BIPHENYL TYPE LIGNIN MODEL COMPOUNDS - SYNTHESIS AND C-13 NMR SUBSTITUENT CHEMICAL-SHIFT ADDITIVITY RULE

被引:17
作者
DRUMOND, MG
VELOSO, DP
COTA, SDS
DEMORAIS, SAL
DONASCIMENTO, EA
CHEN, CL
机构
[1] UNIV FED UBERLANDIA,DEPT QUIM,UBERLANDIA,BRAZIL
[2] N CAROLINA STATE UNIV,DEPT WOOD & PAPER SCI,RALEIGH,NC 27695
关键词
LIGNIN MODEL COMPOUNDS; BIPHENYL DERIVATIVES; SYNTHESIS; SELECTIVE O-ACETYLATION; COMPLETE O-ACETYLATION; C-13 NMR SPECTROSCOPY; SCS ADDITIVITY RULE;
D O I
10.1515/hfsg.1992.46.2.127
中图分类号
S7 [林业];
学科分类号
0829 ; 0907 ;
摘要
A number of 4'-O-monoalkylated bisphenyl (5-5') type lignin model compounds was synthesized from dehydrodivanillin (5) by way of 4-O-acetyldehydrodivanillin (6). The C-13 NMR spectral characteristics of the compounds synthesized verified the usefulness of the generalized substituent chemical shift (SCS) additivity rule elucidated for estimation of the C-13 chemical shift of aromatic carbons in 5-5' type model compounds and probably in 5-5' type substructures in lignins. In addition, preliminary results from a kinetic study on the selective O-acetylation of dehydrodivanillin (5) showed that 4-O-acetyldehydrodivanillin (6) was produced as the major product, more than 75% of the products isolated from the reaction mixture, when a mixture consisting of compound 5, acetic anhydride and pyridine in the molar ratio of approximately 1:1:19 was stirred at room temperature for 20 minutes. A small amount of 4,4'-O-diacetyldehydrodivanillin (7) was isolated as a by-product. In contrast, when the molar ratio of compound 5, acetic anhydride and pyridine was changed to approximately 1:17:20, compounds 6 and 7 were produced during the initial 3 hours of the reaction, and only compound 7 at the reaction time of 3 to 6 hours. However, when the reaction was prolonged beyond 6 hours, compound 7 underwent hydrolysis to afford compound 6, the amount of which increased with increasing reaction time. At the reaction time of 24 hours. the reaction mixture consisted of compounds 6 and 7 in the approximate molar ratio of 1:1. The result is important not only in paving the way for synthesis of 4-O-monoalkylated biphenyl type lignin substructures, but also in better understanding of the factors contributing to the incompleteness in O-acetylation of lignins.
引用
收藏
页码:127 / 134
页数:8
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