DE1234900B - Fragrance composition - Google Patents

Description

C07C 33/02

FEDERAL REPUBLIC OF GERMANY Int.Cl .:

UTSCHES

PATENT OFFICE

EDITORIAL

Uiiuitt

ClIb

German class: 23 a - 6

1λ ir

Number: 1 234 900

File number: Sch 36267 IV a / 23 a

Filing date: December 16, 1964

Launch date: February 23, 1967

The invention relates to a fragrance composition which is characterized by a content of a compound of the general formula

CH ₂ -CH ₂ OX "^ 'Y

Fragrance composition

Applicant:

Schering Aktiengesellschaft,

Berlin 65, Mullerstr. 170/172

where X = H or

- C —R ^s

where R = H or lower alkyl, in particular - CH ₃ or - C ₂ H ₆ and where Y stands for the radicals - CH = CH ₂ or - C ₂₁ H ₅ .

The compounds identified by the general formula are new; they are characterized by one flowery, the compounds with X = H are characterized in particular by a rose-like odor. For example, has the homocitronellol has a strong citronellol-like odor, which compared to that of the Citronellols has greater adhesiveness. The new compounds mentioned are therefore a a valuable addition to the range of fragrances for this type of odor.

The compounds represented by the above formula can be obtained by designating as the inventor:
Dipl.-Chem. Dr. Arthur Bokranz,
Dipl.-Chem. Dr. Karl Heinz Müller, Kamen

Hydronopol, especially cis-Hydronopol, a thermal isomerization by pyrolysis in the vapor phase subjects and the 7-methyl-3-vinylocten- (6) -ol- (l) obtained is isolated and that one optionally then either

a) 7-methyl-3-vinyl-octen- (6) -ol- (l) directly with lower aliphatic carboxylic acids, in particular Formic acid or acetic acid, or esterified in a manner known per se

b) the 7-methyl-3-vinyl-octen- (6) -ol- (l) first of all a partial hydrogenation according to known methods Subjects to methods and the obtained 7-methyl-3-vinyl-octen- (6) -ol- (l) (homocitronellol) isolated and optionally in a manner known per se with lower aliphatic carboxylic acids, in particular formic acid or acetic acid, esterified.

CH ₂ -CH ₂ OH

CH ₂ -CH ₂ OH

Pyrolysis

CH ₂ -CH ₂ OH

partial
Hydrogenation

Hydronopoly

7-methyl-3-vinyl-octen- (6) -ol- (l) 7-methyl-3-ethyl-octen- (6) -ol- (l) (Homocitronellol)

The starting material used is hydronopol, in particular cis-hydronopol, which is easily produced by catalytic Hydrogenation of commercial nopol produced from /? - pinene and formaldehyde can be obtained.

With the specified process it is possible to obtain the new compounds not only in racemic form, but also in optically active form, depending on whether one is racemic or optical running out of active starting material.

The pyrolysis process takes place in the vapor phase. It was found that the pyrolysis in the Surprisingly, the case of the cis-hydronopoly is more uniform or different than in the case of similar ones Substances such as B. Myrtanol or Nopol, and that even with a single rectification a very pure one and uniform pyrolysis product, namely 7-methyl-3-vinyl-octen-6-ol- (1), can be obtained can.

709 510/507

During the pyrolysis of Nopol in the vapor phase in addition to a number of isomeric cyclic unsaturated alcohols, there is also an acyclic unsaturated one Alcohol, but of the alloociment type, d. That is, the alcohol does not have a vinyl group like 7-methyl-3-vinyl-octen-6-ol- (1).

In the pyrolysis of cis-myrtanol one obtains an alcohol with a vinyl group, but also mixed with an isomeric alcohol with a butenyl group, which even predominates in percentage terms and as a result of a boiling point that is only 4 ° C lower is very difficult to separate by distillation.

Thermal isomerization of the Hydronopols can be carried out in a suitable pyrolysis furnace at temperatures between 500 and 600 ⁰ C. A diluent, for example nitrogen, steam or ammonia, is preferably used in vacuo. Sales is kept appropriately between 50 and 80 ° / _0th The condensed pyrolysate is then rectified in an effective ao column in vacuo, 7-methyl-3-vinyl-octen- (6) -ol- (1) being obtained in a very pure form.

Any unreacted hydronopole boils higher than 7-methyl-3-vinyl-octen- (6) -ol- (l) and can be used again as a starting material. The process for the production of 7-methyl-3-vinylocten- (6) -ol- (l) can also be made continuously by connecting the pyrolysis furnace with a rectifying apparatus connects, the higher-boiling product continuously withdraws and the lower-boiling product again the pyrolysis supplies.

The size and type of pyrolysis apparatus depends on the quantities to be processed Products. Since the 7-methyl-3-vinyl-octen- (6) -ol- (l) changes slightly at the pyrolysis temperatures used suffers, for example water is split off or cyclized, the contact time in the reaction zone should be kept very short or the flow rate of the starting material can be very high. It is therefore useful in a vacuum, for example to pyrolyze between 100 and 0.5 torr. In addition, it is appropriate to use materials which do not favor the separation of water, for example steel made of V2A or V4A material.

The 7-methyl-3-vinyl-octen- (6) -ol- (l) can easily be partially converted into 7-methyl-3-ethyl-octen- (6) -ol- (l) by methods known per se, Homocitronellol, hydrogenate. Both direct methods, such as B. the hydrogen addition in the presence of Raney nickel, as well as indirect, such . B. the reaction with an organoaluminum compound, in particular diisobutylaluminium hydride, and subsequent hydrolysis. In this way, about 90% homocitronellol is obtained, which can be produced in pure form by known purification methods, for example by rectification in a vacuum.

The esters derived from 7-methyl-3-vinyl-octen- (6) -ol- (1) and from homocitronellol can be prepared according to known Methods are made.

60 Example 1

Preparation of 7-methyl-3-vinyl-octen- (6) -ol- (l)

An electrically heatable V4A reaction tube with a clear width of 20 mm and a length of 1 m is placed vertically on an evaporating flask of 250 ecm which is provided with a dropping funnel and an inlet tube for inert gas. A tube, closed at the bottom, with an outer diameter of 10 mm and in which a thermocouple is embedded, protrudes from above into the center of the reaction tube. The reaction tube is bent at the head and merges into a descending condenser, at the end of which a collecting flask of 2 l is connected. The collecting flask is connected to a vacuum pump via a cold trap, the apparatus is evacuated and kept at 5 to 8 Torr. The evaporator flask is heated to 185 to 195 ⁰ C and the reaction tube temperature regulated to 560 to 58o C ^0.

With the help of the dropping funnel are then within a period of 4 _^3/4 hour 1198 g of cis-Hydronopol ( "f = 1.4892, df - 0.961;? [<X] ^ä = ₀ ° -28.9 °) in the evaporator flask added dropwise, while at the same time with the help of the inlet tube, a nitrogen stream is introduced at an average rate of 0.215 Nml / h.

In this way, 1122 g of pyrolysate are obtained which, according to gas chromatographic analysis, contain 49% 7-methyl-3-vinyl-octen-6-ol- (1) and 27% unreacted cis-hydronopol. The pyrolysate is rectified in vacuo with the aid of a 1.8 m long column with an internal diameter of 30 mm, which is filled with 4 × 4 mm wire mesh rings made of V2A. In the case of 10 Torr and a reflux ratio of 10 to 20,478 g of 7-methyl-3-vinylocten- (6) -OL- (l) (bp. _Lo 112-113 ⁰ C) and then still 245 g of unreacted cis-Hydronopol (Bp. _Lo 121 to 123 ° C) obtained.

The yield of 7-methyl-3-vinyl-octen- (6) -ol- (1) is thus 50% based on the converted cis-hydronopole.

The pure 7-methyl-3-vinyl-octen- (6) -ol- (l) is characterized by the following physical constants: bp. _Xo 112 to 113 ⁰ C; nf = 1.4670; df = 0.868; [*] f - + 14.4 °.

Example 2

Production of 7-methyl-3-vinylocten- (6) -ol- (l) -formate

A mixture of 30 g (0.18 mol) 7-methyl-3-vinylocten- (6) -ol- (1), 16, 4 g (0.36 mol) of formic acid, 0.5 g of p-toluenesulfonic acid and 54 ecm of benzene were added. The mixture is refluxed until no more water is discharged. After cooling, the reaction mixture is neutralized with 80 ecm of a saturated soda solution and the upper phase is extracted twice more with 50 ecm of water each time. After the separation, the benzene solution is filtered and distilled. At 10 torr and 111 to 115 ⁰ C are obtained 32 g of 7-methyl-3-vinyl-octene (6) -OL- (l) formate. This corresponds to a yield of 91% of theory.

The ester has the following characteristic constants: bp ₁₃ 113 to 114 ⁰ C; nf = 1.4550; df = 0.904; [«] F = + 9.2 °.

Example 3

Preparation of 7-methyl-3-vinylocten- (6) -ol- (l) -acetate

In a 500 ccm three-necked flask equipped with a stirrer, Reflux condenser and dropping funnel is provided, 50 g (0.3 mol) of 7-methyl-3-vinyl-

5 6

octen- (6) -ol- (l), 36 g (0.3 mol) of dimethylaniline and the cooled hydrogenation product was heated to boiling from 54 ecm of ether. It is slowly filled, filtered and distilled. At 10 Torr and 110 up to and including a solution of 22.7 g (0.3 mol) 121 ^° C., 35 g of distillate passed over, the 90% of 7-Me-acetyl chloride being added dropwise to 27 ml of ether and then ethyl-3 -äthyl-octen- (6) -ol- (l) contained. This corresponds to refluxing for another 3 hours. A yield of 71% of theory is then added, followed by 40 ecm of water and the mixture is used for so long. stirs until all diethylaniline hydrochloride has gone into solution B e ι s ρ ι e 16. The upper phase is separated off, 7-methyl-3-ethyl-octen-(6) -ol- (1) times with 10% sulfuric acid solution and formate (homocitronellol formate) twice with 10% sodium carbonate solution are extracted and distilled . io In a 250 ccm round bottom flask, which is connected ^{to a reflux condenser via a xylene bridge at 13 torr and 117 to 124 0} C, 58 g of distillate is transferred, the 90% 7-methyl-3-vinyl-octene (6) -ol- (l) -acetate contains a mixture of 13.5 g (0.079 mol) of 7-methyl-3-ethyl. This corresponds to a yield of 83% octen- (6) -ol- (l), 6.7 g (0.145 mol) of formic acid, theoretically. The ester purified by rectification, 0.217 g of p-toluenesulfonic acid and 50 ecm of benzene, has the following characteristic constants: 15. The mixture is refluxed for so long. _lo 119 to 120 ⁰ C; n ^s S = 1.4530; d ²⁰ "= 0.8983; boils until no more water is discharged. According to [λ] ο "= + 9.95 °. Cooling, the reaction mixture Example 2, as in the _Ώ.. Specified, worked up. In the distilling ^{e 1 ΰ s} P ^{'l e 4} are then at 10 torr and 111 to 113 , 5 ° C 13.2 g

Preparation of 7-methyl-3-ethyl-octen- (6) -ol- (l) _ao 7-methyl-3-ethyl-octen- (6) -ol- (l) -formate obtained.

(HomocitroneUol) This corresponds to a yield of 84% of theory.

For a mixture of 145 g (0.86 mol) 7-methyl- The ester has the following characteristic constants

3-vinyl-octene (6) -OL- (l) and 145 g of toluene, resulting in th at: Kp _lo 113-114 ° C;. n'g = 1.4482; df

a 1-1 three-necked flask equipped with a stirrer = 0.904; [x]% ° = -3.34 °.

The dropping funnel and cooler are located, 35

slowly 372 g (2.6 mol) of di-i-butylaluminum-ü e 1 s ρ 1 e 1 7

hydride was added dropwise. Since the handling of aluminum- production of 7-methyl-3-ethyl-octen- (6) -ol- (l) -

organic compounds are dangerous, acetate (homocitronellol acetate)

with nitrogen as protective gas and oil as cooling liquid In a 250 ccm round bottom flask, which is filled with a xylene

worked. While isobutene is evolving, a bridge connected to a reflux condenser rises

the reaction temperature gradually to about 8O ⁰ C. a mixture of 19.5 g (0.115 mol) 7-methyl-

When all the di-i-butyl-aluminum hydride has been added, 3-ethyl-octen- (6) -ol- (l), 13 g (0.217 mol) of glacial acetic acid,

the reaction mixture is added to 0.324 g of p-toluenesulfonic acid and 50 ml of benzene for a further 4 hours

100 ⁰ C held. boiled under reflux until no more water

After cooling, the reaction mixture is allowed to carry. After cooling, the reaction mixture is worked up into a mixture of mixture, as indicated in Example 2, with thorough stirring. 600 g of i-propanol and 600 g of ether flow, which result in When distilling are then at 10 Torr and 120.5 a 4-1 flask is located, with a stirrer up to 122.5 ° C 22 g of 7-methyl-3-ethyl-octen- (6) -ol- (l) - and a well-functioning reflux condenser equipped with acetate. This corresponds to a yield of is. The reaction mixture heats up quickly to 40-90.5% of theory.

40 to 45 ° C and begins to boil with the development of The ester has the following characteristic cone-butane and hydrogen. When everything is on the move: Kp. _Lo 122 to 123 ⁰ C, «f = 1.4462; is given, reflux is continued until df - 0.894; [α] ² S = -4.35 °. any gas evolution ceases.

The cooled reaction mixture then becomes long

sam stirred into 7.6 kg of 10% sulfuric acid, amount in

while ice water is used for cooling so that the reac component is parts by weight

tion temperature does not rise ^{above 3O 0 C.} The upper 1st HomocitroneUol 400

Phase is separated off with 10% soda solution neu-Geraniol 400

neutralized, dried over potassium carbonate and de- 50 phenylethyl alcohol 200

breastfeeds. Citral 1

140 g of 2nd geraniol 800 are obtained at 10 Torr and 113 ° to 119 ° C.

Distillate in which 92% of 7-methyl-3-ethyl-octen- (6) -HomocitroneUol 100

ol- (l) are included. This corresponds to a yield of phenylethyl alcohol 72

of 88% of theory. 55 Linalool 20

The pure 7-methyl-3-ethyl-octen- (6) -ol- (l) has homocitronellol acetate 10

the following physical constants: Kp. _lo 116 to Citral 3

117 ⁰ C; U ² S = 1.4592; df = 0.8599; [<x] ¹ S = -3.18 °. 3. Citronellol 400

_. . ... Geraniol 400

^{B e 1 s} P ^{J e} * ⁵ 60 phenylethyl alcohol 200

Preparation of 7-methyl-3-ethyl-octen- (6) -ol- (l) homocitronellol formate 50

(HomocitroneUol) Citral 1

A mixture of 4. Geraniol 700

from 44.5 g of 7-methyl-3-vinyl-octen- (6) -ol- (l), 37 g of Me-7-methyl-3-vinyl-octen- (6) -ol- (l) 100

ethanol and 2.5 g of Raney nickel. Then 65 phenylethyl alcohol became 200

Injected hydrogen and the mixture for so long with 7-methyl-3-vinyl-octen- (6) -ol- (l) -acetate 5

lOatü and held 80 to 9O ⁰ C until no water Citral 5

Substance uptake was more noticeable. 7-methyl-3-vinyl-octen- (6) -ol- (l) -formate ... 4

Claims (1)

7 8 claims: 2. fragrance composition according to claim 1, 1. Fragrance composition, g e k e η n- characterized in that they are effective characterized by a content of a component such compounds of the general bond of the general formula I contains formula I, which have been obtained by 5 that one Hydronopol, especially cis-Hydronopol, thermal isomerization --'-. Subjects to pyrolysis in the vapor phase and that Γ Υ obtained 7-methyl-3-vinyl-octen- (6) -ol- (l) isolated ; 1 and that one given / alls then either "\ ¹⁰ a) 7-methyl-3-vinyl-octen- (6) -ol- (1) directly ) L. with lower aliphatic carboxylic acids, especially . _v ha particular formic acid or acetic acid, in where Λ - H oüer _{at skh known wejse} or 15 b) the 7-methyl-3-vinyl-octen- (6) -ol- (l) initially _, _p after partial hydrogenation known methods and that with R = H or lower alkyl, in particular tene 7-methyl-3-ethyl-octene (6) -ol- (l) (homo- - CH ₃ or - C ₂ H ₅ and wherein citronellol) is isolated and optionally in esterified in a known manner with lower aliphatic ^Y CH — CH ₂ or —C ₂ H ₈ carboxylic acids, in particular formic acid or acetic acid. 709 510/507 2.67 © Bundesdruckerei Berlin