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Uninzi lweeHeterocycle ezintle kwiLizwe

Uninzi lweeHeterocycle ezintle kwiLizwe

Heterocyclic compounds

I-heterocyclic compound, eyaziwa nangokuthi isakhiwo sesigxina ngokukodwa isakhiwo esiqukethe i-athomu ezimbini zezinto ezihlukeneyo njengamalungu endandatho / izindandatho zayo. I-Heterocyclic compounds mhlawumbi yakha ininzi kakhulu kunye nenani elikhulu kwinani leemveliso eziphilayo.

Kungakhathaliseki ukusebenza kunye nesakhiwo, yonke into eyenziwa yi-carbocyclic ingaguqulelwa kwiimpawu eziqhelekileyo ze-heterocyclic ngokufaka enye i-atom okanye enye i-atom i-atom i-atom. Ngenxa yoko, ii-heterocycle zinike iqonga lokutshintshiselwa uphando kwimimandla eyahlukeneyo kubandakanya kodwa kungagqibekanga kumachiza, amayeza, ukuhlalutya, kunye ne-organic chemistry ye-heterocyclic compounds.

Imimandla emikhulu ye-heterocyclic compounds yilezi zonyango, i-nucleic acids, uninzi lweeyunithi zendalo kunye nezendalo, kunye neninzi ye-biomass ezifana ne-cellulose kunye nezinto ezihambelanayo.

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Nangona i-heterocyclic compounds ingaba yendalo okanye iimpawu ezingekhoyo, ubuninzi banenani elilodwa lekhabhoni. Ezi zixhobo ziyakwazi ukuhlonywa ngokwezakhiwo zazo zombane. Iimveliso ze-heterocyclic ezigciniweyo ziziphatha ngendlela efanayo ne-acyclic derivatives. Ngenxa yoko, i-tetrahydrofuran kunye ne-piperidine zi-ethers eziqhelekileyo kunye nama-amine kunye neeprofayili zendalo ezinokuguqulwa.

Ukufundisisa i-heterocyclic chemistry, ngoko ke, igxininise kakhulu kwiimveliso ezingenayo i-insaturated kunye nezicelo zibandakanya izithandathu ezingenasiphelo kunye nezindandatho ezinamathandathu. Oku kuquka u-furan, i-pyrrole, i-thiophene, ne-pyridine. Iklasi elikhulu elandelayo ye-heterocyclic compounds ixutywa kwiimigodi ze-benzene, ezenziwe nge-furan, pyrrole, thiophene, kunye ne-pyridine ziyi-benzofuran, i-indole, i-benzothiophene kunye ne-quinoline, ngokulandelanayo. Ukuba amabini amabini e-benzene ahlanjululwa, oku kubangela omnye usapho olukhulu lweemveliso, eziyi-dibenzofuran, carbazole, i-dibenzothiophene, kunye ne-aridine. Amacangci angagqithwanga angabalwa ngokusekelwe kwinxaxheba ye-heteroatom kwinkqubo ye-pi, inkqubo edibeneyo.

Ukulungiselela nokuphendula

Amacenge e-3

I-Heterocyclic i-atom emithathu kwi-ring isendlela yokusebenza ngokukhawuleza yenkxaso yomngcipheko. Ii-heterocycle ezine-heteroatom enye zizinzile. Ezi ziqulethe i-heteroatoms ezimbini zenzeke, ngokubanzi njengezivumelwano eziphambili.

I-Oxiranes, eyaziwa nangokuthi i-epoxides yizona ziqhelekileyo ze-heterocycle ze-3. I-Oxiranes iyalungiswa ngokuphendula i-peracids kunye ne-alkenes, ene-stereospecificity. I-Oxiranes iyasebenza ngakumbi kune-ethers engasetshenzisiweyo ngokukhawuleza kwenkxala ephezulu ye-3-ring ring. Ukongezwa kwenyathelo oluqhubekayo ngokuvula i-nucleophilic kunye ne-electrophilic yokuvota yinkalo yokuphendula ngokubanzi.

Ukuphendulwa kwaloo hlobo kubandakanyeka kwizenzo zeevendi ze-pharmacy ezenziwe phakathi kwezilwanyana zokuqala zonyango. Ukuvalwa kwendandatho ye-intramolecular njengoko kwimeko ye-agent ye-antiticancer mechlorethamine yenza i-aziridium ion ephakathi. I-ejenti esebenzayo eyenziwa yi-ejensi esebenzayo yokuhlaselwa kweeseli ezibandakanya iiseli zengqamzana ngokumelana nokuphindaphinda kwe-DNA. Iimvini ze-nitrojeni nazo zisetyenziselwa njengama-agent anticancer.

I-aziridine yezohwebo kunye ne-oxirane ziyimfuneko yeekhemikhali zamashishini ezininzi. Kwi-scale scale production of oxirane, i-ethylene ithathwa ngokuthe ngqo nge-oxygen. Ukuphendula kwamakhemikhali, okuyiyona nto ibonakalayo yilezi zindandatho ze-3, kukuba ziyakwazi ukuhlaselwa ngama-reagents e-nucleophilic ukuvula isangqa njengoko kuboniswe ngezantsi:

Iintlobo ezintathu eziqhelekileyo i-heterocyclic compounds enye heteroatom iquka:

Nelisekile Unsaturated
Thiirane (episulfides) Thiirene
Phosphirane Phosphirene
I-epoxides (oxirane, i-ethylene oxide) Oxirene
Aziridine Azirine
Borirane Borirene

Iimpawu eziqhelekileyo ezinama-heterocyclic amathathu kunye ne-heteroatoms ezimbini ziquka i-Diaziridine njenge-derived and Diazirin njenge-derivated derivative kunye ne-Dioxirane ne-Oxaziridine.

Izindandatho ezineBulungu

Iinkqubo ezahlukeneyo zokulungiselela ii-heterocycle zee-4 ezineengqungquthela ziboniswa kwisalathisi esingezantsi. Inkqubo yokusabela i-amine, i-thiol okanye i-3-halo ene siseko isetyenziswa ngokufanelekileyo kodwa ivelisa isivuno. Ukunciphisa nokunciphisa iimeko eziqhelekileyo zempendulo. Eminye imisebenzi inokukhuphisana nokuphendula.

Kwimzekelo yokuqala, ukuqhubela i-cyclization kwi-oxirane ihlala ikhuphisana kunye nokwakheka kwe-thietane, kodwa i-nucleophilic ephezulu ilawulwa ngokukodwa xa umntu esebenzisa isiseko esibuthakathaka.

Ngokomzekelo wesibini, ukubunjwa kwe-azetidine kunye ne-aziridine kunokwenzeka, kodwa kuphela oku kubonakala. Umzekelo isibalo sesine sibonisa ukuba le ndlela yokwenza imisebenzi ye-azetidine kakuhle xa kungekho ukhuphiswano.

Ngokomzekelo wesithathu, ukucwangciswa okuqinileyo kwe-substrate kufisa ukwakheka kwe-oxetane kwaye kuvimbela ukujikeleza kwe-oxirane. Kwimimiselo ye-5 kunye ne-6, i-photocyclisations ye-Paterno-Buchi ifaneleke ngokukodwa ekubunzeni i-oxetane.

Izindlela zokulungiselela ii-heterocycle zeenxalenye ze-4

Ukuphendula

Ukuphendula kweenxalenye ze-4 i-heterocyclic compounds Kwakhona kubonisa impembelelo yoxinzelelo. Umzobo olandelayo ubonisa imizekelo. I-Acid-catalysis yinto ebonakalayo yeendlela ezahlukahlukeneyo zokuvula iingcamango eziboniswe kwimimiselo ye-1,2, ne-3a. Ukuphendula nge-2 ye-thietane, i-sulfur iphantsi kwe-electrophilic chlorination ekhokelela ekwakheni i-chlorosulfonium ephakathi kunye nokufakwa kwe-chloride ion. Ukuphendula nge-3b, i-nucleophiles ezinamandla ziyabonakala ukuba zivule i-ether ebunzima. Ukuphendulwa kwe-beta-lactones ye-cleavage ingenzeka mhlawumbi nge-acid-catalyzed exchange acyl ebonakalayo kwi-4a. Inokuthi iqhutywe yi-alkyl-O yahlukana ngama-nucleophile afana ne-4b.

Umzekelo i-6 ibonisa into ekhangayo yokulungiswa kwe-intramolecular ye-ortho-ester. Ukuphendula i-6 ibonisa ukucoca kwe-Beta-lactam ye-penicillin G echaza indlela yokusabela ngokunyanisekileyo kwe-acrylation system.

Imizekelo yeempendulo ze-4-membered heterocyclic compounds

Eyona nto iluncedo i-heterocyclic compounds kunye neendandatho ze-4 zineziqulatho ezimbini ze-antibiotics, i-cephalosporins kunye ne-penicillin. Iingqungquthela ezimbini ziqulethe i-azetidinone ring eyaziwa ngokuba yi-Beta-lactam ring.
Ininzi ze-oxetanes zingaphantsi kophando njengemilenze, i-antiticancer, i-anti-inflammatory, kunye ne-antitifungal agents. I-Oxetanones, ngakolunye uhlangothi, isetyenziswa kakhulu kwezolimo njenge-bactericides, i-fungicides, kunye ne-herbicide kunye nokuveliswa kwe-polymeri.
Umzali we-thietane watholakala kwioli ye-shale ngelixa i-odoriferous derivatives yayo isebenza njengabakhonkco bama-polecats aseYurophu, i-ferrets kunye ne-minks. I-thietanes ifakwa njenge-fungicides kunye ne-bactericides kwipende, njenge-iron corrosion inhibitors kunye nokuveliswa kwama-polymers.

Amakhonkco amane anomnxeba ahlanganiswe ne-heteroatom enye

I-Heteroatom Inelisekile i-Unsaturated

Heteroatom Nelisekile Unsaturated
Sulfure Thietane Azete
Oxygen I-Oxetane Oxete
Iitrogen Azetidine Azete

Amakhonkco amane anomnxeba ahlanganiswe nama-heteroatom amabini

Heteroatom Nelisekile Unsaturated
Sulfure IDithietane IDithiete
Oxygen Dioxetane Dioxete
Iitrogen Diazetidine Diazete

Iindandatho ze-5 ezinomnxeba kunye ne-heteroatom enye

I-thiophene, u-furan, kunye ne-pyrrole yimixube yomncuba womzali we-5-membered membered heterocycles. Nazi izakhiwo zabo:

Iziphumo ezigcweleyo ze thiophene, furan, kunye ne-pyrrole yi-thiophane, i-tetrahydrofuran, ne-pyrrolidine ngokulandelanayo. Iibicyclic ezicanjwe nge-thiophene, furan, okanye i-pyrrole yangxoweni efakwe kwi-ringene ring zibizwa ngokuba yi-benzothiophene, i-benzofuran, i-isoindole (okanye i-indole) ngokulandelanayo.
I-nitrojeni ye-heterocycle pyrrole ngokuqhelekileyo ivela kwioli yeethambo eyenziwa ngokuchithwa kweeprotheni ngokufudumeza. Amacenge e-pyrrole afumaneka kwi-amino acid ezifana ne-hydroxyproline kunye ne-proline eziyinxalenye yeeprotheni ezahlukahlukeneyo eziphezulu kwiiprotheyini zakhiwo zemizila, i-tendon, isikhumba, namathambo kunye ne-collagen.
Izixhobo ezivela kwi-Pyrrole zifumaneka kwi-alkaloids. I-Nicotine yiprrrole eyaziwa kakhulu equkethe i-alkaloid. I-Hemoglobin, i-myoglobin, i-Vitamin B12, kunye ne-chlorophyll, zonke zenziwa ngokujoyina iiyunithi ezine ze-pyrrole kwinkqubo enkulu ebizwa ngokuthi i-porphyrin, njengaleyo ye-chlorophyll B iboniswe ngezantsi.

Iibhabisi zebhile zenziwa ngokuqhekeka kwendandatho ye-porphyrin kwaye zineketshe le-4 pyrrole izindandatho.
Ukulungiselela ii-heterocycle zangaphakathi ze-5
Ukulungiswa kwemveliso ye-furan ngenjongo njengoko kuboniswe ngezantsi ngeendlela ze-aldehyd, ezivuthayo, ezivela kwi-pentose equkethe izinto ezibonakalayo ezifana ne-corncobs. Amalungiselelo afana ne-thiophene kunye ne-pyrrole aboniswa kumqolo wesibini we-equations.
Umgca wesithathu we-equation omnye ubonisa ukulungiswa ngokubanzi kwama-thiophenes, ama-pyrroles, ama-furans avela kwi-1,4-dicarbonyl. Ezinye iimpendulo ezininzi ezikhokelela ekwakheni i-heterocycle echanekileyo yolu hlobo ziqalisiwe. Eminye yale nkqubo iye yaboniswa kwisigqibo sesibini nesithathu. I-Furan iyancitshiswa yi-palladium-catalyzed hydrogenation kwi-tetrahydrofuran. I-ether ehamba nge-cyclic iyisisombululo esibalulekileyo esingenakuguqulwa kuphela kwi-4-haloalkylsulphonates kodwa kunye ne-1,4-dihalobutanes engasetyenziselwa ukulungiselela i-thiolane ne-pyrrolidine.

Amakhonkco amahlanu ahlanganiswe ne-heteroatom enye

Heteroatom Unsaturated Nelisekile
IAntimony Stibole Stibolane
Arsenic Arsole Arsolane
Bismuth Bismole Bismolane
Boron Borole Borolane
Iitrogen Pyrrole Pyrrolidine
Oxygen Furan Tetrahydrofuran

Iindandatho ze-5 ezineenxalenye ze-2 heteroatoms

Iimvumi ezinamathandathu ezinamatholo ane-2 heteroatoms kwaye ubuncinane enye ye-heteroatoms yi-nitrogen, yaziwa ngokuba yi-azoles. I-Isothiazoles kunye ne-thiazoles zine-nitrogen ne-athile ye-sulfure. Iimveliso ezimbini ngee-atyulfure zibizwa ngokuba yiDithiolanes.

Heteroatom I-Unsaturated (kunye ne-unsaturated) Nelisekile
Iitrogen

/ nitrogen

I-Pyrazole (Pyrazoline)

Imidazole (Imidazoline)

Pyrazolidine

Imidazolidine

Iitrogen / oksijini Isoxazole

Oxazoline (oxazole)

Isoxazolidine

oxazolidine

Iitrogen / isulfure Isothiazole

Thiazoline (Thiazole)

Isothiazolidine

Thiazolidine

Oxygen / oksijini Dioxolane
Sulfure / sulfure Dithiolane

Ezinye i-pyrazoles zivela ngokwemvelo. Izixhobo zeli klasi zilungiselelwe ngokuphendula ii-1,3-diketones kunye ne-hydrazines. Uninzi lwamakhemikhali e-pyrazole asetyenziswa njengamayeza kunye nodayi. Zibandakanya ukunciphisa i-aminopyrin, i-phenybutazone, i-phenybutazone, i-phenybutazone esetyenziselwa unyango lwe-arthritis, idayi yefayibhile kunye nombala we-tartrazine yomnxeba wokutya, kunye neninzi yeetayiti ezisetyenziswe kumbala wezithombe njengama-agent avuselelayo.

Iindandatho ze-5 ezineenxalenye ze-3 heteroatoms

Kukho kwakhona iqela elikhulu leeloni ezinamalungu amahlanu ahlanganiswe kunye ne-3 heteroatoms. Omnye umzekelo weempawu ezinjalo zi-dithiazoles eziqukethe i-atome ye-nitrogeni kunye neesulfure ezimbini.

Iindandatho ze-6 ezinezixhobo ze-1 heteroatom

I-nomenclature esetyenziswe kwi-monocyclic ene-nitrogen equkethe i-6-ring membered ring compounds ingezantsi. Izithuba kwi-ring for pyridine ziboniswa, iinombolo zesiArabhu zikhethwa ngakumbi kwiincwadi zesiGrike, nangona zombini iinkqubo zisetyenziswa. Iipyridrid ziimveliso eziqhenkcelayo ezinobungakanani beminikelo yokuhlambulula i-hybrid kwiifom ze-resonance ezihlawulisiweyo njengoko kuboniswe kwi-4-pyridone.

Ii-coenzymes ezibini ezibandakanyekayo kwiimpembelelo eziphambili ze-metabolic kwiiseli, i-NAD (eyaziwa ngokuba yi-coenzyme1) kunye ne-NADP (eyaziwa ngokuba yi-coenyme II), ivela kwi-nicotinamide.
Uninzi lwe-alkaloids luqulethe i-piperidine okanye i-pyridine isangqa sesakhiwo, phakathi kwazo i-piperine (enye yezinto ezikrakra ezikrakra zompompe omnyama nomhlophe) kunye ne-nicotine. Izakhiwo zabo ziboniswe ngezantsi.

I-Pyridine eyake yanyuswa kwindoda yamarha kodwa ngoku iyalungiswa ngokusuka kwi-ammonia kunye ne-tetrahydrofurfuryl utywala kubaluleke kakhulu kunye ne-solvent esetyenziselwa ukwenza ezinye iifom. I-Vinylpyridines ibaluleke kakhulu kwiibhloko zee-plastiki, kwaye i-piperidine egcweleyo, i-pyridine isetyenziswe njengemveliso yendalo yemveliso kunye ne-rubber processing.

Iipriridines ezixhaswa ngamachiza

Iipriridines ezixutywa ngamachiza ziquka i-isonicotinic acid hydrazide (i-tuberculostat isoniazid), isicatshulwa se-anti-AIDS-virus esaziwayo njenge-nevirapine, i-nicorandil-avasodilator esetyenziselwa ukulawula i-angina, i-phenazopyridine-i-urinary-tract analgeic kunye ne-anti-inflammatory drug sulfa. I-Diflufenican, i-clopyralid, i-paraquat, kunye ne-diquat yinto efunyenwe yi-pyridine ezisetyenziswa njenge-herbicides.

Iindandatho ze-6 ezineenxalenye ze-2 okanye ii-heteroatom ezingaphezulu

I-3 monocyclic i-heterocycle ring yangamalungu ayisithupha kunye ne-2 nitrogen heteroatoms (diazines) zibalwa kwaye zibizwa ngokuba ziboniswe ngezantsi.

I-hydrazide yamadoda iyisiphumo se-pyridazine esisetyenziswa njenge-herbicide. Amanye ama-pyrazines afana ne-aspergillic acid akwenzeka ngokwemvelo. Nazi izicwangciso zezinto ezikhankanywe ngentla apha:

I-Pyrazine ring isecandelo lamacandelo e-polycyclic eyahlukeneyo okubalulekileyo kwezoshishino nakwizinto eziphilayo. Amalungu abalulekileyo eentsapho ze-pyrazine zi-phenazines, alloxazines, nee-pteridines. I-Pharmacologically kunye ne-biologically, eyona nto ibaluleke kakhulu iiprimrimidines. I-Cytosine, thymine, kunye ne-urrac yi-3 ye-5 iziseko ze-nucleotide ezenza i-genetic code kwi-RNA ne-DNA. Ngezantsi zizo izakhiwo zazo:

I-Vitamin thiamin ine-ring pyrimidine kwaye ngaphezu kwee-barbiturates ezenziwe ngama-synthetic kubandakanya i-amobarbital isetyenziswa ngamayeza. I-Morpholine (umzali we-tetrahydro-1,4-oxazine) ikhiqizwa kwinqanaba elikhulu ukusetyenziswa njenge-fungicide, i-inhibitor ye-corrosion kunye ne-solvent. Umngca we-Morpholine ufumaneka kwi-drug-hypnotic drug trimetozine kunye nezinye iifungicides ezifana ne-fenpropimorph kunye ne-tridemorph. Nantsi ifom yokwakheka kwe-morpholine:

Amacenge e-7

Njengoko ubukhulu beendandatho buyanda, iintlobo zeemveliso ezifumanekayo ngokuhlula indawo, uhlobo, kunye nenani lama-heteroatoms landa kakhulu. Nangona kunjalo, i-chemistry ye-heterocycle kunye neendandatho ze-7 ezinamatholo okanye ngaphezulu kuncinci kuphuhliswe kune-6 kunye ne-5-ring membered heterocyclic compounds.
I-Oxepine kunye ne-Azepine izindandatho zibaluleke kakhulu kwiimveliso ezahlukeneyo zemvelo zendalo kunye ne-alkaloids. I-azepine derivative eyaziwa ngokuba yi-caprolactam yenziwe ngezorhwebo ngobuninzi ekusebenziseni ekwenzeni i-nylon-6 njengomphakathi kunye nokuveliswa kweenkozo zokwenziwa, iingubo kunye nefilimu.
I-7-membered heterocyclic compounds kunye ne-athomu enye okanye enye ye-atrojeni ye-nitrogen kwindandatho yawo yileyunithi yesakhiwo se-psychopharmaceuticals Prazepine (i-tricyclic anti-depressant) kunye ne-tranquilizer diazepam eyaziwa nangokuthi yi-valium.

Amacenge e-8

Imizekelo yeemveliso ze-heterocyclic kule klasi ziquka i-azocane, i-oxocane, ne-thiocane kunye ne-nitrogen, i-oksijini, ne-sulfure yi-heteroatom. Iziphumo zabo ezingenayo i-insaturated zi-azocine, i-oxocine kunye ne-thiocine ngokulandelanayo.

Amacenge e-9

Imizekelo yeemveliso ze-heterocyclic kule klasi ziquka i-azonane, i-oxonane, ne-thionane kunye ne-nitrojeni, i-oksijini, ne-sulfuri yi-heteroatom efanelekileyo. Iimveliso zabo ezingenayo i-insaturated yi-azonine, i-oxonine, ne-thionine ngokulandelana.

Ukusetyenziswa kwezixhobo ze-heterocyclic

IiHeterocycle zi luncedo kwimimandla ethile yobomi bezesayensi nobugcisa. Njengoko sele sibonile kwingxoxo yethu, ezininzi iziyobisi ziyi-heterocyclic compounds.

Ucaphulo

IUPAC Book Book, i-heterocyclic compounds. Isixhumanisi:

WH Powell: Ukuhlaziywa kweNkqubo yeHantzsch-widman yeNomenclature ye-Heteromonocycles, kwi: Appl efanelekileyo. Chem.1983, 55, 409-416;

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

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