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Feem ntau Cov Heterocycles Hauv Lub Ntiaj Teb

Feem ntau Cov Heterocycles Hauv Lub Ntiaj Teb

Heterocyclic tebchaw

Heterocyclic compound, los yog lub nplhaib sib luag yog ib qho uas muaj cov ntsiab lus uas muaj cov ntsiab lus ntawm cov ntsiab lus ntawm nws lub nplhaib / rings. Heterocyclic compounds tej zaum yuav tshwm sim rau feem ntau ntau thiab ntau tshaj tus naj npawb ntawm tsev neeg ntawm cov organic sib txuas.

Tsis hais txog kev ua haujlwm thiab tus qauv, txhua hom xyaw carbocyclic yuav raug hloov mus rau ntau hom heterocyclic analogs los ntawm kev hloov ib lossis ntau ntau lub nplhaib cov nplhaib nrog lwm lub caij. Yog li, heterocycles tau muaj lub platform rau kev sib pauv kev tshawb fawb hauv ntau qhov chaw xws li tab sis tsis txwv rau cov chaw muag tshuaj, tshuaj, soj ntsuam, thiab organic chemistry ntawm heterocyclic compounds.

Cov piv txwv tseem ceeb ntawm heterocyclic compounds yog cov tshuaj feem ntau, nucleic acids, feem ntau cov khoom cua thiab ntuj dyes, thiab feem ntau cov paj ntoos xws li cellulose thiab lwm yam ntaub ntawv.

Classification

Txawm hais tias heterocyclic tebchaw yuav ua tau cov organic los yog inorganic compounds, feem ntau muaj tsawg kawg yog ib cov pa roj carbon. Cov tebchaw no tuaj yeem faib ua kom raws li lawv cov qauv hluav taws xob. Cov kabmob hnoos heterocyclic muaj peev xwm ua rau tib yam li cov tshuaj lom kabmob (acyclic derivatives). Yog li ntawd, tetrahydrofuran thiab piperidine yog cov pa ethers thiab amines nrog hloov steric profiles.

Kev kawm txog heterocyclic chemistry, yog li ntawd, tsom xam cov ntsiab lus ntawm cov tsis muaj feem xyuam thiab cov ntawv thov koom nrog rau kev sib xyaw tsib zaug thiab cov tswvcuab rau tus tswvcuab rau cov tswvcuab. Qhov no muaj xws li furan, pyrrole, thiophene, thiab pyridine. Cov tom qab loj chav kawm ntawm heterocyclic compounds yog fused rau benzene rings, uas rau furan, pyrrole, thiophene, thiab pyridine yog benzofuran, indole, benzothiophene, thiab quinoline, feem. Yog tias ob lub nkev benzene rings, qhov no ua rau lwm tsev neeg loj sib txuas, uas yog dibenzofuran, carbazole, dibenzothiophene, thiab aridine. Cov suab paj nruag uas tsis tau muab cais tawm yuav raug cais raws li kev koom tes ntawm heteroatom nyob rau hauv cov system pi, conjugated system.

Npaj thiab tshua

3-membered rings

Heterocyclic compounds nrog peb atoms nyob rau hauv ib lub nplhaib yog txoj kev ntau reactive courtesy ntawm lub nplhaib lim. Heterocycles uas muaj ib qhov kab mob heteroatom feem ntau ruaj khov. Cov khoom uas muaj ob hom heteroatoms tshwm sim, feem ntau yog cov kev sib tshuam nruab nrab.

Oxiranes, tseem hu ua epoxide yog cov kab mob HOM X-xuabmoos uas tuaj yeem tshaj plaws. Oxiranes yog npaj los ntawm reacting peracids nrog alkenes, nrog zoo stereospecificity. Oxiranes muaj ntau dua dua li tsis muaj kev sib tw los ntawm kev sib tw siab ntawm lub kaum ntse ntse siab ntawm 3 tus neeg koom tes. Cov kev sib ntxiv ua ke uas tau npaj los ntawm ib qho nucleophilic thiab electrophilic qhib ntawm lub nplhaib yog hom kev tshaj tshuaj.

Qhov kev tawm tsam ntawm hom no yog kev koom tes hauv nitrogen mustards 'kev ua tshuaj ua lag luam uas yog ntawm thawj cov tshuaj anticancer tsim. Muab kaw ntawm lub nplhaib intramolecular zoo li nyob rau hauv rooj plaub ntawm anticancer tus neeg saib xyuas mechlorethamine cov ntaub ntawv ib nrab intermediate aziridium ion. Tus kab mob ua muaj roj ntsha tuaj yeem ua rau cov qoob loo muaj hlwb loj xws li kev mob hlwb los ntawm kev tsis sib haum ntawm lawv cov DNA. Nitrogen mustards kuj tau raug siv los ua cov koom haum tshuaj lom neeg.

Kev lag luam aziridine thiab oxirane yog qhov tseem ceeb muaj cov chemicals. Txog cov nplai loj ntawm cov oxirane, ethylene ncaj qha reacted nrog cov pa. Cov tshuaj tiv thaiv, nws yog qhov tseem cwj pwm ntawm cov 3 tus neeg rings, yog tias lawv raug sus tau los tua los ntawm nucleophilic reagents qhib lub nplhaib raws li qhia hauv qab no:

Feem ntau peb tug tswv cuab heterocyclic tebchaw nrog ib heteroatom xws li:

Teem ncaj ncees Unsaturated
Thiryane (episulfides) Thiirene
Phosphirane Phosphirene
Epoxides (oxirane, ethylene oxide) Oxirene
Aziridine Azirine
Borirane Borirene

Feem ntau peb cov tswvcuab heterocyclic compounds nrog ob heteroatoms muaj xws li Diaziridine ua tus derourative thiab Diazirine ua ib qho tsis muaj kev sibcog zoo li Dioxirane thiab Oxaziridine.

Plaub Ntug Raug

Muaj ntau txoj kev npaj ntawm 4 cov neeg koom ua ke heterocycles muaj nyob hauv daim duab hauv qab no. Tus txheej txheem ntawm reacting ib amine, thiol los yog 3-halo nrog lub hauv paus yog qhov zoo tab sis nrog nruab nrab yields. Dimerization thiab kev tshem tawm yog raug kev phiv cov neeg. Lwm yam dej num kuj tseem yuav sib tw rau hauv cov tshuaj tiv thaiv.

Hauv thawj tus piv txwv, cyclization mus rau ib qho chaw oxirane ib txwm sib tw nrog tsim ntawm thietane, tab sis ntau dua nucleophilicity dominates tshwj xeeb tshaj yog tias ib tug siv qis qis.

Nyob rau hauv lub thib ob piv txwv, tsim ntawm azetidine thiab aziridine yog ua tau, tab sis tsuas yog yav tas yog pom. Piv txwv plaub muaj qhia tias qhov kev qhia no yog tsim los ntawm kev tsim tawm ntawm azetidine zoo heev yog tias tsis muaj kev sib tw.

Hauv qhov piv txwv thib peb, qhov sib txeeb ntawm lub substrate favors tsim ntawm oxetane thiab tiv thaiv kev kho ntawm oxirane. Hauv kev piv txwv 5 thiab 6, cov qauv luam ntawm Paterno-Buchi yog cov tsim tshwj xeeb rau kev tsim oxetane.

Txoj kev ntawm kev npaj 4 cov neeg koom ua ke heterocycles

Tshua

Qhov tshwm sim ntawm 4 tus tswv cuab heterocyclic tebchaw kuj nthuav tawm lub nplhaib sib txawv. Cov duab hauv qab no qhia txog qee cov qauv. Acid-catalysis yog ib qho kev raug ntawm ntau lub suab nrov-qhib kev pom tshwm hauv cov qauv 1,2, thiab 3a. Hauv cov tshuaj tiv thaiv 2 ntawm thietane, leej faj nyob rau hauv electrophilic chlorination ua rau chlorosulfonium intermediate thiab hloov ntawm lub nplhaib qhib chloride ion. Hauv cov tshuaj tiv thaiv 3b, muaj zog nucleophiles tseem pom tau qhib lub strained ether. Beta-lactones 'cleavage tshua yuav tshwm sim los ntawm cov kua qaub-catalyzed acyl txauv raws li pom hauv 4a. Nws tuaj yeem siv qhov chaw los ntawm al-O rupture los ntawm nucleophiles zoo li hauv 4b.

Piv txwv naj npawb 6 qhia tau hais tias muaj kev tshwm sim zoo ntawm kev txav ntawm cov txheej txheem ntawm cov qauv ortho-ester. Cov tshuaj 6 qhia tau tias Beta-lactam cleavage ntawm penicillin G uas yog piav txog qhov ua kom muaj zog zoo tshaj plaws ntawm lub nplaub tshev fused.

Piv txwv ntawm kev tshua ntawm 4 tus tswvcuab heterocyclic compounds

Qhov tseem ceeb tshaj heterocyclic tebchaw nrog 4 cov tub koom ua ke yog ob hom tshuaj tua kab mob, cov cephalosporins, thiab penicillins. Ob koob muaj azetidinone lub nplhaib uas yog hu ua Beta-lactam nplhaib.
Muaj ntau oxetanes nyob rau hauv kev tshawb nrhiav raws li antiviral, anticancer, anti-inflammatory, thiab antifungal cov neeg ua hauj lawm. Oxetanones, ntawm qhov tod tes, feem ntau yog siv rau kev ua liaj teb ua bactericides, fungicides, thiab herbicides thiab hauv kev tsim cov polymer.
Niam txiv thietane tau pom nyob rau hauv cov roj shale roj thaum nws cov ntxhiab tsw ua haujlwm ua haujlwm ua ntxhiab rau European polecats, ferrets, thiab minks. Cov thietanes siv cov fungicides thiab bactericides nyob rau hauv cov xim, raws li cov hlau txhuam kev lim dej, thiab hauv kev tsim cov polymers.

Plaub tug neeg koom ua ke nrog sib txuas nrog ib tus neeg heteroatom

Heteroatom Raug Accidented Unsaturated

Heteroatom Teem ncaj ncees Unsaturated
sulfur Thietane Azete
pa Oxetane Oxete
nitrogen Azetidine Azete

Plaub tug neeg koom ua ke nrog ob lub heteroatoms

Heteroatom Teem ncaj ncees Unsaturated
sulfur Dithietane Dithiete
pa Dioxetane Dioxete
nitrogen Diazetidine Diazete

5-tus neeg koom ua ke nrog ib tus heteroatom

Thiophene, furan, thiab pyrrole yog leej niam leej txiv cov kab txawv ntawm 5 cov neeg koom ua ke heterocycles. Ntawm no yog lawv cov lug:

Cov phom kub ntawm cov thiophene, furan, thiab pyrrole yog thiophane, tetrahydrofuran, thiab pyrrolidine feem. Bisicic compounds ua los ntawm thiophene, furan, los yog pyrrole nplaum fused rau lub nplhaib benzene yog hu ua benzothiophene, benzofuran, isoindole (los yog indole).
Nitrogen heterocycle pyrrole feem ntau tshwm sim hauv cov pob txha roj uas tsim los ntawm cov kabmob ntawm cov nqaijrog los ntawm cov cua kub. Cov pyrrole rings muaj nyob rau hauv cov amino acids xws li hydroxyproline thiab proline uas yog cov khoom ntawm ntau cov proteins uas muaj nyob rau hauv cov khoom muaj zog hauv cov khoom ua pa ntawm ligaments, tendons, tawv, thiab cov pob txha thiab cov roj hmab.
Pyrrole derivatives muaj nyob hauv cov alkaloids. Nicotine yog tus paub khov heev uas muaj alkaloid. Hemoglobin, myoglobin, Vitamin B12, thiab chlorophylls, yog tag nrho tsim los ntawm koom nrog plaub pyrrole units hauv lub nplhaib loj hu ua porphyrin, zoo li chlorophyll B hauv qab no.

Cov pob pigments raug tsim los ntawm kev siv lub suab porphyrine nplhaib thiab muaj cov saw 4 pyrrole rings.
Npaj ntawm 5 tus tswv cuab ntawm lub suab sib txuas heterocycles
Muaj kev npaj ua lag luam qhib raws li qhia hauv qab no los ntawm txoj kev aldehyd, furfural, uas yog tsim los ntawm pentose uas muaj cov khoom raw li corncobs. Zoo nkaus li kev npaj thiophene thiab pyrrole yog qhia nyob rau hauv ob kab hauv kab zauv.
Qhov thib peb kab ntawm kab zauv ib qho qhia txog kev npaj hloov thiophenes, pyrroles, furans los ntawm 1,4-dicarbonyl compounds. Muaj ntau lwm cov kev ua rau txoj kev hloov heterocycles ntawm hom no tau pib. Ob ntawm cov txheej txheem no tau tshwm sim nyob rau hauv qhov kev txiav txim siab thib ob thiab peb. Furan yog txo los ntawm palladium-catalyzed hydrogenation rau tetrahydrofuran. Qhov kev hloov ntawm no yog ib qho tseem ceeb uas tsis tau hloov dua siab tshiab rau 4-haloalkylsulfonates tab sis kuj 1,4-dihalobutanes uas siv tau los npaj thiolane thiab pyrrolidine.

Tsib tus neeg koom ua ke sib txuas nrog cov tib neeg heteroatom

Heteroatom Unsaturated Teem ncaj ncees
antimony Nqa dej Stibolane
arsenic Arsole Arsolane
cov bismuth Bismole Bismolane
boron Borole Borolane
nitrogen Pyrrole Pyrrolidine
pa Furan Tetrahydrofuran

5-membered rings nrog 2 heteroatoms

Tsib tsib ceg sib txuas ua ke nrog 2 heteroatoms thiab tsawg kawg yog ib qho ntawm heteroatoms yog Nitrogen, raug hu ua azoles. Isothiazoles thiab thiazoles muaj nitrogen thiab sulfur atom nyob rau hauv lub nplhaib. Cov qoob loo uas muaj ob hom tshuaj uas muaj xoos hnoos tau raug hu ua Dithiolanes.

Heteroatom Unsaturated (thiab cov unsaturated) Teem ncaj ncees
nitrogen

/ nitrogen

Pyrazole (Pyrazoline)

Imidazole (Imidazoline)

Pyrazolidine

Imidazolidine

Nitrogen / oxygen Isoxazole

Oxazoline (oxazole)

Isoxazolidine

oxazolidine

Nitrogen / sulfur Isothiazole

Thiazoline (Thiazole)

Isothiazolidine

Thiazolidine

Cov pa / oxygen Dioxolane
Sulfur / sulfur Dithiolane

Ib txhia pyrazoles tshwm sim lawm. Cov chav kawm ntawm hoob kawm no yog npaj los ntawm reacting 1,3-diketones nrog hydrazines. Feem ntau cov khoom cua pyrazole sib txuas yog siv tshuaj thiab dyes. Cov no muaj xws li ua npaws-txo kev mob ntawm cov kab mob hauv cov ntshav qab zib, phenybutazone siv tshuaj kho mob, fiber ntau thiab xim daj tartrazine, thiab feem ntau ntawm cov dyes siv hauv cov xim thaij duab raws li cov neeg siv tshuaj.

5-membered rings nrog 3 heteroatoms

Kuj tseem muaj ib pawg coob coob ntawm tsib lub koomhaum nplhaib nrog tsawg kawg 3 heteroatoms. Ib tug piv txwv ntawm xws li sib txuas yog dithiazoles uas muaj ib tug nitrogen atom thiab ob sulfur.

6 cov tub koom ua ke nrog 1 heteroatom

Cov npe siv hauv lub tshuab xaw pob zeb uas muaj 6-membered ringtone muaj nyob rau ntawm no. Cov haujlwm ntawm lub nplhaib rau pyridine yog qhia, Arabic cov najnpawb yog cov najnpawb ntau dua rau cov ntawv Greek, txawm tias ob lub tshuab siv. Pyridones yog cov kab mob uas muaj ntxhiab los ntawm kev sib koom tes rau cov kab mob resonance hybrid los ntawm cov ntaub ntawv uas muaj resonance raws li pom tias rau 4-pyridone.

Ob tug coenzymes loj txuam rau ntau yam tseem ceeb hauv metabolic hauv hlwb, NAD (tseem hu ua coenzyme1) thiab NADP (tseem hu ua coenyme II), muab los ntawm nicotinamide.
Feem ntau cov alkaloids muaj cov piperidine los yog pyridine lub nplhaib, ntawm cov piperine (yog ib qho ntawm cov ntsiab lus ntse ntawm dub thiab dawb kua txob) thiab nicotine. Lawv cov qauv qhia nram qab no.

Pyridine uas yog ib zaug muab rho tawm los ntawm cov thee thee, tab sis tam sim no yog npaj los ntawm ammonia thiab tetrahydrofurfuryl cawv yog ib qho tseem ceeb heev thiab ua kom hnyav siv los ua lwm lub tebchaw. Vinylpyridines yog ib qho tseem ceeb ntawm monomer tsev ntawm plastics, thiab saturated piperidine, pyridine yog siv tshuaj chemical raw khoom thiab roj hmab ua.

Pharmaceutical kuj pyridines

Pharmaceutically beneficial pyridines muaj xws li isonicotinic acid hydrazide (tuberculostat isoniazid), tshuaj tiv thaiv anti-AIDS-virus hu ua nevirapine, nicorandil - avasodilator uas siv los tswj cov kev muaj mob angina, phenazopyridine-lub qhov zis quav tshuaj xws li tshuaj anti-inflammatory sulfa. Cov kab mob, clopyralid, parquat, thiab diquat yog nrov pyridine derivatives uas yog siv los ua herbicides.

6-membered rings nrog 2 los yog ntau dua heteroatoms

3 monocyclic six-membered ring heterocycles nrog 2 nitrogen heteroatoms (diazines) yog suav thiab teev npe raws li qhia hauv qab no.

Txiv neej hydrazide yog ib qho khoom siv pyridazine siv los ua herbicide. Qee cov pyrazines xws li aspergillic acid tshwm sim lawm. Ntawm no yog cov qauv ntawm cov lus sib txuas:

Pyrazine ring yog ib qho kev tivthaiv ntau hom tshuaj tua kabmob (polycyclic bacteria) ntawm kev tsim tawm thiab kev coj noj coj ua. Cov neeg tseem ceeb ntawm tsev neeg pyrazine yog phenazines, alloxazines, thiab pteridines. Pharmacologically thiab biologically, feem ntau tseem ceeb heev diazines yog pyrimidines. Cytosine, thymine, thiab uracil yog 3 ntawm 5 nucleotide bases uas yog lub caj dab hauv RNA thiab DNA. Hauv qab no lawv cov lug:

Vitamin thiamin muaj pyrimidine ntiv nplhaib thiab ntxiv rau cov khoom siv sib txuas nrog cov tshuaj amobarbital uas yog siv cov tshuaj. Morpholine (niam txiv tetrahydro-1,4-oxazine) yog tsim los ntawm cov nplai loj rau kev siv ua fungicide, corrosion inhibitor, thiab hnyav. Morpholine ntiv nplhaib kuj pom muaj nyob rau hauv cov tshuaj sediments-hypnotic trimetozine thiab qee yam kev phungicides zoo li cov tshuaj tawg paj thiab tridemorph. Ntawm no yog cov qauv qauv rau morpholine:

7-membered rings

Raws li lub nplhaib loj tuaj, ntau hom kev sib txuas uas tau txais los ntawm qhov sib txawv ntawm qhov chaw, hom, thiab cov heteroatoms ntau zog. Txawm li cas los xij, chemistry ntawm heterocycles nrog 7 cov npe neeg los yog ntau dua yog tsim tsawg dua li 6 thiab 5 koom nrog lub tebchaw heterocyclic.
Oxepine thiab Azepine rings yog cov khoom tseem ceeb heev ntawm cov khoom muaj tshwm sim ntawm cov khoom siv roj ntsha thiab cov alkaloids. Tus neeg tsim tawm lub npe hu ua caprolactam yog muag khoom hauv kev ua khoom siv ntawm cov ntaub lis loos-6 ua ib nrab thiab hauv cov tawv hluavtaws, coatings, thiab cov yeeb yaj kiab.
7-membered heterocyclic compounds nrog ob los sis ib tug nitrogen atom nyob rau hauv lawv lub nplhaib yog cov yam ntxwv ntawm kev siv cov tshuaj psychopharmaceutical Prazepine (tricyclic antidepressant) thiab tranquilizer diazepam hu ua valium.

8-membered rings

Piv txwv ntawm heterocyclic compounds hauv chav kawm no muaj xws li azocane, oxocane, thiab thiocane nrog Nitrogen, oxygen, thiab sulfur yog cov heteroatoms. Lawv cov khoom xyaw unsaturated yog azocine, oxocine, thiab thiocine.

9-membered rings

Piv txwv ntawm heterocyclic compounds hauv chav kawm no muaj xws li azonane, oxonane, thiab thiaane nrog Nitrogen, oxygen, thiab sulfur yog cov heteroatoms. Cov lawv cov khoom xyaw unsaturated yog azonine, oxonine, thiab thiaine feem.

Siv cov kab mob heterocyclic

Heterocycles yog ib qho tseem ceeb nyob rau ntau qhov chaw ntawm lub neej ywj pheej thiab kev siv tshuab. Raws li peb twb pom hauv peb cov kev sib tham, ntau cov tshuaj yog heterocyclic tebchaw.

References

IUPAC kub phau, heterocyclic tebchaw. Txuas:

WH Powell: Kev hloov kho ntawm Hantzsch-Widman System ntawm Nomenclature rau Heteromonocycles, nyob rau hauv: Pure Appl. Chem.1983, 55, 409-416;

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

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