Diazoacetyl azide

Buten-l-yl diazoacetate, 2377 tert-Butyl diazoacetate, 2423 tert-Butyl 2-diazoacetoacetate, 3009 5-/er/-Butyl-3-diazo-3//-pyrazole, 2831 Cyanodiazoacetyl azide, 1346 5-Cyano-4-diazo-4//-l,2,3-triazole, 1345 Diazoacetaldehyde, 0710 Diazoacetonitrile, 0675 Diazoacetyl azide, 0679... 

Diazirine-3,3-dicarboxylic acid, 1077 Diazoacetaldehyde, 0706 Diazoacetonitrile, 0671 Diazoacetyl azide, 0675... 

Diazoacetyl azide N2=CHCON3 m.p. 7-8° can be distilled in vacuo, but is very explosive. 

Diazidocarbony lliydrazine, 0720 Diazoacetyl azide, 0679 Disulfuiyl diazide, 4780... 

Cyano-4-diazo-4/Y-l.2.3-triazolc. 1345 Diazoacetaldehyde, 0710 Diazoacetonitrile, 0675 Diazoacetyl azide, 0679... 

In a-aminoacetohydrazide (2.29), the amino group and the N()8)-atom of the hydrazino group will be nitrosated (2-11). The result is diazoacetyl azide (2.30) which is, surprisingly enough, claimed to be stable in spite of the cumulation of two potentially explosive substituents (Neunhoeffer et al., 1968). The yield, however, is only 10-15%. 

Acetoacetyl-3,4-dihydro-2(lF/)-qumoxahnone (211) with mesyl azide gave 4-(2-diasoacetoacetyl)-3,4-dihydro-2(lF/)-quinoxahnone (212) (Et3N, MeCN, 20°C, 8 h 91% of crude), which underwent deacetylation to afford 4-diazoacetyl-3,4-dihydro-2(lF/)-qumoxalmone (213) (NaOH, THF, H2O, 20°C, 1 h 69%) ... 

The use of PAL in enzyme modifications was first described in 1962, when Westheimer and coworkers reported on the use of a diazoacetyl group to inactivate chymotrypsin [29]. Considerable research on the development of new PAL reagents has taken place ever since [27, 28, 30-36], but only a few photophores, which largely meet the above-mentioned requirements, are being used nowadays in A/BPs. These are aryl azides (first reported use in 1969) [37], diazirines (1973) [38] and benzophenones (1973) [39]. The chemistry of these three photoreactive groups after photolysis as well as their use in recently reported A/BPs will be discussed in Sects. 3.1-3.5. 

Acetylphenyl butyl tellurium is formylated at the acetyl-methyl group by methyl formate and sodium in diethyl ether. The formyl compound is converted to butyl 2-(diazoacetyl)-phenyl tellurium upon treatment with 4-methylbenzenesulfonyl azide The diazoacetyl group is converted to the dibromoacetyl group by bromine in diethyl ether . 

The syntheses of diazoacetyl compounds have been described ( 5.8.2). Because pf their potential utility, the synthesis of an ethyl diazomalonyl derivative and an aryl azide precursor of carbenes and nitrenes, respectively, are presented below. 

The imidazo[5,l -e]-l.2,3,5-Letrazine-8-carbonyl chloride 17 reacts preferentially with nucleophiles (Nu ) at the 8-carbonyl group rather then at the 4-oxo group, allowing the preparation of a wide range of ester, thioester, amide, hydroxamic acid, hydrazide, sulfoximide, azide, and diazoacetyl derivatives.42... 

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