Dimethyl sulfoxide

Source: Wikipedia, the free encyclopedia.
"DMSO" redirects here. For other uses, see DMSO (disambiguation).
Dimethyl sulfoxide
Stereo structural formula of dimethyl sulfoxide with an explicit electron pair and assorted dimensions
Stereo structural formula of dimethyl sulfoxide with an explicit electron pair and assorted dimensions
Spacefill model of dimethyl sulfoxide
Spacefill model of dimethyl sulfoxide

A sample of dimethyl sulfoxide
Names
Preferred IUPAC name
(Methanesulfinyl)methane
Systematic IUPAC name
(Methanesulfinyl)methane (substitutive)
Dimethyl(oxido)sulfur (additive)
Other names
Methylsulfinylmethane
Methyl sulfoxide (2:1), Dermasorb[1]
Identifiers
3D model (
JSmol
)
Abbreviations DMSO, Me2SO
506008
ChEBI
ChEMBL
ChemSpider
DrugBank
ECHA InfoCard
 100.000.604 Edit this at Wikidata
EC Number
  • 200-664-3
1556
KEGG
MeSH Dimethyl+sulfoxide
RTECS number
  • PV6210000
UNII
  • InChI=1S/C2H6OS/c1-4(2)3/h1-2H3 checkY
    Key: IAZDPXIOMUYVGZ-UHFFFAOYSA-N checkY
  • InChI=1/C2H6OS/c1-4(2)3/h1-2H3
    Key: IAZDPXIOMUYVGZ-UHFFFAOYAR
  • CS(=O)C
  • CS(C)=O
Properties
C2H6OS
Molar mass 78.13 g·mol−1
Appearance Colourless liquid
Density 1.1004 g⋅cm−3
Melting point 19 °C (66 °F; 292 K)
Boiling point 189 °C (372 °F; 462 K)
Miscible
Solubility in Diethyl ether Not soluble
Vapor pressure 0.556 millibars or 0.0556 kPa at 20 °C[2]
Acidity (pKa) 35[3]
1.479
εr
= 48
Viscosity 1.996 cP at 20 °C
Structure
Cs
Trigonal pyramidal
3.96 D
Pharmacology
G04BX13 (WHO) M02AX03 (WHO)
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Irritant
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 2: Must be moderately heated or exposed to relatively high ambient temperature before ignition can occur. Flash point between 38 and 93 °C (100 and 200 °F). E.g. diesel fuelInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
1
2
0
Flash point 89 °C (192 °F; 362 K)
Safety data sheet (SDS) Oxford MSDS
Related compounds
Related sulfoxides
 Diethyl sulfoxide
Related compounds
Supplementary data page
Dimethyl sulfoxide (data page)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

Dimethyl sulfoxide (DMSO) is an

miscible in a wide range of organic solvents as well as water. It has a relatively high boiling point. DMSO is metabolised to compounds that leave a garlic-like taste in the mouth after DMSO is absorbed by skin.[5]

In terms of chemical structure, the molecule has idealized Cs symmetry. It has a trigonal pyramidal molecular geometry consistent with other three-coordinate S(IV) compounds,[6] with a nonbonded electron pair on the approximately tetrahedral sulfur atom.

Synthesis and production

Dimethyl sulfoxide was first synthesized in 1866 by the Russian scientist

Alexander Zaytsev, who reported his findings in 1867.[7] Its modern use as an industrial solvent began through popularization by Thor Smedslund at the Stepan Chemical Company.[8] Dimethyl sulfoxide is produced industrially from dimethyl sulfide, a by-product of the Kraft process, by oxidation with oxygen or nitrogen dioxide.[9]

Reactions

Reactions with electrophiles

The sulfur center in DMSO is

methyl iodide it forms trimethylsulfoxonium iodide
, [(CH3)3SO]I:

(CH3)2SO + CH3I → [(CH3)3SO]I

This salt can be

deprotonated with sodium hydride to form the sulfur ylide
:

[(CH3)3SO]I + NaH → (CH3)2S(CH2)O + NaI + H2

Acidity

The methyl groups of DMSO are only weakly acidic, with a pKa = 35. For this reason, the basicities of many weakly basic organic compounds have been examined in this solvent.

Deprotonation of DMSO requires strong bases like

diaminocarbenes
. It is also a potent nucleophile.

Oxidant

In organic synthesis, DMSO is used as a mild oxidant.[10] It forms the basis of several selective sulfonium-based oxidation reactions including the Pfitzner–Moffatt oxidation, Corey–Kim oxidation and the Swern oxidation.[11] The Kornblum oxidation is conceptually similar. These all involve formation of an intermediate sulfonium species (R2S+X where X is a heteroatom)

Ligand and Lewis base

Related to its ability to dissolve many salts, DMSO is a common

dichlorotetrakis(dimethyl sulfoxide)ruthenium(II) (RuCl2(dmso)4). In this complex, three DMSO ligands are bonded to ruthenium
through sulfur. The fourth DMSO is bonded through oxygen. In general, the oxygen-bonded mode is more common.

In carbon tetrachloride solutions DMSO functions as a Lewis base with a variety of Lewis acids such as I2, phenols, trimethyltin chloride, metalloporphyrins, and the dimer Rh2Cl2(CO)4. The donor properties are discussed in the ECW model. The relative donor strength of DMSO toward a series of acids, versus other Lewis bases, can be illustrated by C-B plots.[13][14]

Applications

Solvent

Distillation of DMSO requires a partial vacuum to achieve a lower boiling point.

DMSO is a

pKa values (C-H, O-H, S-H and N-H acidities) for thousands of organic compounds have been determined in DMSO solution.[16][17]

Because of its high boiling point, 189 °C (372 °F), DMSO evaporates slowly at normal atmospheric pressure. Samples dissolved in DMSO cannot be as easily recovered compared to other solvents, as it is very difficult to remove all traces of DMSO by conventional

cryodesiccation to remove both DMSO and water. Reactions conducted in DMSO are often diluted with water to precipitate or phase-separate products. The relatively high freezing point of DMSO, 18.5 °C (65.3 °F), means that at, or just below, room temperature it is a solid, which can limit its utility in some chemical processes (e.g. crystallization
with cooling).

In its

hygroscopicity, which leads to an overwhelming H2O resonance in the 1H-NMR spectrum. It is often mixed with CDCl3 or CD2Cl2
for lower viscosity and melting points.

DMSO is used as a solvent in in vitro and in vivo drug testing.

DMSO is used to dissolve test compounds in

stock solutions of test compounds (important when working with a large chemical library),[19] is readily miscible with water and cell culture media, and has a high boiling point (this improves the accuracy of test compound concentrations by reducing room temperature evaporation).[18] One limitation with DMSO is that it can affect cell line growth and viability, with low DMSO concentrations sometimes stimulating cell growth, and high DMSO concentrations sometimes inhibiting or killing cells.[18]

DMSO is used as a vehicle in

flavonol glycoside Icariin in the nematode worm Caenorhabditis elegans.[21] As with its use in in vitro studies, DMSO has some limitations in animal models.[22][23] Pleiotropic effects can occur and, if DMSO control groups are not carefully planned, then solvent effects can falsely be attributed to the prospective drug.[22] For example, even a very low dose of DMSO has a powerful protective effect against paracetamol (acetaminophen)-induced liver injury in mice.[23]

DMSO is finding increased use in manufacturing processes to produce microelectronic devices.[24] It is widely used to strip photoresist in TFT-LCD 'flat panel' displays and advanced packaging applications (such as wafer-level packaging / solder bump patterning). DMSO is an effective paint stripper, being safer than many of the others such as nitromethane and dichloromethane.

Biology

DMSO is used in

DNA primers. It is added to the PCR mix before reacting, where it interferes with the self-complementarity of the DNA, minimizing interfering reactions.[25]

DMSO in a PCR is applicable for supercoiled plasmids (to relax before amplification) or DNA templates with high GC-content (to decrease thermostability). For example, 10% final concentration of DMSO in the PCR mixture with Phusion decreases primer annealing temperature (i.e. primer melting temperature) by 5.5–6.0 °C (9.9–10.8 °F).[26]

It is well known as a reversible cell cycle arrester at phase G1 of human lymphoid cells.[27]

DMSO may also be used as a cryoprotectant, added to cell media to reduce ice formation and thereby prevent cell death during the freezing process.[28] Approximately 10% may be used with a slow-freeze method, and the cells may be frozen at −80 °C (−112 °F) or stored in liquid nitrogen safely.

In cell culture, DMSO is used to induce

skeletal muscle cells
.

Medicine

Use of DMSO in medicine dates from around 1963, when an

EDTA. It is frequently compounded with antifungal medications, enabling them to penetrate not just skin but also toenails and fingernails.[30]

DMSO has been examined for the treatment of numerous conditions and ailments, but the U.S.

genitourinary disorders that were studied.[32]
The authors recommended DMSO for genitourinary inflammatory conditions not caused by infection or tumor in which symptoms were severe or patients failed to respond to conventional therapy.

In

Onyx liquid embolic agent, which is used in embolization
, the therapeutic occlusion of blood vessels.

In

bone marrow transplant the DMSO is re-infused along with the patient's own hematopoietic stem cells
.

DMSO is metabolized by

halitosis
symptom.

Alternative medicine

DMSO is marketed as an alternative medicine. Its popularity as an alternative cure is stated to stem from a 60 Minutes documentary in 1980 featuring an early proponent.[33] However, DMSO is an ingredient in some products listed by the U.S. FDA as fake cancer cures[34] and the FDA has had a running battle with distributors.[33] One such distributor is Mildred Miller, who promoted DMSO for a variety of disorders and was consequently convicted of Medicare fraud.[33]

The use of DMSO as an alternative treatment for cancer is of particular concern, as it has been shown to interfere with a variety of chemotherapy drugs, including cisplatin, carboplatin, and oxaliplatin.[35] There is insufficient evidence to support the hypothesis that DMSO has any effect,[36] and most sources agree that its history of side effects when tested warrants caution when using it as a dietary supplement, for which it is marketed heavily with the usual disclaimer.

Veterinary medicine

DMSO is commonly used in veterinary medicine as a liniment for horses, alone or in combination with other ingredients. In the latter case, often, the intended function of the DMSO is as a solvent, to carry the other ingredients across the skin. Also in horses, DMSO is used intravenously, again alone or in combination with other drugs. It is used alone for the treatment of increased intracranial pressure and/or cerebral edema in horses.[citation needed]

Taste

The perceived garlic taste upon skin contact with DMSO may be due to

trigeminal ganglia.[37] Unlike dimethyl and diallyl disulfides (which have odors resembling garlic), mono- and tri-
sulfides (which typically have foul odors), and similar odiferous sulfur compounds, the pure chemical DMSO is odorless.

Safety

Toxicity

DMSO is a non-toxic solvent with a median lethal dose higher than ethanol (DMSO: LD50, oral, rat, 14,500 mg/kg;[38][39] ethanol: LD50, oral, rat, 7,060 mg/kg[40]).

Early clinical trials with DMSO were stopped because of questions about its safety, especially its ability to harm the eye. The most commonly reported side effects include headaches and burning and itching on contact with the skin. Strong allergic reactions have been reported.[full citation needed] DMSO can cause contaminants, toxins, and medicines to be absorbed through the skin, which may cause unexpected effects. DMSO is thought to increase the effects of blood thinners, steroids, heart medicines, sedatives, and other drugs. In some cases this could be harmful or dangerous.[41]

In Australia, it is listed as a Schedule 4 (S4) Drug, and a company has been prosecuted for adding it to products as a preservative.[42]

Because DMSO easily penetrates the

mil / 0.4 mm) latex gloves are recommended.[43] Nitrile gloves, which are very commonly used in chemical laboratories, may protect from brief contact but have been found to degrade rapidly with exposure to DMSO.[44]

On September 9, 1965,

bone marrow transplant.[47]

DMSO disposed into sewers can cause odor problems in municipal effluents: waste water bacteria transform DMSO under hypoxic (anoxic) conditions into dimethyl sulfide (DMS) that has a strong disagreeable odor, similar to rotten cabbage.[48] However, chemically pure DMSO is odorless because of the lack of C-S-C (sulfide) and C-S-H (mercaptan) linkages. Deodorization of DMSO is achieved by removing the odorous impurities it contains.[49]

Explosion hazard

Dimethyl sulfoxide can produce an explosive reaction when exposed to acyl chlorides; at a low temperature, this reaction produces the oxidant for Swern oxidation.

DMSO can decompose at the boiling temperature of 189 °C at normal pressure, possibly leading to an explosion. The decomposition is catalyzed by acids and bases and therefore can be relevant at even lower temperatures. A strong to explosive reaction also takes place in combination with halogen compounds, metal nitrides, metal perchlorates, sodium hydride, periodic acid and fluorinating agents.[50]

See also

  • Varying oxidation of sulfur
    • Dimethyl sulfide (DMS), the corresponding sulfide, also produced by marine phytoplankton and emitted to the oceanic atmosphere where it is oxidized to DMSO, SO2 and sulfate
    • Dimethyl sulfone, commonly known as methylsulfonylmethane (MSM), a related chemical often marketed as a dietary supplement
  • Related compounds with methyl on oxygen
  • Gloria Ramirez
    , also known as the "Toxic Woman"

References

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  2. ^ "Dimethyl Sulfoxide (DMSO) -- Technical". Atofina Chemicals, inc. Retrieved 26 May 2007.
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  4. ^ "Dimethyl sulfoxide". pubchem.ncbi.nlm.nih.gov.
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  7. ^ von Demselben (1867). "Ueber die Einwirkung von Saltpetersäure auf Schwefelmethyl und Schwefeläthyl" [On the effect of nitric acid on methyl sulfide and ethyl sulfide]. In Erlenmeyer, E.; Rieckher, T.; Volhard, J.; Liebig, J.; Wöhler, F. (eds.). Annalen der Pharmacie (in German). Meyer ; Winter. p. 148.
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  14. doi:10.1021/ed054p612. The plots shown in this paper used older parameters. Improved E&C parameters are listed in ECW model
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  17. ^ "Bordwell pKa Table (Acidity in DMSO)". Archived from the original on 9 October 2008. Retrieved 23 April 2019.
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  32. ^ Shirley SW, Stewart BH, Mirelman S (March 1978). "Dimethyl Sulfoxide in Treatment of Inflammatory Genitourinary Disorders".
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  34. ^ "187 Fake Cancer "Cures" Consumers Should Avoid". FDA. Archived from the original on 23 July 2017.
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  50. ISBN 3-609-48040-8

External links

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