ISSN:
0009-2940
Keywords:
Ethylboronic carboxylic acid anhydrides, comproportionation of
;
Bicyclo[3.3.1]nonadienes, heteroatom-containing
;
Bicyclo[3.3.3]undecadienes, heteroatom-containing
;
1,3,2-Diboroxanes
;
Oxygen atom exchange
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Chelate-Stabilized 1,3-Bis(acyloxy)-1,3-diethyldiboroxanes from Triethylboroxin and Carboxylic Acid AnhydridesTriethylboroxin (A) reacts with carboxylic acid anhydrides (RCO)2O [R = Me: 1a; Et: 1b; tBu: 1d; Ph: 1e] with various rates to give high yields of the 3,7-dialkyl-1,5-diethyl-4,8,9-trioxa-2,6-dioxonia-1,5-diboratabicyclo[3.3.1]nona-2,6-dienes OB(Et)OC(R)OB(Et)OC(R)O (2) [R = Me: 2a (X-ray crystal structure analysis); Et: 2b; tBu: 2d; Ph: 2e], presumably via the unstable compounds OB(Et)OB(Et)OC(R)OB(Et)OC(R)O (3a,b, d, e). Compound 1c (R = CF3) reacts with A to form a mixture of 1,3-diethyl-1,3-bis(trifluoroacetoxy)diboroxane O=C(CF3)OB(Et)OB(Et)O(CF3)C=O (2c′) and 2c (R = CF3) at room temperature. Whereas two compounds of the type 2 do not comproportionate, 1a-e spontaneously form the mixed substituted carboxylic acid anhydrides 1ab etc. on mixing at room temperature (GC, 13C NMR). - From the 17O-enriched A* and 1a-e the 17O-enriched compounds 2a*-e* with BO*B and YYBO*OCR groups are obtained. A* exchanges O atoms up to 200°C with succinic anhydride (1f) forming 1f* or with phthalic acid anhydride (1g) forming 1g* and 3g*. - The mixed carboxylic acid anhydrides 1xy are cleaved, and the mixtures of 1 are separated with A to yield the uniform 3,7-dialkyl-substituted compounds 2.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19941270704
