US3857898A - 1-(3{40 -hexenyl)-1-cycloalkanols - Google Patents

1-(3{40 -hexenyl)-1-cycloalkanols Download PDF

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US3857898A
US3857898A US00212780A US21278071A US3857898A US 3857898 A US3857898 A US 3857898A US 00212780 A US00212780 A US 00212780A US 21278071 A US21278071 A US 21278071A US 3857898 A US3857898 A US 3857898A
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hexenyl
compounds
cycloalkanols
fragrances
compound
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US00212780A
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A Schleppnik
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Monsanto Co
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Monsanto Co
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C35/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
    • C07C35/06—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a five-membered rings
    • 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
    • C07C403/02—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 containing only carbon and hydrogen atoms
    • 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

  • This invention relates to the art of fragrance compositions and, more particularly, to a novel class of compounds possessing a' characteristic aroma. More specifically, this invention is directed to a novel class of useful compounds, their preparation and the utility of these compounds as fragrances or as components in fragrance compositions.
  • perfumery began, perhaps, in the ancient cave dwellings of prehistoric man. From its inception. and until comparatively recently, the perfumer has utilized natural perfume chemicals of animal and vegetable origin. Thus, natural perfume chemicals such as the essential oils, for example, oil of rose and oil of cloves, and animal secretions such as musk, have been manipulated by the perfumer to achieve a variety of fragrances. In more recent years, however, research perfume chemists have developed a large number of synthetic odoriferous chemicals possessing aroma characteristics particularly desired in the art.
  • the principal object of the present invention is to provide a new class of aroma chemicals consisting of l-(3'-hexenyl)-l-cy'cloalkanols and their esters.
  • Another object of the present invention is to provide a specific class of compounds having a characteristic aroma which is utilized inthe preparation of fragrances and fragrance compositions.
  • These compounds have very pleasant, strong and long lasting green, floral, rosy aromas and are useful as fragrances or as components in fragrance compositions.
  • alkyl groups characterized by R in the above formula include methyl, ethyl, n-propyl, ipropyl, n-butyl, i-butyl, tert-hutyl, n-amyl, i-amyl, tertamyl, n-octyl.
  • Groups other than alkyl characterized by R in the above formula include phenyl, napthyl and phenylalkyl and. the like.
  • n has the same meaning as defined hereinbe fore, with 3-hexenyl magnesium halides as illustrated in the following equation (wherein X represents a halogen, chlorine, bromine or iodine):
  • novel esters of this invention can be prepared by reacting the l-(3'-hexenyl)-l-cyeloalkanols with an appropriate organic acid as illustrated in the following equation:
  • the reaction conditions are not critical but should be such as to facilitate the preparation of the products.
  • the Grignard reaction is normally conducted at a temperature of from ambient temperatures upto about C. and the esterification reaction is norm ally conducted within this same range.
  • novel compounds of this invention are useful as fragrances in the preparation and formulation of fragrance compositions such as perfumes and perfumed products due to their pleasing, strong and long lasting aroma.
  • these novel compounds can be utilized as the primary fragrance in many such compositions.
  • the compounds of this invention are used in concentrations of from trace amounts up to about 50 percent of the fragrance composition into which they are incorporated. As will be expected, the concentration of the compound will vary depending on the particular fragrance desired in the composition and even within the same composition when compounded by different perfumers.
  • EXAMPLE 1 l( 3 -hexenyl )-l -cyclopentanol 12.2 grams of magnesium were mixed with 50 ml. of anhydrous tetrahydrofuran and activated with 0.5 ml. of methyl iodide. To this mixture was added a solution of 59.3 grams (0.5 moles) of cis-l-chloro-B-hexene in I50 ml. of tetrahydrofuran. The hexene solution was added drop-wise with stirring. A greenish turbid solution formed but no exothermic reaction took place. The reaction was initiated by warming the mixture containing about one-third of the halide solution to 55C. and adding a few drops of methyl iodide. A fast exothermic reaction started which was controlled with a cold water bath to keep the temperature at about 50C. A clear brown solution formed.
  • EXAMPLE 4 The compounds of Examples 1, 2 and 3 can be reacted with equimolar amounts of acetic anhydride in pyridine to form the acetate ester of the cycloalkanols.
  • n is an integer of from 1 to 3.
  • a compound as defined in claim 1 which is l-(3- hexenyl)-l-cyclopentanol.
  • a compound as defined in claim 1 which is l-(3'- hexenyl)-l-cyclohexanol.

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

Abstract

1-(3''-Hexenyl)-1-cycloalkanols and their esters characterized by the structural formula

WHEREIN R represents hydroxyl or R1COO-, wherein R1 represents alkyl having from one to eight carbon atoms, aryl or aralkyl and n is an integer from one to 3. These compounds can be in the cis or trans forms or mixtures thereof. The compounds have very pleasant, strong and long lasting green, floral, rosy aromas and are useful as fragrances or as components in fragrance compositions.

Description

United States Patent [191 Schleppnik Dec. 31, 1974 l-(3 -IIEXENYL)-l-CYCLOALKANOLS [75] Inventor: Alfred A. Schleppnik, St. Louis, Mo.
[73] Assignee: Monsanto Company, St. Louis, Mo.
[22] Filed: Dec. 27, 1971 [21] Appl. No.: 212,780
[52] U.S. Cl. 260/617 R,'252/522, 260/476 R, 260/488 R, 260/617 M, 260/631 R [51] Int. Cl... C07c 35/06, C07c 35/08, C070 35/20 [58] Field of Search 260/617 R, 617 M, 631, 260/631 R [56] References Cited OTHER PUBLICATIONS Johnson et a1., J, Org. Chem., Vol. 30, pp. 1785 & 1786, (1965). Newman, Tetrahedron Letters, No. 47, pp. 4571 and 4572 (1971). Marvel et al., J. Am. Chem. Soc, Vol. 63, pp. 2630-2632 (1941). Schulte et a1., Chem. Abstracts," Vol. 53, p. 259C (1959). Pallaud et a1., CR. Acad. Sci., Paris, T265, pp. 1479-1482 (Dec. 18, 1967).
Moncrieff, The Chemistry of Perfumery Materials," United Trade Press, London, pp. 13-15 (1949).
Primary Examiner.loseph E. Evans Assistant Examiner-D. B. Springer 'Attorney, Agent, or Firm-H. C. Stanley; J. E. Maurer; N. E. Willis [5 7] ABSTRACT 1 (3'-I-1exeny1)-l-cyc1oalkano1s and their esters characterized by the structural formula R CH CHzCH=CHCH1CIh wherein R represents hydroiIFSrRCOO- wherein 4 Claims, No Drawings l-(3'-HEXENYL)-l-CYCLQALKANQLS This invention relates to the art of fragrance compositions and, more particularly, to a novel class of compounds possessing a' characteristic aroma. More specifically, this invention is directed to a novel class of useful compounds, their preparation and the utility of these compounds as fragrances or as components in fragrance compositions.
The art of perfumery began, perhaps, in the ancient cave dwellings of prehistoric man. From its inception. and until comparatively recently, the perfumer has utilized natural perfume chemicals of animal and vegetable origin. Thus, natural perfume chemicals such as the essential oils, for example, oil of rose and oil of cloves, and animal secretions such as musk, have been manipulated by the perfumer to achieve a variety of fragrances. In more recent years, however, research perfume chemists have developed a large number of synthetic odoriferous chemicals possessing aroma characteristics particularly desired in the art. These synthetic aroma chemicals have added a new dimension to the ancient art of the perfumer, since the compounds prepared are usually of a stable chemical nature, are inexpensive as compared with the natural perfume chemicals and lend themselves more easily to manipulation than natural perfume chemicals since such natural perfume chemicals are usually a complex mixture of substances which defy chemical analysis. In contrast thereto, the synthetic aroma chemicals possess a known chemical structure and may therefore be manipulated by the perfumer to suit specific needs. Accordingly, there is a great need in the art of fragrance compositions for new compounds possessing specific characteristic aromas.
The principal object of the present invention is to provide a new class of aroma chemicals consisting of l-(3'-hexenyl)-l-cy'cloalkanols and their esters.
Another object of the present invention is to provide a specific class of compounds having a characteristic aroma which is utilized inthe preparation of fragrances and fragrance compositions.
These and other objects, aspects and advantages of this invention will become apparent from a consideration of the accompanying specification and claims.
In accordance with the above objects, there is provided by the present invention a novel class of compounds characterized by the structural formula R CHzCI-h CH: CHCHzCHa wherein R represents hydroxyl or R'C00, wherein R represents alkyl having from one to eight carbon atoms, aryl and aralkyl and n is an integer from 1 to 3.
These compounds have very pleasant, strong and long lasting green, floral, rosy aromas and are useful as fragrances or as components in fragrance compositions.
Representative alkyl groups characterized by R in the above formula include methyl, ethyl, n-propyl, ipropyl, n-butyl, i-butyl, tert-hutyl, n-amyl, i-amyl, tertamyl, n-octyl.
Groups other than alkyl characterized by R in the above formula include phenyl, napthyl and phenylalkyl and. the like.
wherein n has the same meaning as defined hereinbe fore, with 3-hexenyl magnesium halides as illustrated in the following equation (wherein X represents a halogen, chlorine, bromine or iodine):
(Cl'mr CIIaCIhCII=C1ICIhCIIiMgX DiF HO CH2CHzCH=CHCHzCH3 The novel esters of this invention can be prepared by reacting the l-(3'-hexenyl)-l-cyeloalkanols with an appropriate organic acid as illustrated in the following equation:
wherein R and n have the same meaning as defined hereinabove.
The reaction conditions are not critical but should be such as to facilitate the preparation of the products. Thus, the Grignard reaction is normally conducted at a temperature of from ambient temperatures upto about C. and the esterification reaction is norm ally conducted within this same range.
The novel compounds of this invention are useful as fragrances in the preparation and formulation of fragrance compositions such as perfumes and perfumed products due to their pleasing, strong and long lasting aroma. Perfume compositions and the use thereof in cosmetic, detergent and bar soap formulations and the CHzCHz CH=CHCH2CH3 like are exemplary of the utility thereof. Likewise, these novel compounds can be utilized as the primary fragrance in many such compositions.
The compounds of this invention are used in concentrations of from trace amounts up to about 50 percent of the fragrance composition into which they are incorporated. As will be expected, the concentration of the compound will vary depending on the particular fragrance desired in the composition and even within the same composition when compounded by different perfumers.
The following examples will serve toillustrate certain specific embodiments within the scope of this invention and are not to be construed as limiting the scope thereof.
EXAMPLE 1 l( 3 -hexenyl )-l -cyclopentanol 12.2 grams of magnesium were mixed with 50 ml. of anhydrous tetrahydrofuran and activated with 0.5 ml. of methyl iodide. To this mixture was added a solution of 59.3 grams (0.5 moles) of cis-l-chloro-B-hexene in I50 ml. of tetrahydrofuran. The hexene solution was added drop-wise with stirring. A greenish turbid solution formed but no exothermic reaction took place. The reaction was initiated by warming the mixture containing about one-third of the halide solution to 55C. and adding a few drops of methyl iodide. A fast exothermic reaction started which was controlled with a cold water bath to keep the temperature at about 50C. A clear brown solution formed.
To this solution a solution of 42.1 grams (0.5 moles) of cyclopentanone in 70 ml. ether can be added at such a rate that the mixture will reflux gently. After the addition is completed the product obtained, after fractional distillation, will be l-(3'-hexenyl)-l-cyclopentanol.
EXAMPLE 2 l 3 '-hexenyl l -cyclohexanol Following a procedure similar to the precedure described in Example 1 but substituting cyclohexanone for cyclopentanone results in the formation of the title compound.
stituting cycloheptanone for cyclopentanone results in the formation of the title compound.
EXAMPLE 4 The compounds of Examples 1, 2 and 3 can be reacted with equimolar amounts of acetic anhydride in pyridine to form the acetate ester of the cycloalkanols.
While the invention has been described herein with regard to certain specific embodiments, it is not so limited. [t is to be understood that variations and modifications thereof may be made by those skilled in the art without departing from the spirit and scope of the invention.
The embodiments of this invention in which an exclusive property or privilege is claimed and defined as follows:
l. A compound characterized by the structural formula wherein n is an integer of from 1 to 3.
2. A compound as defined in claim 1 which is l-(3- hexenyl)-l-cyclopentanol.
3. A compound as defined in claim 1 which is l-(3'- hexenyl)-l-cyclohexanol.
4. A compound as defined in claim 1 which is l-(3-

Claims (4)

1. A COMPOUND CHARACTERIZED BY THE STRUCTURAL FORMULA
2. A compound as defined in claim 1 which is 1-(3''-hexenyl)-1-cyclopentanol.
3. A compound as defined in claim 1 which is 1-(3''-hexenyl)-1-cyclohexanol.
4. A compound as defined in claim 1 which is 1-(3''-hexenyl)-1-cycloheptanol.
US00212780A 1971-12-27 1971-12-27 1-(3{40 -hexenyl)-1-cycloalkanols Expired - Lifetime US3857898A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009093175A1 (en) * 2008-01-22 2009-07-30 Firmenich Sa Perfuming ingredients imparting sap and/or earthy type notes

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
Johnson et al., J. Org. Chem., Vol. 30, pp. 1785 & 1786, (1965). *
Marvel et al., J. Am. Chem. Soc., Vol. 63, pp. 2630 2632 (1941). *
Moncrieff, The Chemistry of Perfumery Materials, United Trade Press, London, pp. 13 15 (1949). *
Newman, Tetrahedron Letters, No. 47, pp. 4571 and 4572 (1971). *
Pallaud et al., C.R. Acad. Sci., Paris, T265, pp. 1479 1482 (Dec. 18, 1967). *
Schulte et al., Chem. Abstracts, Vol. 53, p. 259C (1959). *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009093175A1 (en) * 2008-01-22 2009-07-30 Firmenich Sa Perfuming ingredients imparting sap and/or earthy type notes
US20100291016A1 (en) * 2008-01-22 2010-11-18 Firmenich Perfuming ingredients imparting sap and/or earthy type notes
CN101918345A (en) * 2008-01-22 2010-12-15 弗门尼舍有限公司 Perfuming ingredients imparting sap and/or earthy type notes
JP2011514388A (en) * 2008-01-22 2011-05-06 フイルメニツヒ ソシエテ アノニム Perfuming ingredients that give sap and / or earthy notes
US8178732B2 (en) 2008-01-22 2012-05-15 Firmenich Sa Perfuming ingredients imparting sap and/or earthy type notes

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