US3709929A

US3709929A - 4-methyl-2-pentanol crotonate

Info

Publication number: US3709929A
Application number: US00074228A
Authority: US
Inventors: F Exner; T Leidig
Original assignee: Haarmann and Reimer GmbH
Current assignee: Haarmann and Reimer GmbH
Priority date: 1970-04-10
Filing date: 1970-09-21
Publication date: 1973-01-09
Anticipated expiration: 1990-01-09
Also published as: FR2089509A5; GB1279080A; CH550133A; NL7014250A; DE2017208A1

Abstract

SUBJECTED OF THE INVENTION IS 4-METHYL-2-PENTANOL CROTONATE, A PROCESS FOR ITS PRODUCTION WHEREBY 4-METHYL-2PENTANOL IS ESTERIFIED WITH CROTONIC ACID AND THE USE OF THE CROTONATE FOR PERFUME COMPOSITIONS AND AS AN ODORANT.

Description

3,709,929 4-METHYL-2-PENTANOL CROTONATE Fritz Exner and Theodor Leidig, Holzminden, Germany, assignors to Haarmann & Reimer Gesellschaft mit beschrankter Haftung, Holzminden, Germany No Drawing. Filed Sept. 21, 1970, Ser. No. 74,228 Claims priority, application Germany, Apr. 10, 1970, P 20 17 208.1 Int. Cl. C07c 6'9/56 US. Cl. 260486 R 1 Claim ABSTRACT OF THE DISCLOSURE Subject of the invention is 4-methyl-2-pentanol crotonate, a process for its production whereby 4-methyl-2- pentanol is esterified with crotonic acid and the use of the crotonate for perfume compositions and as an odorant.

This invention relates to the crotonic acid ester of 4-methyl-2-pentanol, to its preparation and to its application.

The compound according to this invention can be obtained by esterification methods known per se, preferably by the direct esterification of crotonic acid with 4-methyl- 2-pentanol, the water of reaction formed preferably being removed azeotropically, in the presence of an acid catalyst, for example concentrated sulphuric acid or p-toluene sulphonic acid, and a hydrocarbon boiling at 80 to 150 C., preferably toluene or xylene, as entraining agents.

The ester according to the invention is distinguished by desirable odoriferous properties and adds a valuable odorant to the perfume materials hitherto available for synthesizing fruit-like notes.

For some years now, the fruit-like note, partly dominating, partly as a nuance of an odor complex, has been acquiring increasing significance in the manufacture of perfumes for general use and in the synthesis of certain types of odor in fine erfumery. This may be attributable to the fact that an awareness of culinary odors is associated more or less unconsciously with a feeling of Wellbeing.

The odorants preferably used for the synthesis of fruitlike notes, such as iso-amyl acetate, hexyl acetate, ethyl acetate and other esters of lower fatty acids, readily bring to mind undesirable notions of bonbons or solvents or commercial products. For this reason they are not easy to handle in the composition of perfumes and have to be harmonically rounded off in terms of odor by skillfully combining several of these substances in order to restrict the occurrence of aesthetically unpleasant notes.

4-methyl-2-pentanol crotonate does not have any of these disadvantages. It has a very pleasant, pure fruit-like note reminiscent in particular of plum and apple preserves. It differs from conventional fruit-like odorants not only in its type of odor but also in the fact that it can be used more easily and more widely. Although distinct effects in the perfume composition can be obtained even with small quantities of the odorant, it can also be used in a high concentration in the composition or even without any other odorants for perfuming preparations by virtue of its aesthetically pleasing odor, without the aforementioned negative side etfects encountered in conventional fruity odorants.

By virtue of its type of odor and its service properties, the compound according to the invention can be used for a very wide variety of applications. It is suitable for use in perfume compositions for numerous end products of the cosmetics, fine-perfumery, detergent and chemical specialities industries.

In high concentrations it is preferably used for plum United States Patent 3,709,929 Patented Jan. 9, 1973 notes, in average concentrations as the main carrier of the fruit-like character in conjunction with other suitable odorants for the production of other fruit-like notes such as apple, pear, peach and grape. In low concentrations, 4-methy1-2-pentanol crotonate is advantageously also used in compositions where the dominating odor note cannot be regarded as fruit. In this way, a natural character can be imparted to some of these compositions.

The possibilities of composition are further enriched by using 4-methyl-2-pentanol crotonate insofar as novel extremely harmonic odor accords can be obtained with this odorant, especially by combining it with flower and green odorants.

EXAMPLE 1 The following formulation is given as an example of the preparation of a perfume with a plum-like odor which is a suitable fragrance for dishwashing detergents:

fi -hexanol isobutyrate, 10% 5 Bergramot oil, Reggio 1O Geraniol Geranyl acetate Citronellyl acetate 40 Citronellyl isobutyrate a 50 Citronellol 50 Phenylmethyl glycidic acid ethyl ester, 1% 5 Terpineol 20 Phenylethyl isobutyrate 50 4-methyl-2-pentanol crotonate 500 4-methyl-2-pentanol crotonate produces a pleasant fullfruit plum note without being found to be overdosed in this concentration as is often the case with conventional plum odorants.

A dishwashing detergent scented with this formulation can have the following composition for example:

Sodium alkyl sulphonate or sodium alkyl benzosulphonate 200 Fatty alcohol ether sulphate 70 Coconut fatty acid diethanolamide 30 Sodium chloride 20 Water, coloring and skin preservative 677 Perfume oil 3 EXAMPLE 2 The following formulation is given as an example of the preparation of a flower bouquet with a freshening fruit nuance which is suitable for perfuming creams:

The somewhat flat, harmless, phantasy bouquet is distinctly freshened and aesthetically improved by the small addition of 4-methyl-2-pentanol crotonate. The fruit nuance introduced gives the perfume more freshness and a natural character.

A skin cream perfumed with this composition can be prepared as follows for example:

Phase A: 50 g. of oleic acid decyl ester, 125 g. of glycerine monostearate (self-emulsifying), 50 g. of paraffinum per liquidum, 20 g. of cetaceum DAB 7, 1 g. of p-hydroxybenzoic acid propyl ester.

Phase B: 720 g. of distilled water, 1 g. of p-hydroxybenzoic acid methyl ester, 30 g. of sorbitol, 3 g. of perfume oil.

Phase A and phase B are heated to 75 C., after which phase B is stirred into phase A, cooled with stirring to 40 C. and perfumed.

EXAMPLE 3 The following formulation is given as an example of the preparation of a perfume with a lemon odor which is suitable for perfuming an insect spray:

In the lemon odor of the perfume, the fruit component is enhanced by the 4-methyl-2-pentanol crotonate, the odor is fuller and more pleasant.

An insect spray. perfumed with this composition can be prepared as follows, for example:

2,2-dichlorovinyl dimethyl phosphate 5 Epichlorohydrin 2 Isopropyl alcohol 40 Odorless kerosene 100 Perfume oil 3 Monofluorotrichloromethane 11 425 2,2-dichl0rovinyl dimethyl phosphate and epichlorohydrin are dissolved in isopropyl alcohol, odorless kerosene and perfume oil are added, the can is closed with a valve and, after pressure-filling, is filled with the propellent gas mixture 11/ 12 50:50.

EXAMPLE 4 The following formulation is given as an example of the preparation of a lavender composition which is suitable for perfuming tissues:

Difluorodichloromethane 12 The herb-like, lavandin oil note is sweetened by the 4-methyl-2-pentanol crotonate and displaced more towards the lavender type.

Tissues perfumed with this composition can be produced by impregnating paper webbing with a solution which can have the following composition for example:

Percent Alcohol Perfume oil 3 Distilled Water 17 EXAMPLE 5 A mixture of 6 mols=516 g. of crotonic acid, 5 mols =S60 g. of 4-methyl-2-pentanol, 20 g. of p-toluene sulphonic acid and 2 liters of xylene is heated under reflux in an apparatus provided with a water separator until no more water is separated (theoretical 90 g.).

In general this is achieved after 4 hours when cc. of the Water have been separated off.

The reaction mixture is washed first with 2 litres of 10% soda solution to remove the acids and then with water until the reaction mixture reacts neutrally.

After the xylene has been distilled off, the product is distilled in vacuo, giving at B.P. 80-85 C. 780 g. or 91.7% of the theoretical of crude crotonic acid 4-methyl- 2-pentanol ester.

The crude ester is re-washed with soda solution and water and then re-distilled. Yield 764 g.=89.5% of the theoretical.

B.P. 86-88 C.; D 0.875; 11 1.4324.

We claim: 1. 4-methyl-2-pentanol crotonate.

References Cited Kulka, K., Chemical Abstracts, vol. 58, 778111, 1963.

LORRAINE A. WEINB'ERGER, Primary Examiner P. J. KILLOS, Assistant Examiner U.S. Cl. X.R. 252522