Heptane, 2-iodo

Acetoxy-4-iodo-3,7,7-trimethylbicyclo[4.1.0]heptane, 3544 Ammonium iodate, 4513... 

Treatment of 3,7,7-trimethylbicyclo[4.1.0]heptane (A3-carene) with iodine and copper acetate in methanol gave 3-iodo-4-methoxy-4,7,7-trimethylbicyclo[4.1.0] heptane. A 50 g sample exploded violently after standing at ambient temperature in a closed container for 10 days. This and the corresponding iodoacetoxy... 

The fruit of a shrub which grows in Sierra Leone is very toxic and has been used as a rat poison. The toxic principle has been identified as Z-18-fluoro-9-octadecenoic acid. Suggest a synthesis for this material from 8-fluorooctanol, l-chloro-7-iodo-heptane, acetylene, and any other necessary organic or inorganic reagents. 

A synthetic study has revealed that the combination of anhydrous hydrogen chloride and zinc(II) chloride in the presence of a nucleophile, e.g. benzenethiol, promotes the ring cleavage of cyclobutanones such as bicyclo[3.2.0]heptan-6-one (28) to provide / -sulfanyl ketones such as 3-phenylsulfanylcycloheptanone (27).63 Alternatively, iodotrimethylsilane in the presence of either mercury/water or zinc(II) iodide also converts cyclobutanones to /i-iodo ketones 29.64 The synthetic applications of these transformations are summarized in Table 5. 

In the presence of proton and/or Lewis acid and strong nucleophiles bicyclo[3.2.0]heptan-6-ones are converted to 3-substituted cycloheptanones (Table 15). Bicyclo[3.2.0]heptan-6-ones rearrange to give 3-iodocycloheptanones on treatment with iodotrimethylsilane. Zinc(II) iodide or mercury(II) halides as catalysts enhance the rate and the selectivity of the reaction.31 If a second, enolizable carbonyl group is present, an intramolecular alkylation may follow the ring enlargement under these reaction conditions.32 Consecutive treatment with tributyltin hydride/ 2,2 -azobisisobutyronitrile affords reduced, iodo-free cycloheptanones, whilst treatment with l,8-diazabicyclo[5.4.0]undecene yields cycloheptenones.33 Similarly, benzenethiol adds to the central bond of bicyclo[3.2.0]heptan-6-ones in the presence of zinc(II) chloride and hydrochloric acid under anhydrous conditions to form 3-(phenylsulfanyl)cycloheptanones.34... 

Ethynyl-2-nitrophenol (Attempted Alternate Synthesis). To a stirred solution of 4-iodo-2-nitrophenol (14.Og, 0.053 mole)(7) in 150 ml of tetrachloroethylene was added bis(triphenylphosphine) palladium dichloride (0.74g, 0.001 mole), cuprous iodide (0.40g, 0.002 mole), triphenyl phosphine (0.03g, 0.001 mole), and 50 ml of dry triethylamine. After the reactants were thoroughly mixed, 2-methyl-3-butyn-2-ol (5.4g, 0.064 mole) was added. The stirred reaction mixture was heated slowly to 70-75°C and maintained at that temperature for 16 hours. The tetrachloroethylene and triethylamine were removed under reduced pressure and the red gumlike residue was extracted with hot heptane. The heptane solution was treated with charcoal and the heptane was stripped off to give a yellow solid (9.5g). The solid was dissolved in benzene and was placed in a silica gel column. Elution with 1 1 benzene/hexane yielded 1.8g of product. The remainder of the product was removed... 

The spectrum of the heptyl ion is given in Table 18. The results for the source spectra are obtained from the spectrum of 1-iodo-n-heptane after correction for the fragments containing iodine. Bu" is by far the most abundant ion. The formation of propyl ion in the source might be astonishing, since it does not correspond to Stevenson s rule it could be formed by successive eliminations of two ethylenes, but we will show later... 

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