P-Chloropropionyl chloride

A 100 gallon lined jacketed kettle provided with cooling is charged with 100 lb of benzylamine and 150 liters of water. The mixture is cooled to 5°C and with stirring 119 lb of p-chloropropionyl chloride and a solution of 45 lb of sodium hydroxide pellets in 40 liters of water are added simultaneously at such a rate that the temperature does not exceed 10°C. During this period the pH of the... 

Acetylene reacts with hydrogen chloride and carbon monoxide in presence of RhCl2 as catalyst to give acrylic add chloride [459] whereas with complex Pd-salts mainly succinic acid dichloride [460] and smaller amounts of p-chloropropionyl chloride are formed. When hydrogen chloride is replaced by phosgene, trans, trans-muconic acid dichloride besides fumaric add dichloride is obtained [463]. 

To a solution of 10 g (0.035 mole) of ethyl phenthiazine-2-carbamate in 30 ml of anhydrous toluene is added dropwise 5.3 g (0.042 mole) of 3-chloropropionyl chloride, and the mixture is refluxed at 110-120°C for 4 hours, followed by clarifying the mixture with activated carbon and cooling it to room temperature. A precipitate of ethyl 10-(3-chloropropionyl)-phenthiazine-2-carbamate is removed by filtration. The yield is 10.2 g (77.5% of the theoretical amount), M.P. 169-170°C. 

The reaction flask is allowed to cool and is then immersed in an ice-watcr bath. A solution of 160-180 g. (4 4.5 moles) of sodium hydroxide pellets in 500 ml. of water is added slowly with stirring until the pH rises to 5. After the addition of400 ml. of ether, the products are transferred to a 5-1. separatory funnel and then shaken. I he darkly colored organic upper layer is separated and the aqueous layer extracted with two 500-ml. portions of ether. The combined ether extracts are dried over anhydrous magnesium sulfate and concentrated to about 800 ml. under reduced pressure in a rotary evaporator. The concentrated extract is transferred to a 1-1. round-bottomed flask and fractionated through a 25-cm. Vigreux column under reduced pressure. A forerun of dioxane is collected and then tctrahydro-4H-pyranc-4-onc distils as a colorless liquid, b.p. 59 60°/l3 mm. The yield is 102 112 g. (50 55%) for the two steps, based on 3-chloropropionyl chloride. 

The Nierenstein reaction has been applied in the synthesis of 4-(P-chloromethyl)-2-aminothiazole by Carroll and Smith in 1933. The a, P-dichloromethylethyl ketone 22 was prepared via the Nierenstein reaction of the corresponding chloropropionyl chloride 21. Reaction with thiourea yielded the cyclized product 23. The authors additionally prepared the same ketone using an alternative approach involving the addition of ethylene to chloroacetyl chloride with aluminium chloride as a condensing agent. 

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