Wikipedia:WikiProject Chemicals/Chembox validation/VerifiedDataSandbox and 2-Methyltetrahydrofuran: Difference between pages

| Watchedfields = changed

| verifiedrevid = 477214694

| ImageFile = Methyltetrahydrofuran.svg

| ImageSize = 150px

| ImageAlt =

| PIN = 2-Methyloxolane

| OtherNames = 2-Methyltetrahydrofuran, 2-Methyl-THF

| Section1 = {{Chembox Identifiers

| index_label = ([[Racemic]])

| index1_label = (''R'')

| index2_label = (''S'')

| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}

| CASNo1 = 63798-13-0

| CASNo2 = 63798-12-9

| UNII_Ref = {{fdacite|correct|FDA}}

| UNII = FCD0VD8ALF

| PubChem = 7301

| EC_number = 202-507-4

| UNNumber = 2536

| ChEMBL = 1580503

| DTXSID = DTXSID9030258

| SMILES = O1C(C)CCC1

| Section2 = {{Chembox Properties

| C=5 | H=10 | O=1

| MolarMass =

| Appearance =

| Density = 0.854 g/mL

| MeltingPtC = -136

| MeltingPt_ref = <ref name = aycock/>

| BoilingPtC = 80.2

| BoilingPt_ref = <ref name = aycock/>

|Solubility = 21.0 wt% (0.0 °C)<br>17.8 wt% (9.5 °C)<br>14.4 wt% (19.3 °C)<br>11.4 wt% (29.5 °C)<br>9.2 wt% (39.6 °C)<br>7.8 wt% (50.1 °C)<br>6.6 wt%(60.7 °C)<br>6.0 wt% (70.6 °C)<ref>Sicaire, Anne-Gaëlle; Vian, Maryline Abert; Filly, Aurore; Li, Ying; Bily, Antoine; Chemat, Farid (2014), Chemat, Farid; Vian, Maryline Abert (eds.), "2-Methyltetrahydrofuran: Main Properties, Production Processes, and Application in Extraction of Natural Products", Alternative Solvents for Natural Products Extraction, Berlin, Heidelberg: Springer Berlin Heidelberg, pp. 253–268, doi:10.1007/978-3-662-43628-8_12, ISBN 978-3-662-43627-1</ref>}}

| Section3 = {{Chembox Hazards

| ExternalSDS = [http://msds.chem.ox.ac.uk/ME/2-methyltetrahydrofuran.html External MSDS]

| GHSPictograms = {{GHS02}}{{GHS05}}{{GHS07}}

| GHSSignalWord = Warning

| HPhrases = {{H-phrases|225|302|315|318|319|335|336}}

| PPhrases = {{P-phrases|210|233|240|241|242|243|261|264|270|271|280|301+312|302+352|303+361+353|304+340|305+351+338|310|312|321|330|332+313|337+313|362|370+378|403+233|403+235|405|501}}

| MainHazards =

| FlashPt =

| AutoignitionPt = }}

'''2-Methyltetrahydrofuran''' (2-MeTHF) is an [[organic compound]] with the molecular formula C₅H₁₀O. It is a highly flammable, mobile liquid. It is mainly used as a replacement for [[Tetrahydrofuran]] (THF) in specialized applications for its better performance, such as to obtain higher reaction temperatures, or easier separations (as, unlike THF, it is not [[miscible]] with water). It is derived from sugars via [[furfural]] and is occasionally touted as a [[biofuel]].<ref>{{cite journal |last1=Leal Silva |first1=Jean Felipe |last2=Mariano |first2=Adriano Pinto |last3=Maciel Filho |first3=Rubens |title=Economic potential of 2-methyltetrahydrofuran (MTHF) and ethyl levulinate (EL) produced from hemicelluloses-derived furfural |journal=Biomass and Bioenergy |volume=119 |issue=December 2018 |pages=492–502 |doi=10.1016/j.biombioe.2018.10.008 |year=2018|bibcode=2018BmBe..119..492L |s2cid=104836889 }}</ref>

==Structures and properties==

2-Methyltetrahydrofuran is "inversely soluble" in water. That is, its solubility decreases with increasing temperature, which is a rare property.<ref>{{Citation|last1=Sicaire|first1=Anne-Gaëlle|title=2-Methyltetrahydrofuran: Main Properties, Production Processes, and Application in Extraction of Natural Products|date=2014|work=Alternative Solvents for Natural Products Extraction|pages=253–268|editor-last=Chemat|editor-first=Farid|place=Berlin, Heidelberg|publisher=Springer Berlin Heidelberg|language=en|doi=10.1007/978-3-662-43628-8_12|isbn=978-3-662-43627-1|last2=Vian|first2=Maryline Abert|last3=Filly|first3=Aurore|last4=Li|first4=Ying|last5=Bily|first5=Antoine|last6=Chemat|first6=Farid|editor2-last=Vian|editor2-first=Maryline Abert}}</ref> The solubility of water in 2-methyltetrahydrofuran is reported to be 4.4 g/ 100 g at 23 °C.<ref>{{Cite web |title=Zeon Corporation |url=https://www.zeon.co.jp/business_e/enterprise/spechemi/cpme_tec_sup_e_200906.pdf |archive-url=https://web.archive.org/web/20110722102229/http://www.zeon.co.jp/business_e/enterprise/spechemi/cpme_tec_sup_e_200906.pdf |archive-date=2011-07-22 |access-date=2024-08-05}}</ref> Much like tetrahydrofuran, 2-methyltetrahydrofuran can act as a [[Lewis base]] in organometallic reactions.<ref name = aycock>{{cite journal | author = Aycock, David F. | title = Solvent Applications of 2-Methyltetrahydrofuran in Organometallic and Biphasic Reactions | journal = [[Org. Process Res. Dev.]] | year = 2007 | volume = 11 | pages = 156–159 | doi = 10.1021/op060155c}}</ref> 2-Methyltetrahydrofuran is usually produced as a [[racemic]] mixture.

==Preparation==

2-Methyltetrahydrofuran is usually synthesized by [[catalytic hydrogenation]] of [[furfural]].<ref>{{cite journal| doi =10.1021/cr068360d | pmid=16967928 | volume=106 | title=Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering | date=September 2006 | journal=Chem. Rev. | pages=4044–98 | last1 = Huber | first1 = GW | last2 = Iborra | first2 = S | last3 = Corma | first3 = A| issue=9 | url=https://works.bepress.com/cgi/viewcontent.cgi?article=1058&context=george_huber }} ref 306</ref>

:OC₄H₃CHO + 4 H₂ → OC₄H₇CH₃ + H₂O

Furfural is produced by the acid-catalyzed digestion of [[pentosan]] sugars, C₅ [[polysaccharide]]s, in [[biomass]]. Thus, the raw materials of 2-methyltetrahydrofuran are renewable biomass rich with [[cellulose]], [[hemicellulose]]s, and [[lignin]], such as corncobs or [[bagasse]] and other plant and agricultural waste.<ref>{{Ullmann | author = Hoydonckx, H. E. | author2 = Van Rhijn, W. M. | author3 = Van Rhijn, W. | author4 = De Vos, D. E. | author5 = Jacobs, P. A. | title = Furfural and Derivatives | doi = 10.1002/14356007.a12_119.pub2}}</ref>

2-Methyltetrahydrofuran can also be produced starting from [[levulinic acid]]. [[Cyclization]] and reduction gives [[gamma-valerolactone|γ-valerolactone]]:<!-- {{doi|10.1021/cr068360d}} p4084 and ref 294, and also refs in image-page -->

:[[File:Cyclization of levulinic acid.svg]]

[[Gamma-Valerolactone|γ-Valerolactone]] can be [[hydrogenated]] to 1,4-pentanediol, which can then be dehydrated to give 2-methyltetrahydrofuran:

:[[File:Reaction of Valerolactone to 2Me-THF.svg]]

==Applications==

2-Methyltetrahydrofuran is mainly used as a higher boiling substitute for tetrahydrofuran as a specialty [[solvent]]. It also is used in the [[electrolyte]] formulation for secondary [[lithium]] [[electrode]]s and as a component in [[alternative fuel]]s. It is a valued solvent for low-temperature reactions. 2-Methyltetrahydrofuran forms a glass, which does not crystallize, and is frequently used as a solvent for spectroscopic studies at −196&nbsp;°C.<ref name = aycock/>

Other common uses of 2-methyltetrahydrofuran is as a solvent for [[Grignard reaction|Grignard reagents]] used in organometallic and biphasic [[chemical process]]es, because of the [[oxygen]] atom's ability to coordinate to the [[magnesium]] ion component of the Grignard reagent, or to azeotropically dry products. The use of 2-methyltetrahydrofuran provides very clean organic water [[phase separation]]s. It is a popular, but costlier substitute for tetrahydrofuran.

2-Methyltetrahydrofuran <!-- has an [[octane number]] of 74 ({{doi|10.1021/cr068360d}} ref 305 maybe) or 87 ({{doi|10.1021/cr068360d}} itself, p4084). It --> is approved by the [[United States Department of Energy]] as an additive to gasoline. Furfural and other furyl compounds (furfuryl alcohol, methylfuran, tetrahydrofufuryl alcohol) have a tendency to polymerize and are quite volatile. 2-Methyltetrahydrofuran itself, however, is more stable and less volatile, and thus is suitable for use as a motor fuel.<!-- {{doi|10.1021/cr068360d}} ref 305 -->

2-Methyltetrahydrofuran has been promoted as an ecologically-friendly alternative to THF.<ref>{{cite web|url=https://www.sigmaaldrich.com/deepweb/assets/sigmaaldrich/product/documents/115/677/greener_solvent_alternatives.pdf |title=Greener Solvent Alternatives – Brochure |website=Sigmaaldrich.com |date= |accessdate=2010-02-15}}</ref> Whereas 2-MeTHF is more expensive, it may provide for greater overall process economy. 2-MeTHF has solvating properties that are intermediate between diethyl ether and THF, has limited water miscibility, and forms an [[azeotrope]] with water on distillation. Its lower melting point makes it useful for lower temperature reactions, and its higher boiling point allows procedures under reflux at higher temperatures (relative to THF).

== References ==

{{Reflist}}

* {{cite journal | last1 = Huber | first1 = George W. | last2 = Iborra | first2 = Sara | last3 = Corma | first3 = Avelino | year = 2006 | title = Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering | url = https://works.bepress.com/cgi/viewcontent.cgi?article=1058&context=george_huber| journal = Chemical Reviews | volume = 106 | issue = 9| pages = 4044–4098 | doi = 10.1021/cr068360d | pmid=16967928}}

==Further reading==

* {{cite journal | author = Zheng, Hong-Yan | title = Towards understanding the reaction pathway in vapour phase hydrogenation of furfural to 2-methylfuran | journal = Journal of Molecular Catalysis A: Chemical| doi = 10.1016/j.molcata.2005.10.003 | year = 2006 | last2 = Zhu | first2 = Yu-Lei | last3 = Teng | first3 = Bo-Tao | last4 = Bai | first4 = Zong-Qing | last5 = Zhang | first5 = Cheng-Hua | last6 = Xiang | first6 = Hong-Wei | last7 = Li | first7 = Yong-Wang | volume = 246 | issue = 1–2 | pages = 18–23}}

* https://cms.chempoint.com/ChemPoint/media/ChemPointSiteMedia/Emails/MeTHF-System-Advantages-in-Organometallic-Chemistry-and-Biphasic-Reactions.pdf

{{DEFAULTSORT:Methyltetrahydrofuran, 2-}}

[[Category:Tetrahydrofurans]]

[[Category:Ether solvents]]