Favorskaya, T. A.;Yakovlev, I. P. published 《Tertiary alcohols with a cyclobutyl radical. II. Reaction of methylphenylcyclobutylcarbinol with hydrochloric and sulfuric acids》. The research results were published in《Zhurnal Obshchei Khimii》 in 1952.Safety of Diethyl cyclobutane-1,1-dicarboxylate The article conveys some information:
Et cyclobutanecarboxylate (10 g.) and 30 ml. EtOAc passed over 40 g. Cr-Mn catalyst (60 g. CrO3 treated with 36.5 ml. 26% NH4OH, diluted to 300 ml., added to 110 g. Mn nitrate in 300 ml. H2O, treated with 36.5 ml. 26% NH4OH, filtered, washed, dried at 110°, decomposed by vigorous heating in a dish, and deposited on glass wool) at 440° gave 63% Me cyclobutyl ketone (I), b754 137-9°, b11 36°, nD10 1.4339, d410 0.9093 (semicarbazone, m. 135.5°), and a little dicyclobutyl ketone. I (50 g.) treated with PhMgBr and worked up as usual gave 16.5 g. (methylphenylmethylene)cyclobutane (IA), b0.5 80-3°, nD12.5 1.5551, d40 0.9859, d412.5 0.9743, d420 0.9683 [oxidation with KMnO4 gave AcPh and (CH2CO2H)2], and 10 g. methylphenylcyclobutylcarbinol (II), b1 100.5-4.0°, nD20 1.5358, d40 1.0388, d410 1.0350, d420 1.0316. CH2(CO2Et)2 (3 moles) and 3 moles Br(CH2)3Cl in 500 ml. Et2O added at once to EtONa from 800 ml. EtOH and 2 atoms Na, kept 4 hrs. at 35°, then let stand 24 hrs., diluted with 2.5 l. H2O, and extracted with Et2O, gave 93% di-Et (3-chloropropyl)malonate, b10 142°, this, added at once to an equivalent amount of EtONa in 250 ml. EtOH at 80°, and most of EtOH distilled off, gave upon acidification 88% di-Et 1,1-cyclobutanedicarboxylate which, hydrolyzed by 40% NaOH and decarboxylated by distillation, gave 90% cyclobutanecarboxylic acid, yielding with PCl5 78.5% acyl chloride, b40 52-4°. This (100 g.) added to 200 g. AlCl3 in 750 ml. C6H6 at 60° gave 68% cyclobutyl Ph ketone (III), b10 121.5-2.0°, nD20.5 1.5472, d40 1.0610, d410 1.0525, d420 1.0440 (semicarbazone, m. 177°). III with Br yielded a mono-Br derivative, m. 61°; III (60 g.) with MeMgBr (from 40 g. MeBr) gave 90% II. II with K2Cr2O7-H2SO4 gave AcPh and BzOH; it did not react with 25% H2SO4 at 90°; with 50% H2SO4 it gave in 6 hrs. some 60% unsaturated hydrocarbons, which were separated into 2 fractions, b8 98-101° and b8 101-2°, both of which appeared to be moderately pure IA. II in 6 hrs. with 18° HCl at 85° gave an unsaturated hydrocarbon, the normal dehydration product, identified as IA in part, possibly contaminated by 1-phenyl-1-cyclobutylethylene (IV). II with 36% HCl gave in 24 hrs. at 0° 2 hydrocarbons, identical with those described above. Careful distillation gave the pure constituents, 3 parts IA and 1 part IV, b9 105-7° nD21 1.5608, d421 0.9838. To complete the study, the researchers used Diethyl cyclobutane-1,1-dicarboxylate (cas: 3779-29-1) .
Diethyl 1,1-cyclobutanedicarboxylate(cas:3779-29-1 Safety of Diethyl cyclobutane-1,1-dicarboxylate) reacts with silicon to form diethyl esters and magnesium to form magnesium salts. The reaction time for this compound is short, which may be due to its ability to undergo debromination.
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