Diethyl copper chloride

Diethyl ether Copper chloride, oxalate, sulfate... 

To a solution of copper chloride (2.4 mg, 0.024 mmol) in DMF (1.5 ml) was added l-chloro-2-phenylacetylene (50 mg, 0.37 mmol) at r.t. To the mixture was added trimethyl(4-methoxyphenylethynyl)silane (50 mg, 0.25 mmol). The reaction mixture was stirred for 48 h at 80 °C, quenched with 3 M HCl, and extracted with diethyl ether (25 ml x 2). The combined ethereal layer was washed with aqueous NaHCOj solution, then with brine and dried over MgS04. Filtration and evaporation provided a brown oil. Purification by column chromatography (Si02, hexane dichloromethane = 10 1) gave l-(4-methoxyphenyl)-4-phenyl-1,3-butadiyne (36 mg, 65% yield) as a colorless solid. 

Trimethylene dibromide (Section 111,35) is easily prepared from commercial trimethj lene glycol, whilst hexamethylene dibromide (1 O dibromohexane) is obtained by the red P - Br reaction upon the glycol 1 6-hexanediol is prepared by the reduction of diethyl adipate (sodium and alcohol lithium aluminium hydride or copper-chromium oxide and hydrogen under pressure). Penta-methylene dibromide (1 5-dibromopentane) is readily produced by the red P-Brj method from the commercially available 1 5 pentanediol or tetra-hydropyran (Section 111,37). Pentamethylene dibromide is also formed by the action of phosphorus pentabromide upon benzoyl piperidine (I) (from benzoyl chloride and piperidine) ... 

To a mixture of 100 ml of THF and 0.10 mol of the epoxide (note 1) was added 0.5 g Of copper(I) bromide. A solution of phenylmagnesium bromide (prepared from 0.18 mol of bromobenzene, see Chapter II, Exp. 5) in 130 ml of THF was added drop-wise in 20 min at 20-30°C. After an additional 30 min the black reaction mixture was hydrolysed with a solution of 2 g of NaCN or KCN and 20 g of ammonium chloride in 150 ml of water. The aqueous layer was extracted three times with diethyl ether. The combined organic solutions were washed with water and dried over magnesium sulfate. The residue obtained after concentration of the solution in a water-pump vacuum was distilled through a short column, giving the allenic alcohol, b.p. 100°C/0.2 mmHg, n. 1.5705, in 75% yield. 

After the air in the flask had been replaced completely with nitrogen, 100 ml of dry diethyl ether, 0.20 mol of the cumulenic ether (see Chapter V, Exps. 7, 8 and 11) and 1 g (note 1) of copper(l) bromide were placed in it. A solution of the Grignard-reagent, prepared from 0.50 mol of the chloride (see Chapter II,... 

To a suspension of a tinc-copper couple in 150 ml of 100 ethanol, prepared from 80 g of zinc powder (see Chapter II, Exp. 18), was added at room temperature 0.10 mol of the acetylenic chloride (see Chapter VIII-2, Exp. 7). After a few minutes an exothermic reaction started and the temperature rose to 45-50°C (note 1). When this reaction had subsided, the mixture was cooled to 35-40°C and 0,40 mol of the chloride was added over a period of 15 min, while maintaining the temperature around 40°C (occasional cooling). After the addition stirring was continued for 30 min at 55°C, then the mixture was cooled to room temperature and the upper layer was decanted off. The black slurry of zinc was rinsed five times with 50-ml portions of diethyl ether. The alcoholic solution and the extracts were combined and washed three times with 100-ml portions of 2 N HCl, saturated with ammonium chloride. 

Aluminium can be deposited from complex organic solutions if sufficient precautions are taken, and such coatings are now being produced commercially in North America. Two of the systems on record are (1) aluminium trichloride and lithium aluminium hydride dissolved in diethyl ether used at 40°C and 50A/m, and (2) aluminium chloride, n-butylamine and diethyl ether used at 20°C and 970 A/m. Deposits of 0-010 mm can be obtained on mild steel or copper at 20°C and 970 A/m using aluminium-wire anodes and nitrogen or argon atmospheres. 

Dermal Effects. Skin irritation was noted in wildlife officers at the RMA after they handled sick or dead ducks without gloves (NIOSH 1981). Although the investigators concluded that diisopropyl methylphosphonate contributed to the local effects, a number of other compounds were present. Analysis of the pond water indicated the presence of a number of organic and inorganic contaminants, including diisopropyl methylphosphonate (11.3 ppm) aldrin (0.368 ppm) dieldrin (0.0744 ppm) dicyclo-pentadiene, bicycloheptadiene, diethyl benzene, dimethyl disulfide, methyl acetate, methyl isobutyl ketone, toluene, and sodium (49,500 ppm) chloride (52,000 ppm) arsenic (1,470 ppm) potassium (180 ppm) fluoride (63 ppm) copper (2.4 ppm) and chromium (0.27 ppm). Because of the presence of numerous compounds, it is unclear whether diisopropyl methylphosphonate was related to the irritation. 

Diethyl N-[2,4-bis(dimethylamino)-1,3,5-triazin-6-yl]aminomethylene-malonate was prepared in the reaction of 2,4-bis(dimethylamino)-6-isocya-no-l,3,5-triazine and diethyl malonate in boiling benzene in the presence of copper(I) chloride for 4 hr in 83% yield (89JHC901). 

PdCf-catalysed methoxycarbonylation of organic tellurides with carbon monoxide (typical procedure)In a two-necked, 50 mL, round-bottomed flask with a septum inlet and a three-way stopcock were placed PdCl2 (0.017 g, 0.1 mmol), copper(ll) chloride (0.270 g, 2.0 mmol) and a telluride (1.0 mmol). The system was then flushed with CO from a CO balloon connected to the flask at 25°C, to which dry methanol (10 mL) and triethylamine (0.303 g, 3.0 mmol) were added by a syringe. After the mixture was stirred for 75 h at 25°C, during which time the green colour turned to dark brown, the brown solid was filtered off The filtrate was poured into NH4CI aqueous solution and extracted with diethyl... 

The efficient At-nitration of secondary amines has been achieved by transfer nitration with 4-chloro-5-methoxy-2-nitropyridazin-3-one, a reagent prepared from the nitration of the parent 4-chloro-5-methoxypyridazin-3-one with copper nitrate trihydrate in acetic anhydride. Reactions have been conducted in methylene chloride, ethyl acetate, acetonitrile and diethyl ether where yields of secondary nitramine are generally high. Homopiperazine is selectively nitrated to At-nitrohomopiperazine or At, At -dinitrohomopiperazine depending on the reaction stoichiometry. At-Nitration of primary amines or aromatic secondary amines is not achievable with this reagent. 

Diphenylacetic acid has been obtained by the reduction of benzilic acid with hydriodic acid and red phosphorus 1 by the treatment of phenylbromoacetic acid with benzene and zinc dust,2 or with benzene and aluminum chloride 3 by the hydrolysis of diphenylacetonitrile 4 by heating a-diphenyldichloroethyl-ene with alcoholic sodium ethylate 5 by heating benzilic acid 6 from diphenylmethane, mercury diethyl, sodium and carbon dioxide 7 by the oxidation of a,a,5,S-tetraphenyl- 8-butine 8 by the decomposition of some complex derivatives obtained from diphenylketene 9 by the hydrolysis of diphenyl-5,5-hydan-toin 10 by the treatment of diphenylbromoacetic acid with copper 11 by the oxidation of dichlorodiphenylcrotonic acid.12... 

Nitric acid, N-Methyl gluconamide. Acetic anhydride. Sodium bicarbonate. Methanol Dimethylurea, Nitric acid, Sulfuric acid. Methylene chloride, Sodium carbonate Anhydrous hydrazine, Cyanogen bromide, Isopropyl alcohol, Sodium nitrite, Sodium bicarbonate, Copper nitrate trihydrate, Nitric acid, Diethyl ether, Dimethyl sulfate... 

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