1- Phenyl-2-hexene

Bei der Reduktion von 6-Brom-l-phenyl-hexin-(l) bei -2,85 V wird unter gleich-zeitiger C-Br-Hydrogenolyse l-Phenyl-hexen-(l) (100% d. Th.) erhalten (vgl. a. S. 620)7. 

Die Elektrolyse von 1-Chlor (bzw. Brom, Jod)-l-phenyl-l-hexin liefert in Abhangig-keit vom Kathodenpotential verschiedene Produkte. So wird z.B. bei -2,85 V ausschlieB-lich 1 -Phenyl-hexan erhalten, bei anderen Potentialen fallen Gemische von 1-Phenyl-cy-clohexen, Benzyl-cyclopentan und l-Phenyl-hexen-(5)-in-(l) an. l-Brom-5-decin liefert bei -2,7 V neben 5-Decin (59% d.Th.) 1 -Butyl-cyclohexen (38% d.Th.)1. 

Russische Autoren [zitiert bei Sorensen (207)] fanden bei emeuter Untersuchung von Artemisia capillaris neben dem Capillen (LXV) einen zweiten Kohlenwasserstoff mit der Summenformel C12H12, dem sie die Struktur eines l-Phenyl-hexen-(2)-ins-(4) zuordnen, was der alten Agropyren -Formel (LXIV) entsprechen wurde. Nahere Angaben fehlen jedoch. 

Reaction ofn-Bu4Te with phenylacetylene (typical procedure for the reaction ofRfTe with acetylenes). To a stirred suspension of TeCl4 (323 mg, 1.2 mmol) in 6 mL of Et20 at 0°C was added n-BuLi (4.8 mmol, 3.1 mL, 1.58 M in hexane) dropwise. The suspension turned brown initially and then yellowish orange as the addition came to completion. The mixture was stirred for 0.5 h at 0°C and phenylacetylene (123 mg, 1.2 mmol) was added to it. The mixture was then warmed to room temperature and stirred until no more increase of B (1-phenyl hexene) was observed by GC (8 h). GC analysis of the mixture using dodecane as an internal standard showed that n-Bu2Te, B and D were formed in 93%, 62% E Z= 8 92) and 4% (ElZ = 50 50) yields, respectively. The reaction mixture was then poured into water... 

Phenyl-hexen-(2)1 eine intramolekuiare Reaktion unter Bildung von 1,3-Additions-produkten XI-XIV statt ... 

Methyl-6-phenyl-hexen-(5)-oI-(4) 6 II 550. 5.0n-4.4-djmetnvl-5-phenyl-penten.(l)... 

Ozy.phenyl]-6-[4.dimethylainmo> phenyl].hexen-(5)-on-(4)-dicarbon< saure-(l.l) 14II426. Carbathozybulbocapnin 18 II363. des-Methylhydraatin, Metbylhy aatin 18, 430, II446. 

R = CH2CH,C6H5 5-methyl-l-phenyl-5-hexen-3-ol yield 88%... 

Wittig reagent, for preparation of 1,4-di-phenyl-1,3-butadiene, 40, 36 for preparation of methylenecyclo-hexene, 40,66... 

Analog erhalt man aus 1-Phenyl-propen J-Phenyl-propan6 bzw. aus 4-Methyl-cyclo-hexen 4-Methyl-cyclohexan6. 

Der Bis-[2-phenyl-2-cyan-vinyl]-ather (1) wird iiberwiegend zum 2,5-Diphenyl-hexen-(2)-disdure-nitril (III) reduziert. Je nach Kathodenpotential wird zusatzlich 2,5-Diphe-nyl-hexadien-(2,4)-disaure-dinitril (II) bzw. bei 2 V das 2,5-Diphenyl-hexandisaure-dinitril (IV) erhalten. Da es sich hier primar um die Rekombination zweier radikalischer Spaltprodukte des Athers I handelt, ist cine hohe Depolarisator-Konzentration vorteil-haft2 ... 

Table 3 summarizes the scope and limitation of substrates for this hydrogenation. Complex 5 acts as a highly effective catalyst for functionalized olefins with unprotected amines (the order of activity tertiary > secondary primary), ethers, esters, fluorinated aryl groups, and others [27, 30]. However, in contrast to the reduction of a,p-unsaturated esters decomposition of 5 was observed when a,p-unsaturated ketones (e.g., trans-chalcone, trans-4-hexen-3-one, tra s-4-phenyl-3-buten-2-one, 2-cyclohexanone, carvone) were used (Fig. 3) [30],... 

Bis(imino)pyridine iron complex 5 acts as a catalyst not only for hydrogenation (see 2.1) but also for hydrosilylation of multiple bonds [27]. The results are summarized in Table 10. The reaction rate for hydrosilylations is slower than that for the corresponding hydrogenation however, the trend of reaction rates is similar in each reaction. In case of tra s-2-hexene, the terminal addition product hexyl (phenyl)silane was obtained predominantly. This result clearly shows that an isomerization reaction takes place and the subsequent hydrosilylation reaction dehvers the corresponding product. Reaction of 1-hexene with H2SiPh2 also produced the hydrosilylated product in this system (eq. 1 in Scheme 18). However, the reaction rate for H2SiPh2 was slower than that for H3SiPh. In addition, reaction of diphenylacetylene as an atkyne with phenylsilane afforded the monoaddition product due to steric repulsion (eq. 2 in Scheme 18). 

In the reaction of a-sulfonyl carbanion with lactones, the corresponding hydroxy-co-ketosulfones were obtained " . Thus, various o-hydroxyketones were shown by Umani-Ronchi and coworkers to be formed from the corresponding lactones. For example, the reaction of a, a-dilithioalkyl phenyl sulfones with lactones in THF at low temperatures afforded co-hydroxy-jS-ketosulfones which, upon desulfonylation with aluminium amalgam, gave the corresponding hydroxyketones . This process was applied for the syntheses of cis-jasmone and dihydrojasmone by treating y-valerolactone with ds-3-hexen-l-yl phenyl sulfone and n-hexyl phenyl sulfone. ... 

This interpretation was supported by further investigations by GiacomelH and coworkers [73]. Racemic 4-phenyl-l-hexene was kineticaUy resolved by isomerization of the double bond using a catalyst system consisting of Al Buj, (R)-N,N-di-methyl-l-phenylethylamine and Ni(mesal)2. Very poor enantioselectivities (ee < 0.3%) were observed for both the isomerization product and the unreacted alkene. The authors note that it is essential to first react the alane with the chiral amine. No... 

The intramolecular formal [3+3] cycloaddition reaction of l- [l-phenyl-2-(4-oxobut-2-enyloxy)ethyl]amino cyclo-hexen-3-one at 150°C in the presence of piperidinium acetate afforded /ra 3--l,4a-77-l-phenyl-l,2,4,4a,7,8,9,10-octahydro[l,4]oxazino[4,3- ]quinolin-7-one <2002JA10435>. At 85°C, the 6-(l-piperidnyl)-l,2,4,4a,5,6,7,8,9,10-dec-ahydro derivative formed, which could be converted into the l,2,4,4a,7,8,9,10-octahydro derivative by heating at 150 °C. Cyclization of iV-[(2-butyl-2-oxoethoxy)acetyl]-3,4-dimethoxyphenylethylamine on the action of TFA gave llb-butyl-1,3,4,6,7,1 lb-hexahydro[l,4]oxazino[3,4- ]isoquinolin-4-one <1997JOC2080>. 

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