2, 3-Diphenyl-7-benzylidene

A.2.7 2,3-Diphenyl-7-benzylidene-3,3a,4,5,6,7-hexahydro-2H-indazole and 1,3-diphenyl-7-benzylidene-3,3a,4,5,6, 7-tetvahydroindazole... 

To a suspension of 1.7 g (6.2 mmol) 2,6-dibenzylidenecyclohexanone 1 in 70 ml of ethanol 0.7 ml (6.2 mol) of phenylhydrazine was added and the mixture was refluxed for 2-3 h until the initial ketone had completely disappeared, then the solvent was evaporated and the residue was diluted with benzene and chromatographed on an A1203 column with benzene (Scheme A. 14). The first fraction eluted exhibited luminescence and contained 2,3-diphenyl-7-benzylidene-3,3a,4,5,6,7-hexahydro-2//-indazole 2. After evaporation of the solvent and crystallization from a mixture of ethanol and benzene, 1.35 g (60%) of 2 with a melting point of 157-159°C was obtained. The next fraction was evaporated and 0.56 g (25%) of l,3-diphenyl-7-benzylidene-3,3a,4,5,6,7-tetrahydroindazole 3 with a melting point of 175-177°C was obtained. 

In this example, the catalyst was prepared in situ from (dba)2Pd, CHC13 (dba = diphenyl-benzylidene acetone) and triphenylphosphane. The single product results from axial attack of the TMM unit onto the ketone. 

The primary dihydro product (3) can be obtained by reduction of the quinoid (4). Compound 3, in which Ri = CeH= -CH= and Rj CgH can also be obtained by direct condensation of benzylidene selenosemicar-bazone with 2.3-dibromo-l,4-diphenyl-l,4-butanedione (Scheme 49). 

H-Pyran, 2-alkoxy-4-methyl-2,3-dihydro-conformation, 3, 630 4H-Pyran, 2-amino-IR spectra, 3, 593 synthesis, 3, 758 4H-Pyran, 4-benzylidene-synthesis, 3, 762 4H-Pyran, 2,3-dihydro-halogenation, 3, 723 hydroboration, 3, 723 oxepines from, 3, 725 oxidation, 3, 724 reactions, with acids, 3, 723 with carbenes, 3, 725 4H-Pyran, 5,6-dihydro-synthesis, 2, 91 4H-Pyran, 2,6-diphenyl-hydrogenation, 3, 777 4H-Pyran, 6-ethyl-3-vinyl-2,3-dihydro-reactions, with acids, 3, 723 4H-Pyran, 2-methoxy-synthesis, 3, 762 4H-Pyran, 2,4,4,6-tetramethyl-IR spectra, 3, 593 4H-Pyran, 2,4,6-triphenyl-IR spectra, 3, 593... 

The primary dihydro product can be obtained by reduction of the quinonoid dyestuff. Thus for example 4,4 -diphenyl-2,2 -dioxo-A -biselenazol-5,5 -inylidene bis-benzylidenehydrazone could be reduced to 4,4 -diphenyl-2,2 -benzylidene hydrazino-5,5 -biselenazoie (13). This... 

With the synthesis of the benzylidene hydrazones of selenazoles, it was possible to prepare formazans containing a selenazole ring. Of the compounds already described (Section I,C,1), 2-benzylidene-hydrazino-4,5-diphenyl- and 2-benzylidenehydrazino-4-methyl-5-carb-ethoxy-selenazole were used to couple with diazonium salts in order... 

Ebenfalls iiber einen Dreiring (Bis-[benzyliden]-cyclopropanon) verlauft die Reduktion von 2,4-Dibrom-3-oxo-l,5-diphenyl-l,4-pentadien in DMF [isoliert wild3-Oxo- 1,5-di-phenyl-penten-(4)-in-( 1)]. In Methanol hingegen bildet sich 5-Oxo-2,3-diphenyl-cydo-penten3. 

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... 

Reactions of PdCl2(PhCN)2 with (5)- VV,VV -bis[2-(diphenylphosphino)benzylidene]-2,2 diimino-1,1 -binaphthylene and (5,5, )-iV,iV -bis[2-(diphenylphosphino)benzylidene]-1,2-diimino-1,2-diphenyl-ethane give unexpected results, as shown in Scheme 10 593... 

Only a few reactions with bidentate ligands have been described. 32, reacting with the chiral carbohydrate derivative phenyl-4,6-o-(R)-benzylidene -2,3, 0-bis(diphenyl-phosphino-/ -D-glucopyranoside) (Ph-/ -glup), gave the compound [TcBr(CO)3 (Ph-/Tglup)] (56) in 53% yield. The complex was characterized by elemental analysis and i.r. spectroscopy [71]. Furthermore, reaction with dithio-... 

A derivative of the oxo form of a 3-hydroxyselenophene has been obtained by a quite different route.123 1,5-Diphenyl-1,4-pentadiyn-3-one (94) adds hydrogen selenide and gives a mixture of 2,6-diphenyl-1-seleno-y-pyrone (95) and 2-benzylidene-3-oxo-5-phenyl-2,3-dihydroselenophene (96). 

Sidky, M.M., Soliman, F.M., and Shabana, R., Organophosphorus compounds. XIV. Reaction of dialkyl phosphites and thiol acids with 4-benzylidene-l,2-diphenyl-3,5-pyrazolidinedione, Egypt. J. Chem., 15, 79, 1972. 

Conversely, activated methylene compounds undergo an addition reaction across the C=N bond of imines. For example, benzylic ketones react with benzylidene anilines to from P-aminoketones [35], whereas the analogous reaction of diphenyl-methylene-protected a-amino esters, and nitriles, produces a disastereomeric mixture of the A-protected a,p-diamino esters, and nitriles [36, 37]. 

The square-planar geometry (with slight tetrahedral distortion) of these derivatives can be proved by that of the related Rh(I) complex with 2,2/-bis [o-(diphenylphosphine)benzylidene]amine -6,6/-dimethyl-diphenyl, [Rh(PPNN)]+, Figure 23.26... 

Benzyliden-amino)-l, 3,4-oxadiazole reagieren als Azadiene mit Diphenyl-keten unter Cycloaddition zu 2,7-Diaryl-6,6-diphenyl-5-oxo-6,7-dihydro-5H-685 ... 

Bei der Elektrolyse eines 1 10-Gemisches von N-Benzyliden-anilin und 1,4-Dibrom-butan in Dimethylformamid in Gegenwart von Tetrabutylammonium-jodid an einer Quecksil-ber-Kathode entsteht durch reduktive Cyclokondensation 1,2-Diphenyl-piperidin1 ... 

Chloroform and toluene yield by this process dimethyl-9 10-ditolyl-9 10-dihydroanthracene using aluminium chloride, tetratolylethane is obtained (B., 14, 1530). Benzylidene chloride and toluene yield dimethyl-9 10-diphenyl-9 10-dihydroanthracene. 

When methyl 4,6-benzylidene-2-desoxy-a-D-galactoside (LXXXVI)126 was treated with phosphorus oxychloride in pyridine at —40°, followed by barium hydroxide,236 it gave amorphous barium methyl 4,6-benzyli-dene-2-desoxy-a-D-galactoside 3-phosphate (LXXXVII). If diphenyl-phosphoryl chloride [diphenylchlorophosphonate, (PhO)2POCl]236 240 in pyridine was used as the phosphorylating agent, then crystalline (methyl... 

Benzyliden-2,4-pentandion E2, 851 2-Alkoxy-3,5-diphenyl-2,3-dihydro- -2-oxid XII/1, 409... 

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