Diphenyl Ditelluride1

[32294-60-3]  · C12H10Te2  · Diphenyl Ditelluride  · (MW 409.42)

(parent member of the diaryl ditellurides, useful reagents for the formation of alkyl, aryl, and vinyl tellurides by either nucleophilic, electrophilic, or radical pathways; alkyl and vinyl tellurides and especially alkyl 2-thienyl tellurides undergo very clean transmetalation reactions, providing alkyl and vinyl metal reagents;1 alkyl aryl tellurides give alkyl radicals with tributyltin hydride1)

Physical Data: mp 66-67 °C; d 2.23 g cm-3.

Solubility: sol acetone, chloroform, tetrachloromethane; moderately sol ether; slightly sol ethanol.

Form Supplied in: nonvolatile, orange crystals.

Preparative Methods: diaryl ditellurides are prepared by the action of aryllithium or arylmagnesium halides on tellurium powder followed by oxidation with air or with aqueous potassium ferricyanide.2 Electron-rich diaryl ditellurides (e.g. bis(2,4-dimethoxyphenyl) ditelluride3) are prepared by reaction of the arene with tellurium tetrachloride to give the aryltellurium trichloride followed by reduction with Na2S2O5.

Purification: crystallization from ethanol.

Handling, Storage, and Precautions: air stable; unknown toxicity. Use in a fume hood.

Arenetellurolates.

Diaryl ditellurides are reduced with Sodium wire in THF/DMF, Samarium(II) Iodide in THF/HMPA, or Sodium Borohydride in ethanol to give the powerfully nucleophilic arenetellurolates which take part in substitution reactions with alkyl, aryl, and benzyl halides (eq 1).4 PhTeTePh may also be reduced electrochemically or with sodium in liquid ammonia and the resulting PhTeNa used as an effective nucleophile in the SRN1 substitution of haloarenes.5 Substitution of iodoarenes to give mixed diaryl tellurides also takes place, with catalysis by Copper(I) Iodide, with benzenetellurolate formed from PhTeTePh and NaBH4 in HMPA.6 Acyl chlorides react with benzenetellurolate derived from NaBH4 and PhTeTePh in THF/EtOH to give acyl aryl tellurides, which are effective precursors of acyl radicals7 and acyl lithiums.8 Trapping with Chlorotrimethylsilane gives PhTeSiMe3 which, in the presence of Zinc Iodide, reacts with lactones to give Me3Si esters of o-phenyltelluro acids and with cyclic ethers to give o-phenyltelluro alcohols as their Me3Si ethers.9

Reduction with Diisobutylaluminum Hydride gives PhTeAl(i-Bu)2 (see also Diisobutylaluminum Phenyl Selenide), which undergoes conjugate addition to a,b-unsaturated carbonyl compounds. The intermediate aluminum enolates react with aldehydes to give aldols. Subsequent treatment with m-Chloroperbenzoic Acid gives a-alkylidene aldols (eq 2).10 PhTeAl(i-Bu)2 is also an excellent nucleophile toward acetals, alkyl sulfonates, and oxiranes.11

Electrophilic Species.

Diaryl ditellurides react with Grignard and organolithium reagents to give alkyl aryl tellurides. The reaction has been used to titrate these organometallics.12 Activation of PhTeTePh with Bromine and t-Butyl Hydroperoxide (TBHP) in alcohols provides electrophilic reagents for alkoxytelluration of alkenes.13 PhTeTePh readily takes part in telluro-cycloetherifications and lactonizations of hydroxy and carboxy alkenes on activation with p-Nitrobenzenesulfonyl Peroxide (NBSP) (eq 3).14

Radical Reactions.

Diaryl ditellurides are very efficient traps for alkyl radicals generated by a variety of means, as in eq 4.15 PhTeTePh adds across alkynes on initiation with Azobisisobutyronitrile (AIBN) to give 1,2-bis(phenyltelluro)-alkenes.16 Vinyl-, allyl- and alkylmercurials undergo photostimulated radical substitution with PhTeTePh to give the corresponding phenyl tellurides.17

Reductions.1

1,2-Dibromides are converted to alkenes with a catalytic amount of ditelluride and NaBH4.18 A variation is the generation of o-quinodimethane from a,a-dibromo-o-xylene with PhTeNa.19 NaBH4 reduces nitrobenzene to azoxybenzene in aqueous methanolic NaOH at rt with a catalytic amount of PhTeTePh. At reflux the product is azobenzene.20

Related Reagents.

Diphenyl Diselenide; Diphenyl Disulfide.


1. (a) Petragnani, N.; Comasseto, J. V. S 1986, 1; 1991, 793, 897. (b) Engman, L. ACR 1985, 18, 274. (c) Irgolic, I. R. The Organic Chemistry of Tellurium; Gordon and Breach: New York, 1974. (d) Toshimitsu, A.; Uemura, S. In The Chemistry of Organic Selenium and Tellurium Compounds; Patai, S.; Rappoport, Z., Eds.; Wiley: New York, 1987; Vol. 2, Chapter 14.
2. (a) Engman, L.; Cava, M. P. OM 1982, 1, 470. (b) Engman, L.; Persson, J. JOM 1990, 388, 71 and references therein.
3. Tarbell, D.; McCall, M. JACS 1952, 74, 48.
4. (a) Uemura, S.; Fukuzawa, S.; Yamauchi, T.; Hattori, K.; Mizutaki, S.; Tamaki, K. CC 1984, 426. (b) Fukuzawa, S.; Niimoto, Y.; Fujinami, T.; Sakai, S. HC 1990, 491. (c) Uemura, S.; Fukuzawa, S.; Ohe, K. TL 1985, 26, 921
5. (a) Degrand, C.; Prest, R.; Compagnon, P. JOC 1987, 52, 5229. (b) Pierini, A.; Rossi, R. JOC 1979, 44, 4667. (c) Pierini, A.; Peñeñory, H.; Rossi, R. JOC 1984, 49, 486.
6. Susuki, H.; Abe, H.; Ohmasa, N.; Osuka, A. CL 1981, 1115.
7. (a) Chen, C.; Crich, D.; Papadatos, A. JACS 1992, 114, 8313. (b) Chen, C.; Crich, D. TL 1993, 34, 1545.
8. Hiiro, T.; Morita, Y.; Inoue, T.; Kambe, N.; Ogawa, A.; Ryu, I.; Sonoda, N. JACS 1990, 112, 455.
9. Sasaki, K.; Aso, Y.; Otsubo, T.; Ogura, F. TL 1985, 26, 453.
10. Sasaki, K.; Aso, Y.; Otsubo, T.; Ogura, F. CL 1989, 607.
11. Sasaki, K.; Mori, T.; Doi, Y.; Kawachi, A.; Aso, Y.; Otsubo, T.; Ogura, F. CL 1991, 415.
12. Aso, Y.; Yamashita, H.; Otsubo, T.; Ogura, F. JOC 1989, 54, 5627.
13. (a) Uemura, S.; Fukuzawa, S.; Toshimitsu, A. JOM 1983, 250, 203. (b) Uemura, S.; Fukuzawa, S.; Toshimitsu, A.; Okano, M. TL 1982, 23, 1177.
14. Yoshida, M.; Suzuki, T.; Kamigata, N. JOC 1992, 57, 383.
15. (a) Abe, T.; Aso, Y.; Otsubo, T.; Ogura, F. CL 1990, 1671. (b) Barton, D. H. R.; Bridon, D.; Zard, S. Z. H 1987, 25, 449.
16. Ogawa, A.; Yokoyama, K.; Obayashi, R.; Han, L.-B.; Kambe, N.; Sonoda, N. T 1993, 49, 1177.
17. (a) Russel, G.; Hershberger, J. JACS 1980, 102, 7603. (b) Russel, G.; Tashtoush, H.; JACS 1983, 105, 1398. (c) Russel, G.; Ngoviwatchai, P.; Tashtoush, H.; Pla-Dalmau, A.; Khanna, R. JACS 1988, 110, 3530.
18. Engman, L.; Byström, S. E. JOC 1985, 50, 3170.
19. Kambe, N.; Tsukamoto, T.; Miyoshi, N.; Murai, S.; Sonoda, N. BCJ 1986, 59, 3013.
20. (a) Ohe, K.; Takahashi, H.; Uemura, S.; Sugita, N. CC 1988, 591. (b) Ohe, K.; Uemura, S.; Sujita, N. JOC 1989, 54, 4169.

David Crich & Qingwei Yao

University of Illinois at Chicago, IL, USA



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