A diol is a chemical compound containing two hydroxyl groups (−OH groups). [1] An aliphatic diol is also called a glycol. [2] This pairing of functional groups is pervasive, and many subcategories have been identified. They are used as protecting groups of carbonyl groups, making them essential in synthesis of organic chemistry. [3]
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 HO−(CH2)4−OH and propylene-1,3-diol, or beta propylene glycol, HO−CH2−CH2−CH2−OH.
A geminal diol has two hydroxyl groups bonded to the same atom. These species arise by hydration of the carbonyl compounds. The hydration is usually unfavorable, but a notable exception is formaldehyde which, in water, exists in equilibrium with methanediol H2C(OH)2. [4] Another example is (F3C)2C(OH)2, the hydrated form of hexafluoroacetone. Many gem-diols undergo further condensation to give dimeric and oligomeric derivatives. This reaction applies to glyoxal and related aldehydes.
In a vicinal diol, the two hydroxyl groups occupy vicinal positions, that is, they are attached to adjacent atoms. These compounds are called glycols. [5] Examples include ethane-1,2-diol or ethylene glycol HO−(CH2)2−OH, a common ingredient of antifreeze products. Another example is propane-1,2-diol, or alpha propylene glycol, HO−CH2−CH(OH)−CH3, used in the food and medicine industry, as well as a relatively non-poisonous antifreeze product.
On commercial scales, the main route to vicinal diols is the hydrolysis of epoxides. The epoxides are prepared by epoxidation of the alkene. An example in the synthesis of trans-cyclohexanediol [6] or by microreactor: [7]
For academic research and pharmaceutical areas, vicinal diols are often produced from the oxidation of alkenes, usually with dilute acidic potassium permanganate or Osmium tetroxide. [8] 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 acyloins [9] and the pinacol coupling reaction.
1,3-Diols are often prepared industrially by aldol condensation of ketones with formaldehyde. You can use many different starting material to produce syn- or anti-1,3-diols. [10] The resulting carbonyl is reduced using the Cannizzaro reaction or by catalytic hydrogenation:
2,2-Disubstituted propane-1,3-diols are prepared in this way. Examples include 2-methyl-2-propyl-1,3-propanediol and neopentyl glycol.
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 ketones 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 where the hydroxyl groups are separated by several carbon centers are generally prepared by hydrogenation of diesters of the corresponding dicarboxylic acids:
1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol are important precursors to polyurethanes. [11]
From the industrial perspective, the dominant reactions of the diols is in the production of polyurethanes and alkyd resins. [11]
Diols react as alcohols, by esterification and ether formation. [12]
Diols such as ethylene glycol are used as co-monomers in polymerization reactions forming polymers including some polyesters and polyurethanes. [12] 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. [13] Protecting groups are used so that the functional group does not react to future reactions. Benzylidene groups are used to protect 1,3-diols. [13] There are extremely useful in biochemistry as shown below of a carbohydrate derivative being protected.
Diols can also be used to protect carbonyl groups. [14] 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. [15]
Diols can also be converted to lactones employing the Fétizon oxidation reaction.
In glycol cleavage, the C−C bond in a vicinal diol is cleaved with formation of ketone or aldehyde functional groups. See Diol oxidation.
In general, organic geminal diols readily dehydrate to form a carbonyl group.
In chemistry, an alcohol is a type of organic compound that carries at least one hydroxyl functional group bound to a saturated carbon atom. Alcohols range from the simple, like methanol and ethanol, to complex, like sugar alcohols and cholesterol. The presence of an OH group strongly modifies the properties of hydrocarbons, conferring hydrophilic (water-loving) properties. The OH group provides a site at which many reactions can occur.
In organic chemistry, an alkene, or olefin, is a hydrocarbon containing a carbon–carbon double bond. The double bond may be internal or in the terminal position. Terminal alkenes are also known as α-olefins.
In organic chemistry, a ketone is an organic compound with the structure R−C(=O)−R', where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group −C(=O)−. The simplest ketone is acetone, with the formula (CH3)2CO. Many ketones are of great importance in biology and in industry. Examples include many sugars (ketoses), many steroids, and the solvent acetone.
In organic chemistry, an aldehyde is an organic compound containing a functional group with the structure R−CH=O. The functional group itself can be referred to as an aldehyde but can also be classified as a formyl group. Aldehydes are a common motif in many chemicals important in technology and biology.
In organic chemistry, an acetal is a functional group with the connectivity R2C(OR')2. Here, the R groups can be organic fragments or hydrogen, while the R' groups must be organic fragments not hydrogen. The two R' groups can be equivalent to each other or not. Acetals are formed from and convertible to aldehydes or ketones and have the same oxidation state at the central carbon, but have substantially different chemical stability and reactivity as compared to the analogous carbonyl compounds. The central carbon atom has four bonds to it, and is therefore saturated and has tetrahedral geometry.
Ethylene glycol is an organic compound with the formula (CH2OH)2. It is mainly used for two purposes, as a raw material in the manufacture of polyester fibers and for antifreeze formulations. It is an odorless, colorless, flammable, viscous liquid. It has a sweet taste, but is toxic in high concentrations. This molecule has been observed in outer space.
In chemistry, a hydration reaction is a chemical reaction in which a substance combines with water. In organic chemistry, water is added to an unsaturated substrate, which is usually an alkene or an alkyne. This type of reaction is employed industrially to produce ethanol, isopropanol, and butan-2-ol.
In organic chemistry, an epoxide is a cyclic ether, where the ether forms a three-atom ring: two atoms of carbon and one atom of oxygen. This triangular structure has substantial ring strain, making epoxides highly reactive, more so than other ethers. They are produced on a large scale for many applications. In general, low molecular weight epoxides are colourless and nonpolar, and often volatile.
In organic chemistry, a dicarbonyl is a molecule containing two carbonyl groups. Although this term could refer to any organic compound containing two carbonyl groups, it is used more specifically to describe molecules in which both carbonyls are in close enough proximity that their reactivity is changed, such as 1,2-, 1,3-, and 1,4-dicarbonyls. Their properties often differ from those of monocarbonyls, and so they are usually considered functional groups of their own. These compounds can have symmetrical or unsymmetrical substituents on each carbonyl, and may also be functionally symmetrical or unsymmetrical.
In organic chemistry, ozonolysis is an organic reaction where the unsaturated bonds are cleaved with ozone. Multiple carbon–carbon bond are replaced by carbonyl groups, such as aldehydes, ketones, and carboxylic acids. The reaction is predominantly applied to alkenes, but alkynes and azo compounds are also susceptible to cleavage. The outcome of the reaction depends on the type of multiple bond being oxidized and the work-up conditions.
In organic chemistry a halohydrin is a functional group in which a halogen and a hydroxyl are bonded to adjacent carbon atoms, which otherwise bear only hydrogen or hydrocarbyl groups. The term only applies to saturated motifs, as such compounds like 2-chlorophenol would not normally be considered halohydrins. Megatons of some chlorohydrins, e.g. propylene chlorohydrin, are produced annually as precursors to polymers.
A geminal diol is any organic compound having two hydroxyl functional groups (-OH) bound to the same carbon atom. Geminal diols are a subclass of the diols, which in turn are a special class of alcohols. Most of the geminal diols are considered unstable.
A pinacol coupling reaction is an organic reaction in which a carbon–carbon bond is formed between the carbonyl groups of an aldehyde or a ketone in presence of an electron donor in a free radical process. The reaction product is a vicinal diol. The reaction is named after pinacol, which is the product of this reaction when done with acetone as reagent. The reaction is usually a homocoupling but intramolecular cross-coupling reactions are also possible. Pinacol was discovered by Wilhelm Rudolph Fittig in 1859.
2-Iodoxybenzoic acid (IBX) is an organic compound used in organic synthesis as an oxidizing agent. This periodinane is especially suited to oxidize alcohols to aldehydes. IBX is prepared from 2-iodobenzoic acid, potassium bromate, and sulfuric acid. Frigerio and co-workers have also demonstrated, in 1999 that potassium bromate may be replaced by commercially available Oxone. One of the main drawbacks of IBX is its limited solubility; IBX is insoluble in many common organic solvents. In the past, it was believed that IBX was shock sensitive, but it was later proposed that samples of IBX were shock sensitive due to the residual potassium bromate left from its preparation. Commercial IBX is stabilized by carboxylic acids such as benzoic acid and isophthalic acid.
Dioxolane is a heterocyclic acetal with the chemical formula (CH2)2O2CH2. It is related to tetrahydrofuran (THF) by replacement of the methylene group (CH2) at the 2-position with an oxygen atom. The corresponding saturated 6-membered C4O2 rings are called dioxanes. The isomeric 1,2-dioxolane (wherein the two oxygen centers are adjacent) is a peroxide. 1,3-dioxolane is used as a solvent and as a comonomer in polyacetals.
The Danishefsky Taxol total synthesis in organic chemistry is an important third Taxol synthesis published by the group of Samuel Danishefsky in 1996 two years after the first two efforts described in the Holton Taxol total synthesis and the Nicolaou Taxol total synthesis. Combined they provide a good insight in the application of organic chemistry in total synthesis.
Glycol cleavage is a specific type of organic chemistry oxidation. The carbon–carbon bond in a vicinal diol (glycol) is cleaved and instead the two oxygen atoms become double-bonded to their respective carbon atoms. Depending on the substitution pattern in the diol, these carbonyls will be ketones and/or aldehydes.
The Prins reaction is an organic reaction consisting of an electrophilic addition of an aldehyde or ketone to an alkene or alkyne followed by capture of a nucleophile or elimination of an H+ ion. The outcome of the reaction depends on reaction conditions. With water and a protic acid such as sulfuric acid as the reaction medium and formaldehyde the reaction product is a 1,3-diol (3). When water is absent, the cationic intermediate loses a proton to give an allylic alcohol (4). With an excess of formaldehyde and a low reaction temperature the reaction product is a dioxane (5). When water is replaced by acetic acid the corresponding esters are formed.
Alcohol oxidation is a collection of oxidation reactions in organic chemistry that convert alcohols to aldehydes, ketones, carboxylic acids, and esters where the carbon carries a higher oxidation state. The reaction mainly applies to primary and secondary alcohols. Secondary alcohols form ketones, while primary alcohols form aldehydes or carboxylic acids.
The Criegee oxidation is a glycol cleavage reaction in which vicinal diols are oxidized to form ketones and aldehydes using lead tetraacetate. It is analogous to the use of periodate but uses a milder oxidant. This oxidation was discovered by Rudolf Criegee and coworkers and first reported in 1931 using ethylene glycol as the substrate.