944-38-7Relevant articles and documents
Renewable production of phthalic anhydride from biomass-derived furan and maleic anhydride
Mahmoud, Eyas,Watson, Donald A.,Lobo, Raul F.
, p. 167 - 175 (2014/01/06)
A route to renewable phthalic anhydride (2-benzofuran-1,3-dione) from biomass-derived furan and maleic anhydride (furan-2,5-dione) is investigated. Furan and maleic anhydride were converted to phthalic anhydride in two reaction steps: Diels-Alder cycloaddition followed by dehydration. Excellent yields for the Diels-Alder reaction between furan and maleic-anhydride were obtained at room temperature and solvent-free conditions (SFC) yielding 96% exo-4,10-dioxa-tricyclo[5.2.1.0]dec-8-ene-3,5-dione (oxanorbornene dicarboxylic anhydride) after 4 h of reaction. It is shown that this reaction is resistant to thermal runaway because of its reversibility and exothermicity. The dehydration of the oxanorbornene was investigated using mixed-sulfonic carboxylic anhydrides in methanesulfonic acid (MSA). An 80% selectivity to phthalic anhydride (87% selectivity to phthalic anhydride and phthalic acid) was obtained after running the reaction for 2 h at 298 K to form a stable intermediate followed by 4 h at 353 K to drive the reaction to completion. The structure of the intermediate was determined. This result is much better than the 11% selectivity obtained in neat MSA using similar reaction conditions.
On the Diels-Alder approach to solely biomass-derived polyethylene terephthalate (PET): Conversion of 2,5-dimethylfuran and acrolein into p-xylene
Shiramizu, Mika,Toste, F. Dean
, p. 12452 - 12457 (2011/12/15)
Polyethylene terephthalate (PET) is a polymeric material with high global demand. Conventionally, PET is produced from fossil-fuel-based materials. Herein, we explored the feasibility of a sustainable method for PET production by using solely bio-renewable resources. Specifically, 2,5-dimethylfuran (derived from lignocellulosic biomass through 5-(hydroxymethyl)furfural) and acrolein (produced from glycerol, a side product of biodiesel production) were converted into the key intermediate p-xylene (a precursor of terephthalic acid). This synthesis consists of a sequential Diels-Alder reaction, oxidation, dehydration, and decarboxylation. In particular, the pivotal first step, the Diels-Alder reaction, was studied in detail to provide useful kinetic and thermodynamic data. Although it was found that this reaction requires low temperature to proceed efficiently, which presents a limitation on economic feasibility on an industrial scale, the concept was realized and bio-derived p-xylene was obtained in 34 % overall yield over four steps. Making PET as green as grass: Polyethylene terephthalate (PET) can be prepared from solely bio-renewable sources by converting 2,5-dimethylfuran and acrolein into the key intermediate p-xylene (see scheme). This atom-economic route consists of a sequential Diels-Alder reaction, oxidation, dehydrative aromatization and decarboxylation. We examined the feasibility of this process with an emphasis on the Diels-Alder reaction step. Copyright
Formation of 1,1,3,3-tetrafluoro-1,3-dihydroisobenzofurans in reactions of phthalic acids with sulphur tetrafluoride. Evaluation of the steric and electronic effects of the substituents
Dmowski, Wojciech
, p. 139 - 142 (2007/10/02)
4,5-Dinitrophthalic acid and 3,6-dimethylphthalic anhydride have been reacted with sulphur tetrafluoride to give mixtures of the corresponding bis(trifluoromethyl)benzenes and 1,1,3,3-tetrafluoro-1,3-dihydroisobenzofurans in a 5:1 and 1:3.6 ratio, respectively.These and earlier results on the reactions of sulphur tetrafluoride with substituted and unsubstituted phthalic and pyromellitic acids are compared and structural factors in the acids influencing the competitive formation of cyclic and non-cyclic products discussed.The stability of 1,1,3,3-tetrafluoro-1,3-dihydroisobenzofurans against cleavage by anhydrous hydrogen fluoride has also been investigated.