PATENTS

2556. OLIN, J. F., AND DEGER, T. E. (Sharples Chemicals, Inc.). Aliphatic Amines and Acid Amides. United States Patent 2,422,631, June 17, 1947. Chem. Abs., vol. 41, 1947, p. 5892.

An olefin of formula RR1C:CR2R3 (I), CO or CO2, an aminating agent R4R5NH (II), and H react to give aliphatic amines and acid amides. R, R1, R2, and R3 are H or alkyl radicals, and R4 and R5 are H or aliphatic, cycloaliphatic, heterocyclic, or aromatic radicals. The reactions proceed as follows: (I)+CO+(II)+2H2→RR1CHCR3R3CH2NR4R5 (III)+H2O. (I)+CO2+(II)+3H2→(III)+2H2O. (I)+CO+(II)→RR1CHCR2R3CONR4R5 (IV). (I)+CO2+(II)+H2→(IV)+H2O. A mixture of primary, secondary, and tertiary amines is formed. The 3d equation represents an intermediate reaction for the 1st equation. Where the olefin contains between 2-10 C atoms, the reaction is carried out in the vapor phase. The reaction mixture is preheated and then passed through a reactor at 250-450 but preferably at 325-375. A pressure of 500-20,000 p. s. i. is desirable. A mixture of dehydrating and dehydrogenating catalysts or a single catalyst promoting the amide formation and the hydrogenation is desirable. Single catalysts of this type are ZnCrO4, ZnWO4, MnCrO4, Mn3(PO4)2, or MnO mixed with phosphates, sulfates, or halides of metals of groups (I) and (II) of the periodic system. Thus a 2-cu. ft. stainless- steel chamber is filled with a mixture of 10% MnO and 90% ZnCrO4 activated by heating at 350 5 hr. in a H2-NH3 atm. A mixture of CO, H2, NH3, and C2H4 in 30:5:3:1 mol. ratio is pumped into the preheater at a space velocity of 2,000 and then passed into the reactor kept at 350 and 8,700 p. s. i. The crude product is passed through a gas-liquid trap under 1,000 p. s. i. where the excess CO and H2 are bled off and recirculated. From the crude mixture pure propylamine is obtained. Similarly, there are obtained a mixture of AmNH2 and iso-BuNH2, iso-BuNHMe, b. 67-70, d20 0.735, and PrNHMe b. 62-65, d20 0.717.