Hex-l-ene

WCls is effective in conjunction with Et4Sn and (Mc3SiCH2)4Sn, as judged by evolution of ethene (Bespalova 1975) also using 1, 2, or 3 as cocatalysts 

For a series of methylhex-l-enes, the reactivity decreases as the substituent(s) are placed closer to the double bond, no matter whether the catalyst is Re207/CsN03/ AI2O3 (Kawai 1989), WCl6/Me4Sn (Kawai 1994), or W(sCCMe3)(Cl)3(dme) (Weiss 1988c). 4,4-Dimethylhex-l-ene has a reactivity intermediate between that of 4-methyl- and 3-methylhex-l-ene (Kawai 1989). Double-bond shift reactions and dimerization tend to predominate when the substituent is close to the double bond (Kawai 1992, 1994). 

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Tri-n-hexylborane [1188-92-7] M 265.3. Treated with hex-l-ene and 10% anhydrous Et20 for 6h at gentle reflux under N2, then vacuum distilled through an 18in glass helices-packed column under N2 taking the fraction b 130"/2.1mm to 137"/1.5mm. The distillate still contained some di-n-hexylborane [Mirviss J Am Chem Soc S3 3051 7967]. 

Experiments were earned out to investigate the transparency of various materials produced by copolymerising 4MP1 with other olefins such as but-1-ene, hex-l-ene and oct-l-ene. 

The rather knobbly side groups have a stiffening effect on the chain and result in high values for T (245°C) and Tg(50-60°C). Copolymerisation with hex-l-ene, oct-l-ene, dec-l-ene and octadec-1-ene which may be practised to reduce voidage causes some reduction in melting point and crystallinity as indicated in Table 11.9. 

The methodology of a Lewis acid dissolved in an ionic liquid has been used for Friedel-Crafts alkylation reactions. Song [85] has reported that scandium(III) tri-flate in [BMIM][PFg] acts as an alkylation catalyst in the reaction between benzene and hex-l-ene (Scheme 5.1-55). 

Scheme 5.1-55 The alkylation of benzene with hex-l-ene, catalyzed by scandium(lll) triflate...

The carbonyl complex [Ru(EDTAH)(CO)] has been reported to be a very good catalyst for reactions like hydroformylation of alkenes, carbonylation of ammonia and ammines as well as a very active catalyst for the water gas shift reaction. The nitrosyl [Ru(EDTA)(NO)] is an oxygen-transfer agent for the oxidation of hex-l-ene to hexan-2-one, and cyclohexane to the corresponding epoxide. 

Methoxytrimethylsilane, 123 Methyl acetoacetate, 92 Methyl bromoacetate, 107 Methyl 11-hydroxyundecanoate, 58 Methyl lithium, 27,28 Methyl 10-undecenoate, 58 2-Methyl-l, 3-dithiane, 81 (fl/ ,5 )-Methyl-3-phenyldiniethyl-silyl-3-phenylpropionic acid, 53-4 2-Methyl-3-Phenylprop-2-cnal, 111 2-Methyl 2-lrimethylsilyl-1,3-dithiane, 81 2-Methyl-l-(trimcthylsilyloxy)cyclo-hex-l-ene, 100,109 2-Melhyl-l-lrimethylsilyloxy)cyclo-hcx-6-enc, 100 2-Methyl-2-trimethylsilyloxy-pentan-3-one, 132 2-Methylacetophenone, 42-3 2-Methylbutyraldehyde, 85 2-Methylcyclohexanone, 99,100 2-Methylcyclohexanone, 131 4-Methyldec-4-ene, 67-8 Methylenation, 63 2-Methylpropen-l-ol, 131 Methyltriphenylphosphonium bromide, 27 Michael addition, 85 Monohydridosilanes, 128 Monohydroalumination, 29... 

Degradation of hex-l-ene has been observed in a methanogenic consortium (Schink 1985a) that converted the substrate into methane, and a plausible pathway involving hydration and oxidation was suggested. 

An allyl samarocene catalyst, [(CMe2C5H4)2SmCl(C3H5)MgCl2(THF)4, was employed for the synthesis of trans-Vl-b-VCL copolymers and poly(fra s-isoprene-co-hex-l-ene)-fr-PCL terpolymers [111]. The copolymerizations... 

Another strained alkylidenecyclopropane, 2-methylbicyclo[3.1.0]hex-l-ene (21), formed by cyclization of the carbenoid generated from dibromide 20 at 0 °C gave, in the presence of an excess of 1,3-diphenylisobenzofuran (10), a very small amount (5%) of a 2 1 mixture of diastereoisomeric Diels-Alder adducts 22 (Scheme 4) [11a]. The parent furan does not capture 21 even when used as solvent for the carbenoid cyclization. 

Analogues endo and exo cycloadducts have been observed in the reactions of cyclopentadiene (6) with 21 or methoxybicyclo[3.1.0]hex-l-ene (23) (Scheme 5) [11]-... 

The cyclooctene dimer [IrCl(C8H]4)2] can selectively hydrogenate cy-clooctene in mixtures with hex-l-ene, and an unsaturate route [Eq. 1(b)] via a monomeric olefin complex was demonstrated (181). The pentamethylcyclopentadienyl dimer was mentioned at the end of Section II, B, 2. 

The two alkenes were so similar electronically and sterically, with the ester group too far away to have any affect on the double bond, that there was very little cross-/self-metathesis selectivity. An approximately statistical mixture of ester 13 and diester 14 was isolated. The high yield of the cross-metathesis product 13 obtained is due to the excess of the volatile hex-l-ene used, rather than a good cross-/self-metathesis selectivity. Although not as predominant as in the reactions involving styrene, trans alkenes were still the major products. 

As expected, although TS-1 is more active and selective in the epoxidation of linear alkenes (such as hex-l-ene and dodec-l-ene), the large-pore Ti-beta is more active in the case of the bulkier cyclohexene (TON of 14 v.v. 1 for TS-1) and cyclododecene (TON of 20 vs. 5 Table VII) (11). 

The epoxidation of hex-l-ene catalyzed by Ti-beta samples synthesized in the conventional, basic medium (Ti-beta(OH)) is compared in Table X with that catalyzed by a sample synthesized in a fluoride-containing medium (Ti-beta(F)) (13). The latter was more hydrophobic. Results for the reaction catalyzed by TS-1 are also included in Table X. Ti-beta(F) is superior to TS-1 for reaction in acetonitrile solvent. The most significant difference between Ti-beta(F) and Ti-beta(OH) is in their selectivities. Although the selectivity to the epoxide for reaction in acetonitrile is always very high, regardless of the zeolite for reaction in methanol, Ti-beta(F) is more selective than Ti-beta(OH) (76.6 vi. 54.9%, Table X). Both Ti-beta samples are, however, less selective than TS-1 for reaction in methanol. 

Epoxidation of hex-l-ene catalyzed by Ti-containing zeolites influence of method of preparation... 

Catalyst Ti02 (wt%) Solvent Hex-l-ene conversion Epoxide selectivity (%) h2o2 selectivity (%) TONb... 

Relative reaction rates for epoxidation between different alkenes and hex-l-ene on Ti-beta with H202 and TBHP... 

The rate also decreases with an increase in the chain length of the alkene molecule (hex-l-ene > oct-1-ene > dodec-l-ene). Although the latter phenomenon is attributed mainly to diffusion constraints for longer molecules in the MFI pores, the former (enhanced reactivity of terminal alkenes) is interesting, especially because the reactivity in epoxidations by organometallic complexes in solution is usually determined by the electron density at the double bond, which increases with alkyl substitution. On this basis, hex-3-ene and hex-2-ene would be expected to be more reactive than the terminal alkene hex-l-ene. The reverse sequence shown in Table XIV is a consequence of the steric hindrance in the neighborhood of the double bond, which hinders adsorption on the electrophilic oxo-titanium species on the surface. This observation highlights the fact that in reactions catalyzed by solids, adsorption constraints are superimposed on the inherent reactivity features of the chemical reaction as well as the diffiisional constraints. 

The epoxidation rates of various alkenes relative to hex-l-ene on Ti-beta with H2O2 and TBHP are summarized in Table XV. In the absence of diffiisional constraints, the branched alkenes are more reactive than the linear ones (see also Section V.C. 13). 

The unsaturated aldehyde (0.1 mol) is added to a two-phase system of thiolacetic acid (7.6, 0.1 mol) in aqueous NaOH (50%, 16 ml) and TBA-I (0.1 g, 0.27 mmol) in CH2CI2 (100 ml) over a period of ca. 30 min at 0°C. The mixture is stirred for 2.5 h at 0°C and then heated under reflux for 20 min. The organic phase is separated, diluted with Et20 (50 ml), washed with H20 (3 x 25 ml), and dried (MgS04). Evaporation of the solvent gives i-formyl-5-thiacyclohex-l-ene (41%) from acrolein and 1-formyl-4,6-dimethyl-5-thiacyclo-hex-l-ene (81%) from crotonaldehyde. 

A simple epoxy alkanol to begin with is 1,2-epoxyhexan-3-ol (10.47), which has been postulated as a metabolite of the air pollutant hex-l-ene (10.46). This compound was found to be a good substrate for rat liver microsomal EH, yielding hexane-1,2,3-triol (10.48) [127], 1,2-Epoxyhexan-3-ol contains two stereogenic centers and exists as four stereoisomers that were hydrated at different rates, in the order (2S,3R)-erythro > (2S,3S)-threo > ( 2R,3S)-erythro > (2R,3R)-threo. In other words, the metabolic hydrolysis of this substrate is not influenced by the configuration at C(3), but clearly by that at C(2), with the (25)-epimers being better substrates than the (2/7)-cpi-... 

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