Sodium methylsulfinylmethylide

Sodium methylsulfinylmethylide (also called NaDMSO or dimsyl sodium) is the sodium salt of the conjugate base of dimethyl sulfoxide. This unusual salt has some uses in organic chemistry as a base and nucleophile.

Sodium methylsulfinylmethylide
Names
Preferred IUPAC name
Sodium (methanesulfinyl)methanide
Other names
sodium dimsylate, dimsylsodium, NaDMSYL
Identifiers
3D model (JSmol)
Abbreviations NaDMSO
ChemSpider
UNII
  • InChI=1S/C2H5OS.Na/c1-4(2)3;/h1H2,2H3;/q-1;+1 checkY
    Key: CWXOAQXKPAENDI-UHFFFAOYSA-N checkY
  • InChI=1S/C2H5OS.Na/c1-4(2)3;/h1H2,2H3;/q-1;+1
    Key: CWXOAQXKPAENDI-UHFFFAOYAA
  • Key: CWXOAQXKPAENDI-UHFFFAOYSA-N
  • [Na+].O=S([CH2-])C
Properties
C2H5NaOS
Molar mass 100.13
Appearance White solid, solution in DMSO is green
Reacts forming DMSO
Solubility Very soluble in DMSO and many polar organic solvents
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 decomposes to 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).
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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]

CH3SOCH3 + NaH → CH3SOCH2−Na+ + H2
CH3SOCH3 + NaNH2 → CH3SOCH2−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.[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]

Reactions of b-ketosulfoxides

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); Collective Volume, 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.
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