US2790005A - Preparation of civetone and its homologs - Google Patents
Preparation of civetone and its homologs Download PDFInfo
- Publication number
- US2790005A US2790005A US552228A US55222855A US2790005A US 2790005 A US2790005 A US 2790005A US 552228 A US552228 A US 552228A US 55222855 A US55222855 A US 55222855A US 2790005 A US2790005 A US 2790005A
- Authority
- US
- United States
- Prior art keywords
- macrocyclic
- civetone
- symmetrical
- hydroxyketone
- homologs
- 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 - Lifetime
Links
Classifications
-
- 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
- C07C45/64—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 introduction of functional groups containing oxygen only in singly bound form
-
- 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
- C07C45/65—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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
- C07C45/66—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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
Definitions
- This invention relates .to the production of chemicals and in particular to the production of large-ring or macrocyclic-monoketones.
- A- principal object of the present invention is to provide a process for the production of-ho'mol'ogs of civetone from symmetrical macrocyclic diketones.
- Another object of the invention is to provide a process for the production of S-cycloliexadecen-l-one from 1,9- cyclohexadecanedione.
- Still another object of the invention is to'provide a process for the production: of 9-cyclooctadeeen-1-one from 1,l O cyclooctadec'anedione.
- the invention accordingly comprises the process involving the several steps and the relation and the order of one or more of such stepswith. respect to each of the others which are exemplified in the following detailed disclosure, and the scope of the application of which is indicated in the claims.
- Civetone. or 9-cycloheptadecen-l-one of the following structure is a naturally occurring substance secreted by the civet cat. exceptional value to the perfume industry as a. perfume base and fixative. Homol'ogs. of civetone having from 14 to 18 ring members also possess a musk-like odor very similar to that of the naturally occurring civetone. Although there are described in Chemistry of; Carbon Compounds, E. Rodd, ed., New York,,Elsevier Publishing. Company, 1953, volume. II, part A, pages. 277- 284, several syntheses for the. perfumery fixativecivetone,
- the preferred symmetrical macrocyclic diketones are 1,9-cyc1ohexadecanedione. and l,l0-cyclooctadecanedione, and the civet'one homologs. produced therefrom are 8 cyclohexadecen-l-one and 9-cyclooctadecenl-one respectively.
- the symmetrical macrocyclic diketones employed as starting materialin the present invention may be prepared accordingto the methods described in U. S. Patent 2,584,664.
- Example I An acetic acid solution of 0.503 gramof l,9-cyclohexadecanedione was hydrogenated in a semi-micro apparatus, using 70 milligrams of prereduced Adams catalyst (finely divided platinum. produced. by the reductionof platinum oxide), until, about 1.04 percent of one. equivalent of. hydrogcn had been absorbed. After separation, of the catalyst andreinoval. of. the acetic acid. invacuo, the residual solid was treated, with about 60 milliliters of hexane at room temperature. There was obtained 0.07 grain of crude 1,9-cycl0hexadecanediol which was insoluble in hexane. Coolingthe filtered hexane solution to 0-5 C.
- the above process is also applicable to the production of 7-cyclotetradecen-l-one from 1,8-cyclotetradecanedione.
- the partial reduction of the symmetrical macrocyclic diketones having from 14 to 18 ring members (12 to 16 methylene groups between the keto groups) may be achieved in many alternative ways other than through the use of Adams catalyst in acetic acid.
- Adams catalyst for example, Raney nickel, palladium on charcoal, nickel on kieselguhr, copper chromite, platinum or palladium on various other Well-known supports may also be used as catalysts.
- the above catalysts are used typically in solvents such as ethanol, ethyl acetate, acetic acid and the like.
- Conditions of reaction such as temperature, pressure, use of solvents, etc., depend on the particular hydrogenation method employed.
- the hydrogenation must be closely controlled so that but one ketonc group of the cyclic diketone employed is reduced to a secondary alcoholic grouping.
- Complete hydrogenation of the cyclic diketone is undesirable since it produces cyclic diols. For instance, the complete hydrogenation of 1,9-cyclohexadecanedione or 1,10-cyclooctadecanedione results in 1,9-cyclohexadecanediol and 1,10-cyclooctadecanediol respectively.
- the partial reduction of the preferred diketones results in symmetrical hydroxyketones having the same number of ring members as the starting material from which it was produced.
- the number of methylene groups (CH2) between the hydroxy group and keto group of the hydroxyketone are equal to the number of methylene groups between the two keto groups of the starting material.
- the dehydration of the symmetrical macrocyclic hydroxyketone may also be achieved by additional methods other than through the use of potassium hydrogen sulfate.
- the dehydration may be accomplished by heating the hydroxyketone with sulfuric, phosphoric, formic, oxalic or sulfonic acids or with reagents such as fused zinc chloride, iodine and the like or by passing the vapors of the hydroxyketones over substances such as alumina, thoria, titania, aluminum silicates and the like at suitable temperatures. Conditions of reaction for the dehydration such as temperatures, use of solvents and the like depend upon the particular dehydration method employed.
- the dehydration of the preferred hydroxyketones results in unsymmetrical unsaturated monoketones which, however, contain the same number of ring members as the diketone and hydroxyltetone from which they are obtained.
- the preferred macrocyclic unsaturated monoltetones having from 14 to 18 ring members but containing one less methylene group between the functional groups than are present between the functional groups of the symmetrical cyclic diketone or hydroxyketone, possess the valuable musk odor.
- a process for the production of civetone homologs which comprises the steps of partially reducing a symmetrical macrocyclic diketone selected from the group consisting of 1,S-cyclotetradecanedione, 1,9cyclohexadecanedione and 1,10-cyclooctadecanedione to the corresponding symmetrical macrocyclic hydroxyketone and dehydrating said symmetrical macrocyclic hydroxyketone to a macrocyclic unsaturated monoketone of the general formula where n and n are whole numbers of from 6 to 8 and where n and n are numerically equal.
- a process for the production of civetone homologs which comprises the steps of partially reducing 1,9-cyclohexadecanedione to 9-hydroxycyclohexadecanone and dehydrating said 9-hydroxycyclohexadecanone to S-cyclohexadecen-l-one.
- a process for the production of civetone homologs which comprises the steps of partially reducing 1,10- cyclooctadecanedione to 10-hydroxycyclooctadecanone and dehydrating said lO-hydroxycyclooctadecanone to 9-cyclo0ctadecen-1-one.
- a process for the production of civetone homologs which comprises the steps of partially reducing 1,8-cyclotetradecanedione to 8-hydroxycyclotetradecanone and dehydrating said 8-hydroxycyclotetradecanone to 7-cyclotetradecen-l-one.
- a process for the production of macrocyclic unsaturated monoketones which comprises the steps of partially reducing a macrocyclic diketone to the corresponding macrocyclic hydroxyketone and dehydrating said macrocyclic hydroxyketone to a macrocyclic unsaturated monoketone having one less methylene group between the unsaturation and keto group than is present between the keto groups of said macrocyclic diketone.
- a process for the production of macrocyclic unsaturated monoketones which comprises the steps of partially reducing a symmetrical macrocyclic diketone to the corresponding symmetrical macrocyclic hydroxyketone and dehydrating said symmetrical macrocyclic hydroxy- 'ketone to an unsymmetrical macrocyclic unsaturated monoketone.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Description
United States Patent PREPARATION OF CIVETONE AND ITS HOMOLOGS Alfred T. Blomquist, and Joseph Wolinsky, Ithaca, N. Y.
No Drawing. Application December 9, 1955, SerialNo. 552,228
6 Claims. (Cl. 260-586) This invention relates .to the production of chemicals and in particular to the production of large-ring or macrocyclic-monoketones.
A- principal object of the present inventionis to provide a process for the production of-ho'mol'ogs of civetone from symmetrical macrocyclic diketones.
Another object of the invention is to provide a process for the production of S-cycloliexadecen-l-one from 1,9- cyclohexadecanedione.
Still another object of the invention is to'provide a process for the production: of 9-cyclooctadeeen-1-one from 1,l O cyclooctadec'anedione.
Other objects of? the invention will in part be obvious and will in-part appear-hereinafter.
The invention accordingly comprises the process involving the several steps and the relation and the order of one or more of such stepswith. respect to each of the others which are exemplified in the following detailed disclosure, and the scope of the application of which is indicated in the claims.
Fora fuller, understanding of. the nature and objects of the invention, reference should. be had to the following detailed description.
Civetone. or 9-cycloheptadecen-l-one: of the following structure is a naturally occurring substance secreted by the civet cat. exceptional value to the perfume industry as a. perfume base and fixative. Homol'ogs. of civetone having from 14 to 18 ring members also possess a musk-like odor very similar to that of the naturally occurring civetone. Although there are described in Chemistry of; Carbon Compounds, E. Rodd, ed., New York,,Elsevier Publishing. Company, 1953, volume. II, part A, pages. 277- 284, several syntheses for the. perfumery fixativecivetone,
little attention has been given to.the.synt1hesi s of civetone homologs such as 7-cyclotetradecen-l-one, 8-cyclohexadecen-l-one and 9-cyclooctadecen-l-one. One method for producing these civetone homologs, described. in
Swiss Patent 135,921. 1928)v and U. S. Patent 1,873,154,.
Due to its characteristic musk-like odor, it is. of
ketone. In one preferred embodiment of the invention, the reaction proceeds as follows:
2) CH(0H2) n-1 -n o l noon 1'0 I 00 where n and n are whole numbers of from 6 to 8 and where n and n, are numerically equal. In another embodiment, the preferred symmetrical macrocyclic diketones are 1,9-cyc1ohexadecanedione. and l,l0-cyclooctadecanedione, and the civet'one homologs. produced therefrom are 8 cyclohexadecen-l-one and 9-cyclooctadecenl-one respectively. The symmetrical macrocyclic diketones employed as starting materialin the present invention may be prepared accordingto the methods described in U. S. Patent 2,584,664.
Specific detailed methods of practicing the present invention are set forth in the following non-limiting examples.-
Example I An acetic acid solution of 0.503 gramof l,9-cyclohexadecanedione was hydrogenated in a semi-micro apparatus, using 70 milligrams of prereduced Adams catalyst (finely divided platinum. produced. by the reductionof platinum oxide), until, about 1.04 percent of one. equivalent of. hydrogcn had been absorbed. After separation, of the catalyst andreinoval. of. the acetic acid. invacuo, the residual solid was treated, with about 60 milliliters of hexane at room temperature. There was obtained 0.07 grain of crude 1,9-cycl0hexadecanediol which was insoluble in hexane. Coolingthe filtered hexane solution to 0-5 C.
1 gave 0.22 gram of 9-hydroxycyclohexadecanone. The remaining hexane solution was then. placed on on a magnesol-celi-te column. Elution with a pentane-benzene mixture gave 0.09 gram of the starting material, 1,9-cyclohexadecanedione. Elution with a chloroform-benzene mixture gave an additional 0.09 gram oi 9-hydroxycyclohexadecanone as fine fluflfy needles. After recrystallization, the cyclic hydroxyketone obtained had a melting point of 7677 C. The'total quantity of 0.31 gram of' 9-hydroxycyclohexadecanone produced represented a 61 percent yield.
The above reaction proceeded as follows:
Arnixture of. 170 milligrams of 9-hydroxycyclohexadecanone and 1.5 grams of potassium hydrogen sulfate was heated for about 5 minutes at about 250 C. The resulting mixture was cooled and extracted with pentane. Evaporation of the pentane solution gave a residual oil having. an intense musk odor. On cooling, this liquid solidified. About 145 milligrams of 8.-cyclohexadecen-lone with a melting point of 1'7'-22 C. were obtained. This represented a yield of about. percent.
The above reaction proceeded as follows:
An acetic acid solution of 0.81 gram of 1,10-cyclohexadecanedione was partially hydrogenated using the procedure described in Example I. After separation of the catalyst and removal of the acetic acid, the residue was dissolved in hexane and placed on an alumina column. Elution with a hexane-heptane mixture gave 0.23 gram of unreduced 1,IO-cyclohexadecanedione. Elution with a hexane-benzene mixture gave 0.23 gram of 10- hydroxycyclooctadecanone. Final elution with chloroform also gave 0.16 gram of 1,10-cyclooctadecanediol. After recrystallization from pentane, the cyclic hydroxyketone obtained had a melting point of 80-81 C.
The above reaction proceeded as follows:
CO HOCH 155 milligrams of -hydroxycyclooctadecanone were fused with 2 grams of potassium hydrogen sulfate using the procedure described in Example I. Crude 9-cyclooctadecen-l-one was obtained directly from the fused mixture by sublimation. After resublimation, 95 milligrams of 9-cyclooctadecen-1-one were obtained as a Waxy solid with a melting point of 4041 C. This material had a musk odor similar to that of cyclooctadecanone. The total quantity of 9-cyclooctadecen-1-one obtained represented a yield of 66 percent.
This reaction proceeded as follows:
The above process is also applicable to the production of 7-cyclotetradecen-l-one from 1,8-cyclotetradecanedione.
The partial reduction of the symmetrical macrocyclic diketones having from 14 to 18 ring members (12 to 16 methylene groups between the keto groups) may be achieved in many alternative ways other than through the use of Adams catalyst in acetic acid. For example, Raney nickel, palladium on charcoal, nickel on kieselguhr, copper chromite, platinum or palladium on various other Well-known supports may also be used as catalysts. The above catalysts are used typically in solvents such as ethanol, ethyl acetate, acetic acid and the like.
Conditions of reaction such as temperature, pressure, use of solvents, etc., depend on the particular hydrogenation method employed. The hydrogenation must be closely controlled so that but one ketonc group of the cyclic diketone employed is reduced to a secondary alcoholic grouping. Complete hydrogenation of the cyclic diketone is undesirable since it produces cyclic diols. For instance, the complete hydrogenation of 1,9-cyclohexadecanedione or 1,10-cyclooctadecanedione results in 1,9-cyclohexadecanediol and 1,10-cyclooctadecanediol respectively.
The partial reduction of the preferred diketones results in symmetrical hydroxyketones having the same number of ring members as the starting material from which it was produced. Thus the number of methylene groups (CH2) between the hydroxy group and keto group of the hydroxyketone are equal to the number of methylene groups between the two keto groups of the starting material.
The dehydration of the symmetrical macrocyclic hydroxyketone may also be achieved by additional methods other than through the use of potassium hydrogen sulfate. For example, the dehydration may be accomplished by heating the hydroxyketone with sulfuric, phosphoric, formic, oxalic or sulfonic acids or with reagents such as fused zinc chloride, iodine and the like or by passing the vapors of the hydroxyketones over substances such as alumina, thoria, titania, aluminum silicates and the like at suitable temperatures. Conditions of reaction for the dehydration such as temperatures, use of solvents and the like depend upon the particular dehydration method employed.
The dehydration of the preferred hydroxyketones results in unsymmetrical unsaturated monoketones which, however, contain the same number of ring members as the diketone and hydroxyltetone from which they are obtained. The preferred macrocyclic unsaturated monoltetones, having from 14 to 18 ring members but containing one less methylene group between the functional groups than are present between the functional groups of the symmetrical cyclic diketone or hydroxyketone, possess the valuable musk odor.
Although specific separation techniques were illustrated in the examples, it should be pointed out that the use of other solvents and separation techniques may be employed in the recovery of either the hydroxyketone or the unsaturated monoketone.
Since certain changes may be made in the above process without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.
What is claimed is:
1. A process for the production of civetone homologs which comprises the steps of partially reducing a symmetrical macrocyclic diketone selected from the group consisting of 1,S-cyclotetradecanedione, 1,9cyclohexadecanedione and 1,10-cyclooctadecanedione to the corresponding symmetrical macrocyclic hydroxyketone and dehydrating said symmetrical macrocyclic hydroxyketone to a macrocyclic unsaturated monoketone of the general formula where n and n are whole numbers of from 6 to 8 and where n and n are numerically equal.
2. A process for the production of civetone homologs which comprises the steps of partially reducing 1,9-cyclohexadecanedione to 9-hydroxycyclohexadecanone and dehydrating said 9-hydroxycyclohexadecanone to S-cyclohexadecen-l-one.
3. A process for the production of civetone homologs which comprises the steps of partially reducing 1,10- cyclooctadecanedione to 10-hydroxycyclooctadecanone and dehydrating said lO-hydroxycyclooctadecanone to 9-cyclo0ctadecen-1-one.
4. A process for the production of civetone homologs which comprises the steps of partially reducing 1,8-cyclotetradecanedione to 8-hydroxycyclotetradecanone and dehydrating said 8-hydroxycyclotetradecanone to 7-cyclotetradecen-l-one.
5. A process for the production of macrocyclic unsaturated monoketones which comprises the steps of partially reducing a macrocyclic diketone to the corresponding macrocyclic hydroxyketone and dehydrating said macrocyclic hydroxyketone to a macrocyclic unsaturated monoketone having one less methylene group between the unsaturation and keto group than is present between the keto groups of said macrocyclic diketone.
6. A process for the production of macrocyclic unsaturated monoketones which comprises the steps of partially reducing a symmetrical macrocyclic diketone to the corresponding symmetrical macrocyclic hydroxyketone and dehydrating said symmetrical macrocyclic hydroxy- 'ketone to an unsymmetrical macrocyclic unsaturated monoketone.
- No references cited.
Claims (1)
1. A PROCESS FOR THE PRODUCTION OF CIVETONE HOMOLOGS WHICH COMPRISES THE STEPS OF PARTIALLY REDUCING A SYMMETRICAL MACROCYLIC DIKETONE SELECTED FROM THE GROUP CONSISTING OF 1,8-CYCLOTETRADECANEDIONE, 1,9-CYCLOHEXADECANEDIONE AND 1,10-CYCLOOCATDECANEDIONE TO THE CORRESPONDING SYMMETRICAL MARCROCYLIC HYDROXYKETONE AND DEHYDRATING SAID SYMMETRICAL MACROCYLIC HYDROXYKETONE TO A MACROCYCLIC UNSATURATED MONOKETONE OF THE GENERAL FORMULA
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US552228A US2790005A (en) | 1955-12-09 | 1955-12-09 | Preparation of civetone and its homologs |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US552228A US2790005A (en) | 1955-12-09 | 1955-12-09 | Preparation of civetone and its homologs |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2790005A true US2790005A (en) | 1957-04-23 |
Family
ID=24204433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US552228A Expired - Lifetime US2790005A (en) | 1955-12-09 | 1955-12-09 | Preparation of civetone and its homologs |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2790005A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2916517A (en) * | 1957-07-25 | 1959-12-08 | Nat Res Corp | Separation of compounds |
| US3254127A (en) * | 1966-05-31 | Process for the manufacture of cyclodec-s-en-l-one | ||
| DE1793801B1 (en) * | 1966-12-08 | 1977-09-29 | Firmenich & Cie | METHOD FOR PRODUCING MACROCYCLIC COMPOUNDS |
| EP0025870A1 (en) * | 1979-08-28 | 1981-04-01 | Haarmann & Reimer Gmbh | Cyclopentadecen-8-one-1, process for its preparation, and its use as odorant |
| US20050137120A1 (en) * | 2003-12-23 | 2005-06-23 | Symrise Gmbh & Co. Kg | (Z)-7-cyclohexadecen-1-one as an odorant |
| CN108553455A (en) * | 2018-07-10 | 2018-09-21 | 中国科学院海洋研究所 | Application of the three aldehyde radical phloroglucin thiosemicarbazones heterozygote compounds in antitumor drug |
-
1955
- 1955-12-09 US US552228A patent/US2790005A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3254127A (en) * | 1966-05-31 | Process for the manufacture of cyclodec-s-en-l-one | ||
| US2916517A (en) * | 1957-07-25 | 1959-12-08 | Nat Res Corp | Separation of compounds |
| DE1793801B1 (en) * | 1966-12-08 | 1977-09-29 | Firmenich & Cie | METHOD FOR PRODUCING MACROCYCLIC COMPOUNDS |
| EP0025870A1 (en) * | 1979-08-28 | 1981-04-01 | Haarmann & Reimer Gmbh | Cyclopentadecen-8-one-1, process for its preparation, and its use as odorant |
| US20050137120A1 (en) * | 2003-12-23 | 2005-06-23 | Symrise Gmbh & Co. Kg | (Z)-7-cyclohexadecen-1-one as an odorant |
| WO2005063670A1 (en) * | 2003-12-23 | 2005-07-14 | Symrise Gmbh & Co. Kg | Use of (z)-7-cyclohexadecene-1-one as a perfume |
| US7129380B2 (en) | 2003-12-23 | 2006-10-31 | Symrise Gmbh & Co. Kg | (Z)-7-cyclohexadecen-1-one as an odorant |
| JP2007519627A (en) * | 2003-12-23 | 2007-07-19 | シムライズ・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング・ウント・コンパニー・コマンジツト・ゲゼルシヤフト | (Z) -7-cyclohexadecene-1-one as odorant |
| JP4688818B2 (en) * | 2003-12-23 | 2011-05-25 | シムライズ・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング・ウント・コンパニー・コマンジツト・ゲゼルシヤフト | (Z) -7-cyclohexadecene-1-one as odorant |
| CN108553455A (en) * | 2018-07-10 | 2018-09-21 | 中国科学院海洋研究所 | Application of the three aldehyde radical phloroglucin thiosemicarbazones heterozygote compounds in antitumor drug |
| CN108553455B (en) * | 2018-07-10 | 2020-05-15 | 中国科学院海洋研究所 | Application of trialdehyde phloroglucinol thiosemicarbazone heterozygote compound in antitumor drugs |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jacobson et al. | Three-carbon annelations. Regiocontrolled reactivity of trimethylsilyl-and ethoxyethyl-protected cyanohydrins. Versatile homoenolate and acyl anion equivalents | |
| US2933506A (en) | 1, 1-dimethyldecaline lactones and their 6-and 7-pyridyl, thienyl and furyl substituted derivatives | |
| Nakano et al. | Terpenoids. XLVI. 1 Copalic Acid2 | |
| US2790005A (en) | Preparation of civetone and its homologs | |
| WARNER | Preparation of Substituted Cyclopropanes Containing Aldehyde and Ketone Groups | |
| US4261866A (en) | Spirodienones and spirocyclic ketones | |
| House et al. | Stereochemistry of Favorskii rearrangement of chloromethyl ketones | |
| DE1003702B (en) | Process for the preparation of aliphatic saturated alcohols | |
| US3265739A (en) | Preparation of 2-octalones | |
| US3660489A (en) | Novel caranone derivatives perfume compositions containing same and process for their preparation | |
| DE2945812C2 (en) | ||
| US3328426A (en) | Process for the manufacture of cyclic ethers | |
| DE2252865A1 (en) | TRICYCLIC KETONE | |
| US4203925A (en) | Process for the production of spirodienones and spirocyclic ketones | |
| US3970682A (en) | Novel cyclopentanone odoriferous agent | |
| DE2107413C3 (en) | Substituted hydrogenated 2-hydroxy- or 2-oxonaphthalenes, their preparation and odoriferous and / or flavoring compositions containing them | |
| US3932515A (en) | Novel oxygenated derivatives of thujopsene | |
| US2849457A (en) | Gamma-monolactone of 4-hydroxysuberic acid, its salts and esters, and the salts and amides of 4-hydrosuberic acid, their preparation and use | |
| US3246036A (en) | Production of 2-cyclohexylcyclo-hexanone | |
| CH513791A (en) | Preparing macrocyclic ketones | |
| DE2314697C3 (en) | 1 -Amino ^ -hydroxy-SJ-dimethyloctane and process for their preparation | |
| DE2848095A1 (en) | Substd. per-hydro-naphtho-furan derivs. - used as stable amber-type perfumes, prepd. by cyclisation of cyclohexanol derivs. and hydrogenation | |
| Agarwal et al. | Application of oxonolysis to the study of substituted derivatives of vulpinic acid: Constitution of pinastric and isopinastric acids | |
| GB1564293A (en) | Oxa-spiro-decan-7-one and its use as a flavourant and/or odourant | |
| US3085107A (en) | Cyclododecylacetic acid esters, derivatives thereof and intermediates therefor |