Simple synthesis of furfuryl sulfides via extrusion of COS from the xanthates and its mechanistic aspects

Eto, Masashi; Nishimoto, Mituhiro; Uemura, Toshihiro; Hisano, Takuzo; Harano, Kazunobu

doi:10.1039/p29950001155

Cited by 6 publications

(11 citation statements)

References 19 publications

(9 reference statements)

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“…These phenomena shed light on the mechanism for the conversion reaction of furfuryl xanthates to furfuryl alkyl sulfides. 109 In the thermal isomerization between provitamin D 3 and vitamin D 3 in an aqueous solution, the forward and reverse rate constants were increased by β-CD complexation by more than 40 and 600 times, respectively, compared with those in hexane. The reaction in aqueous solution is the fastest reported rate for this isomerization 110 (Figure 32).…”

Section: Transfer Elimination Isomerization and The Other Reactionsmentioning

confidence: 96%

“…This is because the furan ring of the guest molecules is entirely included within the cavity and the CS group makes a hydrogen bond with the hydrogen groups of the CD. These phenomena shed light on the mechanism for the conversion reaction of furfuryl xanthates to furfuryl alkyl sulfides 31 The effect of CD as polarity controller on the pyrolysis of xanthate …”

Section: 26 Transfer Elimination Isomerization and The Other Reactionsmentioning

confidence: 99%

“…These phenomena shed light on the mechanism for the conversion reaction of furfuryl xanthates to furfuryl alkyl sulfides 31 The effect of CD as polarity controller on the pyrolysis of xanthate …”

Section: 26 Transfer Elimination Isomerization and The Other Reactionsmentioning

confidence: 99%

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Organic Reactions Mediated by Cyclodextrins

1998

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Section: Transfer Elimination Isomerization and The Other Reactionsmentioning

confidence: 96%

Section: 26 Transfer Elimination Isomerization and The Other Reactionsmentioning

confidence: 99%

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Organic Reactions Mediated by Cyclodextrins

1998

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“…For instance, the thermolysis of the S-methoxycarbonylmethyl derivative proceeds at a rate approximately 16 times faster than that of the S-methyl derivative. 4) The energy barriers for the [3,3]-rearrangement and SN itype rearrangement of 1a calculated at the B3LYP/6-31Gϩ(d) level are 19.9 and 32.5 kcal/mol, respectively. These values suggest that the formation of the sulfide (3a) from O-furfuryl xanthate (1a) via aromatic [3,3]-rearrangements is energetically more favorable than the SNi-pathway.…”

Section: Resultsmentioning

confidence: 99%

“…It was initially assumed that the sulfide (3) had formed via an intramolecular SNi-type fragmentation reaction mechanisms (Chart 2). 4) These considerations prompted us to reinvestigate the key step of the conversion of the furfuryloxy (ArCH 2 O-) moiety to the furfurylthio (ArCH 2 S-) moiety in the formation of the trithiocarbonate from sodium O-furfuryl dithiocarbonates as well as in the formation of S-furfuryl S-alkyl dithiocarbonates (2) and furfuryl alkyl sulfides (3) from O-furfuryl Salkyl xanthates (1) with the assumption that aromatic [3,3]sigmatropic rearrangement was operative.…”

mentioning

confidence: 99%

Formation Mechanism of Furfuryl Sulfides from O-Furfuryl Dithiocarbonates: Density Functional Theory Study for Aromatic [3,3]-Sigmatropic Rearrangement

Eto

Yamaguchi

Yoshitake

et al. 2011

CHEMICAL & PHARMACEUTICAL BULLETIN

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Recently, we proposed a new reaction mechanism for the formation of allylic trithiocarbonate from sodium O-(2-alkenyl) dithiocarbonate, 1) in which a suspension of sodium hydride in benzene, containing 2-alkenol and an excess of carbon disulfide is heated to obtain the corresponding di(2-alkenyl)trithiocarbonates in good yields.2,3) The trithiocarbonates are convenient precursors of the thermodynamically stable allylic thiols (Chart 1).Based on data obtained from density functional theory (DFT) calculations at the B3LYP/6-31G(d) level, we demonstrated that sodium O-(3-phenylallyl) dithiocarbonate undergoes [3,3]-sigmatropic rearrangement to form sodium S-(1-phenylallyl) dithiocarbonate, which then allylically isomerizes to the more thermodynamically stable sodium S-(3-phenylallyl) dithiocarbonate.Furfuryl and benzyl alcohols were subjected to xanthation in dimethyl sulfoxide (DMSO) containing excess CS 2 in the presence of NaOH followed by alkylation to give the mixtures of trithiocarbonates. 3)On the other hand, it was observed that heating of O-furfuryl S-alkyl dithiocarbonates (xanthates) (1) afforded furfuryl alkyl sulfides (3) together with S-furfuryl S-alkyl dithiocarbonates (2). It was initially assumed that the sulfide (3) had formed via an intramolecular SNi-type fragmentation reaction mechanisms (Chart 2). 4)These considerations prompted us to reinvestigate the key step of the conversion of the furfuryloxy (ArCH 2 O-) moiety to the furfurylthio (ArCH 2 S-) moiety in the formation of the trithiocarbonate from sodium O-furfuryl dithiocarbonates as well as in the formation of S-furfuryl S-alkyl dithiocarbonates (2) and furfuryl alkyl sulfides (3) from O-furfuryl Salkyl xanthates (1) with the assumption that aromatic [3,3]-sigmatropic rearrangement was operative. This paper presents a detailed discussion of the reaction mechanisms in the formation of O-furfuryl dithiocarbonates on the basis of the DFT calculations 5) at the B3LYP/6-31G(d) and B3LYP/6-31Gϩ(d) levels. Results and DiscussionRearrangement of O-Furfuryl Dithiocarbonate Anion (1-Anion) On the basis of the reaction behavior of the Oallyl dithiocarbonate anion, 1) two possible reaction pathways were proposed for the formation of the S-furfuryl dithiocar- ; 4-22-1 Ikeda, Kumamoto 869-1404, Japan: and b Liberal Arts Education Center, Aso Campus, Tokai University; 5435 Kawayo, Minami-Aso, Kumamoto 869-1404, Japan. Received October 27, 2010 accepted February 28, 2011; published online March 7, 2011 Density functional theory (DFT) calculations at the B3LYP/6-31G(d) and B3LYP/6-31G؉(d) levels demonstrated that O-furfuryl S-alkyl dithiocarbonate (1) undergoes aromatic [3,3]-sigmatropic rearrangement to the energetically unfavorable S-(2-methylene-2,3-dihydrofuran-3-yl) S-alkyl dithiocarbonate (2), which then rearranges to furfuryl alkyl sulfide (3) with COS extrusion to regain the aromaticity lost in the first step. Formation Mechanism of Furfuryl Sulfides from O-Furfuryl

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Understanding the Kinetics and Topological Events Within the Thione‐to‐Thiol Rearrangement of Xanthates

2022

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The heating of O‐furfuryl S‐methyl xanthate in p‐xylene solvent that is known from the literature to yield in parallel S‐furfuryl S‐methyl dithiocarbonate and furfuryl methyl sulfide via the thione‐to‐thiol rearrangement and carbon oxysulfide extrusion, respectively, have been studied theoretically. The CBS‐QB3 energies in conjugation with the solvation model density and B3LYP/6‐311G(2d,d,p) monodeterminantal wave functions have been used to investigate the kinetics of the parallel reaction by means of canonical transition state theory and molecular mechanism of the thione‐to‐thiol rearrangement by means of topological approaches. According to the supplied kinetic data the considered reactions are assisted strongly by the solvent molecules implying implicit solvent model cannot account properly the effect of solvent media. The cross topological analysis of the thione‐to‐thiol rearrangement via [1,3]‐sigmatropic rearrangement revealed that the electron density flow along the reaction is not concerted and the sequence of catastrophes can be summarized as 4‐EF†C‐0. In simple chemical term, chemical events through the reaction are heterolytic breaking of C−O bond, formation of pseudoradical center on the C atom, and creation of a new chemical C−S bond via the C‐to‐S coupling of pseudoradical centers, respectively.

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Simple synthesis of furfuryl sulfides via extrusion of COS from the xanthates and its mechanistic aspects

Cited by 6 publications

References 19 publications

Organic Reactions Mediated by Cyclodextrins

Organic Reactions Mediated by Cyclodextrins

Formation Mechanism of Furfuryl Sulfides from O-Furfuryl Dithiocarbonates: Density Functional Theory Study for Aromatic [3,3]-Sigmatropic Rearrangement

Understanding the Kinetics and Topological Events Within the Thione‐to‐Thiol Rearrangement of Xanthates

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