CH523859A - Thuyopsanone derived from thuiyopsene used - in fragrant comps - Google Patents
Thuyopsanone derived from thuiyopsene used - in fragrant compsInfo
- Publication number
- CH523859A CH523859A CH323269A CH323269A CH523859A CH 523859 A CH523859 A CH 523859A CH 323269 A CH323269 A CH 323269A CH 323269 A CH323269 A CH 323269A CH 523859 A CH523859 A CH 523859A
- Authority
- CH
- Switzerland
- Prior art keywords
- formula
- thuyopsanone
- comps
- pref
- fragrant
- Prior art date
Links
- 150000004965 peroxy acids Chemical class 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- -1 polycyclic ketone Chemical class 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007704 transition Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract 1
- 102000010825 Actinin Human genes 0.000 abstract 1
- 108010063503 Actinin Proteins 0.000 abstract 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 abstract 1
- 229960001701 chloroform Drugs 0.000 abstract 1
- AHXGRMIPHCAXFP-UHFFFAOYSA-L chromyl dichloride Chemical compound Cl[Cr](Cl)(=O)=O AHXGRMIPHCAXFP-UHFFFAOYSA-L 0.000 abstract 1
- 239000003599 detergent Substances 0.000 abstract 1
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 abstract 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 abstract 1
- 231100000489 sensitizer Toxicity 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 241001342522 Vampyrum spectrum Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000012437 perfumed product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/123—Ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/417—Saturated compounds containing a keto group being part of a ring polycyclic
- C07C49/423—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system
- C07C49/453—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having three rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Thuyopsanone, a fragrant polycyclic ketone used in perfumed comps. esp. detergents, has the formula and is produced by oxidation of thuyopsene which has the formula by using: (a) a peracid e.g. peracetic in chloro-form at 0-50 degrees C; (b) oxidised derivs. of transition elements. pref. chromyl chloride in CCl4 at 10-20 degrees C, or (c) an oxidising gas, either pure. O2 or O2 mixed with eg N2, in combination with actinin irradiation e.g. Hg or Na vapour arc, and in the presence of an energy-transfer sensitiser e.g. rosin or pref. Rose-Bengale, pref. using a solvent such as methanol.
Description
Procédé pour la préparation de composés carbonylés polycycliques
Le brevet principal No 497360 a pour objet un procédé pour la préparation des composés de formule:
EMI1.1
lequel consiste à oxyder le thuyopsène de formule:
EMI1.2
par a) un peracide, ou b) un dérivé oxydé d'un élément de transition pour obtenir directement le composé
I, ou c) l'oxygène gazeux en présence de radiations actiniques, l'intermédiaire II de formule:
EMI1.3
formé étant alors isomérisé par un acide, pour obtenir I. La formule I représente une cétone tricyclique, la thuyopsanone; elle comprend différents isomères configurationnels dont l'existence résulte de la présence de centres d'asymétrie.
On a trouvé que les composés de formule I, qui sont particulièrement stables en milieu alcalin, sont doués de propriétés organoieptiques intéressantes et sont utilisés avantageusement dans la préparation de parfums et produits parfumés.
On a maintenant trouvé que si les composés de formule:
EMI1.4
sont obtenus par oxydation du thuyopsène au moyen d'un peracide on peut opérer par un procédé caractérisé en ce que:
a) l'on sépare par cristallisation du mélange réactionnel contenant les composés de formule I déjà formés un glycol monoacylé de formule:
EMI1.5
dans laquelle R représente le reste acyle dérivé du peracide utilisé;
b) l'on chauffe ledit solide aux alentours de son point d'ébullition pour donner un mélange de thuyopsanone et des alcools de formule:
EMI1.6
c) on isomérise les alcools de formule II au moyen d'un agent acide pour fournir la thuyopsanone pure.
li est également possible d'utiliser le glycol monoacylé III, obtenu selon le procédé décrit sous lettre a), comme produit de départ pour la préparation d'un com posé de formule I: ledit glycol est alors saponifié en diol correspondant qui, après traitement par un agent acide, est converti en thuyopsanone.
L'exemple suivant sert à illustrer l'invention d'une manière plus détaillée. Dans ledit exemple, les températures sont indiquées en degrés centigrades.
Exemple:
Préparation de la (-)-thuyopsanone-(3)
et de l'(-)-sothuyopsanone-(3)
a) Chauffage de l'acétate du glycol:
L'acétate du glycol (long), préparé suivant la méthode décrite au paragraphe c), a été soumis à 2 distillations successives entre 145 et 1600. Par titration d'une aliquote du produit distillé on a constaté que la quantité théorique d'acide acétique a été libérée. On a lavé le distillat jusqu'à neutralité, puis on l'a soumis à l'analyse chromatographique en phase gazeuse qui a mis en évidence l'existence d'un mélange environ 1:1 de thuyopsanone (2 isomères) et de l'alcool de formule IIa.
EMI2.1
Ce mélange a été utilisé sans autre dans la suite des opérations. Rendement pratiquement quantitatif.
b) Isomérisation du composant de formule lia:
Le mélange de thuyopsanone et de l'alcool lia (130 g) préparé suivant la méthode décrite au paragraphe a) a été dissous dans 160 ml d'alcool. 50 ml de H2SO4 (50 o/o) ont été ajoutés et la solution a été agitée 4 heures à 400.
En cas de trouble, on a dilué avec encore un peu d'alcool. On a dilué à l'eau et extrait à l'éther de pétrole (50-7oe). Après le traitement habituel de l'extrait, on a obtenu par distillation 120 g de thuyopsanone pratiquement pure contenant la (-)-thuyopsanone-(3) et l'(-)-isothuyopsanone dans un rapport approximativement 1:1.
(-)-thuyopsanone-(3): F. 680. Spectre U.V. (EtOH): 2010A (e = 339,9), 2830 A (e = 28,5). Spectre RMN (Varian HA-100): 0,64 (3vs), 1,2 (3H,d, J = 0,7 cps), 1,1 et 1,2 (2 X 3H,s), 0,6-0,8 (2H, bande large), 1,3-1,9 (7H), 2,1-2,3 (2H,d, J = 1,5 cps), 2,3-2,55 (1H, bande large) 6 ppm.
(-)-isothuyopsanone-(3): F. 38-400; [2n0 = - 1560 (cl14).
Analyse: Calculé pour C15H24O:
C 81,76 o/o H 10,98 O/o ; Trouvé : C 81,930/o H 10,87 .
Spectre U.V. (EtOH): 2020 (8 = 353,8), 2870 A (e = 23,3). Spectre RMN (Varian HA-100) : 0,64 (3H,s), 1,1 (3bd, J = 0,7 cps), 1,1 et 1,2 (2 X 3H,s), 0,2-0,6 (2H, -bande large), 1,2-1,8 (7H), 2,05-2,2 (2H,d J= 1,6 cps), 2,45-2,75 (1H, bande large) 6 ppm.
L'acétate du glycol de formule:
EMI2.2
utilisé comme produit de départ pour la préparation indiquée ci-dessus peut être préparé ainsi:
c) A un mélange en agitation contenant 3565 g de thuyopsène naturel, 10 litres de toluène et 350 g d'acétate de soude anhydre, on a ajouté, entre 18 et 35O, 4210 g d'acide peracétique à 39,5 O/o . Pendant l'addition qui a duré 5 h, on a contrôlé la température de réaction au moyen d'un bain refroidissant. On a lavé la solution de réaction jusqu'à neutralité et on l'a concentrée sous pression réduite. On a obtenu 4480 g de produit qu'on a abandonné au froid pendant la nuit. On a essoré 1880 g de l'acétate du glycol brut.
Les eaux mères, après séparation de l'acétate, ont été purifiées par fractionnement et ont fourni un mélange contenant 17,5 oxo de thuyopsanone, F. 680, et 82,5 O/o d'isothuyopsanone, F. 400.
L'acétate du glycol brut a été purifié par recristallisation dans l'éther de pétrole (50-700), F. 108-1090. Spectre RMN (CCl4) : 0,54 (3vs), 1,0 (3H,s), 1,1 (3H,s), 1,3 (3H,s), 2,0 (3H,s), 4,62 (1H,d de d, J=4 et 12cps) 6 ppm.
Process for the preparation of polycyclic carbonyl compounds
The main patent No 497360 relates to a process for the preparation of compounds of formula:
EMI1.1
which consists in oxidizing thuyopsene of formula:
EMI1.2
by a) a peracid, or b) an oxidized derivative of a transition element to directly obtain the compound
I, or c) gaseous oxygen in the presence of actinic radiation, intermediate II of formula:
EMI1.3
formed being then isomerized with an acid, to obtain I. Formula I represents a tricyclic ketone, thuyopsanone; it comprises different configurational isomers whose existence results from the presence of asymmetric centers.
It has been found that the compounds of formula I, which are particularly stable in an alkaline medium, are endowed with interesting organoieptic properties and are advantageously used in the preparation of perfumes and perfumed products.
It has now been found that if the compounds of formula:
EMI1.4
are obtained by oxidation of thuyopsene using a peracid, it is possible to operate by a process characterized in that:
a) a monoacylated glycol of formula is separated by crystallization from the reaction mixture containing the compounds of formula I already formed:
EMI1.5
in which R represents the acyl residue derived from the peracid used;
b) said solid is heated to around its boiling point to give a mixture of thuyopsanone and alcohols of formula:
EMI1.6
c) the alcohols of formula II are isomerized by means of an acidic agent to provide pure thuyopsanone.
It is also possible to use the monoacylated glycol III, obtained according to the process described under letter a), as starting material for the preparation of a compound of formula I: said glycol is then saponified into the corresponding diol which, after treatment by an acidic agent, is converted into thuyopsanone.
The following example serves to illustrate the invention in more detail. In said example, temperatures are given in degrees centigrade.
Example:
Preparation of (-) - thuyopsanone- (3)
and (-) - sothuyopsanone- (3)
a) Heating of the glycol acetate:
The glycol acetate (long), prepared according to the method described in paragraph c), was subjected to 2 successive distillations between 145 and 1600. By titration of an aliquot of the distilled product, it was found that the theoretical quantity of acid acetic has been released. The distillate was washed to neutrality and then subjected to gas chromatographic analysis which showed the existence of an approximately 1: 1 mixture of thuyopsanone (2 isomers) and alcohol of formula IIa.
EMI2.1
This mixture was used without further ado in the rest of the operations. Virtually quantitative yield.
b) Isomerization of the component of formula IIa:
The mixture of thuyopsanone and alcohol IIa (130 g) prepared according to the method described in paragraph a) was dissolved in 160 ml of alcohol. 50 ml of H2SO4 (50o / o) was added and the solution was stirred 4 hours at 400.
In the event of cloudiness, diluted with a little more alcohol. Diluted with water and extracted with petroleum ether (50-7oe). After the usual processing of the extract, 120 g of substantially pure thuyopsanone were obtained by distillation containing (-) - thuyopsanone- (3) and (-) - isothuyopsanone in an approximately 1: 1 ratio.
(-) - thuyopsanone- (3): F. 680. U.V. spectrum (EtOH): 2010A (e = 339.9), 2830 A (e = 28.5). NMR spectrum (Varian HA-100): 0.64 (3vs), 1.2 (3H, d, J = 0.7 cps), 1.1 and 1.2 (2 X 3H, s), 0.6 -0.8 (2H, broadband), 1.3-1.9 (7H), 2.1-2.3 (2H, d, J = 1.5 cps), 2.3-2.55 ( 1H, broadband) 6 ppm.
(-) - isothuyopsanone- (3): F. 38-400; [2n0 = - 1560 (c14).
Analysis: Calculated for C15H24O:
C 81.76 o / o H 10.98 O / o; Found: C 81.930 / o H 10.87.
UV Spectrum (EtOH): 2020 (8 = 353.8), 2870 A (e = 23.3). NMR spectrum (Varian HA-100): 0.64 (3H, s), 1.1 (3bd, J = 0.7 cps), 1.1 and 1.2 (2 X 3H, s), 0.2 -0.6 (2H, -brandband), 1.2-1.8 (7H), 2.05-2.2 (2H, d J = 1.6 cps), 2.45-2.75 ( 1H, broadband) 6 ppm.
Glycol acetate of formula:
EMI2.2
used as the starting material for the preparation indicated above can be prepared as follows:
c) To a stirring mixture containing 3565 g of natural thuyopsene, 10 liters of toluene and 350 g of anhydrous sodium acetate, between 18 and 35O, 4210 g of peracetic acid at 39.5 O / o were added. . During the addition, which lasted 5 h, the reaction temperature was controlled by means of a cooling bath. The reaction solution was washed until neutral and concentrated under reduced pressure. 4480 g of product were obtained which was left in the cold overnight. 1880 g of the acetate were filtered off from the crude glycol.
The mother liquors, after separation of the acetate, were purified by fractionation and gave a mixture containing 17.5 oxo of thuyopsanone, F. 680, and 82.5 O / o of isothuyopsanone, F. 400.
The crude glycol acetate was purified by recrystallization from petroleum ether (50-700), mp 108-1090. NMR spectrum (CCl4): 0.54 (3vs), 1.0 (3H, s), 1.1 (3H, s), 1.3 (3H, s), 2.0 (3H, s), 4 , 62 (1H, d of d, J = 4 and 12cps) 6 ppm.
Claims (1)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH323269A CH523859A (en) | 1968-03-08 | 1969-03-04 | Thuyopsanone derived from thuiyopsene used - in fragrant comps |
| CH688371A CH516497A (en) | 1969-03-04 | 1969-03-04 | Thuyopsanone derived from thuiyopsene used - in fragrant comps |
| DE1911440A DE1911440C3 (en) | 1968-03-08 | 1969-03-06 | Tricyclic keto derivatives of thuyopsan, their preparation and their use as odoriferous substances |
| FR6906401A FR2003503A1 (en) | 1968-03-08 | 1969-03-07 | |
| US00805353A US3845132A (en) | 1968-03-08 | 1969-03-07 | Fragrant polycyclic ketones |
| NL696903596A NL139299B (en) | 1968-03-08 | 1969-03-07 | PROCESS FOR PREPARING A FRAGRANCE COMPOSITION, PROCESS FOR PREPARING A PERFUMED PRODUCT AND PROCESS FOR PREPARING A FRAGRANCE. |
| GB02597/69A GB1216048A (en) | 1968-03-08 | 1969-03-10 | Ketones derived from thuyopsene |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH350668A CH497529A (en) | 1968-03-08 | 1968-03-08 | Use of polycyclic carbonyl compounds as odoriferous agents |
| CH1484169A CH497360A (en) | 1968-03-08 | 1968-03-08 | Process for the preparation of polycyclic carbonyl compounds |
| CH323269A CH523859A (en) | 1968-03-08 | 1969-03-04 | Thuyopsanone derived from thuiyopsene used - in fragrant comps |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH523859A true CH523859A (en) | 1972-06-15 |
Family
ID=27174206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH323269A CH523859A (en) | 1968-03-08 | 1969-03-04 | Thuyopsanone derived from thuiyopsene used - in fragrant comps |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH523859A (en) |
-
1969
- 1969-03-04 CH CH323269A patent/CH523859A/en not_active IP Right Cessation
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased |