quinine kull sanshleshan

praakritik roop seey honey vaali maleria rodhi dawa quinine kaa kull sanshleshan 150 saal kii avadhi mein vikasit kiya gayaa thaa. synthetic quinine key vikas koo carbonic rasayan vigyaan mein ack meal kaa patthar maanaa jaataa haye, halanki iska utpaadan kabhi bhee praakritik quinine key vikalp key roop mein audyogik roop seey naheen kiya gayaa haye. iss vishay parr kuchh vivaad bhee hue hainh gilbert saaras ney 2001 mein quinine kaa pahala stereoselective kull sanshleshan prakaashit kiya, iss beach robbert key pahale daave parr sandeh chhodate hue 1944 mein woodward burns aur villium doaring ney daavaa kiya kii unake antim synthetic madhyavarti, quinotoxin koo quinine mein badalane key liye aavashyak antim kadam kaam naheen karate aggar woodward aur doaring ney prayog karane kaa prayaas kiya hotaa. chemical aind engineering news" mein prakaashit 2001 key ack sampadakiya mein saaras kaa paksh liya gayaa, lekin vivaad antatah hamesha key liye shaant hoe gayaa jaba williams aur sahakarmiyon ney 2007 mein woodward key quinotoxin key prastaavit roopaantaran koo safaltapurvak dohraya.
rasayanik sanrachana.
quinine anu kaa sugandhit ghatak ack quinoline haye jisamen ack methoxy pratisthaapan hotaa haye. amine ghatak mein ack quinuclideen kankal hotaa haye aur donon ghatakon key beach mein mithileen pull mein ack hydroxyl samooh hotaa haye. 3 sthiti parr pratisthaapan ack vinail samooh haye. anu paanch stereogenic kendron kendron aur acidic ack ekal asmamit ikai kaa gathan karate hue) key saath prakaashik roop seey sakriya haye, jisase sanshleshan sambhaavit roop seey kathin hoe jaataa haye kyonki yeh 16 stereoisomers mein seey ack haye.
saaras quinin kull sanshleshan.
saaras quinin sanshleshan kieral ("s")-4-vinilbutrolactone 1 seey shuru hotaa haye. yaugik kieral resolution dwara praapt kiya jaataa haye aur vaastav mein, baad key charanon mein sabhi stereogenic kendron koo kieral preran dwara jagah dee jaati haih anukram mein asmamit charan naheen hotey hain.
lactone koo diethylamine seey amide 2 key liye ring-khola jaataa haye aur iska hydroxyl samooh 3 mein "turt"-butyldymethyl silil eather (tii. bee. aiss.) key roop mein sanrakshit hotaa haye. haye aur aur parmaanuon koo "turt"-butyldefinylacil (tii. bee. dee. pee. aiss.) sanrakshit iodoathenol key roop mein jodaa jaataa haye, joe kii acidic acidic key nucleophilic pratisthaapan mein lithium disopropylamide (ell. dee. aeye.) key saath-78 degree celsius seey 4 parr sahee stereochemistry key saath hotaa haye. pee"-toluensulphonic acid key saath silil suraksha samooh koo alcohol 4bee mein hataane aur azotropic aasavan dwara ring-closure seey yaugik koo lactone 5 mein vaapas curr diyaa jaataa haye (1 kaa pratyaksh alkylation agyaat samasyaon seey bharaa huaa haye).
lactone koo phir diasobutyluminium hydride key saath lactol 5bee mein cumm curr diyaa jaataa haye aur iska mukt aldehyde methoxymethylnasphinephinephalphiphine methoxymethylnasphinephinephalphiphine paramanu vitarit karane vaalaa) key saath ack whittig pratikriya mein pratikriya kartaa haye aur inol eather 6 banaata haye. hydroxyl samooh koo ack mitsunobu pratikriya mein 7 mein diphenylphosphoryl azide key saath ack azide samooh dwara pratisthaapit kiya jaataa haye aur acid hydrolysis seey azido aldehyde 8 praapt hotaa haye.
6-methoxy-4-methylquinoline" 9 mein methyl samooh 8 mein aldehyde samooh mein apane aayan (lda key saath pratikriya dwara) key nucleophilic jodd key liye paryaapt roop seey amleeya haye taaki 10 koo epimer key mishran key roop mein banaaya jaa sakey. stereocontrol key liye iska koee parinam naheen haye kyonki agale charan mein alcohol koo keaton 11 mein swarn okseekaran mein aukseekrit kiya jaataa haye. triphenylphosphine key saath ack stoudinger pratikriya keaton aur azide key beach key valay koo tetrahydropyridine 12 key liye bund curr detee haye. iss yaugik mein emine samooh koo sahee stereosphaciphysity key saath sodium borohydride key saath amine 13 mein cumm curr diyaa jaataa haye. silil suraksha samooh koo hydrogen fluoride seey alcohol 14 key saath hataa diyaa jaataa haye aur phir pyridine mein messile chloride key saath pratikriya dwara ack messile chhodane vaale samooh key roop mein sakriya kiya jaataa haye joe teesare valay koo 15 taka bund karane mein saksham banaata haye. antim charan mein mein hydroxyl samooh koo sodium hydride, dimethylsulfoxide aur 14:1 key quinine aur epiquinine anupaat key saath oxygen key saath okseekaran dwara pesh kiya gayaa thaa.
lakadi kii or-karane vaalaa aupchaarik quinine kull sanshleshan.
1944 kaa lakadi kii or-karane kaa sanshleshan quinuclideen kankal key liye 7-hydroxyisoquinoline 3 seey shuru hotaa haye joe kuchh hudd taka vipareet sahaj gyaan haye kyonki koee ack sthir visham-chakreeya sugandhit pranali seey poori tarah seey santript saikil chakr mein jaataa haye. yeh yaugik (1895 seey pahale seey jaanaa jaataa haye) dou charanon mein taiyar kiya jaataa haye.
pahala pratikriya charan 3-hydroxybenzylde 1 kii sankshepan pratikriya haye (aupchaarik roop seey) aminoacetaldehyde key diasettle key saath emine 2 key liye aur doosara pratikriya charan kendrit sulfuric acid mein cyclisation haye. isoquinoline 3 koo phir formaldehyde aur piperidine dwara ack anya sanghanan mein alkilate kiya jaataa haye aur utpaad koo 4 key sodium namak key roop mein alag kiya jaataa haye.
sodium methoxide key saath methanol mein 10 ghante key liye 220 degree celsius parr hydrogenikaran piperidine samooh koo mukt kartaa haye aur methyl samooh koo 5 mein chhod detaa haye jisamen pahale seey hii sabhi carbon aur nitrogen paramanu hotey hain. ack doosara hydrogenikaran acetic acid mein addam utprerak key saath "tetrahydroisocvinoline" 6 mein hotaa haye. aage hydrogenikaran taba taka naheen hotaa haye jaba taka kii amino samooh koo methanol mein acetic enhydride key saath accellate naheen kiya jaataa haye, lekin taba taka 7 koo phir seey 150 degree celsius parr ethanol mein renee nickle key saath hydrogenykrit kiya jaataa haye, uchch dabaav mein "decahydroisoquinoline" 8. "sis" aur "trance" isomers key mishran koo phir acetic acid mein chromic acid dwara keaton 9 mein aukseekrit kiya jaataa haye. kewal sis isomer kristalikrit hotaa haye aur agale pratikriya charan mein upayog kiya jaataa haye, ethanol mein sodium ethanol nitrite key saath ack ring opening 10 seey ack navgathit carboxylic ester aur ack samooh oxime samooh key saath. oxime samooh koo acetic acid mein platinum key saath amine 11 mein hydrogenykrit kiya jaataa haye aur iodomethane key saath alkilation seey chaturthansh amonium namak 12 aur baad mein silver oxide key saath pratikriya key baad beaten 13 milata haye.
quinine key vinail samooh kaa nirmaan 140 degree celsius parr paani mein sodium hydroxide key saath hoffman unmoolan dwara kiya jaataa haye. iss prakriya key saath ester aur amide samooh donon kaa jall apghatan hotaa haye, lekin yeh mukt amine naheen haye joe alag hotaa haye, balki potasium sinet key saath pratikriya dwara euria 14 hotaa haye. agale charan mein carboxylic acid samooh koo ethanol key saath asterified kiya jaataa haye aur euria samooh koo benzoil samooh key saath badal diyaa jaataa haye. antim charan ethyl quininate 16 key saath 15 kaa classen sanghanan haye, joe amleeya kasrat key baad resemic quinotoxin 17 utpann kartaa haye. vaanchhit anantiomer koo tartaric acid key kieral diabenzoil ester key saath kieral resolution dwara praapt kiya jaataa haye. iss yaugik kaa quinine mein roopaantaran samay-kaal mein charcha kiye gaye reb-kindler rasayan vigyaan parr adharit haye.

