Nitrobenzoyl chloride, reduction

Kiss reported that p-benzoylaminobenzoyl esters of sugars usually crystallize extraordinarily well and can be hydrolyzed under conditions (O.IM NaOH in H2O-CH3OH) to which most sugars are stable. They are prepared by acylation with p-nitrobenzoyl chloride, reduction of the nitro group with Raney nickel, and benzoylation. 

Preparation by Friedel-Crafts acylation of bromobenzene with m-nitrobenzoyl chloride, reduction of the obtained 4-bromo-3 -nitrobenzophenone and diazotization of the resulting 3-amino-4 -bromobenzophenone, followed by hydrolysis of the diazonium salt [900]. 

Arninobenzoyl-L-glutarnic acid (12) is obtained by condensation of -nitrobenzoyl chloride [122-04-3] (18) with L-glutamic acid [56-86-0] (19) under Schotten-Baumann conditions. This is followed by reduction of the nitro group with either sodium hydrogen sulfide (29) or by electrochemical methods (30). 

Thus, acylation of 3(W,iV-dibutylamino)propanol (39) with p-nitrobenzoyl chloride affords the intermediate, 40. Reduction of the nitro group gives butacaine (41), an agent equipotent as cocaine as a topical anesthetic. 

Replacement of chlorine on the pendant benzoyl group by azide is apparently consistent with antiinflammatory activity. Acylation of indomethacin intermediate with p-nitrobenzoyl chloride leads to the corresponding amide (7). Saponification ( ) followed by reduction of the nitro group gives the amine 9. The diazonium salt (10) obtained on treatment with nitrous acid is then reacted with sodium azide there is thus obtained zidomethacin (11). 

The properties and reactions of amino-alcohols, obtained largely by hydrolysis of naturally occurring alkaloids, were investigated primarily for the purposes of structural analysis and the preparation of physiologically active derivatives. Many authors have described acylation of pyrrolizidine alcohols with benzoyl chloride and acetic anhydride (see, e.g., refs. 83 and 101). Trachelanthamidine benzoate and p-aminobenzoate were prepared especially for testing of their physiological activity.102 The p-aminobenzoate was obtained by treatment of trachelanthamidine with p-nitrobenzoyl chloride and subsequent reduction of the nitro group with iron in 20% acetic acid. The compound exhibited an anesthetic activity close to that of cocaine. 

Stannous chloride reduction, in an acidic ethanol solution, of l-(o-nitrobenzoyl)isatin followed by treatment with base gave 71.153... 

Reaction of L-glutamic acid with /7-nitrobenzoyl chloride under Schotten-Bauman conditions gave (29), from which the diester (30) was obtained using refluxing 5 % ethanolic HC1. Catalytic reduction of the nitro group then yielded (31) [48] Scheme 3.4). 

Dyes containing the pyridinium group linked to the diazo component via a carboxylic ester function (e.g., 40) [32017-47-3] are obtained by condensation of 4-nitrobenzoyl chloride with chloroethanol, reaction of the ester with pyridine, reduction of the nitro to an amino group, diazotization, and coupling with aromatic amines [124],... 

Antibiotic substances related in structure to amicetin have been isolated from other Streptomyces cultures. Sensi and coworkers166 have isolated amicetin B, which only differs from amicetin by the absence of the dexfro-a-methylserine moiety in its structure. This antibiotic substance is identical with Plicacetin, an antibiotic substance isolated by Haskell and coworkers167 176 from Streptomyces plicatus. The structural relationship of Plicacetin (amicetin B) to amicetin was also established by partial synthesis.167 Acylation of cytosamine (XXXVII) with p-nitrobenzoyl chloride, followed by reduction of the nitro group of the mono-acylated derivative, yielded Plicacetin. 

A sirupy pentapropionate of L-sorbose was described by Hurd and Gordon.142 Crystalline esters of L-sorbose, such as the 1-benzoyl-,55 1-p-aminobenzoyl-148 and 1-tosyl-, 144,56 have also been synthesized. 1-p-Aminobenzoyl-L-sorbose was prepared as a possible substance for measuring the rate of glomerular filtration. It was synthesized by esterifying 2,3 4,6-diisopropylidene-L-sorbose with p-nitrobenzoyl chloride, with subsequent reduction of the nitrobenzoyl ester to 1-p-amino-benzoyl-2,3 4,6-diisopropylidene-L-sorbose. Removal of the isopropyli-dene groups by dilute acid hydrolysis furnished the desired product. 1-Tosyl-L-sorbose was independently prepared by two different methods. The first method,55 discussed on page 110, involves the oxidation of a properly substituted sorbitol derivative, while the latter method144 is similar to the one used for the preparation of the 1-p-aminobenzoyl derivative, namely esterification of 2,3 4,6-diisopropylidene-L-sorbose, followed by acid hydrolysis. This cyclic acetal has also been esterified to the crystalline l-mesyl-2,3 4,6-diisopropylidene-L-sorbofuranose by... 

Pillai developed the 2 -nitrobenzhydryl PS resin [20] (8, NBH resin) as an a-substituted nitrobenzyl Hnker. The NBH resin was prepared from o-nitrobenzoyl chloride and 1% cross-Hnked PS resin by Friedel-Crafts acylation and ketone reduction (Scheme 17.7). Photolysis of single amino acids from the NBH resin... 

A -(4-Aminobenzoyl)-(5)-glutamic acid is obtained by acylation of ( S)-glutamic acid with 4-nitrobenzoyl chloride followed by reduction of the NO2 group by catalytic hydrogenation. 

Condensation of a molecule each of ethylene chlorohydrin and diethyl amine yields diethyl amino ethanol, which on treatment with a mole of/>-nitrobenzoyl chloride gives rise to diethyl amino ethyl-p-nitrobenzoate. This on reduction with tin and hydrochloric acid yields the procaine hydrochloride. 

This compound has been known since 1892 and was previously synthesized in 1915 by oxidation of isatin with neutral potassium permanganate 134). Bird 135) has synthesized 53 from 0-methylisatin and o-aminobenzaldehyde. The isatin-a-(2-formylanil) 54 (appears to exist predominantly as 55) was converted to 53 by oxidation with CrO. The reaction of 7 l-sodioi satin with o-nitrobenzoyl chloride gave l-(2 -nitrobenzoyl)isatin, and its reduction afforded 53 (756). Bergman et al. 126,153) have developed a simple method heating of isatin, isatoic anhydride, and diisopropyl carbodiimide in pyridine with A-meth-ylpiperidine as catalyst afforded 53 in high yield. For information on other... 

This reaction was initially reported by Reissert in 1905 and extended by Grosheintz and Fischer in 1941 It is the synthesis of aldehyde involving the formation of 1 -acyl-2-cyano-1,2-dihydroquinoline derivatives from acyl chlorides, quinoline, and potassium cyanide and the subsequent hydrolysis of said dihydroquinoline derivatives under acidic conditions to produce quinaldic acid and aldehydes. The original procedure occurs smoothly for aroyl or cinnamoyl chloride in liquid SO2 but not in benzonitrile, ether, dioxane, acetone, or CHCb. However, the modification from Grosheintz and Fischer using hydrogen cyanide and 2 eq. quinoline in absolute benzene is also adaptable for aliphatic acid chlorides. This is one of the methods that converts acyl chlorides into aldehydes and is found to be superior to the normal Rosenmund Reduction. For example, o-nitrobenzoyl chloride has been converted into o-nitrobenzaldehyde in 60% yield by the current reaction, whereas the Rosenmund Reduction is not suitable for such conversion. Therefore, this reaction is referred to as the Grosheintz-Fischer-Reissert aldehyde synthesis or Reissert aldehyde synthesis. ... 

The procedure described for the preparation of l-(m-nitro-phenyl)-3,3-dimethyltriazene is the method of Elks and Hey,2 and the preparation of m-nitrobiphenyl is also a modification of their procedure. The other principal methods for the preparation of m-nitrobiphenyl are the decomposition of N-nitroso-w-nitroacetanilide in benzene 3 and the decomposition of alkaline m-nitrobenzenediazohydroxide in benzene.4 Other methods that have been reported include the decomposition of potassium ire-nitrobenzenediazotate in benzene with acetyl chloride,6 the decomposition of m-nitrobenzoyl peroxide in boiling benzene,6 the decomposition of benzenediazonium borofluoride in nitrobenzene 7 at 70°, and the reduction of 4-(3 -nitrophenyl)-benzenediazonium acid sulfate in boiling ethanol.8... 

---