Richard, A. published an article in 1911, the title of the article was Some Derivatives of Pinacolin.Name: Methyl 2-hydroxy-3,3-dimethylbutanoate And the article contains the following content:
cf. C. A., 4, 2303. Methyl pivalate, obtained by adding 62 g. Me2SO4 to 11.5 g. Na in 150 g. MeOH and 50 g. pivalic acid and boiling 30 min., b. 101-3°, d40 0.891. Yield, 90%. Ethyl ester, prepared by boiling 10 g. acid, 10 g. EtOH and 5 g. concentrate H2SO4, b. 120°, d40 0.875. Yield, 85%. A solution of 110 g. in 400 alc. slowly dropped upon 105 g. Na in large pieces gives 40 g. trimethylethyl alcohol, m. 50°, b100 64°, b. 113-5°; phenylurethan, CMe3CH2OCONHPh, from the alc. and PhNCO, m. 114°; pyruvate, b23 78-80°, pyruvate semicarbazone, CMe3CH2OCOCMe : NNHCONH2, m. 166°. CMe3CH2MgCl in Et2O and dry O2 give Me2CEtOH which, when heated with pyruvic acid, yields Me2C : CHMe. With CO2 the Mg compound forms Me2CEtCO2H. Pinacolyl alcohol CMe3CHMeOH, is best obtained (80% yield) by dissolving pinacolin in 5 pts. Et2O, adding 2 pts. 30% K2CO3 and dropping 0.6 pt. Na in small pieces into the mixture; pyruvate, b17 78-80°; pyruvate semicarbazone, m. 17.5°. CMe3CHMeMgCl gives HOCMe2CHMe2 with O2; and with CO2 dimethylisopropylacetic acid, m. 50°, b15 106°. From CMe3CMe2MgCl and CO2 are obtained Me3CCMe3, CMe3CMe2OH (from the O in the air in the apparatus), and CMe3CMe2CO2H. Trimethylpyruvic acid, protected from the air, crystallizes slowly and m. 125°; in the air it crystallizes rapidly, contains 0.5 H2O and m. 90°; oxime, CMe3C( : NOH)CO2H, scales, m. 85°; azine, [CMe3C(CO2H) : N]2 S-yellow needles, m. 207°; semicarbazone, m. 195° (decompose). Methyl ester, b20 69-70°, b. 160-2°, d40 0.994; ethyl ester, b20 76-7°, 0.965. Methyl ester semicarbazone, m. 125°; oxime, m. 66°, b20 125°. Ethyl ester semicarbazone, m. 115°; oxime, viscous liquid, b20 131-3°, gives a few crystals in ice, m. 22-3°; oxime phenylurethan, CMe3C(CO2Et) : NOCONHPh, needles, m. 123-4°. Ethyl α-amino-ββ,β-trimethylpropionate, from CMe3C(:NOH)CO2Et, Zn dust and alc. HCl, b15 83°, d40 0.952; picrate, m. 134°. Ethyl α-phenylurea-β,β,β-trimethylpropionate, CMe3CH(CO2Et)NHCONHPh, m. 78°. Ethyl pseudobutylhippurate, CMe3CH(NHBz)CO2Et from the above amino compound and BzCl, m. 64°, b15 198-200°. CMe3COCO2H, heated with PhNH2, gives the aldehyde and trimethylethylideneaniline, CMe3CH : NPh, which b20 101-2° has d40 0.941, yields CMe3CHO and PhNH2 when heated on the H2O bath with 20% H2SO4. Trimethylacetaldehyde oxime, b20 65°, m. 41°; azine, m. 79°. EtO2CC(CN)(OH)CMe3, allowed to stand 1 week with concentrate H2SO4, gives ethyl pseudobutyltartronamide, EtO2CC(CONH2)(OH)CMe3, m. 60°, b15 162-4°. Alc. NH3 acting 2 hrs. at 100° on CMe3COCO2Et gives a compound C12O21O2N3, m. 225°, whose constitution, owing to lack of material, could not be determined MeMgI and CMe3COCO2Me, or MeMgBr and CMe3COCO2Et give a compound (a) b18 82-3° (see below) and 75-80% of tetramethyllactic acid, CMe3CMe(OH)CO2H, scales, m. 141-2°, b14 130°. The acid can also be obtained from pinacolin through the nitrile (by the action of HCN) which is saponified in 2 ds. by cold concentrate H2SO4 to the amide, m. 140-1°, b10 170° (partial decompose). This, in turn, on boiling with fuming HCl gives the acid. Methyl ester, from the acid, Me2SO4 and NaOMe, b12 65.5°, d40 1.002. Ethyl ester, from the acid, EtOH and H2SO4, b12 74°, d40 0.975. Chloralide, CMe3CMe CHCl3 obtained by heating the acid with 3 mols. CCl3CHO 2 hrs. at 120°, m. 85°, b14 126-7°. From 33.6 g. Mg, 200 g. MeI and 64 g. CMe3CMe(OH)CO2Me were obtained 12 g. of the compound (a) above and 11 g. trimethylpseudobutylglycol, HOCMe2CMe(OH)CMe2, m. 22°, b16 96-8°. The Et ester gives poorer yields than the Me derivative The compound (a) is tetramethyllactaldehyde, b16 82-4°, d40 0.967, does not react with pyruvic acid at 120-30°; is only slightly oxidized by cold alk. KMnO4 to pivalic acid and CMe3CMe(OH)CO2H. Oxime, m. 65°, b15 126-7°, in Ac2O gives with HCl a little pinacolin and CMe3CMe(OH)CN.HOCMe2CMe(OH)CMe2, heated 6 hrs. with 3 volumes 20% H2SO4 gives (CMe3)2CO (Haller and Bauer, C. A. 4, 2092). Trimethyllactic acid chloralide, m. 63°, b15 130°. When heated, the acid begins to lose water at 190° to form the lactide which at 240° begins to evolve CO, giving CMe3CHO (see above). The residue from the distillation of the aldehyde yields the trimeric compound, (CMe3CHO)3, m. 12°, b18 104-5°, d40 0.979, and trimethyllactic acid dilactide, scales, m. 84°, b13 148°. The trimeric compound is depolymerized by distilling at ordinary pressure with anhydrous FeCl3. The aldehyde and HCN give trimethyllactonitrile, CMe3CHOHCN, b100 100°, d40 0.911; with concentrate H2SO4 at 0° this gives after 1 d. the amide, m. 135°, which, in turn, yields the acid when boiled with fuming HCl. Methyl ester, CMe3CHOHCO2Me, b16 69-70°, d40 1.044. Ethyl ester, b16 79-80°, d40 0.987. The acid and PCl5 and MeOH give a compound CMe3CH(CO2Me)OPO(OMe)2, b23 165-70°, d40 1.437, and, in very small quantities, 2 acids, b22 75-90° and 150-5°, resp. The use of PBr5 instead of PCl5, and of PBr3 or PI3 and the Me or Et esters instead of the acid was no more successful in giving the desired compound CMe3CHXCO2R. The experimental process involved the reaction of Methyl 2-hydroxy-3,3-dimethylbutanoate(cas: 121129-31-5).Name: Methyl 2-hydroxy-3,3-dimethylbutanoate
Methyl 2-hydroxy-3,3-dimethylbutanoate(cas:121129-31-5) belongs to ethers. Oxygen is more electronegative than carbon, thus the alpha hydrogens of ethers are more acidic than those of simple hydrocarbons. They are far less acidic than alpha hydrogens of carbonyl groups (such as in ketones or aldehydes), however. Name: Methyl 2-hydroxy-3,3-dimethylbutanoate
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