ulat electron-magani dials-adhik pratikriya

ulat electron magani dials-ulder pratikriya, kinwa dynav kinwa ayadada hii eka sendriya rasayanik pratikriya aahe, jyamadhye done naveen rasayanik bandh aanee sahaa-sadasyanchi ring tayar hote. heey dials-ulder abhikriyeshi sambandhit aahe, parantu dials-ulder (kinwa daa) abhikriyechya ulat, dynav heey electron-samruddha dynophile aanee electron-garib dyne yanchyatil cycloadition aahe. dynav abhikriyedarmyan, teen paay-bandh tutatat aanee done sigma bandh aanee eka naveen paay-bandh tayar hotat. ujavikade eka namunatmak dinavh pratikriya darshavili aahe.
dynavy pratikriyanmadhye anekada heteroatumcha samavesh asato aanee heterocyclic sanyuge tayar karnyasathi vaparale jaau shakatat. yamule naisargik utpadananchya sanshleshanat, jethe lakshyit sanyuganmadhye bahudha vishamchakra asatat, visheshtah denve abhikriya upayukt tharate. alikade, prostate karkarogala lakshya daan aushadh vahtook pranaliche sanshleshan karnyasathi denve abhikriyecha vapar keela gela aahe.
itihas.
dials-ulder pratikriyechi nond pahilyanda 1928 madhye oto dials aanee curt ulder yanni kelee hotee; tyanna tyanchya kamasathi 1950 madhye rasayanshastratil nobel puraskar denyat aala hota. tevhapasoon, dials-ulder pratikriyecha vapar vyapak jhaala aahe. yaulat, dinavchi sthapanechi spasht tarikh nahee aanee tyat manak dials-ulder pratikriyeche tulanatmak mahatva nahee. aadhunik sanganakeey paddhatinchya aagmanapurvi rasayanshastradnyanna inverse electron-demand dials-ulder pratikriyanpasun normal vegale karnyat aalelya adchanimule, denavkade shodhachi spasht tarikh nahee. yaa kshetratil bahutansh kamache shrey dell bogarla dile jaate, jaree itar lekhakanni yaa vishayavar asankhya shodhanibandh prakashit kele aahet.
yantrana.
aupcharik yantrana
dinav pratikriyechi yantrana vadgrast aahe. jaree teey aupcharik [4 + 2] cycloodition mhanoon sweekarle gele asale taree pratikriya kharokhar ektrit aahe qee nahee heey changle samajale jaat nahee. bahutek dynav pratikriya eka atulyakalik yantranedvare hotat, asey manya mutt aahe. pratikriya ekach sankraman avasthetun pudhe jaate, parantu serve bandh ekach velee tayar kinwa tutalele nasatat, jase qee ektrit yantranet hoil.
acrolin aanee methyl vinail itharchya abhikriyesathi aupcharik denve yantrana ujavikadil aakrutimadhye darshavili aahe. jaree teey purnapane achook nasale taree teey pratikriyesathi eka upayukt namuna pradan karate. pratikriyechya darmyan, teen paay-bandh (laal label kelele) tutatat aanee teen naveen bandh tayar hotat (nilya rangat label kelele): done sigma bandh aanee eka naveen paay-bandh.
sankraman sthitee
manak daa pramanech, ektrit naan hounahi, dinavh pratikriya ekach nauka sankraman avasthetun pudhe jaatat. eka boat sankraman sthitee hii eka saralikaran aahe, parantu dii. eff. tii. ganana soochit karate qee bandh vichhedan aanee nirmitimadhil velecha farak qamee aahe aanee sambhavya asynchronicta asoonahi, pratikriya ektrit kelee jaate, sambandhit bandh ektar anshatah tutalele asatat kinwa anshatah tayar hotat. denvechi jawaljawal samanvayata mhanje tyavar manak dials-ulder pratikriyepramanech upchar kele jaau shakatat.
serve bandh kahee vishisht tappyavar tayar honyachya kinwa tutanyachya prakriyet asatana, bund, naukesarkhi sankraman sthitee vaparoon pratikriya tayar kelee jaau shakate aanee mhanoon woodward-hofmanchya samanya nivadichya niyamanche palan karane aavashyak aahe. yacha arth assa qee teen ghatak, sahaa electron pranalisathi, serve ghatakanni atimukheey paddhatine (kinwa eka atimukheey aanee done antamukheey) parasparkriya karane aavashyak aahe. serve ghatak atimukheey asalyane, parvanagi asaleli sankraman sthitee botisarkhi asate; khurchisarkhi sankraman sthitee teen done-electron antarmukheey ghatakanmadhye parinami hoil. khurchisarkhi cases woodward-hoffman niyamandware ushnadrushtya parvanagi nahee.
aanvik kakshiy siddhant.
manak daa pratikriya
manak dials-ulder abhikriyemadhye, done ghatak asatatah diane, jeey electron samruddha aahe aanee dynophile, jeey electron kharab aahe. abhikarkanchi sapeksh electron-samruddhi aanee electronchi kamatarata yanche aanvik kakshiy aakrutimadhye drushyadrushtya sarvottam varnan kele jaau shakate. manak dials-uldermadhye, electron samruddha dianmadhye aanvik kakshiy asatat jyaa electronchya kharab dynophyllchya kakshiyanpeksha urjemadhye jaast asatat. sapeksh kakshiy urjetil yaa farkacha arth assa aahe qee, seema aanvik kakshanmadhil dianche homo (homodine) aanee dynophyllche (lumodianophile) lumo heey homodeanophyl aanee lumodinpeksha urjemadhye adhik samaan aahet. sarvat majboot kakshiy parasparkriya hii sarvat samaan seema aanvik kakshanmadhil aaheh homodine aanee lumodianophile.
[4 + 2] dimerisation pratikriya
dimerisation pratikriya samanyatah kinwa ulatya vegane hott naheet aanee samanyatah qamee utpadan detat. yaa prakaranat, done monomers daa paddhatine pratikriya detat. kakshiy urja eksarkhi asalyamule, dyne kinwa dynophyllchya homo kinwa lumochya parasparsanvadala pradhanya nahee. dimerisation pratikriyanche qamee utpann heey shakate kramankachya vikshobh siddhantadvare spasht kele jaate. pratyek prajatiche lumo aanee homo heey samanya kinwa ulatya vegane vadhalelya dials-aldarpeksha dimerisationmadhye urjemadhye adhik door asatat. yacha arth assa qee kakshiy kakshanmadhye qamee parasparkriya hote aanee dimerisationsathy qamee thermodynamic drive asate.
ulat electron maganisah dials-adhik
dimerisation pratikriyanmadhye, diane aanee dynophile heey samaan pramanat electron samruddha (kinwa titkech electron kharab) hote. jarr diane qamee electron samruddha jhaale, kinwa dynophile aanakhi jaast jhaale, tarr sambhavya [4 + 2] cycloodition pratikriya nantar eka dynav pratikriya asel. dynav abhikriyemadhye, lumodine aanee homodeanophyl heey homodine aanee lumodianophylpeksha urjechya jawal asatat. asha prakare, lumodine aanee homodynophyl heey simavarti kakshiy aahet jeey sarvat adhik jordarpane parasparsanvad karatat aanee parinami sarvat urjavandrushtya anukool bandh tayar hotat.
regiochemistry aanee stereochemistry auph denve.
regiochemistry
anek prakarananmadhye, dynav pratikriyanmadhil regiochemistrycha vishvasarh andaj lavala jaau shakato. heey ektar sthir vidyut (charge) niyantranadvare kinwa kakshiy niyantranadvare donpaiki eka prakare kele jaau shakate. charge niyantranadvare regiochemistrycha andaj lavnyasathi, ekhadyane abhikarkanchya anunad prakarancha vichar karane aavashyak aahe. yaa anunad swarupancha vapar pratyek anoola aanshik shulk nirdharit karnyasathi keela jaau shakato. dianaveryl anshatah nakaratmak anoo dynophylvaryl anshatah sakaratmak anoonshi jodale jaatil aanee tyaulat.
kakshiy niyantranadvare abhikriyechya regiochemistrycha andaj lavnyasathi abhikarkanchya pratyek anoovaril sapeksh kakshiy gunank mojane aavashyak aahe. dynophylcha homo dianechya lumoshi pratikriya deto. pratyek anoovaril sapeksh kakshiy aakar haah seema aanvik kakshiy siddhantatil (eff. emm. oo.) kakshiy gunankadware darshavila jaato. orbitals bandh parasparsanvad jastit jaast karnyasathi aanee bandhvirodhi parasparsanvad qamee karnyasathi sanrekhit hotil.
ulder -stein tattva
elder-stein tattva asey sangate qee dials-ulder pratikriyedarmyan utpadananchya stereochemistrymadhye abhikriyakanchi stereochemistry rakhali jaate. yacha arth assa qee prarambhik samgrimadhye ekmekanchya sandarbhat see. aay. ess. asalele gut utpadanat ekmekanshi susangat asateel aanee prarambhik samgrimadhye ekmekanshi sanlagn asalele gut utpadanat virodhi asateel.
heey lakshat ghene mahatvache aahe qee elder-stein tattvacha done prarambhik samgrivaril gatanchya sapeksh abhimukhtashi konatahi sambandh nahee. yaa tattvadvare, dianaveryl paryay dynophylvaryl paryayas siin kinwa virodhi asel qee nahee yacha andaj konihi lavu shakat nahee. ulder-stein tattva keval ekach prarambhik samgrimadhye susangat aahe. heey naate keval dineveryl gatansathi kinwa dynophylvaryl gatansathich vaidh aahe. done abhikarkanmadhil gatanchya sapeksh abhimukhatacha andaj 'endo selection niyam' dware lavala jaau shakato.
endo nivad niyam
manak dials-ulder pratikriyepramanech, denve dekhil samanya endo nivad niyamache palan karato. manak dials-uldermadhye, heey dnyat aahe qee dynophylvaryl electron mage ghenare gut dianechya sandarbhat endokade jaatil. yaa nivadakteche nemke kaaran adyap vadgrast aahe, parantu sarvat sweekrut mutt asey aahe qee endo drushtikon duyyam kakshiy ativyapti vadhavato.
dynofilever electron daan daan paryayanchya endo abhimukhatache denve samarthan karate. serve dials-ulder pratikriya boat sankraman avasthetun pudhe jaat asalyane, sankraman sthiticha eka 'aat' aanee eka 'baher' (boatchya aat aanee baher) asato. dynophylvaryl paryay jarr botichya 'aat' asateel tarr 'endo' aanee jarr teey baher asateel tarr 'exo' manale jaatat.
exo marg sterixdware anukool asel, mhanoon endo utpadananchya samanya varchasvache samarthan karnyasathi vegalya spashtikaran aavashyak aahe. haah parinam spasht karnyasathi seema aanvik kakshiy siddhant vaparla jaau shakato. jevha dynophyllche paryay exo asatat, tevha teey paryay aanee dyne yanchyat konatahi parasparkriya hott nahee. tathapi, jevha dynophyllche paryay endo asatat, tevha dynesse lakshaniy kakshiy aachchadan hote. dynavchya babatit, dinechya kakshanshi electronchya mage mage pratisthapananchya kakshanche ativyapti eka anukool bandh parasparkriya nirman karate, jyamule exo sankraman sthitichya sapeksh sankraman sthitee sthir hote. qamee sakriyan urjesah pratikriya adhik darane pudhe jaeel.
samanya aahar.
diane electron samruddha asalelya manak dials-ulderchya tulanet, diancechi ulat electron magani dials-uldermadhye vaparlya jaanarya diance tulanene electron-kamatarata asalelya prajati aahet. yaa electron-garib prajatinmadhye tyanchya manak daa samakakshanpeksha qamee aanvik kakshiy urja asate. hii qamee jhaleli urja ektar aaa) electron mage ghenara gut kinwa buub) electronegative heteroaatamchya samaveshamule hote. sugandhi sanyuge trigins aanee tetrazinsarkhya dynav pratikriyanmadhyehi pratikriya deu shakatat. dianeche itar samanya varg mhanje auxo-aanee aaza-beautadinese.
manak daa dianechya tulanet, homo aanee lumo haah changla dynave dianecha mukhya guna aahe. khalee eka sarani aahe jyat kahee samanyatah vaparlya jaanarya dinav dyne, tyanchya homo aanee lumo urja aanee kahee manak daa dyne, tyanchya sambandhit moow urjesah darshavilya aahet.
samanya dynophils.
inverse electron demand dials-ulder pratikriyanmadhye vaparlya jaanarya dynophiles, manak daa chya vipareet, eka kinwa adhik electron daan gut asalele atishay electron samruddha asatat. yamule kakshiy urja jaast vadhate aanee tyamule dianechya lumoshi adhik kakshiy aachchadan hote. dynov abhikriyesathi dyneophileschya samanya varganmadhye vinail eather aanee vinail acetal, emine, anamines, alkine aanee atyant tanalele olephine yancha samavesh hoto.
dynophyllchya nivaditil sarvat mahattvacha vichar mhanje tyachi sapeksh kakshiy urja. homo aanee lumo donhi pratikriyechya daravar aanee nivadaktevar parinam karatat. samanya dynophils, manak dynophils aanee tyanchya sambandhit moow urjechi sarani khalee pahili jaau shakate.
shakate taktyat hexachlorocyclopentine yaa atyant kharab electron dynesse, dynophilsmadhil electron samruddhi pratikriyechya daravar kassa parinam karate heey darshavile aahe. dynophile jitka adhik electron samruddha asel, titka pratikriyecha darr jaast asel. styrenechya pratikriyechya sapeksh darachi aanee qamee electronyukt pii-nitrostyrene tulana kartana heey agadi spasht aahe; pii-nitrostyrenepeksha electronyukt styrenechya pratikriya sadharanpane 40 takke vegwan asatat.
vyapti aanee anuprayog.
dynav abhikriya krutrim lakshyanchya samruddha granthalayasathi marg pradan karatat aanee nivadak sanrakshit sakharesah anek atyant karyaksham pranali tayar karnyasathi vaparlya jaatat, jeey sakhar rasayanshastra kshetrat eka mahattvache yogdan aahe. yavyatirikt, denve pratikriya ekach prarambhik samgripasoon vegvegalya utpadananchi eka shreni tayar karoo shakatat, jase qee tetrazin.
anek naisargik utpadananchya sanshleshanasathi dynav pratikriyancha vapar keela gela aahe, jyat (-)-see. see. see.-1065, ducarmycin maliketil eka mool sanyug, jyacha karkarogvirodhi upchar mhanoon vapar keela jaato. yaa maliketil anek aushadh umedvaranni vaidyakeey chachanyanmadhye pragati kelee aahe. (-)-cc-1065 chya pde-i aanee pde-III vibhaganche sanshleshan karnyasathi dynav abhikriyecha vapar keela gela. yaa kramatil pahili abhikriya mhanje tetrazin aanee vinail acetal yanchyatil dynav abhikriya, tyanantar 1,2-diazine utpadan parvadanyasathi retro-dials-ulder abhikriya. aanakhi anek anek, eka intramolecular denve pratikriya udbhavate, tyanantar punha eka retro dials-ulder inn seatoo, indolin utpadan parvadanyasathi. heey indolin kahee krutrim charananmadhye ektar pii. dii. eae.-aay. kinwa pii. dii. eae.-aay. madhye rupantarit kele jaate.
2,3,4,5-tetrachlorotheophine-1,1-dioxide (dyne) aanee 4,7-dihydroidoil derivative (dynophile) yanchyatil dynavy abhikriyemule perchlorinated sugandhi rings asalelya tetranafthoporphyrins (tnp) eka naveen purvavarti midala. sugandhit eldehydes levis acid-utprerit ghanikaran aanee dii. dii. kyu. dware pudhil oxidationdware yaa purvavartiche sambandhit porphirinsmadhye rupantar kele jaau shakate. tii. aine. pii. pranalichya polychlorination tyachya vidravyatevar kholvar anukool parinam hoto. mool tetranafthoporphyrich judd ektrikaran aanee kharab vidravyata yaa sambhavya atishay maulyavan porphyrine kutumbachi upayuktata gambhirpane qamee karate. tyamule polychlorination disun aalela parinam atishay swagatarh aahe. vidravyatevar vidravyatevar parinamavyatirikt, polychlorinationmule yaa sanyuganchi photooxidation dishene sthirata lakshaniyaritya sudharali, jee tetranaphthopherphyrine aanakhi eka gambhir kamatarata mhanoon olakhali jaate.

