Sodium acetamide ethylate

A one-pot synthesis of 3,5-disubstituted 7-hydroxy-3//-l,2,3-triazolo[4,5-d]pyrimidines (130) has been carried out by using benzyl azide, cyano-acetamide, ethyl or methyl esters of the appropriate carboxylic acid, and sodium ethoxide as catalyst. The reaction proceeds via a 5-amino-l-benzyltriazole-4-carboxamide intermediate (85JHC1607). 7-Amino-3H-l,2,3-triazolo[4,5-d]pyrimidines 133 (R2 = H) were prepared starting from benzyl azide, malononitrile, and an aliphatic or aromatic nitrile, or by reaction of 130 with phosphorus oxychloride followed by amination. Compound 132 was formed in most reactions from two molecules of the 5-amino-4-cyano-l-benzyltriazole intermediate by an intermolecular nucleophilic at-... 

Chapter III. 1 Heptene (111,10) alkyl iodides (KI H3PO4 method) (111,38) alkyl fluorides (KF-ethylene glycol method) (111,41) keten (nichrome wire method) (111,90) ion exchange resin catalyst method for esters (111,102) acetamide (urea method) (111,107) ethyl a bromopropionate (111,126) acetoacetatic ester condensation using sodium triphenylmethide (111,151). 

The methyl ethyl ketazine forms an immiscible upper organic layer easily removed by decantation. The lower, aqueous phase, containing acetamide and sodium phosphate, is concentrated to remove water formed in the reaction and is then recycled to the reactor after a purge of water-soluble impurities. Organic by-products are separated from the ketazine layer by distillation. The purified ketazine is then hydrolyzed under pressure (0.2—1.5 MPa (2—15 atm)) to give aqueous hydrazine and methyl ethyl ketone overhead, which is recycled (122). The aqueous hydrazine is concentrated in a final distillation column. 

The organic phase is dried over sodium sulfate, filtered, the dichloroethane is evaporated off and the residue is crystallized from ethyl alcohol (95%). The product is dried in the oven and there is thus obtained about 800 grams (yield 90%) of the N-(2,5-diethoxyphenyl)-4-butoxy phenoxy acetamide, MP 101°C. 

The nonionic monomer can be acrylamide, N,N-dimethylacrylamide, N-vinyl-2-pyrrolidone, N-vinyl acetamide, or dimethylamino ethyl methacrylate. Ionic monomers are AMPS, sodium vinyl sulfonate, and vinylbenzene sulfonate. The terpolymer should have a molecular weight between 200,000 to 1,000,000 Dalton. 

N-vinyl acetamide, or dimethylamino ethyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, sodium vinyl sulfonate, and vinylbenzene sulfonate... 

Materials and Purification. Chemicals were purchased from Aldrich chemical company and used as received unless otherwise noted 1,1,1,3,3,3-hexamethyl disilazane, ethylene glycol, triphosgene, poly(ethylene oxide) (MW = 600), poly(tetramethylene oxide) (MW = 1000), poly(caprolactonediol) (MW = 530), toluene diisocyanate (TDI), anhydrous ethanol (Barker Analyzed), L-lysine monohydride (Sigma) and methylene bis-4-phenyl isocyanate (MDI) (Kodak). Ethyl ether (Barker Analyzer), triethylamine and dimethyl acetamide were respectively dried with sodium, calcium hydride and barium oxide overnight, and then distilled. Thionyl chloride and diethylphosphite were distilled before use. 

Stereostructures of a co-crystal of (li )-l- 4-[(9aA)-perhydropyrido[l,2- ]pyrazin-2-yl]phenyl -2-phenyl-7-hydroxy-l, 2,3,4-tetrahydroisoquinoline with ERa-LBD301-553/C — S triple mutant <2005JME364> and iV-[2-(4-hydroxyphenyl)ethyl]-a-propyl-3-[(4-hydroxyphenyl)methyl]-l,4-dioxo-l,2,3,4,ll,l la-hexahydro-67/-pyrazino[l,2- ]isoquinoline-3-acetamide with fructose-1,6-biphosphatase <2003JBC51176> were determined by X-ray crystallography. The structure of a complex formed from 3-[( -methylphenyl)amino]-4-[(4-methylphenyl)imino]-4//-pyrido[l,2-tf]pyrazine with sodium bis(trimethylsilyl)amide and (norbornadiene)Mo(CO)4 in THF was characterized by single crystal X-ray diffraction <1995JPR38>. 

Chloroethyl vinyl ether, 2-Chlorophenol, Cyclohexene, Dalapon-sodium. Diallate. 1,1-Dichloroethane, 2,3-Dimethylamine, Dimethylbutane, 1,4-Dioxane, Ethylamine, Ethyl ether, Erhvl sulfide. 2-Heptanone, Metaldehvde. 2-Methvlbutane. 2-Methvl-2-butene. 2-Methyl phenol, Nitromethane, 4-Nitrophenol, 2-Nitropropane, 1-Octene, 2-Pentanone, Phenol, Toluene, Triethylamine, Vinyl chloride, o-Xylene, m-Xylene Acetamide, see Acetonitrile, Acrylamide, Acrylonitrile, Ethylamine... 

Condensation, of paraldehyde with diethyl malonate, 32, 54 of a-phene thyl chloride with diphenylacetonitrile, 39, 74 of phenylacetylene with ethyl orthoformate, 39, 59 of 1-phenylbiguanide with ethyl chloroacetate, 38,1 of potassium diphenylacetonitrile with benzyl chloride, 39, 73 of potassium trithiocarbonate with potassium chloroacetate, 39, 77 of sodium acetylacetonate to tetraacetylethane, 39, 61 of sodium formylacetone with cyano-acetamide, 32, 32 of tetracyanoethylene with N,N-dimethylaniline, 39, 68 of thiophene, paraldehyde, and hydrogen chloride, 38, 86 of thiourea with furfuryl alcohol, 36,66... 

Moreover, the formation of enoxy-silanes via silylation of ketones127 by means of N-methyl-N-TMS-acetamide (1 72) in presence of sodium trimethylsilanolate (173) was reported in 1969 and since then, the use of silylating reagents in presence of a catalyst has found wide appreciation and growing utilization as shown in recent papers128-132 (Scheme 27). Diacetyl (181) can be converted by trifluoromethylsul-fonic acid-TMS-ester (182) into 2,3-bis(trimethylsiloxy)-l, 3-butadiene (7treatment with ethyl TMS acetate (7 5)/tetrakis(n-butyl)amine fluoride l-trimethylsiloxy-2-methyl-styrene (i<56)130. Cyclohexanone reacts with the combination dimethyl-TMS-amine (18 7)/p-toluenesulfonic acid to 1-trimethylsiloxy-l-cyclohexene (iSS)131. Similarly, acetylacetone plus phenyl-triethylsilyl-sulfide (189) afford 2-triethylsiloxy-2-pentene-4-one (790)132. ... 

In 1 L of water there is dissolved 116.0 g (1 mole) of N,N-diethylethylenediamine and, under vigorous stirring at a temperature maintained below 50°C, there is added 205.0 g (1 mole) of the chloride of p-chlorphenoxyacetic acid. The solution becomes rapidly homogeneous the formation of the basic amide hydrochloride is rapidly completed by further stirring the reaction mixture for 2 h at about 20°C. Then an excess of soda lye is added and the basic amide formed is extracted by ether. The ethereal solution is dried on anhydrous sodium sulfate and ether is distilled after that the residue is dried. So 2-(p-chlorophenoxy)-N-(2-(diethylamino)ethyl) acetamide is obtained. 

After the reaction was complete, the reaction mixture was slowly added to a mechanically stirred, pre-cooled (0°-5°C) quench mixture of ethyl acetate (1.7 L) and water (800 mL). At the same time, 50% (w/w) aqueous sodium hydroxide (185 mL) was added to the quench mixture at such a rate that the pH was maintained between 3-5 and the internal temperature was maintained below 25°C. The pH was then further adjusted to 7.0-7.5 with additional sodium hydroxide, and the mixture stirred for 1 h at 30°C. The mixture was filtered to remove the sodium sulfate, and the filter cake washed with ethyl acetate (300 mL). The filtrate and cake washes were combined, and the mixture partitioned. The aqueous (lower) phase was extracted once with ethyl acetate. The organic (upper) phases were combined and then concentrated in vacuo (10 mBar, 50°C) to a volume of 100 mL. Hexane (300 mL) was added slowly, and the mixture stirred for 1 h at 20°-22°C. The mixture was filtered, and the product cake washed with hexane (1 bed volume). The product was air-dried, then dried in vacuo (100 mBar, nitrogen sweep, 30°-35°C) to constant weight. Yield 31.0 g (95% based on HPLC wt % purity) of crude acetamidosulfone as a white solid. The crude product also contains a small amount of acetamide and sodium acetate. 

Ozonolysis of vinylpyrazine in methanol at — 30° furnishes pyrazine aldehyde in 73% yield.196 Vinylpyrazine undergoes a variety of addition reactions and pyrazylethyl derivatives of amines, ketones, ethyl phenyl acetate, phenylacetonitrile, and acetamide have been obtained.197-199 2-(2-Pyrazylethyl)cyclohexanone (42) has been prepared both by the condensation of vinylpyrazine with cyclohexanone in the presence of sodium metal and by interaction of vinylpyrazine with the pyrrolidine enamine of cyclohexanone followed by hydrolysis.200... 

Condensation, of 1-phenylbiguanide and ethyl chloroacetate, 38, 1 of sodium formylacetone with cyano-acetamide, 32, 32... 

Some reactions of 2,3,4-trisubstituted isoxazolium salts (exemplified by 70) leading to ring transformations, are summarized in Scheme 14.180 Other active methylene compounds such as ethyl acetoacetate and cyano-acetamide give analogous results to those with diethyl malonate products of base-induced ring opening by ethoxide are also obtained. When the reaction with phenylhydrazine is carried out in the presence of sodium hydroxide in ethanol the product is 71, presumably formed via the im-inoketene 72. 

The isothiocyanates are transformed into thiocarbamates by reaction with alcohols or into the acetamides by reaction with acetic acid or anhydride and sodium acetate. These transformations have also been applied to the preparation of unsaturated aminosugars73,74. Thus, suprafa-cial rearrangement of ethyl 2.3,4-trideoxy-6-0-methanesulfonyl-4-thiocyan ato-a-D-t/ireo-hex-2-enopyranoside to the 2-isothiocyanatc occurs in refluxing toluene (1 h), whereas the erythro-epimer needs to be heated in dimethylformamide for 6 hours73. This difference in reactivity might be due to an unfavorable anomeric effect and C-6 in an axial orientation in the transition state of the errr/iro-epimer, respectively. 

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