Deamination of amines

DEAMINATION OF AMINES. 2-PHENYLETHYL BENZOATE VIA THE NITROSOAMIDE DECOMPOSITION... 

Notable examples of general synthetic procedures in Volume 47 include the synthesis of aromatic aldehydes (from dichloro-methyl methyl ether), aliphatic aldehydes (from alkyl halides and trimethylamine oxide and by oxidation of alcohols using dimethyl sulfoxide, dicyclohexylcarbodiimide, and pyridinum trifluoro-acetate the latter method is particularly useful since the conditions are so mild), carbethoxycycloalkanones (from sodium hydride, diethyl carbonate, and the cycloalkanone), m-dialkylbenzenes (from the />-isomer by isomerization with hydrogen fluoride and boron trifluoride), and the deamination of amines (by conversion to the nitrosoamide and thermolysis to the ester). Other general methods are represented by the synthesis of 1 J-difluoroolefins (from sodium chlorodifluoroacetate, triphenyl phosphine, and an aldehyde or ketone), the nitration of aromatic rings (with ni-tronium tetrafluoroborate), the reductive methylation of aromatic nitro compounds (with formaldehyde and hydrogen), the synthesis of dialkyl ketones (from carboxylic acids and iron powder), and the preparation of 1-substituted cyclopropanols (from the condensation of a 1,3-dichloro-2-propanol derivative and ethyl-... 

As has been mentioned previously, one is most likely to find analogies to catalytic reactions on solids with acidic and/or basic sites in noncatalytic homogeneous reactions, and therefore the application of established LFERs is safest in this field. Also the interpretation of slopes is without great difficulty and more fruitful than with other types of catalysts. The structure effects on rate have been measured most frequently on elimination reactions, that is, on dehydration of alcohols, dehydrohalogenation of alkyl halides, deamination of amines, cracking of the C—C bond, etc. Less attention has been paid to substitution, addition, and other reactions. 

Eremenko and co-workers used nitryl fluoride for the deamination of amines at subambient temperatures in acetonitrile. The same reaction occurs with primary nitramines and their alkali metal salts bis-nitramines react to give the corresponding bis-nitrate esters. 

Amine oxidase catalyses the oxidative deamination of amines to the corresponding aldehyde, hydrogen peroxide and ammonia. The copper containing amine oxidase from pig plasma (PPAO) is one of the better characterised in this class of enzyme. The homogeneously pure enzyme has a molecular weight of 190,000 composed of two subunits with equal molecular weight. The present evidence suggests that copper is essential for catalytic activity and therefore much effort has been made to determine the structure of copper sites... 

Amine oxidase from Aspergillus niger and monoamine oxidase from Escherichia coli can be used for the oxidative deamination of amines, forming the corre-... 

For a review of the deamination of amines, see Baumgarten Curtis, in Patai The Chemistry of Functional Groups. Supplement F. pt. 2 Wiley New York, 1982, pp. 929-997. 

An important reaction is the deamination of amines by dilute nitrous acid. This reagent, by a complex mechanism, converts the amino groups of cytidine, adenosine, and guanosine to hydroxyl groups hydroxy compounds tautomerize to the corresponding amides (Eq. 5-14). 

Deamination of amines often gives rise to hot, short-lived carbocations (Section 5.2, p. 226). Deamination of ( + )-1,1-diphenyl-2-amino-l-propanol specifically labeled with 14C in one of the two phenyl groups (25) gives a-phenyl-propiophenone as product, 88 percent of it inverted and 12 percent retained. All the inverted ketone comes from migration of the 14C-labeled phenyl and all the retained from migration of the unlabeled phenyl group (Equation 6.22).39 This... 

The products obtained in the nitrous acid deamination of amine 117 in acetic acid are shown in Scheme 10 (Nishimura et ol., 1967, 1970). Nitrogen loss occurs from a primary saturated carbon atom and this case is therefore not strictly pertinent to this section. To account for the formation of ketone 118 among the reaction products the authors... 

The oxidative deamination of amines to ketones, via oxaziridines, was reported as a model for the process found in oxidative deamination of a-amino-acids to pyruvic acids in biochemical systems." The primary amine, such as (58) or (59) with pyridine-2-carboxaldehyde, was converted into the imine (60) which was oxidized with m-chloroperbenzoic acid to the oxaziridine (61). Ring opening of (61) was effected with KOH in MeOH or in DMF (Scheme 8). Acetone was added to trap regenerated pyridine-2-carboxaldehyde. When other bases were used a competing reaction resulting in (62) occurred. 

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