Preparation of 3-(hydroxymethyl)-4,4-dimethylpentanoic acid .gamma.-lactone

Abstract

DeBoer and Hxjnter tance reading recorded. By noting the direction of any drift and its magnitude, and assuming the drift to be constant throughout the run, the corrected infinity point was calculated. Rate constants were then calculated using the hatsol2 computer program (see above). In several runs, we have plotted the concentrations of substrate from the computer output and found excellent first-order behavior over the 2 half-fifes examined.Using the above procedure with the M-D Mini-Cell,15 30 ml of 10_s M substrate solution is adequate to produce duplicate rate constants at two temperature and potentiometrically determined infinity titer checks at both temperatures.

Base catalysis as an alternative explanation for an apparent deuterium solvent isotope effect in the photochemical reactions of α,β-unsaturated esters

“…Ethyl 3-hydroxy-3,4,4-trimethylpentanoate (12, R = Me) was prepared in 36% yield by the Reformatsky reaction between pinacolone and ethyl bromoacetate (17,18). Compound 12 (R = Me) (10 g, 0.053 mol), N,N-dimethylaniline (7 g, 0.058 mol), and acetyl chloride (4.4 g, 0.056 mol) were dissolved together in chloroform (30 mL) and the solution was refluxed for 9 h after which time gc (5% SE 30, 120°C) of a worked-up sample indicated complete reaction.…”

[2 + 3] Cycloaddition of Nitrones to Platinum-Bound Organonitriles: Effect of Metal Oxidation State and of Nitrile Substituent

“…In particular, the addition of electrophiles 1 or nucleophiles [2][3][4][5][6][7][8][9][10][11] to the CtN triple bond offers an attractive route for creation of novel C-C, C-N, and C-O bonds. Among the nucleophiles used, much attention has been drawn to additions of water to RCN to give carboxylic acids or amides, 2,3 alcohols to produce iminoethers or esters, [4][5][6][7] amines to give amidines, 8 and also compounds exhibiting significant C-H acidity to form the new C-C bond due to the addition. [9][10][11] One of the main problems encountered in reactions of nucleophilic addition is insufficient electrophilic activation even by very strong electron-accepting groups R at RCN, e.g.…”

“…In organic chemistry, transformations of organonitriles play an important role in both laboratory and industry due to their chemical versatility. In particular, the addition of electrophiles or nucleophiles − to the C⋮N triple bond offers an attractive route for creation of novel C−C, C−N, and C−O bonds. Among the nucleophiles used, much attention has been drawn to additions of water to RCN to give carboxylic acids or amides, , alcohols to produce iminoethers or esters, − amines to give amidines, and also compounds exhibiting significant C−H acidity to form the new C−C bond due to the addition. − One of the main problems encountered in reactions of nucleophilic addition is insufficient electrophilic activation even by very strong electron-accepting groups R at RCN, e.g.…”

“…In particular, the addition of electrophiles or nucleophiles − to the C⋮N triple bond offers an attractive route for creation of novel C−C, C−N, and C−O bonds. Among the nucleophiles used, much attention has been drawn to additions of water to RCN to give carboxylic acids or amides, , alcohols to produce iminoethers or esters, − amines to give amidines, and also compounds exhibiting significant C−H acidity to form the new C−C bond due to the addition. − One of the main problems encountered in reactions of nucleophilic addition is insufficient electrophilic activation even by very strong electron-accepting groups R at RCN, e.g. Cl 3 CCN, to perform the addition, and numerous examples of limitations of so-called pure organic chemistry in this field are illustrative. − These difficulties, however, can be overcome with the use of metal ions 9 sometimes even in low-oxidation-statesas extremely strong activators toward nucleophilic attack.…”