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Yakawanda Inoshandiswa Heterocycles Munyika

Yakawanda Inoshandiswa Heterocycles Munyika

Heterocyclic compounds

A heterocyclic compound, iyo inozivikanwawo sechindori chine musimboti inowanzo inamo maatomu ezvikamu zviviri zvakasiyana sezvikamu zvechindori chayo / zvindori. Heterocyclic compounds zvingangodaro inoumba zvakasiyana-siyana uye inonyanya kuwanda yemhuri yezvinhu zvakasikwa.

Pasinei nebasa uye sarudzo, mhando dzose dze carbocyclic dzinogona kuchinjwa kuva mifananidzo yakasiyana-siyana yeheterocyclic nekutsvaga imwe kana kuti yakawanda yekombhoni maatomu maatomu ane chimwe chinhu chakasiyana. Somugumisiro, heterocycles dzakapa chikwata chekutsinhanisa kwekutsvaga munzvimbo dzakasiyana-siyana kusanganisira asi kwete kumigumisiro yemishonga, mishonga, kuongorora, uye chimiro chemakemikari yeheterocyclic compounds.

Mienzaniso mizhinji yemakemikari eheterocyclic ndeyemishonga yakawanda, nucleic acids, yakawanda yezvinhu zvakagadzirwa uye zvisikwa dyes, uye ruzhinji rwezvinyorwa zvakadai sa cellulose nezvimwe zvinhu zvakabatana.

kupatsanura

Kunyange zvazvo heterocyclic compounds inogona kunge yakasikwa kana inorganic compounds, yakawanda ine kaboni imwe chete. Izvi zvinokonzerwa zvinogona kuenzaniswa maererano nekugadzirwa kwemagetsi. Zvakagadziriswa heterocyclic compounds inoita nenzira imwechete seyakagadzirwa nema acyclic. Somugumisiro, tetrahydrofuran uye piperidine inowanikwa ethers uye amines ane maitiro akachinjwa steric.

Chidzidzo cheheterocyclic chemistry, saka, chinonyanya kuisa pane zvisikwa zvisiri izvo uye zvikuro zvinosanganisira kusina kusvibiswa uye zvindori zvitanhatu. Izvi zvinosanganisira furan, pyrrole, thiophene, uye pyridine. Chikamu chikuru chinotevera chemakemikari anonzi heterocyclic chinosungirirwa kuita mabheti ebenene, ayo anonzi furan, pyrrole, thiophene, uye pyridine ari benzofuran, indole, benzothiophene, uye quinoline, pamwe chete. Kana mabheji maviri eBenene akanganiswa, izvi zvinoita kune imwe mhuri huru yemakemikari, ayo ari dibenzofuran, carbazole, dibenzothiophene, uye aridine. Zvindori zvisiri izvo zvinogona kusarudzwa zvichienderana nekubatanidzwa kwe heteroatom mu pi system, conjugated system.

Kugadzirira uye kugadzirisa

3-membered ring

Heterocyclic zvinokonzerwa neatomu matatu mumhete ndezvimwe nzira dzakagadzikana dzakagadzikana dzechirongwa chendin'i. Heterocycles ine imwe heteroatom inowanzosimba. Izvo zvine maviri heteroatoms zvinowanzoitika, kazhinji sevashandi vanoita zvekare.

Oxiranes, inozivikanwawo se epoxides ndiyo yakanyanya kufanana neHCC-membered heyococycles. Oxiranes yakagadzirirwa nekuita ma peracids ane alkenes, neine stereospecificity yakanaka. Oxiranes yakanyanya kupindira kupfuura ye-unsaturated ethers yakaropafadzwa nechepamusoro-soro yerin'i ye 3-membered. Kuwedzerwa kwezvakaitika zvinopfurikidza neyucleophilic uye electrophilic kuvhura kwendori ndiyo inowanzoita kirasi yekuita.

Kuita kworudzi urwu kunobatanidzwa mune nitrogen mustard 'chiito chemasikirwo chaiva pakati pemishonga yekutanga yekurapa yakagadzirwa. Kuvharwa kwechindori inonzi ring inoratidzika kune anticancer agent mechlorethamine inoumba pakati pezizidium ion. Iko yakagadzirwa biologically yakashanda nhengo inoswisa masero anowedzera aisanganisira masero emukenza kuburikidza nekudziviswa kweDNA yavo kudzokorora. Nitrogen mashuvha zvakare akashandiswa seanticancer agents.

Zvekutengeserana aziridine uye oxirane zvinokosha mumakemikari akawanda emabhizimisi. Pakuwanda kwekugadzirwa kwei oxirane, ethylene inopindurwa zvakananga ne oksijeni. Maikemikisi anopindura, iyo ndiyo inonyanya kuonekwa yezvindori izvi zveC3, ndeyokuti inogona kurwiswa nemaitiro eucleophilic reagents kuti izarure rhete sezvinoratidzwa pasi apa:

Nhengo dzinowanikwa katatu heterocyclic compounds pamwe chete heteroatom inosanganisira:

Saturated Unsaturated
Thiirane (episulfides) Thiirene
Phosphirane Phosphirene
Epoxides (oxirane, ethylene oxide) Oxirene
Aziridine Azioni
Borirane Borirene

Iyo inowanzobatanidzwa neyemakumbo matatu eheterocyclic makundi maviri heteroatoms inosanganisira Diaziridine sechibereko chakazara uye Diazirine sechinhu chisingawanikwi uye chinonzi Dioxirane uye Oxaziridine.

Vane-Nhengo dzakanyorwa

Nzira dzakasiyana-siyana dzekugadzirira mhete dze 4-membered heterocycles dzinoratidzwa mumufananidzo uri pasi apa. Nzira yekuita amine, thiol kana 3-halo ine nheyo inowanzobudirira asi ine zvibereko zvishoma. Kuderedza uye kuparadza kunowanzoita maitiro. Mimwe mabasa inogonawo kukwikwidzana mumhinduro.

Mumuenzaniso wokutanga, cyclization kune an oxirane nguva dzose inokwikwidzana nekuumbwa kwe thietane, asi nucleophilic yakakwirira inonyanya kunyanya kana imwe inoshandisa nheyo isina simba.

Muchiitiko chechipiri, kuumbwa kwezvose mbiri kusvikatidine uye aziridine kunokwanisika, asi chete yekupedzisira inoonekwa. Muenzaniso nhamba yechina inoratidza kuti nzira iyi yekuumbwa kwezetidine inoshanda zvakanaka kana pasina kukwikwidza.

Mumuenzaniso wechitatu, kusagadzikana kwegadziriro ye substrate kunobatsira kugadzira oxetane uye kunodzivirira cyclization ye oxirane. Mune mienzaniso 5 uye 6, maPcyno-Buchi photocyclizations anonyanya kukodzera pakuumbwa kwei oxetane.

Nzira dzekugadzira 4-membered rings heterocycles

Reactions

Kugadziriswa kwe4-nhengo heterocyclic compounds uyewo kuratidza runyararo rune simba. Mufananidzo unotevera unoratidza mimwe mienzaniso. Acid-catalysis iyo inowanzoonekwa pamakakatani akasiyana-siyana ekuzarura zvinoratidzwa mumuenzaniso 1,2, uye 3a. Muchiratidzo 2 ye thietane, sulfuri iri pasi pe electrophilic chlorination inotungamirira pakuumbwa kwe chlorosulfonium mukati uye kushandiswa kwekeri-kuzarura ion chloride ion. Pakuita 3b, nucleophiles yakasimba inoonekwawo kuti izarure ether yakashata. Beta-lactones 'cleavage reactions zvinogona kuitika kana acid-catalyzed acyl exchange sezvinowanikwa mu4a. Inogonawo kuitika ne-al-O kuputika nemaikoropolisi akadai mu4b.

Muenzaniso nhamba 6 inoratidzira chiitiko chinonakidza chekugadziriswa kwetemorrangement ye ortho-ester. Mhinduro 6 inoratidzira Beta-lactam cleavage ye penicillin G inotsanangura kuwedzerwa kwemagetsi ekutenderera kweiyo yakagadzirwa ring.

Mienzaniso yekushushikana kwezvikamu zveHNUMX-membered heterocyclic

Inonyanya kukosha heterocyclic compounds uye zvigunwe zve 4-memberedzi zvikamu zviviri zvemishonga inorwisa mabhakitiriya, cephalosporins, uye penicillin. Izvo zvakatevedzana zvakanyora ringti azetidinone iyo inozivikanwawo seBeta-lactam ring.
Nyuchi dzakawanda dziri pasi pekutsvakurudzwa sechirwere chekuvhara ropa, chirairo, anti-inflammatory, uye antifungal agents. Oxetanones, kune rumwe rutivi, inonyanya kushandiswa mune zvekurima sezvinonzi bactericides, fungicides, uye herbicides uye pakugadzira polymer.
Mubereki thietane akawanika mufuta we shale apo zvinyorwa zvayo zvinopisa zvinoshanda sekunhuhwirira kwemaEurope polecats, ferrets, uye minks. Thietanes inoshandiswa semafungicides uye mabhaktericides mupende, sesimbi corrosion inhibitors, uye pakugadzira mapuroymeri.

Zvindori zvina zvakasanganiswa zvine huroatom imwe chete

Heteroatom Saturated Unsaturated

Heteroatom Saturated Unsaturated
Sulfur Thietane Azete
Oxygen Oxetane Oxete
Nitrogen Azetidine Azete

Zvindori zvina zvakasanganiswa zvine maheteroatom maviri

Heteroatom Saturated Unsaturated
Sulfur Dithietane Dithiete
Oxygen Dioxetane Dioxete
Nitrogen Diazetidine Diazete

5-nhengo dzindori dzine heteroatom imwe chete

Thiophene, furan, uye pyrrole ndiwo mishonga anonhuwira emubereki weHNUMX-membered rings heterocycles. Heano maitiro avo:

Izvo zvakagadzirwa zvakakwana zve thiophene, furan, uye pyrrole ndeye thiophane, tetrahydrofuran, uye pyrrolidine pamwe chete. Bicyclic mishonga yakagadzirwa ne thiophene, furan, kana pyrrole ring yakakanganiswa kumhete yeBenene inonzi benzothiophene, benzofuran, isoindole (kana kuti indole) maererano.
Nitrogen heterocycle pyrrole kazhinji inowanikwa mumapfupa epafu anoumbwa nekuparara kwemapuroteni kuburikidza nekupisa kwakasimba. Zvindori zveplrrole zvinowanikwa mumamino acids zvakadai sehydroxyproline uye proline zvinenge zvikamu zvepuroteni zvakasiyana-siyana zvinowanikwa munzvimbo dzakakwirira mumapuroteni ezvigadzirwa zvemagetsi, tete, ganda, nemapfu uye collagen.
Zvinyorwa zvePyrole zvinowanikwa mu-alkaloids. Nicotine ndiyo pyrrole inonyanya kuzivikanwa ine alkaloid. Hemoglobin, myoglobin, Vitamin B12, uye chlorophylls, zvose zvinoumbwa nokubatanidza zvikamu zvina zvepirrole muchetheni huru inonzi porphyrin, yakafanana neyechiroro chlorophyll B inoratidzwa pasi apa.

Birai mavara akaumbwa kuburikidza nekuputsika kweketeni ye porphyrine uye vane ketani yezvindori zve 4 pyrrole.
Kugadzirira kweHNUMX-membered ring heterocycles
Kugadzirwa kwehushani ye furan inowedzera sezvinoratidzwa pasi apa nenzira yealdehyd, furfural, iyo inogadzirwa kubva pentose ine zvigadzirwa zvakasara zvakadai semakona. Saizvozvowo kugadzirira kwe thiophene uye pyrrole kunoratidzwa mumutsara wechipiri wean equations.
Mutsara wechitatu wean equation mumwe unoratidza kugadziriswa kwegadziriro yewaini inonzi substituted thiophenes, pyrroles, furans kubva ku1,4-dicarbonyl makundi. Mamwe maitiro akawanda anotungamirira kumagadziro emakemikari eheterocycle akashandiswa akadaro akatanga. Maviri emitambo iyi yakaratidzwa muchipiri uye chechitatu. Furan yakaderedzwa ne palladium-catalyzed hydrogenation kune tetrahydrofuran. Iyi ether eclic is a solvent worth which can not only be converted to 4-haloalkylsulfonates asiwo 1,4-dihalobutanes inogona kushandiswa kugadzirira thiolane uye pyrrolidine.

Zvindori zvishanu-maune zvinokonzerwa ne heteroatom imwe chete

Heteroatom Unsaturated Saturated
Antimony Stibole Stibolane
Arsenic Arsole Arsolane
Bismuth Bismole Bismolane
Boron Borole Borolane
Nitrogen Pyrrole Pyrrolidine
Oxygen Furan Tetrahydrofuran

5-nhengo dzindori ne 2 heteroatoms

Nhengo dzenzou shanu dzine makumbo ane 2 heteroatom uye imwechete ye heteroatoms ndiyo Nitrogen, inozivikanwa seAzoro. Isothiazoles uye thiazoles vane nitrogen uye sulfuri atomu munhete. Mishonga nemaatomu maviri sulfur anozivikanwa seDithiolanes.

Heteroatom Unsaturated (uye chikamu isina unsaturated) Saturated
Nitrogen

/ nitrogen

Pyrazole (Pyrazoline)

Imidazole (Imidazoline)

Pyrazolidine

Imidazolidine

Nitrogen / oksijeni Isoxazole

Oxazoline (oxazole)

Isoxazolidine

oxazolidine

Nitrogen / sulfuri Isothiazole

Thiazoline (Thiazole)

Isothiazolidine

Thiazolidine

Oxygen / oksijeni Dioxolane
Sulfure / sulfuri Dithiolane

Dzimwe pyrazoles dzinoitika zvakasikwa. Mishonga yeklasi iyi yakagadzirirwa nekuita 1,3-diketoni ne hydrazines. Yakawanda inogadzirwa nemishonga inonzi pyrazole inoshandiswa semushonga uye dyes. Zvinosanganisira fever-kuderedza analgesic aminopyrine, phenybutazone inoshandiswa mukurapa kweArthritis, fiber dye uye yellow yellow color tartrazine, uye huwandu hweadhayi hunoshandiswa muvaraidza mifananidzo sekukurudzira.

5-nhengo dzindori ne 3 heteroatoms

Ikoko kunewo boka guru reine nhengo shanu dzenzou rinoumbwa pamwe ne3 heteroatoms. Mumwe muenzaniso wemakemikisi akadaro ndiwo dithiazoles ane atomu ye nitrogen uye maviri sulfuri.

6-nhengo dzindori ne 1 heteroatom

Izwi rine zita rakashandiswa mu monocyclic nitrogen-rine 6-membered ring ring ine pasi apa. Nzvimbo dziri pamhete ye pyridine dzinoratidzwa, mazita echiArabhu anonyanya kufarirwa kune tsamba dzechiGiriki, kunyange zvazvo zvose zviripo zvishandiswa. Pyridones inhengo dzakasvibiswa dzakakosha zvezvipo zvekugadzirisa hutachiona kubva kumafomu ekuregererwa kwemhosva sekuratidzwa kwe4-pyridone.

Zvinyorwa zviviri zvakakura zvakabatanidzwa mune zvakasiyana-siyana zvinokonzerwa nemagetsi mumasero, NAD (inozivikanwawo se coenzyme1) uye NADP (inozivikanwawo se coenyme II), inotorwa kubva ku nicotinamide.
Ruzhinji rwealkaloids dzine piperidine kana pyridine ring ring, pakati pavo piperine (inoumba chimwe chezvinhu zvakakomba-zvinonaka zvepepuru yakasviba nemuchena) uye nicotine. Zvirongwa zvavo zvinoratidzwa pasi apa.

Pyridine iyo yakambodzingwa kubva mumarata emarasha asi ikozvino yakagadzirirwa chinokonzerwa neammonia uye tetrahydrofurfuryl alcohol inokosha uye inoshandiswa inoshandiswa pakugadzira zvimwe zvimiti. Vinylpyridines yakakosha mumamera ekugadzira matanda epurasitiki, uye piperidine yakazara yakazara, pyridine inoshandiswa semakemikari zvakagadzirwa nezvinhu uye rubber processing.

Mishonga yemishonga inobatsira mapirini

Mishonga inoshandiswa nemishonga inoshandiswa nemishonga inosanganisira isonicotinic acid hydrazide (tuberculostat isoniazid), mishonga inorwisa AIDS-ine-virus inonzi nevirapine, nicorandil - avasodilator inoshandiswa kuronga angina, phenazopyridine-urinary-tract analgesic uyewo anti-inflammatory drug sulfa. Diflufenican, clopyralid, paraquat, uye diquat inowanzobudiswa nemiti inonzi pyridine iyo inoshandiswa searbicide.

6-nhengo dzindori zvine 2 kana zvimwe heteroatom

I3 monocyclic ring-membered ring heterocycles ne 2 nitrogen heteroatoms (diazines) inotarwa uye inodanwa seyakaratidzwa pasi apa.

Maleic hydrazide is derivative ya pyridazine inoshandiswa seye herbicide. Mimwe pyrazines yakadai seaspergillic acid inowanzoitika. Heino zvivako zvezvikwata zvakambotaurwa:

Chindori chePyrazine chikamu chezvinhu zvakasiyana-siyana zve polycyclic makemikari emabhizimisi uye ezvakakosha zvakakosha. Mhuri inokosha yemhuri ye pyrazine ndiyo phenazines, alloxazines, uye pteridines. Pharmacologically uye biologically, inonyanya kukosha diazines ndi pyrimidines. Cytosine, thymine, uye uracil ndiyo 3 yezvigadziko zve 5 nucleotide zvinoumba genetic code muRNA uye DNA. Pasi pane zvivakwa zvavo:

Vitamin thiamin ine pirimididine ringinowedzera uye kuwedzera pakugadzirisa maitiro emishonga anosanganisira amobarbital inowanzoshandiswa zvinodhaka. Morpholine (mubereki tetrahydro-1,4-oxazine) inobudiswa pamwero mukuru kushandiswa sefungicide, corrosion inhibitor, uye solvent. Morpholine ring rinowanikwawo mune sedative-hypnotic drug trimetozine uye zvimwe fungicides sefenpropimorph uye tridemorph. Heino mhemberero ye morpholine:

7-membered ring

Sezvo sendiro yekasi inowedzera, zvakasiyana-siyana zvezvikamu zvinogona kuwanikwa nekusiyana siyana, nzvimbo, uye nhamba ye heteroatoms inowedzera zvikuru. Zvisinei, makemikari eheterocycles ane zvindori zve 7-memberedzwa kana zvimwe zvishoma zvakasimudzika kupfuura ye6 uye 5-membered ring ring heterocyclic compounds.
Oxepine uye Azepine zvindori zvikamu zvakakosha zvezvinhu zvakasiyana-siyana zvinowanzoitika zvinokonzerwa nemagetsi emhando dzegungwa uye alkaloids. Iyo yevenpine yakagadzirirwa inonzi caprolactam inoshandiswa nebhizimisi muzhinji iyo inoshandiswa mukugadzira nylon-6 sepakati uye pakugadzirwa kweganda rekugadzira, kupfeka, uye mafirimu.
7-membered heterocyclic inokonzerwa neatomu maviri kana imwe yeatrogen muchetheni yavo inhengo dzezvikamu zvepamusoro zvakashandiswa psychopharmaceuticals Prazepine (tricyclic antidepressant) uye runyararo che diazepam rinozivikanwa sevalium.

8-membered ring

Mienzaniso yemakemikari eheterocyclic mukirasi ino inosanganisira azocane, oxocane, uye thiocane neNitrogen, okisijeni, uye sulfuri iyo inonzi heteroatoms. Zvinazvo zvinotumirwa zvisiri izvo zvinonzi azocine, oxocine, uye thiocine.

9-membered ring

Mienzaniso yemakemikari eheterocyclic mukirasi ino inosanganisira azonane, oxonane, uye thionane neNitrogen, okisijeni, uye sulfuri ndiyo iyo heteroatomes yakagadzirwa. Zvinyorwa zvavo zvisingatumidzi zvinonzi azonine, oxonine, uye thionine zvakaenzana.

Zvishandiso zveHercocyclic compounds

Heterocycles inobatsira mune dzimwe nzvimbo dzoupenyu sciences uye teknolojia. Sezvatave tatoona mukukurukurirana kwedu, mishonga yakawanda inokonzerwa nemakemikari.

References

IUPAC Gold Book, heterocyclic compounds. Link:

WH Powell: Kuvandudzwa kweHantzsch-Widman System yeNenenclature yeHeteromonocycles, In: Pure Appl. Chem.1983, 55, 409-416;

A. Hantzsch, JH Weber: Ueber Verbindungen des Thiazols (Pyridins der Thiophenreihe), In: Ber. Dtsch. Chem. Ges. 1887, 20, 3118-3132

O. Widman: Zur Nomenclatur der Verbindungen, shingai Stickstoffkerne enthalten, In: J. Prakt. Chem. 1888, 38, 185-201;