2- Aroyl-4-aryl

Die thermische Zersetzung von 2-Aryl-l-azido-2-oxo-ethanen in Diphenylether bei 180-240= fiihrt zu 2-Aroyl-4-aryl-imidazolen (46-84%)229. Analoge Produkte werden auch bei der thermischen Zersetzung von 1,1-Dimethyl-1-(2-oxo-2-phenyl-ethyl)-hydrazinium-Salzen erhal-ten230,231. Bei beiden Reaktionen werden die entsprechenden a-Imino-ketone als Zwischen-produkte angenommen. 

Sodium arenetellurolates condensed with aroyl chlorides6 to produce aroyl aryl tellurium derivatives (p. 501). Acetic and propanoic anhydrides reacted similarly7. Butyl aroyl or acyl tellurium compounds were obtained from reactions between lithium (sodium) butanetellurolates and aroyl chlorides6-8, acyl chlorides8, or acetic anhydride9. 

Butyl vinyl ether reacts with aroyl chlorides using Pd(OAc)2 without a ligand to give the unsaturated ketone 839, which is a precursor of a 1-aryl-1,3-dicarbonyl compound. The reaction is regioselective /3-attack. Addition of PhjP inhibits the reaction[718]. 

The alkylphenylacetyi chloride 843 and benzoyl chloride undergo decarbo-nylative cross-condensation to give the enone 845 in the presence of EtiNf723]. The reaction is e.xplained by the insertion of the ketene 844 into the Pd-aryl bond and, 3-elimination. To support this mechanism, o, d-unsaturuted ketones are obtained by the reaction of ketenes with aroyl chlorides[724]. 

Similarly, 5-thiazole alkanoic acids and their salts are obtained from thioamides and /3-halo -y-keto acids (695). Thus thioarylamides condensed with 3-aroyl-3-bromopropionic acid (88) in isopropanolic solution in the presence of Na COs give first 4-hydroxy-2-aryl-A-2-thiazoline-5-acetic acid intermediates (89), which were dehydrated in toluene with catalytic amounts of p-toluene sulfonic acid to 2,4-diaryl-5-thiazole acetic acid (90) (Scheme 39) (657), with R = H or Me Ar = Ph, o-, m- or p-tolyl, o-, m-, or P-CIC6H4, 0-, m-, or p-MeOC(iH4, P-CF3C6H4, a-thienyl, a-naphthyl (657). 

Simple aziridines are optically transparent in the UV region of the electromagnetic spectrum (B-69MI50401). In more highly substituted aziridines, such as the 2-aroyl-3-arylaziridines (9), there is an interaction between the carbonyl and aryl ring substituents... 

Benzimidazole, 2-amino-5-bromo-l-methyl-diazo coupling, 5, 429 Benzimidazole, 2-amino-6-bromo-1 -methyl-diazo coupling, 5, 429 Benzimidazole, 2-amino-1-ethyl-alkylation, 5, 438 Benzimidazole, 2-amino-1-methyl-acylation, 5, 438 bromination, 5, 429 tautomerism, 5, 368 Benzimidazole, 4-amino-2-methyl-diazo coupling, 5, 429 Benzimidazole, 2-aroyl-mass spectra, 5, 360 Benzimidazole, 1-aryl-metallation, 5, 448 reactions... 

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-... 

Jap-KIingermarm reactions, 4, 301 oxidation, 4, 299 reactions, 4, 299 synthesis, 4, 362 tautomerism, 4, 38, 200 Indole, 5-amino-synthesis, 4, 341 Indole, C-amino-oxidation, 4, 299 tautomerism, 4, 298 Indole, 3-(2-aminobutyl)-as antidepressant, 4, 371 Indole, (2-aminoethyl)-synthesis, 4, 278 Indole, 3-(2-aminoethyl)-synthesis, 4, 337 Indole, aminomethyl-reactions, 4, 71 Indole, 4-aminomethyl-synthesis, 4, 150 Indole, (aminovinyl)-synthesis, 4, 286 Indole, 1-aroyl-oxidation, 4, 57 oxidative dimerization catalysis by Pd(II) salts, 4, 252 Indole, 1-aroyloxy-rearrangement, 4, 244 Indole, 2-aryl-nitration, 4, 211 nitrosation, 4, 210 synthesis, 4, 324 Indole, 3-(arylazo)-rearrangement, 4, 301 Indole, 3-(arylthio)-synthesis, 4, 368 Indole, 3-azophenyl-nitration, 4, 49 Indole, 1-benzenesulfonyl-by lithiation, 4, 238 Indole, 1-benzoyl photosensitized reactions with methyl acrylate, 4, 268 Indole, 3-benzoyl-l,2-dimethyl-reactions... 

Isoxazole, 5-(p-anisyl)-3-phenyI-synthesis, 6, 63 Isoxazole, 4-aroyl-3,5-diaryI-synthesis, 6, 71 Isoxazole, aryl-UV spectra, 6, 4 Isoxazole, 3-aryl-5-unsubstituted ring cleavage, 6, 30 Isoxazole, 5-aryl-3-chloro-reactions, 5, 104 Isoxazole, 3-aryI-4-formyl-synthesis, 6, 84 Isoxazole, 3-aryl-5-methoxy-thermal isomerization, 6, 15 Isoxazole, 3-aryl-5-methyl-synthesis, 6, 63, 84 Isoxazole, 4-azorearrangement, 5, 719... 

Dioxo-l,3-diaryl-propane dimerisieren reduktiv zu 3,4-Dihydroxy-1,6-dioxo-1,3,4.6-tetra-aryl-hexanen I, 1,3,5,6-Tctraaryl-2,4,7-trioxa-tricyclo[3.2.1.13 6]n0nanen II und 1,2,4-Trihydroxy-l,2,4-triaryl-3-aroyl-cyclopentancn III4 ... 

Thermolysis of 3-alkyloxy- and 3-aroyloxy-5-phenyl-l,2,4-pyrrolo[l,2- ]quinoxaline-l,2,4-triones afforded 5-phenyl-9-(4-phenyl-3-oxo-3,4-dihydro-2-quinoxalinyl)-6,8,10-trioxo-5,6,9,10-tetrahydro-87/-pyrido[l,2-tf ]quinoxaline-7,9-dicarboxylates <2000CHE615, 2004CHE1295> and 7-aroyl-8-aroyloxy-5-phenyl-9-(4-phenyl-3-oxo-3,4-dihydro-2-quinoxalinyl)-5,6-dihydro-1077-pyrido[l,2- ]quinoxaline-6,10-diones <2002CHE498>, respectively. Thermolysis of 3-aryl-2-(5-aryl-2,3-dioxo-2,3-dioxo-4-furanyl)quinoxalines gave 7-aroyl-8-aroyloxy-6-aryl-9-(3-aryl-2-quinoxalyl)-10/7-pyrido[l,2- ]quinoxalin-10-ones <2001CHE1314, 2002RCB850>. 

Reaction of l-aroyl-2-aryl-3a,6a-diazapentalenes 105 with 1 equiv of DMAD in the presence of Pd/C is reported to provide 3% yield of 107, presumably via the corresponding primary adduct 106 <1966PNA1385>. The reaction with more than 2 equiv of acetylene dicarboxylates affords surprisingly unusual anti-Bredt s adducts having the... 

Ar = p-tolyl, p-anisyl, p-(tert. butyl)phenyl R = CH3, C(CH3)3, a-naphthyl R = alkyl, aryl, NH-Ph, O-alkyl R" = CN, NO2, acyl, aroyl... 

With 4,4-diacyl triafulvenes two principal fragmentation pathways have been observed5 s In 4-aroyl-4-acetyl triafulvenes 241 the molecular ion is followed by a fragment ion of probable structure 242 arising from primary loss of (CvI R), which surprisingly has incorporated a CH2 unit from the acetyl group and the exo-cyclic aryl residue. It is not unlikely that the (C7H6R)-residue corresponds to a substituted tropyl radical due to its well-known formation from electron-impact of benzylic precursors. 

Aroylformamido-4-aryl-l,2,5-thiadiazoles 120 on treatment with MCPBA in chloroform at reflux afford 3-amino-4-aryl-l,2,5-thiadiazoles 121 (Scheme 18), but in the presence of ethanol the 3-ethoxycarbamoyl-4-aryl-l,2,5-thiadiazole 122 was also isolated <1999JHC515>. A-Aroylation could readily be achieved to give thiadiazoles 123 using the acid chloride in chloroform at room temperature. 

Several approaches to the 1,2,3-triazole core have been published in 2000. Iodobenzene diacetate-mediated oxidation of hydrazones 152 led to fused 1,2,3-triazoloheterocycles 153 <00SC417>. Treatment of oxazolone 154 with iso-pentyl nitrite in the presence of acetic acid gave 1,2,3-triazole 155, a precursor to 3-(W-l,2,3-triazolyl)-substituted a,P-unsaturated a amino acid derivatives <00SC2863>. Aroyl-substituted ketene aminals 156 reacted with aryl azides to provide polysubstituted 1,23-triazoles 157 <00HC387>. 2-Aryl-2T/,4/f-imidazo[43-d][l,2,3]triazoles 159 were prepared from the reaction of triethyl AM-ethyl-2-methyl-4-nitro-l//-imidazol-5-yl phosphoramidate (158) with aryl isocyanates <00TL9889>. 

Recent notable improvements by Knochel and co-workers include iron-catalyzed cross-coupling reactions of various acid chlorides 148 with dialkylzinc reagents (Equation (24))324 as well as the iron-catalyzed arylation of aroyl cyanides 149 with Grignard reagents (Equation (25)).3 5 In the first case Knochel s reaction conditions tolerate ester groups on the organozinc compounds, while in the latter case ester, aryl alkyl ether, cyano, and chloro functionalities on the aromatic moieties are compatibles with the reaction conditions. 

Itahara has also found that the phenylation of A-aroylpyrroles can be achieved using Pd(OAc>2 [30, 31]. Although A-benzoylpyrrole (22) yields a mixture of diphenylpyrrole 23, cyclized pyrrole 24, and bipyrrolyl 25 as shown, l-(2,6-dichlorobenzoyl)pyrrole 26 gives the diphenylated pyrrole 27 in excellent yield. The IV-aroyl groups are readily cleaved with aqueous alkali and the arylation reaction also proceeds with p-xylene and p-dichlorobenzene. Unfortunately, N-methyl-, iV-acetyl-, and A-(phenoxycarbonyl)pyrroles give complex mixtures of products. 

In the presence of sodium acetate in acetic acid, the arylhydrazones 54 (available from the reaction of tu-halogen-tu-(arylhydrazono)acetophenones with 3-amino[l,2,4]triazole) undergo cyclization to yield 3-aroyl-l-aryl-l//-[l,2,4]-tria-zolo[3,4-c][l,2,4]triazoles 55 (Equation 7) <1987CB965>. 

The cyclocondensation of 3-acyl/3-aroyl-5-aryl[l,3,4]oxadiazol-2(3//)-ones 98 with hydrazine hydrate gives the corresponding 3,6-disubstituted-[l,2,4]triazolo[3,4- ][l,3,4]oxadiazoles 99 (Equation 26) <1991H(32)237>. 

The treatment of arylglyoxylhydroximoyl chlorides with 2 equiv of 3-amino-277-[l,2,4]-triazole 107 in the presence of triethylamine produces a mixture of 3-aroyl-[l,2,4]triazolo[4,3-6][l,2,4]triazole 108 and 5-aryl-6-nitroso-17/-imidazo-[l,5-d[l,2,4]triazole 109 (Equation 28) <1984JHC1029>. 

A series of aryl- and aroyl-hydrazide derivatives was obtained from d-gly-ccro-D- u/oheptono-1,4-lactone (132). The reaction was faster with arylhy-drazines than with aroylhydrazines. The aroylhydrazides may be decomposed by copper(II) sulfate or nitrous acid to regenerate the precursor lactone. 

D-Glucono-1,5-lactone reacted with aroylhydrazines (133) to give the corresponding l-aroyl-2-D-gluconylhydrazides (113), which underwent cy-clization upon heating with triethyl orthoformate, affording 5-aryl-2-eth-oxy-3-D-gluconyl-2,3-dihydro-1,3,4-oxadiazoles (114). 

Our experimental results (Table 1) showed that this approach does work for the series of alkoyl salts but it fails to predict the considerably greater solubilities of the aroyl and aryl salts which are also shown in Table 1. 

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