Eastman Chemical Company

Steven J Adams

Robert Thomas Hembre

Sumit Chakraborty

Scott Donald Barnicki

David Alan Jenkins

Yue Rachel Hu

Gerald Charles Tustin

David Scott Porter

Zhufang Liu

Wentao Li

Leslie Sharon Depew

Michael Richard Laningham

Sarah Exley Goetz

Aireal Denise Pressley

Amit Vasant Desai

Randy Lynn Jennings

Gerarld Wayne Ollis

Vikram Seshadri

Provided is a process for the preparation of certain 1,4-bicyclo[2.2.2]octane derivatives. The new synthetic procedure involves treating 1,4-dimethylene cyclohexane with an oxidizing agent in the presence of a transition metal catalyst to afford an oxo-substituted bicyclo[2.2.2]octane species. This intermediate structure can then be further derivatized. The processes of this disclosure thus affords a novel and simplified means for the commercial production of a wide variety of bicyclo[2.2.2]octane derivatives.

Synthesis of bicyclo[2.2.2]octane derivatives

A semi-crystalline polyester comprising a repeat unit of the formula: wherein A is an aliphatic, aromatic, or heterocyclic group; Ris selected from the group consisting of 1,4-butanediol residue and 1,4-cyclohexanedimethanol residue; Ris neopentanediol residue; m is between 50 and 99 inclusive; n is between 1 and 50 inclusive; x is between 1 and 200 inclusive; and wherein said semi-crystalline polyester exhibits a minimum crystallization half-time of about 0.3 minutes or greater, or about 0.5 minutes or greater or about 0.6 minutes or greater or about 0.7 minutes or greater is described. The polyesters of the present invention may in various embodiments demonstrate one or more desirable performance characteristics and accordingly are particularly useful in applications and utilities wherein those high levels of performance for such characteristics are required. A process for forming the semi-crystalline polyester is also disclosed.

Polyesters with specified crystallization half-times

A process for the transesterification of methyl-2-ethylhexanoate with triethylene glycol to produce triethylene glycol di-2-ethylhexanoate is provided. In the process, methyl-2-ethylhexanoate is combined with triethylene glycol to form a first mixture. The first mixture is heated in the presence of a catalyst to form a second mixture comprising methanol and triethylene glycol di-2-ethylhexanoate. Methanol is separated from the second mixture to yield triethylene glycol di-2-ethylhexanoate. NaCO, CsCO, KCO, RbCO, sodium methoxide or titanium isopropoxide are suitable catalysts.

Synthesis of triethylene glycol bis(2-ethylhexanoate)

A process for making methyl esters in high yields is provided. The process comprises contacting aliphatic or aromatic aldehydes and methanol with an iron catalyst, to catalyze the dehydrogenative coupling between aliphatic or aromatic aldehydes and methanol. The reaction is highly selective (&#x3c;99.9%) toward the formation of methyl esters over homoesters and alcohols and operates at temperatures of less than 100&#xb0; C. for 2-8 hours.

Iron-catalyzed selective production of methyl esters from aldehydes

A process for making methyl esters in high yields. The process comprises contacting aliphatic or aromatic aldehydes and methanol with a homogeneous dimeric ruthenium catalyst, to catalyze the dehydrogenative coupling between aliphatic or aromatic aldehydes and methanol. The reaction is highly selective (&#x3c;99.9%) toward the formation of methyl esters over homoesters and alcohols and operates at temperatures of less than 100&#xb0; C. for 2-8 hours.

Process for the production of esters

A process for preparing a variety of secondary and tertiary alkyl formate esters via the coupling of methanol and secondary (or tertiary) alcohols. Iron-based catalysts, supported by pincer ligands, are employed to produce these formate esters in high yields and unprecedentedly high selectivities (&#x3e;99%). Remarkably, the coupling strategy is also applicable to bulkier tertiary alcohols, which afford corresponding tertiary formate esters in moderately high yields and high selectivities.

Iron-catalyzed cross-coupling of methanol with secondary or tertiary alcohols to produce formate esters

Iron-based homogeneous catalysts, supported by pincer ligands, are employed in the transfer hydrogenation of esters using C-Calcohols as sacrificial hydrogen donors to produce corresponding alcohols from the esters. No external Hpressure is required. The reaction can be carried out under ambient pressure.

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Gray, TN, United States of America

Steven J Adams