4-Hexenal, 6-chloro-4-methyl

In another paper from the Jackson Laboratories of the du Pont Company (Calcott et al., 34) there is reported a repetition of some of the reactions of Simons and Archer, as well as additional ones. Mono-, di-, and 1,2,4,5 tetraisopropylbenzene were obtained from propylene and benzene both l -chloro-i-butylbenzene and di-(l/-chloro)-d-butylben-zene were obtained from 3-chloro-2-methyl-propene-l and benzene p-f-butyltoluene and di-i-butyltoluene were obtained from diisobutylene and toluene tetraisopropylnaphthalene was obtained from propylene and naphthalene naphthyl-stearic acid was obtained from oleic acid and naphthalene mixed isopropyltetrahydronaphthalene was obtained from propylene and tetrahydronaphthalene 2,4,6-triisopropylphenol was obtained from propylene and phenol a mixture of monoisopropylated m-cresols was obtained from propylene and wi-cresol and di-(s-hexyl)-diphenyl oxide was obtained from hexene-3 and diphenyl oxide. 

Problem 6.6 Write structural formulas for (a) ( )-2-methyl-3-hexene trans), b) (S)-3-chloro-l-pentene, (c) (R),(Z)-2-chloro-3-heptene (c/s). 

Previous work has shown that the electronic characteristics of the benzene substituent in triarylphosphine chlororhodium complexes have a marked influence on the rate of olefin hydrogenation catalyzed by these compounds. Thus, in the hydrogenation of cyclohexene using L3RhCl the rate decreased as L = tri-p-methoxyphenylphosphine > triphenylphosphine > tri-p-fluorophenylphosphine (14). In the hydrogenation of 1-hexene with catalysts prepared by treating dicyclooctene rhodium chloride with 2.2-2.5 equivalents of substituted triarylphosphines, the substituent effect on the rate was p-methoxy > p-methyl >> p-chloro (15). No mention could be found of any product stereochemistry studies using this type of catalyst. 

Hexenal 6-Chloro-heptafluoro-2-methyl- EI0b2. 353 (—HF - En) C7H4C12F3P... 

Hexene 4-Chloro-5-methyl-1,1,1-triFI uoro-2-tri flu oromelhyl-ElOb,. 442 (R2CCI2 + R-CHO)... 

C7H8N203 2,5-dimethyl-4-nitropyridine-1-oxide 21816-42-2 412.70 35.564 1,2 10940 C7H9CI 5-chloro-5-methyl-1-hexen-3-yne 819-44-3 413.41 35.630 2... 

C8H1403 ethyl 4-methyl-3-oxopentanoate 7152-15-0 446.15 38.735 1,2 14751 C8H15CI 1 -chloro-4-ethyl-3-hexene 82507-04-8 446.15 38.822 ... 

C8H15CI 6-chloro-2-methyl-2-heptene 80325-37-7 204.26 20.875 2 14929 C8H16 2-ethyl-1-hexene 1632-16-2 163.70 13.886 2... 

Chiral aminophosphane-phosphinites (AMPP), prepared by the reaction of chloro(diphenyl)-phosphane with optically active amino alcohols, such as ephedrines, prolinol and A -methyl-phenylglycinol, are used as ligands in transition metal catalyzed cyclodimerization of butadiene to 4-vinylcyclohexene62,10 . With a nickel(0)LJ catalyst (L = Proliphos), (—)-4-vinylcyclo-hexene with 15% ee was obtained in 50% yield6. ... 

If there is only enough electrophilic reagent to add to one of the double bonds, it will add preferentially to the more reactive double bond. For example, in the reaction of 2-methyl-l,5-hexadiene with HCl, addition of HCl to the double bond on the left forms a secondary carbocation, whereas addition of HCl to the double bond on the right forms a tertiary carbocation. Because the transition state leading to formation of a tertiary carbocation is more stable than that leading to a secondary carbocation, the tertiary carbocation is formed faster (Section 4.4). So in the presence of a limited amount of HCl, the major product of the reaction will be 5-chloro-5-methyl-l-hexene. 

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