The author of 《The fulminic synthesis of isoxazoles. V. Nitrile oxides》 were Quilico, A.; Speroni, G.. And the article was published in Gazzetta Chimica Italiana in 1946. Application of 29278-09-9 The author mentioned the following in the article:
cf. C.A. 39, 2753.4. With a view to obtaining exptl. facts in support of the hypothesis that the synthesis of isoxazoles from hydroxamic chlorides and β-ketones (cf. Q. and Fusco, C.A. 32, 2117.4) and from arylacetylenes (cf. Weygand, Bauer, and Heynemann, C.A. 22, 1159) involves the addition of the corresponding nitrile oxides to the enolic -CH:C(OH)- group or to the acetylenic triple bond, an investigation was made of the action of benzonitrile oxide (I) on numerous β-ketones, NCCH2CO2Et (II), and various derivatives of C2H2. I does not react with these in neutral or acid medium, but in alk. medium the reaction is both energetic and exothermic. The results show also the parallelism in the behavior of nitrile oxides, aliphatic diazo compounds, and diazoimides in these reactions. The method of Wieland (C.A. 1, 1981) for the preparation of I was modified and better operating conditions established. Cold 14% aqueous NaOH (25 cc.) was added slowly to a suspension of 5 g. PhC(:NOH)Cl in 50 cc. ice-water, and the mixture was agitated several min. until the product solidified, filtered through a porous plate (kept cold with CO2 snow), and dried at a very low temperature The yield was 3.5 g. (90%), and the product should be used immediately. Alc. I (2 g. in 10 cc.) and 2.2 g. AcCH2CO2Et, treated with several drops of 20% aqueous NaOH (exothermic), allowed to stand 2 days, the precipitate separated, the mother liquor concentrated, the combined yields (77%) saponified by heating with a slight excess of 50% aqueous NaOH, the EtOH evaporated, diluted with water, filtered, acidified with dilute H2SO4, and the precipitate purified by EtOH, yielded O.N:CPh.C(CO2H):CMe, m. 189-90° (cf. Q. and Fusco, C.A. 32, 2117.4). By the same procedure I and BzCH2CO2Et yielded O.N:CPh.C(CO2H): CPh, m. 233° (cf. Fusco, C.A. 33, 8611.4). The yield was not given, but 3.1 g. of the Et ester was obtained as intermediate product. Likewise, 3.15 g. EtO2CCOCH2CO2Et and 2 g. I gave, after purification by C6H6, 0.5 g. O.N:CPh.C(CO2H):CCO2H, m. 86° (cf. Q. and Fusco, loc. cit.) Alc. I (2 g.) and 1.9 g. II, made alk. with NaOH (heat was evolved and the mixture turned greenish yellow) and concentrated, yielded 1.6 g. O.N:CPh.C(CO2Et):CNH2 (III), m. 122-3°, which, treated with excess hot aqueous NaOH and allowed to stand overnight, precipitated O.N:CPh.CH:CNH2, m. 109-10°. III (0.5 g.), dissolved in boiling aqueous Ba(OH)2, cooled, acidified with AcOH, and the precipitate purified by EtOH, gave O.N:CPh.C(CO2H):CNH2, m. 179-80° (cf. Fusco, loc. cit.). Alc. I (2 g. in 25 cc.), 1.7 g. Ac2CH2, and 5-6 drops 20% NaOH (evolved heat and turned dark yellow), allowed to stand 24 hrs., evaporated, and the product purified by EtOH, gave 2.4 g. O.N:CPh.CAc:CMe, m. 60° (cf. Fusco, loc. cit.). Prepared similarly from I and BzCH2Ac, O.N:CPh.CBz:CMe m. 115-16° (cf. Fusco, loc. cit.). Alc. I (2 g. in 25 cc.), 1.7 g. PhCCH, and 4-5 drops 20% NaOH (much heat evolved; had to be cooled with ice to avoid violent boiling), allowed to stand and the precipitate purified from hot EtOH, gave 2.7 g. O.N:CPh.CH:CPh, m. 141° (cf. Goldschmidt, Ber. 28, 2540(1895)). The solution of alc. HCCCO2H (1.5 g. in 10 cc.), alc. I (2 g. in 10 cc.), and several drops 20% NaOH (heat evolved; turned yellow), when evaporated, the residue allowed to crystallize (several days), dissolved in EtOH, filtered, the filtrate evaporated, and the residue purified by hot ligroin, gave O.N:CPh.CH:CCO2H, m. 176-8° (cf. Betti, Gazz. chim. ital. 45, I, 362(1915)). Alc. MeCCCO2H (cf. Feist, Ann. 345, 104(1906)) (1.4 g. in 10 cc.), 2 g. I, and 4-5 drops 20% NaOH, allowed to stand 2 days, concentrated, the crystallized mass dissolved in hot aqueous Na2CO3 (dark yellow solution), acidified, and the precipitate purified by EtOH, gave a small yield of O.N:CPh.C(CO2H):CMe (IV), m. 187-8° (cf. Betti, loc. cit.). Treated with SOCl2 on a steam bath, the excess SOCl2 evaporated in vacuo, PhNH2 in Et2O added, and the product purified by EtOH, IV formed an anilide, m. 192-3°. Alc. PhCCCO2H (2.4 g. in 20 cc.), alc. I (2 g.), and several drops 20% NaOH (heat evolved) when allowed to stand, filtered, the mother liquor concentrated, and the combined products purified by EtOH, gave 3.1 g. O.N:CPh.C(CO2H):CPh, m. 233° (decomposition) (cf. Betti, loc. cit; B. and Berlingozzi, Gazz. chim. ital. 45, II, 156(1915) and C.A. 16,932; Q. and Fusco, loc. cit.). Alc. HO2CCCCO2H (2 g. in 10 cc.), 2 g. I, and several drops 20% NaOH, when evaporated to a pitchy mass which was taken up in boiling water, filtered, the yellow filtrate concentrated to a small volume, concentrated HCl added, the mixture allowed to stand, and the slowly separating product pressed and dried in an oven at 100°, gave a very small yield of a compound which, although in too small quantity to analyze, was probably O.N:CPh.C(CO2H):CCO2H, m. approx. 150° (decomposition). Under the same conditions, I did not react with PhCCPh, MeCCPh, and PhCCCCH. It remains to be explained how in the case of acetylenic carboxylic acids like MeCCCO2H and PhCCCO2H, the addition of a quantity of alkali much less than that necessary to neutralize the acid was capable of starting the reaction with I and giving good yields. The velocity of the transformation of I into a form capable of reacting with the HCCH derivative must be greater than the velocity of salification in alc. medium. In the experiment, the researchers used Ethyl 5-amino-3-phenylisoxazole-4-carboxylate(cas: 29278-09-9Application of 29278-09-9)
Ethyl 5-amino-3-phenylisoxazole-4-carboxylate(cas: 29278-09-9) belongs to anime. Reduction of nitro compounds, RNO2, by hydrogen or other reducing agents produces primary amines cleanly (i.e., without a mixture of products), but the method is mostly used for aromatic amines because of the limited availability of aliphatic nitro compounds. Reduction of nitriles and oximes (R2C=NOH) also yields primary amines.Application of 29278-09-9
Referemce:
Isoxazole – Wikipedia,
Isoxazole | C3H3NO – PubChem