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Syntheses and Reactions of Hexavalent Organotellurium Compounds Bearing Five or Six Tellurium-Carbon Bonds

机译:带有五个或六个碲碳键的六价有机碲化合物的合成与反应

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摘要

A variety of hexaorganotellu-rium compounds,Ar_(6-n)(CH_3)_nTe [Ar=4-CF_3C_6H_4,n=0 (la),n=1 (3a),n=2 (trans-4a and cis-4a),n=3 (mer-5a),n=4 (trans-6a);Ph,n=0 (Ib),n=1 (3b),n=2 (trans-4b);4-CH_3C_6H_4,n=0 (1c),n=1 (3c),n=2 (trans-4c),n=4 (trans-6c);4-BrC_6H_4,n=0 (1d)] and Ar_5(R)Te [Ar=4-CF_3C_6H_4,R=4-CH_3OC_6H_4 (8);Ar=4-CF_3C_6H_4,R=vinyl (9),Ar=Ph,R-vinyl (10),Ar=4-CF_3C_6H_4,R-PhSCH_2 (11),Ar=Ph,R-PhSCH2 (12),Ar=4-CF_3C_6H_4,R=77Bu (13)] and pentaorganotellurium halides,Ar.TeX [Ar=4-CF_3C_6H_4,X=Cl (2a-Cl),X-Br (2a-Br);Ar-Ph,X=C1 (2b-Cl),X-Br (2b-Br);Ar=4-CH_3C_6H_4,X=C1 (2c-Cl),X-Br (2c-Br);Ar-4-BrC_6H_4,X-Br (2d-Br)] and (4-CF_3C_6H_4)_4(CH_3)TeX [X=C1 (trans-7a-Cl)and X=Br (trans-7a-Br)] were synthesized by the following methods:1)one-pot synthesis of la,2)the reaction of SO2C12 or Br2 with Ar_5Te~-Li~+generated from TeCl_4 or TeBr_4 with five equivalents of ArLi,3)reductive cleavage of Ar_(6-m)(CH_3)_mTe (m=0 or 2)with KC_8 followed by treatment with CH_3I,4)valence expansion reaction from low-valent tellurium compounds by treatment with KC_8 followed by reaction with CH3I,5)nucleophilic substitution of Ar_(6-y-z)(CH_3)_zTeX_(y-z)(X=C1,Br,OTf;z=0,1;y=1,2)with organo-lithium reagents.The scope and limitations and some details for each method are discussed and electrophilic halo-genation of the hexaorganotellurium compounds is also described.
机译:各种六有机tel化合物Ar_(6-n)(CH_3)_nTe [Ar = 4-CF_3C_6H_4,n = 0(la),n = 1(3a),n = 2(trans-4a和cis-4a ),n = 3(mer-5a),n = 4(trans-6a); Ph,n = 0(Ib),n = 1(3b),n = 2(trans-4b); 4-CH_3C_6H_4,n = 0(1c),n = 1(3c),n = 2(trans-4c),n = 4(trans-6c); 4-BrC_6H_4,n = 0(1d)]和Ar_5(R)Te [Ar = 4-CF_3C_6H_4,R = 4-CH_3OC_6H_4(8); Ar = 4-CF_3C_6H_4,R =乙烯基(9),Ar = Ph,R-乙烯基(10),Ar = 4-CF_3C_6H_4,R-PhSCH_2(11) ,Ar = Ph,R-PhSCH2(12),Ar = 4-CF_3C_6H_4,R = 77Bu(13)]和五有机碲化卤化物,Ar.TeX [Ar = 4-CF_3C_6H_4,X = Cl(2a-Cl),X- Br(2a-Br); Ar-Ph,X = C1(2b-Cl),X-Br(2b-Br); Ar = 4-CH_3C_6H_4,X = C1(2c-Cl),X-Br(2c- Br); Ar-4-BrC_6H_4,X-Br(2d-Br)]和(4-CF_3C_6H_4)_4(CH_3)TeX [X = C1(trans-7a-Cl)和X = Br(trans-7a-Br )]通过以下方法合成:1)一锅法合成la,2)SO2C12或Br2与由TeCl_4或TeBr_4生成的Ar_5Te〜-Li〜+与五当量的ArLi反应,3)还原裂解Ar_ (6-m)(CH_3)_mTe(m = 0或2),用KC_8,然后用CH_3I,4处理)价扩展低价碲化合物经KC_8处理,然后与CH3I,5)亲核取代Ar_(6-yz)(CH_3)_zTeX_(yz)(X = C1,Br,OTf; z = 0,1; y = 1,2)。使用有机锂试剂。讨论了每种方法的范围,局限性和一些细节,还描述了六有机碲化合物的亲电子卤代反应。

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