US1702843A - Process for the preparation of monocyclic ketones and their alkyl derivatives having more than nine ring members - Google Patents

Description

Patented Feb. 19, "1929 UNITED STATES 1,702,843 PATENT OFFICE.

v LEOPOLD BUZICKA, OF GENEVA, SWITZERLAND, ASSIGNOR TO M. NAEF (30., 0F

GENEVA, SWITZERLAND,

PROCESS FOR THE PREPA A COMPANY OF SWITZERLAND.

ATION 0F MONOCYCLIC KETONES AND THEIR ALKYL DE- BIVATIVES HAVING MORE THAN NINE RING MEMBERS.

No Drawing. Application filed November 19,

In the prior application Serial No. 36,049 filed June 9, 1925, there is described a process of preparing monocyclic ketones having more than nine ring members, which comprises heating a normal straight chain aliphatic dicarboxylic acid salt of the fourth group of the periodic system especially thorium and cerium, said acid having a carbon chain containing more than ten carbon atoms, the carboxylic acid groups being linked to the end carbons thereof.

It has also been discovered that in a general manner for the preparation of monocyclic ketones having more than nine ring members and of their alkyl derivatives, from the dicarboxylic acids having more than ten carbon atoms in a normal chain or from their alkyl derivatives, the metals and the compounds of metals belonging to the fourth group of. the periodic system may advanta-- geously be employed.

According to the present invention titanium, which belongs to the said metals, or its compounds such as for instance titanium oxide are employed either alone or mixed with another metal or metal compound belonging to the said fourth group of the periodic system.

It is also advantageous to use a mixtureof several metals of thethird group of the periodic system or of the rare earths, these mixtures being obtained artificially or otherwise.

Mixtures of the above mentioned dicarboxylic acids or their alkyl derivatives, pre-' as perfume as Well as a primary material for preparing other interesting technical compounds.

Ewample 2.

3-methyltetradecane-LM-dicarbonylic acid and has a smell like that- 1926, Serial No. 149,535, and in Switzerland Decemberpared from the pure acids or as they are obtained in certain technical methods or from natural products give, according to the present lnvention, mixtures of the ketones, or their alkyl derivatives, which, in this form, can also be employed in practice.

For obtaining the mentioned monocyclic ketones, it is possible to directly heat the acids or the acid anhydrides alone or in presence of metals or metal compounds at a comparatively high temperature, instead of first transforming the corresponding dicarboxylic acids into salts. In this case the use of metals of the fourth group of the periodic system is also advantageous.

The ketones or their alkyl derivatives obtained by the described process can be used as perfumes or as primary materials for the preparation of compounds.

Example 1.

The titanium salt of 3-methyl-tetradecane- 1.14-dicarboxylic acid is heated, preferably in a vacuum, up to from 300 to 500 degrees centigrade and the distillate obtained therefrom is worked up by fractional distillation. The fractions distilling at from to C. at a pressure of 0.5 mm. are then treated with semicarbazide or other reagent usually employed for isolating the ketones.

other technically important The formation of the 3-methyl-cyclopentadecanone can be represented by the follow ing equation:

A mixture of the titanium and thorium salts of 4-methyl-tetradecane-Ll4-discarb0xylic acid is heated and worked up as de- Example 4.

d methyl tetradecane 1.1 1 dicarboxylic acid is heated at about 300 to 500 C. and towards the end of the reaction preferablyin a vacuum, with titanium oxide. The product obtained is worked up as described in Example 3.

Example 5.

The titanium salt of tetradecane-lli-dicarboxylic acid is heated and worked up as described in Example 1. The cycle-pentadecanone is obtained which distills at about 120 C. (at 0.3 mm.) and melts at 63 C.

Example 6.

Tetradecane-l.14rdicarboxylic acid is heat ed at about 300 to 500 6., towards the end of the reaction preferably in yacuum, with titanium hydroxide. The distillate resulting therefrom is worked up as described in Example 5.

Ewample 7.

The anhydride of tetradecane-1.14-dicar-' boxylic acid is heated to about 300 to 500 G, towards the end of the reaction preferably in a vacuum with titanium hydroxide and Worked up as described in Example 5.

Example 8.

A titanium salt of tetradecane-1.14ldicarboxylic' acid is prepared by only partially v neutralizing this dicarboxylic acid with sodium hydroxide nium chloride. The resulting titanium salt is decom used by heating and worked up as describe in Example 5.

r (at 0.3 min),

andprecipitating with titalicence Example .9.

fied by crystallization from alcohol and melt-' mg at 184 C. This lretone boils at 160 C. melts at 72 C. and has a smell which nearly corresponds to that of civetone. It can therefore be used as a perfume and as an intermediate for preparing other interesting technical compounds; by oxidizing the cyclononadccanone with chromic acid heptadecane-Lli-dicarboxylic acid is formed.

Example 1'0.

A mixture of clohexadecanone is obtained by working up according to the method described inExample l a mixture of titanium and thorium salts of tetradecane-l.lei-dicarboxylic and pentadecane-1.15-dicarboxylic acid.

1 claim: a

1. A process for the preparation of monocyclic ketoneshaving more than nine ring members comprising heating titanium salts of polymethylene dicarboxylic acids having more than ten carbon atoms in a normal chain, the carboxylic acid groups being linked to the end carbons thereof. 1

2. A process for the preparation of mono cyclic ketones having more than nine ring members comprising heating amixture of titanium and thorium salts of polymethylene dicarboxylic acids having more than ten carbon atoms in a normal chain, the carboxylic in this manner be 1 cyclopentadecanone and cyacid groups being linked to the end carbons thereof.

In testimony whereof I aflix LEOPQLD my signature.

RUZICKA.