L- ethylamines

The amination of styrene, however, led to two products (1-phenyl-1-ethylamine and 2-phenyl-l-ethylamine) in a 1 3 ratio [113], indicating that the hydrozirconation was not completely regioselective [114,115]. Since it is well known that hydrozirconation of trisubsti-tuted alkenes places zirconium at the least hindered carbon of the chain by a process involving zirconium migration, this class of alkenes was not investigated [5,116], On the other hand, hydrozirconation/amination of 3-methyl-l,2-butadiene gave an allylic amine. Reaction of the latter could either occur at the terminal carbon or proceed with... 

Ethoxy aniline. See Aminophenetole A240-R Ethyl Abietate. See under Abietic Acid and Derivatives A3-R A4-L Ethylacardite. See Acardite III A8-R Ethylaldehyde. See Acetaldehyde A14-L Ethylamine. See Aminoethane A199-R 3-(/8-Ethyl aminoethyl-o-syrn-triazole) Dipicrate A208-R... 

First, the solvent effect in the enantioseparation of racemic l-(4-methylpheny-l)ethylamine with (R)-2-hydroxy-4-phenylbutyric acid was examined. The system using 2-butanone, 2-propanol, or water as a solvent was found to give higher total resolution efficiency, whereas their mixed solvents resulted in lower total resolution efficiency (Table 5.12). For industrial-scale production, the use of a single solvent is better, and water is the best solvent for both economic and environmental reasons. Therefore, water was selected as a solvent, although 2-butanone gave the best total resolution efficiency... 

Preparation of the very active catalyst (X-Phos)2Pd from (MeCN)2PdCl2 starts by ligand exchange with TMEDA, which is followed by reaction with MeLi at 0°, and further treatment with X-Phos and 2-(o-chloropheny l)ethylamine, prior to warming to room temperature to split off indoline. The precatalyst (before elimination of indoline) can he used directly for A-arylation of arylamines. 

Total energies of the neutral and protonated imidazole (13), 2-methylimidazole (14), 4-methylimidazole (15)l 4-chloroimidazole (16)Fl,4-nitroimidazole (17) l, ethylamine (18), Na-methyl-ethylamine (19), Na,Na-dimethyl-ethylamine (20), thiazole (21), and 2-aminothiazole (22) were also calculated at the same level than previous molecules, and they are presented in Table 6. Tautomers for 15-17 are considered N(s)-H. 

Recently, in our laboratory, polypropylene sulfides with an asymmetric lateral aminated chain have been prepared and described by Huguet et al [110—112]. OA oxiranylalkyl-amines have been synthesized by reaction of l-chloro-2,3-epoxypropane on iS-methyl-1-propylamine (XLVa) or S -phenyl-l-ethylamine (XLVh) and the reaction of potassium thiocyanate with the amino-oxiranes gave the thiiranyl derivatives without any perceptible racemization. 

Synthesis of (A) started with the combination of 2,4,6-trimethylphenol and allyl bromide to give the or/Ao-allyl dienone. Acid-catalyzed rearrangement and oxidative bydroboration yielded the dienone with a propanol group in porlactone ring were irons in the product as expected (see p. 275). Treatment with aqueous potassium hydroxide gave the epoxy acid, which formed a crystalline salt with (R)-l-(or-naphthyl)ethylamine. This was recrystallized to constant rotation. 

The submitters report that both l,4-diazabicyclo[2.2.2]octane and triethylamine have been used to catalyze this decomposition. Tri-ethylamine was less satisfactory as a catalyst because of its relatively rapid reaction with the solvent, carbon tetrachloride, to form triethylamine hydrochloride and because of difficulty encountered in separating triethylamine from the dicarbonate pi oduct. The 1,4-diazabicyclo-[2.2.2]octane was efficiently separated from the dicarbonate product by the procedure described in which the crude product was washed with very dilute aqueous acid. 

Fig. 8.4. Logarithm of the first-order rate constants for the hydrolysis of substituted benzylidene-l,l-dimethyl-ethylamines as a fiinction of pH. [Reproduced fiom J. Am. Chem. Soc. 85 2843 (1963) by permission of the American Chemical Society.]...

The ci i-fused lactone A was resolved using (-t-)-l-(l-naphthyl)ethylamine to give the enantiomer required for the synthesis of prostanoids (Ref. 3). 

Anhalonine and Lophophorine. Spath and Gangl showed that each of these alkaloids contains a methylenedioxy group and that the quarternary iodide prepared from dZ-anhalonine is identical with lophophorine methiodide so that lophophorine must be N-methylanhalonine. Anhalonine was synthesised from 3 4-methylenedioxy-5-methoxybenzaldehyde by condensation with nitromethane, reduction of the product to the corresponding -ethylamine, the acetyl derivative (VII) of which, on treatment with phosphoric anhydride, condensed to 6-methoxy-7 8-methylenedioxy-l-methyl-3 4-dihydrofsoquinoline, m.p. 60-2°. This, on reduction, furnished the corresponding tetrahydrofsoquinoline, which proved to be anhalonine (VIII), and on conversion to the quaternary methiodide the latter was found to be lophophorine (IX) methiodide. The possible alternative, 8-methoxy-6 7-methylenedioxy-l 2-dimethyl-l 2 3 4-tetrahydrofsoquinoline, was prepared by Freund s method and the methiodide shown not to be identical with lophophorine methiodide. 

Treatment of a 3-aminotriazolopyridine with acid gave the imidazopyridine 242 (81T1787), also obtained from the 3-nitro derivative by catalytic reduction (83AHC79). Quaternary salts derived from compound 2, when treated with tri-ethylamine and subsequently heated give 2-pyridylcyanamides 243 or 2-(oxazol-l-yl)pyridines 244 depending on the alkyl group (86H(24)2563) the ylides are presumably intermediates (see also Section IV.I). 

When diazomethane is slowly added to excess lactam, the anions formed can interact with unreacted lactam by means of hydrogen bonds to form ion pairs similar to those formed by acetic acid-tri-ethylamine mixtures in nonpolar solvents. The methyldiazonium ion is then involved in an ion association wdth the mono-anion of a dimeric lactam which is naturally less reactive than a free lactam anion. The velocity of the Sn2 reaction, Eq. (7), is thus decreased. However, the decomposition velocity of the methyldiazonium ion, Eq. (6a), is constant and, hence, the S l character of the reaction is increased which favors 0-methylation. It is possible that this effect is also involved in kinetic dependence investigations have shown that with higher saccharin concentrations more 0-methylsaccharin is formed. 

Amine bound to a Wang-polystyrene resin 381 was acylated with 4-oxo-4Ff-pyrido[l,2-u]pyrazine-3-carboxylic acid in the presence of bromotrispyrrolidinophosphonium hexafluorophosphate and /-Pr2NEt in A-methylpyrrolidone (98MIP16). l-(4-Cyclohexyl-4-r / r-butylaminocarbo-nyl-l-piperidyl)-2-(4-fluorophenyl)ethylamine was acylated with perhydro-pyrido[l,2-u]pyrazine-3-carboxylic acid (01MIP19). An amino group of a macrocyclic compound attached to a solid support was acylated with... 

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