Nucleophilic addition to acetylenes in superbasic catalytic systems: XVII. Vinyl ethers with furyl and cycloacetal fragments: Synthesis and structure

Опарина, Л. А.; Vysotskaya, O. V.; Степанов, А. В.; Гусарова, Н. К.; Chernyshev, K. A.; Krivdin, Leonid B.; Трофимов, Б. А.

doi:10.1134/s1070428010090204

Cited by 7 publications

(5 citation statements)

References 8 publications

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“…In addition to several industrial applications, furfural has received consideration as a substrate for the production of biofuels . For example, Dumesic has published reports regarding the catalytic production of gasoline and diesel range alkanes starting from furan precursors. , The acetalization of glycerol with furfural has also been previously realized; however in all examples, the synthesis has been carried out in refluxing organic solvent with a water separation apparatus. , The products, furyl-1,3-dioxacyclanes, have been noted for their significant potential as synthetic platforms as well as practical applications …”

Section: Introductionmentioning

confidence: 99%

Solvent-Free Methods for Making Acetals Derived from Glycerol and Furfural and Their Use as a Biodiesel Fuel Component

Wegenhart

Liu

Thom³

et al. 2012

ACS Catal.

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The increased production of biodiesel has resulted in the overproduction of glycerol. Many researchers have begun investigating new uses for glycerol, including its conversion to fuel additives. In this paper, glycerol has been reacted with furfural to yield the corresponding acetal. This condensation reaction is carried out under neat conditions with 5-fold excess of furfural, and a number of homogeneous Lewis acids and heterogeneous solid acids as catalysts. Reactions are routinely carried out at 100 °C, allowing for yields up to 90%. The addition of a dry stream of nitrogen gas purging the headspace was found to improve yields and allowed for a reduction in the excess amount of furfural. These reaction methods are applicable to crude glycerol, affording up to 80% yield with short reaction times. The isolated acetal products can be hydrogenated, and the free hydroxyl group can subsequently be acetylated. The resulting materials have been investigated as additives to biodiesel, aiming to improve the low temperature properties. While there was no benefit to the low temperature properties, we have no evidence that would preclude the use of these materials as biodiesel additives.

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Section: Introductionmentioning

confidence: 99%

Solvent-Free Methods for Making Acetals Derived from Glycerol and Furfural and Their Use as a Biodiesel Fuel Component

Wegenhart

Liu

Thom³

et al. 2012

ACS Catal.

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“…1 Н, 13 С NMR spectra differ from those described in [33,34]. 1 1,4-Divinyloxybenzene (4). Yield 5.84 g (72%), bp 79-80°С (6 mmHg), n D 20 1.5334 (n D 20 1.5342 [11]).…”

Section: Methodsmentioning

confidence: 84%

“…The suggested pathway of the tarry products formation is supported by IR and NMR spectra where aromatic and aliphatic groups are clearly identified. 1 Under these conditions also the side processes were accelerated leading to the formation of a considerable amount of tar and (methylsulfanyl)methoxybenzene (3) (4-6%). The formation of the latter we also observed at the phenol vinylation with acetylene in the system K 2 СО 3 -DMSO (140°С, 3 h) [44].…”

mentioning

confidence: 99%

Nucleophilic addition to acetylenes in superbasic catalytic systems: XVIII. Vinylation of phenols and naphthols with acetylene

et al. 2015

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Phenols and naphthols react with acetylene in a superbasic system KOH-DMSO forming the corresponding aryl vinyl ethers in up to 80% yields. * For communication XVII, see [1].Aryl vinyl ethers compared with aliphatic analogs are more stable against hydrolysis and are more reactive in the radical polymerization. They are highly reactive building blocks for organic synthesis. The pioneering research in this field was carried out by the scientific school of A.V. Kalabina [2-4] who widely used aryl vinyl ethers for the preparation of polymer materials [5][6][7][8][9][10][11][12], in the diene synthesis [13][14][15][16], and also in the design of biologically active compounds, in particular, of insecticides and herbicides [17]. The chemistry of aryl vinyl ethers has been actively developed in the recent decades [18][19][20][21]. They were utilized for designing new polymer compositions [20,21], reagents for the chemical plant protection [22]. A high selectivity of aryl vinyl ethers was found at the ammetric titration of metal ions, in particular, of Ag(I) [23]. Vinyl ether of fluorescein was recommended as a highly sensitive fluorescent probe for organomercury compounds in cells and living bodies [24]. New methods of aryl vinyl ethers production are under development, among which the following are worth considering: catalytic reaction of phenols with various vinyl equivalents, e.g., vinyl halides [25, 26], vinylboronic acids [27, 28], tetravinyl-and tributyl-(vinyl)tin [29], vinyl esters of carboxylic acids [21, 30], and also the synthesis of aryl vinyl ethers from 2-phenylselenyl-ethanol [31-33] or 2-phenylsulfonylethanol [34] and phenols at treating with Mitsunobu reagent (diethyl ether of azodicarboxylic acidtriphenylphosphine). Recently a new two-stage method was patented of the production of aromatic vinyl ethers in a low yield (10-38%) involving vinylation of 2-aryloxyethanols (100 о С, 3-6 h, acetylene pressure 1.4 at, KОН-DMSO) with the formation of the corresponding 2-aryloxyethyl vinyl ethers followed by heating of the latter (130-140 о С, 6-10 h, DMSO) in the presence of double molar excess of KОН [35].The classic synthesis method of aryl vinyl ether through direct phenol vinylation with acetylene under the basic catalysis conditions not only conserves its importance but possesses obvious advantages before the mentioned procedures [21,[25][26][27][28][29][30][31][32][33][34][35] since it is atomeconomical, one-stage, and is based on a raw material of a large-scale production. Phenols add to acetylene in the presence of KОН at a high pressure (30-50 at) and a high temperature (180-200 о С) [2,[36][37][38][39][40].The aim of this study is the development of a technologically more convenient procedure of the synthesis of aryl vinyl ethers by vinylation of phenols and naphthols with acetylene in superbasic catalytic environment (alkali metal hydroxide-polar hydroxylfree solvent). The application of superbasic media in the acetylene chemistry made it possible to improve the most important reactions of nucleophili...

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“…The attention toward the acetalization of furfural with glycerol to give fuel additives has been rising rapidly (Table 2). [86][87][88][89][90][91][92][93][94][95][96][97][98][99][100][101] The acetalization of furfural with glycerol, nevertheless, is more challenging in comparison with the acetalization of furfural with ethylene glycol owing to the high viscosity of glycerol. Moreover, the acetal products originated from the acetalization of furfural with glycerol are more complicated because glycerol embraces two kinds of hydroxyl groups, which results in acetalization between furfural and 1,2-diol (affording dioxolane product) or…”

Section: Acetalization Of Furfural With Glycerolmentioning

confidence: 99%

“…Early research using homogeneous acid catalysts ( e.g. , p -toluenesulfonic acid, 86 4-methylbenzenesulfonic acid, 87 oxorhenium( v ) oxazoline complex, 88 and FeCl 3 ·6H 2 O (ref. 89)) contributed to affording high yield of acetals from the acetalization of furfural with glycerol (entries 1–3, Table 2).…”

Section: Synthesis Of Cyclic Acetals From Furfuralmentioning

confidence: 99%

Acetalization strategy in biomass valorization: a review

Qian

et al. 2024

Ind. Chem. Mater.

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Nucleophilic addition to acetylenes in superbasic catalytic systems: XVII. Vinyl ethers with furyl and cycloacetal fragments: Synthesis and structure

Cited by 7 publications

References 8 publications

Solvent-Free Methods for Making Acetals Derived from Glycerol and Furfural and Their Use as a Biodiesel Fuel Component

Solvent-Free Methods for Making Acetals Derived from Glycerol and Furfural and Their Use as a Biodiesel Fuel Component

Nucleophilic addition to acetylenes in superbasic catalytic systems: XVIII. Vinylation of phenols and naphthols with acetylene

Acetalization strategy in biomass valorization: a review

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