Ethyl yield

Figure 2. Solubilities and molecular weights of a vitrinite (80.8% C, daf) after nonreductive ethylation (yields calculated on ethylated product (daf))...

Substitution with R=methyl or ethyl yielded solvent-free compounds, which appeared to be in the low spin state (neff=ca. 2.12 B.M. over the temperature range 78-320 K) [119]. However, the phenyl derivative shows an abrupt and almost complete transition, but now centred near room temperature (T1/2T=299 K and T1/2 =290 K) [119]. 

A further pathway of 1,2-dimethylhydrazine metabolism is A-dem ethylation, yielding monomethylhydrazine and formaldehyde. This can be catalysed by the mitochondrial enzyme monoamine oxidase (Coomes Trough, 1983) and, most probably, by microsomal cytochrome P450 (Fiala, 1977 Hietanen et al., 1986). 

Dimethylhydrazine is readily absorbed. It can be A -dein ethylated, yielding formaldehyde, and can be oxidized through several steps to yield methylazoxymethanol. It binds covalently to protein, DNA and RNA in many mammalian tissues. The colon of rats is a target organ for 1,2-dimethylhydrazine toxicity, where it can produce aberrant crypts. In developmental studies, it is embryo- and feto-toxic in rats. 

Reaction of 3-formyl derivative 375 with ethyl bromoacetate in boiling ethanol in the presence of sodium ethylate yielded 2-[(ethoxycarbonyl) methoxy]-3-formylpyrido[ 1,2-a]pyrimidin-4-one 376 [91 IJC(B)839]. The... 

The ( )-tricyclic lactam ester 39, yet another emetine precursor (34), was also prepared by Takano s group (32,33,35) from ( )-norcamphor (74). Baeyer-Villiger oxidation of ( )-74 and subsequent ethylation yielded the ( )-lactone 75, which was then condensed with 3,4-dimethoxyphenethyla-mine and oxidized. The resulting ( )-ketone 76 was cleaved through the ( )-thioketal 77 to afford the ( )-amido acid 78. Exposure of ( )-78 to Mel... 

When alkyl 7-cyano-3-oxoheptanoates are reduced by baker s yeast, the configuration of the product is S in every case but the yield and the ee are significantly increased when the octyl ester is used (yield 77 %, 82% ee) rather then the ethyl (yield 46%, 56% ee) or / 7-butyl ester (yield 60%, 46% ee)129. 

Since all parameters required for evaluating these equations are available for mixed alkyl halide systems from measurements on the individual solutes, the validity of the equations can be critically tested. The individual CH3 and C2H5 yields expected from methyl bromide-ethyl bromide mixtures calculated on this basis are given in Table V. The agreement is reasonable with however the ethyl yields being slightly greater and the... 

XXV). In the same way ethylation yielded 0,0-diethylaromoline which was identical with 0,0-diethyl-V-methyldaphnoline. Thus aromoline is V-methyldaphnoline and since daphnoline has been assigned the struc-... 

When concentrated sulphuric acid is added to ethanol, the mixture becomes hot owing to the formation of ethyl hydrogen sulphate, the yield of which is increased if the mixture is then gently boiled under reflux ... 

Ethylene can be similarly prepared by the action of ethanolic potash on ethyl bromide, but the yield is usually very low. 

CH3COOH + HOC2H5 - CH3GOOC2H3 + H2O If, however, concentrated sulphuric acid is present, the water is absorbed, the back reaction prevented, and a high yield of ethyl acetate is obtained. In practice the reaction is not so simple. It was formerly supposed that, since the sulphuric acid is usually added to the alcohol, ethyl hydrogen sulphate and water are formed, the latter being absorbed by the excess of sulphuric acid, A mixture of ethanol and acetic acid is then added to the ethyl hydrogen sulphate,... 

Actually 50 g. of ester were obtained. Hence yield of ethyl acetate... 

Similarly, since 60 g. of acetic acid should theoretically give 88 g. of ethyl acetate, 52 g. should give 77 g. of the ester, and hence the yield. 

Run off the lower layer of bromide, dry it with calcium chloride (as in the above preparation of ethyl bromide) and finally distil the filtered bromide from a small flask, preferably through a short column. Collect the n-butyl bromide as a colourless liquid of b.p. 99-102°. Yield, 30 g. 

As a general rule esterification by the Fischer-Speier method should be carried out using absolute cthanob in the following preparation of ethyl benzoate, however, the yield is not sensibly affected by the use of the cheaper rectified spirit. 

Fit the flask with a 100° thermometer and a water-condenser, and distil the ethyl iodide carefully from a water-bath, collecting the fraction which distils between 68° and 73°. Yield, about 24 g. 

Carry out this preparation in precisely the same way as the above preparation of oxamide, using 2 ml. (2-4 g.) of benzoyl chloride instead of the ethyl oxalate, and observing the same precautions. Considerably more heat is generated in this reaction therefore hold the cork very securely in position during the shaking. After vigorous shaking for 15 minutes, no trace of oily benzoyl chloride remains. Filter off the fine flakes of benzamide, wash with cold water, and then recrystallise from hot water yield, 1-5 g. Colourless crystals, m.p. 130°. 

Add in turn benzyl chloride (8 3 g., 8 o ml.) and powdered thiourea (5 gm.) to 10 ml. of 95% ethanol in a 100 ml. flask fitted with a reflux condenser. Warm the mixture on the water-bath with gentle shaking until the reaction occurs and the effervescence subsides then boil the mixture under reflux for 30 minutes. Cool the clear solution in ice-water, filter off the crystalline deposit of the benzylthiouronium chloride at the pump, wash it with ice-cold ethyl acetate, and dry in a desiccator. Yield, 11-12 g., m.p. 170-174°. The white product is sufficiently pure for use as a reagent. It is very soluble in cold water and ethanol, but can be recrystallised by adding ethanol dropwise to a boiling suspension in ethyl acetate or acetone until a clear solution is just obtained, and then rapidly cooling. 

Dissolve 3-8 g. of sodium in 75 mi. of rectified spirit, using otherwise the same conditions as in the preparation of anisole. Then add 15 g. of phenol, and to the clear solution add 13 2 ml. (19-1 g., n mois.) of ethyl bromide. Continue precisely as in the preparation of anisole, shaking the ethereal extract with sodium hydroxide solution as before in order to eliminate any unchanged phenol. Finally collect the fraction boiling at 168-172°. Yield, 14 g. 

Dissolve 10 g. of chloro- 2,4-dinitrobenzenet in 50 ml. of dioxan in a 250 ml. conical flask. Dilute 8 ml. of hydrazine hydrate with an equal volume of water and add this slowly with shaking to the dioxan solution, keeping the temperature between zo " and 25°. Heat under reflux for 10 minutes to complete the reaction and then add 5 ml. of ethanol and heat again for 5 minutes. Cool and filter oflF the orange 2,4-dinitrophenylhydra-zine. Recrystallise the dry product from ethyl acetate m.p. 200° (decomp.). Yield, 7 g. 

While the sodium ethoxide solution is cooling, prepare a solution of 7 7 g. of finely powdered iodine in 60 ml. of ether. When this solution is ready, add 9 ml. (9 6 g.) of ethyl malonate to the ethanolic sodium ethoxide solution, mix w ell and then allow to stand for 30-60 seconds not longer) then cautiously add the ethereal solution of the iodine, mixing thoroughly during the addition in order to avoid local overheating by the heat of the reaction. (If, after the ethyl malonate has been added to the sodium ethoxide, a considerable delay occurs before the iodine is added, the yield of the final product is markedly decreased.)... 

Fit securely to the lower end of the condenser (as a receiver) a Buchner flask, the side-tube carrying a piece of rubber tubing which falls well below the level of the bench. Steam-distil the ethereal mixture for about 30 minutes discard the distillate, which contains the ether, possibly a trace of unchanged ethyl benzoate, and also any biphenyl, CeHs CgHs, which has been formed. The residue in the flask contains the triphenyl carbinol, which solidifies when the liquid is cooled. Filter this residual product at the pump, wash the triphenyl-carbinol thoroughly with water, drain, and then dry by pressing between several layers of thick drying-paper. Yield of crude dry product, 8 g. The triphenyl-carbinol can be recrystallised from methylated spirit (yield, 6 g.), or, if quite dry, from benzene, and so obtained as colourless crystals, m.p. 162. ... 

Gently warm a mixture of 32 g. (32 ml.) of ethyl acetoacetate and 10 g. of aldehyde-ammonia in a 400 ml. beaker by direct heating on a gauze, stirring the mixture carefully with a thermometer. As soon as the reaction starts, remove the heating, and replace it when the reaction slackens, but do not allow the temperature of the mixture to exceed 100-no the reaction is rapidly completed. Add to the mixture about twice its volume of 2A -hydrochloric acid, and stir the mass until the deposit either becomes solid or forms a thick paste, according to the quality of the aldehyde-ammonia employed. Decant the aqueous acid layer, repeat the extraction of the deposit with more acid, and again decant the acid, or filter off the deposit if it is solid. Transfer the deposit to a conical flask and recrystallise it twice from ethanol (or methylated spirit) diluted with an equal volume of water. The i,4-dihydro-collidine-3,5-dicarboxylic diethyl ester (I) is obtained as colourless crystals, m.p. 130-131°. Yield 12 5 g,... 

Dissolve 13 g. of sodium in 30 ml. of absolute ethanol in a 250 ml. flask carrying a reflux condenser, then add 10 g. (9 5 ml.) of redistilled ethyl malonate, and place the flask on a boiling water-bath. Without delay, add a solution of 5 3 g. of thiourea in a minimum of boiling absolute ethanol (about 100 ml.). The sodium salt of thiobarbituric acid rapidly begins to separate. Fit the water-condenser with a calcium chloride guard-tube (Fig. 61, p. 105), and boil the mixture on the water-bath for 1 hour. Cool the mixture, filter off the sodium salt at the pump and wash it with a small quantity of cold acetone. Dissolve the salt in warm water and liberate the acid by the addition of 30 ml. of concentrated hydrochloric acid diluted with 30 ml. of water. Cool the mixture, filter off the thiobarbituric acid, and recrystallise it from hot water. Colourless crystals, m.p. 245 with decomposition (immersed at 230°). Yield, 3 5 -4 0 g. 

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