3-Nitrobenzoyl alcohol

Several attempts have been made to combine LC online with MALDI [53]. In one approach, a continuous-flow probe, similar to that used for CF-FAB, has shown success in introducing LC effluents directly into the MALDI source [54,55]. The matrix solution, composed of 3-nitrobenzoyl alcohol, 0.1% TFA, 1-propanol, and ethylene glycol (3 3 5 9 by volume), is mixed postcolumn with the LC flow. A UV laser beam is focused onto the tip of the probe to ionize the emerging LC effluent. 

A crystalline derivative of benzyl alcohol cannot be obtained by using benzoyl chloride, because the benzyl benzoate, C HiCOOCHiCaHj, so obtained has m.p. 18°, and is thus usually liquid the present preparation illustrates therefore the use of a substituted benzoyl chloride (p-nitrobenzoyl chloride, m.p. 75°) in order to obtain a crystalline derivative of suitably high m.p. 

Place I ml. of benzyl alcohol in a boiling-tube and add 6 ml. of 10% sodium hydroxide solution add also 6 ml. of water to moderate the subsequent reaction, otherwise the rise in temperature may cause hydrolysis of some of the ester produced. Now add r-q g. of finely powdered />-nitrobenzoyl chloride, and shake the well-corked tube vigorously. The mixture becomes warm, and the solid ester rapidly... 

The benzoyl compounds frequently occlude traces of unchanged benzoyl chloride, which thus escape hydrolysis by the caustic alkali it is therefore advisable, wherever possible, to recrystaUise the benzoyl derivatives from methyl, or ethyl alcohol or methylated spirit, since these solvents will esterify the unchanged chloride and so remove the latter from the recrystalKsed material. Sometimes the benzoyl compound does not crystallise well this difficulty may frequently be overcome by the use of p-nitrobenzoyl chloride or 3 5-dinitro-benzoyl chloride, which usually give highly crystalline derivatives of high melting point (see Section IV,114j. 

These formulae explain the scission products of the two alkaloids and the conversion of evodiamine into rutaecarpine, and were accepted by Asahina. A partial synthesis of rutaecarpine was effected by Asahina, Irie and Ohta, who prepared the o-nitrobenzoyl derivative of 3-)3-amino-ethylindole-2-carboxylic acid, and reduced this to the corresponding amine (partial formula I), which on warming with phosphorus oxychloride in carbon tetrachloride solution furnished rutaecarpine. This synthesis was completed in 1928 by the same authors by the preparation of 3-)S-amino-ethylindole-2-carboxylic acid by the action of alcoholic potassium hydroxide on 2-keto-2 3 4 5-tetrahydro-3-carboline. An equally simple synthesis was effected almost simultaneously by Asahina, Manske and Robinson, who condensed methyl anthranilate with 2-keto-2 3 4 5-tetrahydro-3-carboline (for notation, see p. 492) by the use of phosphorus trichloride (see partial formulae II). Ohta has also synthesised rutaecarpine by heating a mixture of 2-keto-2 3 4 5-tetrahydrocarboline with isatoic anhydride at 195° for 20 minutes. 

Cevadine contains neither a methoxyl nor a methylimino group it yields crystalline benzoyl and o-nitrobenzoyl derivatives, m.p. 255° and 236° respectively, and a methiodide, which decomposes at 210-2°, and is converted by silver oxide into eevadinemethylhydroxide.i When warmed with alcoholic soda, cevadine undergoes hydrolysis into eevine and angelic and tiglic acids. When hydrogen chloride is passed into cevadine in alcohol, ethyl tiglate and eevine are formed. ... 

Finally, the action of acid chlorides on alcohols and phenols is also used to separate them from solutions or to characterise them. For this purpose benzoyl chloride is usually employed. Methyl alcohol, for example, gives with p-nitrobenzoyl chloride the beautifully crystalline methyl ester and small amounts of the alcohol can thus be separated from aqueous solution. 

Whereas diborane in tetrahydrofuran reduces oximes only at 105-110 , oxime ethers and oxime esters are reduced to amines and alcohols at room temperature in good yields. For example the p-nitrobenzoyl ester of cyclohexanone oxime gave a 67% yield of cyclohexylamine and 81% yield of p-nitrobenzyl alcohol [948]. 

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. 

Di-(p-nitrobenzoyl)-furoxan5 Dll86 Dinitrobenzyl alcohol 2 B92 Dinitrobenzyl alcohol nitrate 3 B92 Dinitrobenzylamine 2 B93 Dinitrobenzylaniline 2 B93 Dinitrobenzylazide 2 B94—B95 Dinitrobenzyl benzoate 2 B9S Dinitrobenzyl cyanide 2 B96... 

General methods for the preparation of acid halides from aliphatic carboxylic acids are described in Section 5.12.1, p. 692. Phosphorus pentachloride is the preferred chlorinating agent for aromatic acids which contain electron-withdrawing substituents, and which do not react readily with thionyl chloride. The preparation of both p-nitrobenzoyl chloride and 3,5-dinitrobenzoyl chloride is described in Expt 6.161. These particular acid chlorides are valuable reagents for the characterisation of aliphatic alcohols and simple phenols, with which they form crystalline esters (see Section 9.6.4, p. 1241 and Section 9.6.6, p. 1248). 

Alcohols react readily with p-nitrobenzoyl chloride to yield p-nitrobenzoates ... 

Show the conformation of each of the following alcohols and arrange them in order of decreasing ease of esterification with p-nitrobenzoyl chloride. 

Used to introduce chromophores into alcohols and amines, using pyridine as the solvent with silica gel as the stationary phase, relatively low-viscosity, low-polarity solvents can be used for detection of digitalis glycosides by HPLC following derivatization with p-nitrobenzoyl chloride Reference 32... 

Carbonyl chloride or acetic anhydride Picolinoyl chloride [64] 4-Nitrobenzoyl chloride [60] Pentafluorobenzoyl chloride [65] Acetic anhydride [66] Both phenolic OH and alcoholic OH LC-ESP/MS/ MS LC-APCI/ MS/MS GC-EP/MS LC-APCP/ MS2... 

Desilylation of 135 afforded alcohol 136, which was oxidized to enal 137 by Parikh-Doering oxidation in 62% yield. Removal of the p-nitrobenzoyl group and the menthyl group resulted in completion of the total synthesis of mniopetal F (6). 

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