Alkyl-, halogeno

There appears to be no significant inner-sphere pathway via the Br end of the molecule since no [Co LBr] " product is detected. In an extension of the work to other metal ions, aminopolycarboxylates, and oxidants it is reported that, whereas the rates of oxidation of [Fe L] by Brg, Bra , and Ig appear to be controlled by the rate at which the oxidant enters the primary co-ordination sphere of the metal ion (Table 4), the rates of oxidation of [Fe L] by Ig and of [Co L] and [Mn L] by Ig, Ig", Brg, and Brg are limited by electron-transfer steps subsequent to co-ordination of the oxidant. Linear free-energy relationships for these reactions have been presented in terms of a Marcus correlation. In the cleavage reactions of alkyl-chromium(m) cations [RCr(HgO)6] + by Brg (R = alkyl, halogeno-alkyl, or 4-pyridinomethyl) the overall stoicheiometric reaction,... 

Quantitative eomparisons of aromatic reactivities were made by using the competitive method with solutions of nitronium tetrafluoroborate in sulpholan, and a concentration of aromatic compounds 10 times that of the salt. To achieve this condition considerable proportions of the aromatic compoimds were added to the medium, thus depriving the sulpholan of its role as true solvent thus, in the nitration of the alkyl- and halogeno-benzenes, the description of the experimental method shows that about 50-60 cm of mixed aromatic compounds were dissolved in a total of 130 cm of sulpholan. 

Lower aliphatic primary alcohols including octanol, halogeno alcohols, and benzylic alcohols yield only alkyl fluorides [81, 82 The reaction of higher primary alcohols gives a mixture of fluorides and alkyl 2,3,3,3-tetrafluoropropionates [S3] and 2-nitro alcohols, alcohols branched at C-2 [82, 84 and unsaturated alcohols [55] give 2,3,3,3-tetrafluoropropionates exclusively... 

Alkyl-/l -pyrrolines (8, n = 1) and 2-alkyl-/l -piperideines (8, n = 2) are readily formed by the methods used to prepare y- and S-amino ketones (3-6). The reaction of corresponding halogeno ketones with ammonia belongs to the classical reactions of this type. 

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

Studies of the relative rates of the zinc chloride-catalysed bromination of alkyl-and halogeno-benzenes in nitromethane at 25 °C have lead to the suggestion that the rate-determining step of the reaction is formation of Ji-complex, since low substrate selectivity was found to be coupled with high (i.e. normal) positional selectivity323. Under some conditions (column 1 in Table 75) the low selectivity... 

The conversion of a primary amino substituent into a halogeno substituent is usually done by diazotization in the presence of an excess of the appropriate halogenide ion, by treatment in a nonaqueous solvent with alkyl nitrite and copper (II) halogenide, or by treatment with a freshly made solution of bromopyridinium perbromide [(CH)5N+ Br. Br2 ] or the like. These routes are illustrated in the following examples. 

Many nitroquinoxalines have been prepared by primary synthesis (see Chapter 1), from halogeno quinoxalines (see Section 3.2.7), or by passenger introduction (e.g., on deoxidative alkylation of an M-oxide see Section 4.6.2.2). However, one major route and one minor preparative route remain, and they are illustrated in the following subsections. 

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