Ethyl azide

Ethyl acetate Azide, Ethyl azidoacetic Acid or Azidoacetlc Acid Ethyl Ester, N3CH2.CX>.OC2H5 ... 

Ethoxycarbonyl nitrene is readily formed by thermolysis or photolysis of cthoxycarbonyl azide (ethyl azidoformate), as well as by the base-induced a-elimination of (4-nitrophenylsulfonyloxy)-carbamate9 13> 158> 159. 

Caution Elhoxycarbonyl azide (ethyl azidoformale) can decompose explosively at 160rC and its vapors arc toxic13. 

Cycloaddition Cyanogen azide. Ethyl azidoformate. Tetracyanoethylene (cyclobutane formation). Trimethylsilyl azide. 

Miscellaneous Azides. Ethyl (A-methanesulfonyl)azidoformimidate [N3C (0Et)=NS02Me] has been used to aminate chiral cyclopentanone enamines but the yields are low and the reaction could not be extended to the corresponding cyclohexanone enamines.303 Trimethylsilyl azide (TMSN3) transfers the TMS rather than the azide group to a lactam enolate.339... 

The chemical reactivity of l,l-diamino-2,2-dinitroethene has been further explored in a joint investigation by FOI (Sweden) and SNPE (France) [38]. No evidence was found for the participation of the C = C bond of 1,1-diamino-2,2-dinitroethene in [2 -l- 1] cycloadditions (with CI2C ) or [3 + 2] cycloadditions (with benzyl azide, ethyl diazoacetate and benzonitrile oxide). Furthermore, acetylation on the amino groups with acetyl chloride only succeeded if a catalyst was present, the mono-N-acetyl derivative being produced (Scheme 20). 

Nitro Groups. The Curtius d radation has been applied to only one nitro aliphatic azide ethyl nitrocyanoacetate is converted through its hydrazide and azide to a urethan. In the aromatic series, nitro-... 

Curtius transformation An alternative to the Hofmann transformation for obtaining an amine from an ester via the hydrazide, azide and isocyanate. Thus ethyl ethanoate is converted into melhylamine by the following series of reactions ... 

The Curtius rearrangement in acetic anhydride of the azide (8) prepared from 4-carboxythiazole yields 4-acetamidothiazole (Scheme 8) (47). The same reaction starting with ethyl-2-methyl-4-thiazolyl carboxy-late, failed to give the 4-aminothiazole (48). Heterocyclizations are more convenient synthetic methods (Chapter II. Table 40). 

Automobile safety air bags use sodium azide [26628-22-8] NaN, for gas generation. It can be made from hydrazine by refluxing ethyl or Abutyl nitrite with hydrazine hydrate and sodium hydroxide in alcohol (209,210) ... 

Hydrazoic acid Hydrides, volatile Hydrogen cyanide (unstabilized) Hydrogen (low pressure) Hydrogen peroxide (> 35% water) Magnesium peroxide Mercurous azide Methyl acetylene Methyl lactate Nickel hypophosphite Nitriles > ethyl Nitrogen bromide... 

The photolytic and thermolytic decomposition of azides in the presence of olefins has been applied to aziridine synthesis. However, only a limited number of steroid aziridines have been prepared in this manner. The patent literature reports the use of cyanogen azide at ca. 50° for 24 hours in ethyl acetate for the preparation of an A-nor- and a B-norsteroidal aziridine. The addition is believed to proceed via a triazoline. The reaction of cholest-2-ene with ethyl azidoformate takes place in a nonselective manner to produce a mixture of substances, including C—H insertion products. 

A solution of 5 g (14 mmoles) of 5a-cholest-2-ene in 100 ml ethyl acetate and 8 ml of 2.8 M (22 mmoles) cyanogen azide (CAUTION See Chapter 15 and ref. 139b) in ethyl acetate is heated at 50-53° for 24 hr, during which time about 22 mmoles of nitrogen is evolved. Solvent is removed by evaporation and the residue is applied in benzene to a column of 160 g of neutral alumina (activity grade III). Elution with petroleum ether-benzene (1 1) gives 1.6 g of... 

Incorporation of the phenethyl moiety into a carbocyclic ring was at first sight compatible with amphetamine-like activity. Clinical experience with one of these agents, tranylcypromine (79), revealed the interesting fact that this drug in fact possessed considerable activity as a monamine oxidase inhibitor and as such was useful in the treatment of depression. Decomposition of ethyl diazoacetate in the presence of styrene affords a mixture of cyclopropanes in which the trans isomer predominates. Saponification gives acid 77. Conversion to the acid chloride followed by treatment with sodium azide leads to the isocyanate, 78, via Curtius rearrangement. Saponification of 78 affords tranylcypromine (79). 

Thi abut azide 358 Thialbarbital 1, 275 Thiamphenicol 2 45 Thiamprine 2, 464 Thiamylal I, 274 Thiazinium chloride 3, 240 Thi azolsul Tone 14T Thi ethyl perazi ne 1, 382 Thiobarbital 1, 275 Thiofuradene T, 231 Thioguanine 464... 

Iodine azide, generated in situ from an excess of sodium azide and iodine monochloride in acetonitrile, adds to ethyl l//-azepine-l-carboxylate at the C4 — C5 and C2 —C3 positions to yield a 10 1 mixture of the rw-diazidodihydro-l//-azepines 1 and 2, respectively.278 The as stereochemistry of the products is thought to be the result of initial trans addition of the iodine azide followed by an SN2 azido-deiodination. The diazides were isolated and their stereochemistry determined by conversion to their bis-l,3-dipolar cycloadducts with dimethyl acetylene-dicarboxylate. 

Thermolysis of the vinyl azide 11 in toluene furnishes a mixture of ethyl 2-phenyl-l//-3-benz-azepine-4-carboxylate(12), ethyl 4-(2-phenylvinyl)indole-2-carboxylate(13) and ethyl 1-benzyl-isoquinoline-3-carboxylate (14).82... 

Thermolysis of the azide 15, bearing an allyl side chain, is more complex, and in addition to ethyl 4-allylindole-2-carboxylate and ethyl 4-methyl-l//-3-benzazepine-2-carboxylate (16 oil), two unstable tricyclic aziridines 17 and 18 are produced.82 A mechanistic rationale for these results has been suggested. 

Thermolysis of the vinyl azide 26 in xylene yields ethyl 8-(mcthoxymcthyl)-l,8-dihydro-benz[2,3]azepino[4,5- >]indole-2-carboxylate (27) by attack of the vinyl nitrene at the 2-phenyl group.83... 

Ethyl 1 -phenyl-1,8b-dihydroazirino[2,l- ]isoquinoline-3-carboxylate (2), obtained by decomposition of azide 1 (see Section 3.2.1.1.1.1.) in the presence of triethyl phosphite, on heating under reflux in toluene, rearranges quantitatively to the 3//-3-benzazepine 3.82... 

Oxalyl-ethyl ester Azide (Azido-oxalic acid Ethyl-ester, Azldo-oxalsaure-athylester or Oxalsaure-... 

Analogous to the decomposition of diazoalkanes, thermolysis of azides leads to the production of nitrenes. This is exemplified for ethyl... 

C2JH49N3OJS 80082-62-8) see Aztreonam 2-(tribUtylstannyl)vinyl ethyl ether (C H340Sn 20420-43-3) see Fluvastatin sodium tributyltin azide... 

Treatment of N-benzoyl-L-alanine with oxalyl chloride, followed by methanolic triethylamine, yields methyl 4-methyl-2-phenyloxazole-5-carboxylate 32 <95CC2335>. a-Keto imidoyl chlorides, obtained from acyl chlorides and ethyl isocyanoacetate, cyclise to 5-ethoxyoxazoles by the action of triethylamine (e.g.. Scheme 8) <96SC1149>. The azetidinone 33 is converted into the oxazole 34 when heated with sodium azide and titanium chloride in acetonitrile <95JHC1409>. Another unusual reaction is the cyclisation of compound 35 to the oxazole 36 on sequential treatment with trifluoroacetic anhydride and methanol <95JFC(75)221>. 

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