高锰酸钾氧化马鞭草烯酮的研究

高锰酸钾氧化马鞭草烯酮的研究 第31卷第5期 2011年10月 林产化学与工业 ChemistryandIndustryofForestProducts VoI.3lNo.5 0ct.2011 OxidationofVerbenonewithPotassium Permanganate SUNXiao—ling,WANGRui (1.SchoolofChemicalandEnvironmentalEngineering,ShanghaiInstituteof Technology,Shanghai200235,China;2.CollegeofFoodScienceand Technology,ShanghaiOceanUniversity,Shanghai201306,China) Abstract:Effectsofreactiontemperature,reactiontime,potassiumpermanganateamountandratiooface— SUNXiao-lingticacidtowateronpreparationofpinononicaicdbyoxidationofverben0newithpotassiumpemanganate wereinvestigated.Theresultsshowedthatbykeepingthemolarratioof(+)一 verbenonetopotassiumpermanganateas1:4,reac— tiontemperature10?,reactiontime2handtheratioofaceticacidtowater10:1,theyieldof(+)一pinononicacidreached 77%.Furthermore.theeffectofsilicagelasasupportonthisreactionwasalsodiscussed.Theresultsshowedthattakingsilica gel— supportedpotassiumpermanganateasoxidant.theyieldofthetargetproductcouldbeincreasedto81%. Keywords:verbenone;oxidations;pinononicacid;potassiumpermanganate CLCnumber:TQ351Documentcode:AArticleID:0253—2417(2011)05一O095—05 高锰酸钾氧化马鞭草烯酮的研究 孙小玲,王蕊 (1.上海应用技术学院化学与环境学院,上海200235;2.上海海洋大学食品学院, 上海201306) 摘要:考察了反应温度,反应时间,高锰酸钾用量,乙酸与水溶液体积比对高锰酸钾 氧化马鞭草烯酮制备低蒎酮酸的影 响,研究结果表明:控制原料与高锰酸钾的物质的量比1:4,反应温度10?,反应时间 2h,乙酸与水溶液体积比10:1,得 到低蒎酮酸的收率77%.讨论了硅胶作为载体对此实验的影响,结果显示使用硅胶 一高锰酸钾作为氧化剂,目标产物的 产率可提高到81%. 关键词:马鞭草烯酮;氧化;低蒎酮酸;高锰酸钾 Inrecentyears,(+)-verbenone(1)[(+)一4,6,6-trimethyl—bicyclo[3.1.1]一3-heptene-2 一ketone]has beenusedwithincreasing~equencyasaconvenient"chiralpool"startingmaterialforenantio specificnatural productsynthesisandforthepreparationofchiralligandsfortransitionmetalsl1-3].Itsoxidat ionproduct, (+)一pinononicacid(2)[(+)一1,3S一3一acetyl一 2,2-dimethylcyclobutanecarboxylicacid]isalsoanimportant pharmaceuticalandpesticideintermediate.Forinstance,itcouldbeconvertedtocyclobutyld ehydroamino acids[. T-aminoacids[]andsomeinsectsexpheromonescontaining4-memberedring[一.Aconveni ent methodforthepreparationof(+)-pinononicacidisoxidativecleavageofthedoublebondof(+) 一verbenone. AlthoughRuC12/NaIO4E6,83andozonecouldbeenusedinratherhighyield , potassiumpermanganate (KMnO4)isoneofconvenientandefficientreagentsforroutineoxidativecleavageofcarbon—carbondouble bonds.Sinceitischeap,effective,environmenta1.friendly,ithasgainedimportanceingreenchemistry一l2]. 收稿日期:2010—12—13 基金项目:上海市重点学科建设基金资助项目(J1503);上海市教委研究生创新能 力培养专项资金项目(YC200905);上海应用技术 08) 学院科技发展基金(KJ2008— 作者简介:孙小玲(1962一),女,江苏泰兴人,教授,博士,硕士生导师,主要从事有机合 成及绿色化学等研究工作; E?mail:xiaolingsun@sit.edu.cn. 林产化学与工业第31卷 Inthispaper,takingpotassiumpermanganateasthereagentforoxidativecleavageofverbenone,allparame— tersincludingreagentamount,reactiontime,reactiontemperature,andsolventratiowerestudiedinorderto optimizethereactionconditions. 1Experimental 1.1Reagentandinstrument Allanalyticalgradereagentsandsolventsexcept(+)一 verbenonewerepurchasedcommerciallyandused withoutfurtherpurification.(+)一 Verbenone(98%)waspurchasedfromAldrichChemicalCompany. GC9790一 IIGaschromatographwasusedtofollowthetracksofoxidationreactionandanalyzereaction productqualitativelyandquantitatively.Agilent5975CGaschromatography-massspectrometry,Magana—IR 500FouriertransforminfraredrayandVarianmercury一 300(300MHz)nuclearmagneticresonancespectrome— terwereappliedtoconfirmtheoxidationproducts. 1.2Method ReactionofverbenonewithKMnO4:(+)一 Verbenone(1,2.00g,13.3mmo1)wasdissolvedinamix— tureofaceticacidandwater(volumeratio10:1),followedbyportion— wiseadditionofKMnO4(8.41g, 53.2mmo1)over0.5h.Themixturewasstirred(1.5h),andthenthereactionwasstopped.Na2CO3 (10g,94.3mmo1)wasaddedandthenfiltered,thefiltratewasextractedwithethylacetate(3× 15mL). Thecombinedorganicswascollected.TheaqueouslayerwasacidifiedtopHvalue2withhydrochloricacid andagainextractedwithmethylenechloride(3× 10mL).TheorganicslayerwasdriedwithNa2SO4, filtered,andconcentratedwitharotaryevaporator.Thecruderesiduewasdriedundervacuumtoobtain pinononicacid1ofmorethan90%purity.IR(,cm):3218(COOH),2962(C—H),1715(c一 0), 1690(c一0).HNMR(300MHz,CDC1):6:0.95[s,3H],1.43[s,3H],1.89[dt,lH],2.05[s, 3H],2.61[m,1H],2.75[dd,1H],2.81[dd,1H],7.2[bs,1H].MS:m/z171,152,128,109,83, 43.AlldateweI.eagreedwiththeliterature[]. 2ResultsandDiscussion 2.1Mechanismofreaction Permanganateoxidationsofalkenesandtheirderivativeshavebeensuggestedtobeassociatedwitha cyclicmanganese(V)intermediate".Instronglyacidicmedia,thedouble— bondcleavageOccurscompletely, atthesametime.C—HbondsonC— Cdoublebondsareoxidativelycleavedtooxygenatedcompounds-- ketones0racids['. Accordingtothemechanismofalkenesoxidationswithpotassiumpermanganate,wecouldinferthatthe mechanismofpotassiumpermanganateoxidationof(+)一verbenonewasasfollowes: H H3C H H3C MnO; . =H H3C 第5期孙小玲,等:高锰酸钾氧化马鞭草烯酮的研究97 2.2Optimizationofreactionconditions Singlefactorexperimentswereusedtoidenti~theoptimalconditions.Fourimportantparameterswere discussedtoestimatetheoptimumconditionsforthesynthesisof(+)一 pinononicacid,namely,molarratioof (+)一 verbenonetoKMn04,reaetiontemperature,reactiontime,andvolumeratioofaceticacidtowater?The detailinfl0邢 ation0fthesinglefactorexperimentsisgiveninFig.1,whichincludestheinitialconditionsof eachentryandtheresultsobtainedafterperformingtheexperiments? Theureliminaryexperimentswereconductedintherangeof1.0— 3.0htodeterminetheoptimumreac— tiontimefortheoxidati0nwithKMnO4undertheconditionsofKMnO4toverbenoemolarratio4:1,reaction temperature10oC,aceticacidtowatervolumeratio3:1.Fig.1(a)showsthatthemostfavorabletimeis2h, atthattimetheyieldof(+).pinononicacidisthehighest.However,theyieldstartedtodecreasewhenthe reactiontimewasmorethan2h.Therefore,insubsequententries,theinitialreactiontimewassteadily2h? Acc0rdingtotheoxidationmechanism,theoxidativeabilityofKMnO4inacidicmediaisstrongerthan thatinothermedia.Therefore,undertheconditionsofKMnO4toverbenonemolarratio4:1,reactiontempera. ture10? reactiontime2.0h,weincreasedvolumeratioofaceticacidtowaternamelyacidityofsystem? Asthevo1umeratiointhereactionsystemincreases,theoxidativeabilityofKMnO4alsoincreases,thuslead. ingtotheincreasingoftheyield.FromFig.1(b),itcanbeseenthat10:1isthebestmolarratioofacetlc acidtowater.However,whentheratioisover10:1andthecontentofthewaterisinadequate,thereaction equilibriumcouldnotbepromotedrightwardstostartthereactioninthehomogeneoussystem,thatiswhythe yieldofproductsdecreasesatlast. Changingthereacti0ntemperatureundertheconditionsofKMnO4toverbenonemolarratio4:1,acetic acidtowatervolumeratio10:1,reactiontime2.0h,theresultwasshowninFig.1(c).Fig.1(c)shows thatthebestresuhswereobtainedat10c 【=.Adecreaseoftheproductyieldwillresultinanincreaseinthe reactiontemperature.Thereas0nisthatthereactionisanexothermicreaction.Withthewholereactioncarried through.0therimpuritiesoccurowingtotheexcessivelyhightemperature.Consequently,wechose10as theoptimalreactiontemperature. Assh0wninFig.1(d),thechangeoftheyieldissimilartothatinFig.1(c).Byvaryingthemolarratio flr0m2:1to6:1underthec0nditionsofreactiontemperature10?,aceticacidtowatervolume ratio10:1, reacti0ntime2.0h.theyieldincreasesatthebeginning,butafterreachingthemaximumvalueitstartstode. crease. ItwasreportedthatKMnO4impregnatedoneithersilicagel,oralumina,asaheterogeneousoxidant,can beeffectivelvusedtocleavecarbon.carbondoublebondundermildconditionwithgoodyield一1".Sowe tookthesilicage1-supportedKMnO4astheheterogeneousoxidantfortheoxidationof(+).verbenoneto(+)一 pinononicacid. Effects0fsiliea只 e1onoxidationofverbenonewasshowninTable1undertheconditionsofKMnO4tover— ben0nem01arrati04i1.reactiontemperature10?,aceticacidtowatervolumeratio10:1,reac tiontime 2.0h.ComparedwiththeexperimentNo.1(theconversionofverbenonewasupto100%,andtheyieldof (+)一 pinononicacidwas77%),theresultsinTable1showthattheyieldofthetargetproductusingsilicagel. supponedKMnO4isalittlehigher(reach81%).Thereactionconditionsaremilder,makingpost?treatment easier.Thedosageofsilicagelat1.32ggavetheoptimumquality.Thesimplicityofthismethod,thelow costofthereagent?theeaseofuseandverymildreactionconditionsmakethereagentsystemdescribedhere tobeveryattractive. 98林产化学与工业第31卷 '量 '暑 00.51.01.52.02.5 time/h temperature/oC 文 堡 互 .兰 O48 KMnO4/verbenone Fig?1Effectsofdifferentconditionsontheyield0f(+).pinononicacid Table1Effectsofsilicagelonoxidationofverbenone 3Conclusions (+)'Pinononicacidcouldbesynthesizedbyrapidoxidationof(+).verbenonewithKMn0inanacidic solution.Singlefactordesignexperimentsweredesignedtooptimizetheconditionsforobtaininghighyield. Theratioofaceticacidtowaterandtemperaturewereidentifiedasthemainfactorsaffectingtheyieldoftarget product.Theoptimalconditionsareasfollows:molarratioof(+).verbenonetoKMnO41:4,reactiontemper. ature10?,reactiontime2handtheratioofaceticacidtowater10:1. Underoptimalconditions.thecon. versionofverbenonewasupto100%andtheyieldof(+).pinononicacidcouldreach77%.Takingsilica gel-supposedKMnO4asoxidant,theyieldofthetargetproductreached81%. References [1]OHLOFFG,GIERSCHW.Accesstoopticallyactiveipsdieno|fromverbenone[J].Helvc himActa,1977,60(5):1496—1500. [2]MORIARTYKJ,ROGERSRD,PAQUETYELA.Stereoselectiveformationfroma(1S,5S).(一).verbenone—derivedcyclopentadieneofdimeric andmixedtitaniumandzirconiumdichloridecomplexes[J].Organometallics,1989,8:1512—1517. [3]lieLA0,ALVAREZLARENAA,BACEIREDOA,eta1.Highlystereoselectiveandeasysynthesisofenantiopuphosph0mnyl0ximnes『J].Tet— rahedroa:Asymmetry,2007,18(22):2617—2620. [4]AGUADOGP,MOGLIONIAG.Enantiodivergentsynthesisofcyclobutyl一 (z).d,JB.dehydro-ct-amin0aciddeftvativesflrnm(一).c一pin0nonic acid[JJ.Tetrahedron:Asymmetry,2003,14(2):217—223. [5]PABLODR,ALBERTINAGM,GRACIELAYM.Stereoseleetivesynthesisofchiralpreeurs0rstocyc1obutanecarh0cyclicnucleosi(Iesand a/一 .........,. r.............,.......,........,.......... —? 第5期孙小玲,等:高锰酸钾氧化马鞭草烯酮的研究 oligopeptides[J].Tetrahedron:Asymmetry,2003,14(2):193—195. [6]ZHANGAJ,NIEJ.Chiralsynthesisofmaconellio1.Anovelcyclobutanoidterpenealcoholfrompinkhibiscusmealybug,Maconellicoccushirsu— tus[J].TetrahedronLett,2004,45(51):9401-9403. [7]PASSAROLc,WEBSTERFX.Synthesisofthefemalesexpheromoneofthecitrusmealybug,Planococcuscitri[J].JAgricFoodChem,2004, 52:2896-2899. [8]AGUILERAJ,MOGLIONIAG,MOLTRASIOGY,eta1.Stereodivergentsynthesisofthefirstbis(cyclobutane)3'-dipeptidesandmixed3'-oli— gomers[J].Tetrahedmn:Asymmetry,2008,19(3):302-308. [9]KUKOVINETSOS,ZVEREVATI,KASRADZEVG.NovelsynthesisofPlanococcuscitripheromone[J].ChemNatCompd,2006,42(2):216 — 2l8. [10]ZANGYX,HACX,SHENDD,eta1.Studyonsynthesisof2-hydroxy-3?pinanonefromOr-pinene[J].ChemIndForestProd,2009,29(3): 69—72. [11]SUKALYAND,SABITAP,BHAYKM.Oxidationbypermanganate:Syntheticandmechanisticaspects[J].Tetrahedron,2009,65(4):707— 739. [12]AHMADS,PEIMANM,SOHEILAN.Greenoxidations.Theuseofpotassiumpermanganatesupportedonmanganesedioxide[J].Tetrahed- FOrt,2004,60(5O):11415-11420. [13]EUGENEY,FRANKWS.Oxidativedegradationandkineticsofchlorinatedethylenesbypotassiumpermanganate[J].JContainHydrol, 1999,37(3/4):343-365. [14]XIAWH,HACY,LIUZM.Studyonanewmethodforsynthesisofpinonieacid[J].ChemIndForestProd,2002,22(3):11-14. [15]MASY,SHENMM,HACY.Preparationofnopinicacidfrom-pineneinhomogeneoussystem[J].ChemIndForestProd,2007,27(2): l14-l16. [16]WANGWJ,DAIQH.Carbon— carbondoublebondcleavagebysilica-supportedpotassiumpermanganateunderconditionsfreeoforganic solvent[J].ChinJSynChem,2002,lO(5):422-424. [17]FERREIRAJ,CRUZWQ,VIEIRAPC.Carbon-carbondoublebondcleavageusingsolid—supportedpotassiumpermanaganateonsilicagel (J].JOrgChem,1987,52(16):3698-3699. 欢迎订阅2012年《黑龙江造纸》 《黑龙江造纸》是由黑龙江省造纸工业研究所,黑龙江省造纸学会主办的制浆造 纸综合性技术刊物,是中国学术 期刊综合评价数据库统计源期-D】,被中国期刊全文数据库全文收录,在"万方数据——数字化期刊群"全文上网,被《中 国核心期刊(遴选)数据库》收录. 该刊立足省内,报道国内外制浆造纸行业中科研,生产,经营,管理的先进技术,实践经验和市场信息,可供广大技术 工人,科技人员,管理干部及大专院校的师生参考.同时为方便各造纸厂,造纸机械厂及相关化工企业,该刊开办了广告 业务,欢迎刊登广告,将为您提供优良的服务. 《黑龙江造纸》为季刊,全年订价25元,订阅者请通过银行或邮局汇款至黑龙江省造纸工业研究所,《黑龙江造纸》 编辑部收.请写清楚订阅份数,单位名称,地址,邮编,电话和收件人的姓名及详细地址.编辑部地址:157013黑龙江省 牡丹江市光华街5号;开户行:牡丹江市工商银行阳明街支行;户名:黑龙江省造纸研究所有限公司;账号: 570;联系人:柳海燕;电话:0453—6320013;传真:0453—6331516;E.mail:hlj—zz@sina.con.