2,2’-biphenyldiyl-

Dimethyldibenzotellurophene. Powder tellurium (0.94 g 7.4 mmol) is thoroughly mixed with 2.61 g (6.1 mmol) of pure 4,4-dimethyl-2,2 -biphenyldiyl mercury, the mixture is placed into a sublimation apparatus equipped with a cold finger, and slowly heated under vacuum in a metal bath to 260-270°C. Colourless needles begin to sublime at 228°C. The temperature is held at 260°C for 12 h. The sublimate is recrystallized from a mixture of 300 mL of methanol and 10 mL of carbon tetrachloride. Yield 1.38 g (79%) m.p. 158°C. Dibenzotellurophene was similarly obtained in 82% yield. 

Mit Salzsaure, Jod oder Methyljodid erhalt man das Ausgangs-Phosphonium-Kation zuruck" 3. Mit Basen in Gegenwart von Ethanol oder Wasser entsteht 5-(2-Biphenylyl)-(dibenzophosphol), mit Butyllithium in THF bei -70° Bis-[2,2 -biphenyldiyl]-butyl-phosphoran31 32 (s.a. S. 891). 

Bis-[2,2 -biphenyldiyl]-phosphoniumjodid ergibt mit Natriumamid in THF Amino-bis-[2,2 -biphenyldiylj-phosphoran (43%)11 ... 

Biphenyldiyl)-phenyl-(2-phenyl-naphthalin-l,2 iyl)-phosphoranf 31% Schmp. 168-170°... 

Auf ahnliche Weise erhalt man 2,2 -Biphenyldiyl-[4,4 bis-(dimethylamino)-2,2 -biphe-nyl-diyl]-phenyl-phosphoran (55%)16-... 

Ris-[2,2 -biphenyldiyl]-butyl-phosphoran15 30 0,55 g (1,33 mmol) Bis-[2,2 -biphenyldiyl]-phenyl phosphoran werden 1 Stde. mit 0,26 g (4 mmol) Butyllithium in 10m/ Diethylether geriihrt. Dann wird hydrolysiert und der Riickstand abfiltriert, mit Wasser gcwaschen und aus Petrolather umkristallisiert Ausbeute 0,43 g (83%) Schmp. 177,5-178° (schwache Zers.). 

Bis-[2,2 -biphenyldiyl]-l-hcxinyl-phosphoran Bis- 2,2 biphenyldiyl]-phenyl-phosphoranIS IS 95°/0... 

His-[2,2-biphenyldiyl]-[2,6-bis-(hydroxyniethyl)-phenyl]-phosphoran22 3,8 g (5,93 mmol) Bis-[2,2 -biphenyl-diyl]-[2,6-bis- (2-tetrahydropyranyloxymethyl)- phenylj-phosphoran werden zusammen mit 1,5 mol konz. Salz-saure 2 Stdn. in einem Gemisch aus 250 ml Chloroform und 100 ml Ethanol auf 50° gehalten. Danach wird das Gemisch mit 7 g Natriumhydrogencarbonat in 150 ml Wasser geschiittelt. 

Pentaphenylphosphoran zerfallt beim Erhitzen auf 130° zu Triphenylphosphan, Benzol, Biphenyl und 2,2 -Biphenyldiyl-phenyl-phosphan2S ... 

Die Thermolyse spirocyclischer Pentaaryl- und Alkyl-tetraaryl-phosphorane fiihrt bei kleinem Rest R zu tert. Phosphanen der Phosphonan-Reihe (S. 907), bei gro8em Rest zu tert. Phosphanen mit 2,2 -Biphenyldiyl-Geriist (s.S. 893) l7,2l ... 

Bis-[trifltiormethyl]-tetrafluor- E2, 903 Difluor-tetrakis-[trifluormethyl]- E2, 903 1,4-Dioxanium-methyl- E2, 605 Ethyl-(2-trimethylammoniono-ethyl)- E2, 506 Imidazolium-diethyl- E2, 507 Isopropyl-(2-trimethylammoniono-cthyl)- E2, 506 Kaliuin-tris-[2,2 -biphenyldiyl]-... 

Bis-[4,4 -dimethyl-2,2 -biphenyldily]- E2, 904 Bis-[4-methy[-2,2 -biphenyldiyl]- E2, 904 (Bis-[trimcthylsiIyI]-amino)-diniethyl-phenyl- ... 

Alkoxy-methyl-trifluor- E2, 858 Alkoxy-phenyl-trifluor- E2, 858 Alkoxy-tetraphenyl- E2, 887 Alkyl-tctrachlor- E2, 857 Alkyltriazenyliden-triamino- E2, 826 Allylamino-difluor-difluormethyl-hydro- E2, 836 Allyl-tetrachlor- XII/1, 343 Amino-bis-[2,2 -biphenyldiylJ- E2, 883 Amino-difluor-hydro-organo- E2, 836 Amino-organo-trifluor- E2, 859, 860 Aryl-(l-hydroxy-alkyl)-trifluor- E2, 864 Aryl-tetrachlor- E2, 857 Aryltriazenyliden-triamino- E2, 826 Benzyl-bis-[2,2 -biphenyldiyl]-... 

Bis-[2,2 -biphenyldiyl]-phosphonium-[bis-(2,2 -bi-phenyldiyl)-l,2-phenylendioxy)- E2, 905 Bis-[phenylcndioxy]-tert.-butyl-hydro- E2, 905 Bis-[phenylendioxy]-hydro-methyl- E2, 905 Bis-[phenylendioxy]-hydro-(pentafluor-phenyl)- E2, 905... 

Dimethyl-2,2 -biphenyldiyl 4,4 -Dimethyl-2 -bromo-2-biphenyl Telluronium Bromide1 200 mg (0.41 mmol) of bis[4,4 -dimethyl-2,2 -biphenyldiyl] tellurium are suspended in 20 ml of carbon tetrachloride, the suspension is cooled in an ice/salt bath, and bromine is added dropwise with stirring until the brown color of bromine persists. The precipitate is filtered, washed with carbon tetrachloride, and dried yield 226 mg (85%) m.p. 278° (from dichloromcthane/ diethyl ether). 

Biphenyldiyl 2-bromo-2 -biphenyl telluronium bromide (m.p. 264°, yield 79%) and the corresponding iodine compound (m.p. 265c, yield 63%) were similarly prepared2,3. Tetraphenyl tellurium transferred an anionic phenyl group to benzaldehydc and triphenyl boron yielding triphenyl telluronium salts4. 

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