Halides chloride

The elimination of sulfur dioxide is apparently more difficult than that of either carbon monoxide or carbon dioxide When fluorosulfonyldifluoroacetyl halide (chloride, bromide, or iodide) is photolyzed, carbon monoxide is quantitatively eliminated to give halodifluoromethanesulfonyl fluonde with increasing ease from chloride to bromide to iodide [95, 100] (equation 67)... 

An interesting extension of the above experiment is the titration of a mixture of halides (chloride/iodide) with silver nitrate solution. Prepare a solution (100 mL) containing both potassium chloride and potassium iodide weigh each substance accurately and arrange for the solution to be about 0.025 M with respect to each salt. A silver nitrate solution of known concentration (about 0.05 M) will also be required. 

Primary alkyl halides (chlorides, bromides, and iodides) can be oxidized to... 

Cadmium halides (chloride, bromide, iodide) react explosively with potassium. No accident has been mentioned with fluoride (but this does not prove anything). 

The primary alkyl halides (chlorides, bromides and iodides) are oxidised to aldehydes in good yields. 

In order to increase the Lewis acidity of the indium centers in compounds such as 52, the preparation of derivatives that incorporate a tetrafluorophenylene backbone has also been pursued. l,2-Bis(halomercurio)tetrafluorobenzene (halide = chloride (53) or bromide (54)) reacts with two equivalents of the corresponding indium(I) halide in THF at 25 °C to afford the tetrakis(T i ) adduct of the respective 9,10-dihalo-9,10-dihydro-9,10-diinda-octafluoroanthracene (halide = chloride (55) or bromide (56)) (Scheme 22). Compound 56 is also prepared by the reaction of (o-C6F4Hg)3 (4) with InBr in refluxing toluene followed by treatment with THF. The formation of the diindacycles 55 and 56 in the reaction of 53 and 54 with two equivalents of the corresponding indium(I) halide is surprising since, in principle, bis(indiumdihalide) complexes would be the expected products. This cyclization... 

Halides (chloride, in particular) also react promptly with surface OH groups, as has been shown for [W(=CCMe3)Cl3(dme)] and several inorganic oxides (silica, alumina, silica-alumina, niobia) [5-7]. The same was observed for the reaction of [V(=0)Cl3] with silica in this case, using a large excess of the vanadium complex, one mole of HCl is released per mole of grafted vanadium [8]. 

Finally, polymer 594 has been used as an arene-catalyst to activate nickel from nickel(II) chloride and lithium, in order to perform hydrogenation of different organic substrates such as afkenes, afkynes, carbonyl compounds and their imines, alkyl and aryl halides (chlorides, bromides and iodides), aromatic and heteroaromatic compounds as well as nitrogen-containing systems such as hydrazines, azoxy compounds or Af-amino oxides, giving comparable results to those obtained in the corresponding reaction in solution . 

Primary alkyl halides (chlorides, bromides, and iodides) can be oxidized to aldehydes easily and in good yields with dimethyl sulfoxide.311 Tosyl esters of primary alcohols can be similarly converted to aldehydes,312 and epoxides313 give a-hydroxy ketones or aldehydes.314 The reaction with tosyl esters is an indirect way of oxidizing primary alcohols to aldehydes (9-3). This type of oxidation can also be carried out without isolation of an intermediate ester The alcohol is treated with dimethyl sulfoxide, dicyclohexylcarbodiimide (DCC),315 and anhydrous phosphoric acid.316 In this way a primary alcohol can be converted to the aldehyde with no carboxylic acid being produced. 

Catalyst-poisoning studies have concentrated on the potential poisons introduced with fuel, particularly on lead, which has been added intentionally to improve the combustion characteristics at the high compression ratios employed in modem internal combustion engines prior to the introduction of exhaust purification catalysts. The lead is usually introduced as motor mix which contains tetraethyllead in a mixture with organic halides, chlorides or bromides. These halides transport the lead in the form of volatile halides out of the engine and into the exhaust, and are hence termed lead scavengers. Thus the potential catalyst-poison elements associated with the additive mixture are Pb, Br, and Cl. 

The alkoxides of both oxidation states were obtained by metathesis of germanium halides (chlorides and iodides) with alkali alkoxides [1488, 1142, 857, 1535]. The yields can be increased by application of GeCl4 solvates with Py or NH3 or amines [3, 222] (method 5) and also by alcohol interchange of ethoxides (method 6) or alcoholysis of Ge[Si(NR3)2]2 [568, 1543] (method 4). The application of alkali alkoxides in the preparation of Ge(OR)4is possible in contrast to that of analogous derivatives of Sn(IV) and Zr due presumably to the much lower stability of corresponding alkoxogermanates the intermediate products of the corresponding reactions because of stability — of the tetrahedral coordination for Ge. The direct electrochemical preparation of Ge(OEt)4... 

Metal acetates are widely used, because they create an optimal magnitude of PH 5-6 for obtaining ICC. At the same time, in these syntheses, halides (chlorides) or nitrates of transition metals can also be used by adjusting the pH of the reaction medium to weakly acidic by addition of alkaline agents, mostly alcohol or aqueous-alcohol solutions of NaOH or KOH, as well as their alcoholates. In such cases, the danger of formation of hydroxides of metal complex-formers appears this fact complicates considerably the obtaining of pure final reaction products. 

N-Alkylation of lf/-pyrrole, indole and carbazole can be accomplished with benzyl halides (chloride and bromide) in acetonitrile and cesium fluoride/Celite employed as a solid base (Equation 12) <2001T9951>. The procedure is convenient and efficient, and generally gives rise to the N-alkylated products exclusively, in high yields (78-93%). 

Berthelette et al. [143] reported a detailed study on the stereochemistry of vinyl halide (chlorides and bromides) synthesis by the Julia-Kocienski method. In the model experiments using chloromethyl PT sulfone and anisaldehyde (Scheme 109), the isomer ratio depends on the countercation. 

A complex of DBU and copper(I) halide (chloride or iodide) was used for the alkylation of terminal acetylene groups in an inert solvent and in the presence of a small amount of hydroxylamine hydrochloride under an argon atmosphere (75FPR2243172 75GEP2344985 78LA658). 

Aliphatic primary halides—chlorides, bromides, and especially iodides—are converted into aldehydes by treatment with dimethyl sulfoxide [998, 999, 1000] or trimethylaniine oxide [993], The reactivity of alkyl chlorides and bromides is increased by converting them in situ to alkyl iodides by the addition of sodium iodide into the reaction mixtures [999] (equation 188). 

The metal(II) halides (chloride, bromide or iodide), carboxylates, and other salts find use, including Hg(II) fulminate ... 

Zinc. The salts used for the Zn reactions are the halides (chlorides, bromides and iodides) both alkyl and aryl compounds are used. Owing to the reactivity of organozinc compounds, air and moisture must be excluded from the reaction. Use of ether or dioxane, on evaporation of the solvent, leads to solvates RZnX-D (X = halide, D = Et20 or dioxane). The exchange between Et2Zn and Znl2 occurs slowly in ether at RT. 

Reaction of thiols or thiolates with acyl halides, chlorides in particular, represents the standard method for preparing thiol carboxylic esters (c/. ref. 33 and the literature cited therein). Since thiols ate strong nucleophiles, the acylation even takes place in the absence of base. However, to obtain excellent yields under mild conditions, tertiary amines are added or metal (Si, Sn, T1 Cu ) derivatives of the thiols are used. The following examples demonstrate the scope of the method. 

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