Ethylamine acetylation

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. 

The reactions of (174) with various amines has been studied." " Hydrolysis of the hexamine salt of (174) gave not the symmetric diamine but (184) via a cyclic intermediate. The pyrolysis of 5-methyl-2-thenyltrimethyl ammonium hydroxide (185) is claimed to give (186) through a 1,6 Hofmann elimination reaction. The Bischler-Napieralski cyclization has been applied to acetyl derivatives of 2-(2-thienyl) ethylamine and 2-(3-thienyl) ethylamine for the preparation of sulfur analogs of isoquinoline. ... 

A-Acetylhomoveratrylamine2 is prepared by adding 190 ml. of acetic anhydride to a stirred solution of 300 g. (1.80 moles) of /3-(3,4-dimethoxyphenyl)ethylamine [Benzeneethanamine, 3,4-dimethoxy-J (Aldrich Chemical Company, Inc.) in 150 ml. of pyridine at such a rate that the temperature is maintained at 90-95° (ca. 1.5 hours is required). After the solution has been stored at room temperature overnight, the volatile material is evaporated under reduced pressure, and the residue is crystallized from ethyl acetate to give 286-306 g. (78-83%) of acetylated product, m.p. 99-100°. 

Cleavage to 2-phenyl-ethylamine, phenyl-acetaldehyde and phenyl-acetic acid N-acetylation... 

Ethyl a acetyl-0 (2,3 dimethoxy-phenyl)propionate, 31, 56 Ethyl a acetyl-0 (3,4 dimethoxy-phenyl)propionate, 31, 58 Ethylamine, 2 chloro N,N-di-... 

Faraone, Parasacco, and Cogrossi (87) have introduced maleic and crotonic ester groups and methacryloyl ethylamine ether groups into partially acetylated celluloses. These cellulose derivatives containing substituents with polymerizable double bonds grafted with styrene when brought in contact in presence of benzoyl peroxide. 

Fig.4.11. Separation of some acetylated amines (see text for details). Peaks 1 = unknown 2 = 0-phenyl-ethylamine 3 tyramine 4 - tryptamine 5 1 methoxytryptamine 6 = serotonin 7 = prednisone.

Ethyl acetoacetate, 31, 1, 57 32, 76, 84 Ethyl a-acetyl-/3-(2,3-dimethoxy-phenyl)acrylate, 31, 5(5, 58 Ethyl a-acetyl-/S-(3,4-dimethoxy-phenyl)acrylate, 31, 58 Ethyl q -acetyl-/3-(2,3-dimethoxy-phenyl)propionate, 31, 56 Ethyl a-acetyl-/3-(3,4-dimethoxy-phenyl)propionate, 31, 58 Ethylamine, 2-chloro-N,N-di-... 

To a stirred solution of p-(3,4-dimethoxyphenyl)-ethylamine (100 g, 0.552 m) and triethylamine (66.6 g, 0,66 m) in CHCI3 (1 liter) was added acetyl chloride (47.1 g, 0.60 mole) dropwise over a period of 30 min and the mixture stirred overnight. The mixture was washed with 3x500 ml H20, dried over MgS04 and evaporated to a solid. The solid was dissolved in 500 ml hot CCI4, 300 ml cyclohexane added and allowed to cool slowly. The crystallized solid was collected by filtration and dried to afford N-acetyl-3,4-dimethoxyphenethylamine as a white solid, 112.1 g (91% yield). MP 99-100°C. 

The pyrimidine ester (323) was amidated with ethylamine and cyclocondensed with DMF to give compound (324) (Equation (47)) <86EUP 188094). 5-Acetyl-6-amino-l,3-dimethyluracil was cyclized using POCI3-DMF to give compound (325) <87EUP24331l>. 

Give the products expected from the following reactions, (a) acetyl chloride + ethylamine O... 

The behavior of 3-acetyl-l,2,5 thiadiazole (87) in several reduction reactions was also studied. The Leukart reaction produced the expected product, l-[3-(l,2,5-thiadiazolyl)]ethylamine, but the Wolff-Kishner reaction failed to yield any ethylthiadiazole under various conditions examined. Sodium borohydride smoothly reduced both acetyl- and benzoylthiadiazole to the corresponding carbinols. 

Preparative Methods by ring-closure of 3-bromobutyric acid with Sodium Carbonate, or by hydrogenation of Diketene. The optically active forms are obtained in the same manner starting from (J )- or (,S)-3-bromobutyric acid, which may be resolved with the (5) form of I-(I-Naphthyl)ethylamine Asymmetric aldol condensation using an enantiopure iron acetyl complex followed by cyclization, or asymmetric hydrogenation of diketene catalyzed by a chiral ruthenium complex, also gives the optically active p-lactone. 

The reactions represented are the combination of hydrogen and chlorine, the decomposition of mercury cyanide, the hydrolysis of acetyl chloride, and the reaction of ethyl chloride with anamonia to form ethylamine and hydrogen chloride. The reagents are shown left and right the products are separated by the horizontal line and by a vertical line where necessary.—O.T.B.]... 

Amidation. Resolution by selective acetylation of l-(heteroaryl)ethylamines is successful. Lipases have also been used to catalyze aminolysis of a-oxygenated esters. 

Ethyl acetoacetate, 29, 214, 399, 540, 629, 794, 887,1075,1128, 1268-1269,1272 p-Ethylacetophenone, 946,1084-1085 Ethyl acetopynivate, 251 Ethyl o-acetoxyacetoacetate, 540 Ethyl o-acetO Qrhexanoic acid, 541 Ethyl acetylacetoacetate, 1097 Ethyl a-acetyl-f3-(2,3-dimethoxyphenyl> propionate, 896 Ethyl acetyl eburicoate, 615 Ethyl acrylate, 928 N-Ethylallenimine, 1637 Ethylamine, 103,372,574,575,578,579,770 Ethyl p-aminobenzoate, 890 Ethyl 3-aminocitrazinate, 520 Ethyl azidoformate, 363-364 Ethyl benzalmalonate, 888 Ethylbenzene, 226,567,576, 719, 779,1061, 1287... 

Ketene and aldehydes undergo [2+2] cycloaddition in the presence of aluminum catalysts (Scheme 6.56). The reaction involves either isolable or in situ-generated unstable ketenes and is regarded as a variant of the aldol reaction. During the development of the Al(l I l)-calalyzed ketene-aldehyde reaction, the optically active Al(in)-triamine complex 88 was found to catalyze the cyclocondensation of acetyl bromide (AcBr) and benzyloxyacetaldehyde, with di(isopropyl)ethylamine (DIEA)... 

ALD-52 (1-acetyl-d-lysergic acid diethylamide) is equally as active a LSD-25. ALA-10 (l-acetyl-d-lysergic acid ethylamine) is 1/10 as active as LSD. 1-Alkylation (e.g. R2 = methyl, ethyl) chain lengthening on the LSD-25 molecule decreases the activity of the parent substance (Jacob 1994). MLD-41 binds to serotonin receptors stronger than that of LSD-25. It has reported to be one third as active as LSD (Abramson 1958). N-6 Alkylation (R3) increases activity (Jacob 1994). 

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