| 词条 | Dioxolane |
| 释义 |
| Verifiedfields = changed | Watchedfields = changed | verifiedrevid = 444710218 | Reference=[1] | Name = Dioxolane | ImageFileL1 = 1,3-dioxolane-2D-skeletal.png | ImageFileR1 = 1,3-dioxolane-3D-balls.png | IUPACName = Dioxolane | OtherNames = 1,3-dioxolane, formal glycol[2] | Section1 = {{Chembox Identifiers | ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}} | ChemSpiderID = 12066 | PubChem = 12586 | ChEBI_Ref = {{ebicite|changed|EBI}} | ChEBI = 87597 | InChI = 1/C3H6O2/c1-2-4-5-3-1/h1-3H2 | InChIKey = SNQXJPARXFUULZ-UHFFFAOYAS | StdInChI_Ref = {{stdinchicite|correct|chemspider}} | StdInChI = 1S/C3H6O2/c1-2-4-5-3-1/h1-3H2 | StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} | StdInChIKey = SNQXJPARXFUULZ-UHFFFAOYSA-N | CASNo_Ref = {{cascite|correct|CAS}} | CASNo = 646-06-0 | SMILES = O1CCOC1 }} | Section2 = {{Chembox Properties | Formula = C3H6O2 | MolarMass = 74.08 g/mol | Density = 1.06 g/cm3 | MeltingPtC = -95 | BoilingPtC = 75}} }} Dioxolane is a heterocyclic acetal with the chemical formula (CH2)2O2CH2. It is related to tetrahydrofuran by interchange of one oxygen for a CH2 group. The corresponding saturated 6-membered C4O2 rings are called dioxanes. The isomeric 1,2-dioxolane (wherein the two oxygen centers are adjacent) is a peroxide. 1,3-Dioxolane is used as a solvent and as a comonomer in polyacetals. As a class of compoundsDioxolanes are a group of organic compounds containing the dioxolane ring. Dioxolanes can be prepared by acetalization of aldehydes and ketalization of ketones with ethylene glycol.[3](+)-cis-Dioxolane is the trivial name for L-(+)-cis-2-methyl-4-trimethylammoniummethyl-1,3-dioxolane iodide which is a muscarinic acetylcholine receptor agonist. Protecting groupsOrganic compounds containing carbonyl groups sometimes need protection so that they do not undergo reactions during transformations of other functional groups that may be present. A variety of approaches to protection and deprotection of carbonyls[4] including as dioxolanes[4] are known. For example, consider the compound methyl cyclohexanone-4-carboxylate, where lithium aluminium hydride reduction will produce 4-hydroxymethylcyclohexanol. The ester functional group can be reduced without affecting the ketone by protecting the ketone as a ketal. The ketal is produced by acid catalysed reaction with ethylene glycol, the reduction reaction carried out, and the protecting group removed by hydrolysis to produce 4-hydroxymethylcyclohexanone. NaBArF4 can also be used for deprotection of acetal or ketal-protected carbonyl compounds.[5][4] For example, deprotection of 2-phenyl-1,3-dioxolane to benzaldehyde can be achieved in water in five minutes at 30 °C.[6]PhCH(OCH2)2 + H2O Natural productsNeosporol is a natural product that includes a 1,3-dioxolane moiety, and is an isomer of sporol which has a 1,3-dioxane ring.[7] The total synthesis of both compounds has been reported, and each includes a step in which a dioxolane system is formed using trifluoroperacetic acid (TFPAA), prepared by the hydrogen peroxide – urea method.[8][9] This method involves no water, so it gives a completely anhydrous peracid,[10] necessary in this case as the presence of water would lead to unwanted side reactions.[8]{{chem|CF|3|COOCOCF|3}} + {{chem|H|2|O|2|•CO(NH|2|)|2}} → {{chem|CF|3|COOOH}} + {{chem|CF|3|COOH}} + {{chem|CO(NH|2|)|2}} In the case of neosporol, a Prilezhaev reaction[11] with trifluoroperacetic acid is used to convert a suitable allyl alcohol precursor to an epoxide, which then undergoes a ring-expansion reaction with a proximate carbonyl functional group to form the dioxolane ring.[8][9] A similar approach is used in the total synthesis of sporol, with the dioxolane ring later expanded to a dioxane system.[7] See also
References1. ^1,3-Dioxolane at Sigma-Aldrich 2. ^[https://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=12586 formal glycol - PubChem Public Chemical Database] 3. ^{{OrgSynth|author=R. A. Daignault, E. L. Eliel|year=1973|title=2-Cyclohexyloxyethanol (involves acetalisation of cyclohexanone)|volume=|pages=|collvol=5|collvolpages=303|prep=CV5P0303}} 4. ^1 {{cite book|chapter = 1,3-Dioxanes, 1,3-Dioxolanes|first1 = Theodora W.|last1 = Greene|first2 = Peter G. M.|last2 = Wuts|title = Greene's Protective Groups in Organic Synthesis|edition = 3rd|publisher = Wiley-Interscience|year = 1999|pages = 308–322, 724–727|url = https://www.organic-chemistry.org/protectivegroups/carbonyl/dioxanes-dioxolanes.htm|accessdate = June 20, 2017|isbn = 9780471160199|archive-date = December 7, 2016|dead-url = no|archive-url = https://web.archive.org/web/20161207144346/http://www.organic-chemistry.org/protectivegroups/carbonyl/dioxanes-dioxolanes.htm}} 5. ^1 {{cite book|chapter = Dimethyl acetals|first1 = Theodora W.|last1 = Greene|first2 = Peter G. M.|last2 = Wuts|title = Greene's Protective Groups in Organic Synthesis|edition = 3rd|publisher = Wiley-Interscience|year = 1999|pages = 297–304, 724–727|url = https://www.organic-chemistry.org/protectivegroups/carbonyl/dimethylacetals.htm|accessdate = June 20, 2017|isbn = 9780471160199|archive-date = December 3, 2016|dead-url = no|archive-url = https://web.archive.org/web/20161203200424/http://www.organic-chemistry.org/protectivegroups/carbonyl/dimethylacetals.htm}} 6. ^{{cite journal|title = Deprotection of Acetals and Ketals in a Colloidal Suspension Generated by Sodium Tetrakis(3,5-trifluoromethylphenyl)borate in Water|first1 = Chih-Ching|last1 = Chang|first2 = Bei-Sih|last2 = Liao|first3 = Shiuh-Tzung|last3 = Liu|journal = Synlett|year = 2007|volume = 2007|issue = 2|pages = 283–287|doi = 10.1055/s-2007-968009}} 7. ^1 {{cite book|url = https://books.google.com/books?id=OjO78KV6USAC&pg=PA222|chapter = 10. Neosporol, Sporol|pages = 222–224|series = The Total Synthesis of Natural Products|volume = 11|title = Part B: Bicyclic and Tricyclic Sesquiterpenes|editor1-first = Michael C.|editor1-last = Pirrung|editor2-first = Andrew T.|editor2-last = Morehead|editor3-first = Bruce G.|editor3-last = Young|publisher = John Wiley & Sons|year = 2000|isbn = 9780470129630}} 8. ^1 2 {{cite journal|last1 = Ziegler|first1 = Fredrick E.|last2 = Metcalf|first2 = Chester A.|last3 = Nangia|first3 = Ashwini|last4 = Schulte|first4 = Gayle|title = Structure and total synthesis of sporol and neosporol|journal = J. Am. Chem. Soc.|year = 1993|volume = 115|issue = 7|pages = 2581–2589|doi = 10.1021/ja00060a006}} 9. ^1 {{cite encyclopedia|doi = 10.1002/047084289X.rt254.pub2|encyclopedia = e-EROS Encyclopedia of Reagents for Organic Synthesis|title = Trifluoroperacetic Acid|first1 = Kenneth C.|last1 = Caster|first2 = A. Somasekar|last2 = Rao|first3 = H. Rama|last3 = Mohan|first4 = Nicholas A.|last4 = McGrath|first5 = Matthew|last5 = Brichacek|year = 2012}} 10. ^{{cite journal|title = Oxidation Reactions Using Urea–Hydrogen Peroxide; A Safe Alternative to Anhydrous Hydrogen Peroxide|journal = Synlett|year = 1990|volume = 1990|issue = 9|pages = 533–535|doi = 10.1055/s-1990-21156|first1 = Mark S.|last1 = Cooper|first2 = Harry|last2 = Heaney|authorlink2 = Harry Heaney|first3 = Amanda J.|last3 = Newbold|first4 = William R.|last4 = Sanderson}} 11. ^{{cite book|chapter = Prilezhaev reaction|pages = 274–281|last = Hagen|first = Timothy J.|url = https://books.google.com/books?id=WZ0DxnPNAdAC&pg=PA274|title = Name Reactions of Functional Group Transformations|editor1-first = Jie Jack|editor1-last = Li|editor2-first = E. J.|editor2-last = Corey|editor2-link = Elias James Corey|publisher = John Wiley & Sons|year = 2007|isbn = 9780470176504}} External links
4 : Dioxolanes|Muscarinic agonists|Solvents|Protecting groups |
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