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Ama-Heterocycle amaningi anengqondo emhlabeni

Ama-Heterocycle amaningi anengqondo emhlabeni

Ama-Heterocyclic compounds

I-heterocyclic compound, eyaziwa nangokuthi isakhiwo sezindandatho ngokuyinhloko isakhi esiqukethe ama-athomu wezinto ezimbili ezihlukene njengamalungu endandatho / izindandatho zayo. Ama-Heterocyclic compounds mhlawumbe ayingxenye ehlukahlukene kunazo zonke futhi eningi kunazo zonke emndenini wezinhlanganisela eziphilayo.

Kungakhathaliseki ukusebenza nokuhlelwa, zonke izingxenye ze-carbocyclic zingashintshwa zibe yizilinganiso ezihlukahlukene ze-heterocyclic ngokufaka esikhundleni se-athomu noma i-athomu ye-carbon ring. Ngenxa yalokho, i-heterocycle inikeze indawo yokushintshanisa ucwaningo ezindaweni ezihlukahlukene ngaphandle kokungapheleli kwimithi yokwelapha, yokwelapha, yokuhlaziywa, kanye ne-organic chemistry yama-heterocyclic compounds.

Izibonelo ezinkulu zama-heterocyclic compounds yizidakamizwa eziningi, i-nucleic acid, iningi lama-synthetic and natural nature, futhi iningi le-biomass njenge-cellulose nezinto ezihlobene.

Ukwahlukanisa

Nakuba ama-heterocyclic compounds angase abe ama-organic or amorganic compounds, iningi linenani okungenani elilodwa. Lezi zinhlanganisela zingahle zihlukaniswe ngokuvumelana nesakhiwo sabo se-elekthronikhi. Ama-heterocyclic compounds agcwele ngendlela efanayo ne-acyclic derivatives. Ngenxa yalokho, i-tetrahydrofuran ne-piperidine yi-ethers evamile nama-amine anamaphrofayli ashintshiwe we-steric.

Ngakho-ke, ukutadisha imithi ye-heterocyclic, igxila ikakhulukazi emithonjeni engasetshenzisiwe kanye nezicelo ezibandakanya izindandatho ezinhlanu ezingekho emthethweni kanye namasongo ayisithupha. Lokhu kuhlanganisa u-furan, i-pyrrole, i-thiophene, ne-pyridine. Iklasi elikhulu elilandelayo lama-heterocyclic compounds lifakwe emasongeni e-benzene, okuyi-furan, pyrrole, thiophene, ne-pyridine yi-benzofuran, i-indole, i-benzothiophene, ne-quinoline, ngokulandelana. Uma izindandatho ezimbili ze-benzene zihlanganiswa, lokhu kuholela komunye umndeni omkhulu wamakhemikhali, okuyi-dibenzofuran, carbazole, dibenzothiophene, kanye ne-aridine. Izindandatho ezingasetshenzisiwe zingahle zihlukaniswe ngokubamba iqhaza kwe-heteroatom ohlelweni lwe-pi, uhlelo oluhlanganisiwe.

Ukulungiselela nokuphendula

Amasongo angama-3

I-Heterocyclic ehlanganiswe nama-athomu amathathu elinezindandatho yindlela yokusebenza ngokuthe xaxa yenkinga yokuvala. Ama-heterocycle aqukethe i-heteroatom eyodwa ejwayelekile. Lawo anama-heteroatom amabili ayenzeka, ngokuvamile njengama-intermediate asebenzayo.

I-Oxiranes, eyaziwa nangokuthi i-epoxides yizindawo ezivamile kakhulu ze-heterocycle ezinama-3. Ama-oxiranes alungiswa ngokuphendula i-peracids ene-alkenes, ene-stereospecificity enhle. Ama-oxiranes ayasebenza kakhulu kune-ethers engasetshenzisiwe ngokuhlonishwa kwe-angle eliphezulu ekhoneni le-3. Ukwengezwa kokuqhubeka okuqhubekayo ngokuvula i-nucleophilic ne-electrophilic yendandatho kuyisigaba esiphezulu kakhulu sokuphendula.

Ukusabela kwalolu hlobo kuhileleka ekwenziweni kwezemithi yamaswiddi 'yezemithi ephakathi kwezidakamizwa zokuqala zokulwa nezilwane. Ukuvalwa kwendandatho ye-intramolecular njengokwenziwe i-antiticancer agent mechlorethamine yakha i-aziridium ion ephakathi. I-ejenti esebenzayo i-agent ehlaselayo ihlasela amangqamuzana ahamba phambili ahlanganisa umdlavuza wamangqamuzana ngokuvimbela ukuphindaphinda kwabo kwe-DNA. I-nitrogen mustard nayo isetshenziswe njengama-antiticancer agents.

I-aziridine ne-oxirane yezohwebo yizo ezibalulekile zamakhemikhali ezimboni. Ngokukhiqizwa okukhulu kwe-oxirane, i-ethylene isabela ngokuqondile nge-oxygen. Ukusabela kwamakhemikhali, okuyinto ephawuleka kakhulu kulezi zindandatho ze-3, ukuthi bangakwazi ukuhlaselwa yi-reagents ye-nucleophilic ukuvula indandatho njengoba kuboniswe ngezansi:

Amalungu amathathu ajwayelekile kakhulu ama-heterocyclic compounds nge-heteroatom eyodwa kuhlanganisa:

Kugculisiwe I-Unsaturated
Thiirane (episulfides) Thiirene
Phosphirane Phosphirene
Epoxide (oxirane, ethylene oxide) Oxirene
Aziridine U-Aziyoni
Borirane Borirene

Okuvame kakhulu emithathu membered compounds heterocyclic nge heteroatoms ezimbili zihlanganisa Diaziridine njengoba esuselwe ayegcwele kanye Diazirine njengenhlangano esuselwe unsaturated kanye Dioxirane futhi Oxaziridine.

Izindandatho ezinamalungu amane

Izindlela ezihlukahlukene zokulungiselela ama-heterocycle angu-4-membered heterocycles aboniswa kumdwebo ongezansi. Inqubo yokwenza i-amine, i-thiol noma i-3-halo ngesisekelo ngokuvamile isebenza kahle kepha isivuno esingaphakathi. Ukunciphisa amandla nokuqedwa kuyindlela ejwayelekile yokuphendula. Eminye imisebenzi ingase iphinde iqhaza ekuphenduleni.

Esikhathini sokuqala, ukuqhutshwa kwe-cyclization kuya kwi-oxirane njalo kuncintisana nokubunjwa kwe-thietane, kodwa i-nucleophilicity ephezulu ilawula kakhulu uma umuntu esebenzisa isisekelo esibuthakathaka.

Esikhathini sesibili, ukwakheka kokubili i-azetidine ne-aziridine kungenzeka, kodwa kuphela okubonakalayo. Isibonelo sesine isibonisa ukuthi le ndlela yokwenza imisebenzi ye-azetidine kahle uma kungekho mncintiswano.

Esikhathini sesithathu, ukulungiswa okuqinile kwe-substrate kufisa ukwakheka kwe-oxetane futhi kuvimbela ukuqhutshwa kwe-oxirane. Kuzibonelo ze-5 ne-6, izithombe ze-Paterno-Buchi photocyclizations zifanelwe ikakhulukazi ekwakheni i-oxetane.

Izindlela zokulungisa izindandatho ze-heterocycle ze-4

Ukuphendula

Ukusabela kwe-4-membered ama-heterocyclic compounds futhi ubonise ithonya lokunciphisa izindandatho. Umdwebo olandelayo ubonisa izibonelo ezithile. I-Acid-catalysis iyisici esivamile sokuphendula okuzungezile kwezingubo eziboniswe kwizibonelo ze-1,2, ne-3a. Ngokuphendula i-2 ye-thietane, isibabule sibheke ukuchithwa kwe-electrophilic okuholela ekusungulweni kwe-chlorosulfonium ephakathi nokufaka i-chloride ion. Ngokuphendula i-3b, i-nucleophiles enamandla nayo ibonakala ukuvula i-ether ene-strained. Ukusabela kwe-beta-lactones 'cleavage kungase kwenzeke nge-acid-catalyzed acyl exchange njengoba kubonwe ku-4a. Kungabuye kwenzeke nge-alky-O ukuhlukana yi-nucleophiles efana ne-4b.

Inombolo yesibonelo i-6 ibonisa isenzakalo esithakazelisayo se-rearrangement ye-intramolecular ye-ortho-ester. Ukusabela i-6 kubonisa ukususwa kwe-Beta-lactam ye-penicillin G echaza ukusabela okwenziwe ngcono kwe-system fused ring.

Izibonelo zokusabela kwamakhemikhali e-heterocyclic e-4

Iwusizo kakhulu ama-heterocyclic compounds ngezindandatho ze-4 ezinamakheli kukhona uchungechunge lwe-antibiotics, i-cephalosporins, ne-penicillin. Uchungechunge olubili luqukethe i-azetidinone ring eyaziwa nangokuthi i-Beta-lactam ring.
Ama-oxetan amaningi aphethwe uphenyo njenge-antiviral, antiticancer, anti-inflammatory, kanye nama-antifungal agents. Ngakolunye uhlangothi, i-Oxetanones, isetshenziswa ikakhulu kwezolimo njengama-bactericides, ama-fungicides, kanye nokukhiqizwa kwemithi kanye nokukhiqizwa kwe-polymer.
Umzali we-thietane watholakala emafutheni we-shale ngenkathi ama-derivative ayo asebenza njengezithombe ezimnandi zama polecats aseYurophu, ama-ferrets nama-minks. Ama-thietanes asetshenziswa njengama-fungicides nama-bactericides epende, njenge-iron corrosion inhibitors, nasekukhiqizeni ama-polymers.

Izindandatho ezine ezinezinyosi zihlanganiswa ne-heteroatom eyodwa

I-Heteroatom Igcwele Unsaturated

I-Heteroatom Kugculisiwe I-Unsaturated
Sulfure Thietane Azete
Umoya-mpilo I-Oxetane I-Oxete
nitrogen Azetidine Azete

Izindandatho ezine ezinezinyosi zihlanganisa ama-heteroatom amabili

I-Heteroatom Kugculisiwe I-Unsaturated
Sulfure Dithietane Dithiete
Umoya-mpilo I-Dioxetane I-Dioxete
nitrogen Diazetidine Diazete

Amasongo angama-5 ane-heteroatom eyodwa

I-thiophene, i-furan, ne-pyrrole yizinhlanganisela ezinomsoco womzali wama-hterocycle wama-5-membered. Nazi izinhlaka zabo:

Izakhi ezigcwele ze-thiophene, furan, ne-pyrrole yi-thiophane, i-tetrahydrofuran, ne-pyrrolidine ngokulandelana. Izakhi ze-bicyclic ezenziwa nge-thiophene, furan, noma i-pyrrole ring ehlangene ne-benzene ring ziyaziwa nge-benzothiophene, benzofuran, i-isoindole (noma i-indole) ngokulandelana.
I-nitrojeni ye-heterocycle pyrrole ngokuvamile ivela emafutheni amathanga ayenziwa ngokuqhekeka kwamaprotheni ngokusebenzisa ukushisa okukhulu. Amasongo pyrrole zitholakala amino acid ezifana hydroxyproline futhi proline ukuthi yizici amaprotheni ehlukahlukene ekhona lokuhlala eliphezulu amaprotheni isakhi nemisipha, imisipha, isikhumba, namathambo collagen.
Ama-derivatives ase-pyrrole atholakala kuma-alkaloids. I-Nicotine yi-pyrrole eyaziwa kakhulu equkethe i-alkaloid. I-hemoglobin, myoglobin, Vitamin B12, futhi chlorophylls, kwakhiwa ngokujoyina amayunithi ezine pyrrole e indandatho uhlelo esikhulu ngokuthi porphyrin, njengalelo chlorophyll B wabonisa ngezansi.

Ama-pigment bile akhiwa ngokuqhekeka kwendandatho ye-porphyrine futhi abe ne-chain ye-4 pyrrole izindandatho.
Ukulungiswa kwama-heterocycle wezinsimbi ze-5
Ukulungiswa kwezezimboni ze-furan kuqhubeka njengoba kuboniswe ngezansi ngendlela ye-aldehyd, e-furfural, eyenziwa nge-pentose equkethe izinto ezibonakalayo ezifana nama-corncobs. Amalungiselelo afanayo we-thiophene ne-pyrrole aboniswa emgqeni wesibili we-equations.
Umugqa wesithathu we-equation eyodwa ubonisa ukulungiswa okujwayelekile kwe-thiophenes, ama-pyrroles, ama-furans avela ku-1,4-dicarbonyl. Okunye okunye ukuphendula okuholela ekusungulweni kwama-heterocycle okufakelwa kuloluhlobo kuqalile. Okubili kulezi zinqubo kukhonjisiwe ekuphenduleni kwesibili nokwesithathu. I-Furan inciphise nge-palladium-catalyzed hydrogenation kuya kwe-tetrahydrofuran. Le ether ye-cyclic iyinhlanganisela ebalulekile engakwazi ukuguqulwa kuphela ku-4-haloalkylsulfonates kodwa futhi ne-1,4-dihalobutanes engasetshenziswa ukulungiselela i-thiolane ne-pyrrolidine.

Amathanga amahlanu ahlanganiswe ne-heteroatom eyodwa

I-Heteroatom I-Unsaturated Kugculisiwe
Antimony Stibole I-Stibolane
arsenic I-Arsole I-Arsolane
I-Bismuth Bismole I-Bismolane
boron Borole Borolane
nitrogen I-Pyrrole I-Pyrrolidine
Umoya-mpilo furan I-tetrahydrofuran

Amasongo angama-5 ane-2 heteroatoms

Amakhemikhali anezinsimbi ezinhlanu ane-2 heteroatoms futhi okungenani i-heteroatoms eyodwa yi-nitrogen, eyaziwa ngokuthi i-azoles. I-Isothiazoles ne-thiazoles inesitomu se-nitrogen nesibabule ngaphakathi kwendandatho. Amakhemikhali ama-athomu amabili esibabule ayaziwa ngokuthi iDithiolanes.

I-Heteroatom I-Unsaturated (futhi ingenalo i-unsaturated) Kugculisiwe
nitrogen

/ nitrogen

I-Pyrazole (i-Pyrazoline)

Imidazole (Imidazoline)

I-Pyrazolidine

Imidazolidine

I-nitrogen / oksijini Isoxazole

Oxazoline (oxazole)

Isoxazolidine

i-oxazolidine

I-nitrojeni / isulfure Isothiazole

I-Thiazoline (Thiazole)

Isothiazolidine

Thiazolidine

Oxygen / oksijini I-Dioxolane
Sulfure / sulfure Dithiolane

Amanye ama-pyrazoles ayenzeka ngokwemvelo. Amakhemikhali alesi sigaba alungiswa ngokuphendula i-1,3-diketones nge-hydrazines. Amakhemikhali amaningi amakhemikhali e-pyrazole asetshenziswa njengemithi kanye nodayi. Zibandakanya i-aminopyrine, i-phenybutazone esetshenziselwa ukumelana nomkhuhlane, i-phenybutazone esetshenziselwa ukwelashwa kwe-arthritis, i-fibre color kanye ne-tartrazine yombala wokudla ophuzi, futhi iningi lamadayi asetshenziselwa ukuthwebula izithombe njengama-agent avuselelayo.

Amasongo angama-5 ane-3 heteroatoms

Kukhona futhi iqembu elikhulu lezinyathelo ezinhlanu ezinamakhemikhali elihlanganisa okungenani ama-heteroatom angu-3. Esinye isibonelo samakhemikhali anjalo yi-dithiazoles aqukethe i-athomu ye-nitrogen nesibili sulfure.

Amasongo angama-6 ane-1 heteroatom

I-nomenclature esetshenziselwa amakhemikhali wezinsimbi ze-6 anezinyosi ze-nitrogen ene-nitrogen lapha ngezansi. Imisebenzi ekhoneni ye-pyridine iboniswa, izinombolo zesi-Arabhu zithandwa kakhulu ezincwadini zesiGreki, yize zombili izinhlelo zisetshenziswa. I-Pyridones yizinhlanganisela ezinomsoco ezinomthelela wokunikela kabusha ama-hybrid kusuka kumafomu e-resonance aqoshiwe njengoba kuboniswe i-4-pyridone.

coenzymes ababili olukhulu oluhilelekile kubalulekile ukusabela okuhlukahlukene umzimba kumaseli, nad (owaziwa nangokuthi coenzyme1) kanye NADP (owaziwa nangokuthi coenyme II), zihlobene nicotinamide.
Iningi lama-alkaloids liqukethe isakhiwo sezindandatho ze-piperidine noma i-pyridine, phakathi kwazo i-piperine (eyenza okunye okuhlosiwe okubukhali kwepelepele omnyama nomhlophe) kanye ne-nicotine. Izakhiwo zabo ziboniswa ngezansi.

I-Pyridine eyayisuswe ku-tar yamalahle kodwa manje isilungiselele ngokuzithandela kusuka ku-ammonia ne-tetrahydrofurfuryl utshwala kuyisimo esibalulekile kanye nesisombululo esisetshenziselwa ukwakha ezinye izinhlanganisela. I-Vinylpyridines iyimithi ebaluleke kakhulu yokwakha ama-plastiki, futhi i-piperidine ephelele ephelele, i-pyridine isetshenziselwa ukukhiqizwa kwezinto zamakhemikhali kanye nokucubungula kwenjoloba.

I-pyridines ewusizo ngokwemithi

I-pyridines ewusizo ngokwemithi ihlanganisa i-isonicotinic acid hydrazide (i-tuberculostat isoniazid), imithi elwa negciwane lesandulela ngculazi eyaziwa ngokuthi i-nevirapine, i-nicorandil - avasodilator esetshenziselwa ukulawula i-angina, i-phenazopyridine-i-analgesic yamagciwane kanye nesidakamizwa sulfa esivuthayo. I-diflufenican, i-clopyralid, i-paraquat, ne-diquat yizidakamizwa ezithandwa kakhulu ze-pyridine ezisetshenziswa njenge-herbicides.

Amasongo angama-6 ane-2 noma ama-heteroatom amaningi

I-3 monocyclic heterocycles yezinsimbi ezinamathandathu ayisithupha ne-2 nitrogen heteroatoms (diazines) ibalwa futhi ibizwa ngokuthi ikhonjiswe ngezansi.

I-hydrazide yama-Maleyi isisetshenziswa se-pyridazine esisetshenziswa njenge-herbicide. Amanye ama-pyrazines afana ne-aspergillic acid ayenzeka ngokwemvelo. Nazi izinhlaka zamakhemikhali ashiwo ngenhla:

I-Pyrazine ring iyinhlanganisela yamakhemikhali ahlukahlukene e-polycyclic okubaluleka kwezimboni neziphilayo. Amalungu abalulekile emndenini we-pyrazine ama-phenazines, alloxazines, nama-pteridines. Ngokwesimo semvelo nangokwemvelo, i-diazines ebaluleke kakhulu yi-pyrimidines. I-Cytosine, thymine, ne-urrac yi-3 yezingxenye ze-nucleotide ze-5 ezenza i-genetic code ku-RNA ne-DNA. Ngezansi kukhona izakhiwo zabo:

I-Vitamin thiamin inomngcele we-pyrimidine futhi ngaphezu kwama-barbiturates wokufakelwa okubandakanya i-amobarbital imithi evame ukusetshenziswa. I-Morpholine (umzali we-tetrahydro-1,4-oxazine) ikhiqizwa ngezinga elikhulu ukusetshenziswa njenge-fungicide, i-inhibitor ye-corrosion kanye ne-solvent. I-morpholine ring nayo itholakala ku-sedative-hypnotic drug trimetozine nezinye izifungicides ezifana ne-fenpropimorph kanye ne-tridemorph. Nansi indlela yokwakha ye-morpholine:

Amasongo angama-7

Njengoba usayizi wendandatho ukwanda, izinhlobonhlobo zezinhlanganisela ezingatholakala ngokushintsha indawo, uhlobo, kanye nenani lama-heteroatoms landa kakhulu. Kodwa-ke, i-chemistry ye-heterocycle enezindandatho ze-7 noma ngaphezulu ayitholakali kancane kuneleyo ye-6 kanye ne-5-membered ring ring heterocyclic.
I-Oxepine kanye ne-Azepine izindandatho ziyisakhi esibalulekile semikhiqizo ehlukahlukene yemvelo yemvelo yezilwane zasolwandle nama-alkaloids. Umkhiqizo we-azepine obizwa ngokuthi i-caprolactam ukukhiqizwa ngokuthengisa ngobuningi bokusetshenziswa ekwakhiweni kwe-nylon-6 njengesikhashana futhi ekukhiqizeni isikhumba, ukugqoka, namafilimu zokwenziwa.
7-membered compounds heterocyclic amabili noma eyodwa nitrogen athomu e indandatho zabo kukhona amayunithi isakhi psychopharmaceuticals ngobubanzi esetshenziswa Prazepine (tricyclic antidepressant) futhi imijovo diazepam yaziwa nangokuthi valium.

Amasongo angama-8

Izibonelo zama-heterocyclic compounds kuleli klasi zihlanganisa i-azocane, i-oxocane, ne-thiocane ne-nitrogen, i-oxygen, nesulfure yi-heteroatom ehambisanayo. Izakhi ezivela ku-unsaturated zazo ziyi-azocine, i-oxocine, ne-thiocine ngokulandelana.

Amasongo angama-9

Izibonelo zama-heterocyclic compounds kuleli klasi zihlanganisa i-azonane, i-oxonane, ne-thionane ene-nitrogen, i-oksijeni, nesulfure yi-heteroatom ehambisanayo. Izakhi ezivela ku-unsaturated zazo ziyi-azonine, i-oxonine, ne-thionine ngokulandelana.

Ukusetshenziswa kwama-heterocyclic compounds

Ama-heterocycle awusizo ezindaweni eziningana zezesayensi yokuphila nobuchwepheshe. Njengoba sesibonile kakade ekuxoxweni kwethu, izidakamizwa eziningi ziyizinhlanganisela ze-heterocyclic.

Okubhekwayo

IUPAC Book Book, ama-heterocyclic compounds. Isixhumanisi:

WH Powell: Ukubuyekezwa kwesistimu ye-Hantzsch-Widman ye-Nomenclature enwetshiwe yamaHeteromonocycles, Ku: I-Appl ehlanzekile. I-Chem.1983, 55, I-409-416;

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

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