US2984673A - Aminomethylpyrrolidinones - Google Patents

Description

United States Patent O 7 2,984,673 AMINOMETHYLPYRROLEINONES Newman M. Bortnick, Oreland, and Marian F. Fegley, Mont Clare, Pa., assign'ors to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware 1- Nb Drawing. Filed June 18, 1958, Ser. No. 742,735

13 Claims. or. 260-3265) This invention deals with specific aminomethylpyrrolidinones as new compositions of matter. It further deals with a method for the preparation of these specific aminomethylpyrrolidinones.

The present compounds are prepared by hydrogenating specific cyanopyrrolidinones having the formula The symbol R represents a hydrocarbon group of one to ten carbon atoms, preferably alkyl, aralkyl cycloalkyl, aryl and alkaryl. The symbol R represents a hydrogen atom or an alkyl group of one to four carbon atoms. The symbols R and R may be hydrogen or hydrocarbon groups of one to ten carbon atoms including alkyl, aralkyl, cycloalkyl, aryl and alkaryl groups. In addi tion, R and R taken together with the carbon atoms to which they are joined may form a carbocyclic ring containing five to six carbon atoms which in turn may have .alkyl substituents containing a total of no more than four additional car-hon atoms. In addition, R and R taken together with the carbon atoms to which they are joined may form a carbocyclic ring containing five to six carbon atoms which in turn mayhave alkyl substituents containing a total of no more than four additional carbon atoms. In addition, R and; R taken together with the carbon atom to which they are joined may form. a carbocyclic ring-containing five to six carbon atomswhich in turn may have alkyl substituents containing a total ofno; more than four additional carbon atoms. The total number ofcarbon atoms in the groups R R R and R should not exceed 20. The preferred embodiments are those in which R and R are alkyl groups, R is a hydrogen atom, and R is a methyl group. R R and R may typically individually represent methyl, butyl, octyl, benzyl, phenylbutyl, cyclopentyl, cyclohexyl; phenyl, naphthyl, butylphenyl groups, and the like.

'Ihe symb ol R represents hydrogen, an alkyl group of one to eighteen carbon atoms, an aryl group of up to ten carbonatoms, an aralkyl group of up toeighteen carbon atoms, an alkarylalkyl group of up to thirty carbon atoms, an alkoxyalkyl group of three to twenty-four carbon atoms, a hydroxyalkyl group of two to twelve carbon atoms, and an alkylaminoalkyll group ofithree to eighteen 2 carbon atoms provided that the amino group is a secondary or tertiary structure, that is non-primary. Alkyl, in the above definition, is to be construed. to include cyclo- =alky1 and alkylcycloalkyl within the range of carbon atoms previously set forth.

Typical R represenations are hydrogen, methyl, ethyl, butyl, octyl, decyl, dodecyl, octadecyl, cyclopentyl, cyclohexyl, butylcyclohexyl, octylcyclohexyl, butylcyclohexylethyl, phenyl, naphthyl, benzyl, phenylethyl, phenylbutyl, phenyldodecyl, methylphenyl, ethylphenyl, butylphenyl, octylphenyl, nonylphenyl, decylphenyl, hexadecyl-phenyl, octadecylphenyl, methylbenzyl, ethylbenzyl, butylbenzyl, octylbenzyl, dodecylbenzyl, butylphenylbutyl, octylphenylethyl, dioctylphenylethyl, dodecylphenyloctyl, methoxyethyl, methoxyp-ropyl, methoxyhexyl, methoxydecyl, methoxyoct-adecyl, ethoxyethyl, ethoxybutyl, ethoxyoctyl, ethoxydodecyl, propoxyethyl, propoxybutyl, propoxyheptyl, propoxytetradecyl, butoxy ethyl, butoxybutyl, butoxyoctyl, b-utoxydodecyl, butoxyoctadecyl, pentoxyethyl, pentoxybutyl, pentoxydecyl, hexoxyethyl, hexoxyhexyl, hexoxydodecyl, hexoxyoctadecyl, heptoxyethyl, heptoxyoctyl, octoxyethyl, octoxybutyl, octoxyoctyl, octoxydodecyl, nonoxypropyl, nonoxyheptyl, nonoxytridecyl, decoxyethyl, decoxyoctyl, undecoxybutyl, dodecoxypropyl, dodecoxydecyl, dodecoxydodecyl, tridecoxyethyl, tetradecoxypropyl, pentadecoxypentyl, hexadecoxybutyl, heptadecoxyethyl, octadecoxyethyl, octadecoxyhexyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyoctyl, hydroxydecyl, hydroxydodecyl, ethylaminoethyl, propylaminoethyl, butylaminopropyl, octylaminohexyl, hexylaminooctyl, heptylaminopentyl, octylaminooctyl, nonylaminoethyl, ethylaminononyl, decylaminopropyl, propylaminododecyl, dodecylaminoethyl, dodecylaminopropyl, dodecylaminobutyl, dodecylaminohexyl, N-methyl-N-ethylaminoethyl, N prop yl N-ethylaminoethyl, N-butyl-N-pentylarninoethyl, N-octyl-N-hexylaminobutyl, and N-decyLN-butyb aminob-utyl.

Typical cya-nopyrrolidinone reactants include S-cyano- 1,3,3,S-tetramethyl-2-pyrrolidinone, 5-cyano-l-butyl-3,3,5- trimethyl 2 pyrrolidinone, S-cyano-lcyclohexyl-3,5-dimethyl-3-(2,2-dimethylpropyl)-2-pyrrolidinone, 7a-cyanol-benzyl 3,3-pentamethylene-2,3,3a,4,5,6,7,7a-octahydro' indol 2 one, S-cyano-l-1auryl-3,3,S-trimethyl-Z-pyrrolidinone, 5 cyano-l-octadecyl-4,S-dimethyl-Z-pyrrolidin one, 5 cyano l,3-dimethyl-3,S biS-(LmethyIpropyl)-2- pyrrolidinone, 7a-cyano-l-p-tolyl-3,3,6-trimethyl-2,3,3a, 4,5,6,7,7a-octahydroindol-Z-one, 5-cyano-l-benzyl-3,3,5- trimethyl-2-pyrrolidinone, S-cyano-1-(2-hydroxyethyl)-3, 3,5-trimethyl-2-pyrrolidinone, S-cyano-1-ethoxyethyl-3,3, 5-trimethyl-2-pyrrolidinone, 5-cyano-1-(3-dimethylaminopropyl) 3,3,S-trimethyl-Z-pyrrolidinone, S-cyano-LB-dimethyl 3,5 dihexyl-Z-pyrrolidinone, 5-cyano-3,3,5-trimethyl 2-pyrrolidinone, 5 cyano-3,5-dimethyl-3-(2,2-dimethylpropyl)-2-pyrrolidinone, 7a-cyano-3,3-pentamethylene-2,3,3a,4,5,6,7,7a-octahydroindol-Z-one, 5-cyan0-4, S-dimethyl-Z-pyrrolidinone, 5-cyano-3-methyl-3,5-bis-(2- methylpropyl') -2- pyrrolidinone, 7a-cyano-3,3,6-trimethyl- 2,3,3a,4,5,6,7,7a-bctahydroindol-Z-one, and 5-cyano-3- methyl-3,S-dihexyl-Z-pyrrolidinone. These reactants may be prepared acording to our copending application Serial Number 735,107, filed May 14, 1958.

The present hydrogenation is carried out in the presence of a catalyst. Suitable as catalysts are Raney nickel, Raney cobalt, cobalt with ammonia, nickel with ammonia, cobalt-copper, nickel-cobalt, palladium, platinum, ruthenium, and the like. The catalyst may be employed in any convenient particle size. Generally, the smaller particle sizes produce the higher rate. If desired, the catalyst maybe deposited on a. carrier material in order to. extend and activate it. Suitable for use as acan rier are activated alumina, activated clays, silica gelgcharcoal, asbestos, pumice, and the like. Room temperatures and somewhat above maybe employed when a noble metal is used as the catalyst. When the other materials are employed as catalysts, temperatures .in the range of about 75 to 250 C. are employed with about l to 200 C. preferred- It is preferred that the hydrogenation be carried out at the lowest temperature at Which reduction can occur within the ranges previously set out. An inert, volatile, organic solvent may be desirable, such as hydrocarbons, alcohols, ethers, and the like. The lower alkanols, such as methanol or ethanol, are particularly suited for this use. When the noble metals are used as catalysts, a small amount of an activating acid, such as acetic or hydrochloric, may be employed.

lPressures in the range 'of. atmospheric to 10,000 p.s.i.g. are employed. Actually, higher pressures may be used ifdesired but in most instances, no apparent advantages are achieved for the'extra effort extended. The reaction shown proceeds'a little more rapidly at the higher pres.- sures but lower pressures may be successfully employed with some of the catalysts, especially Raney'nickel. The preferred range of pressures is atmospheric to 100 p;s.i.g. when noble metal catalysts are employed and 250 to 5000 p.s.i.g." when the transition metal catalysts are used. J Tliepresent reaction should be concluded as soon as two'moles of hydrogen has reacted. Otherwise, if ,the reaction is conducted for periods of time that are substantially longer than that required for two moles of hydrogen to react, there is some chance that hydrogenolysis of the ring may occur. In some instances, this has been observed when the reaction was conducted for prolonged periods of time. While no specific time limit in minutes or hours can be given, since actualtimes will vary with cyanopyrrolidinone reactants, catalysts, temperatures, and pressures, it is emphasized that the reaction should be concluded after substantially two moles of hydrogen has reacted.

A preferred way of consummating the is to introduce the cyanopyrrolidinone reactant along with a catalyst of the type described heretofore into a pressure retention reaction vessel and add hydrogen until a certain desired pressure is reached. The reaction vessel or at least the reaction ingredients may be preferably agitated such as by stirring, rocking, or rotating until a precalculated drop in pressure is observed. This significant drop in pressure indicates that an equivalent amount of hydrogen has reacted. This precalculated pressure drop, indicating that an equivalent amount of hydrogen has reacted, is readily calculable by known methods. Therefore, an indication of reaction completion may be readily calculated and observed.

At the conclusion of the reaction, the product'is obtained by filtering off the catalyst and stripping off the solvent. If desired, the products may be purified by distillation or recrystallization from hydrocarbons, 'ethers, or the like.

The products of this invention are useful as additives for lubricating oils to minimize and prevent the formation and deposition of sludge, as evaluated by standard methods, in the usual concentrations.

Treatment of these amine products with acid chlorides gives rise to amides which contain the pyrrolidinone function. Acylation of the simplest members of these series gives rise to amidopyrrolidinones which have high solvency for polar polymers, such as polyacrylonitrile and nylon; the N,N-bis-cyanomethyl derivatives thereof likewise function as good solvents for such polymers. It is possible to treat addition polymers containing ester groups with these amines and by a process of direct aminolysis introduce pyrrolidinone rings into the polymers. If these polymers are fibers, introduction of the pyrrolidinone ring confers dyeability with acid dyes. 1- hydroxyethyl 5-aminomethyl-3,3,S-trimethyl-Z-pyrrolidinone is bifunctional and introduction of it into condensation polymers prepared from .dicarboxylic acids or diesters present reaction gives polyamido esters containing pyrrolidinone rings. Dyeability of fibers containing such units is greatly enhanced as compared to simple polyester fibers. Treatment of the aminomethyl compounds with urea leads to substituted ureas. When these are condensed with aldehydes, such as formaldehyde, they become valuable constituents of aminoplastic adhesives and textile treating materials. The salts of 2,4-dichlorophenoxyacetic acid with these amines are potent herbicides. The nitrite salts are useful as blowing agents. The latter have the virtue of giving virtually odorless by-products in the course of the blow. Furthermore, the by-products are compatible when polyvinyl chloride is thematerial from which the foams are produced.

The compounds of this invention have been presented in their free-base form, and in this free-base form they possess the valuable characteristics and concurrent utilities previously referred to. However, it isto be; construed that the present invention includes the acidadditionsalts of these free-base products also. It is desirable, in some instances, to employ the present products in their watersoluble salt form. For instance, in pesticidal applications, it is highly desirable to deal, with water-soluble compounds in order that satisfactory spray solutions may be formulated. In other applications, particularly where any physiological benefits are desired, it is frequent ly advantageous to employ the present products in their organic salt form in order to provide substantial neutrality with stability.

In order to prepare the salt forms of the present compounds, it is necessary only to react these compounds with a stoichiometric amount of the selected acid. The salt formation occurs readily at room temperature (about 20 C.) without the aid of a catalyst. Temperatures up to about 80 C. may be conveniently employed. If solid reactants are employed, it may be advantageous to use an inert volatile solvent such as benzene, toluene, xylene, hexane, heptane, methylene chloride, chloroform, or the like. The solvent can then be readily removed at the conclusion of the reaction by conventional methods. The salt product does not require anyfurther purification although recrystallization from a solvent, such as isooctane, may be resorted to if a product of high purity is demanded.

While the method of preparation of the salts is be: lieved to be clear to one skilled in the art from the above description, such salt formation may be specifically illustrated by indicating that one would take anequivalent amount of a selected compound of thisinvention injits free-base form and then add a stoichiometric amount of a selected acid, which would, for instance, be 36.5 parts of hydrochloric acid, 98 parts of sulfuric acid, 60 parts of acetic acid, 72- parts of acrylic acid and the like. The corresponding hydrochloric, sulfuric, acetic and acrylic acid salts respectively are readily formed. Similarly, other salt products may be prepared.

Typical organic and inorganic acids that may be employed are fomric acid, acetic acid, propionic acid, butyric acid, caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, methacrylic acid, crotonic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, propiolic acid, butynoic acid, cyclobutane-carboxylic acid, norcamphane-2 carboxylic acid, benzoic acid, resorcylic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, salicylic acid, maleic acid, fumaric acid, glutaconic, acid, saccharic acid, dodecanedioic acid, octendioic acid, cyclohexaneacetic acid, cyclopentaneacetic acid, tridecanoic acid, hexynedioic acid, phthalic acid, cinnamic acid,,benzenesulfonic acid, ethanesulfonic acid, naphthalenesulfonic acid, toluenesulfinic acid, glutamic acid, glyoxalic acid, phenylglyoxalic, acid, pyruvic acid, levulinic acid,

, glycine, aminocaproic acid, hydrochloric acid, hydrobro- The compounds of this invention, as well as the. methods for their preparation, may be more fully understood from the following examples which are offered by way of illustration and not by way of limitation. Parts by weight are used throughout.

Example S-cyano-1,3,3,5-tetrarnethyl-Z-pyrrolidinone (514 parts) absorbs hydrogen when heated for one hour at 124-- 134 C. under hydrogen at 2000 p.s.i.g. in the presence of Raney nickel catalyst parts). Thereactor is cooled and. vented and the: catalyst is separated by filtration. Distillation of the filtrate gives the product, having a boiling point of'112-114 C. (2.0. mm), (329 parts) whichcrystallizes in the receiver. The product contains 16.2% nitrogen (theoretical 16.5%) and hasa neutral equivalent of 174 (theoretical 170) The product is identified as S-aminomethyb1,3,3,5-tetramethyl-2-pyrrolidinone.

In. a similar fashion are. prepared 5-aminomethyl-1- butyl-B,3,S-trimethyl-Lpyrrolidinone. from l-butyl-S-cyano-3 ,3,5-trimethyl-2apyrrolidinone, S-aminomethyl-l-cy- .clohexyl. 3,5-dimethyl-3-(2,2-dimethylprop-yl)-2-pyrrolidinone from S-cyano-l-cyc1ohexyl-3,5-dimethyl-3-(2,2-dimethylpropyl)-2-pyrrolidinone, S-amino-methyl-l-lauryl- 3,3,itrimethyl-Z-pyrollidinone from S-cyano-l-lauryh 3,3,5 trimethyl 2 pyrrolidinone, 5-aminomethyl.-4,5-dimethylpropyl) -2 -pyrrolidinone, S-amino-methyl l-laurylmethyl-1-octadecyl-Z-pyrrolidinone, and S-aminomethyl- 1,3 dimethyl-3,5-bis-(2 methylpropyl)-2 pyrrolidinone from 5 cyano--1,3-dimethyl-3,15abis-(2-nrethylpropyl)-2- pyrrolidinone. Similarly, 5-cyanos3,3,5-trimethyl-2-pyrrolidinone gives 5-aminomethyl-3,3,5-trimethyl-2-pyrrolidinone and 5-cyano-3,5-dihexyl-1,3-dimethyl-2-pyrrolidinone gives S-aminomethyl-1,3-dimethyl-3,S-dihexyl-Z-pyrrolidinone. The latter examples are more conveniently carried out when an equal weight of methanol is used as a solvent.

Example 2 5 cyano- 1-(2-hydroxyethyl)-3,3,5-trimethyl-2-pyrroli- .dinone (520 parts) and. Raney nickel catalyst, (20 parts) are charged to. a reactor and pressurized with hydrogen at 15 00rp.s.i.g. The theoretical amount of hydrogen is absorbed at 135 -141 C. in the course of two hours in the shaking autoclave. The bomb is cooled and vented and the. catalyst is separated by filtration. "The filtrate is distilled to give the product, having a boiling point of 147150 C. (0.5 mm.) (330 parts). The product has 12 value of' 1.4966 and solidifies on standing at room temperature overnight in the receiver. The 'prod- Example 3 There are added to a reaction vessel 8 parts of mesitilonitrile dissolved in 35 parts of methanol and 5 parts of 1. Ajr'nembe'n from theclass consisting of the compound having theformul'a and the acid addition salts thereof, in which R; taken individually represents a member from the class consisting of alkyl, phenylalkyl, cycloalkyl, phenyl, naphthyl, and alkylphenyl of up to 10 carbon. atoms, R taken individualy represents a member from the class consisting of hydrogen and alkyl of l to 4 carbon atomsgR and R taken individually represent members from the class consisting of hydrogen, alkyl, cycloalkyl, phenylalkyl, phenyl, naphthyl, and alkylpheny of up to 10 carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a member from the class consisting of a carbocyclic ring of 5 to 6 carbon atoms and said ring having alkyl substituents consisting of a total of up to 4 carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a member from the class consisting of a carbocyclic ring of 5 to 6 carbon atoms. and said ring having alkyl substituents consisting of a total of up to 4 carbon atoms, R andR taken collectively with the carbon atoms to which they are joined form a member from the class consisting of a carbocyclic ring of 5 to 6 carbon atoms and said ring having alkyl. substituents consisting. of a total of up to 4 carbon atoms, and R is a .member from the class consisting of hydrogen, alkyl of-l to 18 carbon atoms, phenyl, naphthyl, phenylalkyl, of up to 18-, carbon atoms, alkylphenylalkyl of up to 30 carbon atoms, alkoxyalkyl of 3 to 24 carbon atoms, hydroxyalkyl ofZ to 12 carbon atoms, and alkylarninoalkyl of 3 to 18 carbon atoms.

2. The compound having the formula l CHaNHz R in which R is alkyl of 1 to 18 carbon atoms, R and R taken collectively with the carbon atoms to which they are joined represent a carbocyclic ring containing 5 to 6 carbon atoms, and R and R are alkyl of 1 to 10 carbon atoms.

-4. The compound having the formula R17 -R4 V C gNHzE in which R is alkyl of 1 to 18 carbon atoms, R and R are alkyl of :1 to 10 carbon atoms, and R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of to 6 carbon atoms.

5. The compound having the formula in which R is alkyl of 1 to 18 carbon atoms, R is alkyl -of 1.10 l0.carbon atoms, R is alkyl ,of 1 to 4 carbon atoms, and R and R taken collectively with the carbon atom ,towhichthey are joined form a carbocyclic ring of. 5 to 6 .carbon atoms.

6. The compound-having the formula are hydrogen atoms, R R and R C lNHzit having the formula withsubstantially two. equivalents of hydrogen in the temperature range of about to250 C. inthe presence of a hydrogenation catalyst, in which R taken individually represents a member from the class consisting of alkyl, pheuylalkyl, cycloalkyl, phenyl, naphthyl, and alkylphenyl of up to 10 carbon atoms, R taken individualy represents a member from the class. consisting of hydrogen and alkyl of 1. to 4 carbon atoms, R and R taken individually represent members from the class consisting of hydrogen, alkyl, cycloalkyl, phenylalkyl, phenyl, naphthyl, and alkylphenyl of up to 10 carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a member from the class consisting of a carbocyclic ring of 5 to 6 carbon atoms and said ring having alkyl substituentsconsisting of a total of up to 4 carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a member from the class consisting of a carbocyclic 'ring of 5 to 6 carbon atoms and said ring having alkyl substituents consisting of a total of up to 4 carbon atoms,

R and R taken collectively with thecarbon atoms to -which they are joined form a member from the class consisting of a carbocyclic ring of 5 to 6 carbon atoms and said ring having alkyl substituents consisting of a total of up to 4 carbon atoms, and R is a member from the class consisting of hydrogen, alkyl of 1 to 18 carbon .atoms, phenyl, naphthyl, phenylalkyl of up to 18 carbon References Cited in the file of this patent UNITED STATES PATENTS De Benneville et al. Jan. 1, 1953 Prichard July 1, 1958 OTHER REFERENCES Wenkert et al.: I.A.C.S., vol. 75, p. 5514 (1953).

Claims (1)

1. A MEMBER FROM THE CLASS CONSISTING OF THE COMPOUND HAVING THE FORMULA