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Revision as of 13:22, 3 December 2010 editCheMoBot (talk | contribs)Bots141,565 edits Updating {{chembox}} (no changed fields - added verified revid - updated 'UNII_Ref', 'ChemSpiderID_Ref', 'StdInChI_Ref', 'StdInChIKey_Ref') per Chem/Drugbox validation (report [[Wikipedia_talk:Wi← Previous edit		Latest revision as of 02:35, 23 October 2024 edit undoCitation bot (talk | contribs)Bots5,418,843 edits Add: isbn, pmid. | Use this bot. Report bugs. | Suggested by Dominic3203 | Category:Reagents for organic chemistry | #UCB_Category 144/228
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			{{primary|date=December 2022}}
	{{chembox		{{chembox
			| Watchedfields = changed
	| verifiedrevid = 400306419		| verifiedrevid = 400307579
	|ImageFile=Methanesulfonic anhydride.png		| ImageFile = Methanesulfonic anhydride.svg
	|ImageSize=150px		| ImageSize = 160
	|IUPACName=methylsulfonyl methanesulfonate
			| ImageAlt = Skeletal formula
⚫	|OtherNames=methanesulfonic acid methylsulfonyl ester
			| ImageFile1 = Methanesulfonic-anhydride-3D-balls.png
			| ImageSize1 = 190
			| ImageAlt1 = Ball-and-stick model
			| PIN=Methanesulfonic anhydride
		⚫	| OtherNames=methanesulfonic acid methylsulfonyl ester
	|Section1={{Chembox Identifiers		|Section1={{Chembox Identifiers
	| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}		| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
	| ChemSpiderID = 73591		| ChemSpiderID = 73591
	| InChI = 1/C2H6O5S2/c1-8(3,4)7-9(2,5)6/h1-2H3		| InChI = 1/C2H6O5S2/c1-8(3,4)7-9(2,5)6/h1-2H3
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	| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}		| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
	| StdInChIKey = IZDROVVXIHRYMH-UHFFFAOYSA-N		| StdInChIKey = IZDROVVXIHRYMH-UHFFFAOYSA-N
			| CASNo_Ref = {{cascite|correct|??}}
	| CASNo=7143-01-3		| CASNo=7143-01-3
			| UNII_Ref = {{fdacite|correct|FDA}}
⚫	| PubChem=81560
			| UNII = J492U7J4PB
⚫	| SMILES = O=S(=O)(OS(=O)(=O)C)C
		⚫	| PubChem=81560
		⚫	| SMILES = O=S(=O)(OS(=O)(=O)C)C
	}}		}}
	|Section2={{Chembox Properties		|Section2={{Chembox Properties
			| C=2|H=6|O=5|S=2
	| Formula=C<sub>2</sub>H<sub>6</sub>O<sub>5</sub>S<sub>2</sub>
		⚫	| Appearance=White solid
	| MolarMass=174.20 g/mol
			| Density= 0.92 g/ml<ref>{{cite journal|last1=Wachtmeister|first1=C. A.|last2=Pring|first2=B.|last3=Osterman|first3=Siv|last4=Ehrenberg|first4=L.|last5=Brunvoll|first5=J.|last6=Bunnenberg|first6=E.|last7=Djerassi|first7=Carl|last8=Records|first8=Ruth|title=The Synthesis of Some Tritium-labelled Mutagenic Alkyl Alkanesulfonates.|journal=Acta Chemica Scandinavica|date=1966|volume=20|pages=908–910|doi=10.3891/acta.chem.scand.20-0908|doi-access=free}}</ref>
⚫	| Appearance=
			| MeltingPtC= 69.5-70
	| Density=
			| MeltingPt_ref =<ref name =Field>{{cite journal|last1=Field|first1=Lamar|last2=Settlage|first2=Paul H.|title=Alkanesulfonic Acid Anhydrides|journal=Journal of the American Chemical Society|date=March 1954|volume=76|issue=5|pages=1222–1225|doi=10.1021/ja01634a005}}</ref>
	| MeltingPt=
	| BoilingPt=		| BoilingPt=
	| Solubility=		| Solubility=]
			| SolubleOther = Soluble in most aprotic organic solvents
	}}		}}
	|Section3={{Chembox Hazards		|Section3={{Chembox Hazards
	| MainHazards=		| MainHazards=
	| FlashPt=		| FlashPt=
			| AutoignitionPt =
	| Autoignition=
	}}		}}
	}}		}}
	'''Methanesulfonic anhydride''' is an is the ] of ]. Like ], it may be used to generate ] (methanesulfonyl esters).		'''Methanesulfonic anhydride''' ('''Ms<sub>2</sub>O''') is the ] of ]. Like ] (MsCl), it may be used to generate ] (methanesulfonyl esters).
			==Preparation & purification==
			Ms<sub>2</sub>O may be prepared by the dehydration of ] with ].<ref name=Field />
			:P<sub>2</sub>O<sub>5</sub> + 6 CH<sub>3</sub>SO<sub>3</sub>H → 3 (CH<sub>3</sub>SO<sub>2</sub>)<sub>2</sub>O + 2 H<sub>3</sub>PO<sub>4</sub>
			Ms<sub>2</sub>O can be purified by distillation under vacuum (distillation of a solid) or by recrystallization from ]/].
			==Reactions & Applications in synthesis==
			Passage of ] through molten Ms<sub>2</sub>O yields MsCl.<ref>{{cite journal |last1=Field |first1=Lamar |last2=Settlage |first2=Paul H. |title=Reaction of Methanesulfonic Anhydride with Hydrogen Halides 1 |journal=Journal of the American Chemical Society |date=January 1955 |volume=77 |issue=1 |pages=170–171 |doi=10.1021/ja01606a053 |url=https://pubs.acs.org/doi/10.1021/ja01606a053 |language=en |issn=0002-7863}}</ref>
			Similar to MsCl, Ms<sub>2</sub>O can perform ] of ] to form ]. Use of Ms<sub>2</sub>O avoids the alkyl chloride, which often appears as a side-product when MsCl is used.<ref>{{cite journal |last1=Baumann |first1=W. J. |last2=Jones |first2=L. L. |last3=Barnum |first3=B. E. |last4=Mangold |first4=H. K. |title=The formation of alkyl and alkenyl methanesulfonates and their reduction to hydrocarbons |journal=Chemistry and Physics of Lipids |date=1 November 1966 |volume=1 |issue=1 |pages=63–67 |doi=10.1016/0009-3084(66)90008-9 |url=https://www.sciencedirect.com/science/article/abs/pii/0009308466900089 |language=en |issn=0009-3084}}</ref> Unlike MsCl, Ms<sub>2</sub>O may not be suitable for mesylation of the ] alcohols.<ref name="cegla">{{cite journal |last1=Cegla |first1=Gad |last2=Mangold |first2=Helmut K. |title=A new procedure for the preparation of alkyl methanesulfonates |journal=Chemistry and Physics of Lipids |date=1 May 1973 |volume=10 |issue=4 |pages=354–355 |doi=10.1016/0009-3084(73)90059-5 |url=https://www.sciencedirect.com/science/article/abs/pii/0009308473900595 |language=en |issn=0009-3084}}</ref>
			Examples of mesylation of alcohols with Ms<sub>2</sub>O:
			* Octadecyl methanesulfonate was prepared from ] in ].<ref name="cegla" />
			* Secondary alcohol at the anomeric carbon of 2,3,4,5-O-]-protected ] reacted to form a glycosyl mesylate, which was found to be more stable than its ] counterpart, in ].<ref>{{cite journal |last1=Leroux |first1=Jacques |last2=Perlin |first2=Arthur S. |title=Synthesis of glycosyl halides and glycosides via 1-O-sulfonyl derivatives |journal=Carbohydrate Research |date=1 November 1978 |volume=67 |issue=1 |pages=163–178 |doi=10.1016/S0008-6215(00)83739-8 |url=https://www.sciencedirect.com/science/article/abs/pii/S0008621500837398 |language=en |issn=0008-6215}}</ref>
			Ms<sub>2</sub>O also converts ] to ].<ref>{{cite journal |last1=Lis |first1=Randall |last2=Morgan |first2=Thomas K. |last3=Marisca |first3=Anthony J. |last4=Gomez |first4=Robert P. |last5=Lind |first5=Joan M. |last6=Davey |first6=David D. |last7=Phillips |first7=Gary B. |last8=Sullivan |first8=Mark E. |title=Synthesis of novel (aryloxy)propanolamines and related compounds possessing both class II and class III antiarrhythmic activity |journal=Journal of Medicinal Chemistry |date=October 1990 |volume=33 |issue=10 |pages=2883–2891 |doi=10.1021/jm00172a033 |pmid=1976812 |url=https://doi.org/10.1021/jm00172a033 |language=en |issn=0022-2623}}</ref>
			===Aromatic sulfonation===
			Assisted by ], ] methylsulfonation of ] can be achieved by Ms<sub>2</sub>O. In contrast to MsCl, either ] ] derivatives can form the corresponding sulfonatesin satisfactory yields with Ms<sub>2</sub>O.<ref name="vaillan">{{cite journal |last1=Vaillancourt |first1=Valerie |last2=Cudahy |first2=Michele M. |title=Methanesulfonic Anhydride |journal=Encyclopedia of Reagents for Organic Synthesis |date=15 April 2001 |pages=rm068 |doi=10.1002/047084289x.rm068 |url=https://onlinelibrary.wiley.com/doi/10.1002/047084289X.rm068 |publisher=John Wiley & Sons, Ltd |isbn=0-471-93623-5 |language=en}}</ref>
			Examples of aromatic sulfonation with Ms<sub>2</sub>O:
			* Sulfonation of ] resulted in addition of methylsulfonyl group at ] (with respect to chloride), with a ratio of 2 to 1, respectively; while reaction with ] gave monosulfonylated product at C4 position.<ref name="vaillan" />
			* With ], di-aryl sulfones were synthesized.<ref>{{cite journal |last1=Tyobeka |first1=Themba E. |last2=Hancock |first2=Richard A. |last3=Weigel |first3=Helmut |title=Novel sulphonylating reagent: sulphuric acid–hexafluoroacetic anhydride |journal=Journal of the Chemical Society, Chemical Communications |date=1 January 1980 |issue=3 |pages=114–115 |doi=10.1039/C39800000114 |url=https://pubs.rsc.org/en/content/articlelanding/1980/c3/c39800000114 |language=en |issn=0022-4936}}</ref>
			===Esterification===
			Ms<sub>2</sub>O catalyzes the esterification of alcohols by carboxylic acids. ] was prepared from ] and glacial (anhydrous) ] in the presence of '''Ms<sub>2</sub>O'''. Both ] on ] successfully ] with ] and Ms<sub>2</sub>O. However, for free alcohols on ], the ] was not completed.<ref name=Field />
			===Oxidation of alcohols===
			Like ] and ], with ], Ms<sub>2</sub>O can ] ] and ] to ] and ], respectively, in ].<ref name="albright">{{cite journal |last1=Albright |first1=J. Donald |title=Sullfoxonium salts as reagents for oxidation of primary and secondary alcohols to carbonyl compounds |journal=The Journal of Organic Chemistry |date=June 1974 |volume=39 |issue=13 |pages=1977–1979 |doi=10.1021/jo00927a054 |url=https://pubs.acs.org/doi/pdf/10.1021/jo00927a054 |language=en |issn=0022-3263}}</ref> This method applies to benzylic alcohol.<ref name="albright" /> ] may be substituted by ] but may result in more side-products.<ref name="albright" />
			==See also==
			* ]
			* ]
			* ]
			* ]
			* ]
			==References==
			{{Reflist}}
	]		]
	]		]
			]
	]