The preparation and reactions of some dimetallic compounds derived from tetrachlorothiophene

Smith, M. R.; Gilman, Henry

doi:10.1016/s0022-328x(00)81826-4

Cited by 20 publications

(3 citation statements)

References 19 publications

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“…2,5-Bis(trimethylsilyl)dichlorothiophene (7): bp 81 °C/1 mmHg; IR (neat) 2964, 2906, 1464, 1392, 1310, 1275, 1259, 1034, 846, 762, 740 cm -1 ; 1 H NMR (CDCl 3 ) δ 0.40 (s, 18H); 13 C NMR (CDCl 3 ) δ −1.2; 131.9; 137.8; MS, m/z (relative intensity) 300 (1), 298 (6), 296 (M + , 8), 285 (5), 283 (22), 281 (29), 95 (12), 93 (34), 73 (100), 58 (2), 45 (29), 44 (12), 43 (16). The IR, 1 H NMR, and MS data are in agreement with those reported in the literature …”

Section: Methodssupporting

confidence: 89%

“…These results show that the electrochemical synthesis can be applied to the chlorinated derivatives even though, to date, only silylation of tetrachlorothiophene has been reported. , …”

Section: Resultsmentioning

confidence: 84%

“…Although many chemical methods to accede to thienylsilanes or halothienylsilane thiophenes are known, − they are not general and often require an extreme temperature 4,5,8-12 (Table ). Having to work at low temperatures is not a drawback in the research laboratory, but it would be a major disadvantage on the industrial scale.…”

Section: Introductionmentioning

confidence: 99%

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Selective Electrochemical Mono- and Polysilylation of Halothiophenes

et al. 1996

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Electrochemical trimethylsilylation of mono- and polyhalothiophenes (hal = Cl, Br) has been examined. In order to predict the selectivity of the reaction in accordance with the halogen position on the ring, the reduction potentials of the commercially available halothiophenes have been determined by cyclic voltammetry. Thus, as expected, the bromo derivatives are more easily reduced than the chloro analogs, and the 2-position is more reactive than the 3-position. We obtained 2- and 3-(trimethylsilyl)thiophenes, 2-(trimethylsilyl)-3 (or 5)-halothiophenes, 2-(trimethylsilyl)-3,4,5-trihalothiophenes, 2,5-bis(trimethylsilyl)thiophene, 2,5-bis(trimethylsilyl)-3,4-dihalothiophenes, and 2,3,5-tris(trimethylsilyl)-4-halothiophenes with an excellent selectivity. In contrast, the silylation of 2-(trimethylsilyl)-3-halo- and 2,3,5-tris(trimethylsilyl)-4-halothiophenes occurred with ring opening and afforded 1,1,4,4-tetrakis(trimethylsilyl)-1,2-butadiene and hexakis(trimethylsilyl)-2-butyne, respectively. A coherent interpretation of the synthetic results is proposed in correlation with the measured potential values.

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Section: Methodssupporting

confidence: 89%

“…These results show that the electrochemical synthesis can be applied to the chlorinated derivatives even though, to date, only silylation of tetrachlorothiophene has been reported. , …”

Section: Resultsmentioning

confidence: 84%

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Selective Electrochemical Mono- and Polysilylation of Halothiophenes

et al. 1996

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Substitution Reactions Using Organocopper Reagents

Posner

2011

Organic Reactions

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Carbon‐carbon sigma‐bond formation one of the most fundamental operations in organic chemistry, is often accomplished by interaction of an organometallic reagent with an organic substrate having a suitable leaving group. Selective substitution of halogens and of alcohol derivatives by various hydrocarbon groups in many different types of organic substrates has been achieved most successfully using organocopper reagents. The wide scope and effectiveness of these reagents in coupling with halides and alcohol derivatives have made formation of the unsymmetrical coupling product R‐R' a useful reaction in organic synthesis, allowing efficient and specific substitution of X by alkyl, alkenyl, alkynyl, or aryl groups. Because selective coupling between organic substrate and organocopper reagent is usually achieved more effectively by stoichiometric than by catalytic organocopper reagents, and more effectively still by organocuprates(I) than by mono‐copper or by complexed organocopper reagents, the emphasis in this chapter is on organocuprates (I). Consideration is given to possible mechanisms of substitution reactions using organocopper reagents, to scope, limitations, and synthetic utility of these reactions, and to optimal experimental considerations for their application.

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