Iodide, cuprous

The reaction of 1,3,5-tribromobenzene with excess sodium methoxide in methanol—/V,/V-dimethy1formamide and in the presence of a catalytic amount of cuprous iodide gives ca 90% yield phlorogluciaol trimethyl ether (1,3,5-trimethoxybenzene). The latter is hydrolyzed with 35 wt % hydrochloric acid at room temperature to give a 90% yield of phlorogluciaol (140—142). 

Iodized Salt. Iodized table salt has been used to provide supplemental iodine to the U.S. population since 1924, when producers, in cooperation with the Michigan State Medical Society (24), began a voluntary program of salt iodization in Michigan that ultimately led to the elimination of iodine deficiency in the United States. More than 50% of the table salt sold in the United States is iodized. Potassium iodide in table salt at levels of 0.006% to 0.01% KI is one of two sources of iodine for food-grade salt approved by the U.S. Food and Dmg Administration. The other, cuprous iodide, is not used by U.S. salt producers. Iodine may be added to a food so that the daily intake does not exceed 225 p.g for adults and children over four years of age. Potassium iodide is unstable under conditions of extreme moisture and temperature, particularly in an acid environment. Sodium carbonate or sodium bicarbonate is added to increase alkalinity, and sodium thiosulfate or dextrose is added to stabilize potassium iodide. Without a stabilizer, potassium iodide is oxidized to iodine and lost by volatilization from the product. Potassium iodate, far more stable than potassium iodide, is widely used in other parts of the world, but is not approved for use in the United States. 

Cuprous iodide trimethylphosphite [34836-53-8] M 314.5, m 175-177°, 192-193°. Cuprous iodide dissolves in a C Hg soln containing trimethylphosphite to form the complex. The complex crystallises from C6Hg or pet ether. [Chem Ber 38 1171 7905 Bull Chem Soc Jpn 34 1177 7967.]... 

Another process using butadiene as the starting material was developed by Esso. This involved the reaction of butadiene with iodine and cuprous cyanide to give the cuprous iodide complex of dehydroadiponitrile. This is further reacted with HCN to give a high yield of dehydroadiponitrile and regeneration of the iodine and cuprous iodide. 

When one equiualini of cuprous iodide was treated with one equivalent of methyliithium the yelU)w, ether-insoLubli product wasfonved. Both the precipitate and thi eihir solution... 

Cupro-. cuprous, copper(I), cupro-. -chlorid, n. cuprous chloride, copper(I) chloride, -cy-aniir, n. cuprous cyanide, copper(I) cyanide cuprocyanide, cyanocuprate(I). -jodid, n. cuprous iodide, copper(I) iodide, -mangan, n. cupromanganese. -oxyd, n. cuprous oxide, copper(I) oxide, -salz, n. cuprous salt, cop-per(I) salt, -suifocyantir, n. cuprous thiocyanate, copper (I) thiocyanate, -verbin-dUDg, /. cuprous compound, copper(I) compound. 

Most of the iodine can be recovered as potassium iodide mixed with some potassium carbonate. A little cuprous iodide is also present. 

A synthetically useful virtue of enol triflates is that they are amenable to palladium-catalyzed carbon-carbon bond-forming reactions under mild conditions. When a solution of enol triflate 21 and tetrakis(triphenylphosphine)palladium(o) in benzene is treated with a mixture of terminal alkyne 17, n-propylamine, and cuprous iodide,17 intermediate 22 is formed in 76-84% yield. Although a partial hydrogenation of the alkyne in 22 could conceivably secure the formation of the cis C1-C2 olefin, a chemoselective hydrobora-tion/protonation sequence was found to be a much more reliable and suitable alternative. Thus, sequential hydroboration of the alkyne 22 with dicyclohexylborane, protonolysis, oxidative workup, and hydrolysis of the oxabicyclo[2.2.2]octyl ester protecting group gives dienic carboxylic acid 15 in a yield of 86% from 22. 

Potassium iodide is added as a nutrient to prevent goiter, a thyroid problem caused by lack of iodine, and to prevent a form of mental retardation associated with iodine deficiency. A project started by the Michigan State Medical Society in 1924 promoted the addition of iodine to table salt, and by the mid-1950s three-quarters of U.S. households used only iodized salt. Potassium iodide makes up 0.06 percent to 0.01 percent of table salt by weight. Sometimes cuprous iodide—iodide of copper—is used instead as the source of iodine. 

Cuprous iodide catalyzes the reaction of various alkyl chlorides, bromides, and iodides in hexamethylphosphoric triamide (HMPT), to give the complexed product RaSnXj, which can then be further alkylated with a Grignard reagent, or can be hydrolyzed to the oxide and converted into various other compounds, R2SnY2 (43). This promises to be a useful laboratory method, e.g.,... 

Iodinations can be carried out by mixtures of iodine and various oxidants such as periodic acid,26 I205,27 N02,28 and Ce(NH3)2(N03)6.29 A mixture of a cuprous iodide and a cupric salt can also effect iodination.30... 

Kotschy et al. also reported a palladium/charcoal-catalyzed Sono-gashira reaction in aqueous media. In the presence of Pd/C, Cul, PPI13, and z -Pr2NH base, terminal alkynes smoothly reacted with aryl bromides or chlorides, such as 2-pyridyl chloride, 4-methylphenyl bromide, and so on, to give the expected alkyne products in dimethyl-acetamide (DMA)-H20 solvent. Wang et al. reported an efficient cross-coupling of terminal alkynes with aromatic iodides or bromides in the presence of palladium/charcoal, potassium fluoride, cuprous iodide, and triph-enylphosphine in aqueous media (THF/H20, v/v, 3/1) at 60°C.35 The palladium powder is easily recovered and is effective for six consecutive runs with no significant loss of catalytic activity. 

A rapid MW-assisted palladium-catalyzed coupling of heteroaryl and aryl boronic acids with iodo- and bromo-substituted benzoic acids, anchored on TentaGel has been achieved [174]. An environmentally friendly Suzuki cross-coupling reaction has been developed that uses polyethylene glycol (PEG) as the reaction medium and palladium chloride as a catalyst [175]. A solventless Suzuki coupling has also been reported on palladium-doped alumina in the presence of potassium fluoride as a base [176], This approach has been extended to Sonogashira coupling reaction wherein terminal alkynes couple readily with aryl or alkenyl iodides on palladium-doped alumina in the presence of triphenylphosphine and cuprous iodide (Scheme 6.52) [177]. 

Vinylstannane compounds containing a remote vinyl halide moiety undergo a stereospecific internal coupling reaction, catalysed by cuprous iodide, leading to conjugated dienes, as illustated, for example, in reaction 66. ... 

Quite different from the original Sonogashira conditions, the following cross-coupling was achieved under the Jeffery s ligand-free conditions in the absence of cuprous iodide [63] [64]. 

Wang s approach for the synthesis of enyne-allenes focused on ene-allenyl iodide 45 (Scheme 14.12) [24]. Palladium-catalyzed Sonogashira reaction of 45 with terminal alkynes 46 (R= Ph or CH2OH) proceeded smoothly under mild reaction conditions in the presence of the cocatalyst cuprous iodide and n-butylamine. The initially formed enyne-allene 47b with substituent R= CH2OH cyclized spontaneously to the corresponding a-methylstyrene derivative 48. 

All of the sulfone diols were able to form oligomers in the second step of the reaction sequence, the Ullmann ether synthesis. As with the synthesis of the mono(bromophenoxy)phenol products, two methods were used to form the dibromo materials. Method A used pyridine, potassium carbonate and cuprous iodide, while Method B employed collidine and cuprous oxide with the dibromobenzene and higher molecular weight diol (IV). The major difference between the syntheses of the mono(bromophenoxy)phenols described earlier and these lies in the stoichiometry of the reactions. In order to... 

Mono(bromophenoxy)phenol (I). The mono(bromophenoxy)phenols required for the monomeric models were synthesized by two methods. Method A A mixture of pyridine (90mL), diol (60 mmol), dibromobenzene (56.4g, 240 mmol), anhydrous potassium carbonate (33.3g, 250 mmol) and cuprous iodide (1.62g, 9 mmol) was heated at reflux under nitrogen for 20h. After cooling to room temperature, the reaction mixture was acidified with IN HC1 and the product extracted with chloroform. The chloroform was evaporated and the residue extracted with 10% aq. NaOH. The aqueous phase was acidified, extracted with chloroform, and reduced in volume to an oil that was stirred with 20% aq NaOH to afford the sodium salt of the product. The salt was Isolated and dried to give a white solid. The solid was acidified to pH 1 in water, and the freed mono(bromophenoxy)phenol was washed with water and dried. C-H analysis for products was satisfactory. 

The reaction shown in Scheme 6.6 takes place in HMPA. Photoirradiation results in the formation of undesirable by-products, but the initiation with cuprous iodide leads to the aimed substance with more than 60% yield. 

Another hydride, magnesium hydride prepared in situ from lithium aluminum hydride and diethylmagnesium, reduced terminal alkynes to 1-alkenes in 78-98% yields in the presence of cuprous iodide or cuprous r rt-butoxide, and 2-hexyne to pure cij-2-hexene in 80-81% yields [///]. Reduction of alkynes by lithium aluminum hydride in the presence of transition metals gave alkenes with small amounts of alkanes. Internal acetylenes were reduced predominantly but not exclusively to cis alkenes [377,378]. 

Alkyl bromides and especially alkyl iodides are reduced faster than chlorides. Catalytic hydrogenation was accomplished in good yields using Raney nickel in the presence of potassium hydroxide [63] Procedure 5, p. 205). More frequently, bromides and iodides are reduced by hydrides [505] and complex hydrides in good to excellent yields [501, 504]. Most powerful are lithium triethylborohydride and lithium aluminum hydride [506]. Sodium borohydride reacts much more slowly. Since the complex hydrides are believed to react by an S 2 mechanism [505, 511], it is not surprising that secondary bromides and iodides react more slowly than the primary ones [506]. The reagent prepared from trimethoxylithium aluminum deuteride and cuprous iodide... 

Triphenylstannane reduced the double bond in dehydro-)J-ionone in 84% yield [872], Complex copper hydrides prepared in situ from lithium aluminum hydride and cuprous iodide in tetrahydrofuran at 0° [873], or from lithium trimethoxyaluminum hydride or sodium bis(methoxy-ethoxy)aluminum hydride and cuprous bromide [874] in tetrahydrofuran at 0° reduced the a,p double bonds selectively in yields from 40 to 100%. Similar selectivity was found with a complex sodium bis(iron tetracarbonyl)hydride NaHFe2(CO)g [875]. 

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