1,3-Dithiolane

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1,3-Dithiolane
1,3-dithiolane-2D-skeletal.png
Dithiolane23d.png
Names
IUPAC name
1,3-Dithiolane
Identifiers
3D model (JSmol)
102455
ChEBI
ChemSpider
82036
PubChem CID
UNII
  • InChI=1S/C3H6S2/c1-2-4-5-3-1/h1-3H2 Yes check.svgY
    Key: MUZIZEZCKKMZRT-UHFFFAOYSA-N Yes check.svgY
  • C1CSCS1
Properties
C3H6S2
Molar mass 106.20 g·mol−1
Related compounds
Related compounds
Ethane-1,2-dithiol
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

1,3-Dithiolane is the organosulfur compound with the formula CH2S2C2H4. Also classified as a heterocycle related cyclopentane by replacing two methylene bridges (-CH
2
- units) with thioether groups. It is an isomer of 1,2-dithiolane. [1] 1,3-Dithiolanes are compounds where one or more H atoms of the parent 1,3-dithiolane are replaced by other groups. These species are more widely studied.

Contents

Synthesis

A common family of 1,3-dithiolanes have the formula RCHS2C2H4. They are obtained by treating an aldehyde with 1,2-ethanedithiol. [2] Related compounds with the formula R2CS2C2H4 are obtained by condensation of 1,2-ethanedithiol with ketones. [3] The dithiolane protected aldehydes and ketones are amenable to many reactions without perturbing the dithiolane ring. [4]

Protecting a carbonyl group by converting it to a 1,3-dithiolane, using 1,2-ethanedithiol Carbonyl-protection-with-ethanedithiol-2D.png
Protecting a carbonyl group by converting it to a 1,3-dithiolane, using 1,2-ethanedithiol

Dithiolanes can often be reverted, i.e., deprotected, [5] to the parent aldehyde and ketone. A variety of reagents have been developed for that purpose. [6]

Reactions

1,3-Dithiolanes derived from aldehydes can be deprotonated:

RCHS2C2H4 + BuLi → RCLiS2C2H4 + BuH

These organolithium compounds degrade with loss of ethylene to give the dthiocarboxylate:

RCLiS2C2H4 → RCS2Li + C2H4

In contrast, 2-lithio-1,3-dithianes (RCLiS2C3H6) are long-lived.

1,3-Dithiolanes are susceptible to a variety of degradation processes involving organometallic reagents leading to other organosulfur compounds. [2] [3]

Related Research Articles

<span class="mw-page-title-main">Ketone</span> Organic compounds of the form >C=O

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 industry. Examples include many sugars (ketoses), many steroids, and the solvent acetone.

<span class="mw-page-title-main">Hydrazone</span> Organic compounds - Hydrazones

Hydrazones are a class of organic compounds with the structure R1R2C=N−NH2. They are related to ketones and aldehydes by the replacement of the oxygen =O with the =N−NH2 functional group. They are formed usually by the action of hydrazine on ketones or aldehydes.

<span class="mw-page-title-main">Dicarbonyl</span> Molecule containing two adjacent C=O groups

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.

A diol is a chemical compound containing two hydroxyl groups. An aliphatic diol may also be called a glycol. 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.

<span class="mw-page-title-main">Imine</span> Organic compound or functional group containing a C=N bond

In organic chemistry, an imine is a functional group or organic compound containing a carbon–nitrogen double bond. The nitrogen atom can be attached to a hydrogen or an organic group (R). The carbon atom has two additional single bonds. Imines are common in synthetic and naturally occurring compounds and they participate in many reactions.

<span class="mw-page-title-main">Thiophenol</span> Chemical compound

Thiophenol is an organosulfur compound with the formula C6H5SH, sometimes abbreviated as PhSH. This foul-smelling colorless liquid is the simplest aromatic thiol. The chemical structures of thiophenol and its derivatives are analogous to phenols, where the oxygen atom in the hydroxyl group (-OH) bonded to the aromatic ring in phenol is replaced by a sulfur atom. The prefix thio- implies a sulfur-containing compound and when used before a root word name for a compound which would normally contain an oxygen atom, in the case of 'thiol' that the alcohol oxygen atom is replaced by a sulfur atom.

<span class="mw-page-title-main">Aluminium isopropoxide</span> Chemical compound

Aluminium isopropoxide is the chemical compound usually described with the formula Al(O-i-Pr)3, where i-Pr is the isopropyl group (–CH(CH3)2). This colourless solid is a useful reagent in organic synthesis.

<span class="mw-page-title-main">Tebbe's reagent</span> Chemical compound

Tebbe's reagent is the organometallic compound with the formula (C5H5)2TiCH2ClAl(CH3)2. It is used in the methylidenation of carbonyl compounds, that is it converts organic compounds containing the R2C=O group into the related R2C=CH2 derivative. It is a red solid that is pyrophoric in the air, and thus is typically handled with air-free techniques. It was originally synthesized by Fred Tebbe at DuPont Central Research.

<span class="mw-page-title-main">Ethane-1,2-dithiol</span> Chemical compound

Ethane-1,2-dithiol, also known as EDT, is a colorless liquid with the formula C2H4(SH)2. It has a very characteristic odor which is compared by many people to rotten cabbage. It is a common building block in organic synthesis and an excellent ligand for metal ions.

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<span class="mw-page-title-main">Dithiane</span> Chemical compound

A dithiane is a heterocyclic compound composed of a cyclohexane core structure wherein two methylene bridges are replaced by sulfur. The three isomeric parent heterocycles are 1,2-dithiane, 1,3-dithiane and 1,4-dithiane. They are all colorless solids.

<span class="mw-page-title-main">1,3,5-Trithiane</span> Chemical compound

1,3,5-Trithiane is the chemical compound with the formula (CH2S)3. This heterocycle is the cyclic trimer of the otherwise unstable species thioformaldehyde. It consists of a six-membered ring with alternating methylene bridges and thioether groups. It is prepared by treatment of formaldehyde with hydrogen sulfide.

<span class="mw-page-title-main">Carbonyl reduction</span> Organic reduction of any carbonyl group by a reducing agent

In organic chemistry, carbonyl reduction is the conversion of any carbonyl group, usually to an alcohol. It is a common transformation that is practiced in many ways. Ketones, aldehydes, carboxylic acids, esters, amides, and acid halides - some of the most pervasive functional groups, -comprise carbonyl compounds. Carboxylic acids, esters, and acid halides can be reduced to either aldehydes or a step further to primary alcohols, depending on the strength of the reducing agent. Aldehydes and ketones can be reduced respectively to primary and secondary alcohols. In deoxygenation, the alcohol group can be further reduced and removed altogether by replacement with H.

<span class="mw-page-title-main">Dithiol</span> Organosulfur compound with two –SH groups

In organic chemistry, a dithiol is a type of organosulfur compound with two thiol functional groups. Their properties are generally similar to those of monothiols in terms of solubility, odor, and volatility. They can be classified according to the relative location of the two thiol groups on the organic backbone.

<span class="mw-page-title-main">Propionaldehyde</span> Chemical compound

Propionaldehyde or propanal is the organic compound with the formula CH3CH2CHO. It is the 3-carbon aldehyde. It is a colourless, flammable liquid with a pungent and fruity odour. It is produced on a large scale industrially.

1,3-Dioxane or m-dioxane is an organic compound with the molecular formula (CH2)4O2. It is a saturated six-membered heterocycle with two oxygen atoms in place of carbon atoms at the 1- and 3- positions. 1,4-Dioxane, which is of greater commercial value, is an isomer. Both dioxanes are colorless liquids.

Propynyllithium is an organolithium compound with the chemical formula LiC
2
CH
3
. It is a white solid that is soluble in 1,2-dimethoxyethane, and tetrahydrofuran. To preclude its degradation by oxygen and water, propynyllithium and its solutions are handled under inert gas. Although commonly depicted as a monomer, propynyllithium adopts a more complicated cluster structure as seen for many other organolithium compounds.

<span class="mw-page-title-main">Pinacolborane</span> Chemical compound

Pinacolborane is the borane with the formula (CH3)4C2O2BH. Often pinacolborane is abbreviated HBpin. It features a boron hydride functional group incorporated in a five-membered C2O2B ring. Like related boron alkoxides, pinacolborane is monomeric. It is a colorless liquid. It features a reactive B-H functional group.

Hydroxymethylation is a chemical reaction that installs the CH2OH group. The transformation can be implemented in many ways and applies to both industrial and biochemical processes.

In organic chemistry, methylenation is a chemical reaction that inserts a methylene group into a chemical compound:

References

  1. Teuber, Lene (1990). "Naturally Occurring 1,2-Dithiolanes and 1,2,3-Trithianes. Chemical and Biological Properties". Sulfur Reports. 9 (4): 257–333. doi:10.1080/01961779008048732.
  2. 1 2 Ni, Zhi-Jie; Luh, Tien-Yau (1992). "Nickel-Catalyzed Silylolefination of Allylic Dithioacetals: (E,E)-Trimethyl(4-Phenyl-1,3-Butadienyl)Silane". Organic Syntheses. 70: 240. doi:10.15227/orgsyn.070.0240.
  3. 1 2 Wilson, S. R.; Georgiadis, G. M. (1983). "Mercaptans from Thioketals: Cyclododecyl Mercaptan". Organic Syntheses. 61: 74. doi:10.15227/orgsyn.061.0074.
  4. Dahnke, Karl R.; Paquette, Leo A. (1993). "2-Methylene-1,3-Dithiolane". Organic Syntheses. 71: 175. doi:10.15227/orgsyn.071.0175.
  5. Wuts, P. G. M.; Greene, T. W. (2006). Greene's Protective Groups in Organic Synthesis. NY: J. Wiley. doi:10.1002/0470053488. ISBN   9780470053485. S2CID   83393227.
  6. Banerjee, Ajoy K.; Laya, M. S. (2000). "Reagents for the preparation and cleavage of 1,3-dithiolanes". Russian Chemical Reviews. 69 (11): 947–955. Bibcode:2000RuCRv..69..947B. doi:10.1070/rc2000v069n11abeh000583. S2CID   250918297.