Ethanol alkylation with

Substitution Derivatives of Ethyl Malonate, Ethyl malonate resembles ethyl acetoacetate in that it gives rise to mono- and di-substituted derivatives in precisely similar circumstances. Thus when ethanolic solutions of ethyl malonate and of sodium ethoxide are mixed, the sodium derivative (A) of the enol form is produced in solution. On boiling this solution with an alkyl halide, e.g, methyl iodide, the methyl derivative (B) of the keto form is obtained. When this is treated again in ethanolic solution with sodium ethoxide, the... 

Polyphosphoric acid, P2O5, POCl, and PCl are suitable phosphorylatiag agents. Reaction of an alkyl sulfate with sodium pyrophosphate has also been reported for preparation of alkyl pyrophosphates (77). In general, phosphorylation leads to a mixture of reaction products that are sold without further separation. Thus, when lauryltri(ethyleneoxy)ethanol reacts with 0.3 mol of P2O5 at 50°C and is neutralized with 50% aqueous NaOH, the reaction mixture contains the foUowiag products ... 

Although the first all-sulfur macrocycles were prepared many years ago " the first systematic study of such compounds was initiated by Busch and his coworkers , who were interested in the cation binding properties of such ligands. A sequential synthesis was utilized to produce 1,4,8,11-tetrathiacyclotetradecane [tetrathia-14-crown-4 (70)] . In the first step, 1,3-propanedithiol is metallated using sodium and alkylated with 2-chloroethanol. The diol was then treated with thiourea to form the dimercapto-dithioether compound 9. The latter was once again metallated with sodium and allowed to react with 1,3-dibromopropane. The yield of 70 in the ring closure step, conducted at high dilution in absolute ethanol, was 7.5% after recrystallization. The entire sequence is illustrated in Eq. (6.8) . ... 

Nucleophilic attack of alcohols (e.g., ethanol) on a-lactones gives different regiochemistry depending on the snbstitnent R. In cases where R is alkyl or phenyl, ethanol reacts with a-lactones to prodnce a-ethoxyacids 3, presnmably via zwit-terionic form When R is the strongly electron-withdrawing trifluoromethyl... 

Nitroimidazoles substituted by an aromatic ring at the 2-position are also active as antitrichomonal agents. Reaction of p-fluorobenzonitrile (83) with saturated ethanolic hydrogen chloride affords imino-ether 84. Condensation of that intermediate with the dimethyl acetal from 2-aminoacetaldehyde gives the imidazole 85. Nitration of that heterocycle with nitric acid in acetic anhydride gives 86. Alkylation with ethylene chlorohydrin, presumably under neutral conditions, completes the synthesis of the anti-... 

Two sequential lithiations and treatments with different bifunctional electrophiles make possible one-pot syntheses of relatively complex molecules. Thus, in the [1+2+2] annulation depicted in Scheme 69, alkylation of 1-benzylbenzotriazole 399 with 2-bromoacetaldehyde diethyl acetal to give intermediate 426 is followed by alkylation with W-benzylideneaniline to produce derivative 427. Following treatment with formic acid causes cyclization to ethoxypyrrolidine 428 that subsequently eliminates ethanol and benzotriazole to give pyrrole 429 <1997JHC1379>. 

Izumi and Urabe [105] found first that POM compounds could be entrapped strongly on active carbons. The supported POMs catalyzed etherization of ferf-butanol and n-butanol, esterification of acetic acid with ethanol, alkylation of benzene, and dehydration of 2-propanol [105], In 1991, Neumann and Levin [108] reported the oxidation of benzylic alcohols and amines catalyzed by the neutral salt of Na5[PV2Mo10O40] impregnated on active carbon. Benzyl alcohols were oxidized efficiently to the corresponding benzaldehydes without overoxidation ... 

Rate constants and products have been reported for solvolysis of benzhydryl chloride and /7-methoxybenzyl chloride in 2,2,2-trifluoroethanol (TFE)-water and-ethanol, along with additional kinetic data for solvolysis of r-butyl and other alkyl halides in 97% TFE and 97% hexafluoropropan-2-ol. The results are discussed in terms of solvent ionizing power Y and nucleophilicity N, and contributions from other solvation effects are considered. Comparisons with other 3 nI reactions show that the solvolyses of benzhydryl chloride in TFE mixtures are unexpectedly fast an additional solvation effect influences solvolysis leading to delocalized cations. 

When the 3-thiourea derivative (59) was heated in boiling ethanol for 3 h, and then the evaporated reaction mixture was treated with 10% NaOH solution at 100°C for 20 min, anhydro 2-methyl-3-mercapto-4-hydroxy-5,6,7,8-tetrahydro[l,2-6]pyridazinium hydroxide (61) was obtained (71CPB159). The mercapto group was alkylated with benzyl bromide and was treated with HgCla in boiling ethanol to yield the 3-chloromercurithio derivative. Anhydro 3,4-dihydroxy-2-methyl-5,6,7,8-tetrahydropyrido[l,2-f ]pyridazinium hydroxide (62) was O-acylated with acetic anhydride, but the structure of the product was not elucidated (71CPB159). 

The reaction of arylisothiocyanates with guanidines (233) affords amidinothioureas (234), which can be converted into 3,5-diarylimino-l,2,4-thiadiazolines (235) directly on treatment with bromine in ethanol. Alternatively, (234) can be alkylated with benzyl chloride to give the S-benzyl derivative (236) which on treatment with bromine in chloroform gives (235) (Scheme 51) <87JIC675>. 

Ring opening of the pentanedioic anhydrides 3 with an alkyl or aryl substituent in the 3-position with (/ )-l-(l-naphthalenyl)ethanol proceeds with lower diastereoselectivity, but with the same sense of asymmetric induction except in the case of 3-rm-butylpentanedioic anhydride (3, R = t-Bu)96a. The monoesters 4 are obtained with d.r. values between 16 1 to 1 1 and yields > 80 %. 

Treatment of meso-ionic l,2,3,4-oxatriazole-5-thiones (286) (Section VII, I, 3) with boiling ethanolic ammonia yields the isomers 297.200 These belong to a new class of meso-ionic heterocycle, which by O-alkylation with triethyloxonium tetrafluoroborate yield the salts 298.200 These are useful intermediates for the synthesis of a number of novel types of meso-ionic 1,2,3,4-thiatriazoles (299,207 300,200 and 301).212... 

Kotarska et a/.106-282 attributed the 3-substituted structures to the products obtained from the pyrido[l,2-a]pyrimidine (63 R = H) by alkylation with either 1-chloromethylnaphthalene or allyl bromide, or with benzyl chloride in ethanolic potassium hydroxide in the presence of potassium iodide. The melting point of the 3-benzyl compound agreed with the earlier literature datum but that of the 3-allyl compound differed by more than 20 C.100,112... 

With carbon disulfide and ethanolic potassium hydroxide, ethyl 6-methyl-4-oxo-6,7,8,9-tetrahydro-4ii-pyrido[l,2-tt]pyrimidine gave the dipotassium salt (247), which was methylated with dimethyl sulfate to the 9-methylthio-thiocarbonyl compound (248) and alkylated with 1,2-dibromoethane to the... 

American workers needed to prepare the bis-amino acid 1 and adopted a literature procedure in which two equivalents of diethyl acetamidomalonate were to be alkylated with one equivalent of l,4-dichloro-2-butyne using two equivalents of sodium ethoxide in hot ethanol. Hydrolysis and decarboxylation of the dialkylated malonate would then give 1. This alkylation reaction was carried out, but ten equivalents of sodium ethoxide were used rather than two. This resulted in formation of ethyl 5-methylpyrrole-2-carboxylate in ca. 40% yield. Further study showed that the reaction to produce the pyrrole required equimolar amounts of the acetamidomalonate and the dichlorobutyne, excess of sodium ethoxide, and heating. No pyrrole was formed at room temperature. 

Fig (16) The enone (131), prepared from (130) is alkylated with iodide (133) to obtain the product (134). It reacts with trimethylsilyl cyanide and zinc iodide. The resulting product (135) is converted to tricyclic compound (136) by heating with hydrochloric acid and ethanol. 

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