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United States Patent Office Patented Sept 3,274,211 United States Patent Office Patented Sept. 20, 1966 2 cording to the process of this invention. Other ketones 3,274,211 N-ALKYLATION OF AMDES AND MEDES which may be utilized to give particular N-alkylation Louis Schmerling, Riverside, III., assignor to Universal products include methyl ethyl ketone, methyl propyl Oil Products Company, Des Plaines, Ill., a corporation ketone, methylbutyl ketone, methyl amyl ketone, methyl of Delaware hexyl ketone, methyl heptyl ketone, methyl octyl ketone, No Drawing. Filed Feb. 4, 1964, Ser. No. 342,549 etc., ethyl ethyl ketone, ethyl propyl ketone, ethyl butyl 9 Claims. (Cl. 260-326) ketone, ethyl amyl ketone, ethylhexyl ketone, ethyl hep tyl ketone, etc., propyl propyl ketone, propylbutyl ketone, This invention relates to a novel process for the N propyl amyl ketone, propylhexyl ketone, etc., butylbutyl alkylation of carboxylic acid amides and imides. More ketone, butyl amyl ketone, butyl hexyl ketone, etc. particularly, this invention relates to the reductive alkyla Other suitable but not necessarily equivalent ketones com tion of carboxylic acid amides and imides to give N prise cyclic ketones including cyclohexanone, benzophe alkylation products. none, etc., alkyl aryl ketones, alkyl cyclohexyl ketones, The alkylation products herein contemplated are par aryl aryl ketones, aryl cyclohexyl ketones, etc., including ticularly adapted to the preparation of primary amines. 15 compounds like acetophenone, ethyl phenylketone, propyl For example, N-isobutylacetamide, the reductive alkyla phenyl ketone, butyl phenyl ketone, amyl phenyl ketone, tion product of acetamide and isobutyraldehyde, is hydro etc., methyl cyclohexyl ketone, ethyl cyclohexyl ketone, lyzed to isobutylamine and acetic acid, the latter being propyl cyclohexyl ketone, butyl cyclohexyl ketone, etc. readily converted to the acetamide starting material by Suitable aldehydes include formaldehyde, acetaldehyde, reaction with ammonia. Similarly, N-isopropylphthal 20 propionaldehyde, butyraldehyde, valeraldehyde, etc. It imide, the reductive alkylation product of phthalimide is understood that the particular aldehyde or ketone em and acetone, can be hydrolyzed to isopropylamine and ployed is dependent on the particular product desired. phthalic acid and the latter may be reacted with ammonia The reductive alkylation reaction requires at least one to form the phthalimide starting material. mole of hydrogen per mole of amide or imide being It is an object of this invention to disclose a novel proc 25 treated. In general, it is preferable to operate with at ess for preparing N-alkylated carboxylic acid amides and least a slight molar excess of hydrogen over the stoichio imides. In one of its broad aspects, this invention em metric requirement. This is generally accomplished by bodies a process for the N-alkylation of a compound se conducting the reaction at a hydrogen pressure of from lected from the group consisting of amides and imides about atmospheric to about 100 atmospheres or more, which comprises reacting said compound with a carbonyl 30 and preferably at a hydrogen pressure of from about 10 compound selected from the group consisting of aldehydes to about 100 atmospheres. Suitable reaction tempera and ketones at a hydrogen pressure of from about atmos tures are within the range of from about 60° C. to about pheric to about 100 atmospheres and at a temperature of 250 C., more preferably in the range of from about from about 60° C. to about 250 C. in the presence of 150 C. to about 180° C., the optimum temperature in a reductive alkylation catalyst under acidic reaction con 35 any particular case being dependent in part on the par ditions. ticular reactants involved and the catalyst employed. A more specific embodiment of this invention is in a Any suitable reductive alkylation catalyst can be used, process which comprises reacting phthalimide with ac and may comprise a composite containing platinum, pal etone at a hydrogen pressure of from about 10 atmos ladium, nickel, cobalt, molybdenum, etc., or mixtures pheres to about 100 atmospheres and at a temperature 40 thereof with a suitable carrier material including alumina, of from about 150° C. to about 180° C. in the presence silica, zirconia, titania, thoria, zinc oxide, or mixtures of a reductive alkylation catalyst under acidic reaction thereof, or the naturally occurring bauxite, kaolin or ben conditions and forming the N-alkylation product, N-iso tonite clay, or diatomaceous earth such as kieselguhr, propylphthalimide. montmorillonite, etc. Another of the more specific embodiments of this in 45 It has been found that acidic reaction conditions greatly vention relates to a process which comprises reacting enhance the reductive alkylation reaction herein con acetamide with isobutyraldehyde at a hydrogen pressure templated. When the reaction is effected under substan of from about 10 atmospheres to about 100 atmospheres tially neutral conditions, the reaction does not proceed and at a temperature of from about 150° C. to about to any appreciable extent. However, the inclusion of an 180° C. in the presence of a reductive alkylation catalyst 50 acidic material in the reaction mixture results in a sub under acidic reaction conditions and forming N-isobutyl stantial increase in the desired N-alkylation product and acetamide. by-product formation is substantially if not completely Other objects and embodiments of this invention will eliminated. In most cases the imides, which are them become apparent in the following detailed specification. Selves considered weak acids, impart sufficient acidity The process of this invention is applicable to the N 55 to the reaction mixture. On the other hand, reduc alkylation of the amide and imide derivatives of saturated tive alkylation of the substantially neutral amides requires carboxylic acids in general; for example, the amide deriva the inclusion of an added acidic material in the reaction tive of acetic acid, acetamide, and the corresponding mixture. Weak acids such as boric acid, acetic acid, and imide derivative, acetimide, sometimes referred to as di the like, which are substantially inactive with respect to acylamide. Other suitable amides and imides include 60 the reactants at reaction conditions, may be suitably in formamide, propionamide, n-butyramide, n-valeramide, cluded in the reaction mixture to impart the desired acidic n-caproamide, Stearamide, carbamide, succinamide, glu reaction conditions thereto. taramide, phthalamide, phthalimide, naphthalamide, The process of this invention is suitably carried out in naphthalimide, succinimide, glutarimide, benzamide, a batch type of operation utilizing an autoclave, preferably acetanilide, benzanilide, and the like. 65 a high pressure autoclave, provided with adequate heat N-alkylation is effected utilizing a carbonyl compound, ing and mixing means. Experiments relating to the pres which can be a ketone or an aldehyde, as an alkylating ent invention were suitably carried out in a glass-lined agent. Any suitable ketone or aldehyde may be em rotating autoclave. A carboxylic acid amide or imide, as ployed. For example, where the desired N-alkylation the case may be, is sealed in the autoclave together with product is N-isopropylsuccinimide, acetone is a suitable 70 a suitable aldehyde or ketone, the selected reductive alkyla alkylating agent and may be reacted with succinimide ac tion catalyst, and an acidic material. The autoclave is 3,274,211 3. A. then pressured with hydrogen and heated at the described clave. The autoclave was pressured to about 100 atm. reaction conditions for a predetermined residence time, with hydrogen and heated at 160 C. for 12 hours. The say from about 1 to about 12 hours or more. Since hy final pressure was 50 atm. In this case the reductive al drogen is consumed in the reductive alkylation reaction, kylation product consisted of a mixture of N-isobutyl the extent of the reaction can be ascertained with reference acetamide and N,N-diisobutylacetamide. to pressure. The reductive alkylation product can be re I claim as my invention: covered from the reaction mixture by conventional meth 1. A process for the N-alkylation of a compound se ods. One suitable method is by solvent extraction utiliz lected from the group consisting of amides and imides con ing acetone and methanol. taining only the one functional group and having a hydro In a continuous type process, the catalyst is deposited O gen atom attached to the nitrogen atom which comprises in a reaction zone and the reactants, at the proper tem reacting said compound with a carbonyl compound Se perature, are introduced into the reaction Zone in admix lected from the group consisting of aldehydes and ketones ture with hydrogen in either upward or downward flow. in which carbonyl is the only functional group at a hydro The effluent products from the reaction zone are subjected gen pressure of from about atmospheric to about 100 to fractionation or other suitable means to separate the 5 atmospheres and at a temperature of from about 60° C. to desired products. Unreacted starting materials and excess about 250 C. under acidic reaction conditions and in the hydrogen are recovered and recycled as a portion of the presence of a platinum catalyst. reactor feed. 2. The process of claim 1 further characterized in that The following examples are presented in further illus said catalyst is an alumina-platinum composite. tration of the process of this invention. It is not intended 20 3. A process for the N-alkylation of a noncyclic amide that the said examples be interpreted as an undue limita containing only the one functional group and having a tion on the generally broad scope of this invention. hydrogen atom attached to the nitrogen atom which com Example I prises reacting said amide with a ketone or aldehyde in which carbonyl is the only functional group at a hydro A mixture of 51 grams of phthalimide, 100 grams of 25 gen pressure of from about atmospheric to about 100 at acetone and 20 grams of alumina-platinum catalyst con mospheres at a temperature of from about 60° C.
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