US919762A

US919762A - Process of producing isobornyl esters.

Info

Publication number: US919762A
Application number: US31520306A
Authority: US
Inventors: Curt Philipp
Original assignee: Chemische Fabrik Von Heyden AG
Current assignee: Chemische Fabrik Von Heyden AG
Priority date: 1906-05-04
Filing date: 1906-05-04
Publication date: 1909-04-27
Anticipated expiration: 1926-04-27

Description

UNITED STATES PATENT OFFICE.

OURT PHILIPP, OF DRESDEN, GERMANY, ASSIGNOR TO OHEMISOHE FABRIK VON HEYDEN AKTIENGESELLSOHAFT, OF DRESDEN, GERMANY.

PROCESS OF PRODUCING ISOBORNYL ESTERS.

Specification of Letters Patent.

Application filed May 4, 1906.

To all whom it may concern:

Be it known that I, CURT PHILIPP, a subject of the King of Saxony, and resident of Dresden, in the Kingdom of Saxony, German Empire, have invented a new and useful Improvement in the Manufacture of Isobornyl Esters from Pinene Hydrochlorid or Pinene Hydrobromid, of which the following is a specification.

It is known that by heating a solution of pinene hydrochlorid in glacial acetic acid with silver acetate for several weeks in the water bath, a mixture of much camphene with a small quantity of isobornyl acetate (about 70 grams isobornylacetate from 400 grams of pinene hydrochlorid) is obtained (see Bertchte der Dewischen Chemischen Gesellschaft, Vol. 32, page 2309). It is also known that, by addition of fatty acids to camphene, with or without condensing agents, isobornyl esters are formed (see Uhegmt'schcs Centralblatt, 1902, 1, page 1219 By boiling a solution of pinene hydrochlorid in glacial acetic acid with lead acetate, camphene is obtained, while by heating these ingredients in an autoclave to 180 C. a mixture of bornyland isobornylacetate is obtained (see French Letters Patent 349896). In working according to the improved method hereinafter described, the transformation of pinene hydrochlorid into isobornyl acetate can take place at water bath temperature without the use of an autoclave.

The improved method consists in heating pinene hydrochlorid with the fatty acid salts of heavy metals in an excess of fatty acids. A halogen salt of a heavy metal, for example chlorid of zinc, may also be added. Instead of the fatty acid salts of the heavy metals, the oxids or carbonates of those metals may be employed, these being intermediately transformed into the said salts by the excess of the fatty acids employed. If fatty acid salts of zinc, iron, or copper are employed, the addition of a halogen salt of a heavy metal is not necessary. But if the fatty acid salts of other heavy metals, 6. g. oxid of lead, are employed, the addition of chlorid of zinc is necessary, as otherwise the reaction will take place in a different way. Probably chlorid of lead and the zinc salts of fatty acids are then formed intermediately (see example 7). The reaction takes place at water bath temperature and can be considerably hastened by heating to the boiling point under reflux.

Example 1: 172 parts of pinene hydrochlorid, 500 parts of formic acid of 98 to 100 per cent. strength, 45 parts of oxid of zinc, are heated together using a reflux condenser. Zinc formate insoluble in the excess of the formic acid, is formed and very quickly dissolved on boiling. The process is completed in a short time. The mass is oured into water, the oil floating on the surface is sepa rated off, washed with water and with a solution of soda and distilled in cacao. The distillate consists chiefly of isobornyl for- -mate possessing the known properties.

Example 2: 172 arts of pinene hydrochlorid, 500 arts of glacial acetic acid, 45 parts of oxid of zinc, are digested for 20 hours on a boiling water bath and then worked up according to Example 1. Isobornyl acetate ossessing the known properties is obtained.

Example 3: 172 parts of pinene hydrochlorid, 300 parts of glacial acetic acid, 45 parts of oxid of zinc, are boiled for 1 to 2 hours using a reflux condenser and then worked up according to Example 1. Iso bornyl acetate is obtained in this case also.

Example 4: 172 parts of pinene hydrochlorid, 500 parts of isobutyric acid, 45 parts of oxid of zinc, are boiled for to 1 hour using the reflux condenser and are worked up according to Exam le 1. Isobornyl-isobutyrate having the rnown properties is obtained.

Example 5: 172 parts of pinene hydrochlorid, 500 parts of glacial acetic acid, parts of ferric oxid, are boiled for 20 hours, using the reflux condenser, and then worked up according to Example 1. A good yield of isobornyl acetate is obtained.

Example 6: 172 arts of pinene hydrochlorid, 500 parts of glacial acetic acid, 45 parts of oxid of copper, are boiled for 20 hours using the reflux condenser and are worked up according to Example 1. Isobornyl acetate is obtained.

Example 7: 172 parts of pinene hydrochlorid, 500 arts of glacial acetic acid, 165 parts of oxid of lead, 30 parts of chlorid of zinc, are boiled for'24 to 30 hours using the reflux condenser. The product of the reaction is recipitated with water, neutralized with so a and distilled with steam. The dis tilled oil is separated from the water and disbornyl esters consisting in heating pinene tilled in vacuo. Isobornyl acetate of the hydrochlorid with fatty acids and With fatty known properties is obtained.

Example 8: 172 parts of pinene hydrochlorid, 500 parts of glacial acetic acid, 216 described. parts of oXid of mercury, 30 parts of chlorid v In testimony, that I claim the foregoing of zinc, are boiled for 20 hours using the rel as my invention, I have signed my name in flux condenser and then Worked up accordpresence of two Witnesses, this 23rd day of GURT PHILIPP.

ing to Exam le 7. Isobornyl acetate is ob April, 1906. tained. Ad ition of chlorid of zinc is indis- 19 pensable in this case also.

What I claim is:

Process for the direct manufacture of iso- Witnesses:

PAUL E. SonrLLING, PAUL ARRAs.

l i l acid salts of heavy metals, substantially as 15