2 methyl 5 ethyl aniline hydrogenation

The functionalized ligands were tested for various hydrogenation reactions (see Scheme 12.17). Ir-Josiphos bound to silica gel as well as to a water-soluble complex produced TONs in excess of 100000 and TOFs up to 20000h for the Ir-catalyzed hydrogenation of 2-methyl-6-ethyl aniline (MEA) imine to give an intermediate for (SJ-metolachlor [45a]. The polymer-bound Ir complex was much less active, and in all cases the ee-values were comparable to those for the homogeneous catalyst Selected results are summarized in Table 12.3. However, no immobilized system could compete with the homogeneous catalyst which is used to produce >10000 tonsy of enantioenriched (. S J-metolachlor and which, under optimized condi-... 

Reasonable conversions of NPBA were observed when using ketones as solvents however, product analysis showed increased byproducts formation with the use of ketones. When acetone is used as solvent, GC/MS analysis identified 2-methylindoline and N-phenylisopropylamine as the two major byproducts, which are produced via a secondary reaction between aniline (product), acetone and hydrogen (reductive amination). Similar byproducts were observed when using methyl ethyl ketone (MEK) as a solvent. In a parallel experiment, about 13% of aniline reacted with acetone under the same reaction conditions except in the absence of a catalyst. Most of the reaction product, about 11%, is non-hydrogenated product 2-methylindoline (C9H11N). These results clearly demonstrate that ketones are the least preferred solvents for N-debenzylation due to the secondary reaction between the desired product and the ketones. 

There are several catalysts used in industry more conunonly used ones are MEKP methyl ethyl ketone peroxide), BPO (benzoyl peroxide), CHP (cumene hydrogen peroxide), DMA (dimethyl aniline), and CoNap (cobalt naphthenate). The correct amount of the catalyst for use with a given resin is usually specified by resin suppliers the user must assure the exact amount of the specified catalyst when fabricating composites. 

DL-Isoleucine is synthesized in about 56% over-all yield by the method of Hamlin and Hartung (366). o-Oximino- -methyl-w-valeric acid (A) is prepared in 70% yield from ethyl sec.-bulyl acetoacetate, butyl nitrite and sulfuric acid. DL-Isoleucine is prepared in 80% yield by the reduction of (A) with hydrogen, palladium chloride and ethanol. This method is essentially the same as that originated by Bouveault and Locquin (117, 118, 525). By the comparable procedure of Feofilaktov (264, 265) the phenylhydrazone of methyl ethyl pyruvic acid, prepared from sec.-butyl acetoacetate and phenyldiazonium chloride (aniline and NaN02) in 68% yield, is reduced by means of rinc and alcoholic HCl to nearly the theoretical yield of a mixture of DL-isoleucine and DL-allo-isoleucine. Ehrlich (235) synthesized a mixture of isoleucine and allo-isoleucine from 2-methyl-n-butyraldehyde by the Strecker reaction. 

JV-Ethyl-AT-(2-hydroxyethyl)aniline afforded 52.5% of JV-ethyl-JV-[2-hy-droxyethyljcyclohexylamine and 14% of A-methyl-A-ethylcyclohexylamine upon hydrogenation over Raney nickel at 150 and 65 atm in ethanol [725]. 

Dan et al. found that Brij-35 also produces an enhancement of the CL intensity of the reaction of Ms[yV-[2-(7V -methyl-2,-pyridiniumyl)ethyl]-N-[(trifluoromethyl)sulfonyl]]oxamide with hydrogen peroxide in the presence of some fluorophors [40], To be precise, the CL intensity increased by a factor of 130 for 8-aniline-1-naphthalenesulfonic acid (ANS) and 5.6 forrhodamine B (RH B), compared to the CL intensity in the absence of surfactant. This leads to an increase of 2-3 orders of magnitude in the linear dynamic ranges and a more precise determination of these analytes. However, improvement of the detection... 

Initial efforts to prepare benzoic acid 28 from methyl or ethyl 4-aminobenzoate and biphenyl-2-carboxylic acid (27) afforded poor yields of 28 (48% and 7%, respectively). However, acylation of 4-aminobenzoic acid with biphenyl-2-carbonyl chloride was found to provide 28 in excellent yield (95%) when DMAP was employed as a base. Selective acylation of the anilinic nitrogen of 26 with benzoic acid 28 was accomplished in analogy with the first-generation process synthesis by conversion of 28 to the corresponding acid chloride (SOCl2, CH3CN) followed by acylation of 26 in acetonitrile. Subsequent addition of ethanolic hydrogen chloride to the reaction mixture resulted in the precipitation of conivaptan HCl (1), which was isolated in 90% yield. 

Anilides and toluides of low-molecular-weight carboxylic acids were analysed by GC by Umeh [180,181 ], as follows. A 0.5-ml volume of a solution of Ci—C8 acids (each at a concentration of 0.5 M) in ethyl acetate was pipetted into a dry test-tube containing 0.15 ml of thionyl chloride, and 0.5 ml of aniline was added. The open test-tube was heated in a sand-bath at 60—80°C for 5 min, cooled in an ice-bath for 2 min and, after mixing with 10 ml of 1 M sodium hydrogen carbonate solution, 10 ml of a 0.1% solution of methyl myristate in ethyl acetate were added and the test-tube, still open, was stirred until effervescence ceased. Then the test-tube was stoppered, shaken vigorously for 30 min and allowed to stand until the phases separated. It was possible to inject 2 pi of the acetone layer or to isolate the layer completely and dry and store it. 

Hydrogen Nitrogen -Argon Oxygen -Methane -Ethyl ether Carbon disulphide Benzine -Stannic chloride Aniline -Methyl sahcylate Mercury -Sulphur -... 

---