己二骏含爨西始不瑟垮燕;当嚣已凝、基蠹臻减少爨零露,己二鼗含薰鼗蒸零稼耩不变。麸瑟箍密了箕赣纯敷联淹:繇器酮蓄先经Baeyer-Vittiger惑偬患簸蠢内醋,己蠹蘸经零蕻、最终辍鼗袋聂二菠。
第四零中研究了30%的避鬣健飘为氯化剂,铸酸钠与草酸形成的络合物内催化剂,在无肖机溶剂、溅相转移倦化剂的条件下,氧化环己酮为己内酯的殿成。结暴表明,最佳夏应条{孛麓,鹤黧獭;革酸:环西酶:30%熬过糕讫辙酌耩尔窕为2,0:3,3;100:350,藏叠2℃下反应7小对,邑内醛懿产攀遮戮63.6%。用GC。MS跟踪了氧化过稷中渊种主要产物(环己酮、融内酯)含嫩随殷应时间购变化关系。由于该体系对环融酵、环己酗催化效果较好,本文同时鸯黎了谈落暴辩苍乙醺、3t-IHE(审一瓣麓wi,l’c嚣鑫烧一4-醇)、3翻{K(4+。磷蕊一l。l‘。二丽己浚.4,翳)、樟菰静辍讫凝艨。
第五蘩巾磷究了30%熬过襞稳辍瓷襞强裁,鹤骥镶与摹酸澎袋豹终念物湾壤稔裁,在嚣套爨溶裁、嚣穗转移壤偬裁浆条转下,襞毪苯Z;爨爻苯单酸麓菠旋。磅究表露,巍装售轰纛祭馋下(镶黢锻;莘夔:蓼艺蘩;30%游波糕钱鬣戆摩尔比为2.0{3.2:100:440,张90℃下反应24h),苯甲酸的收率为98.3%。用GC.MS跟踪了氧化过程中四种产物(苯乙烯、粼甲酸、1.苯整-l,2-己:髀、羟鏊苯乙黧)含量筵夏盔辩阕鹣燮缘焚燕,提窭了其畿健爨理尧蕊己爨畿镶魏落率酸可能经避两条途径。第一条逡缀灏#举乙烯酋先环氧化生成邵飘苯藏靛,游戴苯乙烷经水解生成
1.笨潦.1,2.忍二黼、1,苯基.1,2*如二醇进一滞氯化成羟撼=j;l皇己掰,羟基苯己酮再被氧化戚苯翠羧{第=条途径必:苯Z;烯环裁他生娥邵氯苯菇烧,嚣蓑苯己浣与避镐酸盐获盛擞麟二释肇运载纯臻,二簿单遗氧豫糨遴一涉生袋氧正离予(缺电子氧),缱褥蘩捺<t,2.弪基迁移)形成类戳拳镶醛绥襁,嚣戆拳解绘篷笨攀醛,苯零醛鬏嚣氧鬟:兔蕊擎骏。
关键诲:镄过鬟往臻,清涟氧耽,避鬣佬釜,繇己黧,基蠹蘸,蠢=酸,攀己黼,笨甲酸,3HHK,3HHE,笨乙酮,樟脑
雄
Greenoxidationwithaqueoushydrogenperoxidein
organicsyntheses
fifoMin
Zhang
mechanically
Abstract:Theoxidationreactionisoneofthemainreactionsinorganicsyntheses。Butvariousoxidantsincludingsexivalentchromiumcompounds,
potassiumpermanganate,concentratedsulfuricacid,nitricacidareallhazardousandexpensive.Withrespecttoenvironmentalandeconomicconsideration,
oxidantforwateristhesoleexpectedhydrogenperoxideisprobablythebest
byproduct.Howevertheinherentoxidativeactivityandstabili秒ofhydmgenperoxideisrelativelyloweratambienttemperatureandatnormalpHvalues,SOitisofinteresttOfindefficientandenvironmentallyacceptablecatalystsincludingCO—catalyststoimproveitsoxidationability.ThepreviousresearchinourlaboratoryandelsewhereshowedthattheperoxotungstateandperoxomolybadatearetWOkindsofeffieientcatalystsintheoxidationreactionusinghydrogenperoxideasoxidant,Alltheresearchi
ncludedinthisdissertafionisbasedontheideamentionedabove.
Inthesecondsectiontheoxidationofcyclohexanonetoadipicacidwith30%
aqueoushydrogenperoxidecatalyzedbycoordinationcompoundsystemwhichincludestheperoxotungstateformedinsitufromsodiumtungstatedihydrateandoxalicacidwithoutorganicsolventandhalideswasinvestigated.Itisfoundthattheoptimtmqconditionswerethatthereactionmixtureinamolarratioofsodiumtungstatedihydrate,oxalicacid,cyclohexanoneand30%aqueoushydrogenperoxideof2。0:3.3:100:350。andthemixturewasstirred越92℃for12hours,giving80.6%yieldofadipicacid。
Inthethirdsectionweanalyzedtheproductsoftheoxidationof
cyclohexanonetoadipieacidusingGC—MS(EI,CIsource).Themainproductsofthereactionwereanalyzedquantitativelyandqualitatively。强eoptimumconditions(molarratioofsodiumtungstatedihydrate,oxalicacid,cyclohexanoneand30%aqueoushydrogenperoxidewas2.0:3.3:100:3501weredefined.Otherproductsandthereactionintermediateswerecharacterizedtoo。Throughtheanalysis,weprovidedanewreasonablepathwayinwhichthereactiontookplacevia2-oxepanoneintermediatewhichdifferentfrompreviousones.Theprobable
derivationsofvariousbyproductswerealsodeduced.
Inthefourthsectionwestudiedtheoxidationofcyelohexanoneto2.oxepanonewith30%aqueoushydrogenperoxidecatalyzedbyperoxotungstatecomplexes
formedinsitufromsodiumtungstatedihydrateandoxalicacidwithoutorganicsolvent,halideandphasetransfercatalyst.Accordingtostudyingtheconditionsoftheoxidationreaction,suchastemperature,solvent.catalyst,oxalicacidandSOon,wefoundtheoptimumconditionisthatthereactionmixtureinamolarratiooftungstatedihydrate,oxalicacid,cyclohexanoneand30%H202of2.0:3.3:100:350.Themixturewasstirredat90~92。Cfor7hours。giving63.6%yieldof2-oxepanone.Duetotheexcellentcatalyticresultsofthesystemintheoxidationofcyclohexanol,cyclohexanone,wealsoapplyedthesystemtotheoxidationofacetophanone,camphor,3HHE(4’-propyl-【l,1’·bicyclohexyl】-4-01),3HHK(4'-propyl一【l,l’一bicyctohexyl]一4-one)。
Inthefifthsectiontheoxidationofstyrenetobenz
oicacidusing30%aqueoushydrogenperoxideasanoxidantcatalyzedbycoordinationcompoundsystemwhichrunway>act
includingtheperoxotungstateformedinsitufromsodium
tungstatedihydrateand
oxalicacidwithouthalidesandorganicsolventWaSdescribed+Bystudyingtheconditionsofthereactionincludingtemperature,solvent,catalyst,ligandetc.,theoptimumconditionsofthereactionsweregotten:molarratioofsodiumtungstatedihydrate,oxalicacid,styreneand30%aqueoushydrogenperoxideWaS2。O:3.2:100:440,andthetemperatureWaS92。C.Underthiscondition,themixtureWaSstirredfor24hours.giving98.3%yieldofbenzoicacid.Bas
edontheanalysisoftheproductsoftheoxidationofstyrenebyGC—MS(El,CIsource),weproposedthepossiblemechanismoftheoxidativereaction.Twoprospectiveschemeswereelucidatedthatitmaytakeplacethroughtwopathways,oneisviabenzylaldehydeintermediate,theotherisviaphenol-1,2-ethanediolintermediate.Theprobablederivationsofvariousbyproductswerealsodeduced.
Keywords:peroxotungstate,peroxomolybadate,tungstate,cleancatalytic,30%hydrogenperoxide,oxidation,cyclohexone,adipicacid,2-oxepanone,styrene,benzoicacid,4’-propyl—11,I’一bicyclohexyl]-4一ol,4’-propyl-【l,I’·bicyclohexyl]·4-one,camphor,acetophenone,mechanism
V
第一章文献综述
讯飞翻译机>football
一薅涛瓴佳裁避氧纯氯程有惑氧貔中盛霆熬酝究避震
醇类氧化为羰基化合物,酮类氧化为内酯、羧酸类化合物,烯烃环氧化为环氧化合物以凝烯键氧化断裂为羧酸、醛,在机合成讲究和工业妻巨产中具有重骤的意义。瑟蓠霉;理这些爱藏鹃氧魏裁有惑锰酸锷、铬羧及其褥生物、磷酸、蠹繁食氧酸盐、熹梳过酸等驻{,这些氧健裁不是成本暴赛,就是琢予剃弼发穰低,三废排放量大,严重威胁着人体健康和生态环境。在如今普遍提倡环境保护、绿甑化学、讲究原予经济性的年代,这些缺点已逐渐变锝越来越不可容忍。因此,研究翡开发薪静绿色氧毽方法露羲纯蒋系、窭瑶渣渣垒产基藏爻工效界察藉学赛静共谀。
过氧化氯(H202)作为氧化剂,由于其反应的唯~副产物艇水,反应后处理容爨,兹璩02在众多氧纯翅中残颖蕊豳。但由于魄趣水溶渡凫一葶孛中等活性鹪无援氧往熬,直接与袁秘彩反应对,反露天多藏两穗体系,氧穗效率燕+产熬蝗率不高;同时由于H202作为氧化剂熟稳定性差,搦受热或在许多金属离子、非金属离子、阉体微粒等存在下分解,使其反应范围受到限制。因此,寻求能够高效活疆氇02又不爱之分勰爨篷谴裁及秘筵链裁,遴一步攘宽葜疲霸莲蠢一鬟是近年来国簖上亿学科研霄研究的热点课避。迄今发现锚、钨、钌、锻、镊等嚣橇催化剂和钛硅分子筛对№02氧化反J敷媳有良好的催化作用,佩钳、锇等金属价臻昂贵,钛碴分子筛剑蛰圈难,不熊广泛应用。本文主要介绍避譬来钼、钨过飘鬣台耪蘧纯下,H202氧毽烯烃、醇、鹱、藁、蕊醚、及其它獒姒纯台耱蘸磷究避展。
sir
jobtitle
l醇的氧化
无论在蜜验室还怒程工韭生产中,醇鬟讴为穗皮豹羰基拖合物在毒瓤毡举中都是一类搬道要的基本的反应。为了嶷现这个目标,化学科学獬们使用不同的试蠢Ij对大量的氧化体系进行了研究。最早用I-1202氧化醇的是1979年,Jacobson殿箕台瘁者器}笈褒锤、鹊与六军基磷酸麟或邀考磷酸影袋鏊过襞配合物在琴酵中霹仲醇氧化商一定的催他作用,所用}{202的浓度为90%。TrostIal报道了在(NH4k.M07024催化下,30%H202在室温下可以将醇氧化,但催化剂几乎按化学训‘擞加入,反应对阈缳长,经往需要凡天。
随嚣霄荚这方匿斡磷究有不少壤遵降n}。毽爨鼹鹣02滚凌~黢较赛,需掩。2的用量也趟过化学计算擞很多,反成时间长,催化剂的催化活性低,绝大多数实
验都需裂氯代烃作溶剂,淑对人体殿环境相当有鬻。
铡{獠氍蕊{撸4端麓惩二零会端麓镳器零基量喾蒸羲夔氨缭蕊然纯型,谯遐蠹霪馨舂惑,零涎餐器泰孛,稳建襄蕊惑溶潼蠹—暴鼹蘸蔑莛曩禚藤瓣藜器蘩黧。簿于仲醇氧能为相应的酮,蕊选择性和il蹙率都很好,燎筒收率可滤97%;雨彳禽黼槭墩巍羧躐鼬峻率较低,只南52-87%;对于烯丙醇的溉化,该体黼只氧化羟耩,,鼠遵囊装黎磐。√麓+毪噬意淼;√0
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鬟滚惑瓣鬻蒸羹璃镪餐瑟袤基寒鬟攀莛鬟遂搭嫠。》强漆糕莓£臻蚕遂了器瞪T基硫酾熬铵为裙转裙催佬裁、裔潞溶帮和镑§淤襁辩条待下,00%毪魏戴豫蕊醇为羧酸(收率最高为84%),氧化伸蹲氧化为酮(艘高为97%)*该反应时间黼,
筵羹,辩藤爨霆参戮鼹蕊黎势势,t1)§}饕e
E穗躐S器bhabrata繁{4警溪惩龟黎簸豫;黪萱窝瓣聚转下,饔惑蔑懿奢饕觥鬻鏊上的活饿激选择性的氰化为相应的龄。其催化剂辅构如下所永;
军争篇就帮撼上碳氢键的蹴化来说。她体系比较添湖黹且选择蚀黼。但目前·遴粹巍弛具姊瓣理还苓泰撼憋n
聂瓣,蕤整羹誉2警黎蘧一系黧鸯0囊蘩蕊熬:蠢耋蘸懿辫莓筵襄曩狳糕营妨,在不谈用有税溶辩q鞍相转移掩诧帮爵谤蕊下,赛蕊-i-30%魄02氧穗繇撼孚氧化为琊B酮的反应,艇应产率高邀95%以上。㈣时该文还科巍了不同酉己锵;:的钨蘩鍪嚣蠹漆蓬霪蓑杰,聚蹇鎏象繇孵幂翼萋篓熬蠛鼗鎏瑟会躲髓憩霆秀不瓣,蒸孛鞋藩黎磷臻、摹蘩侉凝箨薅羲暴蠛襞,嚣基鬻蔽霉蠢鬟遮95”/;,簧嚣t