Copper thiophenoxide

Carboxylic acids, a-bromination of 55, 31 CARBOXYLIC ACID CHLORIDES, ketones from, 55, 122 CARBYLAMINE REACTION, 55, 96 Ceric ammonium nitrate [Ammonium hexa mtrocerate(IV)[, 55, 43 Chlorine, 55, 33, 35, 63 CHROMIUM TRIOXIDE-PYRIDINE COMPLEX, preparation in situ, 55, 84 Cinnamomtnle, a-phenyl- [2-Propeneni-tnle 2,3-diphenyl-], 55, 92 Copper(l) iodide, 55, 105, 123, 124 Copper thiophenoxide [Benzenethiol, copper(I) salt], 55, 123 CYCLIZATION, free radical, 55, 57 CYCLOBUTADIENE, 55, 43 Cyclobutadieneiron tricarbonyl [Iron, tn-carbonyl(r)4-l,3-cyclo-butadiene)-], 55,43... 

Organobis(cupratesY, spiroannelation.16 1,4-Dilithiobutane, prepared from 1,4-dichlorobutane and lithium in ether at 0°, on reaction with copper thiophenoxide (2 equiv.) forms a biscuprate, formulated as 1 for convenience. This dimetallic reagent adds to 3-halo-5,5-dimethyl-2-cyclohexenones (2) to form the spiro-[4.5]decanone 3 in yields as high as 96%. Cuprates prepared from other Cu(I) sources are less efficient, as is the cuprate prepared from di-Grignard reagents... 

Cuprates derived from copper thiophenoxide and 3 mol equiv. of organomagnesium reagent were also shown to undergo conjugate addition with P-monosubstituted enoates.86 The large molar excess of RMgX is necessary and ether is the preferred solvent for the reaction (equation 42). The results with di-substituted enoates have not been reported, and should provide a further test of the utility of this reagent. 

Dimedone, oxalyl chloride, 1,4-dichlorobutane, and copper thiophenoxide were purchased from Fluka Chemical Corporation, and were used without further purification. The checkers purchased dimedone, oxalyl chloride and 1,4-dichlorobutane from Nacalai Tesque, Inc., Kyoto, Japan and Tokyo Kasei Kogyo Co., LTD, Japan, and prepared copper thiophenoxide from thiophenol and copper(l) oxide. Toluene, diethyl ether and tetrahydrofuran were distilled from sodium-benzophenone ketyl immediately prior to use. 

An earlier application of 1,4-conjugate additions employing azaallyllithium reagents formed from ketone dimethylhydrazones is Kelly s hydrazone version of the classical Knoevenagel route to substituted pyridine derivatives.71 In this chemistry, a mixed cuprate derived from a dimethylhydrazone lithio anion and copper thiophenoxide was first allowed to react with an a,p-unsaturated ketone. The product enolate can then be acylated or protonated to yield either a diketo hydrazone or a keto hydrazone. Addition of... 

CHROMIUM TRIOXIDE-PYRIDINE COMPLEX, preparation in situ, 55, 84 Chrysene, 58,15, 16 fzans-Cinnamaldehyde, 57, 85 Cinnamaldehyde dimethylacetal, 57, 84 Cinnamyl alcohol, 56,105 58, 9 2-Cinnamylthio-2-thiazoline, 56, 82 Citric acid, 58,43 Citronellal, 58, 107, 112 Cleavage of methyl ethers with iodotri-methylsilane, 59, 35 Cobalt(II) acetylacetonate, 57, 13 Conjugate addition of aryl aldehydes, 59, 53 Copper (I) bromide, 58, 52, 54, 56 59,123 COPPER CATALYZED ARYLATION OF /3-DlCARBONYL COMPOUNDS, 58, 52 Copper (I) chloride, 57, 34 Copper (II) chloride, 56, 10 Copper(I) iodide, 55, 105, 123, 124 Copper(I) oxide, 59, 206 Copper(ll) oxide, 56, 10 Copper salts of carboxylic acids, 59, 127 Copper(l) thiophenoxide, 55, 123 59, 210 Copper(l) trifluoromethanesulfonate, 59, 202... 

S)- (113162-02-0), 70, 47 (E)-Clnnamaldehyde, 70, 197, 240 Citric acid, 70, 54 CONJUGATED ENYNES, 70, 215 Copper(l) bromide-dimethyl sulfide complex, 70, 218 Copper cyanide (544-92-3), 70, 196 Copper(l) thiophenoxide, 70, 206 Copper-zinc organometallic, 70, 196 Crown ethers, chiral, 70, 65... 

Mixed cuprates derived fiom deprotonation and transmetalation of ketone dimethylhydrazones, using copper(I) thiophenoxide as the copper(I) source, are effective as enolate equivalents in 1,4-conjugate additions to a,3-unsaturated esters. The mixed phenylthio cuprate was found to exhibit approximately the same selectivity and reactivity in these reactions as a similar homocuprate (63) prepaid from the aza-allyllithium reagents and copper(I) iodide (equation 29). 

Chemists at the Sagami Research Centre constructed the bicyclic compound (139) by thermolysis of (138) in benzene in the presence of copper acetoacetate. Ring opening of (139) with potassium thiophenoxide in r-butanol led to (140) which was elaborated to ( )-ll-deoxy-PGEi via alkylation with methyl 7-iodoheptanoate and decarboxylation to provide the a-chain, and then successive treatment with m-chloroperbenzoic acid and trimethyl phosphite [143]. 9-Deoxyprostagjandins have also been synthesized [144-146]. 

A new ring-expansion sequence leading from cyclobutanone to 2-phenylthiocyclo-pentanone (402) has been described. Addition of lithium diphenylthiomethane to cyclobutanone gives the alcohol (403). Treatment of (403) with copper triflate in presence of di-isopropylamine results in removal of one of the thiophenoxide residues and ring-expansion, presumably via the cationic intermediate (404), to the cyclo-pentanone. 

Thioesters, Selenoesters, and Thioamides.—Commercially available phenyl dichlorophosphate has been reported to be a superior reagent to MV-dimethyl-phosphoramidic dichloride (4, 244) for the preparation of thioesters directly from carboxylic acids and thiols. Carboxylic acid chlorides can be efficiently converted into thioesters by reaction with adducts formed between thiols and l-methylpyridine-3,5-dicarboxylates. Alternatively, copper(i) mercaptides, formed from thiols and CuaO, or thallous thiophenoxide can be used. The latter method can also be used to prepare selenoesters as well as a-phenylthio-and a-phenylseleno-acids and esters from a-halo-acids and a-halo-esters, respectively. 

Treatment of 3-chlorothietan with potassium thiophenoxide or potassium thiobutoxide gave phenyl or n-butyl allyl disulphide. The thietan ring in a tricyclic system is opened in various reactions. While most cyclic sulphides give ylides on treatment with dimethyl diazomalonate, thietan gave 26% of ring-expanded product (165). In the absence of copper sulphate a polymer was obtained. "... 

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