2019-10-22 | Givaudan S.A. | Organic compounds and their use as fragrance ingredients |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1905258A1 (en) * | 1969-02-04 | 1970-08-06 | Dynamit Nobel Ag | Ketonitriles and process for their preparation |
NL143271B (en) * | 1969-02-04 | 1974-09-16 | Naarden International Nv | PROCESS FOR THE PREPARATION OF FRAGRANCE COMPOSITIONS. |
US4107217A (en) * | 1973-07-30 | 1978-08-15 | International Flavors & Fragrances Inc. | Acetals of conjugated alkenals |
GB1515049A (en) * | 1976-10-22 | 1978-06-21 | Ici Ltd | Preparation of halogenated aldehydes |
DE2832699A1 (en) * | 1978-07-26 | 1980-02-14 | Basf Ag | METHOD FOR PRODUCING SATURED ALIPHATIC, CYCLOALIPHATIC AND ARALIPHATIC ALDEHYDES |
US4379754A (en) | 1980-12-04 | 1983-04-12 | International Flavors & Fragrances Inc. | Aliphatic branched olefin dioxolanes, dithiolanes, and oxathiolanes and uses thereof in augmenting or enhancing the aroma and/or taste of consumable materials |
DE3341605A1 (en) * | 1983-11-17 | 1985-05-30 | Consortium für elektrochemische Industrie GmbH, 8000 München | ALPHA-TERTIAERE DIMETHYLACETALE, THEIR PRODUCTION AND USE AS A FRAGRANCE |
EP0738700A4 (en) * | 1993-12-17 | 1997-05-02 | Nippon Zeon Co | Cis-3-hexenal cis-3-hexenyl acetal compound, process for producing the same, and flavor/taste imparting agent, flavor/taste retaining agent and perfume composition each containing the same |
US9850191B2 (en) | 2015-03-27 | 2017-12-26 | International Flavors & Fragrances Inc. | Aldehyde compounds and their use in perfume compositions |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2816117A (en) * | 1957-12-10 | Chi ch | ||
US2852563A (en) * | 1955-10-17 | 1958-09-16 | Eastman Kodak Co | Condensation of isoaldehydes with lower aliphatic aldehydes |
US2962534A (en) * | 1957-04-10 | 1960-11-29 | Union Carbide Corp | Preparation of unsaturated ethers |
GB960003A (en) * | 1959-09-25 | 1964-06-10 | Gulf Research Development Co | Process for condensing an aldehyde with a compound containing at least two active hydrogen atoms on the same carbon atom |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2583112A (en) * | 1950-12-22 | 1952-01-22 | Rohm & Haas | Process for the oxidation of acetals to acids |
US3010997A (en) * | 1958-06-23 | 1961-11-28 | Shell Oil Co | 2, 6-dimethyloct-2-en-1, 8-dial and process of manufacture |
-
1963
- 1963-07-18 CH CH895463A patent/CH422204A/en unknown
-
1964
- 1964-05-15 DE DEH52690A patent/DE1235284B/en 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 SE SE8735/64A patent/SE316161B/xx unknown
- 1964-07-17 DK DK356864AA patent/DK110021C/en active
- 1964-07-17 ES ES0302225A patent/ES302225A1/en not_active Expired
- 1964-08-04 GB GB49150/65A patent/GB1025047A/en not_active Expired
- 1964-08-04 GB GB30586/64A patent/GB1025045A/en not_active Expired
- 1964-08-04 GB GB49149/65A patent/GB1025046A/en not_active Expired
-
1967
- 1967-12-06 US US688378A patent/US3428694A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2816117A (en) * | 1957-12-10 | Chi ch | ||
US2852563A (en) * | 1955-10-17 | 1958-09-16 | Eastman Kodak Co | Condensation of isoaldehydes with lower aliphatic aldehydes |
US2962534A (en) * | 1957-04-10 | 1960-11-29 | Union Carbide Corp | Preparation of unsaturated ethers |
GB960003A (en) * | 1959-09-25 | 1964-06-10 | Gulf Research Development Co | Process for condensing an aldehyde with a compound containing at least two active hydrogen atoms on the same carbon atom |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3896150A (en) * | 1971-09-02 | 1975-07-22 | Basf Ag | 2,6,10-trimethyldodeca-2,6,11-trien-10-ol-1-al-2,6-dimethyl-2,6-undecadien-10-on-1-al and their acetals and processes for their production |
US4191842A (en) * | 1975-01-27 | 1980-03-04 | Hoffmann-La Roche Inc. | Protected alcohols |
US4657926A (en) * | 1983-05-25 | 1987-04-14 | National Research Development Corporation | Behavior modifying compounds |
US4780479A (en) * | 1983-05-25 | 1988-10-25 | National Research Development Corporation | Insect behavior modifying compounds |
US5136061A (en) * | 1990-06-14 | 1992-08-04 | Asahi Denka Kogyo K.K. | Optically active pentane derivatives and intermediates thereof, and process for manufacturing same |
US5243096A (en) * | 1990-06-14 | 1993-09-07 | Asahi Denka Kogyo K.K. | Optically active pentane derivatives and intermediates thereof, and process for manufacturing same |
US10450532B2 (en) | 2014-12-09 | 2019-10-22 | Givaudan S.A. | Organic compounds and their use as fragrance ingredients |
EP3230245B1 (en) * | 2014-12-09 | 2020-06-10 | Givaudan SA | Improvements in or relating to organic compounds and their use as flagrance ingredients |
Also Published As
Publication number | Publication date |
---|---|
SE316161B (en) | 1969-10-20 |
NL6406295A (en) | 1965-01-19 |
DK110021C (en) | 1968-08-26 |
GB1025047A (en) | 1966-04-06 |
DE1235284B (en) | 1967-03-02 |
GB1025045A (en) | 1966-04-06 |
CH422204A (en) | 1966-10-15 |
ES302225A1 (en) | 1965-01-16 |
GB1025046A (en) | 1966-04-06 |
US3428694A (en) | 1969-02-18 |
BE650657A (en) | 1965-01-18 |
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