557-31-3Relevant academic research and scientific papers
Technological method for preparation of allyl ether compounds
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Paragraph 0053-0055, (2017/02/17)
The invention discloses a technological method for preparation of allyl ether compounds; the technological method can obtain the high-purity allyl ether compounds in low cost and high yield, has the advantages of high selectivity of the allyl ether compounds, less side reaction, easy separation and purification of the products, friendly technological process environment and the like, and is suitable for large-scale industrialized production.
Hydrogen-bond-activated palladium-catalyzed allylic alkylation via allylic alkyl ethers: Challenging leaving groups
Huo, Xiaohong,Quan, Mao,Yang, Guoqiang,Zhao, Xiaohu,Liu, Delong,Liu, Yangang,Zhang, Wanbin
supporting information, p. 1570 - 1573 (2014/04/17)
C-O bond cleavage of allylic alkyl ether was realized in a Pd-catalyzed hydrogen-bond-activated allylic alkylation using only alcohol solvents. This procedure does not require any additives and proceeds with high regioselectivity. The applicability of this transformation to a variety of functionalized allylic ether substrates was also investigated. Furthermore, this methodology can be easily extended to the asymmetric synthesis of enantiopure products (99% ee).
Catalytic alkylation of alcohols to liquid ethers and organic compounds to alkylated products
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Paragraph 0031, (2013/08/15)
A catalytic process is taught for non-oxidative alkylation of organic compounds, comprising alcohols, alkanes, glycols, ethers, aldehydes, ketones, carboxylic acids, esters, amines, thiols or phosphines, by alkyl groups produced from alcohols or glycols, forming products comprising ethers and other higher molecular weight alkylated compounds. The process is conducted at a reflux temperature below 200° C. in the presence of an acid, alkali or neutral salt dehydrating agent comprising sulfuric acid, phosphoric acid or their salts, lime or anhydrous calcium sulfate in the absence of zero valent metals and air. Specifically, this catalytic process converts ethanol to ethyl butyl ethers, ethyl hexyl ethers and dibutyl ethers or oxygenated gasoline as well as amines comprising n-butyl amine plus butanol to dibutyl amine and butyl hexyl amines at ambient pressure. This same catalytic alkylation chemistry, which does not constitute a condensation reaction, alkylates 4-hydroxybenzoic acid using ethanol to 4-ethoxyethylbenzoic acid products.
Rate and product studies on the solvolyses of allyl chloroformate
Koh, Han Joong,Kang, Suk Jin
, p. 4117 - 4121 (2013/08/23)
The solvolysis rate constants of allyl chloroformate (CH 2=CHCH2OCOCl, 3) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the NT solvent nucleophilicity scale and YCl solvent ionizing scale, with the sensitivity values of 0.93 ± 0.05 and 0.41 ± 0.02 for l and m, respectively. These l and m values can be considered to support a S N2 reaction pathway. The activation enthalpies (ΔH≠) were 12.5 to 13.4 kcal·mol-1 and the activation entropies (ΔS≠) were -34.4 to -37.3 cal·mol-1·K -1, which is also consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, kMeOH/k MeOD) of 2.16 was also in accord with the SN2 mechanism. The values of product selectivity (S) for the solvolyses of 3 in alcohol/water mixtures was 1.3 to 3.9, which is also consistent with the proposed bimolecular reaction mechanism.
Scope of the allylation reaction with [RuCp(PP)]+ catalysts: Changing the nucleophile or allylic alcohol
Van Rijn, Jimmy A.,Guijt, Marieke C.,De Vries, Dwight,Bouwman, Elisabeth,Drent, Eite
experimental part, p. 212 - 219 (2012/04/17)
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.
Copper(I)-olefin complexes: The effect of the trispyrazolylborate ancillary ligand in structure and reactivity
Martin, Carmen,Munoz-Molina, Jose Maria,Locati, Abel,Alvarez, Eleuterio,Maseras, Feliu,Belderrain, Tomas R.,Perez, Pedro J.
experimental part, p. 3481 - 3489 (2010/10/04)
The spectroscopic and structural characteristics and the relative reactivity of several TpMsCu(olefin) (olefin = ethylene, 1, 1-hexene, 2, allyl ethyl ether, aee, 3, cyclohexene, 4, and styrene, 5) complexes bearing the bulky hydrotris(3-mesitylpyrazolyl)borate ligand have been examined. Experimental data, including an unusual high-field chemical shift in the 1H and 13C NMR spectra, and DFT theoretical calculations support the proposal that the copper-olefin linkage is mainly sustained by σ-donation, lacking a substantial degree of π-back-donation.
Catalytic conversion of liquid alcohols and other reactants to products
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Page/Page column 4-5, (2008/06/13)
Catalyst based reactions are taught for non-oxidative chemical conversion of liquid alcohols to higher boiling alcohols, ethers, glycol ethers and related products, comprising ethanol to butanol, propanols to hexanols, butanols to octanols, and others at ambient pressure. This same catalytic chemistry also converts substituted organic compounds comprising amines, ketones, ethers and other substituted organic compounds possessing at least one active hydrogen to related higher molecular weight products in the absence of air. The catalysts are based on selected transition metal complexes possessing a degree of symmetry. Laboratory results have demonstrated [chromium(II)]2, [cobalt(II)]2, [vanadium(II)]2 and similar families of catalysts to be effective for non-oxidative catalytic conversion of substituted organic compounds to products comprising related higher molecular weight compounds in good yields in the absence of air, at modest temperatures and ambient pressure.
The tris(trimethylsilyl)silane/thiol reducing system: A tool for measuring rate constants for reactions of carbon-centered radicals with thiols
Chatgilialoglu, Chryssostomos
, p. 2387 - 2398 (2007/10/03)
An extension of the well-known 'free-radical-clock' methodology is described that allows one to determine the rate constants of carbon-centered radicals with a variety of thiols by using the tris(trime-thylsilyl)silane/thiol couple as a reducing system. A
Reaction network of aldehyde hydrogenation over sulfided Ni-Mo/Al 2O3 catalysts
Wang, Xueqin,Saleh, Ramzi Y.,Ozkan, Umit S.
, p. 20 - 32 (2007/10/03)
A reaction network of aldehyde hydrogenation over NiMoS/Al 2O3 catalysts was studied with aldehydes with straight and branched carbon chains and different chain lengths as feed materials. The reactions in the gas phase and the liquid phase were compared. The main reaction in the aldehyde hydrogenation process is the hydrogenation of the CO double bond, which takes place over the coordinatively unsaturated sites. The major side reactions are self-condensation of aldehydes and condensation of aldehydes with alcohols. Both reactions involve α-hydrogen and are primarily catalyzed by acid-base bifunctional sites over the exposed Al2O 3 surfaces.
Halide-Free Dehydrative Allylation Using Allylic Alcohols Promoted by a Palladium-Triphenyl Phosphite Catalyst
Kayaki, Yoshihito,Koda, Takashi,Ikariya, Takao
, p. 2595 - 2597 (2007/10/03)
The triphenyl phosphite-palladium complex was found to effect catalytic substitution reactions of allylic alcohols via a direct C-O bond cleavage. The dehydrative etherification proceeded efficiently without any cocatalysts and bases to give allylic ethers in good to excellent yields.
