From formamides

The tiiazole [288-88-OJ (56) lequked foi these products can be made from formamide and hydrazine (182,183) ... 

Hydrogen cyanide has been manufactnied from sodium cyanide and mineial acid, and from formamide by catalytic dehydration. As of this writing. 

Similar reactions occur with acyl radicals, for example with the CONH2 radical from formamide (74AHC(16)123). 

ATHERTON TODD Phosphoramidate Synihasis Synthesis of phosphoramidates from formamides and dialkyl phosphite. 

The chain addition of formamide to alkenes is a closely related reaction. It results in the formation of primary amides. The reaction is carried out with irradiation in acetone. The photoexcited acetone initiates the chain reaction by abstracting hydrogen from formamide ... 

Ql 202.64kcal/mole, Qf 121.39kcal/ mole (Ref 3). Can be prepd from formamide by glow-discharge electrolysis (Ref 4)... 

Chromium aminocarbenes [39] are readily available from the reaction of K2Cr(CO)5 with iminium chlorides [40] or amides and trimethylsilyl chloride [41]. Those from formamides (H on carbene carbon) readily underwent photoreaction with a variety of imines to produce /J-lactams, while those having R-groups (e.g.,Me) on the carbene carbon produced little or no /J-lactam products [13]. The dibenzylaminocarbene complex underwent reaction with high diastereoselectivity (Table 4). As previously observed, cyclic, optically active imines produced /J-lactams with high enantioselectivity, while acyclic, optically active imines induced little asymmetry. An intramolecular version produced an unusual anti-Bredt lactam rather than the expected /J-lactam (Eq. 8) [44]. 

Aminotrimethanephosphonic acid is formed from formamide, acetamide, urea, or alkanenitriles with phosphorous acid [296]. By reaction of monoalkyl phosphite or P406 with glacial acetic acid or the corresponding anhydride ethane-1 -hydroxy-1,1-diphosphonic acid is formed after hydrolysis [297,298]. P406 can be obtained from P4 and 02 in a high yield of 85-90% [299]. 

Similarly, a carbamoyl group can be introduced by the use of the radicals H2N—C or Mc2N—C- generated from formamide or DMF and H2SO4, H2O2, and... 

Luche and coworkers extended their studies on the applications of ultrasound to synthesis to include a variety of systems. Among these applications are the syntheses of lithioorganocuprates(ll), of aldehydes from formamides(12), of organozinc intermediates(13),... 

Carbamoyl radicals can be easily obtained by hydrogen abstraction from formamides [Eq. (48)]. 

A similar cyclization can result from lithiation of an isonitrile lithiation of 553 requires two equivalents of LDA and the organolithium 554 can either be trapped with other electrophiles at low temperature or warmed to give an indole 555 (Scheme 219) . It is quite clear that isonitriles activate purely by conjugation, and indeed they promote deprotonation of methyl groups para to an isonitrile just as well as ortho. The ease with which isonitriles can be made from formamides suggests that these methods could be rather more widely used than they are. 

The three-carbon component in this subgroup is either a /3-dicarbonyl compound or a /3-keto nitrile. The N and C-N components in the reactions with /3-dicarbonyl compounds come from formamide, a nitrile, a thiocyanate, or a cyanamide <1994HC(52)1>. 

The unsubstituted oxadiazole has been prepared from formamide and formamidoxime in glycol diformate used as solvent. By reacting with the solvent, ammonia regenerates formamide. The reaction takes place as follows ... 

Me2NC generated from formamide or dimethylformamide and H2S04, H202, and FeS04 O... 

Since the addition of formamide to olefins is induced photochemically as well as by peroxides at elevated temperatures, it may be safe to assume that we deal here with a free radical reaction. Let us apply this assumption to interpret the results. A reasonable free radical derived from formamide would be a carbamoyl radical CONH2 which can be formed by loss of a hydrogen atom from formamide. Experimental data show that irradiation of formamide in the presence of acetone and in the absence of an olefin leads to the formation of considerable amounts of oxamide. 

An alternative possible route for the formation of carbamoyl radicals may involve a hydrogen atom abstraction from formamide by the excited acetone molecule in its triplet, state (45, 57). Ketonic compounds at this state of excitation mainly if the excitation is of an n - -7r transition, are known to be hydrogen atom abstraction agents, due to the electron deficient oxygen in the excited state. Thus, the formation of carbamoyl radicals through the second route may be summarized by the following scheme ... 

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