2-Hexyl iodide

Nitro-n-hexane. Use 41 g. of dry silver nitrite, 51 g. of n-hexyl iodide (35-5 ml.) and 100 ml. of sodium dried ether. Reflux on a water bath for 8 hours decant the ethereal solution and wash the sohd well with sodium dried ether. Distil the residue, after the removal of the ether from the combined extracts, from 5 g. of dry silver nitrite, and collect the fraction of b.p. 190-192° (13 g.) as 1-nitro -hexane. The pure compound is obtained by distilling under diminished pressure b.p. 81 6°/15 mm. 

The action of hydriodic acid on gdycerol is typical of the polyhychic alcohols. Hychiodic acid converts erythritol into secondary butyl iodide, and mannitol into secondaiy hexyl iodide. The normal iodides are never formed. 

The final step in the sequence can be accomplished with less reactive halides such as hexyl iodide with two modifications to the reaction conditions the lithium dialkylcuprate must b e generated in 1,2-dimethoxyethane instead of diethyl ether and HMPA must be added along with the alkylating agent as illustrated in the following example ... 

Hexanediol, 251,873,879 n-Hexyl alcohol, 247, 253 dehydrogenation of, 322 P n Hexylacrylic acid. 465, 466 n-Hexylbenzene, 510, 516 n-Hexyl bromide. 282 n-Hexyl chloride, 270, 274 n-Hexyl cyanide, 409 n-Hexyl fluoride, 288, 289 n-Hexyl iodide, 288 n-Hexyl magnesium bromide, 237 n-Hexyl mercaptan. 496, 497 n-Hexyl nitrite, 306 1-Hexyne, 896, 899... 

Reaction LXVIH. Simultaneous Reduction and Halogenation of Poly-hydric Alcohols. (A., 138, 364.)—When polyhydric alcohols are heated with hydriodic acid, reduction of all the hydroxyl groups save one occurs this latter is replaced by iodine to form a secondary iodide. In this way, e.g., dulcitol, or any of the hexose alcohols, yields normal secondary hexyl iodide this is of importance in determining the chain structure of the sugars. This reaction probably occurs—... 

The literature authors prepared mixtures of enantiomerically pure 2-methyl-octanal (Md5-8.90°C) (isolated by preparative g.l.c. from the sample prepared by the above procedure from the aldimine of propanal and hexyl iodide) containing w/w amounts of 12.7, 25.7 and 44.6 per cent of hexyl iodide. The [a]D values of these mixtures were plotted against the weight per cent to give a linear relationship. The g.l.c. composition of the reaction product and its extrapolated specific rotation thus allowed an ee per cent value to be calculated. In a similar way the ee per cent of the reaction of the aldimine of octanal and methyl iodide was calculated from the mixtures of octanal with the optically pure 2-methyloctanal of 55.4,74.3 and 87.3 per cent and the plot weight per cent v. [a]D was again linear. 

In a thorough study of the effect of reactant ratio, initiator concentration, temperature and time of reaction, it was found that the optimal reaction conditions for 1 1 adduct formation in the reaction of perfluoro-n-hexyl iodide to vinyl acetate are [210] ... 

Apart from thioacetals, allyl sulfides are among the easiest sulfides to deprotonate and alkylate because of the conjugating ability of the allyl group. However, the very delocalization that assists anion formation means that the anions often react unregioselectively lithiated phenyl allyl sulfide, for instance, reacts with hexyl iodide to give a 3 1 ratio of regioisomers. 

As stated on page 115, the action of hydriodic acid on polyacid alcohols does not yield, as might be expected, the poly-iodine derivatives, but mono-iodine derivatives. Thus from glycerol, isopropyl iodide is obtained from erythrite, normal secondary butyl iodide from man-nite, the normal secondary hexyl iodide. These iodides, as pointed out, may be converted into the corresponding alcohols. The method is of practical value in the preparation of tertiary alcohols from acid-chlorides and zinc alkyls. — Butlerow s synthesis. Compare page 126. 

Ryu, Sonoda and coworkers reported that tris(trimethylsilyl)silane is a useful mediator for a three-component coupling reaction [45]. Table 4 summarizes examples of radical carbonylations mediated by (TMS)3SiH. The first example shows a three-component coupling reaction in which hexyl iodide, CO, and acrylonitrile combine to form a P-cymo ketone. The CO addition step is in competition with the addition to the alkene and the hydrogen abstraction from radical mediator. Thus, it is anticipated that a set of less efficient hydrogen donors, such as (TMS)3SiH, and the use of a smaller excess amount of an alkene is most favorable. Indeed, the reaction can be carried out at only 20 30 atm of CO pressure, substantially below the 80-90 atm which is used for carbonylative acyl radical reactions which are mediated by tin hydride, and a nearly stoichiometric amount (1.2 equiv) of acrylonitrile is sufficient. Some other examples, which include vinyl radical carbonylation, are also shown in Table 4. 

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