Sodium methylsulfinylmethylide

Sodium methylsulfinylmethylide (also called NaDMSO or dimsyl sodium) is the sodium salt of dimethyl sulfoxide. It has the chemical formula C H₃S(O)CH−2Na⁺. This unusual salt has some uses in organic chemistry as a base and nucleophile.

Quick facts Names, Identifiers ...

Sodium methylsulfinylmethylide
Names

Preferred IUPAC name Sodium (methanesulfinyl)methanide
Other names sodium dimsylate, dimsylsodium, NaDMSYL
Identifiers
CAS Number	15590-23-5^Y
3D model (JSmol)	Interactive image
Abbreviations	NaDMSO
ChemSpider	8329518^Y
PubChem CID	10154010
UNII	R6HI470Q52^Y
CompTox Dashboard (EPA)	DTXSID10436194
InChI InChI=1S/C2H5OS.Na/c1-4(2)3;/h1H2,2H3;/q-1;+1^Y Key: CWXOAQXKPAENDI-UHFFFAOYSA-N^Y InChI=1S/C2H5OS.Na/c1-4(2)3;/h1H2,2H3;/q-1;+1 Key: CWXOAQXKPAENDI-UHFFFAOYAA Key: CWXOAQXKPAENDI-UHFFFAOYSA-N
SMILES [Na+].O=S([CH2-])C
Properties
Chemical formula	CH₃S(O)CH₂Na
Molar mass	100.11 g·mol⁻¹
Appearance	White solid, solution in DMSO is green
Solubility in water	decomposes
Solubility	Very soluble in DMSO and many polar organic solvents
Hazards
Occupational safety and health (OHS/OSH):
Main hazards	May form corrosive NaOH, May be explosive in certain circumstances.^[1]
Related compounds
Related compounds	Dimethyloxosulfonium methylide, Dimethyl sulfoxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). N verify (what is ^YN ?) Infobox references

Since the first publication in 1965 by Corey et al.,^[2] a number of additional uses for this reagent have been identified.^[3]

Preparation

Sodium methylsulfinylmethylide is prepared by heating sodium hydride^[4] or sodium amide^[5] in DMSO^[6]

CH₃S(O)CH₃ + NaH → CH₃S(O)CH−2Na⁺ + H₂

CH₃S(O)CH₃ + NaNH₂ → CH₃S(O)CH−2Na⁺ + NH₃

Reactions

As a base

The pK_a of DMSO is 35, which leads NaDMSO to be a powerful Brønsted base. NaDMSO is used in the generation of phosphorus and sulfur ylides.^[7] NaDMSO in DMSO is especially convenient in the generation of dimethyloxosulfonium methylide and dimethylsulfonium methylide.^[2]^[8]

Reaction with esters

NaDMSO condenses with esters (1) to form β-ketosulfoxides (2), which can be useful intermediates.^[9] Reduction of β-ketosulfoxides with aluminium amalgam gives methyl ketones (3).^[10] 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).^[11]

References

[1]
"Sodium Hydride in Aprotic Solvents: Look Out".
[2]
Corey, E. J.; Chaykovsky, M. (1965). "Methylsulfinyl Carbanion (CH₃-SO-CH₂⁻). Formation and Applications to Organic Synthesis". J. Am. Chem. Soc. 87 (6): 1345–1353. doi:10.1021/ja01084a033.
[3]
Mukulesh Mondal "Sodium methylsulfinylmethylide: A versatile reagent" Synlett 2005, vol. 17, 2697-2698. doi:10.1055/s-2005-917075
[4]
Iwai, I.; Ide, J. (1988). "2,3-Diphenyl-1,3-Butadiene". Organic Syntheses{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 6, p. 531.
[5]
Kaiser, E. M.; Beard, R. D.; Hauser, C. R. (1973). "Preparation and reactions of the mono- and dialkali salts of dimethyl sulfone, dimethyl sulfoxide, and related compounds". J. Organomet. Chem. 59: 53–64. doi:10.1016/S0022-328X(00)95020-4.
[6]
"Preparation of dimsyl sodium".
[7]
Romo, D.; Myers, A. I. (1992). "An asymmetric route to enantiomerically pure 1,2,3-trisubstituted cyclopropanes". J. Org. Chem. 57 (23): 6265–6270. doi:10.1021/jo00049a038.
[8]
Trost, B. M.; Melvin, L. S., Jr. (1975). Sulfur Ylides: Emerging Synthetic Intermediates. New York: Academic Press. ISBN 0-12-701060-2.{{cite book}}: CS1 maint: multiple names: authors list (link)
[9]
Ibarra, C. A; Rodgríguez, R. C; Monreal, M. C. F; Navarro, F. J. G.; Tesoreo, J. M. (1989). "One-pot synthesis of β-keto sulfones and β-keto sulfoxides from carboxylic acids". J. Org. Chem. 54 (23): 5620–5623. doi:10.1021/jo00284a043.
[10]
Swenton, J. S.; Anderson, D. K.; Jackson, D. K.; Narasimhan, L. (1981). "1,4-Dipole-metalated quinone strategy to (±)-4-demethoxydaunomycinone and (±)-daunomycinone. Annelation of benzocyclobutenedione monoketals with lithioquinone bisketals". J. Org. Chem. 46 (24): 4825–4836. doi:10.1021/jo00337a002.
[11]
Isibashi, H.; Okada, M.; Komatsu, H.; Ikeda, M. S. (1985). "A New Synthesis of Substituted Cyclopentenones by Olefin Cyclization Initiated by Pummerer Reaction Intermediates". Synthesis. 1985 (6/7): 643–645. doi:10.1055/s-1985-31290. S2CID 95643470.