P- anilidate

Add B.P. H.P Anilide Amide phenacyl Ester benzyl Ester phenacyl Ester uronlum Salt ... 

Acid B.P. M.P. Anilide /hToIuI- dlde Amide phenacyl Ester /(-Nltro- benzyl Ester /cPhenyl- phenacyl Ester S-Beniyl- MO-thlU- ronlum Salt 1 />-Bromo-I anlUde Hydrazlde ... 

Acid B.P. M.P Anilide Tolul- dlde Amide Bromo- pbenacyl Ester Nltro- benzyl Ester Pbenyl- pbenacyl Ester S-Benzyl- wo-tbi- uronlum Salt Other Oeilvatlves... 

Add B.P. M.P. Anilide p-Tolul- dide 1 Amide p-Bromo- phenacyl Ester p-Nltro- benzyl Ester p-Phenyl phenacyl Ester S-Benzyl- tro-thi- uronium Salt Other Derivatives... 

Fig. 7. 80.9 MHz "P NMR spectra of ethyl esters of cyclic 2 -deoxy-AMP prepared from equimolar mixtures of unlabeled cyclic 2 -deoxy-AMP and the cyclic 2 -[ 0]deoxy-AMP samples. (Top) 0-Labeled ester from the axial P-anilidate. The approximate chemicai shift of the unlabeled diester is 3.0 ppm, that of the equatorial ester is 4.5 ppm, and that of the axial ester is 6.5 ppm. From Ref. 25.

Reflux Distillation Unit. The apparatus shown in Fig. 38 is a specially designed distillation-unit that can be used for boiling liquids under reflux, followed by distillation. The unit consists of a vertical water-condenser A, the top of which is fused to the side-arm condenser B. The flask C is attached by a cork to A. This apparatus is particularly suitable for the hydrolysis of esters (p. 99) and anilides (p. 109), on a small scale. For example an ester is heated under reflux with sodium hydroxide solution while water is passed through the vertical condenser water is then run out of the vertical condenser and passed through the inclined condenser. The rate of heating is increased and any volatile product will then distil over. 

Hydrolysis of Acetanilide. Anilides in general, such as acetanilide and benzanilide (p. 245), may be hydrolysed by caustic alkalis or by acids. Alkaline hydrolysis, however, is usually very slow, and therefore... 

Alternatively the semi micro apparatus shown in Fig. 38 (p. 63) may be used. Heat the anilide and sulphuric acid under reflux for 15 minutes in such a manner that the vapour does not rise higher than half-way up the vertical condenser through which water is passed. Then dilute the solution in the flask with 5 ml. of water. Empty the vertical condenser and run cold water through the inclined condenser. Now increase the rate of heating and distil off 1-2 ml. of aqueous acetic acid. 

Hydrolysis to p-Nitroaniline. For this purpose use 70 sulphuric acid, the usual reagent employed for the hydrolysis of anilides (p. 108). Add 5 g. of the recrystallised />-nitro-acetanilide to 30 ml. of 70%sulphuric acid, and boil the mixture gently under a reflux water-condenser for 20 minutes. Then pour the clear hot solution into about 150 ml. of cold water, and finally add an excess of sodium hydroxide solution until precipitation of the yellow p-nitroaniline is complete. Coo the mixture in ice-water if necessary, and then filter at the pump, wash well... 

Anilides, (a) To 1 ml. of aniline in a small conical flask add very slowly and carefully about i ml. of acetyl chloride. A vigorous reaction occurs and a solid mass is formed. Add just sufficient water (about 15 ml.) to dissolve the solid completely on boiling. On cooling, crystals of acetanilide separate out filter and determine the m.p. 

The choice of type of derivative should be based on whether the chloride or anhydride is aliphatic or aromatic, because this factoi largely determines the reactivity. Aliphatic acid chlorides are best converted into their anilides, as in 4 above aromatic acid chloride may be similarly converted into their anilides, or they may be converted into their amides by shaking with an excess of ammonia (p, 120). (M.ps., pp. 544-545.) Aliphatic acid anhydrides should be converted into their crystalline anilides, but aromatic acid anhydrides arc best hydrolysed to the acid, which can then be converted into one of the standard derivatives (p. 349). 

Acetylation. Proceed as in 2 (p. 373). Pour the final acetylation mixture into 10 ml. of water, and add 10% NaOH solution, with stirring, until no more anilide is precipitated (acetyl-monoethylaniline is very soluble even in dil. acetic acid acetyUdiphenylamine readily separates without the addition of alkali). Filter, wash with water and recrystallise. 

Benzyl. tblouroDiuffl Mlt M.p. 1 j Sulphonyl chlotide M.p. Sulphon amide M.p. 1 Solphon. anilide M.p. 

HaUde B.P. M.P.. 20 20 " D Anilide a-Nsphtha- lide Alkyl Mercuric Halide S-Alkyl- jo- thluronlum Plcrate Plcrate of S-naphthyl ether... 

Amides, anilides and p toluidides. The dry acid is first converted by excess of thionyl chloride into the acid chloride ... 

The by-products are both gaseous and the excess of thiouyl chloride (b.p. 78°) may be readily removed by distillation. Interaction of the acid chloride with ammonia solution, aniline or p-toluidiiie yields the amide, anilide or p-toluidide respectively ... 

Anilides. Dilute the acid chloride with 5 ml. of pure ether (or benzene), and add a solution of 2 g. of pure aniline in 15-20 ml. of the same solvent until the odour of the acid chloride has disappeared excess of aniline is not harmful. Shake with excess of dilute hydrochloric acid to remove aniline and its salts, wash the ethereal (or benzene) layer with 3-5 ml. of water, and evaporate the solvent [CAUTION ] Recrystallise the anilide from water, dilute alcohol or benzene - light petroleum (b.p. 60-80°). 

Anilides and p-toluidides may also be prepared directly from the acide% by heating them with aniline or p toluidine respectively ... 

The above simple experiments illustrate the more important properties of aliphatic acid chlorides. For characterisation, the general procedure is to hydrolyse the acid chloride by warming with dilute alkali solution, neutralise the resulting solution with dilute hydrochloric acid (phenol-phthalein), and evaporate to dryness on a water bath. The mixture of the sodium salt of the acid and sodium chloride thus obtained may be employed for the preparation of solid esters as detailed under Aliphatic Acids, Section 111,85. The anilide or p-toluidide may be prepared directly from the acid chloride (see (iii) above and Section III,85,i). 

Anilides or p-toluidides of acids from esters. Esters are converted into the corresponding anilides or p-toluidides by treatment with anilino- or with p-toluidino-magnesium bromide, which are readily obtained from any simple Grignard reagent and aniline or p-toluidine ... 

Beckmann rearrangement of benzophenone oxime to benz-anilide. Dissolve 2 g. of benzophenone oxime in 20 ml. of anhydrous ether in a small conical flask and add 3 g. of powdered phosphorus pentachloride (or 3 ml. of pure tbionyl chloride). Distil off the solvent and other volatile products on a water bath CAUTION ether), add 25 ml. of water, boil for several minutes and break up any lumps which may be formed. Decant the supernatant liquid, and recrystallise, in the same vessel, from boiling alcohol. The product is benzanilide, m.p. 163° confirm this by a mixed m.p. determination with an authentic specimen. 

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