Iodide sodium alloys

Tetraethyltin has been prepared from tin-sodium alloy and ethyl iodide, from tin-sodium-zinc alloy and ethyl bromide, and from tin tetrachloride and ethylmagnesium bromide. The method described is essentially that of Pfeiffer and Schnur-mann. ... 

The alloy-ethyl chloride reaction rate is quite sensitive to alloy composition, the most reactive alloy being the composition NaPb. The alloy becomes less reactive as the composition is raised in sodium, until reaction almost ceases at the composition NasPb2. With such higher sodium alloys, reaction can be obtained with ethyl bromide or iodide, especially in the presence of amine or hydroxyl compounds 289). With the compound composition NagPb4 catalysts such as ketones, esters, or aldehydes allow good reaction with ethyl chloride. 

Ethers Aiuminum bromide. Aluminum chloride. Boron tribromide. Boron trichloride. Diborane. Diphenyl phosphide, lithium salt. Hydrobromic acid. Hydriodic acid. Lithium bromide. Lithium bromide-BFt etherate. Lithium diphenyl. Methylmagnesium iodide. Pyridine hydrochloride. Sodium iodide. Sodium-Potassium alloy. Triphenylphosphine dibromide. 

Various other reagents can be used for this reductive debromination. 1,2-Dipropylcyclopropane was prepared from 4,6-dibromononane using chromium(II) perchlorate in dimethylformami-de/water (yield 93%), lithium amalgam in tetrahydrofuran (75%), lithium biphenylide in te-trahydrofuran (78%), potassium-sodium alloy in tetrahydrofuran (68%), zinc dust and zinc(II) chloride in propan-2-ol/water (95%) and alkyllithiums in tetrahydrofuran (BuLi 16%, i-BuLi 18%, t-BuLi 47%). Ring closure of 1,3-dibromobutane to methylcyclopropane was achieved by treatment with zero-valent copper, which was obtained from reaction of lithium naphthalen-ide and copper(I) iodide/tributylphosphane in tetrahydrofuran (yield 91%) ... 

Thus Cahours (1862) prepared tetramethyllead from methyl iodide,475 and Polis476 prepared tetraphenyllead from bromobenzene. Industrial importance attaches to the preparation of tetraethyllead from ethyl chloride and a lead-sodium alloy at a low or moderate temperature.477... 

The reactivities of alkyl halides are in the sequence RI > RBr > RCl and MeX > EtX > PrX. Benzyl halide reactions with tin do not require catalysts (equation 2). For less reactive halides, the catalysts and promoters employed include metals (sodium, magnesium, zinc, or copper), Lewis bases (amines, triorganophosphines and -stibines, alcohols, or ethers), iodides, and onium salts (R4MX). The use of tin-sodium alloys can result in tri- or tetraorganotin products. Electrochemical synthesis has also been reported, e.g. the formation of R2SnX2 from the oxidation of anodic tin by RX in benzene solution and the formation of R4Sn from RI (R = Me or NCCH2CH2) and cathodic tin. 

Triethylphosphine, ( 2115)3 , is prepared in a variety of ways (1) By the action of phosphorus-sodium alloy on ethyl iodide. (2) A double compound of the phosphine with zinc chloride is produced when zinc diethyl reacts with phosphorus trichloride. (3) The phosphine IS formed together with its oxide when zinc diethyl reacts with phosphorus oxychloride. (4) By heating 1 molecular equivalent of phosphonium iodide with 3 molecular equivalents of ethyl alcohol for 6 to 8 hours at 160° to 180° C., tetraethylphosphonium iodide occurring as a by-product. This process yields the hydriodide of the phosphine. (5) By decomposition wdth potassium hydroxide of the base formed when a zinc phosphide, PHZn (prepared by the action of phosphine on zinc diethyl at a temperature not exceeding —4° C.), is heated with ethyl iodide in a sealed tube for 1 hours at 150° (6) By heating... 

Trimethylphosphine, (CH3)3P, may be prepared as follows (1) Methyl chloride is passed over a phosphorus-calcium alloy, dimethyl-phosphorus, [(CH3)2P]a, being formed at the same time. (2) By the action of methyl iodide on a phosphorus-sodium alloy, the by-products being dimethylphosphorus and tetramethylphosphonium iodide. (3)... 

Triethylphosphine, ( 2115)3 , is prepared in a variety of w ays (1) By the action of phosphorus-sodium alloy on ethyl iodide. (2) A double compound of the phosphine with zinc chloride is produced when zinc diethyl reacts with phosphorus trichloride. (3) The phosphine is formed together with its oxide when zinc diethyl reacts with phosphorus oxychloride. (4) By heating 1 molecular equivalent of... 

The chemistry of catenated organotin compounds began as early as 1852 with the report by Ldwig 187) of the reaction of ethyl iodide with tin-sodium alloy. A product of this reaction, a diethyltin polymer, has only very recently been characterized 11,159,188). A similar situation may be cited in the case of tetrakis (triphenylstannyl) tin which was prepared as early as 1923 189), but was not rigorously identified until 1964 15,190). This compound is the only discrete branched-chain polytin in the literature at present. These two examples are not entirely representative of the state of the science in... 

Indeed separate experiments showed that lithium iodide reacts both with tin tetrachloride and with germanium tetrachloride, so that perfluoro-n-propyllithium made via the lithium-sodium alloy cannot be used to prepare (n-C3F7)4Sn and (n-C3F7)4Ge. Nevertheless, it is now established that perfluoro-re-propyllithium may be used to synthesize a number of new perfluoropropyl derivatives of Group IV elements, and probably similar compounds of other elements as well (9). As a result it is likely that perfluoro-alkyllithium compoimds will play a more important part in synthetic work in the future than they have in the past. 

An alloy of sodium and potassium (NaK) is used as a heat-transfer medium. Many potassium salts are of utmost importance, including the hydroxide, nitrate, carbonate, chloride, chlorate, bromide, iodide, cyanide, sulfate, chromate, and dichromate. 

Iodine was determined by an iodometric titration adapted from White and Secor.(3) Instead of the normal Carius combustion, iodide was separated from the samples either by slurrying in 6M NaOH, or by stirring the sample with liquid sodium-potassium (NaK) alloy, followed by dissolving excess NaK in ethanol. Precipitated plutonium hydroxides were filtered. Iodine was determined in the filtrate by bromine oxidation to iodate in an acetate buffer solution, destruction of the excess bromine with formic acid, acidifying with SO, addition of excess KI solution, and titrating the liberated iodine with standard sodium thiosulfate. The precision of the iodine determination is estimated to be about 5% of the measured value, principally due to incomplete extraction of iodine from the sample. 

The direct reaction of zinc metal with organic iodides dates back to the work of Frankland(67). Several modifications have been suggested since that time to increase the reactivity of the metal. The majority of these modifications have employed zinc-copper couples(68-72), sodium-zinc alloys(73), or zinc-silver couples(77). Some recent work has indicated that certain zinc-copper couples will react with alkyl bromides to give modest yields of dialkylzinc compounds(74,73). However, all attempts to react zinc with aryl iodides or bromides have met with failure. The primary use of zinc couples has been in the Simmons-Smith reaction. This reaction has been primarily used with diiodomethane as 1,1-dibromides or longer chain diiodides have proven to be too unneactive even with the most reactive zinc couples. 

Titanium (IV) iodide may be prepared by a variety of methods. High-temperature methods include reaction of titanium metal with iodine vapor,1-3 titanium carbide with iodine,4 titanium(IV) oxide with aluminum (III) iodide,5 and titanium (IV) chloride with a mixture of hydrogen and iodine. At lower temperatures, titanium (IV) iodide has been obtained by the combination of titanium and iodine in refluxing carbon tetrachloride7 and in hot benzene or carbon disulfide 8 a titanium-aluminum alloy may be used in place of titanium metal.9 It has been reported that iodine combines directly with titanium at room temperature if the metal is prepared by sodium reduction of titanium (IV) chloride and is heated to a high temperature before iodine is... 

IL By the aotion ofthe respective metals alloyed with potassium ot sodium upon the iodides of the monad positive ra cab. ... 

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