Tosylated glycerol carbonate, a versatile bis-electrophile to access new functionalized glycidol derivatives

Rousseau, Jean-Paul; Rousseau, Cyril; Lynikaite, Benita; Šačkus, Algirdas; León, Claudia de; Rollin, Patrick; Tatibouët, Arnaud

doi:10.1016/j.tet.2009.07.095

Cited by 58 publications

(55 citation statements)

References 33 publications

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“…In the present work, functionalization of 1-phenyl-1H-pyrazol-3-ol with tosylated glycerol 1,2-carbonate (TGC) was investigated. TGC is relatively new and efficient reagent, which have found application as an initiator of cationic ring-opening polymerization [9] and as a versatile bis-electrophile to access new functionalized glycidol derivatives [10,11]. TGC can be easily obtained by tosylation of glycerol carbonate (4-(hydroxymethyl)-1,3-dioxan-2-one) [10], the latter is an industrial product of glycerol valorization [12].…”

Section: Introductionmentioning

confidence: 99%

“…It is known that TGC reacts with 4-methoxyphenol in DMF in the presence of K 2 CO 3 to afford Oalkylated product, 4-(3-methoxyphenoxy)methyl-1,3-dioxolan-2-one, in only 41% yield [11], while 55% of the arylsulfanyl analogue is obtained in analogous conditions from m-methoxythiophenol [10]. The reaction of 1-phenyl-1H-pyrazol-3-ol 1 with TGC 2 was carried out in DMF in the presence of K 2 CO 3 and gave chemoselectively 4-{[(1-phenyl-1H-pyrazol-3-yl)oxy]methyl}-1,3-dioxolan-2-one 3 in 71% isolated yield.…”

Section: Introductionmentioning

confidence: 99%

“…TGC is relatively new and efficient reagent, which have found application as an initiator of cationic ring-opening polymerization [9] and as a versatile bis-electrophile to access new functionalized glycidol derivatives [10,11]. TGC can be easily obtained by tosylation of glycerol carbonate (4-(hydroxymethyl)-1,3-dioxan-2-one) [10], the latter is an industrial product of glycerol valorization [12].It is known that TGC reacts with 4-methoxyphenol in DMF in the presence of K 2 CO 3 to afford Oalkylated product, 4-(3-methoxyphenoxy)methyl-1,3-dioxolan-2-one, in only 41% yield [11], while 55% of the arylsulfanyl analogue is obtained in analogous conditions from m-methoxythiophenol [10]. The reaction of 1-phenyl-1H-pyrazol-3-ol 1 with TGC 2 was carried out in DMF in the presence of K 2 CO 3 and gave chemoselectively 4-{[(1-phenyl-1H-pyrazol-3-yl)oxy]methyl}-1,3-dioxolan-2-one 3 in 71% isolated yield.…”

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4-{[(1-Phenyl-1H-pyrazol-3-yl)oxy]methyl}-1,3-dioxolan-2-one

Vilkauskaitė

Hölzer

Šačkus

2012

Molbank

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Abstract:The title compound was obtained by the reaction of tosylated glycerol carbonate with 1-phenyl-1H-pyrazol-3-ol in a good 71% yield. Detailed spectroscopic data ( 1 H-NMR, 13 C-NMR, 15 N-NMR, IR, MS) are presented.Keywords: 1H-pyrazol-3-ol; glycerol; tosylated glycerol 1,2-carbonate; alkylation 1-Phenylpyrazole derivatives are known to have a broad spectrum of biological activities [1][2][3][4][5][6]. Recently, 1-phenyl-1H-pyrazol-3-ol was used as a versatile synthon for the preparation of various (het)aryl-and carbo-functionally substituted pyrazole derivatives employing Pd-catalyzed crosscoupling reactions [7,8]. In the present work, functionalization of 1-phenyl-1H-pyrazol-3-ol with tosylated glycerol 1,2-carbonate (TGC) was investigated. TGC is relatively new and efficient reagent, which have found application as an initiator of cationic ring-opening polymerization [9] and as a versatile bis-electrophile to access new functionalized glycidol derivatives [10,11]. TGC can be easily obtained by tosylation of glycerol carbonate (4-(hydroxymethyl)-1,3-dioxan-2-one) [10], the latter is an industrial product of glycerol valorization [12].It is known that TGC reacts with 4-methoxyphenol in DMF in the presence of K 2 CO 3 to afford Oalkylated product, 4-(3-methoxyphenoxy)methyl-1,3-dioxolan-2-one, in only 41% yield [11], while 55% of the arylsulfanyl analogue is obtained in analogous conditions from m-methoxythiophenol [10]. The reaction of 1-phenyl-1H-pyrazol-3-ol 1 with TGC 2 was carried out in DMF in the presence of K 2 CO 3 and gave chemoselectively 4-{[(1-phenyl-1H-pyrazol-3-yl)oxy]methyl}-1,3-dioxolan-2-one 3 in 71% isolated yield. The structure of compound 3 was confirmed by its spectroscopic data ( 1 H NMR, 13 C and 15 N NMR, IR, MS) as well as by elemental analysis. OPEN ACCESS

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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confidence: 99%

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4-{[(1-Phenyl-1H-pyrazol-3-yl)oxy]methyl}-1,3-dioxolan-2-one

Vilkauskaitė

Hölzer

Šačkus

2012

Molbank

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“…[4] Furthermore, glycerol carbonate is a valuable intermediate for the production of glycidol [5] and is also the main ingredient of an electrolyte for secondary batteries. [6] In particular, glycerol carbonate can be used as a green concrete-curing accelerator at low temperature, even at below 0 8C.…”

Section: Introductionmentioning

confidence: 99%

An Efficient Palladium Catalyst System for the Oxidative Carbonylation of Glycerol to Glycerol Carbonate

Guan

et al. 2011

ChemSusChem

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Glycerol carbonate can be readily synthesized from the oxidative carbonylation of glycerol catalyzed by PdCl(2)(phen) (phen=1,10-phenanthroline) with the aid of CuI. High conversion (95 %) and selectivity (98 %) are achieved and the turnover frequency (TOF) reaches 455 h(-1). Furthermore, a new zeolite-Y-confined Pd catalyst, PdCl(2)(phen)@Y, has been successfully prepared by a ''flexible ligand'' method. The structure and composition of the heterogeneous catalyst have been characterized by atomic absorption spectroscopy, elemental analysis, N(2) sorption, XRD, FTIR, solid-state NMR, and X-ray photoelectron spectroscopy. This catalyst exhibits a comparable activity to its homogeneous counterpart and could be reused five times without significant decrease in activity. This is the most efficient heterogeneous system for synthesizing glycerol carbonate by the oxidative carbonylation of glycerol to date.

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“…With rapidly increasing production of biodiesel, much attention has been focused on the utilization of glycerol for producing value-added chemicals [1]. Among the chemicals derived from glycerol, glycerol carbonate, which can be used as the solvent or reaction intermediate, is a high value-added product with many potential applications [2][3][4][5][6].…”

Section: Introductionmentioning

confidence: 99%

On the deactivation of alkali solid catalysts for the synthesis of glycerol carbonate from glycerol and dimethyl carbonate

Wang

2010

Reac Kinet Mech Cat

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The deactivation of alkali solid catalysts for the synthesis of glycerol carbonate from glycerol and dimethyl carbonate was investigated. Calcium oxide, calcium hydroxide and calcium methoxide were chosen as the representatives of the alkali solid catalysts. When the catalysts were recycled, the yield of glycerol carbonate decreased dramatically. The alkali solid catalyst was converted to the basic calcium carbonate Ca x (OH) y (CO 3 ) z , which was the cause of the decrease of glycerol carbonate yield. It was found that the chemical interactions of the alkali solid catalyst with glycerol and glycerol carbonate led to the formation of the basic calcium carbonate Ca x (OH) y (CO 3 ) z , for which the mechanism was proposed. Based on the deactivation mechanism, calcium diglyceroxide was adopted as a new catalyst for the transesterification of glycerol and dimethyl carbonate. Compared to calcium oxide, calcium hydroxide and calcium methoxide, calcium diglyceroxide showed excellent reusability for the transesterification of glycerol and dimethyl carbonate. For calcium oxide, calcium methoxide and calcium diglyceroxide, there were dissolution losses of the catalysts in the reaction medium. For calcium hydroxide, the catalyst dissolution loss in the reaction medium was nearly negligible. For calcium diglyceroxide, the dissolution of the catalyst in the reaction medium did not influence the yield of glycerol carbonate significantly.

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Tosylated glycerol carbonate, a versatile bis-electrophile to access new functionalized glycidol derivatives

Cited by 58 publications

References 33 publications

4-{[(1-Phenyl-1H-pyrazol-3-yl)oxy]methyl}-1,3-dioxolan-2-one

4-{[(1-Phenyl-1H-pyrazol-3-yl)oxy]methyl}-1,3-dioxolan-2-one

An Efficient Palladium Catalyst System for the Oxidative Carbonylation of Glycerol to Glycerol Carbonate

On the deactivation of alkali solid catalysts for the synthesis of glycerol carbonate from glycerol and dimethyl carbonate

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