598-32-3Relevant articles and documents
Asymmetric Catalysis by Vitamin B12. The isomerization of Achiral Epoxides to Optically Active Allylic Alcohols
Su, Heng,Walder, Lorenz,Zhang, Zhong-da,Scheffold, Rolf
, p. 1073 - 1078 (1988)
Achiral epoxides are isomerized to optically active allylic alcohols under the influence of catalytical amounts of cob(I)alamin in protic polar solvents.
Evidence for a Concerted SN2' Mechanism in the Gas-Phase Acid-induced Nucleophilic Substitutions on Allylic Substrates
Dezi, Emanuela,Lombardozzi, Antonietta,Pizzabiocca, Adriano,Renzi, Gabriele,Speranza, Maurizio
, p. 547 - 548 (1995)
Gas phase nucleophilic substitution on oxygen-protonated but-1-en-3-ol and trans-but-2-en-1-ol by methanol proceeds via the concerted SN2' mechanism in competition with the classical SN2 mechanism.
Active site structure of a lithium phosphate catalyst for the isomerization of 2,3-epoxybutane to 3-buten-2-ol
Kim, Tae Yong,Song, Chyan Kyung,Yun, Yang Sik,Yun, Danim,Han, Jeong Woo,Yi, Jongheop
, p. 133 - 141 (2018)
Basic lithium phosphate (B-LPO) catalyst selectively produces unsaturated alcohols from epoxides. The catalytic activity of B-LPO is known to originate from appropriate acidic-basic properties, but no details were available on the structure of the active site. In this study, experimental methods and DFT calculations were performed in an attempt to identify the active surface structure of B-LPO for the isomerization of 2,3-epoxybutane to 3-buten-2-ol. The experimental results showed that exchanged Na ions in B-LPO suppressed the formation of an acid-catalyzed by-product (methyl ethyl ketone). In addition, H2O had a negative effect on the formation of 3-buten-2-ol due to the preoccupation of the active site. DFT calculations in conjunction with these experimental observations showed that the most plausible active surface for the formation of 3-buten-2-ol is the (001) surface of LPO whose acidic proton is exchanged with Na atom. On this surface, the under-coordinated Li atoms and the surface P[dbnd]O groups are exposed, and these play a role in activating the C–O bond of an epoxide ring, and in receiving a proton from the terminal carbon, respectively.
THE cis REDUCTION OF 4-(TRIMETHYLSILYL)-3-BUTYN-2-OL WITH LITHIUM ALUMINIUM HYDRIDE
Mancini, Michael L.,Honek, John F.
, p. 4295 - 4298 (1983)
A systematic study led to a method for the preparation of (Z)-4-(trimethylsilyl)-3-buten-2-ol (2) in at least 99percent purity by the reduction of the alkyne 4-(trimethylsilyl)-3-butyn-2-ol (1) with lithium aluminium hydride (LAH) as a clear solvate in ether.
Probing Molecular Motion and Chemical Reactions inside the Chiral Tri-o-thymotide Clathrate Cavity by Solid State NMR Techniques
Facey, Glenn,Ripmeester, John A.
, p. 1585 - 1587 (1990)
Solid state NMR techniques offer a non-destructive alternative to wet chemistry methods in following enantiomeric excess and reactions in chiral clathrates, and show that the two optically distinct populations, one of which cannot be defined by X-ray diffraction, can be characterized by their distinct dynamic behaviour.
Regio- And Enantioselective Iridium-Catalyzed Amination of Alkyl-Substituted Allylic Acetates with Secondary Amines
Jung, Woo-Ok,Krische, Michael J.,Migliozzi, Madyson M.,Stivala, Craig E.,Yoo, Minjin,Zbieg, Jason R.
supporting information, (2021/12/27)
Robust air-stable cyclometalated π-allyliridium C,O-benzoates modified by (S)-tol-BINAP catalyze the reaction of secondary aliphatic amines with racemic alkyl-substituted allylic acetates to furnish products of allylic amination with high levels of enantioselectivity. Complete branched regioselectivities were observed despite the formation of more highly substituted C-N bonds.
Vapor-phase dehydration of 1,4-butanediol to 1,3-butadiene over Y2Zr2O7 catalyst
Matsuda, Asami,Matsumura, Yoshitaka,Sato, Satoshi,Yamada, Yasuhiro
, (2021/09/16)
Vapor-phase catalytic dehydration of 1,4-butanediol (1,4-BDO) was investigated over Y2O3-ZrO2 catalysts. In the dehydration, 1,3-butadiene (BD) together with 3-buten-1-ol (3B1OL), tetrahydrofuran, and propylene was produced depending on the reaction conditions. In the dehydration over Y2O3-ZrO2 catalysts with different Y contents at 325°C, Y2Zr2O7 with an equimolar ratio of Y/Zr showed high selectivity to 3B1OL, an intermediate to BD. In the dehydration at 360°C, a BD yield higher than 90% was achieved over the Y2Zr2O7 calcined at 700°C throughout 10 h. In the dehydration of 3B1OL over Y2Zr2O7, however, the catalytic activity affected by the calcination temperature is roughly proportional to the specific surface area of the sample. The highest activity of Y2Zr2O7 calcined at 700 °C for the BD formation from 1,4-BDO is explained by the trade-off relation in the activities for the first-step dehydration of 1,4-BDO to 3B1OL and for the second-step dehydration of 3B1OL to BD. The higher reactivity of 3B1OL than saturated alcohols such as 1-butanol and 2-butanol suggests that the C=C double bond of 3B1OL induces an attractive interaction to anchor the catalyst surface and promotes the dehydration. A probable mechanism for the one-step dehydration of 1,4-BDO to BD was discussed.
Selective production of 1,3-butadiene from 1,3-butanediol over Y2Zr2O7 catalyst
Matsuda, Asami,Matsumura, Yoshitaka,Sato, Satoshi,Yamada, Yasuhiro
, p. 1651 - 1658 (2021/07/21)
The vapor-phase dehydration of 1,3-butanediol (1,3-BDO) to produce 1,3-butadiene (BD) was evaluated over yttrium zirconate, which was prepared through a hydrothermal aging process. 1,3-BDO was initially dehydrated to three unsaturated alcohols, namely 3-buten-2-ol, 3-buten-1-ol, and 2-buten-1-ol, followed by the further dehydration to BD. The catalytic activity of yttrium zirconate was greatly dependent on the calcination temperature. Also, the reaction temperature was one of the important factors to produce BD efficiently. The selectivity to BD was increased with increasing reaction temperature up to 375°C, while coke formation resulted in catalyst deactivation together with by-product formation at higher temperatures. Yttrium zirconate catalyst calcined at 900°C showed a high BD yield of 95% at 375°C and 10 hr on stream.
PROCESS FOR PRODUCING DIENES
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Page/Page column 30-34, (2021/06/26)
A process for producing a diene, preferably a conjugated diene, more preferably 1,3-butadiene, comprising dehydrating at least one alkenol in the presence of at least one catalytic material comprising at least one acid catalyst based on silica (SiO2) and alumina (AI2O3), preferably a silica-alumina (SiO2-Al2O3), said catalyst having an alumina content (Al2O3) lower than or equal to 12% by weight, preferably between 0.1% by weight and 10% by weight, with respect to the catalyst total weight, said alumina content being referred to the catalyst total weight without binder, and a pore modal diameter between 9 nm and 170 nm, preferably between 10 nm and 150 nm, still more preferably between 12 nm and 120 nm. Preferably, said alkenol can be obtained directly from biosynthetic processes, or by catalytic dehydration processes of at least one diol, preferably a butanediol, more preferably 1,3-butanediol, still more preferably bio-1,3-butanediol, deriving from biosynthetic processes. Preferably, said 1,3-butadiene is bio-1,3-butadiene.
Dehydration of 2,3-butanediol to produce 1,3-butadiene over Sc2O3 catalyst prepared through hydrothermal aging
Nakazono, Kazuki,Sato, Satoshi,Takahashi, Ryoji,Yamada, Yasuhiro
, (2021/11/16)
Vapor-phase catalytic dehydration of 2,3-butanediol (2,3-BDO) to form 1,3-butadiene (BD) via 3-buten-2-ol (3B2OL) was studied over various single metal oxide catalysts. Among the catalysts, Sc2O3 prepared under hydrothermal (HT) conditions at 200 °C followed by 800 °C calcination showed the most excellent catalytic activity. The crystallization of precursor ScOOH during HT aging noticeably enhances the catalytic activity of the resulting Sc2O3 for the formation of 3B2OL in the dehydration of 2,3-BDO. The formation rate of 3B2OL from 2,3-BDO over the HT-aged Sc2O3 was twice as high as Sc2O3 without HT aging. Calcination temperatures of Sc2O3 are also important: calcination at 800 °C is efficient for the selective formation of 3B2OL from 2,3-BDO. The HT-aged Sc2O3 also showed an excellent catalytic activity for the formation of BD with the yield higher than 80% in the dehydration of 2,3-BDO at 411 °C.
