Acid chlorides copper with

Thiazole acid chlorides react with diazomethane to give the diazoketone. The later reacts with alcoholic hydrogen chloride to give chloroacetylthiazole (Scheme 16). However, the Wolff rearrangement of the diazoketone is not consistently satisfactory (82). Heated with alcohol in the presence of copper oxide the 5-diazomethylketone (24) gives ethyl 5-thiazoleacetate (25) instead of the expected ethoxymethyl 5-thiazolyl ketone (Scheme 17) (83). 

Route B requires the synthesis of the ketone starting material and this could be done by Grignard methods (chapter 9) or by acylation of an organo-copper compound with an acid chloride. Acylation with diethyl carbonate requires no special control. 

Carboxylic acid chlorides react with copper(i) cyanide to give the corresponding pyruvonitriles. The preparation and dimerization of cyclohexyl-... 

By warming either copper(I) oxide or a mixture of copper(II) chloride and copper with concentrated hydrochloric acid, until a deep brown solution is formed ... 

The conversion of an aromatic diazonium compound into the corresponding arsonic acid by treatment with sodium arsenite in the presence of a catalyst, such as copper or a copper salt, is called the Bart reaction. A modification of the reaction employs the more stable diazonium fluoborate in place of the diazonium chlorid.i. This is illustrated by the preparation of />-nitrophenylarsonic acid ... 

Chlorobenzene. Prepare a solution of phenyldiazonium chloride from 31 g. (30 -5 ml.) of aniUne, 85 ml. of concentrated hydrochloric acid, 85 ml, of water, and a solution of 24 g. of sodium nitrite in 50 ml. of water (for experimental details, see Section IV,60). Prepare cuprous chloride from 105 g. of crystallised copper sulphate (Section 11,50,1), and dissolve it in 170 ml. of concentrated hydrochloric acid. Add the cold phenyl diazonium chloride solution with shaking or stirring to the cold cuprous chloride solution allow the mixture to warm up to room temperature. Follow the experimental details given above for p-chlorotoluene. Wash the chlorobenzene separated from the steam distillate with 40 ml. of 10 per cent, sodium hydroxide solution (to remove phenol), then with water, dry with anhydrous calcium chloride or magnesium sulphate, and distil. Collect the chlorobenzene (a colourless liquid) at 131-133° (mainly 133°), The yield is 29 g. 

Aromatic amines form addition compounds and complexes with many inorganic substances, such as ziac chloride, copper chloride, uranium tetrachloride, or boron trifluoride. Various metals react with the amino group to form metal anilides and hydrochloric, sulfuric, or phosphoric acid salts of aniline are important intermediates in the dye industry. 

Preparation. Thiophosgene forms from the reaction of carbon tetrachloride with hydrogen sulfide, sulfur, or various sulfides at elevated temperatures. Of more preparative value is the reduction of trichi oromethanesulfenyl chloride [594-42-3] by various reducing agents, eg, tin and hydrochloric acid, staimous chloride, iron and acetic acid, phosphoms, copper, sulfur dioxide with iodine catalyst, or hydrogen sulfide over charcoal or sihca gel catalyst (42,43). 

Butyl Ether. -Butyl ether is prepared by dehydration of -butyl alcohol by sulfuric acid or by catalytic dehydration over ferric chloride, copper sulfate, siUca, or alumina at high temperatures. It is an important solvent for Grignard reagents and other reactions that require an anhydrous, inert medium. -Butyl ether is also an excellent extracting agent for use with aqueous systems owing to its very low water-solubiUty. 

Ammoniacal aiptous chloride is made as follows Eoil up copper oxide and metallic copper with cone hydrochloric acid for a short time until the liquid is nearly colourless, and pour the liquid into water. The white cuprous chloride is washed once or twice by decantation and dissolved in a strong solution of ammonium chloride. When required a little ammonia is added sufficient to give a clear blue solution... 

Ttansmetalation of tliioetliets to organocopper compounds can also be performed in some special cases. Tluis, tteatment of the ester 119 with MeyCuLi-LiCN provides the copper reagent 120, which can be treated successfully witli several electrophiles such as allyl bromide ot acid chlorides to afford the expected products such as 121 iScbeme 2.54) [115, 116]. 

An aqueous solution of zinc chloride, acidified with hydrochloric acid, may be used as a flux. A light flux cover is used on the tinning bath and this is normally produced and maintained by the carry-in of flux solution on the work. The bath temperature should be 250-260°C. Bright annealed copper wire may be fluxed in stannous chloride and tinned at 300° C excess tin is wiped off by pulling the emerging wire between lightly clamped rubber blocks. 

The reaction is a sensitive one, but is subject to a number of interferences. The solution must be free from large amounts of lead, thallium (I), copper, tin, arsenic, antimony, gold, silver, platinum, and palladium, and from elements in sufficient quantity to colour the solution, e.g. nickel. Metals giving insoluble iodides must be absent, or present in amounts not yielding a precipitate. Substances which liberate iodine from potassium iodide interfere, for example iron(III) the latter should be reduced with sulphurous acid and the excess of gas boiled off, or by a 30 per cent solution of hypophosphorous acid. Chloride ion reduces the intensity of the bismuth colour. Separation of bismuth from copper can be effected by extraction of the bismuth as dithizonate by treatment in ammoniacal potassium cyanide solution with a 0.1 per cent solution of dithizone in chloroform if lead is present, shaking of the chloroform solution of lead and bismuth dithizonates with a buffer solution of pH 3.4 results in the lead alone passing into the aqueous phase. The bismuth complex is soluble in a pentan-l-ol-ethyl acetate mixture, and this fact can be utilised for the determination in the presence of coloured ions, such as nickel, cobalt, chromium, and uranium. 

Nickel tetranitrophthalocyanine can be reduced to nickel tetraaminophthalocyanine with tin(II) chloride342 or sodium sulfide.319 343 To achieve better solubility, long alkanoyl side chains can be attached by the reaction of the amino groups with carboxylic acid chlorides.342 Copper(ll) tetranitrophthalocyanine 1 is reduced to the tetraamino compound 2 with sodium suinae." "... 

The reaction of tert-alkyl Grignard reagents with carboxylic acid chlorides in the presence of a copper catalyst provides ieri-alkyl ketones in substantially lower yields than those reported here.4,14 The simplicity and mildness of experimental conditions and isolation procedure, the diversity of substrate structural type, and the functional group selectivity of these mixed organocuprate reagents render them very useful for conversion of carboxylic acid chlorides to the corresponding secondary and tertiary alkyl ketones.15... 

We owe to Kato and his colleagues a considerable advance in furan copper reagents. They have demonstrated the formation of the lithium di(3-furyl) cuprate species 87 which is highly reactive and possesses hard properties that suit it to reaction at hard centers, mainly carbonyl carbon.223 The reagent is easily prepared in situ from 3-furyllithium and Cu2I2. Simple copper derivatives do not react with ketones, but this cuprate reacts well and quantitatively with acid chlorides. It also reacts well with some epoxides (oxirans). Moreover, there is another form prepared in the presence of... 

A number of pyridazines have been prepared by standard condensations of enediones with hydrazine but a general synthesis of the intermediate enediones is notable. This involved iodine-copper exchange of an iodoenone 3, followed by reaction of the resulting cuprate with acid chlorides. However, only a few of these enediones were actually converted into pyridazines <06OL1941>. 

Interestingly, the Fischer indole synthesis does not easily proceed from acetaldehyde to afford indole. Usually, indole-2-carboxylic acid is prepared from phenylhydrazine with a pyruvate ester followed by hydrolysis. Traditional methods for decarboxylation of indole-2-carboxylic acid to form indole are not environmentally benign. They include pyrolysis or heating with copper-bronze powder, copper(I) chloride, copper chromite, copper acetate or copper(II) oxide, in for example, heat-transfer oils, glycerol, quinoline or 2-benzylpyridine. Decomposition of the product during lengthy thermolysis or purification affects the yields. 

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