Bis 2,2 -biphenyldiyl

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 ... 

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... 

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... 

Tetramethoxy tellurium and hexamethoxy tellurium reacted with 2,2-dilithiobiphenyI to give bis[2,2 -biphenyldiyl] tellurium3 1. A trisp -biphenyldiyl] tellurium was not detected. 

Bis[2,2 -biphenyldiyl] Tellurium3 A solution of 66.4 mmol of 2,2 -dilithiobiphenyl in 250 ml of anhydrous diethyl ether is prepared from 26.9 g (66.4 mmol) of diiodobiphenyl and 132.8 mmol of butyl lithium and cooled to — 70°. 8.17 g (32.5 mmol) of tetramethoxy tellurium are dissolved in 300 ml of anhydrous diethyl ether and this solution is added dropwise to the cooled, stirred solution of 2.2 -dilithiobiphenyl. The resultant mixture is allowed to warm to 20° and is then heated under reflux for 60 h. The mixture is cooled to — 15° and unreacted lithium compound is destroyed by addition of methanol. The precipitate is collected, washed with water and then with diethyl ether yield 6.9 g (49%) m.p. 205-213° (dec. from tetrahydrofuran). 

Bis[2,2 -biphenyldiyl tellurium was similarly obtained in 36% yield. Because this compound is not as easily converted by water to the telluronium hydroxide as tetraphenyl tellurium is converted, the reaction mixture is poured into ice/water and the precipitated solid recrystallized from acetone2. 

Biphenyldiyl tellurium tosylimide, obtained from 2,2 -biphenyldiyl tellurium and Chloramine-T, reacted with 2,2 -dilithiobiphenyl to produce bis[2,2 -biphenyldiyl tellurium2. 

Bis[2,2 -biphenyldiyl] Tellurium2 2.27 g (10 mmol) of chloramine-T are added to 80 ml of letrahydrofuran and 2.8 g (10 mmol) of 2,2 -biphenyldiyl tellurium are added to the stirred solution. The mixture, which contains a white precipitate, is heated under reflux for 1 h and is then stirred at 20° overnight. The precipitate is filtered oflf under nitrogen and the solid is immediately suspended in 400 ml of diethyl ether. The suspension is cooled to — 70° and 2,2 -dilithiobiphenyl dissolved in 400 ml of anhydrous diethyl ether are added. The mixture is allowed slowly to warm to 20° and is then stirred under nitrogen at 20 for 8 days. The mixture is poured into ice/water, the precipitate is collected, washed with diethyl ether, and recrystallized from benzene yield 1.9 g (44%) m.p. 205-213° (dec.). 

Bis[2,2 -biphenyldiyl] TeDiirium3 A solution of 6.92 mmol of 2,2 -dilithiobiphenyl in 100 m/of diethyl ether is prepared under nitrogen and 1.46 g (3.46 mmol) of 2,2 -biphenyldiyl methyl telluronium iodide are added. The mixture is stirred at 20° overnight and the crystalline product is filtered under nitrogen yield 0.78 g... 

The reaction between 2,2 -biphenyldiyl 2-iodo-2 -biphcnyl telluronium iodide and phenyl lithium produced bis[2,2 -biphenyldiyl] tellurium2. 

Tetrabutyl tellurium and bis[2,2 -biphenyldiyl] arsonium or phosphonium iodide formed tributyl telluronium iodide and butyl bis[2,2 -biphenyldiyl] arsenic or phosphorus1. 

Bis[2,2 -biphenyldiyl] tellurium and at least four equivalents of butyl lithium react to give tetrabutyl tellurium. Butyl triphenyl tellurium is similarly converted to tetrabutyl... 

Heating bis [2,2 -biphenyldiyl] tellurium under vacuum in a sublimation apparatus at 260° for 25 min produced dibenzotellurophene in 76% yield2. 

Bromine, iodine, hydrogen chloride, water, and methyl iodide cleave one Te-C bond in bis[2,2 -biphenyldiyl] tellurium. Telluronium salts of dibenzotellurophene were isolated2,3. 

---