Hemiacetal

Hemiacetal
Skeletal formula of a hemiacetal
Hemiketal

Hemiacetals and hemiketals are compounds that are derived from aldehydes and ketones respectively. The Greek word hèmi means half. These compounds are formed by formal addition of an alcohol to the carbonyl group.

When the alcohol group is replaced by a second alkoxy group, an acetal or a ketal, respectively, is formed.

Contents

Formula and formation

Above: 1-ethoxybutan-1-ol, a hemiacetal. Below: 1,1-diethoxybutan, an acetal

The general formula of a hemiacetal is R1R2C(OH)OR,[1] where R1 or R2 is often hydrogen and R (bonded to O) is not hydrogen.
While in the IUPAC definition of a hemiacetal R1 or R2 may or may not be a hydrogen, in a hemiketal none of the R-groups is an H. Hemiketals are regarded as hemiacetals that have no R-groups being H, thus a subclass of the hemiacetals. [2]

Formation of hemiacetals.png
Formation of hemiacetals

Hemiketal formation.png
Formation of hemiketals

Cyclic hemiacetals and hemiketals

Ribopyranose
Fructopyranose
Left a lactol of ribose, a cyclic hemiacetal.
Right a lactol of fructose, a cyclic hemiketal.

Hemiacetals and hemiketals are generally unstable compounds. In some cases however, stable cyclic hemiacetals and hemiketals, called lactols,[3] can be readily formed, especially when 5- and 6-membered rings are possible. In this case an intramolecular OH group reacts with the carbonyl group. Glucose and many other aldoses exist as cyclic hemiacetals whereas fructose and similar ketoses exist as cyclic hemiketals.

Synthesis

In organic synthesis, hemiacetals can be prepared in a number of ways:

Reactions

Hemiacetals and hemiketals may be thought of intermediate between alcohols and aldehydes or ketones, and acetals and ketals:

-C=O + 2 ROH ⇌ -C(OH)(OR) + ROH ⇌ -C(OR)2 + H2O

A hemiacetal can react with an alcohol under acidic conditions to form an acetal, and can dissociate to form an aldehyde and an alcohol.

An aldehyde dissolved in water exists in equilibrium with low concentrations of its hydrate, R-CH(OH)2. Similarly, in excess alcohol, the aldehyde, its hemiacetal, and its acetal all exist in solution.

Hemiacetal results from addition of the alcohol's hydroxyl group to the carbon in the C=O bond. Acetals are products of substitution reactions catalyzed by acid. The presence of acid improves the leaving capacity of the hydroxyl group and enables its substitution with an alkoxyl group (-OR). The conversion of a hemiacetal to an acetal is an SN1 reaction.

Ketones give hemiketals and ketals. These do not form as readily as hemiacetals and acetals. To increase yields of ketals or acetals, water formed during the reaction can be removed.

See also

References

  1. ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version:  (2006–) "hemiacetals".
  2. ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version:  (2006–) "hemiketals".
  3. ^ IUPAC Gold Book lactols

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Look at other dictionaries:

  • Hemiacetal — Hémiacétal Un hemiacétal est un groupe fonctionnel formé par réaction d un aldéhyde et d un alcool ou un composé chimique contenant ce groupe fonctionnel. Hémiacétal formé par la réaction d un aldédyde et un alcool, R et R sont des groupes… …   Wikipédia en Français

  • hémiacétal — ● hémiacétal, hémiacétals nom masculin Produit d addition d un alcool ROH sur un aldéhyde R′CHO ou une cétone R′R ″CO, de formule R′CH(OH)OR ou R′R ″C(OH)OR …   Encyclopédie Universelle

  • Hémiacétal — Un hémiacétal est un groupe fonctionnel formé par réaction d un aldéhyde et d un alcool ou un composé chimique contenant ce groupe fonctionnel. Hémiacétal formé par la réaction d un aldédyde et un alcool, R et R sont des groupes alkyles ou aryles …   Wikipédia en Français

  • Hemiacetal — En Química de carbohidratos, un hemiacetal es una molécula que contiene un grupo hidroxilo OH y un residuo alcóxido OR unidos a un mismo átomo de carbono. Se forma por reacción de adición nucleófila de un aldehído con un alcohol.[1] OH | R CH=O + …   Wikipedia Español

  • hemiacetal — hemiacetalis statusas T sritis chemija formulė RCH(OH)OR, R₂C(OH)OR atitikmenys: angl. hemiacetal; hemiketal; semiacetal rus. полуацеталь; полукеталь; семиацеталь ryšiai: sinonimas – semiacetalis …   Chemijos terminų aiškinamasis žodynas

  • hemiacetal — noun Date: 1893 any of a class of compounds characterized by the grouping C(OH)(OR) where R is an alkyl group and usually formed as intermediates in the preparation of acetals from aldehydes or ketones …   New Collegiate Dictionary

  • Hemiacetal — Allgemeine Struktur der Acetale Acetale sind eine Stoffgruppe in der organischen Chemie. Sie zeichnen sich durch zwei Alkoxygruppen oder Aryloxygruppen –OR aus, die an ein Kohlenstoff Atom gebunden sind. Bei der Herstellung von Acetalen entstehen …   Deutsch Wikipedia

  • hemiacetal — /hem ee as i tal /, n. any of the class of organic chemical compounds having the general formula RCH(OH)OR, where R is an organic group. [1890 95; HEMI + ACETAL] * * * …   Universalium

  • hemiacetal — noun Any of a class of compounds of general formula RC(OH)OR (where R is not H) …   Wiktionary

  • hemiacetal — RCH(OH)OR′, a product of the addition of an alcohol to an aldehyde (an acetal is formed by the addition of an alcohol to a h.). In the aldose sugars, the h. formation is internal and labile, brought about by the 4 OH or 5 OH attack on the …   Medical dictionary

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