Acetylenes, nitro derivatives

The main index headings for search other than the names of specific compounds are Paraffins nitration of Paraffins, nitro Paraffins, from nitration of— Paraffins, dinitro Hydrocaibons, nitration of Nitration of hydrocarbons Nitration of paraffins Petroleum, nitrogen compounds from Olefins, nitro derivatives and Acetylenes, nitro derivatives. These items are not mutually inclusive, e.g., references under Paraffins, nitration of are not necessarily to be found under Nitration of paraffins. In Chemical Abstracts collective index for 1937 to 1946, there are 19 entries under the first heading and 12 entries under the second only 10 are common to both lists. 

DtfN-pbenylcarboxamideFacetylene, listed as Bis(carboxanilide)-acetylene in Vol 2, p B138-L. Its formula and formula of its hexa-nitro- derivative were given but prepn and props were not described because the ADL Report serving as a source of information was classified at the time of publication of Vol 2 of Encycl... 

In the first example, nitration of the benzoate (140) with nitric acid affords the nitro derivative. Hydrogenation converts this to the anthranilate (141). In one of the standard conditions for forming quinazolones, that intermediate is then treated with ammonium formate to yield the heterocycle (142). Reaction of 142 with phosphorus oxychloride leads to the corresponding enol chloride (143). Condensation of 143 with m-iodoaniline (144) leads to displacement of chlorine and consequent formation of the aminoquinazoline (145). Reaction with the trimethylsilyl derivative of acetylene in the presence of tetrakis-triphenylphosphine palladium leads to replacement of iodine by the acetylide. Tributylammonium fluoride then removes the silyl protecting group to afford the kinase inhibitor erlotinib (146). ... 

Conversion of acetylenes into substituted maleate esters (62) by addition of two carboxy-groups to the unsaturated system is achieved using palladium and mercury salts in the presence of carbon monoxide. Diphenylacetylene and aromatic nitro-derivatives in the presence of carbon monoxide and... 

Nucleophilic substitution of the nitro group in 3-amino 4-nitrofurazan 185 under conditions of phase-transfer catalysis gave a series of acetylene and diacetylene derivatives (Scheme 43) <2001RJ01629>. 

The intramolecular cyclization of a nitro group with a triple bond has been extended to the synthesis of six- and seven-membered ring compounds analogous to isatogens. Thus, the reaction of the acetylene group with the nitro group in 39 yields 2-phenyl-3-oxobenzo[prepared from the corresponding biphenyl derivative.19... 

Diphenyl-diacetylene is the parent hydi ocarhon of indigo blue, and the dye itself can be prepared by means of tliis reaction, starting with o-nitro-phenyl-propiolic acid. By loss of carbon dioxide the acid becomes o-nitro-phenyl-acetylene, the copper derivative of which passes to di-ortho-nitrophenyl-diacety-lene ... 

Nitrile, azo, and nitroso groups, and even the oxygen molecule, take part in such reactions, and acetylenic triple bonds in particular confer reactivity as philodiene. As for dienes, so for philodienes the reactivity depends on the constitution. Activating groups particularly favor addition. The most reactive components include <%,/ -unsaturated carbonyl compounds such as acrolein, acrylic acid, maleic acid and its anhydride, acetylenedicarboxylic acid, p-benzo-quinone and cinnamaldehyde, as well as saturated nitriles and <%,/ -unsaturated nitro compounds. Tetracyanoethylene also reacts with dienes.41,42 Conjugation of the double bond to an active group is not absolutely essential for a philodiene, for dienes add under certain conditions also to philodienes with isolated double bonds examples of the latter type are vinyl esters and vinyl-acetic acid. Ketenes do not undergo the Diels-Alder reaction with dienes, but instead yield cyclobutanone derivatives 43,44... 

A novel insoluble green complex of palladium(II) and N,N -salicylideneethylenedi-amine (salen) functions as a selective heterogeneous catalyst, notably for the reduction of alkynes in the presence of alkenes, and of the latter in the presence of certain functional groups. E ciVEthylene from acetylene derivs. A soln. of startg. acetylene deriv. in EtOH hydrogenated for 17 min in the presence of the palladium(ll) complex (prepared from potassium tetrachloropalladate, salen, and triethylamine) cis-product. Y 100%. Reduction of alkenes is considerably slower however, terminal olefins may be reduced in the presence of internal olefins esters, oxo compds., dibenzyl ether, and iodobenzene were unaffected. F.e., also ar. amines from nitro compds. s. J.M. Kerr et al.. Tetrahedron Letters 29, 5545-48 (1988). 

Internal amine nucleophiles have also been nsed to displace a nitro group forming nitrophen-azines [112] in a process similar to that shown in Scheme 6.28. The amino-debromination pathway shown in Scheme 6.31 may produce benzimidazol-2-one derivatives [242]. An aminodefluorination process is involved in the reaction shown in Scheme 6.32 producing 2-arylindole daivatives. Here, the acetylene function acts as an EWG as weU as a reagent [243]. 

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