Base-catalyzed method

Other base catalyzed methods for N-carboxylation of amines and hydrazines using CO2 and CS2 to generate the corresponding carbamate or thiocarbamate, respectively, are provided (1). Urea derivatives of Step 1 have also been prepared and are described (2). 

Variations of the base-catalyzed method were used to prepare the mixed alkyl-aryl di(ferf-phosphine) (CeH5)2PCH2CH2P(CH3)2, the three tri-phosphines RT(CH2CH2PR2)2 R = CH3, R = CH3 or CeHs, R = CH3), the mixed aliphatio-aromatic linear tetra(fert-phosphine) (I), and the branched penta(tert-phosphine) (II) (17, 18). 

Reportedly, simple alkyl isocyanates do not dimerize upon standing. They trimerize to isocyanurates under comparable reaction conditions (57). Aliphatic isocyanate dimers can, however, be synthesized via the phosgenation of A[,A[-disubstituted ureas to yield /V-(ch1orocarhony1)ch1oroformamidine iatermediates which are subsequendy converted by partial hydrolysis and base catalyzed cycUzation. This is also the method of choice for the synthesis of l-alkyl-3-aryl-l,3-diazetidiones (mixed dimers of aromatic and aUphatic isocyanates) (58). 

As a variation on the base-catalyzed nucleopbilic displacement chemistry described, polysulfones and other polyarylethers have been prepared by cuprous chloride-catalyzed polycondensation of aromatic dihydroxy compounds with aromatic dibromo compounds. The advantage of this route is that it does not require that the aromatic dibromo compound be activated by an electron-withdrawing group such as the sulfone group. Details of this polymerization method, known as the Ullmaim synthesis, have been described (8). 

Use of the trapping agent is recommended as the most efficient method for running acyloin condensations for many reasons. Among them are (a) the work-up is very simple filter and distil (b) the bis-(silyloxy)olefin is usually easier to store than the free acyloin and is readily purified by redistillation (c) unwanted base-catalyzed side reactions during reduction are completely avoided and (d) the bis-(silyloxy)olefin can be easily converted directly into the diketone by treatment with 1 mole of bromine in carbon tetrachloride.Other reactions are described in Riihlmann s review and in Organic Reactions ... 

There are several methods for generation of benzyne in addition to base-catalyzed elimination of hydrogen halide from a halobenzene, and some of these are more generally applicable for preparative work. Probably the most convenient method is diazotization of o-aminobenzoic acid. Concerted loss of nitrogen and carbon dioxide follows diazotization and generates benzyne. Benzyne can be formed in this manner in the presence of a variety of compounds with which it reacts rapidly. 

The 17-ethylene ketal of androsta-l,4-diene-3,17-dione is reduced to the 17-ethylene ketal of androst-4-en-3,17-dione in about 75% yield (66% if the product is recrystallized) under the conditions of Procedure 8a (section V). However, metal-ammonia reduction probably is no longer the method of choice for converting 1,4-dien-3-ones to 4-en-3-ones or for preparing 5-en-3-ones (from 4,6-dien-3-ones). The reduction of 1,4-dien-3-ones to 4-en-3-ones appears to be effected most conveniently by hydrogenation in the presence of triphenylphosphine rhodium halide catalysts. Steroidal 5-en-3-ones are best prepared by base catalyzed deconjugation of 4-en-3-ones. ... 

The direct base-catalyzed alkylation of 3-keto steroids is generally not a very satisfactory method for the preparation of monoalkylated products. However, under optimum conditions (short reaction time with methyl iodide, a Modest excess of potassium t-butoxide in boiling t-butanol) modest yields of... 

Extension of the above method to 3-methoxyestra-3,5(10)-dien-17-one 17-ethylene ketal (46) prepared by base-catalyzed isomerization of 3-methoxy-estra-2,5(10)-dien-17-one 17-ketal (42) with potassium t-butoxide in dimethyl sulfoxide gives the isomeric tropone A-homo-estra-l,4,5(10)-triene-3,17-dione... 

Base catalyzed pinacol rearrangement of vicinal m-glycol monotosylates is a simple and useful general method for preparing perhydroazulenes. Thus, treatment of cholestane-5a,6a-diol 6-tosylate (115a) with either one mole-equivalent of potassium t-butoxide in f-butanol at 25° or with calcium carbonate in dimethylformamide at 100° gives a quantitative yield of 10(5 6/5H)... 

A nonphotochemical method for the preparation of D-norsteroids involves the base-catalyzed pinacol rearrangement of a pregnane-16oc,17a-diol 16a-mesylate. ... 

E. Rapid-Reaction Technique Because this technique and the apparatus involved are considered in detail in the following review, only a qualitative discussion is given here. This is the most valuable method for the confirmation of covalent hydration because it can usually give conclusive results even when the percentage of the hydrated species is as low as 2%. It makes use of the facts that aU known examples of the formation or disappearance of the hydrated species followed first-order kinetics and that the rates are both acid- and base-catalyzed. It also depends on the usual state of affairs that the ratio of the hydrated to the anhydrous species, although pH independent (see Section II, A), is different in the three species, i.e. in the cation, neutral species, and anion. In principle, a solution of one... 

Smiles rearrangement was observed also in base-catalyzed cyclization of 2-hydroxy-2 -nitrodiphenylsulfones leading to low yields (about 5%) of phenoxathiine 10,10-dioxides (34JCS422, 56JA5357). However, this type of compounds can be easily prepared by other methods (05CB1411, 06CB1340). 

The regiochemical control of Pd-catalyzed hydnde transfer reacdon is much more effeedve than that of the radical denitradon, as Shown in Eq 7 98 The base-catalyzed reacdon of nitroolefins with aldehydes followed by denitradon provides a new syntbedc method of homoallyl aicohols fEq 7 99 Exomethylene compounds are obtined by denitradon of cyclic allylic nino compounds with PdfO, HGO-,H and Et- N fEq 7 100 ... 

Phenylcyclopropane has been prepared by the base catalyzed decomposition of 5-phenylpyrazoline (33 %),2 by the reaction of 1,3-dibromo-l phenylpropane with magnesium (68%),3 and by the reaction of 3-phenylpropyltrimethylammomum iodide with sodium amide in liquid ammonia (80%)4 However, the method frequently used at present is the reaction of styrene with the methylene iodide-zinc reagent (32%)5... 

The nitrene can be generated by a variety of methods, the most popular being the thermal or photolytic decomposition of azidoformates. Other methods, particularly the base-catalyzed a-elimination of arylsulfonate ion from 7V-[(arylsulfonyl)oxy]urethanes, are useful as they avoid the use of the potentially explosive azido esters. 

The highest enantioselectivities in the base-catalyzed Michael additions have so far been obtained using achiral bases complexed to chiral crown ethers. The addition of methyl 2,3-dihydro-l-oxo-1//-indene-2-carboxylate (1) to 3-buten-2-one using 4 mol% of a [l,T-binaphthalcnc]-2,2 -diol derived optically active crown ether 3 in combination with potassium AY/-butoxide as the base illustrates this successful method 259 260 It is assumed that the actual Michael donor is the potassium enolate complex of 1 and crown ether 3. 

The direct conversion of 3-methylcyclohex-2-enone into 2-allyl-3-methylcyclohexanone provides an interesting example of the utility of the reduction-alkylation procedure. Synthesis of this compound from 3-methy I cyclohexanone would be difficult because the latter is converted mainly into 2-alkyl-5-methylcyelohexanones either by direct base-catalyzed alkylation11 or by indirect methods such as alkylation of its enamine (see Note 13) or alkylation of the magnesium salt derived from its cyclohexylimine.12... 

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