Carbon heptene

Miller et al. [9] hypothesized rules on the regioselectivity of addition from the study of the base-catalyzed addition of alcohols to chlorotnfluoroethylene. Attack occurs at the vinylic carbon with most fluorines. Thus, isomers of dichloro-hexafl uorobutene react with methanol and phenol to give the corresponding saturated and vinylic ethers The nucleophiles exclusively attack position 3 of 1,1-dichloro-l,2,3,4,4,4-hexafluoro-2-butene and position I of 4,4-dichloro-l,l,2,3,3,4-hexafluoro-1-butene [10]. In I, l-dichloro-2,3,3,4,4,4-hexafluoro-l-butene, attack on position 2 is favored [J/] (equation 5) Terminal fluoroolefms are almost invariably attacked at tbe difluoromethylene group, as illustrated by the reaction of sodium methoxide with perfluoro-1-heptene in methanol [/2J (equation 6). 

The formation of 88 is postulated to be occurring by the nucleophilic attack of a hydride ion (47), abstracted from the secondary amine, on the a-carbon atom of the iminium salt (89). The resulting carbonium ion (90) then loses a proton to give the imine (91), which could not be separated because of its instability (4H). In the case of 2-methyIhexamethylenimine, however, the corresponding dehydro compound /l -2-methylazacyclo-heptene (92) was isolated. The hydride addition to the iminium ion occurs from the less hindered exo side. 

The above procedure is applied to 2-heptene (9.8 g, 0.1 mole), 11.5 g (0.066 mole) of NBS, and 0.1 g of benzoyl peroxide in 50 ml of carbon tetrachloride. The mixture is refluxed with stirring for 2 hours. Final fractionation yields 50-65% of 4-bromo-2-heptene, bp 70-71732 mm. 

Figure 13.10 DEPT-NMR spectra for 6-methyl-5-hepten-2-ol. Part fa) is an ordinary broadband-decoupled spectrum, which shows signals for all eight carbons. Part [b) is a DEPT-90 spectrum, which shows only signals for the two CH carbons. Part (c) is a DEPT-135 spectrum, which shows positive signals for the two CH and three CH3 carbons and negative signals for the two CH2 carbons.

Problem 13.9 Assign a chemical shift to each carbon in 6-methyl-5-hepten-2-ol (Figure 13.10). Problem 13.10 Estimate the chemical shift of each carbon in the following molecule. Predict which... 

Addition, acetic acid to bicyclo[2.2.1]-hepta-2,5-diene to give nortri-cyclyl acetate, 46, 74 1,2,3-benzothiadiazole 1,1-dioxide to cyclopentadiene, 47, 8 benzyne to tetraphenylcyclopentadie-none, 46,107 Br, F to 1-heptene, 46,10 carbon tetrachloride to olefins, 46, 106... 

Oxa-4,5-benzotricyclo[4.1.0.02-7]heptene was readily converted to 1-benzoxepin (1) on treatment with silver(I) perchlorate. Dicarbonylrhodium chloride dimer or j3-allylpalladium chloride dimer can also be used as catalyst. Thermolysis of the starting material in carbon tetrachloride solution gives 2a,7b-dihydrocyclobuta[6]benzofuran (2) as a new isomer. Depending on the temperature the proportion of 2 varies from 50% (150°C) to 100% (225°C).110... 

Benzo-3-thiatricyclo[4.1.0.02-7]heptene (I, X = H) is a valene -type valence isomer of 2 and 3 however, 1 isomerizes to 3 in photochemical and silver(I)-promoted reactions.75 However. when 1 is heated in carbon tetrachloride at 150°C 3 is not produced but instead the isomeric 1,2-disubstituted 2a,7b-dihydrobenzo[f>]cyclobuta[r/]thiophene. When a rhodium(I)... 

Information published from several sources about 1970 presented details on both the halide-containing RhCl(CO)(PPh3)2- and the hydride-containing HRh(CO)(PPh3)3-catalyzed reactions. Brown and Wilkinson (25) reported the relative rates of gas uptake for a number of different olefinic substrates, including both a- and internal olefins. These relative rates are listed in Table XV. 1-Alkenes and nonconjugated dienes such as 1,5-hexadiene reacted rapidly, whereas internal olefins such as 2-pentene or 2-heptene reacted more slowly by a factor of about 25. It should also be noted that substitution on the 2 carbon of 1-alkene (2-methyl-l-pentene) drastically lowered the rate of reaction. Steric considerations are very important in phosphine-modified rhodium catalysis. 

Another rhodium-catalyzed isomerization, by Makino and Itoh [137], allows the conversion of enallenes 216 and 218 to either five-membered methylenecyclopentanes 217 or, under a CO atmosphere in dioxane, seven-membered alkylidenecyclo-heptenes 218 (Scheme 15.70). With one more carbon in the bridge (in 220), methy-lenecyclohexane 221 was accessible, but as much as 20 mol% of catalyst was necessary. A more recent paper also covers this reaction [138]. 

The 7-azabicyclo[2.2.1]heptene derivative (57) decomposes in hot aqueous sodium carbonate solution to give A-benzylpyrrole-3,4-dicarboxylic acid and, presumably, ethylene. Furan-3,4-dicarboxylic acid derivatives are formed analogously on heating the 7-oxabicyclo-[2.2.1]heptene diesters (58). The only thermal decomposition of a... 

Nortriptyline Nortriptyline is 5-(3-methylaminopropyliden)-10,ll-dihydrodibenzcyclo-heptene (7.1.17). Nortriptyline differs from desipramine in the same manner in which amitriptyline differs from imipramine. In nortriptyhne, the nitrogen atom in the central part of the tricyclic system of desipramine is replaced by a carbon atom, which is bound to a side chain by a double bond. 

Trimethylbutene (Triptene). The polymerization of trimethyl-butene is of interest because rearrangement of the olefin, unless of a very radical nature, can give only the starting material. It was found (Cook et al., 41) that polymerization in the presence of 75% sulfuric resulted in a 91% yield of polymer, 70% of which was 2,2,3,5,5,6,6-heptamethyl-3-heptene. The minor products of the reaction consisted of 3.1% of unreacted triptene, 0.9% of 8- to 10-carbon atom olefins, 3.0% of 10-carbon atom olefins, 9.0% of 11- to 14-carbon atom olefins and 12.0% of residue. The formation of the heptamethylheptene is to be expected on the basis of the carbonium ion mechanism ... 

Titanium-catalyzed cyclization/hydrosilylation of 6-hepten-2-one was proposed to occur via / -migratory insertion of the G=G bond into the titanium-carbon bond of the 77 -ketone olefin complex c/iatr-lj to form titanacycle cis-ll] (Scheme 16). cr-Bond metathesis of the Ti-O bond of cis- iij with the Si-H bond of the silane followed by G-H reductive elimination would release the silylated cyclopentanol and regenerate the Ti(0) catalyst. Under stoichiometric conditions, each of the steps that converts the enone to the titanacycle is reversible, leading to selective formation of the more stable m-fused metallacycle." For this reason, the diastereoselective cyclization of 6-hepten-2-one under catalytic conditions was proposed to occur via non-selective, reversible formation of 77 -ketotitanium olefin complexes chair-1) and boat-1), followed by preferential cyclization of chair-1) to form cis-11) (Scheme 16). 

Methyl-5-hepten-2-one is converted into linalool in excellent yield by base-catalyzed ethynylation with acetylene to dehydrolinalool [45]. This is followed by selective hydrogenation of the triple bond to a double bond in the presence of a palladium carbon catalyst. 

A facile intramolecular carbomagnesiation becomes possible by inserting one more carbon between the reactive magnesium center and the double bond. For example, when a 6-chloro-l-heptene was refluxed with magnesium, 1,2-dimethylcyclopentane (cis/trans = ca 1/4) was obtained in 88% yield after hydrolysis (Scheme 47) °. The cyclization shows a 5-exo-trig selectivity and the product derived from 6-endo-trig cyclization (methylcyclohexane) is not observed. 

The reaction of nitrosyl chloride with cyclopentene, cyclohexene, and cyclo-heptene in carbon tetrachloride solution at 5°C afforded the corresponding adducts in good yield, although during the cyclohexene reaction considerable hydrolysis to 2-chlorocyclohexanone took place and, in the case of cyclohep-tene, the crude product was not identified but rather was immediately subjected to levulinic acid hydrolysis to 2-chlorocycloheptene. From the products isolated, it may be inferred that cyclopentadiene adds nitrosyl chloride in a 1,4-manner in moderate yields [55]. 

Solubility in Acetone Carbon tet. Bensene Ether n-Heptene Ethanol Water Water in... 

The demands for new alcohols were to a considerable extent satisfied by the commercialization of the oxo synthesis in the United States (1). The synthesis involves reaction of an olefin with carbon monoxide and hydrogen to produce an aldehyde, which is reduced subsequently to a primary alcohol. From branched chain feeds such as pentene, heptene, nonene, and tetrapropylene-hexyl, isooctyl, isodecyl, and tridecyl alcohols have been made available to the plasticizer industry in large volume. These alcohols are mixtures of branched chain isomers owing to the branched nature of the olefin feed. (Oxo hexyl alcohol contains about H 1-hexanol). 

The hydroformylation of several olefins in the presence of Co2(CO)8 under high carbon monoxide pressure is reported. (S)-5-Methylheptanal (75%) and (S)-3-ethylhexanal (4.8%) were products from (- -)(S)-4-methyl-2-hexene with optical yields of 94 and 72%, respectively. The main products from ( -)(8)-2,2,5-trimethyl-3-heptene were (S)-3-ethyl-6,6-di-methylheptanal (56.6%) and (R)-4,7,7-trimethyloctanal (41.2%) obtained with optical yields of 74 and 62%, respectively. (R)(S)-3-Ethyl-6,6-dimethylheptanal (3.5% ) and (R)(S)-4,7,7-trimethyloctanal (93.5%) were formed from (R)(S)-3,6,6-trimethyl-l-heptene. (+/S)-l-Phenyl-3-methyl-1-pentene, under oxo conditions, was almost completely hydrogenated to (- -)(S)-l-phenyl-3-methylpentane with 100% optical yield. 3-(Methyl-d3)-l-butene-4-d3 gave 4-(methyl-d3)pentarwl-5-d3 (92%), 2-methyl-3-(methyl-d3)-butanal-4-d3 (3.7%), 3-(methyl-d3)pentanal-2-d2,3-d1 (4.3%) with practically 100% retention of deuterium. The reaction mechanism is discussed on the basis of these results. 

S)-4-Methyl-1 -hexene (12), (+) (S)-4-methyl-2-hexene, and ( + )(S)-5-methyl-l-heptene (12) were synthesized and subjected to hydroformylation under a relatively high carbon monoxide pressure. The main product in all instances was the result of formylation of the terminal carbon atom on or next to the double bond of the starting olefin. The optical yields of these products were about 94% (Table I). 

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