Bis formamide

Reaction of the bis-formamide 19 with nitric acid in concentrated sulfuric acid has been reported by Yutilov and Smolyar <2004RJ01526>. Interestingly, the product is reported to decompose by explosion above 225°C (Equation 11). 

The bis-formamide ArCH(NHCHO)2 reacts with hydrazine hydrate to give (590) in high yield (63TL1637). 

SYNS BIFORMYCHLORAZIN BIFORMYLCHLO-RAZIN N,N -BIS(l-FORMAMIDO-2,2,2-TRICHLORO-ETHA L)PIPERAZINE l,4-BIS(l-FORMAMIDO-2,2,2-TRICHLOROETHYL)PIPERAZINE CA 70203 CELA 50 CELA W 524 CME 74770 COMPOUND W CW 524 FORMAAnDE,NJ4 -(l,4-PIPERAZINEDIYLBIS-(2,2,2-TRICHLOROETHYLIDENE))BIS-(8CI,9CI) FUNG-INEX N3SI -(PIPERAZINEDIYLBIS(2,2,2-TRICHL0R0-ETHYLIDENE)) BIS(FORMAMIDE) SAPROL W 524... 

The reductive cyclization of 2-nitrobenzyl-A, A -bis(formamide) with zinc in acetic acid to quinazoline was first described by RiedelT ° The reaction is used successfully for the synthesis of larger quantities of quinazoline and its benzene-ring-substituted derivatives 12 from 2-ni-trobenzyl-A, A -bis(formamides) 11. The method is suitable only for the preparation of 4-un-substituted quinazolines, because 2-nitro-substituted phenones do not condense with aliphatic amides to yield bis(amide) derivatives. Zinc in acetic acid is the reducing agent of choice, but iron in hydrochloric acid or Raney nickel can also be used. " Applications of compounds other than bis(formamides) [e.g., bis(acetamides) ] and preparation of 2-substituted quinazolines by Riedel s synthesis are scarce. 

Other amides have been used for ring closure with only limited success. The bis-acetamides were used to give only 20-25% yields of the macrocycle (Biernat et al., 1979 Mikiciuk-Olasik and Kotelko, 1984). A bis-formamide was used for ring closure to also give very poor yields (Krakowiak and Bradshaw. 1991). 

Synonyms Biformyl chlorazin 1,4-Bis (1-formamido-2,2,2-trichloroethyl) piperazine N,N -Bis (1-formamido-2,2,2-trichloroethyl) piperazine 1,4-Bis (2,2,2-trichloro-1-formamidoethyl) piperazine Formamide, N,N -(1,4-piperazinediylbis (2,2,2-trichloroethylidene)) bis-N,N -[1,4-Piperazinediylbis (2,2,2-trichloroethylidene)]-bis[formamide] N,N -(Piperazinediylbis (2,2,2-trichloroethylidene)) bis (formamide)... 

The best results were achieved with the catalyst system consisting of bis-formamide 21.89 and L-proline (2 equivalents each), giving enantioselec-tivities up to 83%. °... 

AZDN[Azo-Di(Carbonamide)] orABFA [Azo-bis(Formamide)]. Catalysts permit use at lower temperatures coarse particle size permits use at higher temperatures. It is widely used in commodity thermoplastics and even some engineering thermoplastics about 90 percent of the market. 

CgHjiNjOi 8-6fethyl-3.3-dicyan-mopen-(l)-carbons4ure-(l)- thylmter 2 II 695. Aoetondibrenztraabens4are.diimid 8, 830. Benzyliden-bis-formamid 7, 216. BenzylideDhydrazino-ameisem aie-methyl ... 

One example of the reaction of dichlorocarbene with a tertiary amine under phase transfer conditions has been reported [20]. 5,7-Diphenyl-1,3-diazaadamantan-6-one is transformed into l,5-diphenyl-N,N-diformylbispidin-9-one in 23% yield. This unusual reaction may be rationalized as follows. Coordination of dichlorocarbene with a nitrogen lone pair yields a zwitterion (VI). Neighboring nitrogen assists fragmentation and the iminium zwitterion VII results. Protonation and hydrolysis of VII followed by dichlorocarbene reaction with the resulting secondary amine yields the bis-formamide VIII. The sequence is formulated in equation 3.13. 

The concept of connecting two L-prolinamides portions over a chiral backbone structure was applied on the C2-symmetrical bis-formamide catalyst 68 for the... 

Scheme 30.16 Chiral bis-formamides as catalysts for the three-component Strecker reaction.

---