Copper carbonyl chloride

CsICl2 Cesium iododichloride, 4 9 CsNOs Cesium nitrate, 4 6 1-hydrogen nitrate, 4 7 CsN3 Cesium azide, 1 79 CuBr Copper(I) bromide, 2 3 CuCl Copper(I) chloride, 2 1 [CuC1-CO]-2H20 Copper carbonyl chloride, 2 4... 

Copper I) chloride, CuCl. White solid (CuClj plus HCJ plus excess copper or SO2). Gives carbonyl and phosphine complexes. 

The solvent process involves treating phthalonitrile with any one of a number of copper salts in the presence of a solvent at 120 to 220°C [10]. Copper(I)chloride is most important. The list of suitable solvents is headed by those with a boiling point above 180°C, such as trichlorobenzene, nitrobenzene, naphthalene, and kerosene. A metallic catalyst such as molybdenum oxide or ammonium molybdate may be added to enhance the yield, to shorten the reaction time, and to reduce the necessary temperature. Other suitable catalysts are carbonyl compounds of molybdenum, titanium, or iron. The process may be accelerated by adding ammonia, urea, or tertiary organic bases such as pyridine or quinoline. As a result of improved temperature maintenance and better reaction control, the solvent method affords yields of 95% and more, even on a commercial scale. There is a certain disadvantage to the fact that the solvent reaction requires considerably more time than dry methods. 

Intermediates such as 224 resulting from the nudeophilic addition of C,H-acidic compounds to allenyl ketones such as 222 do not only yield simple addition products such as 225 by proton transfer (Scheme 7.34) [259]. If the C,H-acidic compound contains at least one carbonyl group, a ring dosure is also possible to give pyran derivatives such as 226. The reaction of a similar allenyl ketone with dimethyl mal-onate, methyl acetoacetate or methyl cyanoacetate leads to a-pyrones by an analogous route however, the yields are low (20-32%) [260], The formation of oxaphos-pholenes 229 from ketones 227 and trivalent phosphorus compounds 228 can similarly be explained by nucleophilic attack at the central carbon atom of the allene followed by a second attack of the oxygen atom of the ketone at the phosphorus atom [261, 262], Treatment of the allenic ester 230 with copper(I) chloride and tributyltin hydride in N-methylpyrrolidone (NMP) affords the cephalosporin derivative 232 [263], The authors postulated a Michael addition of copper(I) hydride to the electron-... 

In order to modulate the reactivity of intermediate 331, it was transformed into its copper derivative by treatment with copper(I) bromide or iodide in THF at —78 °C, and then was allowed to react with a,/3-unsaturated carbonyl compounds (to give compounds 343 resulting from a conjugated addition), acyl chlorides (to give ketones 344) and copper(II) chloride (to dimerize giving compounds 345) (Scheme 100)"° ". ... 

Later Gronowitz and Maltesson reported the extension of this method to the preparation of thieno[2,3-6]thiophene (1) derivatives. A mixture of 3-(3-thienyl)acrylic acid, thionyl chloride, and pyridine was heated for 24 hours. 2-Chloro-3-(3-thienyl)-acrylic acid (4.5%), 3,5-dichlorothieno[2,3-6]thiophene-2-carbonyl chloride (99) (9.5%), 3-chlorothieno[2,3-Z)]thiophene-2-carbonyl chloride (100) (79.1%), and other compounds were detected by GLC among the reaction products [Eq. (31)]. Hydrolysis of the reaction mixture gave 3-chlorothieno[2,3-Z>]thiophene-2-carboxylic acid in 63% yield dechlorination of the latter by copper in propionic acid converted it into thieno[2,3-6]thiophene-2-carboxylic acid. 

After ARCO patents issued, Stille and coworkers published on butadiene oxycarbonylation(14-16). Palladium was utilized as the oxidative carbonylation catalyst and copper(II) chloride was employed as a stoichiometric reoxidation agent for palladium. Although the desired hex-3 -enedioate is the exclusive product, commercial technology which uses stoichiometric copper is not practical. Once the copper(Il) is consumed, the monoatomic palladium spent catalyst agglomerates affording polymeric palladium which is not easily reoxidized to an active form. 

Carbon oxychloride, 22 Carbonic dichloride, 22 Carbonyl chloride, 22, 49, 75, 101, 184 5-Carboxy-l,3-diamino-2,4,6-trinitrobenzene, 6 Cast booster, 245, 248 Cast explosive, 4-5 Castable explosive, 56, 113 CDNTA, 4, 32, 58, 86, 109, 124, 169, 197. See also 3,5-dinitro-1.2.4-triazole copper salt CE, 4-5,32,58-59,86, 111, 124,173. See also Cast explosive... 

Carbonylchlorocopper(I) is a colorless crystalline substance that decomposes rapidly in the absence of a carbon monoxide atmosphere to give copper(I) chloride and carbon monoxide. The compound is, however, stable for long periods of time if stored under carbon monoxide. Cu(CO)Cl has a polymeric structure,10 which may be described as layers of fused, six-membered, copper-chloride rings in the chair conformation, with terminally bonded carbonyl ligands. The infrared spectrum of Cu(CO)Cl (Nujol mull at 0°C) displays a characteristic large peak at 2127 cm -1 and a vibrational analysis has been reported.13... 

The synthesis of succinic acid derivatives, /3-alkoxy esters, and a,j3-unsaturated esters from olefins by palladium catalyzed carbonylation reactions in alcohol have been reported (24, 25, 26, 27), but full experimental details of the syntheses are incomplete and in most cases the yields of yS-alkoxy ester and diester products are low. A similar reaction employing stoichiometric amounts of palladium (II) has also been reported (28). In order to explore the scope of this reaction for the syntheses of yS-alkoxy esters and succinic acid derivatives, representative cyclic and acyclic olefins were carbonylated under these same conditions (Table I). The reactions were carried out in methanol at room temperature using catalytic amounts of palladium (II) chloride and stoichiometric amounts of copper (II) chloride under 2 atm of carbon monoxide. The methoxypalladation reaction of 1-pentene affords a good conversion (55% ) of olefin to methyl 3-methoxyhexanoate, the product of Markov-nikov addition. In the carbonylation of other 1-olefins, f3-methoxy methyl esters were obtained in high yields however, substitution of a methyl group on the double bond reduced the yield of ester markedly. For example, the carbonylation of 2-methyl-l-butene afforded < 10% yield of methyl 3-methyl-3-methoxypentanoate. This suggests that unsubstituted 1-olefins may be preferentially carbonylated in the presence of substituted 1-olefins or internal olefins. The reactivities of the olefins fall in the order RCH =CHo ]> ci -RCH=CHR > trans-RCH =CHR >... 

Di-jjL-carbonylhexacarbonyldicobalt, 99 Dichlorobis(triphenylphosphine)palla-dium(II), 103 Iron carbonyl, 152 Palladium(II) chloride-Copper(II) chloride, 235... 

A solulion of CuCl in HCI absorbs carbon monoxide, forming copperil) carbonyl chloride. Cu(CO)Cl H 0. This reaction, which is used In gas analysis, is Indicative of the ability of copper to combine with carbon monoxide. Evidence for a true carbonyl is limited to the observation that if hot carbon monoxide is passed over hot copper, a metallic mirror is produced in the hotter parts of the tube. Other organometallic compounds include Ihe very unstable methyl copper, CHiCu. phenyl copper. C<,H5Cu, and bixchlurucopper acetylene CjHrtCuCIi . 

The initial synthetic approach to conivaptan HCl (1) employed by the Yamanouchi discovery group26 commenced with commercially available benzazepinone 10. Acylation of 10 with p-nitrobenzoyl chloride provided benzamide 11. Subsequent hydrogenation of 11 over palladium on carbon yielded aniline 12, which was in turn condensed with biphenyl-2-carbonyl chloride to provide bis(amide) 13. Bis(amide) 13 was subsequently heated with copper(II) bromide in boiling chloroform/ethyl acetate to furnish a-bromoketone 14. It is interesting that condensation of a-bromoketone 14 with acetamidine hydrochloride in the presence of potassium carbonate in boiling acetonitrile afforded not only the desired imidazobenzazepine product (1 53% yield, 2 steps) but also the related oxazolobenzazepine 15 (7% yield, 2 steps), which presumably resulted from nucleophilic attack of the benzazepinone oxygen on the amidine moiety followed by loss of ammonia. Separation of oxazolobenzazepine byproduct 15 from imidazobenzazepine 1 by silica gel chromatography followed by treatment of the purified imidazobenzazepine free-base with hydrochloric acid then provided conivaptan HCl (1). 

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