Article

The Disproportionation of Tetravinyltin with Tin Tetrachloride and the Cleavage of Some Vinyltin Compounds with Bromine

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Abstract

Vinyltin trichloride, divinyltin dichloride and trivinyltin chloride have been prepared in excellent yields by the low temperature disproportionation of tetravinyltin with tin tetrachloride. Dibutyldivinyltin, dimethyldivinyltin and diphenyl-divinyltin have been subjected to bromine cleavage, and it has been found that the ease of displacement of these groups from tin is phenyl > vinyl > methyl > butyl. Divinyltin oxide and trivinyltin hydroxide have been prepared by the hydrolysis of divinyltin dichloride and trivinyltin chloride, respectively, with aqueous sodium hydroxide.

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... It is well known that the ability of organotin compounds to enter into this reaction depends substantially on the nature of an organic group at the tin atom, and those having the substituents with sp 2 carbon atoms disproportionate much easier. Thus, the long-term heating in POCl 3 is needed to convert the mixture of Et 4 Sn and SnCl 4 with 1:3 M ratio to EtSnCl 3 [2], Ph 4 Sn reacts during 3e4 h at 150e180 S [1], and Vin 4 Sn converts fully during 2 h at 70 S [3,4]. ...
... The initial O-TMS derivatives of amides 1a [8], 1b [9], 1c [8] and trichlorostannanes PhSnCl 3 [1], VinSnCl 3 [3,4], AllSnCl 3 [10] were synthesized by described procedures. ...
... Dibutyldi-l-butenyltin, butyltri-l-butenyltin, tetra-1-butenyltin, dibutyldi-3-butenyltin, butyltri-3-butenyltin, and tetra-3-butenyltin were prepared via the Grignard reaction (O'Brien, et al., 1971;Vijaymaaghavan, 1945;Rosenberg, Gibbons, & Ramsden, 1957;Seyferth & Stone, 1957;Clark & Poller, 1970). The appropriate Grignard reagent was prepared from approximately 10 g of 1-bromo-l-butene or 4-bromo-l-butene in 10 mL anhydrous tetrahydrofuran and an excess of magnesium chips. ...
Chapter
Trimethyltin-oxygen compounds (1.4.1.1.1.1) and triethyltin-oxygen compounds (1.4.1.1.1.2) have been described in “Organotin Compounds” 11, 1984, pp. 44 and 170, respectively; tripropyltin-oxygen compounds (1.4.1.1.1.3), triisopropyltin-oxygen compounds (1.4.1.1.1.4), tributyltin-oxygen compounds (1.4.1.1.1.5), triisobutyltin-oxygen compounds (1.4.1.1.1.6), tri-secbutyltin-oxygen compounds (1.4.1.1.1.7), and tri-tert-butyltin-oxygen compounds (1.4.1.1.1.8) have been described in “Organotin Compounds” 12, 1985, pp. 1, 33, 36, 231, 234, and 235, respectively.
Article
1. Mono- and di-vinyl compounds of mercury and thallium and divinyl compounds of tin were synthesized. 2. An investigation was made of the reactions of divinylmercury with lithium, mercury salts, and thallium salts and also of the reactions of divinylthallium halides with mercury and with tin and thallium halides.
Article
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Chapter
IntroductionHydrometalation and CarbometalationAddition Reactions of H+ Z− to AcetylenesFriedel–Crafts Type Acylations and Alkylations of AcetylenesAnionic and Organometallic Cyclizations Involving AcetylenesCarbon Chain-extension ReactionsAcknowledgementsReferences
Article
Tributenyltin bromides containing double bonds at carbon atoms C-1, C-2 or C-3 were synthesized from symmetrical tetrabutenyltins. Although all three tetrabutenyltin compounds were stable, only the tributenyltin bromides with double bonds at C-1 and C-3 were sufficiently stable for further studies. In aqueous sodium bromide (NaBr) solution containing 1% acetone, tri-1-butenyltin bromide was more stable in sunlight than tri-3-butenyltin bromide, yet neither compound was as stable as tributyltin bromide. Stability in seawater, in the absence of ultraviolet (UV) light, was less for both tri-1-butenyltin bromide and tri-3-butenyltin bromide than for tributyltin bromide. The relative toxicities of the tributenyltin bromides were determined using a bioluminescent bacteria assay. The concentrations of tributenyltin bromides necessary to produce a toxic response were three to six times greater than for tributyltin bromide.
Article
A series of unsymmetrical organotin bromides has been prepared by the stepwise cleavage of appropriate organotin compounds with bromine in carbon tetrachloride or chloroform at -50, 0 or 40°. The bromides have been converted to acetates by treatment with aqueous potassium hydroxide to form bisorganotin oxides, followed by reaction of these intermediate compounds with glacial acetic acid at 100°.
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Article
Seven phenyl-substituted vinylstannanes have been prepared. (Z)-beta-(trimethylstannyl)styrene, alpha-(trimethylstannyl)styrene, and 1,1-diphenyl-2-(trimethylstannyl)ethene were prepared by Grignard coupling between the appropriate phenyl-substituted vinyl bromide and chlorotrimethylstannane. (E)-beta-(Trimethylstannyl)styrene and (Z)-(trimethylstannyl)stilbene were prepared by AIBN catalyzed hydrostannation of the appropriate phenyl-substituted acetylene. (E)-(Trimethylstannyl)stilbene and methyl (E)-2-(trimethylstannyl)cinnamate were prepared by palladium(0) catalyzed hydrostannation of diphenylacetylene and methyl phenylpropiolate, respectively. Each compound was characterized by H-1, C-13, and Sn-119 NMR. Reactivity of each compound to protodestannylation was determined by spectrophotometric or H-1 NMR measurement of second order rate constants. The relative reactivity is interpreted on the basis of the electronic and steric effects of the phenyl substituents. The stereochemistry of destannylation resulted in retention of configuration for four of the compounds, consistent with an S(E)2 mechanism. However, methyl (E)-2-(trimethylstannyl)cinnamate gave an E/Z product ratio of essentially. This result is consistent with an allenol mechanism for protodestannylation of this compound.
Article
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Article
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Chapter
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Article
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Article
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Article
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Chapter
IntroductionReactions of Vinyl-Metal CompoundsVinyl Compounds of the Alkali MetalsVinyl Compounds of the Group IIA MetalsVinyl Compounds of the Group IIB MetalsVinyl Compounds of the Group III MetalsVinyl Compounds of the Group IV MetalsVinyl Compounds of the Group V MetalsHalogen-Substituted Vinyl-Metal Compounds
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Article
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