7-Acetyl-5-nitro

Acetyl-5-nitro CDCI3 2.95 9.05 8.75 — 8.15 7.80 Coupling constants 66BSF2075... 

N02 cn3 2-Acetyl-5-nitro-2H-... l-Acetyl-5-nitro-lH-... 158-159 (Ethanol) 138-139 (Auelon/Diethylether) 532... 

Strong conformational dependence (SCD). These groups have the structures (a) MZ2 Z and MZ -Z Z, where the snperscript M indicates medinm. (b) Planar n-bonded groups MZ -Z where M and either or both Zs are sp hybridized, snch as phenyl, acetyl, nitro (Xpj, groups), (c) Quasi-planar jr-bonded groups such as dimethylamino and cyclopropyl. 

Acetyl nitro peroxide, see Peroxyacetyl nitrate, 0762 (9-Acetylsalicylic acid, 3131... 

Methyl-8-formylBIPS (71, Z = O) was condensed with amines to give in 36-61% yields the 8-anils (Z = N-R) (R = benzyl and 4-X-phenyl, [X = acetyl, nitro, and methyl]), and with aldehydes to give in 62-76% yields the 8-styryl ketones (Z=CH-R ) (R = methyl, phenyl, and 2-hydroxyphenyl). The styryl ketones were shown by their NMR spectra to be the cis isomers. Of the anils, only the 4-nitrophenyl... 

Acetylated nitro sugar, Diels-Alder reactions, 7... 

Batey has reported Pd-catalyzed cross-coupling reactions of tetraalkylammo-nium aryl trifluoroborate salts bearing functional groups such as acetyl, nitro and chloro with functionalized aryl bromides under mild conditions 35]. These tetra-alkylammonium organofluoroborates are prepared from the respective boronic acids using counter ion exchange protocol. They are air and moisture stable and are soluble in various organic solvents (Scheme 3.21). 

Nitroamlines. Acetyl derivatives (p. 388), Benzoyl derivatives (p. 388). Diamines. Diacet> l derivatives (p. 388), Dibenzoyl derivatives (p. 388). Halogeno-hydrocarbons, a-Naphthyl ethers (from reactive halogen compounds, p. 391, and their Picratcs, p. 394), Nitro-derivatives (p.39i). Carboxylic acid (if oxidisable side chain) (p. 393). 

Reduction of a nitro compound to a primary amine. In a 50 ml. round-bottomed or conical flask fitted with a reflux condenser, place 1 g. of the nitro compound and 2 g. of granulated tin. Measure out 10 ml. of concentrated hydrochloric acid and add it in three equal portions to the mixtiue shake thoroughly after each addition. When the vigorous reaction subsides, heat under reflux on a water bath until the nitro compound has completely reacted (20-30 minutes). Shake the reaction mixture from time to time if the nitro compound appears to be very insoluble, add 5 ml. of alcohol. Cool the reaction mixture, and add 20-40 per cent, sodium hydroxide solution imtil the precipitate of tin hydroxide dissolves. Extract the resulting amine from the cooled solution with ether, and remove the ether by distillation. Examine the residue with regard to its solubility in 5 per cent, hydrochloric acid and its reaction with acetyl chloride or benzene-sulphonyl chloride. 

Certain features of the addition of acetyl nitrate to olefins in acetic anhydride may be relevant to the mechanism of aromatic nitration by this reagent. The rapid reaction results in predominantly cw-addition to yield a mixture of the y -nitro-acetate and y5-nitro-nitrate. The reaction was facilitated by the addition of sulphuric acid, in which case the 3rield of / -nitro-nitrate was reduced, whereas the addition of sodium nitrate favoured the formation of this compound over that of the acetate. As already mentioned ( 5.3. i), a solution of nitric acid (c. i 6 mol 1 ) in acetic anhydride prepared at — 10 °C would yield 95-97 % of the nitric acid by precipitation with urea, whereas from a similar solution prepared at 20-25 °C and cooled rapidly to —10 °C only 30% of the acid could be recovered. The difference between these values was attributed to the formation of acetyl nitrate. A solution prepared at room... 

Under these first-order conditions the rates of nitration of a number of compounds with acetyl nitrate in acetic anhydride have been determined. The data show that the rates of nitration of compounds bearing activating substituents reach a limit by analogy with the similar phenomenon shown in nitration in aqueous sulphuric and perchloric acids ( 2.5) and in solutions of nitric acid in sulpholan and nitro-methane ( 3.3), this limit has been taken to be the rate of encounter of the nitrating entity with the aromatic molecule. 

Reduction of 2.4-dimethyl-5-nitrothiazole with activated iron gives a product that after acetylation yields 25% 2.4-dimethyl-5-acetamido-thiazole (58). The reduction of 2-methyl 5-nitrothiazole is also reported (351 to give a mixture of products. The nitro group of 2-acetylhydrazino-5-nitrothiazole is reduced by TiCl in hydrochloric acid or by Zn in acetic acid (591. 

However, prior protective acetylation of the amino group leads to a good yield of the 5-nitro compound [2-acetamido-4-methyl-5-nitroselenazole, m.p. 185 C (19)j. Similarly. 2-diethylamino-4-methy)-selenazole with nitric acid gives the. 5-nitro derivative [vellow needles, m.p. 93°C (26)],... 

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