Phosgene in toluene

Carbazole-9-carbonyl chloride [73500-82-0J M 300.0, m 100-103 , 103.5-104.5 . Recrystd from C6H6. If it is not very pure (presence of OH or NH bands in the IR) dissolve in pyridine, shake with phosgene in toluene, evaporate and recrystallise the residue. Carry out this experiment in a good fume cupboard as COCI2 is very TOXIC, and store the product in the dark. It is moisture sensitive. The amide has m 246.5-247 , and the dimethylaminoethylamide hydrochloride has m 197-198 . [Weston et al. J Am Chem Soc IS 4006 1953.]... 

A cooled 10% solution of 1 mol of phosgene in toluene was added with stirring to a cooled solution of 1 mol of 2-methyl-2-propyl-1,3-propanediol and 2 mols of dimethylaniline also dissolved in toluene, at such a rate that the temperature of the mixture was maintained at about 25°C. The mixture was allowed to remain at this temperature for several hours, then... 

Diethylmethyl propylmalonate is reacted with LiAIH4, then H2SO4 to give 2-methyl-2-propyl-1,3-propanediol. That is reacted with phosgene in toluene to give the chlorocar-bonate which is in turn reacted with butylamine to give N-butyl-2-methyl-2-propyl-3-hy-droxy-propyl carbamate. 

Phosgene from a commercial cylinder was used (Matheson Company or Ohio Chemical Company). For the preparation of a solution of phosgene in toluene see Organic Syntheses ... 

The aniline was being phosgenated in toluene as solvent, the reaction ran wild and ejected more than 3 tonnes of reactor contents. This is believed to have been due to water contamination, possibly as ice. An initial charge of only part of the phosgene failed to show the exotherm anticipated if water was present, however this may not have been enough, nor was the thermocouple immersed in the solvent. See Diprotium monoxide... 

The ester is made by adding benzyl alcohol slowly to a preformed solution of phosgene in toluene at 12-16°C, toluene solvent finally being distilled off under vacuum. When discoloured phosgene was used (probably containing iron salts from corrosion of the cylinder), a violent explosion occurred during the distillation phase, presumably involving iron-catalysed decomposition of the chloroformate ester. 

Chloropropyl)-2-piperidone and 1 -(2-chloroethyl)-2-pyrrolidone were reacted with phosgene in toluene, and the 2-chloro derivatives (466, n = 0, 1, R2 = H, R3 = (CH2), C1, m = 2, 3, R5 = Cl) were then reacted with Meldrum s acid (421) in the presence of triethylamine to give isopropylidene [l-(3-chloroalkyl)piperidin-2-ylidene]malonate and [l-(2-chloroethyl)pyrrolidin-2-ylidene]malonate (468, n = 0, 1 R2 = H ... 

To this mixture, acetonitrile (1.2 mL) and 20% solution of phosgene in toluene (485 pL) were thereto added, and was shaken at room temperature for 1 h. 

Phosgene in toluene (20% w/w) is added over 0.5 h to 2.1 g (13.9 mmol) of 2-aminobenzoic acid in 3 mL of water containing 1.2 g (30 mmol) of sodium hydroxide at 0 C, stirring is continued for 1 h at 0°C and then the mixture allowed to reach 20 °C. The product is collected by filtration, washed with two 10-mL portions of water and two 10-mi, portions of diethyl ether, then dried in vacuo overnight. It is usually pure enough for the next step, however, it can be purified by recrystallization from ethanol. 

Phosgene in toluene (46.2 mL, 87.0 mmol) (a reagent which is extremely toxic and requires careful handling), was then added dropwise over a period of 30 min at 0 °C. Vigorous stirring, was mandatory to adequately neutrahze HCl. 

A reactor charged with the step 4 product, 75 ml of CH2CI2, and 10.8 ml of pyridine was treated with dropwise addition of 22.5 ml of 1.94 M solution of phosgene in toluene (43.6 mmol) at ambient temperature. The mixture stirred for 3.5 hours and was then diluted with 500 ml of CH2C12 and transferred into a separatory funnel. The mixture was extracted with 0.2 M hydrochloric acid, the organic phase dried over MgS04, concentrated to 150 ml, and precipitated by pouring into 750 ml of hexane and the product isolated. 

NM -Bis(5-nilro-2-methylphenyl)-urea, ndls, (from glac acet ac), mp 300 05° (sublimation) insol in benz, etb chlf si sol in ale sol in glac acet ac. It was prepd by heating 4-nicro-2-aminotoluene phosgene in toluene... 

The ester is made by adding benzyl alcohol slowly to a preformed solution of phosgene in toluene at 12—16°C, toluene solvent finally being distilled off under... 

To 20% solution of phosgene in toluene, agitated and cooled to 0°C, are added over 30 min a solution of l-p-fluoro-benzoyl-l-hydroxy-3-N-[N -(2-methoxyphenyl)]piperazinopropane and triethylamine in anhydrous chloroform. It is agitated at ambient temperature for 5 h, cooled to 0°C and the solution saturated with gaseous ammonia. The solution is agitated at ambient temperature for 3 h, filtered and the filtrate dried under reduced pressure, 4-p-fluorophenyl-5-p-(4-o-methoxyphenylpiperazino)ethyl-4-oxazolin-2-one, melting point 154°C (by alcohol) was obtained. 

Telluroformates 144 were prepared by the treatment of alcohols 143 with a solution of phosgene in toluene, followed by sodium phenyltelluroate, and were isolated as yellow/orange viscous oil in 74% yield. It seems reasonable to say that the saturated selenium-containing rings 145 were formed through intramolecular nucleophilic substitution of the benzylse-leno moiety in telluroformates 144 with decarboxylative loss of phenyl telluride (Scheme 15) <1998JOC3032>. 

In a dry flask containing 4.2 ml of 1.89 M phosgene in toluene was added a solution of 9H-fluoren-9-yl-methyl hydrazine carboxylate (3.91 mmol) dissolved in 40 ml of CH2CI2 and 40 ml of saturated aqueous NaHC03 solution. The mixture ws stirred 15 minutes and 58 mg of product isolated. IR data supplied. 

When 3 4-diaminophenylarsinic acid in alkaline solution is treated with phosgene in toluene, with ice cooling and stirring, a carbamide is formed ... 

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