| Revision as of 15:46, 6 December 2011 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 418118061 of page Sodium_methylsulfinylmethylide for the Chem/Drugbox validation project (updated: 'CASNo'). |
Latest revision as of 04:24, 22 March 2024 edit Mfernflower (talk | contribs)Extended confirmed users7,828 editsNo edit summaryTags: Mobile edit Mobile web edit Advanced mobile edit |
| Line 1: |
Line 1: |
|
{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}} |
|
|
{{chembox |
|
{{chembox |
|
|
| Verifiedfields = changed |
| ⚫ |
| verifiedrevid = 400850784 |
|
|
|
| Watchedfields = changed |
|
⚫ |
| verifiedrevid = 464402379 |
|
| ImageFile = NaDMSO_Structure.png |
|
| ImageFile = NaDMSO_Structure.png |
|
| ImageSize = |
|
| ImageSize = |
|
| IUPACName = Sodium methylsulfinylmethylide |
|
| PIN = Sodium (methanesulfinyl)methanide |
|
| OtherNames = sodium dimsylate, dimsylsodium, NaDMSYL |
|
| OtherNames = sodium dimsylate, dimsylsodium, NaDMSYL |
|
| Section1 = {{Chembox Identifiers |
|
|Section1={{Chembox Identifiers |
|
| Abbreviations = NaDMSO |
|
| Abbreviations = NaDMSO |
|
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
|
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
| Line 17: |
Line 18: |
|
| StdInChIKey = CWXOAQXKPAENDI-UHFFFAOYSA-N |
|
| StdInChIKey = CWXOAQXKPAENDI-UHFFFAOYSA-N |
|
| InChIKey1 = CWXOAQXKPAENDI-UHFFFAOYSA-N |
|
| InChIKey1 = CWXOAQXKPAENDI-UHFFFAOYSA-N |
|
|
| CASNo_Ref = {{cascite|correct|CAS}} |
|
| CASNo = <!-- blanked - oldvalue: 15590-23-5 --> |
|
| CASNo = 15590-23-5 |
|
|
| UNII_Ref = {{fdacite|correct|FDA}} |
|
|
| UNII = R6HI470Q52 |
|
| EINECS = |
|
| EINECS = |
|
| PubChem = |
|
| PubChem = 10154010 |
|
| SMILES = .O=S()C |
|
| SMILES = .O=S()C |
|
| InChI = |
|
|
| RTECS = |
|
| RTECS = |
|
| MeSHName = |
|
| MeSHName = |
|
|
| ChEBI_Ref = {{ebicite|correct|EBI}} |
|
| ChEBI = |
|
| ChEBI = |
|
|
| KEGG_Ref = {{keggcite|correct|kegg}} |
|
| KEGG = |
|
| KEGG = |
|
|
}} |
|
| ATCCode_prefix = |
|
|
⚫ |
|Section2={{Chembox Properties |
|
| ATCCode_suffix = |
|
|
| ATC_Supplemental =}} |
|
| ⚫ |
| Section2 = {{Chembox Properties |
|
|
| Formula = C<sub>2</sub>H<sub>5</sub>NaOS |
|
| Formula = C<sub>2</sub>H<sub>5</sub>NaOS |
|
| MolarMass = 100.13 |
|
| MolarMass = 100.13 |
|
| Appearance = |
|
| Appearance = White solid, solution in DMSO is green |
|
| Density = |
|
| Density = |
|
| Solubility = Reactive |
|
| Solubility = decomposes |
|
|
| SolubleOther = Very soluble in ] and many polar organic solvents |
|
| SolubleOther = Soluble |
|
|
| Solvent = ] |
|
| Solvent = |
|
| pKa = |
|
| pKa = |
|
| pKb = }} |
|
| pKb = }} |
|
| Section8 = {{Chembox Related |
|
|Section7={{Chembox Hazards |
|
|
| MainHazards = May form corrosive ], May be explosive in certain circumstances.<ref>{{cite web|url=https://www.science.org/content/blog-post/sodium-hydride-aprotic-solvents-look-out|title = Sodium Hydride in Aprotic Solvents: Look Out}}</ref> |
|
|
}} |
|
|
|Section8={{Chembox Related |
|
| OtherAnions = |
|
| OtherAnions = |
|
| OtherCations = |
|
| OtherCations = |
|
| OtherFunctn = |
|
| OtherFunction = |
|
| Function = |
|
| OtherFunction_label = |
|
| OtherCpds = ]}} |
|
| OtherCompounds = ], ]}} |
|
}} |
|
}} |
|
|
'''Sodium methylsulfinylmethylide''' (also called '''NaDMSO''' or '''dimsyl sodium''') is the sodium salt of the ] of ]. This unusual salt has some uses in ] as a ] and ]. |
|
|
|
|
|
Since the first publication in 1965 by ] ''et al.'',<ref name="Corey1965">{{cite journal | journal = ] | year = 1965 | volume = 87 | pages = 1345–1353 | title = Methylsulfinyl Carbanion (CH<sub>3</sub>-SO-CH<sub>2</sub><sup>−</sup>). Formation and Applications to Organic Synthesis | doi = 10.1021/ja01084a033 | author1 = Corey, E. J. | author2 = Chaykovsky, M. | authorlink1 = Elias James Corey | issue = 6}}</ref> a number of additional uses for this reagent have been identified.<ref>Mukulesh Mondal "Sodium methylsulfinylmethylide: A versatile reagent" Synlett 2005, vol. 17, 2697-2698. {{doi|10.1055/s-2005-917075}}</ref> |
|
|
|
|
|
==Preparation== |
|
|
Sodium methylsulfinylmethylide is prepared by heating ]<ref>{{OrgSynth | author = Iwai, I.; Ide, J. | title = 2,3-Diphenyl-1,3-Butadiene | collvol = 6 | collvolpages = 531 | year = 1988 | prep = cv6p0531}}</ref> or ]<ref>{{cite journal | journal = ] | 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.}}</ref> in ]<ref>{{cite web|url=http://stenutz.eu/sop/sop401.html|title=Preparation of dimsyl sodium}}</ref> |
|
|
|
|
|
:CH<sub>3</sub>SOCH<sub>3</sub> + NaH → CH<sub>3</sub>SOCH<sub>2</sub><sup>−</sup>Na<sup>+</sup> + H<sub>2</sub> |
|
|
:CH<sub>3</sub>SOCH<sub>3</sub> + NaNH<sub>2</sub> → CH<sub>3</sub>SOCH<sub>2</sub><sup>−</sup>Na<sup>+</sup> + NH<sub>3</sub> |
|
|
|
|
|
==Reactions== |
|
|
|
|
|
===As a base=== |
|
|
The pK<sub>a</sub> of DMSO is 35, which leads NaDMSO to be a powerful ]. NaDMSO is used in the generation of ] and ] ]s.<ref>{{cite journal |title = An asymmetric route to enantiomerically pure 1,2,3-trisubstituted cyclopropanes | journal = ] | year = 1992 | volume = 57 | pages = 6265–6270 | doi = 10.1021/jo00049a038 |author1 = Romo, D. |author2 = Myers, A. I. |issue = 23}}</ref> NaDMSO in DMSO is especially convenient in the generation of ] and ].<ref name="Corey1965" /><ref>{{cite book | author = ]; Melvin, L. S., Jr. | title = Sulfur Ylides: Emerging Synthetic Intermediates | publisher = ] | location = New York | year = 1975 | isbn = 0-12-701060-2}}</ref> |
|
|
|
|
|
===Reaction with esters=== |
|
|
NaDMSO ]s with ]s ('''1''') to form β-ketosulfoxides ('''2'''), which can be useful intermediates.<ref>{{cite journal |title = One-pot synthesis of β-keto sulfones and β-keto sulfoxides from carboxylic acids | journal = ] | 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}}</ref> Reduction of β-ketosulfoxides with ] gives ] ]s ('''3''').<ref>{{cite journal | title = 1,4-Dipole-metalated quinone strategy to (±)-4-demethoxydaunomycinone and (±)-daunomycinone. Annelation of benzocyclobutenedione monoketals with lithioquinone bisketals | journal = ] | 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}}</ref> Reaction with alkyl halides followed by ] gives α,β-unsaturated ketones ('''4'''). β-ketosulfoxides can also be used in the ] to introduce ]s alpha to a ] ('''5''').<ref>{{cite journal | journal = ] | 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 }}</ref> |
|
|
|
|
|
:] |
|
|
|
|
|
==References== |
|
|
{{Reflist}} |
|
|
|
|
|
==External links== |
|
|
* {{cite web | publisher = ] | 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}} |
|
|
|
|
|
] |
|
|
] |