Action of Alkalis

Bucherer reaction Bucherer discovered that the interconversion of 2-naphthol and 2-naphthylamine through the action of alkali and ammonia could be facilitated if the reaction was carried out in the presence of (HSO3]" at about 150 C. This reaction is exceptional for the ease with which an aromatic C —OH bond is broken. It is not of general application, it is probable that the reaction depends upon the addition of [HSO3]" to the normally unstable keto-form of 2-naphthol, and subsequent displacement of —OH by —NH2. 

C2oH4qO- a diterpenic alcohol obtained by the action of alkalis on chlorophyll. Colourless oil b.p. 202-204 C/lOmm. On oxidation it yields a ketone CigHsoO b.p. 175 "C/l I mm. phytoxic Poisonous to plants. 

Silver f) oxide, Ag20, is obtained as a brown amorphous precipitate by the action of alkali on AgN03 solution. It cannot be obtained pure and is soluble in ammonia solution. 

Ammonia may be estimated by dissolving the gas in a known volume of standard acid and then back-titrating the excess acid. In a method widely used for the determination of basic nitrogen in organic substances (the Kjeldahl method), the nitrogenous material is converted into ammonium sulphate by heating with concentrated sulphuric acid. The ammonia is then driven off by the action of alkali and absorbed in standard acid. 

The iodine atom in iodobenzene (unlike that in the corresponding aliphatic compounds) is very resistant to the action of alkalis, potassium cyanide, silver nitrite, etc. This firm attachment of the iodine atom to the benzene ring is typical of aromatic halides generally, although in suitably substituted nitio-compounds, such as chloro-2,4-dinitrobenzene, the halogen atom does possess an increased reactivity (p. 262). 

Phenylglyozel (15, 67) In 40 per cent yield by the action of alkali on diphenyl-dithiodiglycolic acid. Schoberl, Beminger, and Barren, Ber. 67, 1545 (1934). 

There still remains to be settled the point of attachment of the a-aminopropionic acid side-chain in leucenol. As the latter is unaffected by boiling hydrobromic or hydriodic acid, an ether linkage at C in 3-hydroxypyridone-4 is unlikely and as the side-chain is eliminated by either pyrolysis or the action of alkali C for the location, as suggested by Kostermanns see mimosine below) is improbable. The balance of evidence seems to be in favour of attachment to the N-atom and additional data supporting this view have been provided by Adams and Jones. ... 

Bicucine, C20H19O7N, H2O. This alkaloid has m.. 222° (dec.) and — 115 4° (N/10, KHO) but in N/HCl it shows mutarotation — 145° to — 100°,due to the formation of an equilibrium mixture of bicucine and bicuculline. Alkaline permanganate oxidises it to 3 4-methylene-dioxyphthalic acid, isolated as the ethylimide. In view of its formation from bicuculline by the action of alkali, Manske has suggested for its formula (II) or (III), the former representing it as the nomarceine (p. 208) analogue of bicuculline, whilst (III) makes it the hydroxy-acid corresponding to the lactone, bicuculline and is preferred. 

This substance under the action of alkali passed into anhydrodihydro-protopine A, C20H19O4N, m.p. 120° (V), the amine oxide (VI) of which rearranges into protopine by the action of acids. 

Under the action of alkali, according to Kotake, Sakan and Kusumoto, (/(-strychnine yields tryptamine, and N-methyleijano- -stryehnine produces N-methy Itr yp tamine. 

Annotinine, C gHjjOjN, (1). M.p. 232° perchlorate, m.p. 267°. In a later paper (1947) Manske and Marion record the results of the action of alkali and of halogen acids on annotinine, and of the oxidation of the base and discuss the reaction products. They conclude that two of the oxygen atoms are present as a lactone group and that the third oxygen may form an ether bridge in a 5- or 6-membered ring. 

The action of alkali on aqueous Au " solutions produces a precipitate, probably of AU2O3.JCH2O, which on dehydration yields brown AU2O3. This is the only confirmed oxide of gold. It decomposes if heated above about 160°C and, when hydrous, is weakly acidic, dissolving in cone alkali and probably forming salts of the [Au(OH)4] ion. 

The position of quaternization in the isomeric ring system, 1,2,9-tri-azaphenanthrene, was not settled so clearly. The methiodide of 4-amino-10-phenyl-1,2,9-triazaphenanthrene (153) is converted by the action of alkali into a labile compound, which regenerates the quaternary salt on treatment with hydriodic acid. The labile compound gave 3-amino-2-phenylquinoline on heating with soda lime. 

Action of alkali amides and alkyl- and aryl-lithiums on mono-halogeno aromatic compounds,... 

Diaziridines are weak bases, They can be extracted from organic solvents with aqueous mineral acids. With increasing number and chain length of alkyl substituents the solubility in aqueous mineral acids decreases. l-MethyI-2-n-butyl-3-hexyldiaziridine is soluble only in concentrated hydrochloric acid. Stable oxalates can in some cases be prepared from 1-aIkyI-diaziridines (43). The salts are stable indefinitely and by the action of alkali the diaziridines can be recovered. Diaziridines dialkylated on nitrogen (44) are hardly capable of salt... 

The product of condensation remaining in the distilling apparatus is purified by the fractional distillation in vacuo. Under a pressure of 12 mm. a liquid distils off at a temperature of from 143° to 145° C. This product of condensation which I term Pseudo-ionone, is a ketone readily decomposable by the action of alkalis. Its... 

The Action of Alkali on Methyl 2 3-Anhydro-a-D-allopyranoside and l 5-Anhydro-2-deoxy-3-0-toluene-p-sulphonyl-D-arabino-hexitol," A. B. Foster, M. Stacey, and S. V. Vardheim, Acta Chem. Scand., 12(1958) 1819-1824. 

The hydrolytic action of alkalis on the thiophosphate insecticides, such as parathion, yields free phenols that then couple with the diazonium salt to yield azo dyes. 

This intermediate, produced by action of alkali on tetranitromethane, must be kept damp and used as soon as possible with great care, as it may be explosive [1], Material produced as a by-product in a nitration reaction using tetranitromethane was washed with acetone. It exploded very violently after several months storage [2],... 

The metal reacts with cold chlorine strongly exothermically, and the compact metal with bromine even at -33°C, reaction being violent at ambient temperature [1], Interaction of gallium with liquid bromine at 0°C proceeds with a flash, resembling the action of alkali metals with water [2],... 

---