Heterocyclic compound
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] Heterocyclic organic chemistry is the branch of organic chemistry dealing with the synthesis, properties, and applications of organic heterocycles.[2]
Examples of heterocyclic compounds include all of the
Classification
The study of organic heterocyclic chemistry focuses especially on organic unsaturated derivatives, and the preponderance of work and applications involves unstrained organic 5- and 6-membered rings. Included are
Heterocyclic organic compounds can be usefully classified based on their electronic structure. The saturated organic heterocycles behave like the acyclic derivatives. Thus,
Inorganic rings
Some heterocycles contain no carbon. Examples are
Notes on lists
- "Heteroatoms" are atoms in the ring other than carbon atoms.
- Names in italics are retained by Hantzsch-Widman nomenclature
- Some of the names refer to classes of compounds rather than individual compounds.
- Also no attempt is made to list isomers.
3-membered rings
Although subject to ring strain, 3-membered a heterocyclic rings are well characterized.[6]
Three-membered rings with one heteroatom
Heteroatom | Saturated | Unsaturated |
---|---|---|
Boron | Borirane | Borirene |
Nitrogen | Aziridine | Azirine |
Oxygen | Oxirane (ethylene oxide, epoxides )
|
Oxirene |
Phosphorus | Phosphirane | Phosphirene |
Sulfur | Thiirane (episulfides) | Thiirene |
Three-membered rings with two heteroatoms
Heteroatoms | Saturated | Unsaturated |
---|---|---|
2× Nitrogen | Diaziridine | Diazirine |
Nitrogen + oxygen | Oxaziridine | Oxazirine |
2× Oxygen | Dioxirane (highly unstable) |
4-membered rings
Four-membered rings with one heteroatom
Heteroatom | Saturated | Unsaturated |
---|---|---|
Nitrogen | Azetidine | Azete |
Oxygen | Oxetane | Oxete
|
Phosphorus | Phosphetane | Phosphete |
Sulfur | Thietane | Thiete |
Four-membered rings with two heteroatoms
Heteroatoms | Saturated | Unsaturated |
---|---|---|
2× Nitrogen | Diazetidine | Diazete |
2× Oxygen | Dioxetane | Dioxete |
2× Sulfur | Dithietane | Dithiete |
5-membered rings
Five-membered rings with one heteroatom
Heteroatom | Saturated | Unsaturated |
---|---|---|
Antimony | Stibolane | Stibole |
Arsenic | Arsolane | Arsole |
Bismuth | Bismolane | Bismole |
Boron | Borolane | Borole |
Nitrogen | Pyrrolidine ("Azolidine" is not used) | Pyrrole ("Azole" is not used) |
Oxygen | Tetrahydrofuran | Furan |
Phosphorus | Phospholane | Phosphole |
Selenium | Selenolane | Selenophene |
Silicon | Silacyclopentane | Silole
|
Sulfur | Tetrahydrothiophene | Thiophene |
Tellurium | Tellurophene
| |
Tin | Stannolane | Stannole |
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
have two sulfur atoms.Heteroatoms | Saturated | Unsaturated (and partially unsaturated) |
---|---|---|
2× nitrogen | Imidazolidine Pyrazolidine |
Imidazole (Imidazoline) Pyrazole (Pyrazoline) |
Oxygen + sulfur | 1,2-Oxathiolane
|
Oxathiole (Oxathioline) Isoxathiole |
Nitrogen + Oxygen | Oxazolidine Isoxazolidine |
Oxazole (Oxazoline) Isoxazole |
Nitrogen + sulfur | Thiazolidine Isothiazolidine |
Thiazole (Thiazoline) Isothiazole |
2× oxygen | Dioxolane | |
2× sulfur | Dithiolane | Dithiole |
Five-membered rings with at least three heteroatoms
A large group of 5-membered ring compounds with three or more heteroatoms also exists. One example is the class of
Heteroatoms | Saturated | Unsaturated |
---|---|---|
N N N | Triazoles | |
N N O | Furazan Oxadiazole | |
N N S | Thiadiazole
| |
N O O | Dioxazole | |
N S S | Dithiazole
| |
N N N N | Tetrazole | |
N N N N O | Oxatetrazole | |
N N N N S | Thiatetrazole | |
N N N N N | Pentazole |
6-membered rings
Six-membered rings with one heteroatom
Heteroatom | Saturated | Unsaturated | Ions |
---|---|---|---|
Antimony | Stibinin[7] | ||
Arsenic | Arsinane | Arsinine
| |
Bismuth | Bismin[8]
| ||
Boron | Borinane | Borinine
|
Boratabenzene anion |
Germanium | Germinane | Germine
| |
Nitrogen | Piperidine (Azinane is not used) |
Pyridine (Azine is not used) |
Pyridinium cation |
Oxygen | Oxane
|
Oxine is not used)
|
Pyrylium cation |
Phosphorus | Phosphinane | Phosphinine
| |
Selenium | Selenane | Selenopyran[9] | Selenopyrylium cation |
Silicon | Silinane | Siline
| |
Sulfur | Thiane | Thiopyran (2H-Thiine is not used) |
Thiopyrylium cation |
Tellurium | Tellurane
|
Telluropyran | Telluropyrylium cation |
Tin | Stanninane | Stannine
|
Six-membered rings with two heteroatoms
Heteroatom | Saturated | Unsaturated |
---|---|---|
Nitrogen / nitrogen | Diazinane | Diazine |
Oxygen / nitrogen | Morpholine | Oxazine
|
Sulfur / nitrogen | Thiomorpholine | Thiazine |
Oxygen / Sulfur | Oxathiane | Oxathiin |
Oxygen / oxygen | Dioxane
|
Dioxine |
Sulfur / sulfur | Dithiane | Dithiin |
Boron / nitrogen | 1,2-Dihydro-1,2-azaborine |
Six-membered rings with three heteroatoms
Heteroatom | Saturated | Unsaturated |
---|---|---|
Nitrogen | Triazinane | Triazine |
Oxygen | Trioxane | |
Sulfur | Trithiane
|
Six-membered rings with four heteroatoms
Heteroatom | Saturated | Unsaturated |
---|---|---|
Nitrogen | Tetrazine |
Carborazine is a six-membered ring with two nitrogen heteroatoms and two boron heteroatom.
Six-membered rings with five heteroatoms
Heteroatom | Saturated | Unsaturated |
---|---|---|
Nitrogen | Pentazine |
Six-membered rings with six heteroatoms
The hypothetical chemical compound with six nitrogen heteroatoms would be hexazine.
Borazine is a six-membered ring with three nitrogen heteroatoms and three boron heteroatoms.
7-membered rings
In a 7-membered ring, the heteroatom must be able to provide an empty π-orbital (e.g. boron) for "normal" aromatic stabilization to be available; otherwise, homoaromaticity may be possible. Compounds with one heteroatom include:
Heteroatom | Saturated | Unsaturated |
---|---|---|
Boron | Borepin | |
Nitrogen | Azepane | Azepine |
Oxygen | Oxepane | Oxepine
|
Sulfur | Thiepane | Thiepine |
Those with two heteroatoms include:
Heteroatom | Saturated | Unsaturated |
---|---|---|
Nitrogen | Diazepane | Diazepine |
Nitrogen/sulfur | Thiazepine |
8-membered rings
Heteroatom | Saturated | Unsaturated |
---|---|---|
Nitrogen | Azocane | Azocine |
Oxygen | Oxocane | Oxocine |
Sulfur | Thiocane | Thiocine |
Borazocine is an eight-membered ring with four nitrogen heteroatoms and four boron heteroatoms.
9-membered rings
Heteroatom | Saturated | Unsaturated |
---|---|---|
Nitrogen | Azonane | Azonine |
Oxygen | Oxonane | Oxonine |
Sulfur | Thionane | Thionine |
Images of rings with one heteroatom
Saturated | Unsaturated | ||||||
---|---|---|---|---|---|---|---|
Heteroatom | Nitrogen | Oxygen | Sulfur | Nitrogen | Oxygen | Sulfur | |
3-atom ring | Aziridine | Oxirane |
Thiirane | Azirine | Oxirene | Thiirene | |
4-atom ring | Azetidine | Oxetane | Thietane | Azete | Oxete |
Thiete | |
5-atom ring | Pyrrolidine | Oxolane |
Thiolane |
Pyrrole | Furan | Thiophene | |
6-atom ring | Piperidine | Oxane |
Thiane | Pyridine | Pyran | Thiopyran | |
7-atom ring | Azepane | Oxepane | Thiepane | Azepine | Oxepine |
Thiepine | |
8-atom ring | Azocane | Oxocane | Thiocane | Azocine | Oxocine | Thiocine | |
9-atom ring | Azonane | Oxonane | Thionane | Azonine | Oxonine | Thionine | |
Fused/condensed rings
Heterocyclic rings systems that are formally derived by fusion with other rings, either
History of heterocyclic chemistry
The history of heterocyclic chemistry began in the 1800s, in step with the development of organic chemistry. Some noteworthy developments:[10]
- 1818: Brugnatelli makes alloxan from uric acid
- 1832: Dobereiner produces furfural (a furan) by treating starch with sulfuric acid
- 1834: Runge obtains pyrrole ("fiery oil") by dry distillation of bones
- 1906: Friedlander synthesizes indigo dye, allowing synthetic chemistry to displace a large agricultural industry
- 1936: Treibs isolates chlorophyll 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.[2] Many drugs are heterocyclic compounds.[11]
See also
References
- IUPAC Gold Book heterocyclic compounds
- ^ a b Thomas L. Gilchrist "Heterocyclic Chemistry" 3rd ed. Addison Wesley: Essex, England,
1997. 414 pp. ISBN 0-582-27843-0.
- .
- PMID 25255204.)
{{cite journal}}
: CS1 maint: multiple names: authors list (link - ISBN 978-0-471-72091-1
- ^ "Stibinin". chemspider. Royal Society of Chemistry. Retrieved 11 June 2018.
- ^ "Bismin". ChemSpider. Royal Society of Chemistry. Retrieved 11 June 2018.
- ^ "Selenopyranium". ChemSpider. Royal Society of Chemistry. Retrieved 11 June 2018.
- .
- ^ "IPEXL.com Multilingual Patent Search, Patent Ranking". www.ipexl.com. Archived from the original on 24 September 2015. Retrieved 8 September 2010.
External links
- Hantzsch-Widman nomenclature, IUPAC
- Heterocyclic amines in cooked meat, US CDC
- List of known and probable carcinogens, American Cancer Society Archived 13 December 2003 at the Wayback Machine
- List of known carcinogens by the State of California, Proposition 65(more comprehensive)