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A diol is a chemical compound containing two ( groups).. An aliphatic diol may also be called a glycol.. This pairing of is pervasive, and many subcategories have been identified. They are used as of , making them essential in synthesis of organic chemistry.
The most common industrial diol is ethylene glycol. Examples of diols in which the hydroxyl functional groups are more widely separated include 1,4-butanediol and propylene-1,3-diol, or beta propylene glycol, .
On commercial scales, the main route to vicinal diols is the hydrolysis of . The epoxides are prepared by epoxidation of the alkene. An example in the synthesis of trans-cyclohexanedioltrans-cyclohexanediol Organic Syntheses, Coll. Vol. 3, p. 217 (1955); Vol. 28, p.35 ( 1948) http://www.orgsynth.org/orgsyn/pdfs/CV3P0217.pdf. or by microreactor: Advantages of Synthesizing trans-1,2-Cyclohexanediol in a Continuous Flow Microreactor over a Standard Glass Apparatus Andreas Hartung, Mark A. Keane, and Arno Kraft J. Org. Chem. 2007, 72, 10235–10238 .
For academic research and pharmaceutical areas, vicinal diols are often produced from the oxidation of Alkene, usually with dilute acidic potassium permanganate or Osmium tetroxide. Osmium tetroxide can similarly be used to oxidize alkenes to vicinal diols. The chemical reaction called Sharpless asymmetric dihydroxylation can be used to produce chiral diols from alkenes using an osmate reagent and a chiral catalyst. Another method is the Woodward cis-hydroxylation (cis diol) and the related Prévost reaction (anti diol), which both use iodine and the silver salt of a carboxylic acid.
Other routes to vic-diols are the hydrogenation of and the pinacol coupling reaction.
1,3-Diols can be prepared by hydration of α,β-unsaturated ketones and aldehydes. The resulting keto-alcohol is hydrogenated. Another route involves the hydroformylation of epoxides followed by hydrogenation of the aldehyde. This method has been used for 1,3-propanediol from ethylene oxide.
More specialized routes to 1,3-diols involves the reaction between an alkene and formaldehyde, the Prins reaction. 1,3-diols can be produced diastereoselectively from the corresponding β-hydroxy using the Evans–Saksena, Narasaka–Prasad or Evans–Tishchenko reduction protocols.
1,3-Diols are described as syn or anti depending on the relative stereochemistries of the carbon atoms bearing the hydroxyl functional groups. Zincophorin is a natural product that contains both syn and anti 1,3-diols.
Diols such as ethylene glycol are used as co- in polymerization reactions forming including some and . A different monomer with two identical functional groups, such as a dioyl dichloride or dioic acid is required to continue the process of polymerization through repeated esterification processes.
A diol can be converted to cyclic ether by using an acid catalyst, this is diol cyclization. Firstly, it involves protonation of the hydroxyl group. Then, followed by intramolecular nucleophilic substitution, the second hydroxyl group attacks the electron deficient carbon. Provided that there are enough carbon atoms that the angle strain is not too much, a cyclic ether can be formed.
1,2-diols and 1,3-diols can be protected using a protecting group. Protecting groups are used so that the functional group does not react to future reactions. Benzylidene groups are used to protect 1,3-diols. There are extremely useful in biochemistry as shown below of a carbohydrate derivative being protected. Diols can also be used to protect carbonyl groups. They are commonly used and are quite efficient at synthesizing cyclic acetals. These protect the carbonyl groups from reacting from any further synthesis until it is necessary to remove them. The reaction below depicts a diol being used to protect a carbonyl using zirconium tetrachloride. Diols can also be converted to employing the Fétizon oxidation reaction.
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