DE2615393A1 - METHOD FOR MANUFACTURING ALLYL MERCAPTANS - Google Patents

Description

Patent attorneys 2 6 1 5 3 S 3

Dr. Franz Lci2rer
DipUng. fc'ry F. ^ eyer - Apr 8 »

8000 Mü.-rhon 80-Lucile-Grahn-SU. 22, EJ. {di.il). 472347

651OA57

L. Givandan & Cie Soeiete Anonyme, Vernier-Geneve (Switzerland)

Process for the production of allyl mercaptans

The invention relates to a process for the preparation of allyl mercaptans. The procedure is characterized by that you have an allyl xanthogenate, especially one of the formula

R ² R ³ R ⁴ S

! = U_0 -! - SO Ka.® II

R ¹ R ⁵

wherein R to R is hydrogen, optionally carrying an oxygen-containing group lower-alkyl, lower-alkenyl, lower-alkynyl,

Cyclo-lower-alkyl or cyclo-lower-

2 3 alkenyl, where R and R or

2 4 3 4 R and R or R and R also to the ring

can be closed and Kat> - ' 009843/1250

Represents a cation of a base, heated in an aqueous medium.

When using Ällylxanthogenaten of the formula II thereby form, as was surprisingly found, the allyl mercaptans Ia in a mixture with their allyl rearrangement products Ib

ft ² R ³ R * R ² R ³ R ⁴

IJ I I I!

C-C-C-SH HS-C-C = C

R ¹ R ⁵ R ^f R

Ia Ib

wherein R to R have the above meaning.

This finding is surprising insofar as it is actually it was to be expected that when the AlIy! xanthogenate a disintegration into CS_ and that of the allyl xanthate lying allyl alcohol would occur.

Examples of groups represented by R to R are in particular alkyl, alkenyl containing up to 6 carbon atoms or alkynyl groups with a straight or branched chain, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, R denotes in particular also a group of the formula

- Ic

where η is an integer from 1-3 and the dashed bond is also hydrogenated can be.

609843/1230

Further examples of groups represented by R to R are groups of the type mentioned above with oxygen-containing substituents, such as free, esterified or etherified hydroxyl groups, oxo groups or free or esterified carboxyl groups. Esterified hydroxyl groups are for example acyloxy groups, the acyl radical of which is from one lower aliphatic or aromatic carboxylic acid, such as Formic acid, acetic acid, propionic acid, butyric acid etc. or benzoic acid is derived. Etherified hydroxyl groups are, in particular, lower alkoxy groups, such as methoxy, ethoxy, Propoxy, isopropoxy etc., or aryloxy groups such as phenoxy etc. Examples of esterified carboxyl groups are carbalkoxy groups, whose Alky! component differs from a lower one Alkanol derived, such as methanol, ethanol, propanol etc. Further examples of R groups are cyclo-lower-alkyl- or cyclo-lower-alkenyl groups, e.g. cyclopentyl, cyclohexyl, Cyclopentenyl, cyclohexenyl and their derivatives with oxygen-containing substituents, such as those mentioned above free, etherified or esterified hydroxyl groups or free or esterified carboxyl groups.

2 3 3 4 As mentioned above, R can be combined with R, or R can be combined with R or

2 4
R with R must also be closed to form a ring. Examples of such rings are in particular carbocyclic 5- and 6-rings. So

2 3 3 4 2 4

For example, R together with R or R with R or R with R denote a tetramethylene or pentamethylene group. These Rings can in turn have further substituents, for example methyl, isopropyl or isopropenyl radicals, etc. or else also carry bridge members, such as methylene groups. Accordingly, allyl mercaptans of the formula I also come Connections with the p-menthan, thujan, caran, pinan, Bornan (Camphan) scaffolding, etc. in question.

609843/1230

Bases supplying the cation Kat ^ are expediently Alkali hydroxides such as sodium hydroxide or potassium hydroxide, Alkaline earth hydroxides such as magnesium hydroxide, alcoholates such as sodium methylate, sodium ethylate, potassium methylate, potassium ethylate, etc., alkali or alkaline earth hydrides such as sodium hydride, calcium hydride, etc., metal alkyls, e.g. butyllithium, etc. metal aryls, e.g. phenyllithium, etc.

The inventive heating of the AlIy! Xanthogenate expediently takes place at temperatures of approx. 40C-approx. 100 ° C; preferably to approx. 80 ° C - approx. 100 ° C.

The reaction products can be isolated in the usual way: cooling the reaction mixture, neutralization with acid and extraction with ether.

The separation of the mixture of the two isomeric allyl mercaptans (Ia and Ib) in the components can be done by distillation.

The compounds of the formulas Ia and Ib are partly known, partly new compounds, which have valuable organoleptic properties.

Known compounds are, for example, thiogeraniol and thiolinalool (see the Belgian patent No. 784016 and the German Offenlegungsschrift 2404154).

Of the new connections, these are in particular

2-methyl-hept-2-en-1-thiol, 2-methyl-hept-1-en-3-thiol, 1- [1,1,3-trimethyl-3-cyclohexen-2-y1] -but- 2-en-l-thiol, 1- [l _f l, 3-trimethyl-3-cyclohexen-2-yl] -but-l-en-3-thiol,

2-isopropyl-5-methyl-cyclohex-2-en-1-thiol, 3,7,11-tri

609843/1230

methyl-dodeca-l, 6, lO-triene-3-thiol, 3,7,11-trimethyldodeca-2,6,10-triene-l-thiol, Oct-l-en-3-thiol and the oct-2-en-l-thiol

highlighted.

These new sulfur-containing compounds of general formula I are characterized by special odor and / or taste properties, on the basis of which they are used in fragrance and / or flavor compositions, in particular those with berry, fruit and / or flower notes can be used.

The allyl mercaptans obtainable according to the invention can be used due to their interesting aroma properties in the production of high quality fruit aromas for food (e.g. dairy products, yoghurt, etc.), luxury goods (e.g. confectionery products, such as Sweets) and drinks (e.g. table water, mineral water, etc.). Their distinctive aromatic qualities make it possible the use in low concentrations, e.g. in the range of 0.1 ppm - 10 ppm, preferably in the range from 1-10 ppm. But higher concentrations, e.g. 50 ppm, are also possible. For example, a mixture of 3,7, ll-trimethyldodeca-l, 6,10-triene-l-thiol and its rearrangement product 3,7, ll-trimethyl-dodeca-l, 6,10-triene-3-thiol in the ratio of approx. 1: 1 to improve the taste properties, e.g. of citrus aromas, such as grapefruit aromas, or of fruit juice drinks, Mineral waters, etc. of this flavor are used: In particular, the shell character is used here the grapefruit is emphasized in the desired way and the fruit character appears more rounded.

However, the new allyl mercaptans obtainable according to the invention also unfold in fragrance compositions, e.g. in Compositions with a floral note, beneficial properties, adding the smell of such compositions in welcome

609843/1230

-e- 2615333

Way to modify, be able to. Accordingly, you too are körinen as fragrances for the production of perfumes, in particular those with wood and floral notes, are used, the dosages in the range of about 0.001-5% by weight, preferably About 0.01-1% by weight can be. Such fragrance compositions can be used as actual perfumes, also as bases for perfuming products such as solid and liquid detergents, synthetic detergents, Aerosols and cosmetic articles of all kinds (e.g. soaps, lotions, creams, etc.) are used. The new allyl mercaptans obtainable according to the invention are also distinguished by excellent adhesive strength the end.

A particularly interesting fragrance is 3,7,11-trimethyl-dodeca-l, 6,10-triene-l-thiol or its Mlyluolagerungsprodukt. Their use comes in particular due to the sulphurous, fruity, metallic and green notes in question, for example in a composition with a flowery character, e.g. honeysuckle, orange blossom, tuberose, etc.

The compounds of the formula II can be obtained by using an allyl alcohol of the formula

R ² R ³ R ⁴

I I i

= C-C-OH IV

's

R ⁵

in which R to R have the above meanings, after conversion into the alcoholate

609843/1230

R ² R ³ R ^A

C = CCO ⁹ Kat® III

I. I.

R ⁵

where R to R and Kat ^ have the above meaning, Reacts with carbon disulfide.

The conversion into the alcoholate can be carried out according to known methods Methods are carried out under the influence of one of the bases mentioned above. The implementation can be done with the help of a Solvent, such as an ether, e.g. dimethyl ether, Diethyl ether, tetrahydrofuran, take place. However, the presence of a solvent is not essential.

The implementation of the alcoholate produced primarily with carbon disulfide can be used for the production of Xanthates are done using customary methods.

One can thus, for example, the alcoholate III with carbon disulfide at temperatures of from about -20 to +40 ⁰ C, in particular about 10 to 30 together give ° C. If the alcoholate has already been formed in the presence of a solvent, it is not necessary to add a solvent.

However, if the alcoholate formation took place in the absence of a solvent, it is expedient to use one, for example one of the above is added.

The xanthate formed forms as a precipitate which can be isolated by filtration and washing.

609843/1230

Example 1 Method A

0.1 mol of the allyl alcohol IV are at 0-20 ° C with 0.05 Moles of powdered potassium hydroxide are added and the mixture is stirred for 30 minutes at 20 C, then for 1 hour at 90 ° C. After cooling down to 20 ° C 0.06 mol of carbon disulfide and 100 ml of ether were added.

The precipitated allyl xanthate II is filtered off, Washed with ether, mixed with 10 times the amount of water and under a nitrogen atmosphere for 1 hour 100 ° C heated. The mixture obtained is cooled, neutralized with acid and extracted three times with ether. the combined organic phases are washed with water, dried over anhydrous sodium sulfate and evaporated. A mixture of the isomeric allyl mercaptans Ia is obtained in this way and Ib, which can be separated by distillation if desired.

Method B.

0.1 mol of alcohol IV is added to 50 ml of dimethoxyethane with 1.1 equivalents of sodium hydride and the mixture is heated to 50 ° C for 1 hour. After the reaction mixture has cooled, 1.5 equivalents of carbon disulfide become added and stirred for a further 1 hour. The mixture is evaporated in vacuo.

The allyl xanthate II obtained as a residue is

with 10 times the amount by weight of water for 60 minutes to 1OO ° C ι
specified.

heated to 100 ° C. The work-up is carried out as under A

60984 3/12 3 0

method

Allyl alcohol

Xanthate water

(ID

Allyl mercaptans
(Proportions of isomers)

1:50

(72.5)

IV-I

Ib-I

SH

Ia-I
Ia-I ¹

H (2.2)

1:50

(68.5)

IV-2

Ib-2

SH

Ia-2
Ia-2 ¹

SH (13.8)

IV-3

1:10

Ib-3

(40)

Ia-3

1:10

OH c / tr iv-4

1:10

IV-5

Ib-5

(90)

(10)

Ia-5

continuation

IV-6

1:10

Ib-6

(95)

Ia-6

OH

1:10

SH

IV-7

(45) lb-7

(55)

Ia-7

1:10

IV-8

Ib-8

(60)

Ia-8

(AO)

OH

IV-9

1:10

cis-carveol
»10% trans)

(<"" · Ί0% trans)

1:10

(15) SH Ib-IO

cn * co

1:10

Ib-Il

trans)

continuation

OH

IV-13

Myrtle oil

1:10

1:10

(60) SH ia-12

SH

(30) Ia-13

cn co co co

Example 2 Perfume Composition (Base)

Parts by weight Myraldyl acetate 300 Linalyl acetate synthetic 280 Geraniol extra 200 Amyl salicylate 100 Styrallyl acetate 20th Methyl-3-heptenone-5-oxime (10% in
Aethy! Alcohol) 20th 920

80 parts of 3,7,11-trimethyldodeca-1,6,10-triene-1-thiol are added to the above composition and 3,7,11-trimethyl-dodeca-1,6,10-triene-3-thiol in a ratio of approx. 1: 1, the overall complex has a desirably strengthened effect. The fresh and flowery one Effect is now more pronounced.

609843/1 230

Claims (17)

Claims Process for the preparation of allyl mercaptans, characterized in that an allyl xanthogenate in heated in an aqueous medium. 2. The method according to claim 1, characterized in that an allyl xanthogenate of the formula R ² R ³ R ⁴ S III Il θ θ C = CCOCS ⁰ cat ^W II R ¹ R ⁵ wherein R to R is hydrogen, optionally carrying an oxygen-containing group lower-alkyl, lower-alkenyl, lower-alkynyl, Cyclo-lower-alkyl or cyclo-lower- 2 3 alkenyl, where R and R or 2 4 3 4 R and R or R and R also to the ring can be closed and Kat ^ das Represents a cation of a base to a mixture of allyl mercaptan R ² R ³ R ^A U I c = c-c-sH Ia wherein R to R have the above meaning, and its allyl rearrangement product 609843/12 3'G R ² R ³ I I! HS-C-C = C Ih L I R ¹ R ⁵ wherein R to R have the above meanings, are reacted. 3. The method according to claim 1, characterized in that that the Ällylxanthogenat used as the starting material is obtained by converting an allyl alcohol into the allyl alcoholate transferred and this reacts with carbon disulfide. 4. The method according to claim 3, characterized in that an allyl alcohol of the formula R ² R ³ R ⁴ I I I C = C-C-OH R ¹ R ³ in which R to R have the above meanings, in an alcoholate of the formula R ² R ³ R ⁴ C = CCO ⁹ Kat® III _{1 5} R ¹ R ⁵ where R fc> is R have the above meaning and Kat ^ represents the cation of a base, transferred and this with carbon disulfide to Ällylxanthogenat of formula II implements. 60984 3/1230 5. The method according to any one of claims 1-4, characterized in that heating the Allylxanthogenat to a temperature of about 40 C to about 100 ⁰ C. 6. The method according to any one of claims 1-4, characterized in that the mixture obtained from allyl mercaptan and separates its rearrangement product by distillation. 609843/1 230 7. Fragrance or flavor compositions, marked by a content of 2-methyl-hept-2-en-1-thiol or 2-methylhept-2-en-3-thiol, to oct-2-en-l-thiol or oct-l-en-3-thiol, in 3,7, ll-trimethyl-dodeca-l, 6,10-triene-l-thiol or 3,7,11-trimethyl-dodeca-l, 6, lO-triene-3-thiol, to 1- [1,1,3-trimethyl-3-cyclohexen-2-yl] -but-2-en-1-thiol or 1- [l, l, 3-trimethyl-3-cyclohexen-2-yl] -but-1-en-3-thiol or 2-isopropyl-5-methylcyclohex-2-en-1-thiol. 8. 2-methyl-hept-2-en-3-thiol. 9. 2-methyl-hept-2-en-1-thiol. 10. Oct-1-en-3-thiol. 11. Oct-2-en-1-thiol. 12. 3,7,11-trimethyl-dodeca-1,6,10-triene-1-thiol. 13. 3,7,11-trimethyl-dodeca-1,6, 10-triene-3-thiol. 14. 2-Isopropyl-5-methyl-cyclohex-2-en-1-thiol. 15. 1- [1,1,3-Trimethyl-3-cyclohexen-2-yl] -but-2-en-ithiol. 16. 1- [1,1,3-Trimethyl-3-cyclohexen-2-yl] -but-1-en-3-thiol. 609843/1 17. Use of 2-methyl-hept-2-en-1-thiol or 2-methylhept-2-en-3-thiol, of oct-2-en-l-thiol or oct.-l-en-3-thiol, of 3,7,11-trimethyl-dodeca-lfö ^ O-triene-l-thiol or 3,7,11-trimethyl-dodeca-l, 6,10-triene-3-thiol, of 1- [1,1,3-trimethyl-3-cyclohexen-2-yl] -but-2-en-1-thiol or 1- [1,1, 3-trimethyl-3-cyclohexen-2-yl] -but-1-en-3-thiol or of 2-isopropyl-5-methyl-cyclohex-2-en-1-thiol as fragrances and / or flavorings. 609843/1230