Copper© iodide

Akzo Process. Akzo Zout Chemie has developed a route to vinyl chloride and soda ash from salt usiag an amine—solvent system catalyzed by a copper—iodide mixture (13). This procedure theoretically requires half the energy of the conventional Solvay processes. 

AllyHc alkylation o( ally alcohols m the presence of copper Iodide and phosphmimines... 

This complex should be used when the organolithium is in solution in a hydrocarbon solvent. For organolithium reagents prepared in ether (see Note 4), the same complex may be used or, more conveniently, copper iodide (Cull can be used. The Cul purchased from Prolabo or Merck 4 Company, Inc. may be used directly. Other commercial sources of Cul (Fluka, Aldrich Chemical Company, Inc., Alfa Products, Morton/Thiokol, Inc.) furnish a salt which affords better results when purified. 1 mol of Cul is stirred for 12 hr with 500 ml of anhydrous tetrahydrofuran, then filtered on a sintered glass funnel ( 3), washed twice with 50 ml of anhydrous tetrahydrofuran, once with 50 ml of anhydrous ether and finally dried under reduced pressure (0.1 imO for 4 hr. 

Ullman type coupling occurs between aryl halides and trifluoromethyl copper species generated by the action of copper iodide on sodium tnfluoroacetate [168, 169] or on methyl fluorosulfonyldifluoroacetate [170] (equation 145) Similarly the pentafluoroethyl group can be introduced from potassium pentafluoropropion-ate [171] (equation 146)... 

This 1,2-asymmetric induction has been attributed to stcric and stcrcoclectronic factors. Similarly, the cuprate additions to 4-alkylcyclopentenones l7 -19, and 4-alkylcyclohexcnones16 b-18 proceeded with very high trans diastereoselection. The copper iodide catalyzed addition of propylmagnesium bromide to 4-methyl-2-cyclohexenone gave a trans/cis ratio of 80 20, whereas the addition to 5-methyl-2-cyclohexenone produced a transjcis ratio of 93 72 3-Silyloxy system 3 gave the trans-adduct 4 on treatment with butylcopper-boron trifluoride reagent20. 

Lithiation of diaiylbenzotriazol-l-ylmethanes 56 followed by addition of copper iodide gave 6-arylphenanthridine derivatives 57 in moderate yields. According to the substituent effect, it was suggested that the reactions proceed via radical intermediates <96JHC(33)607>. 

The compound (CuI)gP12 can be obtained from the elements at 550 °C. It contains chains of polymeric phosphorus that can be isolated when the copper iodide is extracted with an aqueous solution of potassium cyanide. The molecules consist of P8 cages that are joined via P4 squares (Fig. 11.5, top). Another variety can be obtained in a similar way from (CuI)3P12 its chains consist of P10 cages and P2 dumbbells. 

As shown earlier in many examples, the Claisen rearrangement of allyl vinyl ethers also provides a very powerful method for carbon-carbon bond formation in domino processes. Usually, the necessary ethers are formed in a separate step. However, both steps can be combined in a novel domino reaction developed by Buchwald and Nordmann [306]. This starts from an allylic alcohol 6/4-102 and a vinyl iodide 6/4-103, using copper iodide in the presence of the ligand 6/4-104 at 120 °C to give 6/4-105 (Scheme 6/4.25). The reaction even allows the stereoselective formation of two adjacent quaternary stereogenic centers in high yield. 

Copper iodide was purified prior to use by the method of Kauffman.2... 

Methylene-1,3-dithiolane 1,3-Dithiolane, 2-methylene- (9) (26728-22-3) Copper(l) iodide Copper iodide (8,9) (7681-65-4)... 

Unsymmetrical 3,4-dihalo-l,2,5-thiadiazoles 118 and 119 were prepared from 3-amino-4-chloro-l,2,5-thiadiazole 117 via a Sandmeyer-like reaction involving successively tert-butyl nitrite and either copper bromide or copper iodide in anhydrous acetonitrile (Scheme 17) <2003H(60)29>. The bromo and iodo thiadiazoles 118 and 119 undergo selective Stille and Suzuki C-C coupling chemistry (see Section 5.09.7.6). 

Acetanilide (13.5 g), (substituted) aromatic bromide (25 g), potassium carbonate (13.2 g), and copper iodide (1.9 g) were heated (190°C) and stirred overnight. After cooling to room temperature toluene was added and the precipitate filtered. The solution was concentrated and the excess of bromide removed by distillation under reduced pressure. The residue was dissolved in ethanol (200 mL), potassium hydroxide (10.3 g) was added, and the mixture refluxed overnight. Ethanol was evaporated, the residue dissolved in dichloromethane, and washed with brine. The organic layer was dried over MgS04 and concentrated to obtain the crude diphenylamine. 

The Conia-ene reaction is a thermal cyclization of an alkyl ketone with an alkyne to give the corresponding a-vinylated ketone.98 The catalytic version of this reaction has been reported to generalize the process to more functionalized substrates.99 The intramolecular carbocupration of alkyne 94 has been investigated under basic conditions in the presence of a catalytic amount of copper iodide (Scheme 28).100 The cyclic product 95 is obtained in high yield. 

Potassium tert-butoxide reacts with copper iodide to generate a copper / -butoxide species 98 (Scheme 29). Activation of the alkyne 94 by this copper catalyst (intermediate 96) allows the enolate attack to afford the cyclic... 

Mulliken also studied other band spectra of diatomic molecules. Only one such study will be mentioned here and that is his study of copper iodide (Mulliken 1925c), where he examined the copper isotope effect. Mulliken s pioneering work was followed by more papers on isotope effects on electronic spectra (visible and UV) which will not be detailed here. Many of these papers deal with diatomics since the theory of such spectra is much better understood than that for general polyatomic systems. Further discussion of isotope effects on spectra will be mainly restricted to their use in the discovery of less abundant isotopes. 

Mulliken, R. S. The isotope effect in band spectra III. The spectrum of copper iodide as excited by active nitrogen. Phys. Rev. 26, 1-34 (1925c). 

Suppose that you have an aqueous solution of copper iodide, Cub, which you must precipitate and filter before pouring the remaining liquid into a disposal beaker. You decide to use the common ion effect to precipitate the Cul2. In the laboratory, you find stock solutions of Cu(N03)2 and Nal with the same concentrations. You want to use the smallest volume possible. Which stock solution will you choose to precipitate the Cub Explain your answer. 

Cul COPPER IODIDE 855.8840 -5.7746E+04 -2.9506E+02 1.0189E-01 -1.3492E... 

Better results were obtained for the carbamate of 163 (entry 3) [75, 80). Thus, deprotonation of the carbamate 163 with a lithium base, followed by complexation with copper iodide and treatment with one equivalent of an alkyllithium, provided exclusive y-alkylation. Double bond configuration was only partially maintained, however, giving 164 and 165 in a ratio of 89 11. The formation of both alkene isomers is explained in terms of two competing transition states 167 and 168 (Scheme 6.35). Minimization of allylic strain should to some extent favor transition state 167. Employing the enantiomerically enriched carbamate (R)-163 (82% ee) as the starting material, the proposed syn-attack of the organocopper nucleophile could then be as shown. Thus, after substitution and subsequent hydrogenation, R)-2-phenylpentane (169) was obtained in 64% ee [75]. 

Copper iodide acts as an efficient reagent for the nucleophilic displacement of 1-haloalkynes. It transforms 1-bromoalkynes (72) into 1-iodoalkynes (73) which, on further treatment with copper(II) bis(arenesulfinate), are converted into the corresponding alkynyl aryl sulfones (74). An electron transfer between 1-haloalkynes and copper(I) salts is believed to take place for the copper-assisted halogen-exchange reaction at the acetylenic carbon atom. 

Formation of 772-complexes is known for both mono- and bis-phospho-nio-benzophospholides and has been observed (Scheme 18) in the reactions of the cation 23 with Jonas reagent to give the cobalt complex 49 [49], addition of the zwitterion 25 to a Mo-Mo triple bond to afford the dinuclear complex 50 [47], and finally, upon treatment of 26 with copper iodide to yield the complex 51 [46] which is peculiar because of the presence of the same ligand in two different coordination modes. Whereas it is clear that the metal atoms in all complexes supply inappropriate templates for the formation of 77 -complexes, the preference of rf-(,n)- over a possible a-coordina-tion is less well understood [49]. 

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