- Production of allyl compound (by machine translation)
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[Problem] Chlorine contamination risk of the reaction mass, ester reaction agent, and, because the reaction solution cannot be re-used without using dissolved transition metal complex catalyst, metal oxide catalyst obtained by using a relatively simple operation, a relatively high yield or production or synthesis of allyl compounds, and a manufacturing method for a metal oxide catalyst used in the synthesis. [Solution] Allyl alcohol, alcohols, phenol compounds such as allyl group is applied to the dehydration is introduced, allyl ethers, allyl thioether compound such as allyl compounds such as allyl manufacturing method, and an alcohol, the compound is mixed in the liquid, at least one of titania and zirconia obtained by mixing molybdenum compound, titania and/or zirconia on the surface of the molybdenum oxide film formed using the metal oxide catalyst. Figure 1 [drawing] (by machine translation)
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Paragraph 0046; 0047; 0053; 0055; 0056; 0058; 0060; 0064
(2019/07/17)
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- Versatile etherification of alcohols with allyl alcohol by a titanium oxide-supported molybdenum oxide catalyst: Gradual generation from titanium oxide and molybdenum oxide
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Etherification using allyl alcohol to produce allyl ether via dehydration is a fundamental technique for producing fine chemicals that can be applied to electronic devices. We demonstrate a sustainable method to synthesize allyl ethers from allyl alcohol with various alcohols up to a 91% yield, with water as the sole by-product. In this reaction, the active catalyst is gradually generated as the reaction proceeds through the simple mixing of TiO2 and MoO3. The dispersion of MoO3 on the spent catalyst has been observed by XRD, HAADF-STEM, and STEM-EDS mapping. This catalyst shows excellent catalytic activity by virtue of the highly dispersed nature of MoO3 supported on TiO2, which is reusable at least five times. According to a mechanistic study including the measurement of XPS of MoO3 on TiO2 and control experiments using SiO2 and Al2O3 supports, the suitable reducibility of MoO3 to coordinate the allyl moiety on TiO2 seems to be a key factor for high-yielding syntheses of various allyl ethers even under heterogeneous reaction conditions. The reaction mechanism is considered to be as follows: σ-allyl species are formed from dehydration of the allyl alcohol, followed by a nucleophilic attack by another alcohol against the σ-allyl carbon to give allyl ethers. The developed catalytic system should be suitable for easily handled syntheses of allyl ethers due to the employment of commercially available MoO3 and TiO2 with halide- and organic solvent-free reaction conditions.
- Kon, Yoshihiro,Fujitani, Tadahiro,Nakashima, Takuya,Murayama, Toru,Ueda, Wataru
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p. 4618 - 4625
(2018/09/29)
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- Solid State Polymerization Process for Polyester with Phosphinic Acid Compounds
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Disclosed are phosphinic acid compounds of formula I, II or III where R1 and R1′ are for instance straight or branched C1-C50alkyl, R2 is for instance straight or branched C22-C50alkyl, R3 and R3′ are for instance straight or branched C1-C50alkyl, R4 is for instance straight or branched C1-C50alkylene and m is from 2 to 100. Also disclosed are polyester compositions comprising the compounds of formula I, II and III.
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Paragraph 0160; 0161
(2013/03/26)
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- Scope of the allylation reaction with [RuCp(PP)]+ catalysts: Changing the nucleophile or allylic alcohol
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The scope of the dehydrative allylation reaction using allyl alcohol as allyl donor with [RuCp(PP)]+ complexes as catalysts is explored. Aliphatic alcohols are successfully allylated with allyl alcohol or diallyl ether, obtaining high selectivity for the alkyl allyl ether. The reactivity of aliphatic alcohols is in the order of primary > secondary tertiary. The tertiary alcohol 1-adamantanol reacts extremely slowly in the absence of strong acid, but when HOTs is added, reasonable yields of 1-adamantyl allyl ether are obtained. The alkyl allyl ether is found to be the thermodynamically favored product over diallyl ether. Apart from alcohols, thiols and indole are also efficiently allylated, while aniline acts as a catalyst inhibitor. Allylation reactions with various substituted allylic alcohols give products with retention of the substitution pattern. It is proposed that a Ru(IV) σ-allyl species plays a key role in the mechanism of these allylation reactions.
- Van Rijn, Jimmy A.,Guijt, Marieke C.,De Vries, Dwight,Bouwman, Elisabeth,Drent, Eite
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experimental part
p. 212 - 219
(2012/04/17)
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- Immobilization of ruthenium catalysts for allylations with allyl alcohol
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[RuCp(PP)]+ complexes active for allylation of alcohols with allyl alcohol as the allylating agent were immobilized on solid supports. Two different immobilization methods have been applied: (1) via electrostatic interactions of the cationic complex on ion-exchange resins, where the anion is present on the support and (2) via a coordination bond with a ligand covalently-bound on the support. Both methods give high yields of immobilized complex through relatively simple procedures. The catalysts immobilized via ionic interactions prove to be able to allylate both 1-octanol and 4-tert-butylphenol with very low leaching of the catalyst, thus forming allyl octyl ether and C-allylated phenol, respectively. The accumulation of water in the highly hydrophilic resin precludes the O-allylation of phenol and also retards the C-allylation reaction. The catalysts immobilized via a coordination bond are not hydrophilic; with these catalysts selective O-allylation of phenols is achieved, with recycling of the catalysts over multiple runs. Leaching of the catalyst from the support is somewhat higher than for the electrostatically-bound catalyst and quarternisation (allylation) of the excess of phosphine groups present on the support plays an important role in the activity of the immobilized catalysts for the allylation reaction.
- Van Rijn, Jimmy A.,Bouwman, Elisabeth,Drent, Eite
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experimental part
p. 26 - 34
(2010/12/20)
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- Palladium-diphosphine complexes as catalysts for allylations with allyl alcohol
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Several palladium complexes with bidentate phosphine ligands were tested for their activity in the O-allylation of phenols with allyl alcohol. The use of C3-bridged bidentate phosphine ligands results in very high selectivity for O-allylation. The reactions do not require stoichiometric amounts of additives to control the chemoselectivity. Especially, catalysts with gem-dialkyl substituted C3-bridged bidentate phosphine ligands perform very well, resulting in a (equilibrium) conversion of ~50% of phenol with a selectivity of 99% for O-allylation. The use of diallyl ether as the allylating agent results in a significant increase in phenol conversion while maintaining high selectivity for O-allylation. Apart from Pd(OAc)2 as catalyst precursor, Pd(dba)2 was also employed, making it possible to use other types of phosphine or phosphite ligands. With the palladium catalytic system not only phenol, but also aliphatic alcohols can be allylated, as well as aromatic and aliphatic amines.
- Van Rijn, Jimmy A.,Dunnen, Angela Den,Bouwman, Elisabeth,Drent, Eite
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experimental part
p. 96 - 102
(2010/11/18)
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- Process for producing allyl-containing compounds
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An allyl-containing compound represented by following Formula (3): wherein R2, R3, R4, R5 and R6 may be the same as or different from one another and each represent hydrogen atom or an organic group; R7 represents an organic group; and Y represents oxygen atom or sulfur atom, is produced by reacting an allyl ester compound represented by following Formula (1): wherein R1 represents hydrogen atom or an organic group; and R2, R3, R4, R5 and R6 are as defined above, with a compound represented by following Formula (2):R7-Y-H wherein R7 is an organic group; and Y is as defined above, in the presence of at least one transition element compound.
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- Allylation of Alcohols and Carboxylic Acids with Allyl Acetate Catalyzed by [Ir(cod)2]+BF4- Complex
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A facile method for the synthesis of allyl alkyl ethers from alcohols with allyl acetate was developed by the use of [Ir(cod)2] +BF4- complex. For instance, the reaction of allyl acetate with n-octyl alcohol in the presence of a catalytic amount of [Ir(cod)2]+BF4- complex afforded allyl octyl ether in quantitative yield. Allyl carboxylates were also prepared by the exchange reaction between carboxylic acids and allyl acetate in good yields. The [Ir(cod)2]+BF4- complex catalyzed the reaction of alkyl and aromatic amines with allyl acetate to lead to the corresponding allylamines in fair to good yields.
- Nakagawa, Hideto,Hirabayashi, Tomotaka,Sakaguchi, Satoshi,Ishii, Yasutaka
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p. 3474 - 3477
(2007/10/03)
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- Method for producing allyl compound, and ether or ester compound produced thereby
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A method for producing an allyl compound having a compositional formula different from that of an allyl starting material compound, which comprises reacting the allyl starting material compound with an oxygen nucleophilic agent in the presence of a catalyst containing at least one transition metal compound containing a transition metal selected from the group consisting of transition metals belonging to Group 8 to Group 10 of the Periodic Table and a multidentate phosphite compound.
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- Total synthesis of (+/-)-cameroonan-7alpha-ol and biomimetic rearrangements to related nopsane sesquiterpenes.
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A total synthesis of the novel silphinane sesquiterpene alcohol (+/-)-cameroonanol (6-OH) from bicyclic enone 10 was accomplished by conjugate addition of crotylsilane, photochemical hydrobromination, intramolecular alkylation, and hydride reduction. The stereoisomers cameroonan-7beta-ol (18-OH) and 9-epicamerooonanols (19 and 20) were separated from isomer mixtures and the 9-desmethylcameroonanols (21-OH and 22-OH) were obtained by similar means. Solvolysis of 6-OMs and 18-OMs effected skeletal rearrangements to (+/-)-silphiperfol-6-ene (5), (+/-)-prenopsanol (7) and (+/-)-nopsanol (8), and (+/-)-silphiperfolan-7beta-ol (9) in parallel with biogenetic schemes proposed for these naturally occurring sesquiterpenes. The nor analogues 21-OMs and 22-OMs underwent solvolytic rearrangments to a similar set of nor products. The increase in solvolytic rates for the 7beta-mesylates 18-OMs and 22-OMs in comparison to the 7alpha epimers is attributed to concerted antiperiplanar Wagner-Meerwein rearrangements to the prenopsyl and norprenopsyl carbocations. Further analysis of the kinetic data and comparisons with solvolysis rates for the structurally related silphin-1beta-yl and silphin-1alpha-yl mesylates (28 and 29) are presented. The rearrangements observed afford chemical precedent for the biogenetic pathways in the literature for these silphinane sesquiterpenes.
- Davis, Chad E,Duffy, Bryan C,Coates, Robert M
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p. 6935 - 6943
(2007/10/03)
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- SmI2/water/amine mediates cleavage of allyl ether protected alcohols: application in carbohydrate synthesis and mechanistic considerations.
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[reaction: see text]. SmI2/H2O/amine provides selective cleavage of unsubstituted allyl ethers in good to excellent yields. This method is therefore useful in deprotection of alcohols and carbohydrates.
- Dahlen, Anders,Sundgren, Andreas,Lahmann, Martina,Oscarson, Stefan,Hilmersson, Goeran
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p. 4085 - 4088
(2007/10/03)
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- Palladium catalyzed cross-coupling and tandem cyclization-coupling of α-halo(thio)ethers with organotins
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Pd(0) mediates the cross-coupling of organotins with a variety of α-haloethers/thioethers in moderate-good yields whereas an α-chloroacetoxyalkene failed to react. Tandem cyclization-coupling of the alkyl-palladium intermediate affords novel access to heterocycles.
- Bhatt,Shin, Dong-Soo,Falck,Mioskowski, Charles
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p. 4885 - 4888
(2007/10/02)
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- SYNTHESE D'ETHERS ET DE THIOETHERS ALLYLIQUES FLUORES PAR CATALYSE PAR TRANSFERT DE PHASE
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Several fluorinated allylic ethers, thioethers and diethers have been prepared in excellent yields by phase transfer catalysis (CTP).The used halogenated compounds are allyl chloride and bromide, p-chloromethylstyrene.The used fluorinated alcohols are aromatic pentafluorophenol and various aliphatics: CF3-CH2OH, CF2H-CF2-CH2-OH, ClCF2-CF2-CH2OH, C6F13C2H4OH, HO-CH2-CF2-CFCl-CF2-CH2OH and HO-C6H4-C(CF3)2-C6H4-OH.All these new compounds have been characterized by 1H and 13C NMR.We conclude that CTP is the best method to obtain allylic and diallylic compounds.
- Boutevin, B.,Youssef, B.,Boileau, S.,Garnault, A. M.
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p. 399 - 410
(2007/10/02)
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- Zeolite-Promoted Benzylation of Alcohols
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Zeolite-promoted benzylation of alcohols with benzyl chloride has been investigated.By use of a series of cation-exchanged zeolites, which have the same crystalline structure but different acid and base properties, it is confirmed that the cooperative function of acid sites and base sites of zeolite is required for the effective benzylation of alcohols, although both acid and base strengths are low.It is also found that alcohols show different reactivities in zeolite from those in solution depending on their molecular structures because the benzylation is promoted inside the narrow cavities of zeolite.
- Onaka, Makoto,Kawai, Motomitsu,Izumi, Yusuke
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p. 1761 - 1766
(2007/10/02)
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