Chemo‐ and Regioselective Direct Hydroxylation of Arenes with Hydrogen Peroxide Catalyzed by a Divanadium‐Substituted Phosphotungstate

Kamata, Keigo; Yamaura, Taiyo; Mizuno, Noritaka

doi:10.1002/anie.201201605

Cited by 102 publications

(65 citation statements)

References 46 publications

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“…The reaction smoothly proceeded in acetonitrile and its mixtures with t-BuOH, but in contrast to the oxidation of alkyl-and methoxybenzenes [143], the presence of acid co-catalyst was not crucial.…”

Section: Vanadiummentioning

confidence: 98%

Recent advances in transition-metal-catalyzed selective oxidation of substituted phenols and methoxyarenes with environmentally benign oxidants

Kholdeeva

Zalomaeva

2016

Coordination Chemistry Reviews

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Section: Vanadiummentioning

confidence: 98%

Recent advances in transition-metal-catalyzed selective oxidation of substituted phenols and methoxyarenes with environmentally benign oxidants

Kholdeeva

Zalomaeva

2016

Coordination Chemistry Reviews

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“…Different early transition metals substituted POMs showed different activities in the synthesis of phenol from benzene [17]. Among them, vanadiumsubstituted POMs (for example, PMoV) showed good performance in the hydroxylation of benzene to phenol and aroused many studies [9][10][11][12][13][14][15][16][17]. Multi vanadium have been introduced into POMs in order to improve their catalytic activities, but the yields of phenol achieved by the three catalysts were decreased as follows: H 4 There is a strategy to increase the vanadium content simultaneously avoiding vanadium accumulation in POMs anions: using vanadium-containing cations instead of their usual counter ions (H + , Na + , K + ).…”

Section: Introductionmentioning

confidence: 99%

“…Their catalytic activities can be finely manipulated because various early transition metals can be introduced into their structures at molecular levels [9][10][11][12][13][14][15][16][17][18][19][20][21]. Different early transition metals substituted POMs showed different activities in the synthesis of phenol from benzene [17].…”

Section: Introductionmentioning

confidence: 99%

“…A lot of efforts have been made to develop new techniques to solve these drawbacks, direct synthesis of phenol from benzene is preferred. With regard to the low phenol yields and low selectivities to phenol (due to the fact that benzene is hard to be oxidized and phenol is easily suffered from over oxidation) [3], a series of well performed catalysts for hydroxylation of benzene have been designed and synthesized [4][5][6][7][8][9][10][11][12][13][14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%

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Direct synthesis of phenol from benzene catalyzed by multi-V-POMs complex

Yang¹,

Wu²,

Li³

et al. 2013

Applied Catalysis A: General

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“…When the hydroxylation reaction was examined with benzene-d 6 , there was no KIE (k H /k D ¼ 1.0) observed (Table 2, entries 1 and 8), which indicated that C-H activation in the benzene ring was not the rate-determining step. 41 Therefore, the activation of molecular oxygen may be the rate-determining step.…”

mentioning

confidence: 99%

V_xO_y@C catalyst prepared from biomass for hydroxylation of benzene to phenol with molecular oxygen

Wang

Shi

et al. 2017

RSC Adv.

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A series of V x O y @C catalysts was prepared from different types of biomass and NH 4 VO 3 using a hydrothermal method. The prepared catalysts were characterized using a series of methods including XRD, SEM, FT-IR, SEM and XPS to investigate the mechanism of formation of the V x O y @C catalysts.Furthermore, the factors related to the selectivity of phenol and the mechanism of the hydroxylation of benzene to phenol were studied. It was found that the activity was related to the V species on the catalyst and the selectivity was related to the adsorption of phenol. IntroductionC-H bond activation is important in catalysis, especially the C-H bond of arenes. The C-H bond of benzene has a high binding energy of 473.1 kJ mol À1 at 298 K.1 The functionalization of benzene is vitally important for the green conversion of benzene to other chemicals such as the direct conversion of benzene to phenols, anilines, etc.2,3 However, functionalized benzene derivatives are thermodynamically and kinetically favorable to being further converted compared with benzene, 4,5 which makes the direct conversion of benzene to phenol or aniline a great challenge.The direct conversion of benzene to phenol has attracted much research interest for it is a greener route than the industrial three steps of the cumene process route.6-10 Direct conversion of benzene to phenol requires oxidant agents. Among the oxidant agents (such as H 2 O 2 , O 2 and N 2 O) for the hydroxylation of benzene to phenol, O 2 is believed to be the most conveniently available and low cost oxidant. Much effort has been made to produce phenol by hydroxylation of benzene with molecular oxygen under mild conditions. 11-17 However, the mechanism and the factors affecting the selectivity are still not clear for the hydroxylation of benzene to phenol in the liquid phase. With H 2 O 2 as the oxidant agent, C]O and the armchair conguration defects in the carbon catalyst were reported to have a positive effect on the yield of phenol.18-20 However, with molecular oxygen as the oxidant, research on the factors related to the selectivity is still rarely reported. As stated above, phenol is thermodynamically and kinetically more favourable to being further oxidized than benzene in the hydroxylation reaction of benzene to phenol, which makes the selectivity of phenol a challenge in this kind of continuous reaction.21 Therefore, elucidating the factors affecting the selectivity is vitally important for the direct conversion of benzene to phenol.Vanadium is the effective element for the hydroxylation of benzene to phenol with molecular oxygen as the oxidant. Various catalysts have been prepared to improve the yield and selectivity of phenol, including those with different species of vanadium oxide and supports.22-27 Recently, we have developed a V x O y @C catalyst prepared from sucrose and NH 4 VO 3 by a facile one-pot hydrothermal carbonization (HTC) method for the hydroxylation of benzene with molecular oxygen as the oxidant, 28 which exhibited good yield and selectivity of pheno...

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Chemo‐ and Regioselective Direct Hydroxylation of Arenes with Hydrogen Peroxide Catalyzed by a Divanadium‐Substituted Phosphotungstate

Cited by 102 publications

References 46 publications

Recent advances in transition-metal-catalyzed selective oxidation of substituted phenols and methoxyarenes with environmentally benign oxidants

Recent advances in transition-metal-catalyzed selective oxidation of substituted phenols and methoxyarenes with environmentally benign oxidants

Direct synthesis of phenol from benzene catalyzed by multi-V-POMs complex

V_xO_y@C catalyst prepared from biomass for hydroxylation of benzene to phenol with molecular oxygen

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Chemo‐ and Regioselective Direct Hydroxylation of Arenes with Hydrogen Peroxide Catalyzed by a Divanadium‐Substituted Phosphotungstate

Cited by 102 publications

References 46 publications

Recent advances in transition-metal-catalyzed selective oxidation of substituted phenols and methoxyarenes with environmentally benign oxidants

Recent advances in transition-metal-catalyzed selective oxidation of substituted phenols and methoxyarenes with environmentally benign oxidants

Direct synthesis of phenol from benzene catalyzed by multi-V-POMs complex

VxOy@C catalyst prepared from biomass for hydroxylation of benzene to phenol with molecular oxygen

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Product

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V_xO_y@C catalyst prepared from biomass for hydroxylation of benzene to phenol with molecular oxygen