4- Toluamide

Primary aromatic amides are crystaUine sohds with definite melting points. Upon boiling with 10-20 per cent, sodium or potassium hydroxide solution, they are hydrolysed with the evolution of ammonia (vapour turns red htmus paper blue and mercurous nitrate paper black) and the formation of the alkah metal salt of the acid  

The acid is hberated upon acidification. Hydrolysis may also be efifected (but less readily and usuaUy not quite so satisfactorily) by boiling with dilute h3 drochloric acid (1 1) or 20 per cent, sulphuric acid  

The hydrolysis by alkali is illustrated by the following experimental details for benzamido. Place 3 g. of benzamide and 50 ml. of 10 per cent, sodium hydroxide solution in a 150 ml. conical or round-bottomed flask equipped with a reflux condenser. Boil the mixture gently for 30 minutes ammonia is freely evolved. Detach the condenser and continue the boiling in the open flask for 3-4 minutes to expel the residual ammonia. Cool the solution in ice, and add concentrated hydrochloric acid until the mixture is strongly acidic benzoic acid separates immediately. Leave the mixture in ice until cold, filter at the pump, wash with a little cold water and drain well. RecrystaUise the benzoic acid from hot water. Determine the m.p., and confirm its identity by a mixed m.p. test. 

The characterisation of a primary aromatic amide is based upon its own m.p. and the identification of the acid (see Section IV,175) produced on hydrolysis. A crystalline derivative may be prepared directly with xanthhydrol (for experimental details, see Section 111,110, 1). 

The melting points of a few selected primary aromatic amides (together with those of the xanthylamides, where known) are collected in Table IV,191. A more detailed list will be found in the column headed Amides in Table IV,175 (Armnalic Carboxylic Acids). 

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Repellents are materials that affect insects and other organisms by dismpting their natural behavior of bloodseeking through biting of humans and animals, and are the first line of defense that can be readily used for this purpose (1). The best overall standard repellent is A/,A/-diethyl-y -toluamide [134-62-3] (DEBT), systematically named A/jAZ-diediji-S-methylbenzamide (1). 

EPA JV,IV-Diethyl-m-toluamide (DEFT), Pesticide Registration Standard, U.S. EPA, Washington, D.C., 1980. 

A uV-Diethyl-m-toluamide (DEET) is the active ingredient in many insect-repellent preparations. Plow might you synthesize this substance from m-bromotoluene ... 

The lithio derivative of Ar,Ar-dicthyl-2-toluamide 1 adds to each enantiomerically pure glycer-aldehyde acetonide 4-methoxybenzyl imine [(7 )-2 or (S)-2] to provide only one diastereomer exclusively or (3/ ,TA)-3, respectively]. The moderate yield (50%) is due. in part,... 

As a part of the total synthesis of (+ )-corydalic acid methyl ester (12), a reaction of a cyclic enolate with an imine has been applied. The 2-toluamide enolate 9, which in this case is substituted at the methyl group, adds stereospecifically to imine 10, affording mainly tram-iso-quinolone 11 with a d.r. (transjds) > 95 525. 

A derivative of benzylhydrazine, procarbazine (8), exhibits antineoplastic activity. In an interesting insertion-type sequence, reaction of the p-toluamide (5) with ethyl azodicarboxylate leads directly to the substituted hydrazine (6). It is not unlikely that the first mole of the diazo compound... 

Additions of stabilized carbanions to imines and hydrazones, respectively, have been used to initiate domino 1,2-addition/cyclization reactions. Thus, as described by Benetti and coworkers, 2-subshtuted 3-nitropyrrolidines are accessible via a nitro-Mannich (aza-Henry)/SN-type process [165]. Enders research group established a 1,2-addition/lactamization sequence using their well-known SAMP/ RAMP-hydrazones 2-308 and lithiated o-toluamides 2-307 as substrates to afford the lactams 2-309 in excellent diastereoselectivity (Scheme 2.72) [166]. These compounds can be further transformed into valuable, almost enantiopure, dihydro-2H-isoquinolin-l-ones, as well as dihydro- and tetrahydroisoquinolines. 

Fenvalerate toxicity is antagonized by atropine sulfate or methocarbamol, which may be effective in treating severe cases of poisoning (Hiromori et al. 1986). Conversely, some compounds exacerbate the toxicity of fenvalerate and interfere with a desired use. Domestic cats (Felis domes-ticus) treated with Fendeet (an aerosol mixture of fenvalerate and A-A-diethyl-m-toluamide) to control fleas and ticks sometimes show signs of toxicosis, such as tremors, hypersalivation, ataxia, vomiting, depression, and seizures. Signs usually appeared within hours of topical application, and females and juveniles seem to be the most sensitive groups. The demonstrated ability of N-N-diethyl-m-toluamide to enhance the dermal absorption of fenvalerate is the probable cause of toxicosis (Dorman et al. 1990). 

Topical aerosol treatment of fenvalerate plus Deet (N-N-diethyl-m-toluamide) to control fleas and ticks... 

Dorman, D.C., W.B. Buck, H.L. Trammel, R.D. Jones, and V.R. Beasley. 1990. Fenvalerate/AQV-diethyl-m-toluamide (Deet) toxicosis in two cats. Jour. Amer. Veterin. Med. Assoc. 196 100-102. 

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