But-l-ene

One of the few catalysts to give reasonably selective metathesis to form ethene and hex-3-ene, reaction (6), is M0O3/AI2O3 doped with 2% alkali metal ions (Bradshaw 1967 Alkema 1968) or thallium ions (Kobylinski 1972). The suppression of the isomerization is more effective the larger the cation Cs+ T Rb K Na Li it also correlates with a diminished ability to adsorb ammonia. The polarizability of the cation thus appears to be an important factor in reducing the surface acidity which is the cause of isomerization. 

Catalyst systems suitable for metathesis of but-l-ene in solution are as listed for pent-l-ene in Table 5.5. 

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Numbers refer to the positions of the double bond for example, butylene-1 (or butene-1 or but-l-ene) is CH3CH2CH= or but-2-ene) is CHgCH CHCHg,... 

Butan-3-one, 2-hydroxy-2-(indolyl)-photodecomposition, 4, 233 Butan-3-one, 2-hydroxy-2-(pyrrolyl)-photodecomposition, 4, 233 Butazolidines applications, 5, 782 Butazone, y-hydroxyphenyl-antiinflammatory agents, 5, 296 Butazone, phenyl-metabolism, 1, 239, 5, 301 synthesis, 5, 230 But-l-ene, 1-morpholino-polymers, 1, 291... 

Two random copolymers of this type are of importance, ethylene-propylene copolymers and ethylene-but-l-ene copolymers. The use and properties of polypropylene containing a small quantity of ethylene in stereoblocks within the molecule has already been discussed. Although referred to commercially as ethylene-propylene copolymers these materials are essentially slightly modified polypropylene. The random ethylene-propylene polymers are rubbery and are discussed further in Section 11.9. 

The Phillips process for the manufacture of high-density polyethylene may be adapted to produce copolymers of ethylene with small amounts of propylene or but-l-ene and copolymers of this type have been available since 1958. These soon found application in blown containers and for injection moulding. Properties of two grades of such copolymers are compared with two grades of Phillips-type homopolymer in Table 11.11. 

The nueleophilic displacement of 9-methoxy group of perhydropyr-ido[l,2-c][l,3]oxazin-l-ones 94 was performed by treatment with an excess of 2-(trimethylsilyloxy)but-l-ene in the presence of TiCU to give 9-(2-oxobutyl) derivatives 96 (96CJC2434). The high stereoselectivity observed in... 

The allylic resonance may give rise to formation of a mixture of isomeric allylic bromides, e.g. 6 and 8 from but-l-ene. The product ratio depends on the relative stability of the two possible allylic radical species 5 and 7 ... 

Tetrabutylammonium fluoride (TBAF) is usually used in the form of the trihydrate or as a solution in tetrahydrofuran (THF). The pure form is difficult to isolate, owing to decomposition to FFF, tributylamine, and but-l-ene [18, 19] on dehydration. It has been used for a variety of reactions, including as a catalyst for various reactions with silicon compounds [20, 21]. One of its main uses is in the cleavage of silyl ether protecting groups [22]. 

For example, disproportionation of but-2-yl radicals produces a mixture of butenes as shown (Scheme 1.1 I).138 Thermodynamic considerations suggest thai but-l-ene and but-2-enes should be formed in a ratio of ca 2 98. However, the observed 5 4 ratio of but-1-ene but-2-enes is little different from the 3 2 ratio that is expected on statistical grounds (i.e. ratio of f5-hydrogens in the I- and 3-positions). 

Further evidence against the formation of a free carbonium ion in the alkylation reaction is obtained from the fact that in the presence of boron trifluoride-phosphoric acid catalyst, but-l-ene, but-2-ene, and i-butene react at different rates with alkylbenzenes, yet they would each give the same carbonium ion. In addition, only the latter alkene gave the usual activation order (in this case the hyper-... 

The subsequent hydrogenation of butadiene to but-l-ene and but-2-ene is kineti-cally insignificant, and these hydrocarbons have no influence on the rate of the first step. H2S, however, does influence the rate. Briefly, the reaction proceeds over a site where a sulfur atom in the catalyst is missing (see Chapter 9 for details). A high pressure of H2S simply reduces the number of these vacancies and therefore adversely affects the rate. 

Many other compounds have been shown to act as co-catalysts in various systems, and their activity is interpreted by analogous reactions [30-33]. However, the confidence with which one previously generalised this simple picture has been shaken by some extremely important papers from Eastham s group [34], These authors have studied the isomerization of cis- and Zraws-but-2-ene and of but-l-ene and the polymerization of propene and of the butenes by boron fluoride with either methanol or acetic acid as cocatalyst. Their complicated kinetic results indicate that more than one complex may be involved in the reaction mechanism, and the authors have discussed the implications of their findings in some detail. 

This means that the isopropyl group stabilises the secondary ion sufficiently (compared to but-l-ene) for hydride transfer reactions to be suppressed, at least at low temperature. At about -120 °C a high polymer of structure (IV) is formed. This is a true phantom polymer, since there exists no corresponding monomer. Evidently, at the very low temperature the propagation reaction which would lead to structure (III) becomes much slower than the isomerization reaction ... 

In the results presented in Table 13.5, the addition of tin affects the kinetic selectivity r differently, depending on the catalyst preparation method. When compared to the monometallic PdO catalyst, r slightly decreases for the coimpregnated PdSn catalyst, but it sharply increases for the PdOSn catalyst prepared via the colloidal oxide synthesis. As the intrinsic kinetic constant rates k do not show significant discrepancies between the different catalysts, the main contribution of the variation of the kinetic selectivity is ascribed to the adsorption constant ratio fBo/ Butenes- In the case of the PdOSn catalyst, formation of but-l-ene is favored compared to its consumption because the X Bo/ Butenes ratio increases, indicating that olefin adsorption is much more destabilized than diene adsorption. Thus, the olefin easily desorbs before being hydrogenated into butane. 

The pressure dependence of the reaction between butane-1-thiol and hydrogen atoms at 133, 266, 532, 2660, and 5320 Pa, using two types of fast-flow discharge reactors, have been studied. Butane and but-l-ene were the main products. Pressure dependence indicated decomposition through vibrationally activated species. 

Like the dehydration of some alcohols, the elimination of hydrogen halides from monohaloalkanes can result in the formation of two alkenes. For example, heating 2-chlorobutane with ethanolic potassium hydroxide produces but-l-ene and but-2-ene. 

We have just seen that when H-H or Br-Br or H-Br or H-OH is added to but-2-ene, only one product is formed. However, when a hydrogen halide or water is added to an unsymmetrical alkene, i.e. one in which the groups attached to one carbon of the double bond are not identical to the groups attached to the other carbon atom, two products are formed. For example, when hydrogen chloride is added to the unsymmetrical alkene but-l-ene, both 2-chlorobutane and 1-chlorobutane are formed ... 

In the early days of alkene chemistry, some researchers found that the hydrohalogenation of alkenes followed Markovnikov s rule, while others found that the same reaction did not. For example, when freshly distilled but-l-ene was exposed to hydrogen bromide, the major product was 2-bromopropane, as expected by Markovnikov s rule. However, when the same reaction was carried out with a sample of but-l-ene that had been exposed to air, the major product was 1-bromopropane formed by antl-Markovnikov addition. This caused considerable confusion, but the mystery was solved by the American chemist, Morris Kharasch, in the 1930s. He realised that the samples of alkenes that had been stored in the presence of air had formed peroxide radicals. The hydrohalogenation thus proceeded by a radical chain reaction mechanism and not via the mechanism involving carbocation intermediates as when pure alkenes were used. 

P-Cyclodextrin was modified by attaching 2-(diphenylphosphinoethyl)-thio- (127) and 2-bis(diphenylphosphinoethyl)amino- (126) moieties at the C-6 position [8-11]. The resulting macroligands were reacted with [ RhCl(NBD) 2] to provide the corresponding cationic rhodium-bisphosphine complexes. These catalysts showed pronounced selectivity due to complexation of the substrate by the CD unit adjacent to the catalyticaUy active metal center. For example, in competitive hydrogenation of similarly substituted terminal olefins (Scheme 10.4), 4-phenyl-but-l-ene was... 

I) Ethanol to but-l-yne (II) Ethane to bromoethene (Hi) Propene to 1-nItropropane (Iv) Toluene to benzyl alcohol (v) Propene to propyne (vl) Ethanol to ethyl fluoride (vll) Bromomethane to propanone (viii) But-l-ene to but-2-ene (Ix) 1-Chlorobutane to n-octane (x) Benzene to biphenyl. 

An organic compound (A) (molecular formula C8H16O2) was hydrolysed with dilute sulphuric acid to give a carboxylic acid (B) and an alcohol (C). Oxidation of (C) with chromic acid produced (B). (C) on dehydration gives but-l-ene. Write equations for the reactions involved. 

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