经典合成反应标准操作Word下载.docx
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经典合成反应标准操作Word下载.docx
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e)硝基的还原
f)叠氮的还原
g)Hoffman降解
h)羧酸通过Cris重排
2.羧酸衍生物的合成
a)酰胺化的反应
b)酯化反应
c)腈转化为酯和酰胺
d)钯催化的插羰反应
e)酯交换为酰氨
3.羧酸的合成
a)醇氧化
b)酯水解
c)酰胺的水解
d)腈的水解
e)有机金属试剂的羰基化反应
f)芳香甲基的氧化
4.醛酮的合成
a)Weinreb酰胺合成醛酮
b)醇氧化
c)酯的直接还原
d)有机金属试剂对腈加成合成酮
5.脂肪卤代物的合成
a)醇转化为脂肪溴代物
通过PBr3转化
通过PPh3与CBr4转化
HBr直接交换
通过相应的氯代物或磺酸酯与LiBr交换、
b)醇转化为脂肪氯代物
通过SOCl2转化
通过PPh3与CCl4转化
HCl直接交换
c)醇转化为脂肪碘代物
通过PPh3与I2转化
通过相应的氯代物或磺酸酯与NaI交换
6.芳香卤代物的合成
a)Sandermyyer重氮化卤代
b)直接卤代
c)杂环的酚羟基或醚的卤代
7.醇的合成
a)羧酸或酯的还原
b)醛酮的还原
c)卤代烃的水解
d)吡啶的氧化转位
8.酚的合成
a)Sandermayer重氮化反应
b)醚的水解
c)Bayer-vigerlar氧化
d)硼酸的氧化
9.腈的合成
a)磺酸酯或卤代烃的取代
b)酰胺的脱水
c)芳卤代烃的氰基取代
10.硝化反应
11.醚的合成
a)芳香醚的合成
酚与烷基卤代烃的直接烷基化
Mitsunobu芳香醚化
Buckwald芳香醚化
b)脂肪醚的合成
醇的醚化
12.脲的合成
a)胺与异腈酸酯的反应
b)用三光气合成脲
c)羰基二咪唑(CDI)合成脲
d)对硝基苯酚碳酰胺合成脲
13.烯烃的合成
a)Wittig反应
b)羟基的消除
c)Wittig-Horner反应合成?
?
-不饱和酯
14.磺酸及磺酰氯的合成
a)氯磺化反应合成磺酰氯
b)从硫醇合成磺酰氯
c)磺化反应
15.氨基酸的合成
a)Streck反应合成
b)手性氨基酸的合成
16.偶联反应
a)SuzukiCoupling
b)Buckwald芳胺化,芳酰胺化、
c)Heck反应
17.Mitsunobu反应
a)醇的反转
b)胺的取代
18.脱羟基反应
19.酮还原为亚甲基
20.氨的保护及脱保护策略
a)用碳酰胺作保护基
b)苄基保护
21.醇的保护及脱保护策略
a)用硅醚进行保护
b)其他醚类保护
22.羧基的保护
Boc脱保护-------------------------------------------------------------------------------------------------------1
格氏反应---------------------------------------------------------------------------------------------------------1
还原胺化---------------------------------------------------------------------------------------------------------2
卤化反应---------------------------------------------------------------------------------------------------------2
Suzukicoupling-------------------------------------------------------------------------------------------------2
磺化反应---------------------------------------------------------------------------------------------------------3
酯化反应---------------------------------------------------------------------------------------------------------3
水解反应---------------------------------------------------------------------------------------------------------3
硝化反应---------------------------------------------------------------------------------------------------------4
n-BuLi------------------------------------------------------------------------------------------------------------4
LiAlH4还原-----------------------------------------------------------------------------------------------------4
POCl3的杂环氯代----------------------------------------------------------------------------------------------5
NaH---------------------------------------------------------------------------------------------------------------5
NBS---------------------------------------------------------------------------------------------------------------5
氢化反应---------------------------------------------------------------------------------------------------------6
m-CPBA----------------------------------------------------------------------------------------------------------6
EDC---------------------------------------------------------------------------------------------------------------6
用三光气成脲---------------------------------------------------------------------------------------------------7
芳卤用n-BuLi处理后与Weinreb酰胺成酮-----------------------------------------------------------------7
Boc上保护
ToasolutionofA(2.72g,13.9mmol)andtetramethylammoniumhydroxidepentahydrate(5.62g,31.0mmol)inacetonitrile(270mL)wasaddeddi-tert-butyldicarbonate(3.79g;
17.4mmol)andtheresultingsolutionwasallowedtostir18hatrtandconcentrated.atedtoafford2.58g(63percent)Basawhitefoam.
Return
Boc脱保护
Tert-Butyl2-(2-methoxyphenoxy)ethylcarbamate(23.8g,89mmol)indichloromethane(10ml)wascooledto0degCandstirredasamixtureoftrifluoroaceticacid:
dichloromethane(1:
1,40ml)wasaddeddropwise.Themixturewasallowedtowarmtort,stirredfor2hoursandconcentratedinvacuo.Theresiduewastakenbackupindichloromethane(100ml)andthesolutionwaswashedwithsaturatedaqueoussodiumhydrogencarbonate(3*20ml)andaqueoussodiumhydroxide(10percent,3*20ml),dried(Na2SO4),filteredandconcentratedinvacuotoprovide2-(2-methoxyphenoxy)ethylamine(13g,88percentyield)asalightyellowsolid.
格氏反应
Astirredmixtureofmagnesiumturnings(23.6g,0.98mol)andEt2O(200mL)undernitrogenistreatedwithacrystalofiodineandabout5percentofasolutionofbromoethane(56.3ml,0.75mol)inEt2O(375mL).Whenthereactionstarts,theremainderofthebromoethanesolutionisadded,dropwiseataratesufficienttomaintainagentlereflux.Aftertheaddition,stirringiscontinuedfor1hour.Tothissolutionofethylmagnesiumbromidewasslowlyaddedasolutionof4-cyanopyridine(39g,0.375mol)inEt2O(750ml).Thereactionmixturewaswarmedatrefluxfor12hours,treatedwithconcentratedH2SO4(125ml)/H2O(125ml),andthenwashedthreetimeswithEt2O(250ml).Theaqueousportionwasmadebasic(PH9)with15percentNaOHsolutionandextractedfivetimeswith250mlportionsofEt2O.ThecombinedEt2Oextractsweredried(MgSO4),andthesolventwasremovedunderreducedpressuretoaffordabrownoil(48.4g,95percent).
还原胺化
Asolutionof2-amino-4-ethylphenol(1.00g.7.28mmol),2-naphthaldehyde(1.13g,7.28mmol),andp-toluenesulfonicacid(0.05g)inmethanol(50ML)wasstirredatroomtempfor24h.Totheresultantsolution,sodiumborohydride(0.82g,22mmol)wasaddedinsmallportions.Afteradditionwascompleted,themixturewasstirredatroomtemperaturefor30minandconcentratedundervacuum.Theresiduewasthensubjectedtocolumnchromatographyonsilicagelelutedwith10percentethylacetateinhexaneandfollowedbyrecrystallization(aqueousmethanol)yielded450mg(22percent)ofanalyticallypureproduct.
卤化反应
Toastirredsolutionof8-methyl-1-nitro-naphthalene(10.6g,56.32mmol)andiron(III)chloride(0.45g,2.77mmo)inCCl4(150ml)heatedto60°
Cwasaddeddropwise(3.0ml,58.23mmol)ofbromine.Afteronehour,thereactionmixturewaspouredintosaturatedNaHCO3solution,andthelayerswereseparated.Theaqueouslayerwasre-extractedwithCH2Cl2.Thecombinedorganiclayersweredried(MgSO4)andthesolventwasremovedunderreducedpressure.Thecruderesiduewasrecrystallizedfromethanolandthemotherliquorswereconcentratedandthenflashchromatographedonsilica,eludinghexanes:
ethylacetate(12:
1).
Suzukicoupling
Toamixtureof4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-1H-indole(2g,8.2mnmol)and3-bromobenzene(0.87ml,8.3mmol)inTHF(28ml)wereaddedpalladiumcatalystPd(PPh3)4(284mg,0.25mmol)andthefreshlypreparedsodiumhydroxidesolution(984mgin9mlofwater).Thesystemwasdegassedandthenchargedwithnitrogenforthreetimes.Themixturewasstirredundernitrogenat70°
Coilbathfor6hours.Thereactionsolutionwascooledtoroomtemperature,dilutedwithethylacetateandseparatedfromwaterlayer.Theethylacetatesolutionwaswashedbybrine,driedoverNa2SO4andconcentrated.Theresiduewaspurifiedonasilicagelcolumneludingwithhexanes:
EtOAc9:
1togive1.38g(78%yield)of4-phenyl-1H-indoleasacolorlessliquid.
磺化反应
Chlorosulfonicacid(4.66g,40mmol)isaddeddropwisetoacold(0°
C)solutionof2,3-dihydro-2-trifluoroacetyl-1H-Benz[de]isoquinoline(2.9g,8mmol)inchloroform(800ml).Theresultingsolutionisstirredat0°
Cfor30minutes.Thecoldbathisthenremovedandthesolutionisstirredatroomtemperaturefor1hourthencautiouslypouredintoicewater.Theorganiclayerisseparated,driedovermagnesiumsulfateandconcentratedtoaffordthetitlecompound.Thecrudeproductispurifiedbycolumnchromatographyelutedwith10%aceticetherinpetroleumether(2.36g,81%yield).
酯化反应
Amixtureof4-hydroxymethylnaphthoicacid(10g,50mmol),methanol(300ml),andconcentrateH2SO4(2ml)wasrefluxedovernight.Theinsolubleswerefilteredoffandthefiltratewasconcentrated.TheresiduewastakenupinethylacetateandwashedwithaqueousNaHCO3(2*),brine,driedoverMgSO4,andconcentratedtogiveayellowoil.Silicagelcolumnchromatographyusingethylacetate/hexane(1/3)gavethedesiredproductasayellowoil(3.3g,35%yield).
水解反应
Asolutionof1-Methyl-naphthalene-2-carboxylicacidmethylester(7.20g,35mmol)and2Nsodiumhydroxide(35ml)intetrahydrofuran(130ml)wasstirredunderrefluxfor18hours.Themixturewasneutralisedusing2Nhydrochloricacid,andextractedwithdichloromethane(3x).Thecombinedorganicsolutionsweredried(MgSO4),andevaporatedunderreducedpressure.Thecrudeproductwaspurifiedbycolumnchromatographyonsilicagelusinganelutiongradientofdichloromethane:
methanol(100:
0to97:
3)toaffordthetitlecompoundasasolid(3.11g,47.8%yield).
硝化反应
Toacold(0°
C)suspensionof1-methylnaphthalene(5g,35.2mmol)inHNO3wasaddedH2SO4(5ml)dropwise.Afterstirringthereactionforonehour,thesolutionwasdilutedwithethylacetateandwashedwithwater(3*),aqueoussaturatedNaHCO3(2*)andbrine,driedoverMgSO4,andconcentrated.Theproductwaspurifiedbysilicagelcolumnchromatographyusingethylacetate:
hexane(5:
95)andrecrystallizedfrommethanoltogiveyellowneedles(0.22g,33%yield).
n-BuLi
Toadryth
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