
kronke pyridine synthesis

α-pyridinium methyl kettoon lavanangalum α, β-ansaachurettad carbonyl samyukthangalum thammilulla jaiva samanvayathile prathikaranamaanu kronke pyridine synthesis. pyridinukal prakrithidathavum synthetic uthppannangalilum vyaapakamaayi kaanapedunnu, athinaal avayude samanvayathinulla vazhikalil valia thaalpparyamund. fritts kronkeyude peraanu eee reethikk nalkiyirikkunnath.
prathikarana vikasanam.
kandethal.
geisen sarvakalaashaalayile thante padanatthil, kronke α-pyridinium methyl kettoon lavanangal 1 umm α, β-ansaachurettad carbonyl samyukthangal 2 umm oru maikkal prathikaranatthiloode amonium asattett upayogichu chikilsikkumbol mithamaaya prathikarana saahacharyangalil uyarnna vilavil 2,4,6-trisabstituted pyridinukal nalkunnathu nireekshichu. nirddishta idanilakkaaraaya 1,5-dicarbonyl samyuktham 3 verthirichitilla. athinte kandethal muthal, kronke synthesis dii-, trai, tetrapredine derivateevukal thayyaaraakkunnathin vishalamaaya prayogakshamatha aasvadikkunnu, ithu hantssh pyridine synthesis polulla anubandha prathikaranangale apekshichu niravadhi gunangal prakadamaakkunnu.
samvidaanam.
kronke pyridine sinthasisinte samvidaanam aarambhikkunnath α-pyridinium methyl keetton 4nte enolysation, thudarnnu α, β-ansaachurettad keetton 5-lake 1,4-kootticherkkal, maikkal adakt 6 roopeekarikkunnu, ithu udanadi 1,5-dicarbonyl 7 lake tatomerise cheiyunnu. amonia 7 lake kootticherkkunnathu thudarnnu 8 vazhi nirjjaleekaranam imin intermediat 9 srishtikkunnu. imin intermediat pinneedu 10 enamine aayi deprotonate cheyyukayum intermediat 11 srishtikkaan carbonilumaayi saiklij cheyyukayum cheiyunnu. pinneedu hydroxy-dynamine 12 roopappeduthunnathinu pyridinium kaatteshan illaathaakkunnu. thudarnnulla jalakshaamathiloode 12-nte sugandhavalkkaranam aavasyamulla pyridine hettarosaikkil 13 srishtikkunnu.
reactor synthesis prathikarana avasthakalum.
kronke sinthasisinulla prarambha saamagrikal palappozhum thayyarakkan nissaaramaan, ithu reethiyude soukaryathinum vishalamaaya vyapthikkum vaaypa nalkunnu. pyridine upayogichu anubandha bromomethyl kettoon chikilsikkunnathiloode α-pyridinium methyl kettoon lavanangal eluppathil thayyarakkan kazhiyum. α, β-ansaachurettad kettonukal palappozhum vaanijyaparamaayi labhyamaan allengil ariyappedunna niravadhi reethikal upayogichu thayyarakkam. koodaathe, maannikk baseukal skeeminte maikkal sweekarthaavaayum upayogikkaam, ithu kronke schemil ulppeduthaan kazhiyunna prarambha vasthukkalude vyaapthi kooduthal vaividhyavalkkarikkunnu.
kronke sinthasisinulla prathikarana avasthakal saadhaaranayaayi eluppamaanu, prathikarana thaapanila saadhaaranayaayi 140 digri selshyasil kaviyatha uyarnna vilavil prathikaranangal palappozhum thudarunnu. kronke synthesis saadhaaranayaayi glacial asattik acidillo methanolilo nadathappedunnu, pakshe ithu jaleeya saahacharyangalilum aduthide layakarahitha saahacharyangalilum cheyyaam.
α-pyridinium methyl kettoon lavanangalkk pakaram 1,3-dicarbonyl samyukthangal praayogikamaaya prarambha vasthukkalaanennu theliyikkappettittund. udaaharanathinu, ethanolil bays ulla 1,3-daikketton 14, thudarnnu amonium asattett, asattik assid, anubandha enoon, levis assid enniva upayogichu 15 roopathilulla 3-asyltriarilpyridinukal nalkunnu. eee asail pyridine aakarshakamaaya idanilakkaaraanu, kaaranam avaykku oru electrophilic handle undu, athu thanmathrayil adhika pravartthanam ulppeduthaan anuvadikkunnu. pravarthanakshamamaaya pyridine moyittikal adangiyirikkunna marunnu lakshyangalude library samanvayathinulla aakarshakamaaya reethiyaaya sankeernamaaya poliyaaril samvidaanangalude nerittulla nirmmaanathinu ithu anuvadikkunnu.
mattu reethikalekkaal gunangal.
pyridinukal nirmmikkunnathinulla kronke sinthasisinu mattu reethikalekkaal niravadhi samkshiptha gunangalundu. hantssh synthesisil ninnu vyathyasthamayi, α-pyridinium methyl kettoninu ithinakam sariyaaya ooksideshan avastha ullathinaal aavasyamulla uthppannam uthppaadippikkunnathin kronke reethikk ooksideshan aavasyamilla.
kronke sinthasisinte mattoru nettam athinte uyarnna aattam sambadvyavasthayaanu. udaaharanathinu, chichibabin sinthasisinu apoorithamaaya prarambha meteeriyalinu thulyamaaya 2 gadakangal aavasyamaanu. koodaathe, kronke sinthasisinte upolppannangal vellavum pyridinum aanu, ithu eluppathil workap shudheekarana protocolukalum anuvadikkunnu. pyridine sinthasisinulla thaarathamyappeduthaavunna reethikalil ninnu vyathyasthamayi, krokne synthesis uyarnna vilavu nalkunna oru paathram sinthasisaayi prayojanappedunnu, ithu aathyanthikamayi synthetic paathakalude churukkezhuthu anuvadikkukayum kompinettoriyal library catalogging kooduthal lalithamaakkukayum cheiyunnu.
vyapthiyum parimithikalum.
kronke pyridine sinthasisinte vishalamaaya vyaapthi pyridil, theonyl, furanile moyittikal ennivayulppedeyulla poolii aaril sisttangalude samanvayathinum ithu prathyekichum upayogapradamaakki. eee reethi α-pyridinium methyl kettoon shakalathilum α, β-ansaachurettad carbonyl samyukthangalilum vishalamaaya aril pakarakkaare sahikkunnu, athinaal poolii-aaril sisttangalude vishalamaaya kaattalog srishtikkaan ithu upayogikkaam. koodaathe, incoming aaril pakarakkaare electron-droying grouppukalum electron-donating grouppukalum nannayi sahikkunnu. kronke sinthasisinu alkail, vinail pakarakkar upayogikkaanum kazhiyum, ithu nalla vilavu nalkunnu. vishalamaaya vyaapthi kaaranam, kronke reethi bipyridinukal (16), terpiridinukal (17), kwaattarpairidinukal (18), septipairidinukal (19) vare sinthasisinu vyaapakamaayi baadhakamaan.
vyathiyaanangalum samyojitha padanangalum.
triarylpyridincinte layakarahitha samanvayathil kronke reethi savisheshamaan, athu α, β-ansaachurettad carbonyl samyukthangalkk pakaramaayi rund dayarilukalude homo-kaplingiloode munnott pookunnu. eee thanthram niravadhi upayogapradamaaya marunnu chaaruthakalude pradhana sakalangalaaya pyridnyl aaril samvidaanangal thayyarakkunnathinulla eluppamaarggam vaagdaanam cheiyunnu.
1992-ll robinson sahapravarthakarum enamino nitriles upayogichu oru α-pyridinium methyl kettoninu pakaram moonnu kaarban shakalangalil onnaayi samanamaaya pyridine synthesis vikasippichu. eee mechappeduthal sisttathinte prathipravartthanam vardhippikkukayum poornnamaayum pakaramulla pyridinukalude roopeekaranam anuvadikkukayum cheiyunnu, athesamayam α-pyridinium methyl kettoninte upayogathinu thathfalamaayundaakunna pyridinile 3-allengil 5-sthaanam maattisthaapikkappedaathe vaykkendathundu. enaamo naitrail 20-nte kronke ghaneebhavanam enoon 21-noppam fuse cheytha pyridine 22 labhichu.
eee kronke-type prathikaranatthinte samvidaanam oru vinailgas sianomide 23 vazhi munnott pookunnu, athu hydrocyanic assid illaathaakkukayum deprotonation vazhi inamine 24 roopappedukayum cyclisation vazhi intermediat 25 roopappedukayum cheiyunnu, ithu pinneedu nirjjaleekaranam cheyth aavasyamulla pyridine uthppannam roopappeduthunnu.
jaleeya maadhyamangalile oru shudhamaaya oru-paathram kronke reethi 4 '-aaril-2,2': 6 ', 2'-terpiridinukal srishtikkunnu. 2-asattailpairidin (27) nuu thulyamaaya rund arlil aldehyde 26-nte prathikaranatthil 28 roopathilulla terpiridinukal labhichu.
yadhaartha reethiyile vyathiyaanangalkk purame, kronke synthesis athinte vyathiyaanangalum upayogichu niravadhi samyojitha padanangal valare pravarthanakshamamaaya pyridinukalude vishalamaaya librarikal samanvayippikkaan upayogichittundu. 220 komboundu library srishtikkaan janda sahapravarthakarum general kronke reaction skeem upayogichu. vividha methyl keetonukal 29 umm aldehydeukal 30 umm aldol condensation vazhi jodiyakki 31 roopathilulla enonukal nalki. eee samyukthangal vividha α-pyridinium methyl keetonukal 32-maayi prathipravartthichu aavasyamulla trai-substituted pyridine 33 nalki.
2009-ll, tuvum sahapravarthakarum 3-sayanoderpairidinukal 34 umm 1-amino-2-asselterpiridinukal 35 umm vikasippikkunnathinayi 3-sakalangal, oru-paathram kompinettoriyal thanthram vikasippichu. kronke prathikaranatthinte eee kompinettoriyal vyathiyanangal poolii arylpyridine scarfoldukalkku kaaryakshamamaya synthetic thanthram nalkunnu. eee reethishaasthram jaivashasthraparamaaya parisodhanakalkkum parisodhana pareekshanangalkkum prayojanakaramaakum.
ligandukalilekkum jaivashaasthraparamaayi sajeevamaaya thanmaathrakalilekkum synthetic aaplikkeshanukal.
bipyridine (baipi) polulla polypyridyl complexukal ligandukalaayi vyaapakamaayi upayogikkunnathinaal rasakaramaaya niravadhi mettal-binding ligandukal srishtikkaan kronke reethishaasthram upayogichittundu. tetrahydroquinoline adisthaanamaakkiyulla enn, ezz-type ligaandukalude oru kudumbam thayyarakkan kronke synthesis upayogichu. 2-ethiopeynailaachettopheno (36) iodine vaathakavumaayum pyridinumaayum alavu uthppaadanathil prathipravartthichu asylmethylpyridinium iodide 37 uthpaadippichu. 2-(+)-kaareyinil ninnu uruthirinja β-ansaachurettad keetton, oru kairal cyclic α ennivayumaayulla prathikaranam aavasyamulla n, s-type ligand 38 nalki.
noval, chiral pii, enn-ligandukal kronke reethi upayogichu thayyaaraakkiyittund. pyridine 41 uthpaadippikkunnathinaayi α-pyridinium asail kettoon salt 39 painokaarvon derivative 40 upayogichu cyclise cheythu. 41-nte benzylic sthaanam methylated cheyyukayum thudarnnu pottasyam diphenalphosphydumaayulla snarr prathikaranam ligand 42 srishtikkukayum cheythu.
kompinettoriyal padanangalil pattikappeduthiyavaykku purame niravadhi jaivashaasthraparamaayi sajeevamaaya samyukthangalude samanvayathinum kronke prathikaranam baadhakamaan. kelly sahapravarthakarum saiklo-2,2 ': 4', 4 ': 2', 2 ': 4', 4 ': 2', 2 ', 2': 4 ', 4': 4 ', 4-sesipiridine ennivaykkulla oru root vikasippichu. polypyridine complexes 43 neey nananja tetrahydropheranil enn-bromosusinimide upayogichu chikilsikkukayum thudarnnu pyridine upayogichu asylmethylpyridinium soult 44 uthppaadippikkukayum cheythu, ithu aavasyamulla uthppannam 45 nalkunnathinu staanderd saahacharyangalil macrocyclisation vidheyamaakaam. glazer coupling allengil ulman coupling polulla mattu cyclisation saankethikavidyakalude parajayam kaaranam eee sinthasisile kronke reethi nirnaayakamaayirunnu.
kronke pyridine sinthasisinte mattoru upayogam topoisomerase 1 inhibittarukalaayi anweshikkappetta niravadhi 2,4,6-trisabstituted pyridinukalude uthpaadanamaayirunnu. 2-asattiliyothiyoheen (46) iodine, pyridine enniva upayogichu samskarichu α-pyridinium asail kettoon 47 uthppaadippichu. saadhaarana saahacharyangalil maikkal aakseptar 48-maayi nadatthiya prathikaranam mothatthilulla 60 sathamaanam vilavil 49-aamm sthaanathulla pyridine pravarthanakshamamakki.
aathyanthikamayi, kronke pyridine synthesis pravarthanakshamamaaya pyridinukaludeyum poolii aaril sisttangaludeyum vishalamaaya samanvayathinu eluppavum nerayathumaaya sameepanam vaagdaanam cheiyunnu. rasakaramaaya ligandukalkkum jaivashaasthraparamaayi prasakthamaaya thanmathrakalkkumulla niravadhi thanthrangalil kronke reethishaasthram prayogichittundu. koodaathe, kronke prathikaranavum athinte vyathiyaanangalum pyridine sinthasisilekkulla badal reethikalekkaal oru-paathram, jaiva layaka rahita vyathiyanangal muthal uyarnna aattam sambadvyavastha vareyulla niravadhi gunangal vaagdaanam cheiyunnu.