CH501609A - Unsat aldehydes with four double bonds - used as flavouring materials - Google Patents
Unsat aldehydes with four double bonds - used as flavouring materialsInfo
- Publication number
- CH501609A CH501609A CH920469A CH920469A CH501609A CH 501609 A CH501609 A CH 501609A CH 920469 A CH920469 A CH 920469A CH 920469 A CH920469 A CH 920469A CH 501609 A CH501609 A CH 501609A
- Authority
- CH
- Switzerland
- Prior art keywords
- unsat
- aldehydes
- ocimene
- double bonds
- ether
- Prior art date
Links
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
- C11B9/0069—Heterocyclic compounds
- C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
- C11B9/0076—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing less than six atoms
-
- 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
- C07C45/513—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 an etherified hydroxyl group
-
- 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
- C07C45/67—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 isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
-
- 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
- C11B9/0007—Aliphatic compounds
- C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom
Landscapes
- 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)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Abstract
Unsat. aldehydes with four double bonds used as flavouring materials. Sesquiterpenaldehydes alpha- and beta-sinensal CH2=CH-C( CHn) CH4-n-CH2-CH=C(CH3)-CH2-CH2-CH=C(CH3)-CHO (where one double bond is represented by one of dotted lines and n is 2 or 3), suitable for flavouring food, drink, medicinals and for producing synthetic aromas and ether oils, are prepared by condensing trienals CH2=CH-C( CHn)( CH4-n)-CH2-CH=C(CH3)-CH2-CH2-CHO with N-substituted propionalimines (where substituent is aliphatic or alicyclic group), pref. in ether at -80 to 0 degrees C in an inert atm., in presence of metallising agent and hydrolysing condensate in an acid aqs. medium. Reaction scheme indicates ocimene or myrcene oxidation to epoxide, epoxy ring opening to sec-ocimenol or-myrcenol, and condensation with unsat. vinyl ether to trienal starting materials.
Description
Procédé pour la préparation d'époxydes oléfiniques
La présente invention concerne un procédé pour la préparation des époxydes d'ocimène (cis- ou trans-) de formule:
EMI1.1
Ces monoépoxydes sont doués d'intéressantes propriétés organoleptiques. Ils sont particulièrement utiles pour ameliorer et renforcer la note de tete de compositions de parfums et il est avantageux de les utiliser dans des proportions allant de 0,5 à 3 % du poids total d'une composition de parfum. Ces chiffres ne constituent pas d'ailleurs des limies absolues, car lesdits époxydes peuvent également être utilisés en proportions situées en deçà ou au-delà desdites limites suivant l'effet recherche. Les époxydes dont il est question presentent l'avantage d'être stables en milieu alcalin.
Ils peuvent également être utilisés comme inermédiaires dans la synthèse de l'α-sinensal conformément au brevet N 488642.
Le procédé de l'invention est caractérisé en ce qu'on époxyde la double liaison diméthylée de l'ocimène cisou trans-.
L'époxydation peut etre conduite au moyen d'un peracide dans un solvant organique courant comme par exemple le chlorure de méthylène ou le trichloréthylène, de préférence en présence d'un agent faisant office de tampon, par exemple le sel d'un acide faible et d'une base forte tel l'acétate de soude. Comme peracide on peut employer les peracides organiques habituellement disponibles commercialement par exemple l'acide peracétique ou l'acide perbenzoique. La temperature à laquelle on peut effectuer l'époxydation n'est pas critique.
Cependant, pour des raisons de commodité (vitesse de réaction et rendement convenables) on préfère opérer entre approximativement 0 et 500 C. Il est avantageux mais pas indispensable que la solution à époxyder soit prealablement refroidie aux environs de 0O et qu'on ajoute l'agent époxydant à une vitesse convenable pour que la température du milieu réactionnel se sabilise aux alentours de la temperature ambiante sans qu'il soit nécessaire d'éloigner le dispositif réfrigéran.
L'exemple qui suit dans lequel les températures figurent en degrés centigrades, illustre l'invention de manière détaillée.
Exemple a) Epoxydation du trans-ocimène
On ajoute 204 g (1,5 mole) de trans-ocimène fraichement distillé et 150g d'acetate de soude anhydre dans 750 ml de chlorure de méthylène. On agite pendant 1 h à temperature ordinaire, puis refroidit à 00. On maintient le dispositif de refroidissement et, tout en agitant vigoureusement, on ajoute goutte à goutte une solution de 3 g d'acetate de soude dans 315 g (1,75 mole) d'acide peracétique à 42%, dont le débit est ajuste pour que la temperature du milieu réactionnel se maintienne entre 20 et 250. Dans ces conditions, apres 1 h l'addition est terminée; on maintient 4 h l'agitation en marche puis on essore l'acétate de soude et le rince soigneusement au chlorure de méthylène.
On jette filtrat et liqueurs de rinçage dans l'eau glacée, on secoue vi goureusement et separe la phase organique qu'on lave une fois à l'eau (125 ml), deux fois (125 ml) avec une solution saturée de carbonate de soude et finalement à l'eau (125ml). Les fractions de lavage sont extraites chaque fois avec 250 ml de chlorure de methylene. Apres sechage sur CaCl2 et evaporation du solvant, on distille le residu et obtient 205 g (90 %) de rans-époxyocimène, Eb. 45-47 /0,1 Torr.
Analyse pour C10H16O: Calculé: C 78,89% H10,59% Trouvé: C 78,64% H10,40% n20 = 1,4802; d24 = 0,9082.
b) Epoxydation du cis-ocimène
On époxyde le cis-ociméne avec un rendement de 90%, selon la méthode utilisée pour l'époxydation du trans-ocimène figurant au paragraphe précédent. Les constantes du cis-époxyocimène sont les suivantes: d4 = 0,3996; n20 = 1,4721.
Process for the preparation of olefinic epoxides
The present invention relates to a process for the preparation of epoxides of ocimene (cis- or trans-) of formula:
EMI1.1
These monoepoxides are endowed with interesting organoleptic properties. They are particularly useful for improving and reinforcing the top note of perfume compositions and it is advantageous to use them in proportions ranging from 0.5 to 3% of the total weight of a perfume composition. These figures do not, moreover, constitute absolute limits, since said epoxides can also be used in proportions located below or beyond said limits depending on the desired effect. The epoxies in question have the advantage of being stable in an alkaline medium.
They can also be used as intermediates in the synthesis of α -sinensal in accordance with patent N 488642.
The process of the invention is characterized in that the dimethylated double bond of the cisor trans- ocimene is epoxidized.
The epoxidation can be carried out by means of a peracid in a common organic solvent such as for example methylene chloride or trichlorethylene, preferably in the presence of an agent acting as a buffer, for example the salt of a weak acid. and a strong base such as sodium acetate. As peracid one can use organic peracids usually available commercially, for example peracetic acid or perbenzoic acid. The temperature at which the epoxidation can be carried out is not critical.
However, for reasons of convenience (suitable reaction rate and yield) it is preferred to operate between approximately 0 and 500 C. It is advantageous but not essential that the solution to be epoxidized is previously cooled to about 0O and that the additive is added. epoxidizing agent at a suitable rate so that the temperature of the reaction medium is reduced to around room temperature without it being necessary to remove the refrigeration device.
The example which follows, in which the temperatures appear in degrees centigrade, illustrates the invention in detail.
Example a) Epoxidation of trans-ocimene
204 g (1.5 mol) of freshly distilled trans-ocimene and 150 g of anhydrous sodium acetate are added in 750 ml of methylene chloride. Stirred for 1 h at room temperature, then cooled to 00. The cooling device is maintained and, while stirring vigorously, a solution of 3 g of sodium acetate in 315 g (1.75 mol) is added dropwise. ) 42% peracetic acid, the flow rate of which is adjusted so that the temperature of the reaction medium is maintained between 20 and 250. Under these conditions, after 1 hour the addition is complete; stirring is maintained for 4 h then the sodium acetate is filtered off and rinsed thoroughly with methylene chloride.
The filtrate and rinsing liquors are poured into ice-cold water, the organic phase is shaken vigorously and the organic phase is separated, which is washed once with water (125 ml), twice (125 ml) with a saturated solution of sodium carbonate. soda and finally with water (125ml). The washing fractions are extracted each time with 250 ml of methylene chloride. After drying over CaCl2 and evaporation of the solvent, the residue is distilled and 205 g (90%) of rans-epoxyocimene, Eb. 45-47 / 0.1 Torr.
Analysis for C10H16O: Calculated: C 78.89% H10.59% Found: C 78.64% H10.40% n20 = 1.4802; d24 = 0.9082.
b) Epoxidation of cis-ocimene
The cis-ocimene is epoxidized with a yield of 90%, according to the method used for the epoxidation of trans-ocimene appearing in the preceding paragraph. The constants for cis-epoxyocimene are as follows: d4 = 0.3996; n20 = 1.4721.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH920469A CH501609A (en) | 1967-12-14 | 1967-12-14 | Unsat aldehydes with four double bonds - used as flavouring materials |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1756867A CH488642A (en) | 1967-06-15 | 1967-12-14 | A-sinensal preparation process |
| CH920469A CH501609A (en) | 1967-12-14 | 1967-12-14 | Unsat aldehydes with four double bonds - used as flavouring materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH501609A true CH501609A (en) | 1971-01-15 |
Family
ID=4426411
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1126069A CH491066A (en) | 1967-12-14 | 1967-12-14 | A-sinensal preparation process |
| CH1125969A CH491843A (en) | 1967-12-14 | 1967-12-14 | Process for preparing unsaturated aldehydes |
| CH920469A CH501609A (en) | 1967-12-14 | 1967-12-14 | Unsat aldehydes with four double bonds - used as flavouring materials |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1126069A CH491066A (en) | 1967-12-14 | 1967-12-14 | A-sinensal preparation process |
| CH1125969A CH491843A (en) | 1967-12-14 | 1967-12-14 | Process for preparing unsaturated aldehydes |
Country Status (2)
| Country | Link |
|---|---|
| CH (3) | CH491066A (en) |
| ES (1) | ES369912A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5930347B2 (en) * | 2011-12-20 | 2016-06-08 | フイルメニツヒ ソシエテ アノニムＦｉｒｍｅｎｉｃｈ Ｓａ | New aldehydes as perfuming ingredients |
-
1967
- 1967-12-14 CH CH1126069A patent/CH491066A/en not_active IP Right Cessation
- 1967-12-14 CH CH1125969A patent/CH491843A/en not_active IP Right Cessation
- 1967-12-14 CH CH920469A patent/CH501609A/en not_active IP Right Cessation
-
1969
- 1969-07-24 ES ES369912A patent/ES369912A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ES369912A1 (en) | 1971-07-16 |
| CH491843A (en) | 1970-06-15 |
| CH491066A (en) | 1970-05-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased |