Ethylene derivatives hydroxylamines

Ethylene derivs. and ant/-aldoximes from hydroxylamines and aldehydes... 

Amines can be obtained under mild conditions from amides by reduction with borane and also from ethylene derivatives with borane and hydroxylamine-O-sulfonic acid or chloramine A modified Schmidt reaction gives good yields of N-subst. trifluoro-acetamides... 

Aldehydes of different types can be conveniently prepared from the next lower halides through carbinols which are split by dia-zotized sulfanilic acid Aliphatic aldehydes in particular can be easily obtained from carboxylic acids through N-acylethylenimi-es Aldehydes, in turn, can be converted directly into nitriles with hydroxylamine hydrochloride Ketones can be efficiently prepared from ethylene derivatives via boranes and, in high purity, from labile alcohols by oxidation in an aq.-ethereal two-phase medium Heating aliphatic acids with reduced iron powder proved to be an excellent method for the prepn. of sym. straight-chain ketones /5-Aminoketones unobtainable by Mannich reaction may be prepared via halogenomagnesium enolates... 

Addition of lithium derivatives of acetylenides (Li—C=C-C02R) to chiral nitrones proceeds with high stereoselectivity, giving a-acetylene substituted hydroxylamines (410a,b) (656). This reaction has been successfully applied to the synthesis of y-hydroxyamino-a, 3-ethylene substituted acids (411a,b), formed in the reduction of (410) with Zn in the presence of acid (657, 658), and to chiral 5-substituted-3-pyrroline-2-ones (412a,b) (Scheme 2.184) (658). 

Types of compounds are arranged according to the following system hydrocarbons and basic heterocycles hydroxy compounds and their ethers mercapto compounds, sulfides, disulfides, sulfoxides and sulfones, sulfenic, sulfinic and sulfonic acids and their derivatives amines, hydroxylamines, hydrazines, hydrazo and azo compounds carbonyl compounds and their functional derivatives carboxylic acids and their functional derivatives and organometallics. In each chapter, halogen, nitroso, nitro, diazo and azido compounds follow the parent compounds as their substitution derivatives. More detail is indicated in the table of contents. In polyfunctional derivatives reduction of a particular function is mentioned in the place of the highest functionality. Reduction of acrylic acid, for example, is described in the chapter on acids rather than functionalized ethylene, and reduction of ethyl acetoacetate is discussed in the chapter on esters rather than in the chapter on ketones. 

The reaction of ketone derivatives (89) with chloromethyleneiminium salt (1) gives iminium salts (90) which yield, after hydrolysis, (3-chloroacrolein derivatives (91 Scheme 7).42 Numerous 3-chloroacrolein derivatives have been prepared by this method and yields are generally moderate to good. 3-Chloroacryl-onitrile derivatives (92) are also available in good yield from iminium salts (90 R2 = H) by treatment with hydroxylamine.43 Ketals (93) can be prepared from iminium salts (90) by treatment with the monosodium salt of ethylene glycol followed by hydrolysis under basic conditions (32-69%).44 If the group R1 in ketone (89) is aromatic and electron rich, then intramolecular electrophilic substitution of iminium salt... 

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