Isopropylamine, from acetone

The complexes of long-chain primary-secondary aliphatic amines with TNT have low water solubility and may be useful for the removal of TNT from aq solns (Ref 97). The rapid reaction with isopropylamine in acetone has been studied as a possible procedure for the neutralization of TNT in land mines (Ref 88). No products were isolated, but kinetic and thermal data were obtained... 

NaBH4 has also been crystd from isopropylamine by dissolving it in the solvent at reflux, cooling, filtering and allowing the solution to stand in a filter flask connected to a Dry-ice/acetone trap. After most of the solvent was passed over into the cold trap, crystals were removed with forceps, washed with dry diethyl ether and dried under vacuum. [Kim and Itoh J Phys Chem 91 126 1987.] Somewhat less pure crystals were obtained more rapidly by using Soxhlet extraction with only a small amount of solvent and extracting for about 8h. The... 

Gobolos et al. studied reductive amination of acetone with ammonia in a flow system at 169-210°C and 0.8 MPa H2 (H2/NH3 = 0.5) on Raney Ni that had been modified by organic tin compounds with general formula of SnR l (R = Et, Bu, or benzyl) in order to suppress the formation of isopropyl alcohol.16 By introducing tin from tetraalkyl tin, the selectivity to the formation of secondary amine significantly increased at the expense of the primary amine (isopropylamine/diisopropylamine ratio = 68.2/24.1 at 192°C, compared to 83.6/8.6 at 190°C with unmodified catalyst). By modifying the catalyst with SnBzl2Cl2, the lowest selectivity (<1%) for the formation of isopropyl alcohol was obtained at temperatures of 171-202°C. The isopropy-lamine/diisopropylamine ratio was close to the values obtained on the unmodified catalyst (7.3% selectivity to isopropyl alcohol at 190°C). 

The evolution of a transaminase from Arthrohacter citreus to a thermostable transaminase with increased specific activity and decreased inhibition by the amine product was accomplished using error prone polymerase chain reaction (PCR) [64] The reaction of substituted tetralone 75 and isopropylamine to produce substituted (S) aminotetralin 76 was carried out at greater than 50 °C to facilitate the removal of the acetone by product and drive reaction equilibrium (Figure 14.43). 

Acetone is readily converted to isopropylamines in the vapor phase under conditions that apply for the lower (Cj-C ) aldehydes. The preparation of 2-aminobutane from methylethyl ketone (butanone-2) is satisfactorily carried out in the liquid phase, preferably in the presence of butanol-2 since the latter can also be converted to amine by ammonolysis. The intranuclear ketone cyclohexanone can be converted to cyclohexylamine by hydroammonolysis in the vapor phase. The preparation of 12-amino-stearamide from the corresponding keto acid is, however, best carried out in the liquid phase. The pertinent reactions are ... 

Catalysts for HydroSimmonolysis. The hydrogenation type of catalysts referred to above (i.e., nickel-, cobalt-, and copper-based catalysts) and also noble-metal catalysts are used in the hydroammonolysis of aldehydes and ketones. A foraminate nickel catalyst, made from a 42 58 nickel aluminum alloy was used to convert acetone to isopropylamine by a vapor-phase reaction employing an excess of ammonia and hydrogen. ... 

Barium thiocyanate is a white solid that is very soluble in water but has a very steep temperature-solubility gradient. This solid is also soluble in acetone, methanol, ethanol, methylamine and ethylamine, moderately soluble in isopropylamine and dimethylamine, but insoluble in trimethylamine. The anhydrous salt is very hygroscopic. Crystallization from water yields the 3-hydrate as well-formed, needle-shaped crystals. Double salts are formed with the thiocyanates of the alkali and other alkaline earth metals. ... 

Isopropanol is used in the production of other chemicals such as derivative ketones, isopropylamines, and isopropyl esters. The use of isopropanol in the production of monoisopropylamine for herbicides (primarily glyphosate) continues to be the fastest growing segment (Anonymous 2001b). A minor use for isopropanol is to serve as a feedstock for the production of acetone to meet the demand in excess of the coproduct acetone from phenol production. However, isopropanol is also produced from crude acetone, which is generated as a by-product of propylene oxide manufacture (Anonymous 2001b). 

A narrow substrate spectrum has been described for tiie yeast alcohol dehydrogenase (YADH) from Saccharomyces cerevisiae, making it a suitable biocatalyst only for molecules like methanol, ethanol, or in some cases acetone. Unfortunately the cofactor NADH is needed, which is regenerated by FDH (Scheme 29.6c). For the asymmetric synthesis of (S)-phenylethylamine with isopropylamine (IPA) as amino donor, acetone was converted to isopropyl alcohol catalyzed by YADH. The effectiveness of this method was compared to the reaction without YADH/FDH. A conversion yield of 99% was achieved with the YADH/FDH system while a conversion yield of 63-89% was obtained without YADH/FDH [69]. 

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