Synthesis of some cyclopropane and spiran hydrocarbons was written by Shortridge, R. W.;Craig, R. A.;Greenlee, K. W.;Derfer, J. M.;Boord, C. E.. And the article was included in Journal of the American Chemical Society in 1948.Application In Synthesis of 2-Butyl-2-ethylpropane-1,3-diol The following contents are mentioned in the article:
Details are given of the preparation from Me2CHCHO and HCHO of 76% Me2C(CH2OH)2 which with PBr3 yields 46% Me2C(CH2Br)2, b9 68°, n2D 1.5050, d204 1.6934 (all n and d. are at 20°). A mixture 1900 ml. 95% EtOH, 90 ml. H2O, and 628 g. Zn dust, brought to gentle reflux and treated dropwise with 562 g. Me2C(CH2Br)2, with heating and stirring 24 hrs., gives 162 g. 1,1-dimethylcyclopropane, b760 19.9°, f.p. -108.4 to -107.3°. MeEtCHCH2CHO gives 91% 2,2-diethyl-1,3-propanediol, b13 131°, m. 61-1.6°; PBr3 yields 40% 1,3-dibromo-2,2-diethylpropane, b10 97°, m. 39.2-40.6°; this gives 92% 1,1-diethylcyclopropane (I), b760 88.67°, f.p. -105.91°, n 0.7318, d. 1.4042. EtPrCHCH2CHO yields 70% 2-ethyl-2-butyl-1,3-propanediol, b10 152°, m. 41.4-1.9°; PBr3 gives about 47% 1,3-dibromo-2-ethyl-2-butylpropane, b16 133°, d. 1.4400, n 1.5018; this yields 94% 1-ethyl-1-butylcyclopropane, b760 140.41°, f.p. -102.68°, d. 0.7559, n 1.4183. Five mols. each of (CH:CH2)2 and CH2:CHCHO and 5 g. hydroquinone, heated to 130° (temperature rise to 185°), give 74% 3-cyclohexene-1-carboxaldehyde, b760 164°, f.p. -96.1°, d. 0.9709, n 1.4725; this yields 84% 4,4-bis(hydroxymethyl)cyclohexene, b3 128°, m. 92°, giving on catalytic reduction in MeOH over Raney Ni at 45° and 1000 lb./sq. in. 1,1-bis(hydroxymethyl)cyclohexane, which yields 27% 1,1-bis(bromomethyl)cyclohexane, b6 117°, d. 1.6302, n 1.5390; cyclization yields 91% spiro[2.5]octane (II), b760 125.5°, f.p. -86.2°, d. 0.8282, n 1.4476. (CH:CH2)2 and MeCH:CHCHO give 46% 6-methyl-3-cyclohexene-1-carboxaldehyde, b64 99°, b760 117.8°, d. 0.9500, n 1.4680; this yields 4,4-bis(hydroxymethyl)-5-methylcyclohexene, b6 134°, m. 45°. 1,1-Bis(hydroxymethyl)-2-methylcyclohexane (m. 77°, 51%) yields 28% 1,1-bis(bromomethyl)-2-methylcyclohexane, b4 115°, n 1.5380; cyclization yields 89% 4-methylspiro[2.5]octane (III), b760 149°, f.p. -53.6°, d. 0.8386, n 1.4529. I, hydrogenated over Raney Ni at 180° and 2000 lb./sq. in., gives 80% Me2CEt2; at 155° and 1900 lb./sq. in., II over Raney Ni gives 91% 1,1-dimethylcyclohexane; III gives 1,1,2-trimethylcyclohexane, b760 145.2°, f.p. -29.2°, d. 0.7986, n 1.4385. When a gem-dialkylcyclopropane or a spirane containing a cyclopropane ring is hydrogenated under the above conditions, rupture of the cyclopropane ring occurs almost exclusively at the bond opposite the gem-disubstituted C atom. Thus, hydrogenation under controlled conditions can provide an easy, reliable method for proving the structure of these types of compounds and in some cases it may prove to be a good preparative reaction for synthesizing gem-dimethylcycloalkanes with rings containing more than 3 C atoms. This study involved multiple reactions and reactants, such as 2-Butyl-2-ethylpropane-1,3-diol (cas: 115-84-4Application In Synthesis of 2-Butyl-2-ethylpropane-1,3-diol).
2-Butyl-2-ethylpropane-1,3-diol (cas: 115-84-4) 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.Application In Synthesis of 2-Butyl-2-ethylpropane-1,3-diol
Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts