DE1065842B - - Google Patents

Description

The invention relates to the preparation of new derivatives of 1,1-dimethyloctahydronaphthalene, which in 7-position carry an oxygen-containing organic residue. The procedure is that you go through Adducts obtained from diene synthesis from myrcene (I) and a dienophilic compound of the general formula II, which has the general formula III

-V ^v

own, in the R ₁

CO-R ₁

Hydrogen atoms, alkyl, aryl, aralkyl, cycloalkyl. or heterocyclic radicals (^ and R ₁ denotes -OH or an ether group, such as OCH ₃ , in a manner known per se in the presence of H ₂ SO ₄ or HCOOH or mixtures thereof at -30 to + IO ⁰ C cyclisie rt. The process according to the invention can also be illustrated by the following reaction scheme:

R «

'+ "" CCR ₁

I / Il

RR ₂

C O

3 ^R 4

I /

\ A

R _s

Ri

III

^vv R _a

Ri

IV

example 1

1,1-Dimethyloctahydronaphthalene-7-carboxylic acid methyl ester

1 mole of myrcene was heated together with 1 ¹ J ₂ moles of methyl acrylate with addition of a spatula tip of phenyl / S-naphthylamine, 2 hours at 145 to 150 ° C in an autoclave. The yield of pure myrcene acrylic acid process for the preparation of derivatives of the 1,1-dimethyloctahydronaphthalene series

Addendum to patent 1,045,393

Applicant:

DRAGOCO special factory conc. Fragrances and aromas Gerberding & Co. G.m.b.H., Holzminden / Weser, Dragocostr. 1

Dipl.-Chem. Dr. Günther Ohloff ₁ Mülheim / Ruhr, has been named as the inventor

25th

methyl ester adduct of the general formula III, in which R ₁ = OCH ₃ and R ₂ to R _{4 are} hydrogen atoms, was 90% of theory. _{300 g of the previously unknown monocyclic ester (formula III; R 1} = OCH ₃ ; R ₂ to R ₄ = H) in 600 ecm of ether were added dropwise to 2000 ecm of 62% sulfuric acid with vigorous stirring at - 15 ° C. that the temperature did not exceed ^{+ IO 0 C.} The dropping time was about 45 minutes. The mixture was then stirred for a further 1 hour at -7 ° C. and then worked up in the usual way. In this way, it was possible to obtain 255 g (85% yield) of bicyclic ester with a content of 95%, which after fractional distillation had a content of almost 100%. Constants:

Bp ₀₄ = 105-107 ° C; Df = 1.0100; n'S = 1.4918; Estei content: 100%

The bicyclic ester was a colorless, somewhat viscous oil, which mainly consisted of the / 5 components duration. It had a faint violet and woody odor.

Example 2

1,1,7-trimethyl-d ⁹ - ¹⁰ -octahydronaphthalin-7-carbonsäuremethylester

612 g (4.5 mol) of myrcene and 500 g (5 mol) of methyl ct-methylacrylate (formula II: R ₁ = OCH ₃ ; R _a = CH ₃ ; R ₃ and R ₄ = H) were added with the addition of about 1 g Phenyl- / S-naphthylamine 3 hours to 145 bis

909 629/336

Claims (1)

ι Ubb 150 ° C heated in the autoclave. The subsequent distillation through a column gave 650 g (61% yield) of pure ester of the formula III (R ₁ = OCH ₃ ; R ₂ == CH ₃ ; R ₃ and R ₄ = H). 500 g of monocyclic ester was dissolved in 500 ecm of ether and introduced into 3500 ecm of 62% sulfuric acid with vigorous stirring so slowly that O ^c C was not exceeded. The mixture was then stirred for a further hour at -5 ° C., the reaction mixture was poured onto a lot of ice and it was extracted exhaustively with benzene. The resulting lower layer was separated off by decanting and the remaining benzene solution was washed with water until the wash water was neutral. The purified by distillation bicyclic ester mainly composed of l, l, 7-TrimethyI- ^ ^{fl 'lo} -octahydronaphthalin-7-carbonsäuremethylester existed, was prepared in this way in a yield of 65%.
Constants: B.p. ₂₃ = 128 to 130 ° C; £>. » = 1.0094; nf = 1.4882; Ester content: 100%. Example 3 1,1,6-Trimethyloctahydronaphthalene-7-carboxylic acid methyl ester
. 100g esters of the formula III (R ₁ = OCH ₃ ; R ₂ and R ₃ = H; R ₄ = CH ₃ ), by adding molar amounts of myrcene and crotonic acid methyl ester for 2 hours (formula II: R ₁ = OCH ₃ ; R ₂ and R ₃ = H; R ₄ = CH ₃ ) in an autoclave at 160 ° C., concentrated sulfuric acid, stirred to 500 ecm, was added dropwise at -8 ° C. over the course of 1 hour, and the reaction mixture was poured onto ice after a further hour. The work-up was carried out as indicated in the previous example. In this way, 81 g (81 % theoretical yield) of bicyclic esters with the following constants were obtained: For the preparation of the starting compounds protection in the context of the present invention nii claimed. The gewol nenen by the inventive process new compounds are valuable Riechstofi caused by new and compared to known Vei \ connections through other types of olfactory notes and compared \ to known Octahydronaphthahnderivaten by working, distinguished Sonder good adhesion. 10 Claim: Further development of the process for the preparation of derivatives of the 1,1-dimethyloctahydronaphthalene series according to patent 1,045,393 by cycling compounds of the general formula 35 35 / / N -CO-R ₁ in the R ₁ to R ₄ denotes hydrogen atoms, alkyl, aryl, aralkyl, cycloalkyl or heterocyclic radicals, in which, however, not all radicals R ₁ to R ₄ may be hydrogen atoms at the same time, with sulfuric acid, phosphoric acid, boron trifluoride and formic acid at about -30 to + 75 ⁰ C, characterized in that compounds of the general formula given above, in which R ₁ is OH or an ether residue such as OCH ₃ , are used as starting materials and these are mixed with sulfuric acid or formic acid or mixtures thereof at about -30 cyclized to + IO ⁰ C in a manner known per se. Bp ₂ = 129 to 131 ° C; Z>. » = 0.9815; *?
Ester content: 91.5%. Relevant publications: German Patent Nos. 812 313, 73089,127 424; German interpretation G 15 978 IVb / 12o (published May 3, 1956); Bull. Soc Chim. France, 5th series, vol. 17, 1950, pp. 793 1.4864; 40 to 800; 1956, pp. 391 to 401; 1955, pp. 1466 to 1470; Helv. Chim. Acta, Vol. 32, 1949. pp. 2102-2124. ! 01 909 £ 29/336 9.59