1.2- Epoxy-5-hexene

Scheme 30 Radical addition of allyl alcohol and 1,2-epoxy-5-hexene to polyacrylate chain end.

In contrast, the hydrosilation of Tg with the linear, open chain epoxide, 1,2-epoxy-5-hexene took place to give the fully octafunctional epoxide III. 

Scheme 59. Addition of 1,2-epoxy-5-hexene to the hyperbranched pBPEA [89]...

Sucro.se wa.s modified by GA, glycidyl methacrylate, 1,2-epoxy hexene, methaeryloyl chloride and acetyl chloride and then was polymerized by chemical initiator or gamma irradiation. Hydrolysis in basic solution and strong acidic solittion. Porential use as superabsorbents. Chtm and Park, unpublished data... 

The synthesis of the trisubstituted cyclohexane sector 160 commences with the preparation of optically active (/ )-2-cyclohexen-l-ol (199) (see Scheme 49). To accomplish this objective, the decision was made to utilize the powerful catalytic asymmetric reduction process developed by Corey and his colleagues at Harvard.83 Treatment of 2-bromocyclohexenone (196) with BH3 SMe2 in the presence of 5 mol % of oxazaborolidine 197 provides enantiomeri-cally enriched allylic alcohol 198 (99% yield, 96% ee). Reductive cleavage of the C-Br bond in 198 with lithium metal in terf-butyl alcohol and THF then provides optically active (/ )-2-cyclo-hexen-l-ol (199). When the latter substance is treated with wCPBA, a hydroxyl-directed Henbest epoxidation84 takes place to give an epoxy alcohol which can subsequently be protected in the form of a benzyl ether (see 175) under standard conditions. 

The reactivity of T8[OSiMe2H]g is dominated by its capacity to undergo hydrosilylation reactions with a wide variety of vinyl and allyl derivatives (Figure 30) that have subsequently mainly been used as precursors to polymers and nanocomposites by the introduction of reactive terminating functions as shown in Table 19. For example, T8[OSiMe2H]g has been modified with allyglycidyl ether, epoxy-5-hexene, and 1,2-cyclohexene-epoxide to give epoxy-terminated FOSS. These have then been treated with m-phenylenediamine, with polyamic acids or... 

The complexes Ru(pydic)(tpy), Ru(pydic)(pybox-R ) (pydic=pyridine-2,6-dicarboxylate, pybox-Rj=chiral bis(oxazolinyl)pyridines with R=PP, Ph (Fig. 1.37) [105] epoxidised trani-stilbene (as complex/PhlO, Ph OAc), TBHP or OJ CHjClj). Asymmetric oxidations of trani-stilbene were similarly achieved in toluene, benzene and CH Cl with e.e. values from 40-80% cf mech. Ch. 1) [53, 54, 81,97]. Asynunetric epoxidations of rranx-stilbene, styrene, tranx-fl-methylsty-rene and 1-hexene were catalysed by [RuCl(SOMePh)(bpy)j] /TBHP or Ph(IOAc)y CHjCy40°C e.e. values of 33-94% were obtained of the (R. R) forms of the epoxides of tra i-stilbene, tranx-P-methylstyrene [52]. The system Ru(CO)(TPP)/ (CljpyNO)/HBr/C H epoxidised fullerene (C ) to 1,2-epoxy[60]fullerene with 1,2 3,4 di-epoxy and 1,2 3,4 9,10 h- 1,2 3,4 11,12 tri-epoxy species [106]. 

Isomerization of 1,2-epoxy 3-cyelohexctoe and l,2-epcxy>4 <-y> hexene over magnesium bromide has been reported by Xiffeneau ami Tchoubar17 7 to yield two products in each case (Eq, 442)... 

The intercalated compounds of hydrotalcite [Mg23.3AlI0(OH)66.6] with M07O24 or W12O4 - catalyze the shape-selective epoxidation of olefins epoxi-dation of 2-hexene was favored over theat of cyclohexene (395). 

The carbons of l,2-epoxy-5-hexene can be assigned from the off-resonance decoupled spectrum (Figure 11.32). In the fully decoupled spectrum it is clear that the olelinic carbons ( 115 and 1385) are distinct from die epoxide carbons ( 47 and 525) and from the methylene carbons ( 30 and 325), but it is not possible to assign which is which. In the off-resonance decoupled spectrum, both the olelinic and epoxide carbons are distinguished by their splitting patterns from the numbers of directly attached protons. The methylene carbons, however, are both triplets and cannot be distinguished. 

A variety of ruthenium complexes have been used in conjunction with NaI04 [73],PhIO [74], ferf-BuOOH [38] and 02 [75] in the oxidation of styrene and/or stilbene. The major reaction was oxidative cleavage rather than epoxi-dation (Eqs. 18,19b). Notably in the case of RuC12[PNNP] complexes [74] as catalysts, c/s-diols were formed when treating 1-hexene at elevated temperatures and pressures with oxygen (Eq. 19a). 

A sample of E-2-hexen-l-ol in methylene chloride was epoxldized at 20°C with m-chloroperoxybenzoic acid. The resultant racemic epoxy alcohol, upon conversion to the diastereomeric (+)-a-methoxy-a-(trifluoromethyl)phenylacetic acid esters in the manner described above, provided a GC standard for determination of the enantiomeric excess obtained in the asymmetric epoxldatlon. 

Nitrone 153, obtained by a regiospecific nucleophilic substitution of the nitrogen atom of the (Z)-benzaldoxime and excess of l,2-epoxy-5-hexene, gave as by-product the oxazocine 115, through a 1,3-dipolar cycloaddition as a result of la/3b bonding. The main products were a mixture of three oxazepine cycloadducts 154 as a result of lb/3a bonding (Scheme 33) <1997T13165>. 

Three 500-ml reflux flasks were each charged with a mixture of L-lactide (5.88 g) and l,2-epoxy-5-hexene (4.12 g) dissolved in 50 ml of toluene, and then treated with triethylaluminum pentahydrate (98.6 mg). Each vessel was then sealed and heated to 90 °C for 12, 24, and 36 hours, respectively, and the contents were precipitated in diethyl ether. The polymers obtained were washed with diethyl ether three times and dried in a vacuum oven for 1 day. The polymers were shown to have a double bond content of 7.0,7.5, and 8.1 mol%, respectively, with a M of roughly 10,000 daltons. 

Analysis of the vacuum volatile constituents of fresh tomatoes was carried out using capillary GLC-MS and packed column GLC separation with Infrared, NMR and CI-MS analysis. Evidence was obtained for the presence of the unusual components 3-damascenone, 1-nltro-2--phenylethane, 1-nltro-3-methylbutane, 3-cyclocltral and epoxy-3-1onone. A method for the quantitative analysis of the volatile aroma components In fresh tomato has been Improved and applied to fresh tomato samples. The quantitative data obtained have been combined with odor threshold data to calculate odor unit values (ratio of concentration / threshold) for 30 major tomato components. These calculations Indicate that the major contributors to fresh tomato aroma Include (Z)-3-hexenal, 3-lonone, hexanal, 3-damascenone, 1-penten-3-one, 3-methylbutanal, (E)-2-hexenal, 2-lso-butylthlazole, 1-nltrophenylethane and (E)-2-heptenal. 

SYNS ACROLEIN DIMER, stabiUzed (DOT) 3,4-DIHYDRO-2H-PYRAN-2-CARBOXALDEHYDE 2,3-DIHYDRO-L4-PYRAN-2-KARBOXALDEHYD 2-FORMYL-3,4-DIHYDRO-2H-PYRAN 5-HEXENAL, 2,6-EPOXY- a PYTIAN ALDEHYDE... 

SYNS CHISSONOX206 O EP-206 1.2-EPOXY-4-(EPOXYETHYL)CYCLOHEXANE 1-EPOXYETHYL-3,4-EPOXYCYCLOHEXANE 3-(EPOXYETHYL)-7-OXABI-CYCLO(4.1.0)HEPTANE 3-(l,2-EPOXYETHYL)-7-OXABICYCLO(4.1.0)HEPTANE 4-(EPOXYETHYL)-7-OXABICYCLO(4.1.0)HEPTANE 4-(l,2-EPOXYETHYL)-7-OXABICYCLO(4.1.0)HEPTANE ERLA-2270 ERLA-2271 l-ETHYLENEOXY-3,4-EPOXYCYCLOHEXANE NCI-C60139 O 3-OXIRANYL-7-OXABICYCLO(4.1.0)HEPT-ENE UCET TEXTILE FINISH 11-74 (OBS.) UNOX EPOXIDE 206 VINYL CYCLOHEXENE DIEPOXIDE 4-VINYLCYCLOHEXENE DIEPOXIDE 4-VINYL-l-CYCLOHEXENE DIEPOXIDE 4-VINYL-1,2-CYCLO-HEXENE DIEPOXIDE 1-VINYL-3-CYCLOHEXENE DIOXIDE 4-VINYLCYCLOHEXENE DIOXIDE 4-VINYL-l-CYCLOHEXENE DIOXIDE (MAK)... 

HEXENAL, 2,6-EPOXY- see ADR500 2-HEXEN-l-AL, 2-ISOPROPYL-5-METHYL- see IKMIOO 2-HEXEN-l-AL, 5-METHYL-2-(l-METHYLETHYL)- see IKMIOO... 

Of mechanistic interest in this context is the independent generation of di-ir-methane diradicals of 3-oxa-di-TT-methane systems which do not give the rearrangement, in order to probe whether such diradicals at least in principle are prone to give di-ir-methane products. For this purpose, the cyclopropyldicarbinyl diradical in equation (25) was generated via photochemical carbon monoxide extrusion. Indeed, the expected oxa-di-ir-methane product 2,5-dimethyl-4,5-epoxy-2-hexene was formed, as well as other products. 

The key odorants of fresh tomatoes and tomato paste are compared in Table 6.46. (Z)-3-hexenal (no. 1), p-damascenone (no. 2), epoxy-decenal isomers nos. 3 and 5, p-... 

The high selectivity of catalyst lb toward terminal unfunctionalized alkenes is highlighted by the experiments reported in Fig. 2.2. As a typical example, czs-l,4-hexadiene bears both terminal and cis C=C bonds and in the presence of a stoichiometric amount of m-chloroperbenzoic acid (m-CPBA) leads mainly to czs-4,5-epoxy-l-hexene due to the electrophilic epoxidation of the more electron-rich internal double bond. On the contrary, when the epoxidation is performed with catalyst lb and one equivalent of H2O2, the regioselectivity of the reaction is completely inverted, favoring the product with the terminal oxirane ring. The same applies to frflns-l,4-hexadiene or dienes bearing substituents in the... 

Diethyl l,l-difluoro-3-iodo-6,7-cpoxyhcptylphosphonate is prepared in 63% yield by the palladium-catalyzed addition of diethyl iododifluoromethylphosphonate to l,2-epoxy-5-hexene at room temperature (Scheme 4.22). ° ... 

Similarly, addition of diethyl fluoroiodomethylphosphonate to l,2-epoxy-5-hexene and 1,2-epoxy-7-octene on heating at 75°C in the presence of Pd(PPh3)4 gives the corresponding diethyl l-fluoro-3-iodo-6,7-epoxyheptylphosphonate and diethyl l-fluoro-3-iodo-8,9-epoxynonylphospho-nate in 69% and 65% yields, respectively. ... 

Materials effective as anode catalysts for epoxidation of 1-hexene by the method in Figure 2 were screened. Among various metal oxides, metal salts and metal blacks tested, the most active and selective anode catalyst for the formation of 1,2-epoxy hexane was Pt black (Table 1). The oxidation efficiency for the formation of epoxide defined by equation 9 was about 26% and its selectivity was 66%. Pt black samples obtained from different producers or prepared in this work showed quite low electrocatalytic activity. However, the calcination of these inactive Pt blacks in air at 673 K substantially enhanced the catalytic activities of these samples. XPS studies on various Pt black samples suggested that a Pt02 phase was associated with the active oxygen for the epoxidation. 

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