Hydrochloric Acid → Benzenediazonium, 4-chloro-, chloride

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A 250 ml, three necked, round bottomed flask was equipped with addition funnel, paddle stirrer, and thermometer. The flask was charged with 50 ml methanol, sodium acetate (16.0 g, 0.198 mole), and 6-methyl-5-carbomethoxy-4-hydroxy-2-pyrone (8.0 g, 0.43 mole). p-Chlorobenzenediazonium chloride was prepared on the side by the dropwise addition of sodium nitrite (3.3 g, 0.047 mole) in 10 ml water to a cooled (5°) slurry containing p-chloroaniline (5.6 g, 0.043 mole) in aqueous hydrochloric acid (16.5 ml 12N HCl [0.198 mole] plus 10 ml water). The diazonium chloride solution was added dropwise to the solution containing the pyrone. This addition was carried out during 10 min. with no noticeable exotherm. After complete addition, the resulting orange slurry was stirred for 40 min. at room temperature. Suction filtration gave an orange filter cake which was washed repeatedly with water, then sucked dry during 2 hr. The filter cake thus obtained was placed back into the three necked flask used above. Methanol (200 ml) was added to give a slurry. Morpholine (10.0 g., 0.115 mole) was added in one portion. A mildly exothermic reaction occurred, and a dark, homogeneous solution was obtained. After stirring 10 min., the solution was poured into 300 ml water. This was extracted with methylene chloride (3×100 ml). The combined organic extracts were extracted repeatedly with dilute aqueous sodium hydroxide (pH 8). The combined aqueous basic layers were acidified with 6N hydrochloric acid. With cooling and scratching, a solid crystallized from solution. Suction filtration gave (V) as a light brown powder (8.2 g, 60% yield based on pyrone). NMR (CDCl3): 7.5 ppm (multiplet, 4H); 4.0 (S, 3H); 2.3 (S, 3H). IR (CH2Cl2): 5.75, 6.22, 6.90, mp 203-204 (dec.). An analytical sample was crystallized from methanol.

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