Reaction of aliphatic diazo compounds with unsaturated compounds. XXIV. Reaction of diazoacetic ester with 5-decyne and 4-octyne. Effect of the nature and amount of the catalyst on orientation of the reaction was written by Komendantov, M. I.;D’yakonov, I. A.;Gokhmanova, I.;Kostikov, R. R.. And the article was included in Zhurnal Organicheskoi Khimii in 1965.SDS of cas: 1634-34-0 This article mentions the following:
5-Decyne (30 g.) and 0.05 g. CuSO4 was treated at 90° with 12 g. EtO2CCHN2 over 3 hrs. and gave 12% di-Et fumarate and 39.1% Et 1,2-dibutylcyclopropene-3-carboxylate (I), b3 89-90°, d20 0.8965, ν20D 1.44523, n20D 1.44786, n20F 1.45424. The yield of I rose to 43% with Bz2O2 catalyst, but the mixture required 2-3 hrs. addnl. heating; Cu gave 35.7% yield, CuO 10%, Cu(OAc)2, CUCl, Cu stearate and Cu(NO3)2 were ineffective; without the catalyst, the yield was 19.3%. For best yield (51.6%) the CuSO4 catalyst must comprise 2.15 moles per 1000 moles of 5-decyne. I heated 8 hrs. with MeONaMeOH gave 83% 1,2-dibutyl-1(2)-cyclopropene-3-carboxylic acid, b3 121-2°, 0.9329, 1.45842, 1.46120, 1.46808 (oxidized with KMnO4 it gave divalerylmethane, b5 97-8°). When the condensation with 5-decyne was run with 2.91 moles CuSO4 per 1000 moles alkyne, the reaction gave up to 83.8% 2,3-dibutyl-5-ethoxyfuran (II), b3 104-5°, 0.9113, 1.45599, 1.45894, 1.46624, which with maleic anhydride in 0.5 hr. at 100° gave 2,5-endoxo-1,2-dibutyl-5-ethoxy-6-cyclohexene-3,4-dicarboxylic anhydride, m. 146-8°, or 1,2-dibutyl-5-ethoxybenzene-3,4-dicarboxylic anhydride, m. 107-8°, depending on the reactant ratio. II treated with O in heptane at room temperature gave after warming with H2O 2 hrs. 56.2% Et 3-butyl-2-octen-4-on-1-oate, b0.3 97-9°, d20 0.9746, n20D 1.4638, which with MeOH-KOH 2 hrs. gave the free acid (III), b0.3 123-4°, 0.9936, 1.4625. II and aqueous alc. HCl 2 hrs. under N gave 70.4% 2.3-dibutyl-2,5-dihydro-5-furanone, b0.3 96-8°, 0.9556, 1.4662, which in 30% KOH in MeOH 1 hr. gave 3-butyl-4-octanon-1-oic acid, b0.3 121-2°, 0.9745, 1.4498 (semicarbazone m. 154-5°), also formed by hydrogenation of III over Pd-CaCO3 in EtOH. EtO2CCHN2 and 4-octyne, as above with CuSO4, gave up to 42% Et 1,2-dipropyl-1(2)-cyclopropene-3-carboxylate, b3 78-9°, 0.9053, n20D 1.44253, n20D 1.44513, n20F 1.45160; with Cu catalyst the yield was 51%, while without a catalyst at 135-40° the reaction gave 23.3% yield. The ester was saponified with MeONa-MeOH to the free acid, b1 92-3°, 0.9636, 1.45951, 1.46249, 1.46990 (oxidized with KMnO4 it gave dibutyrylmethane). With larger amount CuSO4 catalyst there was obtained some di-Et fumarate and 53.3% 2,3-dipropyl-5-ethoxyfuran, b5 86-7°, 0.92528, 1.45588, 1.45900, 1.46646. This and maleic anhydride gave 1,2-dipropyl-5-ethoxybeuzene-3,4-dicarboxylic anhydride, m. 133-4°. In the experiment, the researchers used many compounds, for example, 2′,6′-Dihydroxy-4′-methylacetophenone (cas: 1634-34-0SDS of cas: 1634-34-0).
2′,6′-Dihydroxy-4′-methylacetophenone (cas: 1634-34-0) belongs to alcohols. Alcohols are weak acids. The most acidic simple alcohols (methanol and ethanol) are about as acidic as water, and most other alcohols are somewhat less acidic. Tertiary alcohols cannot be oxidized at all without breaking carbon-carbon bonds, whereas primary alcohols can be oxidized to aldehydes or further oxidized to carboxylic acids.SDS of cas: 1634-34-0
Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts