“Heterocyclic compound”的意思、由来-开放百科全书

A heterocyclic compound or ring structure is a cyclic compound that has atoms of at least two different elements as members of its ring(s).^[1]^[2]^[3]^[4]^[5]^[6]^[7]^[8] Heterocyclic chemistry is the branch of organic chemistry dealing with the synthesis, properties, and applications of these heterocycles.^[9]

Examples of heterocyclic compounds include all of the nucleic acids, the majority of drugs, most biomass (cellulose and related materials), and many natural and synthetic dyes.

Classification

Although heterocyclic chemical compounds may be inorganic compounds or organic compounds, most contain at least one carbon. While atoms that are neither carbon nor hydrogen are normally referred to in organic chemistry as heteroatoms, this is usually in comparison to the all-carbon backbone. But this does not prevent a compound such as borazine (which has no carbon atoms) from being labelled "heterocyclic". IUPAC recommends the Hantzsch-Widman nomenclature for naming heterocyclic compounds.

Heterocyclic compounds can be usefully classified based on their electronic structure. The saturated heterocycles behave like the acyclic derivatives. Thus, piperidine and tetrahydrofuran are conventional amines and ethers, with modified steric profiles. Therefore, the study of heterocyclic chemistry focuses especially on unsaturated derivatives, and the preponderance of work and applications involves unstrained 5- and 6-membered rings. Included are pyridine, thiophene, pyrrole, and furan. Another large class of heterocycles are fused to benzene rings, which for pyridine, thiophene, pyrrole, and furan are quinoline, benzothiophene, indole, and benzofuran, respectively. Fusion of two benzene rings gives rise to a third large family of compounds, respectively the acridine, dibenzothiophene, carbazole, and dibenzofuran. The unsaturated rings can be classified according to the participation of the heteroatom in the conjugated system, pi system.

3-membered rings

Heterocycles with three atoms in the ring are more reactive because of ring strain. Those containing one heteroatom are, in general, stable. Those with two heteroatoms are more likely to occur as reactive intermediates.

4-membered rings

5-membered rings

With heterocycles containing five atoms, the unsaturated compounds are frequently more stable because of aromaticity.

Five-membered rings with one heteroatom

Five-membered rings with two heteroatoms

The 5-membered ring compounds containing two heteroatoms, at least one of which is nitrogen, are collectively called the azoles. Thiazoles and isothiazoles contain a sulfur and a nitrogen atom in the ring. Dithiolanes have two sulfur atoms.

Five-membered rings with at least three heteroatoms

A large group of 5-membered ring compounds with three heteroatoms also exists. One example is dithiazoles that contain two sulfur and a nitrogen atom.

6-membered rings

7-membered rings

With 7-membered rings, the heteroatom must be able to provide an empty pi orbital (e.g., boron) for "normal" aromatic stabilization to be available; otherwise, homoaromaticity may be possible. Compounds with one heteroatom include:

8-membered rings

9-membered rings

Images

Fused rings

Heterocyclic rings systems that are formally derived by fusion with other rings, either carbocyclic or heterocyclic, have a variety of common and systematic names. For example, with the benzo-fused unsaturated nitrogen heterocycles, pyrrole provides indole or isoindole depending on the orientation. The pyridine analog is quinoline or isoquinoline. For azepine, benzazepine is the preferred name. Likewise, the compounds with two benzene rings fused to the central heterocycle are carbazole, acridine, and dibenzoazepine. Thienothiophene are the fusion of two thiophene rings. Phosphaphenalenes are a tricyclic phosphorus-containing heterocyclic system derived from the carbocycle phenalene.

History of heterocyclic chemistry

The history of heterocyclic chemistry began in the 1800s, in step with the development of organic chemistry. Some noteworthy developments:^[12]

1832: Dobereiner produces furfural (a furan) by treating starch with sulfuric acid

1906: Friedlander synthesizes indigo dye, allowing synthetic chemistry to displace a large agricultural industry

1936: Treibs isolates chlorophyl derivatives from crude oil, explaining the biological origin of petroleum.

1951: Chargaff's rules are described, highlighting the role of heterocyclic compounds (purines and pyrimidines) in the genetic code.

Uses

Heterocyclic compounds are pervasive in many areas of life sciences and technology.^[13] Many drugs are heterocyclic compounds.^[14]

References

1. ^IUPAC Gold Book heterocyclic compounds
2. ^{{Cite journal|last=Kumar|first=Achutha Dileep|last2=Prabhudeva|first2=Malledevarapura Gurumurthy|last3=Bharath|first3=Srinivasan|last4=Kumara|first4=Karthik|last5=Lokanath|first5=Neratur Krishnappagowda|last6=Kumar|first6=Kariyappa Ajay|date=October 2018|title=Design and Amberlyst-15 mediated synthesis of novel thienyl-pyrazole carboxamides that potently inhibit Phospholipase A2 by binding to an allosteric site on the enzyme|url=https://linkinghub.elsevier.com/retrieve/pii/S004520681830378X|journal=Bioorganic Chemistry|volume=80|pages=444–452|doi=10.1016/j.bioorg.2018.06.023|pmid=29986189|issn=0045-2068}}
3. ^{{Cite journal|last=Dileep Kumar|first=Achutha|last2=Bharath|first2=Srinivasan|last3=Dharmappa|first3=Rekha N.|last4=Naveen|first4=Shivalingegowda|last5=Lokanath|first5=Neratur Krishnappagowda|last6=Ajay Kumar|first6=Kariyappa|date=2018-04-24|title=Design, synthesis and spectroscopic and crystallographic characterisation of novel functionalized pyrazole derivatives: biological evaluation for their cytotoxic, angiogenic and antioxidant activities|journal=Research on Chemical Intermediates|language=en|volume=44|issue=9|pages=5635–5652|doi=10.1007/s11164-018-3445-6|issn=0922-6168}}
4. ^{{Cite journal|last=Prabhudeva|first=Malledevarapura Gurumurthy|last2=Bharath|first2=Srinivasan|last3=Kumar|first3=Achutha Dileep|last4=Naveen|first4=Shivalingegowda|last5=Lokanath|first5=Neratur Krishnappagowda|last6=Mylarappa|first6=Bantaganahalli Ningappa|last7=Kumar|first7=Kariyappa Ajay|date=August 2017|title=Design and environmentally benign synthesis of novel thiophene appended pyrazole analogues as anti-inflammatory and radical scavenging agents: Crystallographic , in silico modeling, docking and SAR characterization|url=https://linkinghub.elsevier.com/retrieve/pii/S0045206817303607|journal=Bioorganic Chemistry|volume=73|pages=109–120|doi=10.1016/j.bioorg.2017.06.004|pmid=28648923|issn=0045-2068}}
5. ^{{Cite journal|last=Lokeshwari|first=Devirammanahalli Mahadevaswamy|last2=Achutha|first2=Dileep Kumar|last3=Srinivasan|first3=Bharath|last4=Shivalingegowda|first4=Naveen|last5=Krishnappagowda|first5=Lokanath Neratur|last6=Kariyappa|first6=Ajay Kumar|date=August 2017|title=Synthesis of novel 2-pyrazoline analogues with potent anti-inflammatory effect mediated by inhibition of phospholipase A2: Crystallographic, in silico docking and QSAR analysis|url=https://linkinghub.elsevier.com/retrieve/pii/S0960894X17306650|journal=Bioorganic & Medicinal Chemistry Letters|volume=27|issue=16|pages=3806–3811|doi=10.1016/j.bmcl.2017.06.063|pmid=28676270|issn=0960-894X}}
6. ^{{Cite journal|last=Lokeshwari|first=Devirammanahalli Mahadevaswamy|last2=Rekha|first2=Nanjappagowda Dharmappa|last3=Srinivasan|first3=Bharath|last4=Vivek|first4=Hamse Kameshwar|last5=Kariyappa|first5=Ajay Kumar|date=July 2017|title=Design, synthesis of novel furan appended benzothiazepine derivatives and in vitro biological evaluation as potent VRV-PL-8a and H + /K + ATPase inhibitors|url=https://linkinghub.elsevier.com/retrieve/pii/S0960894X17305474|journal=Bioorganic & Medicinal Chemistry Letters|volume=27|issue=14|pages=3048–3054|doi=10.1016/j.bmcl.2017.05.059|pmid=28554871|issn=0960-894X}}
7. ^{{Cite journal|last=Raghavendra|first=Kanchipura Ramachandrappa|last2=Renuka|first2=Nagamallu|last3=Kameshwar|first3=Vivek H.|last4=Srinivasan|first4=Bharath|last5=Ajay Kumar|first5=Kariyappa|last6=Shashikanth|first6=Sheena|date=August 2016|title=Synthesis of lignan conjugates via cyclopropanation: Antimicrobial and antioxidant studies|url=https://linkinghub.elsevier.com/retrieve/pii/S0960894X16306163|journal=Bioorganic & Medicinal Chemistry Letters|volume=26|issue=15|pages=3621–3625|doi=10.1016/j.bmcl.2016.06.005|pmid=27318538|issn=0960-894X}}
8. ^{{Cite journal|last=Nagamallu|first=Renuka|last2=Srinivasan|first2=Bharath|last3=Ningappa|first3=Mylarappa B.|last4=Kariyappa|first4=Ajay Kumar|date=January 2016|title=Synthesis of novel coumarin appended bis(formylpyrazole) derivatives: Studies on their antimicrobial and antioxidant activities|url=https://linkinghub.elsevier.com/retrieve/pii/S0960894X1530247X|journal=Bioorganic & Medicinal Chemistry Letters|volume=26|issue=2|pages=690–694|doi=10.1016/j.bmcl.2015.11.038|pmid=26631319|issn=0960-894X}}
9. ^{{cite web |title=Stibinin |url=http://www.chemspider.com/Chemical-Structure.119914.html |website=chemspider |publisher=Royal Society of Chemistry |accessdate=11 June 2018}}
10. ^{{cite web |title=Bismin |url=http://www.chemspider.com/Chemical-Structure.119910.html?rid=d49ac864-bf96-45d3-b78e-c54e585efbc4 |website=ChemSpider |publisher=Royal Society of Chemistry |accessdate=11 June 2018}}
11. ^{{cite web |title=Selenopyranium |url=http://www.chemspider.com/Chemical-Structure.10431325.html?rid=15953636-c58f-4e8d-b945-9912511e750a |website=ChemSpider |publisher=Royal Society of Chemistry |accessdate=11 June 2018}}
12. ^{{Cite journal |doi=10.1021/ed063p860|title=Adrien Albert and the rationalization of heterocyclic chemistry|journal=Journal of Chemical Education|volume=63|issue=10|pages=860|year=1986|last1=Campaigne|first1=E.}}
13. ^¹Thomas L. Gilchrist "Heterocyclic Chemistry" 3rd ed. Addison Wesley: Essex, England,1997. 414 pp. {{ISBN|0-582-27843-0}}.
14. ^Companies with the highest number of patents related to heterocyclic compounds.