4-Benzoyl-7,7-diphenyl

Disubstituted and trisubstituted 3-isonitrosopyrroles rearrange to 3-acylisoxazoles under the influence of hot, dilute mineral acids. For example, isonitrosotriphenylpyrrole (436), when treated with boiling alcoholic mineral acid, is converted into 3-benzoyl-4,5-diphenyl-isoxazole (437) (62HC(17)1, p. 34). 

R = H 3-Benzoyl-5-phenyl-1,2-oxazol R = C6h5 3-Benzoyl-4,5-diphenyl-... 

Benzoyl-diphenyl-phosphanoxid, das aus Benzoesaureanhydrid und Diphenylphosphan-oxid entsteht, ist extrem hydrolyseempfindlich und addiert Spuren von Wasser zu Diphe-nylphosphinsaure-a-diphenylphosphinyl-benzylester und bildet bereits bei 85° ein Dime-... 

Chlor-diphenyl-phosphan greift Benzoesaure-alkylester nukleophil entweder am Carbonyl- oder am Alkyl-C-Atom an104. Im ersten Fall entsteht das entsprechende Alkylchlorid und das nicht nachgewiesene Benzoyl-diphenyl-phosphanoxid. Im zweiten Fall entsteht Benzoylchlorid und Alkyl-diphenyl-phosphanoxid ... 

Dibenzoyloxy-benzil 9 II142. Bi8.[3-oxy.naphthoyl.(2)]-resorcin 10, 336. 4.8-INphenoxy.anthracenKlicarbon< saure-(1.6) 10 II401. 4.4 -Bis-i2-carboxy-benzoyl].diphenyl 10 1 446. 

Polyquinolines form another class of heteroaromatic polymers exhibiting photoconductivity. The interest in the synthesis of polyquinolines has increased rapidly during the last decade because of their excellent oxidative and thermal stability. When doped with alkali metal donor compounds like sodium naphthalide or sodium anthracide, several polyquinolines show electrical conductivity as high as 10 S/cm [336,337], When doped with electron-donor compounds such as TNF or 2,3-dichloro-5,5-dicyano-l,4-benzoquinone some poly-quinolines show distinct photoconductivity. One such polyquinoline is poly(4-phenyl-2,6-(p-phenoxy)-quino-line) (54b) [338,339]. It is obtained by the acid catalysed self-condensation reaction of 4-amino-4 -acetyl-3-benzoyl diphenyl ether (54a). 

The cyclized products 393 can be prepared by the intramolecular coupling of diphenyl ether or diphenylamine(333,334]. The reaction has been applied to the synthesis of an alkaloid 394[335]. The intramolecular coupling of benzoyl-A-methylindole affords 5-methyl-5,10-dihydroindenol[l,2-b]indol-10-one (395) in 60% yield in AcOH[336]. Staurosporine aglycone (396) was prepared by the intramolecular coupling of an indole ring[337]. 

Acyl halides are intermediates of the carbonylations of alkenes and organic-halides. Decarbonylation of acyl halides as a reversible process of the carbo-nylation is possible with Pd catalyst. The decarbonylation of aliphatic acid chlorides proceeds with Pd(0) catalyst, such as Pd on carbon or PdC, at around 200 °C[109,753]. The product is a mixture of isomeric internal alkenes. For example, when decanoyl chloride is heated with PdCF at 200 C in a distillation flask, rapid evolution of CO and HCl stops after I h, during which time a mixture of nonene isomers was distilled off in a high yield. The decarbonylation of phenylpropionyl chloride (883) affords styrene (53%). In addition, l,5-diphenyl-l-penten-3-one (884) is obtained as a byproduct (10%). formed by the insertion of styrene into the acyl chloride. Formation of the latter supports the formation of acylpalladium species as an intermediate of the decarbonylation. Decarbonylation of the benzoyl chloride 885 can be carried out in good yields at 360 with Pd on carbon as a catalyst, yielding the aryl chloride 886[754]. 

The 0- and -monochloro- and 2,4- and 3,4-dichlorobenzotrichlorides are iatermediates ia the manufacture of the corresponding chlotinated benzoic acids and benzoyl chlorides. Fluotination of the chlotinated benzotrichlorides produces the chlotinated benzotrifluorides, iatermediates ia the manufacture of dinitroaniline and diphenyl ether herbicides (76). 

A similar regiospecific [2 -I- 2] cycloaddition across a C=S group occurred when benzoyl isothiocyanate (436) and 2,3-diphenyl-1-azirine were heated in refiuxing benzene for 12 hours. The product obtained was shown to be (438) and an intermediate such as (437) could also be involved in this cycloaddition (74JOC3763). In contrast, thiobenzoyl isocyanate added in a [4-1-2] fashion, and after ring expansion gave a thiadiazepine derivative. 

Isoxazoles largely undergo photochemical isomerization to azirines, which sometimes undergo a further thermal or photochemical reaction. 3,4,5-Triarylisoxazole (529) formed the 2,3-diphenyl-3-benzoylazirine (530) which underwent further reaction to the oxazole (531) 72JA1199). A small amount of the corresponding benzoyl ketenimine was also obtained. 

The treatment of 4-benzoyl-3-phenylisoxazolin-5-one with KOH generated 3,5-diphenyl-isoxazole-3-carboxylic acid via a ring-opened intermediate as shown in Scheme 69 (61CB1956). 

The treatment of 3-acylisoxazoles (438) with hydroxylamine hydrochloride gives furazan ketones (439). On the other hand, furazan ketones (439) rearrange to 3-acylisoxazoles (438) with a loss of hydroxylamine under the influence of a mineral acid. Thus, by refluxing phenacylphenylfurazan with concentrated alcoholic hydrogen chloride, 3-benzoyl-5-phenyl-isoxazole is formed similarly, phenyl(phenacylphenyl)furazan gives 3-benzoyl-3,5-diphenyl-isoxazole (62HC(17)1, p. 35). 

Benzhydryloxy ethoxy diphenyl silane (2). To a solution of benzoyl triphenylsilane 1 (2.5 g, 6 9 mmol) in benzene (25 mL) was added a solution of sodium ethoxide in ethanol (2 mL, 0 S mmol). The solution changed colour and after 11 min laded airmst completely. The solution was washed with water and the solvent removed in vacuum. The oily residue was dissolved in hot ethanol (15 mL) and cooled to give 2 (2 1 g, 74%), np 67-75 C Recrystallizatlon from ethanol gave 1 8 g (64%). mp 77-78,C... 

Many stilbenelike thiophene compounds have been prepared for a study of estrogenic activity, especially by Buu-Hoi et al. Thiophene derivatives of nonhydroxylated stilbene types showed no significant activitywhereas weak estrogenic activity was found in 5-acetyl-, 5-propionyl-, and 5-benzoyl-2-(-stilbenyl)thiophene. 1-Bromo-l,2-diphenyl-2-(5-bromo-2-thienyl)ethylene (258) was found to inhibit body growth and to produce extensive testicular atropy in male rats. A thiophene analog of estrogenic isoflavones (259)... 

The preparation of 82, m.p. 169°, was accomplished by N-benzoylation and ring cleavage of 4,4 -diphenyl-5-oxo-J -l,2,3-tri-azoline (84) followed by ring closure [Eq. (39)]. This appears to be the only known example of an oxazolone of this type. 

Drefahl and Horhold discussed the mechanism of N 0 acyl migration in A -benzoyl-l,2-diphenyl-3-aminopropanols. The migration does not seem to be possible in the erythro isomer as it would give an intermediate tetrahydro-1,3-oxazine with a bulky phenyl group in axial position. Consequently the erythro isomer is cyclized with inversion to form 2,5,6-triphenyl-5,6-dihydro-l,3-4 -oxazine... 

The bicyclic oxepin 8//-3-oxacyclohept[d]oxepin-8-one dissolved in trifluoroacetic acid undergoes a rearrangement to the expected phenol derivative 1. Substituents in the 2- and/or 7-position of the oxepin part, however, give rise to the formation of l-acylazulen-6-ols 2 by ring contraction.148 The 2,7-diphenyl derivative affords a mixture of l-benzoyl-2-phenylazulen-6-ol (37%), l-benzoyl-2-phenylazulen-6(l//)-one (35%), and 2-phenylazulen-6-ol (23%), which was presumably formed via the azulenone and a shift of the benzoyl substituent to the oxygen. 

Highly substituted dimethyl 2,4-diphenyl-3-benzoxepin-l,5-dicarboxylate was converted by irradiation to an indene derivative 4 which had lost one benzoyl group by acidic hydrolysis.146... 

The thermolysis of 4-azidophenyl methyl ketone in morpholine at 170°C yields a mixture of the expected 5-acetyl-2-morpholino-3f/-azepine (33) and 6-acetyl-2-morpholino-3//-azepine (34), the product of a unique and totally unexpected thermal rearrangement of the 5-acetyl derivative.119 Similar results can be obtained in hot piperidine, whereas thermolysis of 4-azido-diphenyl ketone under similar conditions yields only the 6-benzoyl-2-(cycloalkylamino)-3//-azepines (7-18%) accompanied by much tar. 

Dibenz[c 1c ]azepine (32 a) is obtained by acid-mediated cyclization of 2 -(aminomethyl)bi-phenyl-2-carbaldehyde (31 a), which is generated in situ by reduction of the oxime acetal 30a.85 The acetyl 30 a and benzoyl 30c oximes behave similarly and give the dimethyl and diphenyl derivative 32 b and 32 c, respectively. 

Diphenyl ketone benzoyl benzene phenyl ketone diphenyl-methanone alpha-oxodiphenylmethane alpha-oxoditane... 

Ebenfalls gute Ausbeuten sind bei der Hydrodimerisierung von 2- und 3-Acetyl-pyri-din6 bzw. 2-Benzoyl-thiophen7 zu erzielen. Praktisch quantitativ verlauft die Elektrolyse von 6-Oxo-3,3-diphenyl-cyclohexadien-(l,4) zu 6,6 -Dihydroxy-3,3,3, 3 -tetraphenyl-6,6 -bi-cyclohexadien -(1,4)-y Is ... 

N-Diphenylmethylen- 374 N-Diphenylmethylen-O-aminocarbonyl- 612 N-[l,3-Diphenyl-propyl-(2) - 374 N-[l,3-Diphenyl-propyliden-(2)]- 374, 377, 380 N-(4-Halogen-phenyI)- 683 N-Heptyl- 375 N-Heptyl-N-acetyl- 376 N-Heptyliden- 375 N-Hcptyliden-O-acetyl- 376 0-(2-Hydroxy-athyl)-N-athoxycarbonyl- 133 N-(4-Hydroxy-phenyl)- 683 0-(2-Hydroxy-l-phenyl-athyI)-N-athoxycarbonyI-aus 0-(ci-AthoxycarbonyI-benzyl)-N-athoxycar-bonyl-hydroxylamin und Lithiumalanat 133 N-Isopropyl- 682 N-Isopropylidcn- 613 N-Methyl- 133, 682 O-Methyl-N-bcnzyliden- 377 O-Methyl-N-benzyliden- 375 0-Methyl-N-(4-chlor-benzyl)- 375 0-Methyl-N-(4-chlor-benzyliden)- 375 N-Methy -N,0-diacetyI- 682 N-(4-Methyl-phenyl)- 683 0-McthyI-N-( 1 -phenyl-athyliden)- 375 N-(4-Methylthio-phenyl)- 684 N-(4-Nitro-benzyl)- 374 N-[4-Nitro-benzyliden - 374, 377 N-(2-Nitro-phenyl)- 562 N-(4-Nitro-phenyl)- 682 N-Nitroso-N-cyclohexyl- 697 N-Octyl- 374 N-Octyl-(2)-N-acetyl- 376 N-Octyliden- 374 N-0ctyliden-(2)-0-acctyl- 376 N-(Pentafluor-phenyl)-0,N-diacetyl- 697 N-Phenyl- 474, 481, 682, 783 N-Phenylacetyl-O-benzoyl- 265 N-(l-Phenyl-athyl)- 374 N-(l-Phenyl-athyl)-N-acetyl- 376 N-(l-Phenyl-athyliden)-374, 613 N-( l-Phenyl-athyliden)-0-acetyl- 376 N-[ 1 -Phenyl-buten-( 1 )-yl-(3)-iden]- 582 N-f4-Phenyl-butyl-(2)-iden]- 581 N-Phcnyl-N,0-diacetyl- 682 N-(4-Phenylthio-phenyl)- 684 N-Propyl-N-cyclohexyl- 376 N-Propyl-N-isopropyl- 376 O-Sulfonyl- 481 N-(4-Sulfonyl-phenyI)- 683 N-(2-Vinyl-phenyl)- 698... 

If the ligand X2 in a pentacoordinate triorganotin compound is potentially bidentate, such as the anion of l,3-diphenyl-l,3-propanedione or ofiV-benzoyl-N-phenylhydroxylamine, the tin atom is constrained to a cis-RsSnXj type of geometry, e.g., the triphenylstannyl derivatives of... 

Ethers are unaffected by sodium and by acetyl (or benzoyl) chloride. Both the purely aliphatic ethers e.g., di-n-butyl ether (C4H, )30 and the mixed aliphatic - aromatic ethers (e.g., anisole C3HSOCH3) are encountered in Solubility Group V the purely aromatic ethers e.g., diphenyl ether (C,Hj)20 are generally insoluble in concentrated sulphuric acid and are found in Solubility Group VI. The purely aliphatic ethers are very inert and their final identification may, of necessity, depend upon their physical properties (b.p., density and/or refractive index). Ethers do, however, suffer fission when heated with excess of 67 per cent, hydriodic acid, but the reaction is generally only of value for the characterisation of symmetrical ethers (R = R ) ... 

Poly(methyl 3-(l-oxypyridinyl)siloxane) was synthesized and shown to have catalytic activity in transacylation reactions of carboxylic and phosphoric acid derivatives. 3-(Methyldichlorosilyl)pyridine (1) was made by metallation of 3-bromopyridine with n-BuLi followed by reaction with excess MeSiCl3. 1 was hydrolyzed in aqueous ammonia to give hydroxyl terminated poly(methyl 3-pyridinylsiloxane) (2) which was end-blocked to polymer 3 with (Me3Si)2NH and Me3SiCl. Polymer 3 was N-oxidized with m-ClC6H4C03H to give 4. Species 1-4 were characterized by IR and H NMR spectra. MS of 1 and thermal analysis (DSC and TGA) of 2-4 are discussed. 3-(Trimethylsilyl)-pyridine 1-oxide (6), l,3-dimethyl-l,3-bis-3-(l-oxypyridinyl) disiloxane (7) and 4 were effective catalysts for conversion of benzoyl chloride to benzoic anhydride in CH2Cl2/aqueous NaHCC>3 suspensions and for hydrolysis of diphenyl phosphorochloridate in aqueous NaHCC>3. The latter had a ti/2 of less than 10 min at 23°C. 

Various thiourea ligands have been used in the synthesis of mixed ligand complexes. A series of complexes [NiQ2L2] (HQ = ethylacetoacetate, L = thiourea, allyl-, benzoyl-, methyl-, diphenyl-thiourea) have been prepared. The complexes are all paramagnetic (/i = 3.02-3.27/iB) and have been assigned tra 5-octahedral structures.1014... 

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