Allyl Butyl Ether Research Articles

Homo‐ and Copolymerization of Norbornene with Allyl Palladium and Nickel Complexes Bearing Imidazo[1,5‐a]pyridine Sulfonate Ligands

AbstractA series of allyl palladium and nickel complexes based on imidazo[1,5‐a]pyridine sulfonate ligands were synthesized. All these complexes were fully characterized by 1H and 13C NMR, elemental analysis, and high‐resolution mass spectrometry (HRMS). By treatment with Me2AlCl, palladium complexes showed high activities (up to 4.5×107 g of PNB (mol of Pd)−1 h−1) in norbornene polymerization, and the steric hindrance of the catalysts had little effect on the catalytic activities. They could also catalyze the copolymerization of norbornene with butyl vinyl ether (BVE) and ester monomers, but could not catalyze the copolymerization of norbornene with allyl butyl ether (ABE). In addition, the catalytic activities of nickel complexes for norbornene polymerization were similar to that of palladium complexes upon activation with MAO. They could catalyze copolymerization of norbornene with BVE and ABE, but not with ester monomers. In nickel system, the lower steric hindrance of the substituent led to higher activity.

Tin(IV) oxide nanoparticles grafted with N,N-dimethylacrylamide–allyl butyl ether for xylene adsorption

This study presents a two-stage method for modification of tin(IV) oxide using (3-mercaptopropyl) trimethoxysilane and grafting of N,N-dimethylacrylamide-allyl butyl ether copolymer. The resulting sorbent was characterized by Fourier transform infrared spectroscopy, elemental analysis, thermogravimetric analysis, transmission electron microscopy, scanning electron microscopy, and the Brunauer–Emmett–Teller method and evaluated for xylene adsorption from environmental water samples. Batch experiments were conducted to evaluate the effect of the analytical parameters of pH, contact time, initial concentration and temperature. The optimum pH was 5, contact time was 5 min, and temperature for sorption of xylene was 30 °C. The capacity of the sorbent was 8.56 mg g−1. Results showed good accessibility of the active sites. The equilibrium adsorption data of xylene sorption onto grafted nano-tin(IV) oxide were analyzed using the Langmuir, Freundlich, Temkin, and Redlich–Peterson isotherm models. The adsorption data were modeled as pseudo-first-order, pseudo-second-order, and intra-particle diffusion kinetic equations. The results show that adsorption followed by the Langmuir isotherm and the pseudo-second-order model and intra-particle diffusion model showed more than one process is controlling the adsorption process. The sorbent removed more than 90 % of the xylene from the water solution samples.

ChemInform Abstract: Assembly of Substituted 2‐Alkylquinolines by a Sequential Palladium‐Catalyzed C—N and C—C Bond Formation.

AbstractA range of substituted 2‐alkylquinolines is efficiently prepared by reaction of substituted anilines (I) with ethyl vinyl ether (II) or allyl butyl ether (IV) under mild conditions.

Assembly of Substituted 2‐Alkylquinolines by a Sequential Palladium‐Catalyzed CN and CC Bond Formation

A range of substituted 2-alkylquinolines is efficiently prepared by reaction of substituted anilines (I) with ethyl vinyl ether (II) or allyl butyl ether (IV) under mild conditions.

Hydrosilylation in the presence of platinum(II) and rhodium(I) complexes with chloride and trichlorostannate(II) anions

Hydrosilylation of allyl butyl ether and acetophenone with 1,1,3,3-tetramethyldisiloxane in the presence of [Pt(LL′)XY] and [Rh(Ph3P)3X] (L, L′ = cod, dmso, Py, Bn2S, Ph3P; X, y = Cl, SnCl3) was studied.

Iridium-catalyzed carbonyl allylation by allyl ethers with tin(II) chloride

3-Alkoxypropenes, namely allyl ethers such as allyl butyl ether, allyl 2-hydroxypropyl ether, and diallyl ether, serve as reagents for the allylation of aldehydes with tin(II) chloride in the presence of a catalytic amount of [IrCl(cod)] 2 in THF and H 2O at 50 °C to produce the corresponding homoallylic alcohols.

Optimization of Atom Transfer Radical Copolymerization of Allyl Butyl Ether with Acrylonitrile

The optimization of atom transfer radical polymerization (ATRP) conditions for the copolymerization of allyl butyl ether with acrylonitrile has been carried out with the aim of achieving control over molecular parameters. The influence of solvents, initiator concentration and in-feed molar compositions on the rate of copolymerization was also investigated. The molecular weight data as well as kinetic studies suggested conventional ATRP behavior of the copolymerization of acrylonitrile and allyl butyl ether. The variation of copolymer composition (FC) with conversion indicated towards the synthesis of copolymers having significant changes in composition with conversion. The copolymer compositions obtained from 1H NMR spectra were utilized to determine the reactivity ratios. With the help of DEPT (Distortionless Enhancement by Polarization Transfer) and 2D HSQC (Heteronuclear Single Quantum Coherence) NMR spectra, complete spectral assignments of 1H and 13C{1H} NMR spectra were done. All these analysis, considered in aggregate indicated that allyl butyl ether acted as a comonomer instead of a chain-transfer agent under the employed reaction conditions.

Copolymerization of allyl butyl ether with acrylates via controlled radical polymerization

AbstractThe atom transfer radical polymerization (ATRP) and reversible addition–fragmentation chain transfer (RAFT) of acrylates (methyl acrylate and butyl acrylate) with allyl butyl ether (ABE) were investigated. Well‐defined copolymers containing almost 20 mol % ABE were obtained with ethyl‐2‐bromoisobutyrate as an initiator. Narrow molar mass distributions (MMDs; polydispersity index ≤ 1.3) were obtained from the ATRP experiments, and they suggested conventional ATRP behavior, with no peculiarities caused by the incorporation of ABE. The comparable free‐radical (co)polymerizations resulted in broad MMDs. Increasing the fraction of ABE in the monomer feed led to an increase in the level of incorporation of ABE in the copolymer, at the expense of the overall conversion. Similarly, RAFT copolymerizations with S,S′‐bis(α,α′‐dimethyl‐α″‐acetic acid)trithiocarbonate also resulted in excellent control of the polymerization with a significant incorporation of ABE within the copolymer chains. The formation of the copolymer was confirmed with matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS). From the obtained MALDI‐TOF MS spectra for the ATRP and RAFT systems, it was evident that several units of ABE were incorporated into the polymer chain. This was attributed to the rapidity of the cross‐propagation of ABE‐terminated polymeric radicals with acrylates. This further indicated that ABE was behaving as a comonomer and not simply as a chain‐transfer agent under the employed experimental conditions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3271–3284, 2004

Mechanism of spontaneous initiation of altenating copolymerization of sulphur dioxide with electron-donor monomers

It has been shown by the spin method that the RO, HOṠO 2, and RṠO 2 radicals formed by the reaction with SO 2 of traces of hydroperoxides present in monomers are responsible for the spontaneous initiation leading to the formation of polysulfones. It has been further shown that the time of contact of carefully purified monomers with air defines unequivocally the yield of both the initiating radicals and the copolymer. The rate constant of the reaction between SO 2 and allyl butyl ether hydroperoxide was found to be 0.27 1/(mol s) at 183 K.

Electrocatalytic Oxidation of Allylic Ethers, Dihydropyran and Phenol Using a Polypyridyl Complex of Ruthenium(IV)

An electrocatalytic procedure is described for the oxidation of allyl butyl ether, (E/Z)-2-butenyl butyl ether, dihydropyran and phenol using the ruthenium(IV) oxidant [(bpy)(trpy)RuO]2+. The resulting products were respectively, butyl acrylate (42%), butyl (E/Z)-2-butenoate (53%), 2,3-dihydro-4-pyranone (40%) and o-benzoquinone (71%).

Rhodium-catalyzed low pressure hydroformylation of substituted terminal olefins. Role of α,ω-Bis(diphenylphosphino)alkane in combination with excess triphenylphosphine

Rhodium-catalyzed low pressure hydroformylation of typical terminal olefins such as allyl acetate, vinyl acetate, 3-butenyl acetate, ethyl acrylate, ethyl 3-butenate, allyl alcohol, 3-buten-1-ol, allyl butyl ether and 3-butenyl butyl ether has been examined in an aromatic hydrocarbon solution containing a large excess of triphenylphosphine. Most of the above-mentioned substituted terminal olefins are not hydroformylated substantially at low pressure; however when a nearly equimolar amount of α,ω-bis(diphenylphosphino)alkane, Ph 2P(CH 2) n PPh 2 ( n = 2–4), is added to the rhodium complex in combination with a large excess of PPh 3, the hydroformylation proceeds quite smoothly even at 1 atm. It is concluded that the role of the added α,ω-bis(diphenylphosphino)alkane is to suppress the formation of a metastable acyl rhodium complex in which a six-membered ring is formed by coordination to rhodium of the oxygen atom in a carbonyl or hydroxy group of the substrate.

ChemInform Abstract: INTRAMOLECULAR DISPROPORTIONATION OF UNSATURATED ETHERS

We examined the possibility of the disproportionation of ethers on an aluminum--rhenium catalyst promoted by tetraalkylstannanes in a static system in the liquid phase with stirring at 20~ The products were analyzed chromatographically, as well as with the aid of IR, NMR, and mass spectrometry. It was found that the disproportionation of vinyl butyl and allyl butyl ether does not take place. However, the intramolecular disproportionation of diallyl ether (1) and the allyl ether of allylcarbinol (2) takes place with a high rate and a selectivity of ~i00% to form ethylene, 2,5-dihydrofuran, and 2,3-dihydro-u-pyran, respectively:

Intramolecular disproportionation of unsaturated ethers

We examined the possibility of the disproportionation of ethers on an aluminum--rhenium catalyst promoted by tetraalkylstannanes in a static system in the liquid phase with stirring at 20~ The products were analyzed chromatographically, as well as with the aid of IR, NMR, and mass spectrometry. It was found that the disproportionation of vinyl butyl and allyl butyl ether does not take place. However, the intramolecular disproportionation of diallyl ether (1) and the allyl ether of allylcarbinol (2) takes place with a high rate and a selectivity of ~i00% to form ethylene, 2,5-dihydrofuran, and 2,3-dihydro-u-pyran, respectively: