US2394871A

US2394871A - Halogenated amides

Info

Publication number: US2394871A
Application number: US493425A
Authority: US
Inventors: Perrine John Harold
Original assignee: Sun Oil Co
Current assignee: Sunoco Inc
Priority date: 1943-07-03
Filing date: 1943-07-03
Publication date: 1946-02-12
Anticipated expiration: 1963-02-12

Description

stadt Patent 1,931,880).

Patented Feb. 12, 1946 UNITED STATES PATENT. -Ol'-'-FICE rianoonm'mo mamas John Harold Pcrrlnc, Prospect Park, Pa, asslgnor to Sun Oil Company, poration' of New Jersey Philadelphia, Pa, a cor- '1 Claims.

This invention is directed to a new class of halogenated amides, having commercially valuable properties.

The halogenated amides in accordance with this invention are those formed from a group or mixture of saturated acids containing cycloaliphatic rings and Having the generic formula CnHin-rOfl, in. which n, has a value between 13 and 30 and :1: has a value between 4 and 10. More specifically the amides are those formed from a group or mixture of said acids a large proportion, and usually most, of which individually have the generic formula Gama-:02, in which n may vary from 13 to 30 and x is an even number from 4 to 10. Still more specifically the amides are those formed from a group or mixture of said acids which are derived, in various ways, from petroleum.

The acids forming the group in question are obtainable from petroleum'and are present, for example, as alkali salts in the asphaltic still bottoms produced in the distillation of topped crude in the presence of caustic soda to produce lubricating oils (see Pew Patent 1,761,153 and Ang- These may be obtained commercially from the source as a mixture of the various acids by treatment of the still bottoms with a mineral acid to convert the alkali salts to free acids, followed by distillation to obtain the acids as a distillate fraction.

The acids are also obtainable from lubricating oil fractions of naphthenic base crudes distilled without the addition of caustic soda.

The acids are also obtainable from gas oil fractions distilled from Gulf Coastal (and probably -'other) crudes. covered by, for example, the process disclosed in the application of McCorquodale, Magill and Easy, Serial No. 475,318, filed February 9, 1943. 50 to '70 per cent. of these gas oil acids are identical with acid obtainable from the still residue. Since such method for recovering the starting acids forms no part of the present invention, its

description is unnecessary.

The starting acids also appear to be obtainable by oxidation of naphthenic oils, as, for example, by methods similar to that disclosed in the application of Johnson and Bruun, Serial No. 415,- 910, filed October 21, 1941.

, It may be, also, that acids of the class defined may be synthesized from pure compound by tpossibly) some known method or by some process that may be hereafter developed.

4 From a practical or commercial standpoint, however, the starting acids may be' said to be those either naturally occurring in petroleum, or which are formed in petroleum during conventional processes of refining or which may be produced from petroleum by some special process.

The mixture of acids may be separated into Such acids may be so remore or less pure individual acids by fractional distillation in vacuo. The acids distill between about C. and 330 C. at 2 mm. The commercial mixture solidifies at about -50 0. However produced, the mixture of acids will generally contain some hydrocarbons as impurities, reducing the acid number of the mixture, but the presence of these hydrocarbons does not generally prevent the use of the commercial mixture of acids in the production of the product comprising my invention. v

- It has been found that valuable industrial products may be obtained by treatment of the acids comprising this group, either in purified form or as the commercial mixture, with urea for the formation of their amides, with halogenation of the amides so formed.

In general the reaction between'the petroleum acids and urea will be carried out at a temperature of C. to 200 0., at atmospheric pressure, or at higher temperatures at superatmospheric pressure. The reaction will take from 10 to 20 hours at the temperature range given, less at higher temperatures under pressure. Optimum proportions of reactants are two moles of acid to one mole of urea. Details of a preferred procedure may be found in the D'Alelio Patent No. 2,109,941.

The amide or mixture of amides formed in the reaction may be purified by water-washing and drying the reaction product. Or the unreacted urea may be removed by filtering the crude reaction'product through glass wool at a, temperature just below the melting point of urea. The

to reduce gas pressure within the tube, and

opened. The crude reaction product should be washed several times with dilute NaaC'Oa solutions, then with several portions of water, dried, and finally warmed slightly, while being agitated, invacuo.

Other conventional methods of forming amides may also be used to form the amides which are to be halogenated in accordance with the present invention. Thus, the 'acid chlorides or esters of the petroleum acids may be reacted with am-v monia'to form amides; the ammonium salt of the acids may be dehydrated at 100 C.-200 0.; or the nitrile of the acids may be hydrolized at 100 C. in the presence of a mineral acid to the amide.

The described amides of petroleum acids are formula Cn--1II31|z-l, CONHz, where n and a:

have the same values given above for the acids.

and, like the acids, are probably characterized by the presence of five-membered rings.

These amides, after purification as outlined above, may be treated, either after fractional distillation to produce relatively pure individual amides, or as a mixture of amides, with a halogen, as chlorine, bromine, iodine, etc. to form the halogenated amides of the present invention.

Any conventional halogenation procedure may be used. Thus, for example, one mole of puri-- fled amide may be dissolved in 200-400 g. of a suitable organic solvent, as carbon tetrachloride or other halogenated paraifin hydrocarbon, and dry chlorine gas passed through the solution, at a temperature of about 20-30 C. until the desired quantity of chlorine, from 1 to 3 atoms per molecule, e. g. in this case 35.45 to 106.35

grams per mole of amide, hasbeen absorbed. A 2.20

catalyst as iron, or iodine, may be present, if desired. To insure complete reaction it will ordinarily be desirable to add chlorine somewhat in excess of the theoretical quantities given, as some loosely combined chlorine will be lost in purification.

The chlorinated amide may be recovered from the reaction products by distilling off the solvent, and warming the product, with agitation,

under a vacuum.

In similar manner a solution of the amide may be treated with bromine for the production of the brom-amides.

Other methods of halogenati'on known to the art may also be used The purified halogenated amides are viscous liquids or solids, soluble in carbon tetrachloride, acetone, benzene, and hydrocarbon and mineral oil fractions. They are stable at temperatures encountered in lubrication processes, but cannot be distilled, under usual conditions of vacuum and in entirety, without some decomposition. The halogenated amides have higher boiling points than the parent acids. This increase in boiling point amounts to about 50 .01, depending on the degree of halogenation. The boiling range of the chlorinated amides ranges from about 175 C. to about 380 C. at 2 Distillation cannot be carried over 300 C. at 2 mm.,

however, without some decomposition. The distillate at this point represents about 50 per cent. of the original.

.The halogenated amides in accordance with the present invention are characterized by being the halogenation products of amides having the Patent is:

1. A new product comprising a halogenated mixture of amides formed from a mixture of saturated monocarboxylic acids containing from 2 to 5 cycloaliphatic rings per molecule and having the generic formula Gama-.202, wherein n has avalue between 13 and 30 and a: has a value ranging from 4 when the number or cycloaliphatic rings is 2 to 10 when the number of cycloaliphatic rings is 5.

2. A new product comprising a halogenated mixture of amides formed from a mixture or seturated monocarboxylic acids, derived from pctroleum, containing from 2 to 5 cycloaliphatic rings per molecule and having the generic formula Gama-:02, whercinn has a value between 13 and 30 and a: has a value ranging from 4 when the number of cycloaliphatic rings is 2 to 10 when the number of cycloaliphatic rings is 5.

3. A new product comprising a halogenated mixture of amides formed from a mixture of saturated monocarboxylic acids containing from 2 to 5 cycloaliphatic rings per molecule individual acids of which have the generic formula cums-=03, wherein n is a number from 13. to 30, inclusive, and :c is an even number ranging from 4 when the number of cycloaliphatic rings is 2 to 10 when the number of cycloaliphatic rings is 5.

4. A new product comprising a halogenated mixture of amides formed from a mixture of sat-- urated monocarboxylic acids, derived from pctroleum, containing from 2 to 5 cycloaliphatic rings per molecule individual acids of which have the generic formula Cal-121,402, wherein n is a number from 13 to 30, inclusive, and a: is an even number ranging from 4 when the number of cycloaliphatic rings is 2 to 10 when the number of cycloaliphatic rings is ,5.

5. A new product comprising a chlorinated mixture of amides formed from a mixture of saturated monocarboxylic acids containing from 2 to 5 cycloaliphatic rings per molecule and having the generic formula CnH2nz02 wherein n has a value between 13 and 30 and a: has a value ranging from 4 when the number of cycloaliphatic rings is 2 to 10 when the number of cycloaliphatic rings is 5, in which mixture each amide contains 1 to 3 atoms of chlorine per molecule.

A new product comprising a halogenated mixture of amides formed from a mixture of unhalogenated amides of saturated monocarboxylic acids derived from petroleum and containing from 2 to 5 cycloaliphatic rings per molecule, said unhalogenated amides having the group formula. Cn-iHZn-z-ICONI'I'I, wherein n has a value between 13 and 30 and :c has a value between 4 and 10; the halogenated amides being a viscous liquid or a solid, soluble in carbon tetrachloride, acetone, benzene and hydrocarbon and mineral oil fractions, stable at temperatures encountered in lubrication processes, and having I higher boiling points than the parent acids.

'7. A new product comprising a halogenated mixture of amides formed from a mixture of unhalogenated amides of saturated monocarboxylic acids derived from petroleum and containing from 2 to 5 cycloaliphatic rings per molecule, said unhalogenated amides having the group formula Cn1H2n.-:1CONH2, wherein n has a value between 13 and 30 and a: has a value between 4 and 10, and being characterized by the presence of flve-membered rings; the halogenated amides being a viscous liquid or a solid,

soluble in carbon tetrachloride, acetone, benzene and hydrocarbon and mineral oil fractions, stable at temperatures encountered in lubrication processes, and having higher boiling points than the parent acids.

' JOHN HAROLD PERRINE.