Sodium methylsulfinylmethylide

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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
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 checkY☒N ?)

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

Preparation

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

CH3SOCH3 + NaH → CH3SOCH2Na+ + H2
CH3SOCH3 + NaNH2 → CH3SOCH2Na+ + NH3

Reactions

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As a base

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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

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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

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  1. ^ "Sodium Hydride in Aprotic Solvents: Look Out".
  2. ^ a b 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.
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