:Sodium methylsulfinylmethylide
{{chembox
| Verifiedfields = changed
| Watchedfields = changed
| verifiedrevid = 464402379
| ImageFile = Sodium methylsulfinylmethylide.png
| ImageSize =
| PIN = Sodium (methanesulfinyl)methanide
| OtherNames = sodium dimsylate, dimsylsodium, NaDMSYL
|Section1={{Chembox Identifiers
| Abbreviations = NaDMSO
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 8329518
| InChI = 1S/C2H5OS.Na/c1-4(2)3;/h1H2,2H3;/q-1;+1
| InChIKey = CWXOAQXKPAENDI-UHFFFAOYAA
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| StdInChI = 1S/C2H5OS.Na/c1-4(2)3;/h1H2,2H3;/q-1;+1
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = CWXOAQXKPAENDI-UHFFFAOYSA-N
| InChIKey1 = CWXOAQXKPAENDI-UHFFFAOYSA-N
| CASNo_Ref = {{cascite|correct|CAS}}
| CASNo = 15590-23-5
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = R6HI470Q52
| EINECS =
| PubChem = 10154010
| SMILES = [Na+].O=S([CH2-])C
| RTECS =
| MeSHName =
| ChEBI_Ref = {{ebicite|correct|EBI}}
| ChEBI =
| KEGG_Ref = {{keggcite|correct|kegg}}
| KEGG =
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|Section2={{Chembox Properties
| Formula = {{chem2|CH3S(O)CH2Na}}
| C=2|H=5|Na=1|O=1|S=1
| Appearance = White solid, solution in DMSO is green
| Density =
| Solubility = decomposes
| SolubleOther = Very soluble in DMSO and many polar organic solvents
| Solvent =
| pKa =
| pKb = }}
|Section7={{Chembox Hazards
| MainHazards = May form corrosive NaOH, May be explosive in certain circumstances.{{cite web|url=https://www.science.org/content/blog-post/sodium-hydride-aprotic-solvents-look-out|title = Sodium Hydride in Aprotic Solvents: Look Out}}
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|Section8={{Chembox Related
| OtherAnions =
| OtherCations =
| OtherFunction =
| OtherFunction_label =
| OtherCompounds = Dimethyloxosulfonium methylide, Dimethyl sulfoxide}}
}}
Sodium methylsulfinylmethylide (also called NaDMSO or dimsyl sodium) is the sodium salt of dimethyl sulfoxide. It has the chemical formula {{chem2|CH3S(O)CH2-Na+|auto=1}}. This unusual salt has some uses in organic chemistry as a base and nucleophile.
Since the first publication in 1965 by Corey et al.,{{cite journal | journal = J. Am. Chem. Soc. | year = 1965 | volume = 87 | pages = 1345–1353 | title = Methylsulfinyl Carbanion (CH3-SO-CH2−). Formation and Applications to Organic Synthesis | doi = 10.1021/ja01084a033 | author1 = Corey, E. J. | author2 = Chaykovsky, M. | authorlink1 = Elias James Corey | issue = 6}} a number of additional uses for this reagent have been identified.Mukulesh Mondal "Sodium methylsulfinylmethylide: A versatile reagent" Synlett 2005, vol. 17, 2697-2698. {{doi|10.1055/s-2005-917075}}
Preparation
Sodium methylsulfinylmethylide is prepared by heating sodium hydride{{OrgSynth | author = Iwai, I.; Ide, J. | title = 2,3-Diphenyl-1,3-Butadiene | collvol = 6 | collvolpages = 531 | year = 1988 | prep = cv6p0531}} or sodium amide{{cite journal | journal = J. Organomet. Chem. | year = 1973 | volume = 59 | pages = 53–64 | doi = 10.1016/S0022-328X(00)95020-4 | title = Preparation and reactions of the mono- and dialkali salts of dimethyl sulfone, dimethyl sulfoxide, and related compounds | author1 = Kaiser, E. M. | author2 = Beard, R. D. | author3 = Hauser, C. R.}} in DMSO{{cite web|url=http://stenutz.eu/sop/sop401.html|title=Preparation of dimsyl sodium}}
:{{chem2|CH3S(O)CH3 + NaH → CH3S(O)CH2-Na+ + H2}}
:{{chem2|CH3S(O)CH3 + NaNH2 → CH3S(O)CH2-Na+ + NH3}}
Reactions
=As a base=
The pKa of DMSO is 35, which leads NaDMSO to be a powerful Brønsted base. NaDMSO is used in the generation of phosphorus and sulfur ylides.{{cite journal |title = An asymmetric route to enantiomerically pure 1,2,3-trisubstituted cyclopropanes | journal = J. Org. Chem. | year = 1992 | volume = 57 | pages = 6265–6270 | doi = 10.1021/jo00049a038 |author1 = Romo, D. |author2 = Myers, A. I. |issue = 23}} NaDMSO in DMSO is especially convenient in the generation of dimethyloxosulfonium methylide and dimethylsulfonium methylide.{{cite book | author = Trost, B. M.; Melvin, L. S., Jr. | title = Sulfur Ylides: Emerging Synthetic Intermediates | publisher = Academic Press | location = New York | year = 1975 | isbn = 0-12-701060-2}}
=Reaction with esters=
NaDMSO condenses with esters (1) to form β-ketosulfoxides (2), which can be useful intermediates.{{cite journal |title = One-pot synthesis of β-keto sulfones and β-keto sulfoxides from carboxylic acids | journal = J. Org. Chem. | year = 1989 | volume = 54 | pages = 5620–5623 | doi = 10.1021/jo00284a043 |author1 = Ibarra, C. A |author2 = Rodgríguez, R. C |author3 = Monreal, M. C. F |author4 = Navarro, F. J. G. |author5 = Tesoreo, J. M. |issue = 23}} Reduction of β-ketosulfoxides with aluminium amalgam gives methyl ketones (3).{{cite journal | title = 1,4-Dipole-metalated quinone strategy to (±)-4-demethoxydaunomycinone and (±)-daunomycinone. Annelation of benzocyclobutenedione monoketals with lithioquinone bisketals | journal = J. Org. Chem. | year = 1981 | volume = 46 | pages = 4825–4836 | doi = 10.1021/jo00337a002 | author1 = Swenton, J. S. | author2 = Anderson, D. K. | author3 = Jackson, D. K. | author4 = Narasimhan, L. | issue = 24}} Reaction with alkyl halides followed by elimination gives α,β-unsaturated ketones (4). β-ketosulfoxides can also be used in the Pummerer rearrangement to introduce nucleophiles alpha to a carbonyl (5).{{cite journal | journal = Synthesis | year = 1985 | pages = 643–645 | author1 = Isibashi, H. | author2 = Okada, M.| author3 = Komatsu, H. | author4 = Ikeda, M. S. | doi = 10.1055/s-1985-31290 | volume=1985 | title=A New Synthesis of Substituted Cyclopentenones by Olefin Cyclization Initiated by Pummerer Reaction Intermediates| issue = 6/7 | s2cid = 95643470}}
References
{{Reflist}}
External links
- {{cite web | publisher = Gaylord Chemical Corporation | url = http://www.gaylordchemical.com/bulletins/bulletin110b/Bulletin110B.pdf | title = The Dimethyl Sulfoxide (DMSO) Anion — Dimsyl Ion |date=October 2007 | archive-url = https://web.archive.org/web/20110711080250/http://www.gaylordchemical.com/bulletins/bulletin110b/Bulletin110B.pdf | archive-date= 2011-07-11}}
- {{cite web | url = http://stenutz.eu/sop/sop401.html | title = Preparation of dimsyl sodium |date=June 2009}}