Sodium methylsulfinylmethylide

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Sodium methylsulfinylmethylide
NaDMSO Structure.png
Names
IUPAC name
Sodium methylsulfinylmethylide
Other names
sodium dimsylate, dimsylsodium, NaDMSYL
Identifiers
Abbreviations NaDMSO
15590-23-5 N
ChemSpider 8329518 YesY
Jmol-3D images Image
Properties
C2H5NaOS
Molar mass 100.13
Appearance Colorless solid, may be apple-green or purple in solution [1]
Reacts forming DMSO
Solubility Very soluble in DMSO and many polar organic solvents
Hazards
Main hazards decomposes to corrosive NaOH
Related compounds
Related compounds
Dimethyloxosulfonium methylide, dimethyl sulfoxide
Except where noted otherwise, data is given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 N verify (what isYesY/N?)
Infobox references

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.

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

Preparation[edit]

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

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

Reactions[edit]

As a Base[edit]

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.[6] NaDMSO in DMSO is especially convenient in the generation of dimethyloxosulfonium methylide and dimethylsulfonium methylide.[2][7]

Reaction with esters[edit]

NaDMSO condenses with esters (1) to form β-ketosulfoxides (2), which can be useful intermediates.[8] Reduction of β-ketosulfoxides with aluminium amalgam gives methyl ketones (3).[9] Reaction with alkyl halides followed by elimination gives α,β-unsaturated ketones (4). Interestingly, β-ketosulfoxides can also be used in the Pummerer rearrangement to introduce nucleophiles alpha to a carbonyl (5).[10]

Reactions of b-ketosulfoxides

References[edit]

  1. ^ http://www.21chemnet.com/cas/15590-23-5.html
  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. 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". Org. Synth. ; Coll. 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. doi:10.1016/S0022-328X(00)95020-4. 
  6. ^ Romo, D.; Myers, A. I. (1992). "An asymmetric route to enantiomerically pure 1,2,3-trisubstituted cyclopropanes". J. Org. Chem. 57 (23): 6265. doi:10.1021/jo00049a038. 
  7. ^ Trost, B. M.; Melvin, L. S., Jr. (1975). Sulfur Ylides: Emerging Synthetic Intermediates. New York: Academic Press. ISBN 0-12-701060-2. 
  8. ^ 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. doi:10.1021/jo00284a043. 
  9. ^ 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. doi:10.1021/jo00337a002. 
  10. ^ Isibashi, H.; Okada, M.; Komatsu, H.; Ikeda, M. S. (1985). Synthesis: 643.  Missing or empty |title= (help)

External links[edit]