Ethylene glycol dehydration with

Cyclohexadiene has been prepared by dehydration of cyclohexen-3-ol,3 by pyrolysis at 540° of the diacetate of cyclohexane-1,2-diol,4 by dehydrobromination with quinoline of 3-hromocyclohexene,6 by treating the ethyl ether of cyclohexen-3-ol with potassium bisulfatc,6 7 by heating cyclohexene oxide with phthalic anhydride,8 by treating cyclohexane-1,2-diol with concentrated sulfuric acid,9 by treatment of 1,2-dibromocyclo-hexane with tributylamine,10 with sodium hydroxide in ethylene glycol,10 and with quinoline,6 and by treatment of 3,6-dibromo-cyclohexene with sodium.6... 

In a similar manner, coccinelline (99) and precoccinelline (100) have been synthesized from 2,6-lutidine (351) (336,450). Thus, treatment of the monolithium derivative (153) of 351 with P-bromopropionaldehyde dimethylacetal gave an acetal, which was converted to the keto acetal (412) by treatment with phenyllithium and acetonitrile. Reaction of 412 with ethylene glycol and p-toluenesulfonic acid followed by reduction with sodium-isoamyl alcohol gave the cw-piperidine (413). Hydrolysis of 413 with 5% HCl gave the tricyclic acetal (414) which was transformed to a separable 1 1 mixture of the ketones (415 and 416) by treatment with pyrrolidine-acetic acid. Reaction of ketone 416 with methyllithium followed by dehydration with thionyl chloride afforded the rather unstable olefin (417) which on catalytic hydrogenation over platinum oxide in methanol gave precoccinelline (100). Oxidation of 100 with m-chloroperbenzoic acid yielded coccinelline (99) (Scheme 52) (336,450). 

The partial reduction of benzofuroxans, discussed in Section 4.05.5.2.4, represents an effective route to numerous benzofurazans. The conversion may be achieved either directly by deoxygention, for example, with sodium azide in ethylene glycol or acetic acid <75Ci(M)243> or using phosphites, or in two stages via the dioxime with subsequent dehydration as described above. 

Ethanediol (ethylene glycol) [5g] Commercial products are pure enough for most purposes. In order to remove water of 2000 ppm, the ethanediol is dehydrated with sodium sulfate anhydride and distilled twice at reduced pressure in a dry nitrogen atmosphere in order to avoid oxidation to aldehyde. 

Prepared commercially either by dehydration of ethylene glycol with H2SO4 and heating ethylene oxide or bis(B-chloroethyl)ether with NaOH. 

Abeles and associates showed that when dioldehydratase (Table 16-1) catalyzes the conversion of l,2-[l-3H]propanediol to propionaldehyde, tritium appears in the coenzyme as well as in the final product. When 3H-containing coenzyme is incubated with unlabeled propanediol, the product also contains 3H, which was shown by chemical degradation to be exclusively on C-5 . Synthetic 5 -deoxyadenosyl coenzyme containing 3H in the 5 position transferred 3H to product. Most important, using a mixture of propanediol and ethylene glycol, a small amount of inter-molecular transfer was demonstrated that is, 3H was transferred into acetaldehyde, the product of dehydration of ethylene glycol. Similar results were also obtained with ethanolamine ammonia-lyase 399... 

The reaction chemistry of simple organic molecules in supercritical (SC) water can be described by heterolytic (ionic) mechanisms when the ion product 1 of the SC water exceeds 10" and by homolytic (free radical) mechanisms when <<10 1 . For example, in SC water with Kw>10-11 ethanol undergoes rapid dehydration to ethylene in the presence of dilute Arrhenius acids, such as 0.01M sulfuric acid and 1.0M acetic acid. Similarly, 1,3 dioxolane undergoes very rapid and selective hydration in SC water, producing ethylene glycol and formaldehyde without catalysts. In SC methanol the decomposition of 1,3 dioxolane yields 2 methoxyethanol, il lustrating the role of the solvent medium in the heterolytic reaction mechanism. Under conditions where K klO"11 the dehydration of ethanol to ethylene is not catalyzed by Arrhenius acids. Instead, the decomposition products include a variety of hydrocarbons and carbon oxides. 

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