N-arylation

Sydnones are neutral, highly crystalline, stable compounds, soluble in most organic solvents. N-Arylsydnones typically are obtained by treating N-nitroso-N-aryl-glycines with etha-noic anhydride. The parent glycine is regenerated when the sydnone is heated with dilute alkali. 

The action of ammonia on N-(aryl-i,3-oxathiol-2-ylidine) tertiary im-inium salts (254) yields linear intermediates (255) that cyclize to 2-amino-4-phenyl thiazoles (256) on crystallization from acetic acid (Scheme 129) (730). 

R—N=N Aryl diazonium 10ns are formed by treatment of primary aromatic amines with nitrous acid They are ex tremely useful in the preparation of aryl halides phenols and aryl cyanides... 

N,N -dialkyl-/)-PDAs, N-alkyl-N -aryl-/)-PDAs, and N,N -diaryl-/)-PDAs. 

Several types of nitrogen substituents occur in known dye stmetures. The most useful are the acid-substituted alkyl N-substituents such as sulfopropyl, which provide desirable solubiUty and adsorption characteristics for practical cyanine and merocyanine sensitizers. Patents in this area are numerous. Other types of substituents include N-aryl groups, heterocycHc substituents, and complexes of dye bases with metal ions (iridium, platinum, zinc, copper, nickel). Heteroatom substituents directly bonded to nitrogen (N—O, N—NR2, N—OR) provide photochemically reactive dyes. 

Ring-opening reactions are best known in the pyridazine ring. For example, the N-aryl cyclic hydrazides (321) undergo ring opening with alkali to give the N-aminoimides (322),... 

N-Arylation of azoles is achieved either by using arynes, activated halobenzenes (e.g. dinitro) or under Ullmann conditions. Thus benzyne reacts with imidazoles to give N-arylimidazoles (70AHC(12)103), and these compounds have also been prepared under modified Ullmann conditions. 

The N—CO distance of 1.38 A in (58) is rather greater than that of a normal amide (ca. 1.32 A) this has been attributed to ring strain and to inhibition of normal amide resonance by interaction with the N-aryl substituent. This inhibition of resonance is more pronounced in the N-tosyl-4-thioxoazetidin-2-one (59), which exhibits very short C=0 and C=S distances as well as the unusually long C—N bonds (80TL4247). NMR investigations... 

Imidazole, 2-amino-1 -methyl-4,5-diphenyl-tautomerism, 5, 368 Imidazole, 2-aroyl-mass spectra, 5, 360 synthesis, 5, 391, 402 UV spectra, 5, 356 Imidazole, 4-aroyl-synthesis, 5, 474 Imidazole, C-aroyl-UV spectra, 5, 356 Imidazole, aryl-nitration, 5, 396, 433 oxidation, 5, 433 Imidazole, 1-aryl-dipole moments, 5, 351 dearylation, 5, 449 ethylation, 5, 448 H NMR, 5, 353 hydroxymethylation, 5, 404 rearrangement, 5, 108 synthesis, 5, 390 thermal rearrangement, 5, 363 Imidazole, 2-aryl-chlorosulfonation, 5, 397 synthesis, 5, 475 Imidazole, 4-aryl-bromination, 5, 399 Imidazole, C-aryl-electrophilic substitution, 5, 432-433 nitration, 5, 433 Imidazole, N-aryl-reactions, 5, 448-449 structure, 5, 448-449 Imidazole, arylmercapto-... 

Pyrido[2,3-b]pyrazinium salts, N-aryl-2,3-dimethyl-nucleophilic attack, 3, 253 Pyrido[2,3-(i]pyrazinium salts reactions... 

H,3H- Pyrrolo[l, 2-c]oxazole-l, 3-dione, 5,6,7,8-tetrahydro-IR spectra, 6, 978 [2.2](2,5)Pyrrolophane, N-aryl-rearrangements, 4, 209 Pyrrolophanes natural products, 7, 764 synthesis, 7, 771 Pyrrolophanes, N-aryl-synthesis, 7, 774 (2,4)Pyrrolophanes synthesis, 7, 771 Pyrrolo[3,4-c]pyran-4-ones synthesis, 4, 288 Pyrrolopyrans synthesis, 4, 525, 526 Pyrrolopyrazines synthesis, 4, 526 Pyrrolo[l, 2-a]pyrazines synthesis, 4, 516 Pyrrolo[2,3-6]pyrazines Mannich reaction, 4, 504 Vilsmeier reaction, 4, 505 Pyrrolo[3,4-c]pyrazole, 1,3a,6,6a-tetrahydro-structure, 6, 976 synthesis, 6, 1019 Pyrrolopyrazoles synthesis, 5, 164 Pyrrolo[l,2-6]pyrazoles synthesis, 6, 1002, 1006 Pyrrolo[3,4-c]pyrazoles reactions, 6, 1034 synthesis, 6, 989, 1043 Pyrrolo[3,4-c]pyrazolones synthesis, 6, 989 Pyrfolopyridazines synthesis, 4, 517 Pyrrolo[l, 2-6]pyridazines synthesis, 4, 297 6/7-Pyrrolo[2,3-d]pyridazines synthesis, 4, 291 2/f-Pyrrolo[3,4-d]pyridazines synthesis, 4, 291 6/7-Pyrrolo[3,4-d]pyridazines synthesis, 4, 291... 

Boron-nitrogen heterocycles [4,5-diethyl-2,2,3-trimethyl-l-(<9-tnfluoro-methyl)phenyl-2,5-dihydro-l(-)-],2,5-azasilaboroles and -azastannaboroles] are formed in good yields The products demonstrate atropoisomensm due to the hmdered rotation about the N-aryl bond [113] (equation 88)... 

The enamine (28) did not undergo C arylation with p-nitrochlorobenzene under these conditions, and at higher temperatures N arylation and subsequent eleavage with formation of N-(4-nitrophenyl) pyrrolidine takes place (68). 

The photocyclization of N-aryl enamines derived from cyclic or acyclic ketones proceeds under mild conditions to produce 2,3-dihydroindole derivatives (178b). The stereochemistry of the products is predominantly trans, which follows from a photochemical electrocyclic process which should take place in a conrotatory manner (178c,I78d). However, the presence of some cis products is not as easily explained. 

In the arylations of enamines with very reactive aryl halides (352,370) such as 2,4-dinitrochlorobenzene, the closely related mechanistic pathway of addition of the enamine to the aromatic system, followed by elimination of halide ion, can be assumed. The use of n-nitroarylhalides furnishes compounds which can be converted to indolic products by reductive cycliza-tion. Less reactive aryl halides, such as p-nitrochlorobenzene, lead only to N-arylation or oxidation products of the enamines under more vigorous conditions. 

Heterocyclization by catalytic formation of N—Car bond to give indoles, amino-pyridines, and N-aryl-substituted saturated heterocycles 98ACR805. 

The cycloaddition reaction of compound 6 with N-aryl- and N-aralkylazides 23 was also investigated (967(52)7183). Thiadiazabicyclo[3.1.0]hexene derivatives 25 were obtained from the labile triazoline intermediate 24 through nitrogen elimination. This bicyclic system underwent thermal transformation, producing thiadiazine dioxides 26 as the main product together with thiazete dioxides 27 and pyrazoles 28. 

Perhydropyrido[l,2-c]pyrimidine was N-arylated with 6-bromo-l-(2-propyl)indole in the presence of DBU, NaO/-Bu, (/-Bu)3P, and Pd(OAc)2 in boiling xylene (01MIP6). 

Halochromie,/. halochromism, halochromy. Halogen-, halogen, halo- (as in Halogenbenr zoeadure, Halogenpyridin, etc.), halide of (as in Halogenailber, silver halide), -alkyl, n. alkyl halide, -aryl, n. aryl halide. 

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