4- butyl vinyl ether

Butyl vinyl ether reacts with aroyl chlorides using Pd(OAc)2 without a ligand to give the unsaturated ketone 839, which is a precursor of a 1-aryl-1,3-dicarbonyl compound. The reaction is regioselective /3-attack. Addition of PhjP inhibits the reaction[718]. 

VINYLPOLYTffiRS-VINYLETHERMONOTffiRSANDPOLYTffiRS] (Vol24) t-Butyl vinyl ether [926-02-3]... 

Vinyl Ethers. The principal commercial vinyl ethers are methyl vinyl ether (methoxyethene, C H O) [107-25-5], ethyl vinyl ether (ethoxyethene, C HgO) [104-92-2], and butyl vinyl ether (1-ethenyloxybutane, C H 20) [111-34-2]. (See Table 8 for physical properties.) Others such as the isopropyl, isobutyl, hydroxybutyl, decyl, hexadecyl, and octadecyl ethers, as well as the divinyl ethers of butanediol and of triethylene glycol, have been offered as development chemicals (see Ethers). 

Shipment, Stora.ge, ndPrices. Methyl vinyl ether is available in tank cars or cylinders, while the other vinyl ethers are available in tank cars, tank wagons, or dmms. Mild steel, stainless steel, and phenoHc-coated steel are suitable for shipment and storage. If protected from air, moisture, and acidic contamination, vinyl ethers are stable for years. United States bulk prices in 1991 for methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether were listed as about 5.78/kg, 6.28/kg, and 6.08/kg, respectively. 

Specifications and Analytical Methods. Vinyl ethers are usually specified as 98% minimum purity, as determined by gas chromatography. The principal impurities are the parent alcohols, limited to 1.0% maximum for methyl vinyl ether and 0.5% maximum for ethyl vinyl ether. Water (by Kad-Fischer titration) ranges from 0.1% maximum for methyl vinyl ether to 0.5% maximum for ethyl vinyl ether. Acetaldehyde ranges from 0.1% maximum in ethyl vinyl ether to 0.5% maximum in butyl vinyl ether. 

Methyl vinyl ether Ethyl vinyl ether Isopropyl vinyl ether -Butyl vinyl ether Isobutyl vinyl ether... 

VEs do not readily enter into copolymerization by simple cationic polymerization techniques instead, they can be mixed randomly or in blocks with the aid of living polymerization methods. This is on account of the differences in reactivity, resulting in significant rate differentials. Consequendy, reactivity ratios must be taken into account if random copolymers, instead of mixtures of homopolymers, are to be obtained by standard cationic polymeriza tion (50,51). Table 5 illustrates this situation for butyl vinyl ether (BVE) copolymerized with other VEs. The rate constants of polymerization (kp) can differ by one or two orders of magnitude, resulting in homopolymerization of each monomer or incorporation of the faster monomer, followed by the slower (assuming no chain transfer). 

Table 5. Reactivity Ratios in the Copolymerization of n-Butyl Vinyl Ether (Tfj) with Another Vinyl Ether (A ) ...

A series of graft polymers on polychloroprene were made with isobutjiene, /-butyl vinyl ether, and a-methylstyrene by cationic polymerization in solution. The efficiency of the grafting reaction was improved by use of a proton trap, eg, 2,6-di-/-butylpyridine (68). 

VINYL-n-BUTYL ETHER see BUTYL VINYL ETHER ... 

Butyl trichlorosilaiie, 30 Butyl vinyl ether, 30 Butyraldehyde, 30 Butyric Acid, 31 Buzz Uiiichem S.p.A., 178 BYK-Chemie GmbH, 162... 

Legros et al. (2001T2507) carried out the synthesis of acetylquinolines (e.g. 130) via Heck reaction of 3-bromoquinoline (70) and -butyl vinyl ether (Scheme 16) employing either Pd(dba)2 or Pd(OAc)a as the catalyst. In each case it was found that the Heck reaction for this synthesis gave better overall yields than using the Stille reaction (see Section IV.C). Another advantageous point in favor of the Heck is that it avoids the use of toxic stannane. 

The regioselective arylation of butyl vinyl ether was carried out by the same group, using Pd(OAc)2 as catalyst precursor and l,3-bis(diphenylphosphino)-propane (dppp) as the ligand, dissolved in [BMIM][Bp4] (Scheme 5.2-17) [90]. 

Scheme 5.2-17 Pd-catalyzed, regioselective arylation of butyl vinyl ether in a [BMIM][BF4] ionic...

Diethyl ether Ethyl vinyl ether Dipropyl ether Diisopropyl ether Methyl butyl ether Butyl vinyl ether... 

Ethylene oxide Propylene oxide Butyl vinyl ether Ethyl vinyl ether Methyl vinyl ether Divinyt ether Furfuryl alcohol I.A-Dioxan Furan... 

Explosion hazard of industrial synthesis of butyl vinyl ether (tide only translated). 

Di- and trisubstituted nitroalkenes tethered to dipolarophiles (unsaturated esters, nitriles) undergo tandem [4+2]/[3+2] cycloadditions with 2,3-dimethyl-2-butene or butyl vinyl ether in the presence of Lewis acids (Eq. 8.112). For the dimethylene tether, the E-configuration of the dipolarophile is preferred, and the products arise selectively from a syn-endo pathway.177... 

The common by-products obtained in the transition-metal catalyzed reactions are the formal carbene dimers, diethyl maleate and diethyl fumarate. In accordance with the assumption that they owe their formation to the competition of olefin and excess diazo ester for an intermediate metal carbene, they can be widely suppressed by keeping the actual concentration of diazo compound as low as possible. Usually, one attempts to verify this condition by slow addition of the diazo compound to an excess (usually five- to tenfold) of olefin. This means that the addition rate will be crucial for the yields of cyclopropanes and carbene dimers. For example, Rh6(CO)16-catalyzed cyclopropanation of -butyl vinyl ether with ethyl diazoacetate proceeds in 69% yield when EDA is added during 30 minutes, but it increases to 87 % for a 6 h period. For styrene, the same differences were observed 65). 

Cyclopropane 87, obtained from n-butyl vinyl ether, rearranges to dihydrofuran 88 only at elevated temperature, and also partly during work-up on silica gel113). The complete conversion of 87 into veratrole by the action of HCl/CH3OH gave rise to the analogous two-step synthesis of hydrourushiol monomethyl ether from l-diazo-3,3-dimethoxy-2-nonadecanone 89113). Ether cleavage of the product yields hydrourushiol, one of the vesicant components of, inter alia, poison ivy. 

Microwave promoted, palladium-catalyzed, DPPP-controlled arylation of butyl vinyl ether with 4-tert-butylphenyl triflate afforded the branched arylation product and the corresponding methyl ketone, indicating the occurrence of selective internal a-arylation. Addition of water to the reaction mixture and microwave-heating for 2.8 min at 55 W smoothly produced the hydrolyzed product, 4-tert-butylacetophe-none, with an isolated yield of 77% (Eq. 11.2) [17]. 

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