2-benzylidene-4-phenyl

Protonation of sodium phenylethynetellurolate by hydrogen chloride in diethyl ether led to 1,3-ditelluretane derivatives2 4 via cyclodimerization of the tellurol. 3,5-Dibenzylidene-1,2,4-tritellurolane was also isolated3. Protonation of sodium phenylethynetellurolate with trifluoroacetic acid affords 2-benzylidene-4-phenyl-l,3-ditellurole5. 

An alternative method to form the ditellurole ring employs the dimerization of ethynyltellurolates. The products are 2/7-2-alkylidene-l,3-ditelluroles2. Telluroketenes are likely intermediates in these reactions3. When phenylethynetellurolate was treated with trifluoroacetic add, cis- and trans-2-benzylidene-4-phenyl-2H-l, 3-ditelluroles were isolated in low yields2. 

The cis- or /ram-isomers of 2-benzylidene-4-phenyl-2H-l,3-ditellurole were transformed to a 1 1 mixture of the cis- and frans-compounds upon treatment with a trace of acid1. The cis- and frreacted with isopentyl nitrite to produce trans-2-[nitroso(phenyl)methylene]-4-phenyl-2H-l,3-ditellurole and with benzenediazoni->um tetrafluoroborate in dimethylformamide to give cis-2-[benzeneazo(phenyl)methylene -4 -phenyl-2H-1,3-ditellurole1. 

Ditelluroles, 2-benzylidene-4-phenyl-nitrosation and diazo-coupling, 58, 77 synthesis, 58, 50... 

Dibenzylidene-l, 3-ditelluretane was prepared by reacting tellurium with sodium phenylacetylide and acidifying the resulting mixture, which contains sodium phenylethyne-tellurolate, with hydrogen chloride in diethyl ether The structure of the compound was confirmed by single crystal X-ray analysis . The earlier reported formulation of this compound as 2-benzylidene-4-phenyl-l,3-ditelluracyclopent-4-ene is incorrect. ... 

A methanolic soln. of equimolar amounts of 2-benzylidene-4-phenyl-3-oxazolin-5-one and aniline treated with a few drops of trimethylamine, and refluxed 2 hrs. methyl -phenylamino-a-phenylacetaminophenylacetate. Y almost 100%. F. e. s. A. Mustafa et al.. Tetrahedron 20, 1063 (1964). 

Scheme 11.45 shows a proposal for the transition state involved in a related Lewis acid catalyzed cycloaddition where a disubstituted dipolarophile is used and endo/exo issues are examined. By coordination of the bulky titanium Lewis acid catalyst, the a-carbon of the acceptor becomes sterically more hindered, disfavoring exo-approach, which involves a serious steric interaction of the benzylidene phenyl moiety with the ligands on the titanium ion. Accordingly, the endo-cycloadduct is the only product observed. 

Semi- carbazone °C Benzylidene Phenyl-derivative hydrazone °C °C p-Nitro- Other derivatives °C phenyl- hydrazone °C ... 

Aurones (Phe C40(=0)=CH-Phe). Aurones (2-benzylidenebenzofuranones) derive from oxidation and cyclization of chalcone precursors to yield the corresponding benzofura-none (benzene fused with a five-membered furanone ring) Phenyl-CO- CH=CH—Phenyl + O2 — Benzofuranone = CH-Phenyl. Various aurones inhibit iodothyronine deiodinase, namely (numbering 1-9 in the bicyclic benzofuranone and 1 -6 in the benzylidene phenyl) aureusidin (4,6,3, 4 -tetrahydroxyaurone), bracteatin (4,6,3, 4, 5 - pentahydroxyaurone), maritimetin (6,7,3, 4 -tetrahydroxyaurone) and sulfuretin (6,3, 4 -trihydroxyaurone). 

E18, 575 f. (Acridin/LiAlH4) Amin Benzyliden-phenyl- E14b, 228 (CH-NHR - C = NR), 249 (R-CHO + R-N02/CO) 2H-Azirin 3-Methyl-2-(l-naphthyl)-E16c, 323 (N-Sulfonyloxy-amidinen), 324 (aus Hydrazo-nium-Salzen)... 

Gattermann has obtained direct proof of the intermediate formation of phenyl-hydroxylamine by adding benzaldehyde to the solution at the beginning of the electrolysis. He was thus able to isolate a condensation product of phenyl-hydroxylamine with benzaldehyde. In this way he obtained benzylidene-phenyl-hydroxylamine,... 

Pyridine and chloroform added under Ng to a-benzylidene- -phenyl butenolide and thiolacetic acid, refluxed 80 min. 4-benzylidene-2-phenyl-Z 2-thiolen-5-one. Y 56.3%. F. e. s. Y. S. Rao and R. Filler, J. Heterocyclic Ghem. 7,210 (1964). 

O-Benzylidene Phenyl 4,6-O-benzyli-dene-a-D-galactopyranoside C,9H2o06 344.363... 

Benzyl, 4,6-O-benzylidene Phenyl 2-0-benzyl-4,6-0-benzylidene fi-D-glucopyra noside... 

Oxazol-5(2H)-one, 2-benzylidene-4-methyl-tautomerism, 6, 186 Oxazol-5(2ff)-one, 2-methylene-isomerization, 6, 226 Oxazol-5(2H)-one, 2-trifluoromethyl-acylation, 6, 201 Oxazol-5(4ff)-one, 4-allyl-thermal rearrangements, 6, 199 Oxazol-5(4H)-one, 4(arylmethylene)-Friedel-Crafts reactions, 6, 205 geometrical isomerism, 6, 185 Oxazol-5(4ff)-one, 4-benzylidene-2-phenyl-configuration, 6, 185 photorearrangement, 6, 201 Oxazol-5(4ff)-one, 4-benzyl-2-methyl-Friedel-Crafts reactions, 6, 205 Oxazol-5(4ff)-one, 4-methylene-in amino acid synthesis, 6, 203 Oxazol-5(4ff) -one. 2-trifluoromethyl-hydrolysis, 6, 206 Oxazolones... 

The free selenazole hydrazines are solids, sometimes well crystallized compounds. They show the typical properties of hydrazines. Thus they reduce Fehling s solution on warming and liberate silver, even in the cold, from ammoniacal silver nitrate solution. Further, they react with carbonyl compounds for example, benzylidene hydrazones are formed with benzaldehyde. These are identical with the hydrazones formed by direct condensation from benzaldehyde selenosemicarbazone and the corresponding a-halogenocarbonyl compound. 2-Hydrazino-4-phenylselenazole has also been reacted with acetophenone. The 2-a-methylbenzylidenehydrazone of 4-phenyl-selenazole (2, K = CJl, R" = H, R" = NH—N CMe-aH ) forms golden yellow plates mp 171°C. ... 

Substitution of a phenyl residue in the 4-position of the selenazole ring causes only a minor alteration in the position of the absorption maximum. By contrast, the benzylidene compounds are markedly bathochromically shifted compared to the isopropylidene derivatives. Thus the absorption is caused by the whole of the conjugated system, which can be compared to that found in amino derivatives of... 

V-[2-(3-Phenylprop-2-ynyloxy)benzylidene]isopropylamine (the structure in ref 95 is incorrect) undergoes a cyclization reaction to A -isopropyl-4-phenyl-l-benzoxepin-5-amine (1, 52% yield) when treated with butyllithium. 2-(Phenylethynyl)benzofuranis formed as a byproduct (4%).95... 

R = H 3.5-Q-benzylidene-l-deoxy-2-C-phenyl-D-arabinitol yield 77% d.r. (39/40) 100 0 40 R = TBDMS 3,5-0-benzylidene-4-0-tert-butyldimethylsilvl-t-deoxy-2-C-phenyl-D-ribitol yield 89% d.r. (39/40) 0 100... 

More recently, other substituted benzylidene derivatives of the enantiomers of a-methyl-benzylamine have been converted with substituted benzaldehydes to the corresponding phenyl-glycinonitriles using sodium cyanide in aqueous methanol44. 

The method described above may be used for the preparation of a wide variety of butenolides substituted in the arylidene ring with either electron-withdrawing or electron-releasing substituents. y-Lactones such as a-benzylidene-7-phenyl-A 1 -bu-tenolide are isoelectronic with azlactones, but have received much less attention. Like the azlactone ring, the butenolide ring may be opened readily by water, alcohols, or amines to form keto acids, keto esters, or keto amides.7 a,-Benzylidene-7-phenyl-A3,1 -butenolide is smoothly isomerized by aluminum chloride to 4-phenyl-2-naphthoic acid in 65-75% yield via intramolecular alkylation. 

ESTER, 43, 100 BenzOpyrazole, 43, 69 3-Benzoylpropionic acid, condensation with benzaldehyde to give a-benzylidene-y-phenyl-A t-bu-tenolide, 43, 3... 

Analog erhalt man aus 5-Oxo-2-phenyl-4,5-dihydro-1,3-oxazol 2-Benzoylamino-athanol5 (88% d.Th.) und mit Lithiumalanat aus 5-Oxo-4-methyl-2-benzyliden-2,5-dihydro-1,3-oxazol 2-Phenylacetylamino-propanol (30% d.Th.)6. Calciumboranat reduziert 5-Oxo-2-phenyl-4-benzyliden-4,5-dihydro-1,3-oxazol zu oc-Benzoylamino-zimtal-kohol1. 

Brom-(bzw. 6-Jod)-l-phenyl-hexin-( 1) wird an Quecksilber in DMF/Tetrabutylam-moniumperchlorat zu Benzyliden-cyclopentan (24% d.Th.) cyclisiert4. 

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. 

Die Elektrolyse von 6-Brom(Jod)-l-phenyl-hexin-(l) liefert u.a. Benzyliden-cydopro-pan (max. 24% d.Th.)5. 

Benzyl-(4-chlor-benzyliden)- 664 Bis-[fluoracetyl]- 239 Bis-[2-fluor-athyl]- 239 (Bis-[4-methoxy-phenyl]-methyl)- 377 Bis-[2-methyl-propyl]- 358 Bis-[2-phenyl-2-cyan-vinyl]- 58 tert.-Butyl-(hydroxy-tert.-butyl)-... 

Phenyl-benzyliden- -oxid 537 (2-Phenyl-2-cyan-athyl)-bis-[2-phenyl-2-cyan-vinyl)- 581... 

Phenyl-1-acetyl- 258 2-(2-Phenyl-athyl)- 372 Phenyl-athyliden- 612 (l-Phenyl-athyliden)-aminocarbonyl- 612 Phenyl-benzyliden- 612 Phenyl-isopropyliden- 612 Tetraathyl- 259... 

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... 

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