US2033542A - Mixed furyl-alkyl ketones - Google Patents

Description

Patented Mar. 10, 1936' UNITED STATES PATENT OFFICE MIXED FURYL-ALKYL KE TONES Anderson W.

Ralston and Carl -W. Christensen;

Chicago, Ill., assignors to Armour and Company, Chicago, 111., a corporation of Illinois Serial No. 17,875

No Drawing. Application April 2a, 1935,

4 Claims.

wherein R is a furyl radical and R is an alkyl radical having five or more carbon atoms.

The higher fatty acids, and by that we mean those fatty acids derived from vegetable and animal oils and fats are extremely abundant materials and can be obtained at little expense. They have never, however, been used to any great extent as raw materials for the synthesis of more valuable substances. These fatty acids have been used almost exclusively in the soap industry, for melting candles, etc, and in but relatively few instances have they been used as raw materials in what might be termed the fine organic chemical field.

We have now discovered a new class of compounds which can be made from the higher fatty acids and which have chemical and physical properties of marked technical and commercial interest. We have discovered that the higher fatty acid chlorides, such as stearyl chloride, myristyl chloride, lauryl chloride, caproyl chloride, and other acid chlorides derived from, and

corresponding to the higher fatty acids, can be made to react with'furane, or substituted furanes,

to give mixed ketones having valuable properties I which suit them for use in many technical applications. Many of these mixed ketones are waxy solids and can be crystallized from organic solvents such as benzene, alcohol and others, to give pure ketones. The crystalline products, when melted and allowed to cool, yield substances of clearly defined waxy character, appearance and feel. Others are very highboiling liquids. We have discovered that they are excellent dielectries and can be used in electrical insulation. We have also discovered that-these new substances are desirable constituents inwaxing and polishing compounds. When added to lubricating oils, the ketones of the present invention confer beneficial properties on the oil. v

In its broad aspects, our invention comprises new products having the generic formula wherein R is a furyl radical which may be subfalling within the scope of our invention furyl 4 heptadecyl ketone, which can be written struc turally as follows: a

The dibenzofuryl compounds are especially interesting and valuable materials. Dibenzofuryl heptadecyl ketone melts at 83-84 C. and has the formula:

i1 u 0 I so The corresponding undecyl compound melts at 74-75 C.

'All of the ketones of our invention can be made by the Friedel-Crafts reaction or by the Grignard synthesis. We find that the Friedel- Crafts gives high yields.

Thus, for example, when we Wish to make dibenzofuryl heptadecyl ketone, we start with dibenzofurane and stearyl chloride. The stearyl chloride -can be made in any of the known ways from stcaric acid. Generally the stearic acid is reacted with phosphorous pentachloride or other chlorinating agent commonly used for converting aliphatic carboxylic acids to their corresponding acid chlorides. We then prepare a mixture containing about 29 parts by weight of stearyl chloride,.16 parts by weight of dibenzofurane and about 200 parts by weight of carbon disulphide. This mixture is cooled in an ice bath and about 26 parts of aluminum chloride (dry) are slowly added with stirring until there is no further evolution of hydrochloric acid. Thereaction mixture is then poured into a mixture of ice and dilute hydrochloric acid'to hydrolyze the complex aluminum compound formed in the reaction. Finally the resulting acid mixture is placed in a flask and subjected to steam distillation. This removes carbon disulphide and any excess of dibenzoiurane. During the steam distillation, the dibenzoiuryl heptadecyl ketone separates from the aqueous reaction mixture in the distilling flask as an oily supernatant liquid. It does not distil over with the carbon disulphide and can be separated from the aqueous solution of aluminum chloride in the distilling flask by simple decantation. It is then taken up in acetone, carbon tetrachloride or other organic solvent and crystallized therefrom.

In a similar manner we can start with iurane, alkyl-substituted iuranes and other substitution products. Likewise, as stated, we can start with any acid chloride of the higher fatty acids. Generally we start with theacid chlorides or fatty acids having twelve ormore carbon atoms since these fatty acids are readily available and cheap. Our invention is therefore not limited to the specinc compoimds described above, since we are the first to describe mixed ketones in which one wherein R is a iuryl radical and R is an alkyl radical having at least flve carbon atoms.

2. Mixed ketones having the structural formula R-C-R' wherein R is a iuryl radical and R is an alkyl radical having at least eleven carbon atoms.

3. A iuryl heptadecyl ketone. 4. A iuryl undecyl ketone.

ANDERSON W. RAISTON. CARL W. CHRISTENSEN.