CA1097687A - 5-cyclohexadecene-1-one and process for its preparation - Google Patents

5-cyclohexadecene-1-one and process for its preparation

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Publication number
CA1097687A
CA1097687A CA121,608A CA121608A CA1097687A CA 1097687 A CA1097687 A CA 1097687A CA 121608 A CA121608 A CA 121608A CA 1097687 A CA1097687 A CA 1097687A
Authority
CA
Canada
Prior art keywords
cyclohexadecene
halocyclododecanone
process according
heating
temperature ranging
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA121,608A
Other languages
French (fr)
Other versions
CA121608S (en
Inventor
Akihisa Miyake
Masaki Nishino
Hisao Kondo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Takasago International Corp
Toray Industries Inc
Original Assignee
Toray Industries Inc
Takasago Perfumery Industry Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toray Industries Inc, Takasago Perfumery Industry Co filed Critical Toray Industries Inc
Application granted granted Critical
Publication of CA1097687A publication Critical patent/CA1097687A/en
Expired legal-status Critical Current

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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
    • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
    • C11B9/0038—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing more than six carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
    • 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
    • C07C45/512—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 a free hydroxyl group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered

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

Abstract

Abstract 5-cyclohexadecene-1-one, a new compound suitable for use as an odor modifier, is prepared by heat treating 1,2-divinylcyclododecane-1-ol obtained by reacting 2-halocyclododecanone with vinyl magnesium halide.

Description

76~7 me present invention relates to a novel cyclic ketone, 5-cyclo-hexadecene-L-one, which is useful as an odor modifying substance and a fixative in its own right, and as an intermediate for the preparation of other odor forming or modifying materials.
Heretofore, 15 - 18 memkered cyclic ketones have been characterized by a musk-like odor. Differences of the quality or magnitude of the odor are caused by slight differences of chemical structure of the cyclic ketone. For example, the existence of a double bond (L. Ruzicka et al, Helv. Chim. Acta.
15, 1459 [1932]), the position of the double bond tG. Ohloff, Fortschr. Chem.
Forsch. 12, lR5 [1969]), and the position and type of functional group (G. Ohloff, Fortschr. Chem. Forsch., 12, 185 [1969]), have a bearing on this property.
Among these cyclic ketones, 16-membered cyclic ketones have attracted much attention as compounds having a characteristic musk-like odor. As to processes for preparing the same, processes described in L. Ruzicka et al, Helv.
Chim. Acta, 15, 1459 [1932); K. Ziegler et al. Ann, 513, 43 [1943] and U.S.
Patent 2,584,664 have been proposed. However, each of these processes has the drawbacks that the reaction requires complicated steps and that the to~al yield is low.
The present invention relates to a novel unsaturated 16-membered cyclic ketone namely 5-cyclohexadecene l-one having a unique musk-like odor and to a process for the preparation thereof from an easily available starting material with simple reaction steps and a high yield.
Thus, according to this invention, 5-cyclohexadecene-1-one is prepared by heating 1,2-divinylcyclododecane-1-ol, preferably at a temperature ranging from about 150C to 350C.
The novel L6-membered cyclic ketone of the present invention is preferably prepared by reacting a 2-halocyclododecanone with a vinyl magnesium halide, hydrolyzing the reaction product, and heating the 1,2-divinylcyclo-~` dodecane-l-ol thus obtained.
The molar ratio of vinylmagnesium halide to 2-halocyclododecanone in this reaction may be in the range from about 1.5:1 to 10:1 or still higher, but to obtain a high yield, it is preferahle that it be at least about 2:1.

The reaction temperature preferably ranges from about -50C to 150C, and ,, ,,.~ .,~,,.
i,: , , .
,: , .
~, .

76~3~

normally it is preferable to carry out the initial stage of the reaction at a temperature ranging from about -50C to 30C and the final stage of the re-action at a temperature ranging from about 50C to L50C.
'rhe reaction is preferably carried out using as a solvent an ether such as ethylether, tetrahydrofurane, methyltetrahydrofurane, tetrahydropyrane, methylpentylether, dibutylether, anisole, diethyleneglycol diethylether and benzylmethylether or hydrocarbons such as benzene, toluene, xylene, hexane and heptane, for example.
The temperature at which the resuLting 1,2-divinylcyclododecane-1-ol is heated to prepare 5-cyclohexadecene-1-one may be about 150-350C, preferably about 170-250C.
At the time of heating, it is not particularly necessary to use a solvent. However, it is also possible to use a high boiling solvent like hydro-carbons such as decahydronaphthalene and cyclododecane or alcohols such as n-octanol and 2-ethyLhexanol.
As the halogen portion of the 2-halocyclododecanone and vinyl magnesium halide that are the starting materials of the present invention, chlorine, bromine and iodine may be used, however, chlorine and bromine are especially preferable.
The process of the present invention, from the starting material,
2-halocyclododecanone (I) to 5-cyclohexadecene-1-one (III) via 1,2-divinyl-cyclododecane-l-ol (II), occurs as follows. The double bond in the 5-position -~ of (III) may have a cis- or a trans-configuration. ~ tL~r5-cyclohexa-decenone produced by the present invention is a mixture of trans-5-cyclohexa-decenone and cis-5-cyclohexadecenone.
~; ~ ~3 CH=CH2 X ¦ (2) H2O

r ~ ~ ~ Lf .H 2 (III) (II) (X:halogen) '~ - -2 , ~0~7f6B7 5-cyclohexadecenone of the present invention has a distinctive musk-like odor which is clearly differen~ and conslderably stronger than that ke~o~-s of the other 16-membered cyclic ~ 3Res already known; cyclohexadecanone, 2-cyclohexadecenone, 8-cyclohexadecenone, etc. 5-cyclohexadecenone may, there-fore, bu used as a novel and unique odor forming or modifying agent or fixative, and may be compounded into odoriferous compositions in a manner conventional in the perfumery art. Such odoriferous compositions usually contain 0.1 - 50%
of 5-cyclohexadecenone and are useful for incor~oration into perfumes, cosmetics, soaps, etc.

~lso, 5-cyclohexadecene-1-one may be converted to cyclohexadecanones or lactones which are already known ~o be useful as odor forming agen~s and fixatives.
Preferred embodiments o ~he present invention are shown by way of ~he following examples.
Example 1 Into 25 ml of tetrahydrofurane tT~IF), 6.5 g of 2-chloro cyclododec-anone were dissolved, and the resultant solution was added dropwise to 35 ml of a T~IF solution ~2.06N) of vinyl magnesium chloride in 30 minutes while stirring. After the resulting mixture was stirred at room temper~ture for one hour, it was stirred ak 55C for 17 hours. After completion of the reaction, a saturated aqueous solu~ion of 3.0 g of ammonium hydrochlorlde was added at 0C to the reac~ion product, and 500 ml of water was urther added ~hereto.
rhe resultant solution waS extracted twice by 100 ml o ether. After washing an ether layer wlth a satura~ed a~ueous solution o sodium chloride, s~id layer ; was dried with anhydrous sodium sulfate. After distilling off the ether, the remaining liq~id was distilled in vacuo to obtain 5.5 g of a compound having a boiling point of 90 - 100C at 0.~05 mm Hg ~absolute). By further fractionating the r~sulting product, it was possible to produce 1,2-divinylcyclododecane~l-Ql havin~ a boiling poin~ of 112 - 114C at 0.2 mm Hg absolute, the infrared spectrum of which showed a characteristic absorption of the vinyl group at 3080 cm, 1640 cm, 990 cm and 915 cm, in the MMR spectrum of which two kinds of ABX type spectra were recognized in the range o~ ~ = 6.0 - 4.8 ppm, showing , .

' ~ :

, the presence of ~wo vinyl groups. When this 1,2-divinylcyclododecanol was further purified by silica gel chromatography~ i~ became solid (recrystallized from pentane) having a melting point of 50.5 - 52C and elemental analysis as shown below.
Found: C ~ 0% ~l 11.89 Calculated for C16 28 C 81.29~ ~1 11.94~
From the mass spectrum, the molecular ~eight was 236 (calculated value 236.38).
D For the purpose of synthesizing~cyclohexadecenone, the compound having a boiling point of 90 - 100C/0.005 mm Hg obtained in the aforementioned reaction was directly heated at 190C for 1 hour without being further purified.An oily campound, obtained by distillation after the reaction, was dissolved in 10 ml of ethanol and the resulting solution was mixed with a solution of semicarbazide hydrochloride (2.5 g) and sodium acetate ~2.2 g) in 5 ml of water.Immediately, white crystals began to crystallize. After 10 minutes, the crystals were sepaTated by filtration to obtain 4.8 g of 5-cyclohexadecene-1-one semica~bazone, which was recrystallized from ethanol to be purified. ~he melting point was 179.5 - 181.5C ~nd its elemental analysis IS shown below.
Found: C 69.57 H 10.78 N 14.29 Molecular 300 Weight Calculated for Cl ~ 31N30: C 69~58 H 10.65 N 14.32 Molecular 293.44 ; Pure 5-cyclohexadec~none was obtained quanti~a~iYely by hydrolyz-ing the semicarbazone in the presence of an aqueous solution o~ oxalic acid.
This compound had a boiling point of 115C/0.03 mm Hg, a melting point of 21 -23JC and an n2D5 of 1.~865 and an elemental analysis as shown below.
Found: C 81.01 H. 11.72 Molecular weight 232 Calculated for C16H~80: C 81.29 H 11.94 Molecular weight 236.38 From the mass spectrum, the molecular weight was 236.
The 5-cyclohexadecenone obtained above is a mixture of trans- 2nd cis 5-cyclohexadecenone. By hydrogenating 5-cyclohexadecene l-one în the presence of a Pd - carbon catalyst, cyclohexadec~none was obtained. The semi-' carbazone obtained from the hydrogenated product is identical ~lith that of an established and proved cyclohexadecanone and shows no melting point depression (185.5 - 187.0C) when mixed wi~h an established and proved semicarbazone of cyclohexadecanone. When 5-cyclohexadecene-1-one was ozoni~ed and further oxidized with maganese peroxide in an alkaline condition, dodecane-dicarboxylic acid, nonanedicarboxylic acid~ sebacic acid, glutaric acid and succinic acid were obtained.
Ex~mple 2 To a THF solu~ion ~1.75 N, 38 ml) of vinylmagnesium bromide, 6.5 g of 2-chlorocyclododecanone dissolved in 40 ml of benzene was added dropwise at O~C. After the dropping, the reaction mixture was refluxed for 3 hours and 40 minutes. 3.3 g of 5-cyclohexadecenone-semicarbazide was obtained in the same way as in Example 1. The semica~bazone was hydrolyzed with aqueous sulfuric acid to give quantitatively pure 5-cyclohexadecenone.
Example 3__ To 30 ml of a ~IF solution (2006 N) of vinylmagnesium chloride, 20 ~1 of a T~I~ solution having dissolved 7.9 g of 2-bromo-cyclododecanone was added dropwise, and the resultant solution was stirred at 55C for 20 hours.
The resulting system containing 1,2-divinylcyclododecane-1-ol was treated in the same manner as in ~xample 1 to obtain 3.8 g of 5-cyclohexadecene-1-one semicarbazone~ which was treatet in accordance, by ordinary heating, in an S-aqueous solution of oxalic acid to obtain pure7cyclohexadecene-1-one quanta-tively.

An odoriferous composition having the following composition can be used for soaps.
Geraniol (28 parts), phenylethyl alcohol tl5), linalool ~6), geranyl acetate (4~, pheny1ethyl acetate t4~. geranium oil (15), cinnamyl alcohol ~3), diphenyl oxide (2)) patchouly oil ~3) guaiac wood oil t6), rose phenone (4), linalyl butyrate ~2), a-ionone ~4), geranyl butyrate (3) and S-cyclohexadecene-l-one ~2).
This odoriferous composition has a superior odoriferous quality . ., ' ~g7687 and longer las~ing odor when compared to similar previo~sly known soap compositions, for instance, a composition as abo~e but containing 2 parts of musk ambrette instead of 5-cyclohexadecenone.

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Claims (8)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of 5-cyclohexadecene-1-one which comprises heating 1,2-divinylcyclododecane-1-ol.
2. A process according tociaimlin which 1,2-divinylcyclodecane-1-ol is heated at a temperature ranging from about 150°C to about 350°C.
3. A process according to claim 1 or 2 in which the 1,2-divinyl-cyclododecane-1-ol used as starting material is prepared by reacting a 2-halo-cyclododecanone with a vinylmagnesium halide.
4. A process according to claim 1 for the preparation of 5-cyclo-hexadecene-1-one which comprises reacting 2-halocyclododecanone with vinyl-magesium halide, hydrolyzing the reaction product and heating the resulting 1,2-divinylcycloclodecane-1-ol.
5. A process according to claim 4 in which the 2-halocyclododecanone is reacted with at least about 1.5 - 10 mols of vinyl magnesium halide per mol of 2-halocyclododecanone.
6. A process as claimed in claim 4 which comprises reacting 2-halo-cyclododecanone with at least about 2 mols of vinylmagnesium halide per mol of 2-halocyclododecanone at a temperature ranging from about -50°C to 150°C
hydrolyzing the reaction product and heating the resulting 1,2-divinylcyclo-dodecane-1-ol at a temperature ranging from about 150°C to 350°C.
7. A process according to claim 4, 5 or 6 in which the initial reaction is carried out in diethyl ether, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, methylpentylethyl, dibutylether, anisole, diethyleneglycol diethyl ether, benzylmethylether, benzene, toluene, xylene, hexane or heptane.
8. 5-Cyclohexadecene-1-one which comprises a mixture of txans-5-cyclohexadecene-1-one and cis-5-cyclohexadecene-1-one.
CA121,608A 1970-08-28 1971-08-27 5-cyclohexadecene-1-one and process for its preparation Expired CA1097687A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP74933/70 1970-08-28
JP45074933A JPS4930829B1 (en) 1970-08-28 1970-08-28

Publications (1)

Publication Number Publication Date
CA1097687A true CA1097687A (en) 1981-03-17

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ID=13561636

Family Applications (1)

Application Number Title Priority Date Filing Date
CA121,608A Expired CA1097687A (en) 1970-08-28 1971-08-27 5-cyclohexadecene-1-one and process for its preparation

Country Status (9)

Country Link
JP (1) JPS4930829B1 (en)
BE (1) BE771533A (en)
BR (1) BR7105650D0 (en)
CA (1) CA1097687A (en)
CH (1) CH522577A (en)
DE (1) DE2141309B2 (en)
FR (1) FR2104428A5 (en)
GB (1) GB1315438A (en)
NL (1) NL170847C (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5148120A (en) * 1974-10-18 1976-04-24 Lucerne Products Inc KAITENSEIGYO SOCHI
JPS54171743U (en) * 1978-05-24 1979-12-04
JPS5558004U (en) * 1978-10-16 1980-04-19
DE2934683A1 (en) * 1979-08-28 1981-03-12 Haarmann & Reimer Gmbh, 3450 Holzminden 3-METHYL-CYCLOHEXADECEN-5-ON-1, METHOD FOR THE PRODUCTION THEREOF AND ITS USE AS A FRAGRANT.
US4956516A (en) * 1988-05-20 1990-09-11 Shell Oil Company Disproportionation of olefins
JPH11322662A (en) * 1998-05-07 1999-11-24 Takasago Internatl Corp Production of 5-cyclohexadecen-1-one and production unit therefor
CA2390156A1 (en) * 2000-09-04 2002-03-14 Soda Aromatic Co., Ltd. A process for producing an epoxy compound, a flavor and fragrance composition containing the compound, and foods & drinks,perfumes,cosmetics a nd tobaccos respectively containingthe composition
EP1201738A1 (en) * 2000-10-30 2002-05-02 Pfw Aroma Chemicals B.V. Fragrance composition comprising cyclohexadecanone

Also Published As

Publication number Publication date
DE2141309C3 (en) 1974-07-04
NL7111880A (en) 1972-03-01
BE771533A (en) 1971-12-31
BR7105650D0 (en) 1973-05-10
JPS4930829B1 (en) 1974-08-16
DE2141309A1 (en) 1972-03-02
CH522577A (en) 1972-06-30
GB1315438A (en) 1973-05-02
FR2104428A5 (en) 1972-04-14
NL170847C (en) 1983-01-03
DE2141309B2 (en) 1973-11-22

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