Alkyloxy groups

When treated with aleoholie alkalis the y-methoxyl group in skimmianine is replaced by the alkyloxy group of the alcohol used. The ethoxy-analogue, C1JH15O4N, has m.p. 138°, yields a picrate, m.p. 194°, is re-converted to skimmianine by boiling with methyl alcohol, with methyl iodide yields woskimmianine, and is oxidised to the ethoxy-analogues of skimmianal, m.p. 212°, and skimmianic acid, m.p. 225° (I EtO in 4). 

In the mercuration of cinnamic acid and its esters, CsHg.CHg.CHa. CO OH, the mercury residue always attaches itself to the a-carbon atom, and the solvent takes part in the reaction, attacking the -carbon atom, alkyloxy groups becoming linked to the latter (I.). When the mercurated esters are saponified by sodium hydroxide, and the resulting product treated with sulphuric acid, water is eliminated between the hydroxy-mercuri and carboxyl groups, and an anhydride results (II,). 

If one compares the polymers where R is an alkyloxy group, nematic as well as smectic phases are observed. If R is a short substituent (-0CH ), the polymer is nematic, whereas if R is a longer substituent, the polymer is smectic. The diphenyl derivatives exhibit same characteristic. In addition the diphenyl derivatives without a para substituent have a low temperature smectic phase as well as a nematic phase. 

A series of arylynamides with alkyloxy groups at the ortho position of the aryl group has been prepared by an alkylation/cross-coupling/amidation sequence and a subsequent gold-catalysed reaction provides benzofurans with amine functionalities at the 2-position and alkyl groups at the 3-position. The mechanism of gold(III)-catalysed isomerization of alkyl-substituted allenes to conjugated dienes in the presence of a... 

A study of reaction of weakly basic nucleophiles (X ) with 5-(alkoxy)thianthrenium ions (18a-e) in MeCN and DMSO has revealed that E2C elimination competes effectively with 5n2 reaction and reaction at sulfonium sulfur when X = r is used. The proportion of E2C product (21, 53, 52, 35 and 6.6% cycloalkene, respectively) is much higher for (18a-e) than found previously for reaction at primary and acyclic secondary alkyloxy groups (RO). 

Table 30 contains transition data on some compounds with terminal small rings (compounds 2 and 3). Compared with the simple alkyloxy group (compound 1), the small rings have an effect comparable to branched alkyls, but unlike that of five- or six-mem-bered rings. In order to obtain chiral materials, the introduction of an oxirane or thi-irane ring in the terminal chains is useful [143]. 

The ami nolysis of substituted 4-ary lazo-A -thiazolin-5-ones has been investigated, with the results shown in Scheme 3. Treatment of 2-alkoxy-4-arylazo-A -thiazolin-5-ones (153) with strongly basic amines yields, depending on the nature of the 2-alkyloxy-groups [in (153)], the l,2,4-triazolin-5-ones (156) or -5-thiones (155). Aromatic amines yield the 1,2,4-triazoles (154). Probable common intermediate stages of these reactions are shown. ... 

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