M-Chloroaniline

A) m-Chloroaniline (64 g, 0.5 mol) was added dropwise with stirring to 375 ml of chlorosulfonic acid in a 3-liter round bottom, 3-necked flask cooled in an ice bath. Sodium chloride (350 g) was added portionwise over a period of 1 to 2 hours and the mixture then heated gradually in an oil bath to 150°C. After 3 hours at 150° to 160°C, the flask was cooled thoroughly in an ice bath and the contents treated with a liter of cold water. The product was extracted with ether and the extract washed with water and dried over sodium sulfate. 

In 1967, (3) it was discovered that DMAP catalyzes the benzoylation of m-chloroaniline 10 times faster than pyridine. This enormous increase in reaction rate is unmatched by any other nucleophilic acylation catalyst (3. It was shown that the catalytic action of DMAP and PPY is not primarily due to their larger pKa s with respect to pyridine, but is a result of enhanced nucleophilic catalysis. 

Creosol, 33, 17 Crotonaldehyde, 33, IS 34, 29 diethyl acetal, 32, 5 Cupric acetate monohydrate, 36, 77 Cuprous oxide-silver oxide, 36, 36, 37 Cyanamide, 34, 67 36, 8 Cyanoacetamide, 32, 34 Cyanoacetic acid, 31, 25 Cyanoacetylurea, 37, 16 >-Cyanobenzaldehyde, 30, 100 >-Cyanobenzaldiacetate, 36, 59 3-Cyano-5,6-dimethyl-2(l)-pyridone, 32,34 N-2-Cyanoethylaniline, 36, 6 N-2-Cyanoethyl- -anisidine, 36, 7 Cyanoethylation, of aniline, 36, 6 of ethyl phenylcyanoacetate, 30, 80 N-2-Cyanoethyl-m-chloroaniline, 36, 7 Cyanogen, 32, 31 Cyanogen iodide, 32, 29 Cyanogen iodide, complex with sodium iodide, 32, 31... 

To 100 gm of a stirred 40 % solution of hydrogen chloride in methanol maintained at 0°C with an ice bath is added, 14.2 gm (0.1 mole) of A-methyl-m-chloroaniline over a 30 min period at such a rate that the temperature never exceeds 15°C. The reaction system is then cooled to 5°C, and 8 gm (0.11 mole) of 97 % sodium nitrite is added all at once. Stirring is continued for 4 hr while the temperature is allowed to rise to 30°C. The reaction mixture is then filtered and the solid hydrochloride salt is washed well with 50 ml of ether. This is followed by air-drying. 

Diazonium compds, such as diazotized 4 cbloro o-toluidine treated with Na2S, NaHS or Na polysulfide solns, form dangerous expls (Ref 1). Hodgson (Re f 2) reported that the addn of o nitrophenyldiazonium chloride to soln at 0° gives a red ppt which explodes when touched with a glass rod. Similarly, when diazotized m-chloroaniline is added dropwise to Na2S2 soln, every drop reacts violently... 

Carbamates Propham, Chloropropham and Carbetamide Swep Bar ban Aniline 3,4-Dichloroaniline m-Chloroaniline... 

Urea Fenuron, Siduron and Urox Monuion Monoiinuron Metobromuron Diuron, Neburon and Linuron Chlorotoluron Chlorbromuron Fluometuron Aniline m-Chloroaniline p-Chloroaniline p-Bromoaniline 3,4-Dichloroaniline 3-Chloro-4-methylaniline 3-Chloro-4-bromoaniline m-Trifluoromethylaniline... 

Condensation of m-chloroaniline with ethyl acetoacetate in the presence of a catalytic amount of HC1 to give A. 

This procedure may also be employed for m-bromochlorobenzene, b.p. 191-194°C, from m-chloroaniline m-dibromobenzene, b.p. 215-217°C, from m-bromoaniline and o-bromoanisole, b.p. 114-116 °C/29mmHg, from 0-anisidine (the sulphuric acid washing is omitted in the last example). 

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