Coalification by clay-catalyzed oligomerization of plant

Technical Report · Tue Jan 01 04:00:00 EST 1991

OSTI ID:5638342

Orchin, M; Wilson, R M

Research on coalification continued. We have addressed the problem of the lack of regiospecificity exhibited by the radical cation Diels-Alder reaction. The general strategy has been to tether two cinnamates together with a tether that is too short to permit the head-to-tail coupling from occurring, but which is long enough to permit heat-to-head coupling. When this strategy is applied to the tethered dimethyl cinnamate 1 shown in Scheme 1, to cyclized dihydronaphthalenes are isolated as the major products. These products have very similar spectroscopic properties. Consequently their structures were determined by X-ray crystallography. Both of these materials are trans-dihydronaphthalenes and have the plane of the dihydronaphthalene perpendicular to that of the phenyl substituent. Apparently rotation of this phenyl ring through the center of the medium-sized ring formed by the tether does not occur under ambient conditions. We have also tethered two cinnamate units together through their carboxylic acid groups and are in the process of examining the relative merits of this mode of tethering. It should be mentioned that both of these tethering strategies, phenolic tethering 1 carboxylic acid tethering; lead to the formation of substantial quantities of polymeric material. These polymeric materials are highly insoluble, and thus, present significant structure determination problems. While further work is going to be necessary to fully characterize the two tethering strategies it is possible to say that tethering through the phenolic groups tends to favor intramolecular radical cation Diels-Alder reactions, while tethering through the carboxylic acid groups favors intermolecular radical cation Diels-Alder reactions.

• Research Organization: Cincinnati Univ., OH (USA). Dept. of Chemistry
• Sponsoring Organization: DOE; USDOE, Washington, DC (USA)
• DOE Contract Number: FG22-88PC88931
• OSTI ID: 5638342
• Report Number(s): DOE/PC/88931-T7; ON: DE91014723
• Country of Publication: United States
• Language: English

Related Subjects

01 COAL, LIGNITE, AND PEAT
010600* -- Coal
Lignite
& Peat-- Properties & Composition
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
ADDUCTS
AROMATICS
CARBOXYLIC ACIDS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CINNAMIC ACID
CLAYS
COALIFICATION
DIELS-ALDER REACTION
DIMERS
DOCUMENT TYPES
HYDROXY COMPOUNDS
ISOMERS
KINETICS
MOLECULAR STRUCTURE
MONOCARBOXYLIC ACIDS
MONOMERS
ORGANIC ACIDS
ORGANIC COMPOUNDS
PHENOLS
POLYMERIZATION
POLYMERS
PROGRESS REPORT
STEREOCHEMISTRY
YIELDS