Tin acetylides

Both chlorines of 1,1-dichloroethylene (340) react stepwise with different terminal alkynes to form the unsymmetrical enediyne 341 [250]. The coupling of the dichloroimine 342 with tin acetylide followed by hydrolysis affords the dialkynyl ketone 343[2511. The phenylthioimidoyl chloride 344 undergoes stepwise reactions with two different tin acetylides to give the dialkynylimine 345[252],... 

A calcium carbide/stannous mixture combusted. Could it be the exothermic decomposition of a tin acetylide ... 

In the total synthesis of harveynone (152), reaction of the iodide 150 bearing labile functionality took place with the tin acetylide 151, and it was claimed that no reaction occurs with the free amine [70]. However, this claim is not always true, and the coupling of the similar iodide 153 was carried out with the corresponding free terminal alkyne in the presence of diisopropylamine [71]. The coupling of the Mg acetylide 155 with vinyl carbamate 154 to give the enyne 156 is catalysed by a Ni complex [72]. It is true that free alkynes give better results than the corresponding metal acetylides in some cases [73]. 

The alkyne insertion reaction is terminated by anion capture. As examples of the termination by the anion capture, the alkenylpalladium intermediate 189, formed by the intramolecular insertion of 188, is terminated by hydrogenolysis with formic acid to give the terminal alkene 192. Palladium formate 190 is formed, and decarboxylated to give the hydridopalladium 191, reductive elimination of which gives the alkene 192 [81]. Similarly the intramolecular insertion of 193 is terminated by transmetallation of 194 with the tin acetylide 195 (or alkynyl anion capture) to give the dienyne 196 [82], Various heterocyclic compounds are prepared by heteroannulation using aryl iodides 68 and 69, and internal alkynes. Although the mechanism is not clear, alkenylpalladiums, formed by insertion of alkynes, are trapped by nucleophiles... 

Coupling with Tin Acetylides. Trialkyltin acetylides react with the bromooxazinone in the presence of ZnCl2 to furnish... 

Finally, Pd(0) complexes can catalyze the coupling reaction between transition-metal halides 54 and tin acetylides 55 [Eq. (21)]. These reactions occur under the same reaction conditions, leading to the formation of carbon-carbon bonds in the presence of palladium catalysts [33]. 

Stereoselective preparation of ( )-5-stannyl-)/-alkylidenebutenolide 100 was achieved by the reaction of tin acetylide with tributylstaimyl 3-iodopropenoate derivative 99, and the arylbutenolide 101 was obtained by the Migita-Kosugi-Stille reaction of 100 [53]. 

Triphenylmethyl sodium and triphenylmethyl potassium conduct in liquid ammonia although they slowly react with that solvent.887 888 When the liquid ammonia is allowed to evaporate from a solution of triphenylmethyl sodium in ammonia, the residue is a colorless mixture of sodamide and triphenylmethane. The sodium-tin and sodium-germanium compounds analogous to sodium triphenylmethide are also strong electrolytes in liquid ammonia. Sodium acetylide in liquid ammonia is dissociated to about the same extent as sodium acetate in water.889... 

Aluminium, 0048 Ammonium phosphinate, 4554 Barium phosphinate, 0210 f Benzaldehyde, 2731 1,4-Benzenediol, 2333 Bis(hydrazine)tin(II) chloride, 4070 Calcium acetylide, 0585 Calcium phosphinate, 3931 Chromium(II) chloride, 4052 Chromium(II) oxide, 4241 Chromium(II) sulfate, 4244 Copper(I) bromide, 0265 Diacetatotetraaquocobalt, 1780 Diisobutylaluminium hydride, 3082 f 1,2-Dimethylhydrazine, 0955... 

Aluminium, 0048 Ammonium phosphinate, 4549 Barium phosphinate, 0210 f Benzaldehyde, 2727 1,4-Benzenediol, 2326 Bis(hydrazine)tin(II) chloride, 4064 Calcium acetylide, 0582 Calcium phosphinate, 3925 Chromium(II) chloride, 4046 Chromium(II) oxide, 4235 Chromium(II) sulfate, 4238 Copper(I) bromide, 0264 Diacetatotetraaquocobalt, 1774 Diisobutylaluminium hydride, 3076 f 1,2-Dimethylhydrazine, 0951 1,2-Diphenylhydrazine, 3511 Dipotassium phosphinate, 4425 f Ethanedial, 0719 f Formaldehyde, 0415 Formic acid, 0417 Gallium(I) oxide, 4405 Glucose, 2513 f Hydrazine, 4515 Hydroxylamine, 4493 Hydroxylaminium phosphinate, 4550 Hyponitrous acid, 4464 Iron(II) chloride, 4055 Iron(II) hydroxide, 4386 Iron(II) sulfate, 4393 Fead(II) phosphinate, 4526 Fead(II) phosphite, 4530 Fithium dithionite, 4682 Magnesium, 4685 Magnesium phosphinate, 4512 Manganese(II) phosphinate, 4514 f Methylhydrazine, 0500 Phenylhydrazine, 2366 Phosphinic acid, 4498 Phosphonic acid, 4499 Phosphonium iodide, 4510 Potassium, 4640 Potassium hypoborate, 0163... 

Hiickel band calculations, rigid-rod transition metal-acetylide polymers, 12, 371-372 Human health, tin toxic effects, 12, 637 Hybrid magnets, metallocene-containing bimetallic M(II)—Cr(II) oxalates, 12, 427 bimetallic M(II)-Fe(III) oxalates, 12, 432 bimetallic M(III)-Ru(III) oxalates, 12, 435 materials, 12, 437 properties, 12, 425 trimetallic oxalates, 12, 436 Hydantoins, with lead reagents, 3, 888 Hydration... 

With metals, such as copper (Cu) nickel (Ni), when moist, also lead (Pb) or zinc (Zn), when moist and unpurified tin (Sn) is not attacked but sodium yields, upon heating, sodium acetylide (CH CNa) and disodium... 

Compounds Bis-dimethylstibinyl oxide Bis(dimethylthallium) acetylide Butyllithium Nonacarbonyldiiron Octacarbonyldicobalt Pentacarbonyliron Tetracarbonylnickel Dibismuth trisulphide Dicaesium selenide Dicerium trisulphide Digold trisulphide Europium (II) sulphide Germanium (II) sulphide Iron disulphide Iron (II) sulphide Manganese (II) sulphide Mercury (II) sulphide Molybdenum (IV) sulphide Potassium sulphide Rhenium (VII) sulphide Silver sulphide Sodium disulphide Sodium polysulphide Sodium sulphide Tin (11) sulphide Tin (IV) sulphide Titanium (IV) sulphide Uranium (IV) sulphide ... 

Ignition or explosive reaction with metals (e.g., aluminum, antimony powder, bismuth powder, brass, calcium powder, copper, germanium, iron, manganese, potassium, tin, vanadium powder). Reaction with some metals requires moist CI2 or heat. Ignites with diethyl zinc (on contact), polyisobutylene (at 130°), metal acetylides, metal carbides, metal hydrides (e.g., potassium hydride, sodium hydride, copper hydride), metal phosphides (e.g., copper(II) phosphide), methane + oxygen, hydrazine, hydroxylamine, calcium nitride, nonmetals (e.g., boron, active carbon, silicon, phosphoms), nonmetal hydrides (e.g., arsine, phosphine, silane), steel (above 200° or as low as 50° when impurities are present), sulfides (e.g., arsenic disulfide, boron trisulfide, mercuric sulfide), trialkyl boranes. 

OSHA PEL TWA 2 mg(Sn)/m3 ACGIH TLV IW A 2 mg(SnVm3 SAFETY PROFILE Poison by ingestion, intraperitoneal, intravenous, and subcutaneous routes. Experimental reproductive effects. Human mutation data reported. Potentially explosive reaction with metal nitrates. Violent reactions with hydrogen peroxide, ethylene oxide, hydra2ine hydrate, nitrates, K, Na. Ignition on contact with bromine trifluoride. A vigorous reaction with calcium acetylide is initiated by flame. When heated to decomposition it emits toxic fumes of Cl. See also TIN COMPOUNDS. 

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