DE1203765B - Process for the preparation of trans, trans-cyclo-dodecadiene- (5, 9) -ol- (1) and a mixture of the cis, trans- and trans, cis-cyclododecadiene- (5, 9) -ol- (1) - Stereoisomers - Google Patents

Description

Process for the preparation of trans, trans-cyclo-dodecadiene- (5,9) -ol- (1) and a mixture of the cis, trans and trans, cis -cyclodoadecadiene (5,9) -ol- (1) stereoisomers The present invention relates to the preparation of new unsaturated cycloaliphatic Alcohols.

It is known that the cyclododecatriene- (1,5,9), which by trimerization of butadiene according to W i 1 k e (Angew. Chemie, Vol. 69, 1957, p. 397) was obtained, consists of two isomers, one of which, which is liquid, is the configuration trans, trans, cis and the other, melting at 34 ° C, the configuration trans, trans, trans owns.

It has now been found that these compounds are known per se Way saturated aliphatic monocarboxylic acids, which may also be halogenated can be, add to the formation of a mixture of esters, from which one monoester can isolate the streoisomeric cyclododecadiene- (5,9) -ole- (1) by known saponification deliver.

Assuming cyclododecatriene of configuration trans, trans, trans off, this leads to a well-defined monohydric alcohol, which is very likely the cyclododecadiene- (5,9) -ol- (1) is of configuration trans, trans, at 65 to 66 ° C melts and delivers a phenyl urethane with a temperature of 135 to 136 ° C. By exhaustive This alcohol is converted into cyclododecanol by hydrogenation.

If one starts from trans, trans, cis-cyclododecatriene, one obtains a Mixture of cyclododecadienols. An alcohol is isolated from this mixture, which is identical to the one that is derived from trans, trans; trans-cyclododecatriene receives. This alcohol probably results from attack by the cis double bond. This mixture contains another alcohol fraction, which is probably a mixture of cyclododecadiene- (trans-5, cis-9) -ol- (1) and cyclododecadiene- (cis-5, trans-9) -ol- (1) and probably originated from attack by the trans double bonds. This second Fraction is liquid and does not give a solid phenyl urethane. The hydrogenation of this second alcohol fraction also leads to cyclododecanol.

In addition to the alcohols in question, no matter which one is obtained Isomers is used, a fraction of alcohols whose weight analysis of the Formula C18112.0 and its unsaturation is low. This faction probably consists of polycyclic monohydric alcohols with 12 carbon atoms.

As a saturated aliphatic monocarboxylic acid, which is optionally halogenated formic acid, acetic acid and trifluoroacetic acid can be used. One works in the presence or absence of catalysts. If catalysts are used, so these are supposed to have acidic character. There are, for example, ion exchange resins with acidic character, mineral acids such as phosphoric acid, hydrochloric acid or perchloric acid, called.

The reaction between the aliphatic monocarboxylic acid and the cyclododecatrienes takes place at a temperature between 20 and 200 ° C, preferably less than 1 hour or heating the reaction components under reflux for several hours. One uses preferably a large excess of the aliphatic monocarboxylic acid, the Amount of the latter between 2 and 20 times that for making the monoester required theoretical amount may vary. The reaction mass obtained is then treated to remove the unreacted part of the organic acid and optionally to remove the mineral acids used as catalysts. You can take up the reaction mixture, for example, in water and the organic Layer consisting of a mixture of esters with different degrees of saturation, extract with a suitable solvent. Suitable as extraction solvent for example diethyl ether, benzene, chloroform and carbon tetrachloride. Man can also remove the excess of organic acid by distillation after the reaction remove.

The ester mixture obtained, the as yet unreacted cyclododecatriene contains, is separated by vacuum distillation to remove part of the excess at To remove cyclododecatriene and, on the other hand, the various fractions of To separate esters, one of which is rich in monoesters. By saponification in on As is known, the various ester fractions give alcohols. From the monoester fraction obtained from the trans, trans, trans-olefin gives directly the trans, trans-cyclododecadiene- (5,9) -ol- (1), it is sufficient to recrystallize this, if necessary, to complete a to get pure connection. The monoester fraction obtained from the trans, trans, cis olefin on the other hand, saponification produces a mixture of alcohols, from which the constituents are obtained can isolate using conventional methods. One can especially use the unsaturated ones Extract alcohols by making a solution of the mixture of alcohols with a treated aqueous silver nitrate solution.

The cyclododecadiene (5,9) ol (1) stereoisomers obtained from the two forms of cyclododecatriene (1,5,9) are compounds with a pleasant odor that can be used in perfumes. You own the smell of natural ambergris, but with special properties. So gives an addition of 8 0/0 cyclododecadienols to an "artificial geranium" mixture this one an extraordinary adhesion with the note of crushed leaves. at an "artificial sandalwood" mixture, the addition emphasizes the warm Note of sandalwood with a balsamic scent result. The alcohols can be used for the manufacture of plasticizers, used for cellulosic and vinyl polymers. The presence The two double bonds give them interesting chemical properties, in particular a great reactivity that can be used in organic syntheses. For example, you can chlorinate these alcohols in order to repel insects To give effectiveness. The alcohols can also be hydrogenated to cyclododecanol will.

The mixture of cyclic alcohols with 12 carbon atoms that obtained during saponification can also be used in raw form for manufacture plasticizers and products used in perfumery.

The following examples illustrate the invention. Example 1 In a A flask equipped with a stirrer and reflux condenser is charged with 417 g of trans, trans; trans-cyclododecatriene (1,5,9) and 720 g of 99.60 / 0 formic acid.

The mixture is heated with stirring and refluxed for 2 hours. The unreacted formic acid is then distilled under reduced pressure and the residue is fractionated in vacuo. The following fractions are obtained: 265 g of unreacted cyclododecatriene, 22 g of intermediate fraction from b.p. 1 = 86 to 91 ° C with a content of monoesters of 49 0/0, 92.5 g of a monoester fraction from Kp.l = 91 to 1010c.

A residue remains which contains higher-boiling fractions.

The yield of monoesters is, taking into account the recovered Cyclododecatrien 53 0/0. The monoester fraction has a saponification number of 272 (theory for the monoformate 269) and a refractive index no3 = 1.4910.

Analysis: 013H2002 Calculated ... C = 75.04 0/0, H = 9.7 0/0; found ... C = 73.020 / 0, H = 9.970 / 0.

By saponifying using an alcoholic sodium hydroxide solution one obtains trans, trans-cyclododecadiene- (5,9) -ol- (1), which after recrystallization from petroleum ether melts at 65 to 66 ° C and a phenyl urethane with a temperature of 135 to 136 ° C supplies.

Example 2 One works in the same way and with the same Quantitative proportions of reaction components as described in Example 1, however, replaced the trans; trans, trans-cyclododecatriene by the trans, trans; cis stereoisomers.

The distillation of the mixture obtained after the reaction gives 188 g of unreacted cyclododeeatria with a boiling point of 3 = 87 to 89 ° C., 62.5 g of intermediate fraction with a content of 31.8% monoformate of alcohols with 12 carbon atoms from bp 3 = 91 to 115 ° C, 108 g of a fraction of liquid monoesters with the following Key figures: bp 3 = 119.5 to 122.5 ° C; Refractive index nos = 1.4952; Monoformate content of the formula 013H2002: 99.20 / 0. Hydrogen fixed by catalytic hydrogenation: 1.2 mol for 013H2002 # The residue contains a mixture of esters of diols with 12 carbon atoms and of polymers of cyclododecatriene.

Taking into account the recovered cyclododecatriene is the yield of monoformate 43.50 / 0.

By saponifying the formic acid ester obtained with an alcoholic Solution of sodium hydroxide gives a liquid mixture of alcohols with the following Features: Bp.s = 128 to 130 ° C; nos = 1.515 ?.

20 g of this mixture are dissolved in 100 cc of cyclohexane and extracted then 8 times with 25 cc each of an aqueous 300/0 silver nitrate solution.

The organic layer is evaporated and 8.2 g of a viscous layer are obtained Liquid that boils at 122 to 125 ° C at a pressure of 4 mm Hg. Will the If the liquid is subjected to catalytic hydrogenation, it absorbs 0.5 mol Hydrogen based on a formula of 012H200. It consists of a mixture of polycyclic alcohols with 12 carbon atoms.

The aqueous layer of silver nitrate is poured into 300 cc of ammonia with a density of 0.925. 9 g of a product with a temperature of 37 to 47 ° C and bp 4 = 1-23 to 124.5 ° C precipitate. A hydrogenation experiment with an aliquot shows that 2 moles of hydrogen, based on a formula of 012H200, have been taken up, a saturated product having an alcohol function with a temperature of 80 ° C, which is similar to that of Kobelt, Barman, Prelog, R uzicka (Helvetica Chimica Acta, Vol. 32, 1949, p.256) described cyclododecanol is identical. With phenyl isocyanate, the product with a temperature of 37 to 47 ° C gives a phenyl urethane with a temperature of 129.5 to 131.5 ° C in a yield of 59 ° / 9. The recrystallized phenyl urethane melts at 135 to 136 ° C. Analysis of the phenyl urethane: C19H "0aN Calculated... C = 76.2 ° / 9, H = 8.5 ° / 9; found ... C = 75.85 ° / 9, H = 8.3%. At a mixed sample with the phenyl urethane obtained according to Example 1 shows no lowering of the melting point.

The corresponding alcohol is therefore trans, trans-cyclododecadiene- (5,9) -ol- (1). The rest of the mixture of alcohols that does not precipitate in the form of phenyl urethane, consists of cis, trans- and trans, cis-cyclododecadiene- (5,9) -ol- (1). Example 3 Man works as described in Beispie12, but also sets the reaction mixture 0.3 g of 65% perchloric acid. After the reaction one distills and wins 153 g of unreacted cyclododecatriene and 149.5 g of monoformate from section 3 to section 4 = 118.5 to 123.5 ° C, which corresponds to a yield of 47% taking into account the recovered Cyclododecatrien corresponds.

The saponification of the monoformate is carried out as in Example 2. Example 4 Place in a flask equipped with a stirrer and reflux condenser one 162 g trans, trans; ois-cyclododecatriene (1,5,9), 180 g glacial acetic acid and 32.4 g phosphoric acid with a density of 1.7. The mixture is heated with stirring and held for 24 Hours under reflux. Then you cool it down, pour the contents of the flask into water and extracted with ether. After washing with water and drying, the ether extract becomes distilled in vacuum. The following fractions are obtained: 70.9 g of unreacted Cyclododecatriene (bp "" = 58 to 65 ° C), 46.8 g of intermediate fraction with a content of 16.7% monoester (b.p. 75 = 66 to 105 ° C), 38.7 g monoester fraction (b.p. 9.9 = 105 to 125 ° C), 15.3 g residue.

The monoester fraction has a content of monoacetate of the formula Ci4H "0a of 97.00 / 0. Its refractive index is nö5 = 1.4902.

The saponification of the monoester fraction is carried out as in Example 2.

Example 5 In one equipped with a stirrer and reflux condenser Flask is brought to 81 g of trans, trans; cis-cyclododecatriene (1,5,9) and 62.7g trifluoroacetic acid a.

The mixture is refluxed with stirring for 6 hours. After cooling, the reaction mass is taken up in 250 ccm of ether and the ethereal solution is washed with water until the washing liquids have a pH of about 6. The ether solution is dried over anhydrous sodium sulfate, the ether is removed and distilled. 53.8 g of a fraction boiling at 61 ° to 117 ° C. under a pressure of 0.6 mm Hg and 50.7 g of a blackish, very viscous residue are obtained.

When rectified at 0.5 mm Hg, the fraction of 53.8 g yields 14.6 g of a fraction which boils at 53 to 70 ° C. and has a monoester content of 51.501, 10 g of a fraction which boils at 70 ° C , Boils from 5 to 73 ° C and has a monoester content of 95.20 / 0, 23 g of monoester fraction with a boiling point of 73 to 77 ° C., 5.7 g of residue which contains a mixture of mono- and diesters.

The fraction with a boiling point of 73 to 77 ° C. has a content of monotrifluoroacetate of the formula C14H "0aF3 of 98.50 /, and has a refractive index nö5 = 1.4450.

The saponification of the monoester fraction is carried out as in Example 2.

Claims (1)

Claim: Process for the preparation of trans, trans-cyclododecadiene- (5,9) -ol- (1) and a mixture of the cis, trans and trans, cis -cyclododecadiene- (5,9) -ol- (1) -stereoisomers, d a d u r c h e k e n n -z e i c h n e t that one trans, trans, trans- and trans, trans, cis-cyclododecatriene- (1,5,9) in a manner known per se with saturated aliphatic, optionally halogenated Monocarboxylic acids and the monoester fraction isolated from the reaction mixture saponified in a known manner. Publications considered: German Auslegeschriften Nos. 1058 506, 1061775, 1058 987, 1029 823, 1059 904; U.S. Patents No. 2,426,725; 2,414,089; J. Am. Chem. Soc., Vol. 69, 1947, pp. 1826, 1827; J. Chem. Soc., 1953, pp. 3329, 3330; Chem. Reviews, Vol. 49, 1951, p.143. Considered older patents: German Patent No. 1089 753.