Residual ethoxy

The deprotection process illustrated in Figs. 5 and 6 was followed by solid-state CP/MAS NMR spectroscopy. As illustrated in Fig. 7, the carbonyl (158.2 ppm), aromatic (128.2 and 137.4 ppm), and benzylic (67.4 ppm) resonances decreased due to cleavage of those functional groups by the carbamate deprotection. However, the propyl tether resonances at 10.5, 23.1, and 43.2 ppm remained intact (Fig. 7b). Incomplete hydrolysis left a small amount of residual ethoxy moieties at 54.1 and 17.5 ppm. The degree of deprotection achieved in the material resulted in an amine number density of approximately 0.25mmol/g, as ascertained by nonaqueous titration of the amines with benzoic acid [42]. 

Distillation of the residue gave 1-ethoxy-l,4-hexadiyne, b.p. 50°C/15 timHg,... 

Benzhydryloxy ethoxy diphenyl silane (2). To a solution of benzoyl triphenylsilane 1 (2.5 g, 6 9 mmol) in benzene (25 mL) was added a solution of sodium ethoxide in ethanol (2 mL, 0 S mmol). The solution changed colour and after 11 min laded airmst completely. The solution was washed with water and the solvent removed in vacuum. The oily residue was dissolved in hot ethanol (15 mL) and cooled to give 2 (2 1 g, 74%), np 67-75 C Recrystallizatlon from ethanol gave 1 8 g (64%). mp 77-78,C... 

The contents of the flask while still hot are poured into a 30-cm. evaporating dish and the alcohol is evaporated on a steam bath. The dry salt is pulverized and thoroughly mixed with 390 g. of calcium oxide, placed in a 2-I. copper retort (Note 3), and heated with the full flame of a Meker burner. The distillate is placed in a distilling flask and heated on a steam bath all material distilling under 90 is removed and discarded. The residue is then allowed to stand over solid potassium hydroxide for twelve hours and is finally fractionated. The dimethyl-pyridine distils at i42-i44°/743 mm. The yield is 35-36 g. or 62-64 per cent of the theoretical amount based on the 3,5-dicarb-ethoxy-2,6-dimethylpyridine, or 30-36 per cent based on the original ethyl acetoacetate. 

In a 2-1. flask fitted with a total-reflux, variable-take-off distillation head is placed a solution of 53 g. (0.472 mole) of dihydroresorcinol (Note 1), 2.3 g. of -toluenesulfonic acid monohydrate and 250 ml. of absolute ethanol in 900 ml. of benzene. The mixture is heated to boiling and the azeotrope composed of benzene, alcohol, and water is removed at the rate of 100 ml. per hour. When the temperature of the distilling vapor reaches 78° (Note 2), the distillation is stopped and the residual solution is washed with four 100-ml. portions of 10% aqueous sodium hydroxide which have been saturated with sodium chloride. The resulting organic solution is washed with successive 50-ml. portions of water until the aqueous washings are neutral and then concentrated under reduced pressure. The residual liquid is distilled under reduced pressure. The yield of 3-ethoxy-2-cyclohexenone (Note 3), b.p. 66-68.5°/0.4 mm. or 115-121°/11 mm., Mq 1.5015, is 46.6-49.9 g. (70-75%). 

A solution of 0.3 of 3j9-acetoxy-21-ethoxy-17a-pregn-5-en-20-yn-17/3-ol in 7 ml of pure pyridine is hydrogenated over 90 mg of 2.5% palladium-on-calcium carbonate at room temperature and atmospheric pressure. The reaction mixture is filtered and evaporated and the residue recrystallized to give 80 % of the 17a-vinyl product. 

The excess diethyleneglycol is removed in vacuo and the residue dissolved in water and then in benzene. The benzene extract is washed several times in water, then purified in vacuo. The 1-p-chlorobenzhydryl-4-<2 -[2"- 2" -hydroxyethoxy)-ethoxy] -ethyDpiperazine obtained distills at 250°C/0.01 mm Hg. 

The filtrate is washed four times with water, dried and evaporated, yielding dl-N-[ (ethoxy-carbonyDmethyl] -1 -phenylethylamine. This residue is dissolved in 4 00 parts xylene while refluxing and to this solution are added 450 parts formic acid. After boiling for a few hours, the mixture is cooled and washed successively three times with a 20%solution of formic acid, water, sodium hydrogen carbonate solution. 

A) The preparation of [H-chloroethoxyjchloromethyl]phosphonic acid Acetaldehyde (1.1 mol) and hydroxymethylphosphonlc acid (1 mol) in 500 ml of benzene are saturated with hydrogen chloride gas at 10°C to 15°C. The mixture is aged at 25°C for 24 hr, the solvent distilled out in vacuo and the residue flushed three times with benzene to remove all traces of hydrogen chloride. The residue is taken up in benzene (500 ml), treated with tert-butyl hypochlorite (0.8 mol) and azobisisobutyronitrile (0.8 mm) at 40°C until titration shows the absence of hypochlorite and the solution is then evaporated to yield [(1-chloro-ethoxy)chloromethyll phosphonic acid in the form of an oil. 

A mixture of 0.1 mol of N-mono-1-p-chlorobenzohydrylpiperazine and 0.1 mol of 1-chloro-2-(2-hydroxy-ethoxy)-ethane is heated for 3 hours to 150°C. The mass is then taken up in 100 ml of benzene and 100 ml of a 10% aqueous solution of NaOH decanting takes place, and the benzene solution is washed with water and the solvent is evaporated. Vacuum distilling of the residue yields 1-p-chlorobenzohydryl-4-[2-(2-hydroxy-ethoxy)-ethyl]-piperazine, BP 220 C/0.5 mm Hg. 

Polyacrylamide gels were dissolved in 30% peroxide solution and added to a scintillation mixture in 1 1 2-ethoxy ethanol-toluene. After counting, the mixtures were bulked and evaporated intermittently with heat dining a 4 week period, and the accumulated peroxidised residues eventually exploded violently [1], A subsequent comment indicated that peroxidised materials may not necessarily have been formed, because solutions of organic materials in aqueous peroxide are themselves potentially explosive [2],... 

The mixture is then fractionally distilled until the temperature reaches 140°. The first fraction boiling at 75-95° consists mostly of alcohol and water, and is discarded. The fraction boiling between 95° and 140° contains water and 25-30 g. of j8-ethoxy-propionitrile. This is extracted twice with 50-cc. portions of benzene, and the benzene extracts are added to the cooled residue in the distilling flask. The mixture is filtered (Note 2), the solid material is washed with 75 cc. of benzene, which is added to the filtrate, and the whole is distilled. The fraction boiling at 169-174° is collected it weighs 178-200 g. (52-58 per cent of the theoretical amount). 

A mixture of diethyl 2-bromo-l-phenylethenylphosphonite (30.3 g, 0.1 mol) and dimethyl maleate (14.4 g, 0.1 mol) was stirred for 4 h at room temperature under an argon atmosphere. At this time, hexane was added to the reaction mixture sufficient for complete precipitation, and the resultant crystals (unreacted dimethyl maleate) were removed by filtration. The oily residue was treated on a silica gel column (40/100 pm) using a pentane/acetone (8 2) mixture, allowing the elution and isolation after evaporation of pure l-ethoxy-2-phenyl-4,5-dimetho x yea rb o n y I - A2-X5-phospholene 1-oxide (8.9 g, 27%), which exhibited spectra and analytical data in accord with the proposed structure. 

Dissolve 3.3 g 4,5, or 6 methoxy (or ethoxy, methyl, etc.)-tryptamine or its HC1 salt in 350 ml 0.1 N HC1 heat on steam bath two hours with 1.1 g glycoaldehyde (reaction over when aliquot no longer gives a precipitate with dinitrophenylhydrazine). Filter, concentrate by heating on water bath or evaporate in vacuum basify with 20% NaOH and extract with ether (best to do in an extractor for eighteen hours). Dry and evaporate in vacuum the extract to get about 5 g residue or oil which may precipitate on standing. Add 250 ml 90% phosphoric acid and heat on steam bath two hours. Evaporate in vacuum (or dilute with water, basify with 20% NaOH extract with ether in extractor and dry, evaporate in vacuum the... 

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