Pyrrolyog tsib-tus tswv cuab heterocyclic compound nrog cov tshuaj tseem ceeb thiab kev ua haujlwm lom neeg. Muaj ntau ntau txoj kev hluavtaws ntawm Pyrrole, feem ntau suav nrog cov hauv qab no.
1. Paal-Knorr synthesis method
Txoj kev Paal-Knorr yog ib txoj hauv kev siv cov pab pawg ua haujlwm xws li 1, 4- dialdehyde thiab 1, 3-diketone li reactants. Txoj kev no siv cov tshuaj carbonyl nucleophilic ntxiv cov tshuaj tiv thaiv ntawm ob lub tebchaw no los ua ib qho 5-hydroxy-2, 3-disubstituted pyridine-1,4-dione, ua raws li cov deoxidation cov tshuaj tiv thaiv kom tawm los ntawm cov khoom lag luam. Txoj kev Paal-Knorr muaj qhov zoo ntawm cov tshuaj tiv thaiv yooj yim, cov txiaj ntsig siab, thiab kev siv ntau yam, thiab tau dhau los ua ib qho ntawm cov kev siv hluavtaws feem ntau rau kev sib txuas ntawm pyrrole.
Pyrrole yog tsib-tus tswv cuab heterocyclic compound nrog ntau yam tshuaj lom neeg thiab kev ua haujlwm lom neeg. Raws li ib qho tseem ceeb ntawm cov organic synthesis lub hom phiaj, nws tuaj yeem ua ke los ntawm ntau txoj hauv kev, ntawm cov txheej txheem Paal-Knorr synthesis yog ib txoj hauv kev siv ntau tshaj plaws. Paal-Knorr synthesis yog ib txoj hauv kev los tsim cov pyrroles los ntawm reacting 1, 4-dihydroxybutane (los yog lwm yam tsim nyog 1, 4-dihydroxyalkanes) nrog amides los yog esters. Txoj kev no muaj cov yam ntxwv ntawm kev xaiv zoo heev, cov tshuaj tiv thaiv me me, thiab siab purity ntawm cov khoom siv tshuaj tiv thaiv, yog li nws tau siv dav hauv kev sib txuas cov organic intermediates thiab tshuaj molecules.
Cov kauj ruam:
Cov hauv qab no yog cov theem pib ua haujlwm ntawm Paal-Knorr synthesis txoj kev, thiab cov txheej txheem kev sim kom ntxaws yog raws li hauv qab no:
(1) Ntxiv 1,4-dihydroxybutane, amide los yog ester thiab hnyav rau hauv lub khob peb-caj dab qhuav.
(2) Ntxiv qhov tsim nyog cov kua qaub catalyst xws li p-TsOH, thiab lwm yam.
(3) Pib cua sov, thiab tswj cov cua kub ntawm 5 degree / min.
(4) Cov tshuaj tiv thaiv niam cawv tau nplawm tas li, thiab hnov mob hauv chav sov li 15 teev.
(5) Tom qab cov tshuaj tiv thaiv, txias rau chav sov thiab lim.
(6) Cov kuab tshuaj yog evaporated los ntawm filtrate los muab cov khoom lag luam.
2. Hantzsch synthesis method:
Txoj kev Hantzsch yog lwm txoj hauv kev tseem ceeb ntawm Pyrrole, siv -substituted- -ketoesters (xws li -methoxyethoxyethanone) thiab amines li reactants, nrog cov tshuaj tiv thaiv me me thiab cov txiaj ntsig siab. Txoj kev Hantzsch yog ib qho ntawm feem ntau siv txoj hauv kev rau kev sib xyaw pyrrole hauv keeb kwm, thiab nws tseem tuav nws tus nqi hluavtaws qub kom deb li deb.
Hauv qab no yog cov kauj ruam ntxaws ntxaws ntawm Hantzsch synthesis.
Kauj Ruam 1: Condensation cov tshuaj tiv thaiv ntawm acetone thiab acetylacetone:
Ua ntej, acetone thiab acetylacetone tau ntxiv rau cov tshuaj sulfuric acid ntawm qhov sib piv ntawm 1: 2, thiab ib qho me me ntawm ethanol tau ntxiv los ua cov kuab tshuaj. Cov tshuaj tiv thaiv condensation tshwm sim hauv qhov sib tov thiab tsim cov organic ketone dibasic acid ntsev hauv qab cua sov.
Kauj Ruam 2: Ntxiv cov tshuaj tiv thaiv ntawm Barbarychic acid:
Cov kauj ruam tom ntej yog ntxiv cov barbalic acid rau cov tshuaj tiv thaiv sib tov. Hauv cov tshuaj tiv thaiv ib-kauj ruam no, barbarylic acid ua haujlwm zoo li quaternary amine thiab nucleophile, thiab ua rau cov tshuaj tiv thaiv condensation nrog cov ketone compound. Cov khoom yog Hantzsch acid uas muaj peb halogen atoms.
Kauj Ruam 3: Txo cov tshuaj tiv thaiv:
Cov kauj ruam kawg yog qhov txo qis ntawm Hantzsch acid. Cov kauj ruam no yog ua tiav los ntawm kev ntxiv sodium hydroxide lossis lwm cov tshuaj txo qis. Cov khoom tom qab txo qis yog 2,3,5-trisubstituted pyrrole. Nov yog cov kauj ruam ntxaws ntxaws ntawm Hantzsch synthesis. Cov txheej txheem hluavtaws no suav nrog kev sib xyaw ua ke, ntxiv thiab txo cov qib tshuaj tiv thaiv, txhua qhov tseem ceeb. Hantzsch synthesis yog ib txoj hauv kev zoo heev rau kev sib txuas ntawm pyroles thiab tau siv dav.
3. Hatch Synthesis:
Lub Haack synthesis yog C-H functionalization-raws li lub tswv yim tsim los ntawm BM Trost thiab H. Amii li al. tsim kom muaj ntau yam tseem ceeb me me organic molecules. Nyob rau hauv xyoo tas los no, txoj kev no kuj tau siv los tsim ntau yam tetraphenylsulfide ligands thiab pyrrole tebchaw.
Cov kauj ruam ua haujlwm ntawm Hatch synthesis txoj kev yuav tau piav qhia hauv qab no.
Kev sim cov kauj ruam:
Kauj Ruam 1: Kev npaj ntawm ammonium iodide:
Noj 60 g ntawm iodine, ntxiv ib me me ntawm dej kom yaj, ntxiv 50mL ntawm concentrated hydrochloric acid nyob rau hauv chav tsev kub, ua rau pH ntawm cov tshuaj tsawg tshaj li 1, ntxiv distilled dej rau 1.5 L; Ua kom sov cov tshuaj npaj rau 80 degree, ntxiv 50g ntawm anhydrous ammonium chloride nyob rau hauv me me ib los ntawm ib tug, thiab do tusyees; Tom qab ntawd, cov tshuaj tau evaporated rau dryness, thiab cov khoom raug muab tshem tawm thiab crushed rau hauv ammonium iodide.
Kauj Ruam 2: Kev kho mob ua ntej:
Sib tov 1.25g ntawm ammonium iodide, 1g ntawm , -unsaturated ketone thiab 0.75g ntawm aldehyde, ntxiv rau 2mL ntawm glacial acetic acid, do kom yaj; passivate MgSO4 rau 1h, lim tawm MgSO4, thiab mloog zoo rau cov lim rau {{10}}.5 ~ 1.0mL.
Kauj Ruam 3: Cov txheej txheem tshuaj tiv thaiv:
Ntxiv cov concentrated reactant rau 100 mL ntawm 30/100 isopropanol / dej tov nyob rau hauv ib tug silicone roj da dej, ntxiv 50 mL ntawm npaj 4.0 mol / L ammonia dej, tshav kub rau boiling, thiab ua kom cov tshuaj tiv thaiv boiling. 20 feeb. Cov tshuaj tiv thaiv tau txias rau hauv chav tsev kub, muab rho tawm nrog dej, thiab ntxiv ua tiav raws li qhov purity ntawm cov khoom xav tau hauv kev sim.
Kauj Ruam 4: Purify cov khoom:
Tsom ntsoov rau cov khoom rho tawm, ua ntej yaug nws hauv cov tshuaj methanol kub thiab tom qab ntawd siv cov dej kub kub tas li los kho cov pH tus nqi ntawm cov tshuaj, thiab tom qab ntawd muab tso rau hauv cov tshuaj ntsuab rau kev nqus thiab purification.
Kauj Ruam 5: Kev Ntsuam Xyuas Lub Koom Haum:
Cov qauv thiab purity ntawm Pyrrole cov khoom tau txais los ntawm qhov kawg NMR thiab huab hwm coj spectrometry tsom xam.
Ntawm lwm yam, nws yuav tsum raug sau tseg tias cov reactants ntawm Hatch synthesis cov tshuaj tiv thaiv yuav tsum tau ua tib zoo txheeb xyuas thiab tswj kom tsis txhob muaj cov tshuaj tiv thaiv los ntawm kev raug rau lwm cov tebchaw. Nyob rau tib lub sijhawm, cov tshuaj tiv thaiv yuav tsum ruaj khov thaum lub sij hawm cov tshuaj tiv thaiv, thiab cov tshuaj tiv thaiv yuav tsum tau nplawm tas li kom ntseeg tau tias qhov sib xws ntawm cov tshuaj tiv thaiv.
Txoj kev Haack synthesis muaj qhov zoo ntawm qhov yooj yim ntawm cov khoom siv tshuaj lom neeg, cov tshuaj tiv thaiv me me, thiab cov tswv yim synthesis yooj yim. Tsis tas li ntawd, los ntawm kev hloov pauv ntawm cov qauv kev ua haujlwm ntawm cov pab pawg prosthetic thiab nuclear リArginn muaj kev tswj hwm kev ua tau zoo ntawm cov tshuaj tiv thaiv, uas ua rau muaj txiaj ntsig zoo rau kev sib xyaw ntawm chirality thiab kev sib txawv ntawm cov qauv.
4. Kev tshawb fawb txog lwm txoj kev siv hluavtaws
Ntxiv rau cov kev qhia saum toj no, muaj ntau lwm txoj hauv kev uas tuaj yeem siv rau kev sib txuas ntawm pyrrole, xws li siv imine zaus ntxiv, Pictet-Spengler cov tshuaj tiv thaiv, thiab lwm yam. Nyob rau hauv niaj hnub organic synthesis, tib neeg tau nrhiav tshiab, muaj txiaj ntsig zoo. , thiab ib puag ncig tus phooj ywg txoj hauv kev los ua ke pyrrole thiaj li tau txais cov khoom sib txuas nrog cov khoom siv roj ntsha ntau dua thiab cov nqi tshuaj.
Hauv cov ntsiab lus, cov hau kev saum toj no yog ib txoj hauv kev rau kev sib xyaw Pyrrole, ntawm cov txheej txheem Paal-Knorr thiab Hantzsch txoj kev yog ob txoj kev siv, thiab Haack txoj kev tau siv ntau dua nyob rau xyoo tas los no.