US3352871A

US3352871A - Fatty acid phenylalkylpiperidies

Info

Publication number: US3352871A
Application number: US445719A
Authority: US
Inventors: Francis E Cislak
Original assignee: Reilly Tar and Chemical Corp
Current assignee: Reilly Tar and Chemical Corp
Priority date: 1965-04-05
Filing date: 1965-04-05
Publication date: 1967-11-14
Anticipated expiration: 1984-11-14

Description

United States Patent 3,352,871 FATTY ACID PHENYLALKYLPWEEDES Francis E. Cislak, lndianapolis, IntL, assignor to Reilly Tar & Chemical Corporation, Indianapolis, Ind., a corporation of Indiana No Drawing. Filed Apr. 5, 1965, Ser. No. 445,719 Claims. (Cl. 260-2947) This invention relates to a new composition of matter. More specifically, it relates to a new class of organic compounds.

The new class of organic compounds which are the subject matter of my present invention are fatty acid phenylalkylpiperidides. These new fatty acid phenylalkylpiperidides have the following general formula:

l a C wherein R R and R represent hydrogen or lower alkyl, they may be alike or they may be different, and R represents an alkyl or alkenyl radical having from 1 to 29 carbon atoms.

In general, my new class of compounds may be prepared by the interaction of a phenylalkylpiperidine with a carboxylic acid, a carboxylic acid ester, or a carboxylic acid chloride.

My fatty acid phenylalkylpiperidides are useful in the formulation of industrial paints. In the protection of steel tanks, bridge structures, pipe lines, etc., coal-tar pitch paints have been used for decades. In areas Where subzero temperatures are encountered, it is necessary that the coal-tar pitch be flexible enough to avoid cracking the film at these sub-Zero temperatures. Flexibility in coaltar pitch is achieved by leaving more of the lower-boiling coal-tar oils in the pitch. While such pitch has the desired flexibility during the sub-zero exposure, it is not Well adapted to the hot summer temperatures. The lowerboiling oils are volatilized by the sun during the summer with the result that a more brittle pitch must be able to go through the following Winter. Because of their low volatility and their compatibility, my fatty acid phenylalkylpiperidides may be added to a coal-tar pitch free of lower-boiling oils and achieve a pitch that is flexible from winter to winter. I need use only 5 to (-based on the coal-tar pitch) of my fatty acid phenylalkylpiperidides to obtain a coal tar pitch suitable for the manufacture of coal-tar paints.

The fatty acid phenylalkylpiperidides having a higher molecular weight fatty acid radical may be used in printing inks to modify their tackiness; only minor amounts are required to obtain the desired result. The tack of printing inks is of great importance, particularly in process inks for color printing. Successful application of successive colors require that each color be more tacky than the color applied over it, in order that film rupture may occur in the top rather than in the bottom film.

Ordinary Window putty is usually composed simply of a thick plastic paste of Whiting (calcium carbonate) and linseed oil. The putty hardens and therefore is not satisfactory for sealing Where there may be slight relative movement of the components. The addition of from 10 to 30% (based on the linseed oil) of my fatty acid phenylalkylpiperidides so modifies the putty that it may be used for sealing even though there may be some relative movement of the components.

My fatty acid phenylalkylpiperidides are useful as plasticizers. Because of their low volatility, they are useful in plasticizing polyvinylchloride used in high temperature wire insulation applications. Usually from 25 to 50 parts of plasticizer are used for each 100 parts of polyvinylchloride homopolymer.

The phenylalkylpiperidines used in carrying out my invention are made by the catalytic hydrogenation of phenylalkylpyridines.

The manner in which the compounds of my invention may be prepared is illustrated by the following examples. It is to be understood that these examples are given by way of illustration only and are not intended as a limitation upon my invention.

EXAMPLE 1 Stearic acid 4-phenylpropylpiperidide Into a flask equipped with a stirred and a condenser is placed 500 grams of methyl stearate. The ester is warmed to liquefy it. To the liquid methyl stearate there is added 186 grams of 4-phenylpropylpiperidine. While stirring the mixture, its temperature is gradually raised. A reaction occurs causing an evolution of methanol and the formation of the stearic acid 4-phenylpropylpiperidide. Heating is continued, in the range of ISO-175 C., until about 32 cc. of methanol has been collected. Then the excess methyl stearate is removed from the reaction mixture by distil lation under vacuum. The residue remaining after the methyl stearate has been distilled is a semi-pure stearic acid 4-phenylpropylpiperidine. If a lighter colored product is desired, the residue is distilled under high vacuum, about 0.5-1.0 mm. Hg; the product distills over at at temperature above about 250 C.

The piperidide is insoluble in water and alcohol; it is soluble in benzene.

EXAMPLE 2 Laurie acid 4-(1'-ethyl3'-p'lzenylpr0pyl)piperidide CgH5 O=( 3-CnH23 The procedure of Example 1 is repeated with the exception that 500 grams of methyl laurate is used in place of the methyl stearate and 214 grams of 4-(l-ethyl-3'- phenyl) propylpiperidine is used in place of the 186 grams of 4-phenylpropylpiperidine.

EXAMPLE 3 Acetic acid Z-phenylpropyI-S-ethylpiperidia'e OH2CH2OH N has been added, the mixture is heated under reflux conditions for from about two hours to about five hours. During the refluxing the acetic anhydride acetylates the piperidine to form the piperidide, acetic acid is also formed. After the refluxing is concluded, the acetic acid formed and the unreacted acetic anhydride are removed by distillation. The residue, a quite pure acetyl Z-phenylpropyl- S-ethylpiperidide, is purified by distillation under vacuum.

EXAMPLE 4 21 -triacontenic acid 4-phenylpropylpiperidide CHzCHgCHr Into a flask equipped with a stirrer and a condenser there is placed 473 grams of 21-triacontenoic acid (commonly called lumequeic). The acid is heated to about 80 90 and then there is added to it 186 grams of 4-phenylpropylpiperidine. Then the reaction mixture is heated slowly causing the temperature of the mixture to rise gradually. A reaction occurs causing an evolution of water and the formation of the lumequeic acid-4-phenylpropylpiperidide. When the temperature reaches about 150 C., it is maintained there until no more water is evolved (this usually takes about four to five hours). The product now in the flask is 21-triacontenoic acid-4-phenylpropylpiperidide.

EXAMPLEv 5 Linoleic acid 4-phcnylpropyIpiperidide N O=( J(CH;) -CH=CH-CHg-CLI=CH(CHQ) -CHs The procedure of Example 1 is repeated with the exception that 500 grams of the methyl ester of linoleic acid is used in place of the methyl stearate.

EXAMPLE 6 Butyric acid 3-phcnylpropylpiperidia'e ornament-Q s EXAMPLE 7 Oleic acid 4-phenylpropylpiperidide The procedure of Example 1 is repeated with the exception that 500 grams of the methyl ester of oleic acid is used in place of the methyl stearate.

EXAMPLE 8 Palmitz'c acid 4-phenylpr0pyIpiperidide The procedure of Example 1 is repeated with the exception that 500 grams of methyl palmitate is used in place of the methyl stearate.

EXAMPLE 9 Propionic acid 4-phenylpropyl-2,6-dimethylpiperidide mammoth-Q CH3 N Adipic acid-di-4-phcnylpropylpiperidide oniomoni prncnicrn t t O=CCH CH CI-ICH -C=O The procedure of Example 4 is repeated with the exception that 73 grams of adipic acid is used in place of the lumequeic acid.

EXAMPLE 11 T erephthalic acid-di-4-phenylpropylpiperia'ide The procedure of Example 1 is repeated with the exception that 92 grams of dimethylterephthalate is used in place of the methyl stearate.

In the examples above I have used individual .fatty acids or their derivatives. Commercially it would be desirable to use the regular grades of commercially available fatty acids. Then I would obtain a mixture of piperidides but these are preferred commercially because of their lower cost.

If in place of the methyl laurate used in Example 2, I use the methyl ester of coconut fatty acids, I obtain a mixture of piperidides with the lauric acid one predominating but also present in significant amounts are the piperidides of myristic, palmitic, capric, and caprylic acids. Or I might use the coconut oil itself, distilling oflunder vacuum the glycerine as it is formed. I can use rapeseed oil, in which case the piperidide of erucic acid (C H COOH) will predominate in my mixture and ap- 3,352,871 5 6 preciable quantities of oleic acid and linoleic acid 2. Stearic acid 4-phenylpropylpiperidide. piperidides will be present. 3. Laurie acid 4-phenylpropylpiperidide.

1 Claim 35 y i vention: 4. Linoleic acid 4-phenylpropylpiperidide. 1. Phenylalkylpipendrdes of the formula 5 Ol i id 4 h l ro l i eridide.

Rs 5 R1 Rewrences Cited S C-OHzCH Ra H UNITED STATES PATENTS N 2,116,118 7/1939 Bousquet 260-294 (i=0 10 3,219,612 11/1965 Skau et al. 260294.7 L 3,219,659 11/1965 Ska-u et a1. 260294.7 wherein R R and R are selected from the class con- 3222203 12/1965 Skau et 260 294'7 sisting of hydrogen and lower alkyl, and R is selected from the class consisting of alkyl and alkenyl radicals WALTER MODANCE P'Zmary Exammer' having from 1 to 29 carbon atoms. 15 AVROM D. SPEVACK, Assistant Examiner.

Claims

1. PHENYLALKYLPIPERIDIDES OF THE FORMULA