4- Chloro-N-methylaniline

N-Nitroso-3-chloro-N-methylaniline or (3. -ChlorophenyD-methylnitrosamine, lfts, mp 36-38°(Refs 2 4) and N-Nitroso-4-chloro-N-methylaniline or (4 -ChlorophenyD-methylnitrosamine, lt-brn crysts (from gasoline), mp 5 l°(Refs 2 4)... 

Dinitro-4-chloro-N-methylaniline, orn ndls, mp 100-100.5° was prepd by treating... 

N,2,6 Trinitro 4 chloro-N-methylaniline or (2,6mDimtro-4-chlorophenyl)-methylnitramine, (02N)2C1.C6H2.N(N02)CH3, crysts, mp 100° was obtd by nitration of 2-nitro-4-chloro-N -methylaniline(Refs 1 2) and... 

Dinitro N nitTosO -4-chlorO N methylaniline or (2,6-Dinitro-4 Chlorophenyl)-methylnitrosamine, (O N)2Cl.CgH2.N(NO).CH3, Ic yel ndls(from ale) mp 99-99.5° was prepd bytreating4-chloro-N -methylaniline in cold ale soln with nitrous acid(Refs 1 2)... 

ZnClg added to a mixture of 2-benzoyl-4-chloro-N-methylaniline, methyl vinyl ketone, and methylene chloride, and stirred 1 hr. at room temp. 3-acetyl-6-chloro-4-hydroxy-l-methyl-4-phenyl-l,2,3,4-tetrahydroquinoline. Y 74%. F. e. s. A. Walser, G. Zenchoff, and R. I. Fryer, J. Heterocyclic Chem. 13, 131 (1976). 

Finally, a method of making medazepam from 4-chloro-A -methylaniline is snggested. The last is reacted with ethyleneimine in the presence of alnminum chloride, giving N-(4-chlorophenyl)-iV-methylethylenediamine (5.1.43). Acylation of the resulting product with benzoyl chloride gives the respective amide (5.1.44), which cyclizes into the desired medazepam (5.1.40) using phosphorous oxychloride [44,45],... 

Nitroso-2-chloro-N-methylaniline or 2-Chloro -1,4 -benzoquinone-4-me thy limide-1-oxime, ON.(C1)CsH3.NH.CH3 or H0.N (C1)C-H3 N.CH3, dk gm prisms(from benz), mp 134-36, (dec)... 

Nitroso-3-chloro-N-methylcmiline or 2-chloro -1,4- benzoquinone-1- m ethylimi de-4-oximin e, grn prisms(from petr eth), mp 131-32°(Refs 1 3) N-Nitroso-2-chloro-N-methylaniline or (2-Chloro-phenyl)-methylnitrosamine, Cl.CgH4. N(NO).CH3, golden-yel oil, bp 89° at 1.2mm, d 1.266 at 15° (Refs 2 4)... 

Nitro-N-nitroso-2-chloro-N-methylaniline or (4 -Nitro-2-chlorophenyl)-methy Ini trosamine,... 

Dinitro-2-chloro-N-methylaniline, yel nds (from ale), mp 133° was prepd by reaction of 4, 6-dinitro-l,2-dichlorobenzene with an ale soln of methylamine(Ref 6)... 

Trinitro-3 chlorophenyl)-methylnitramine, (02N)3C1.C6H.N(N02).CH3, yel crysts(from chlf), mp 119° was prepd by nitration of 2-nitro-5-chloro-N-methylaniline(Refs 1 2). 

Bromo-4-chlorobutanoyl bromide (300 mmol) was added to a solution of N-methylaniline (320 mmol) and triethylamine (330 mmol) in toluene (340 mL). The reaction was exothermic, and the mixture was cooled to maintain the temperature at about 40°C. After the addition was complete, the resulting mixture was stirred for 30 minutes, 150 mL water was added, and the mixture was stirred further. The aqueous and organic phases were separated, and the organic phase was washed with 5% hydrochloric acid and with water. The toluene was evaporated completely under vacuum to yield 86.3 g 2-bromo-4-chloro-N-methyl-N-phenylbutanamide (98% yield, approximately 95-96% pure). 

Dinitro N nitroso 2-chloro-N methylaniline or (4.6 DinitTQ 2 chlorophenyl) methylnitTos amine, compd not recrystd because it decompd when petr eth was added to its benz soln at RT was obtd by treating an ice-cold soJn of 2-chloro-N-m ethyl aniline with HNO NaNO (Ref 3)... 

Materials. 2, 3-dinitroaniline (8), -methyl-N, N-dimethyl-aniline (9), p-chloro-N, N-dimethylaniline (9), p-nitro-N, N-dimethylaniline (1 ), N-methyl-p-toluidine (11), p-chloro-N-methylaniline (11), N, 2, 4-trinitroaniline (12), 2, 4-dinitro-N-methylaniline (13), 2, 4-dinitro-N, N-dimethylaniline (13) and N, 2, 4-trinitro-N-methylaniline (14) were prepared by known methods. Spectroscopic grade nitromethane and methylene chloride were dried using a molecular sieve. The other substrates were either available from related studies or were purchased and purified by standard methods. 

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