Friedel–Crafts reaction

Set of reactions to attach substituents to an aromatic ring

Friedel-Crafts reaction

Named after  | Charles Friedel
James Crafts
Reaction type  | Coupling reaction
Reaction
| Aromatic Ring

Alkyl Halide, Alcohol, Alkene or Alkyne

Coupling Product
Conditions
Catalyst |

Strong lewis acid:
Zeolite, AlCl3

Identifiers
RSC ontology ID  | RXNO:0000369

The Friedel–Crafts reactions are a set of reactions developed by Charles Friedel and James Crafts in 1877 to attach substituents to an aromatic ring.[1] Friedel–Crafts reactions are of two main types: alkylation reactions and acylation reactions. Both proceed by electrophilic aromatic substitution.[2][3][4][5]

## Alkylation

[edit]

Friedel-Crafts alkylation

Named after  | Charles Friedel
James Crafts
Reaction type  | Coupling reaction
Reaction
| Aromatic Ring

Alkylating Agent

Friedel-Crafts aromatic addition product

HCl (reaction type dependent)
Conditions
Catalyst |

Strong lewis acid:
Zeolite, AlCl3

Identifiers
Organic Chemistry Portal  | friedel-crafts-alkylation
RSC ontology ID  | RXNO:0000046

### With alkenes

[edit]

In commercial applications, the alkylating agents are generally alkenes, some of the largest scale reactions practiced in industry. Such alkylations are of major industrial importance, e.g. for the production of ethylbenzene, the precursor to polystyrene, from benzene and ethylene and for the production of cumene from benzene and propene in cumene process:

Industrial production typically uses solid acids derived from a zeolite as the catalyst.

### With alkyl halides

[edit]

Friedel–Crafts alkylation involves the alkylation of an aromatic ring. Traditionally, the alkylating agents are alkyl halides. Many alkylating agents can be used instead of alkyl halides. For example, enones and epoxides can be used in presence of protons. The reaction typically employs a strong Lewis acid, such as aluminium chloride as catalyst, to increase the electrophilicity of the alkylating agent.[6]

This reaction suffers from the disadvantage that the product is more nucleophilic than the reactant because alkyl groups are activators for the Friedel–Crafts reaction. Consequently, overalkylation can occur. However, steric hindrance can be exploited to limit the number of successive alkylation cycles that occur, as in the t-butylation of 1,4-dimethoxybenzene that gives only the product of two alkylation cycles and with only one of three possible isomers of it:[7]

Furthermore, the reaction is only useful for primary alkyl halides in an intramolecular sense when a 5- or 6-membered ring is formed. For the intermolecular case, the reaction is limited to tertiary alkylating agents, some secondary alkylating agents (ones for which carbocation rearrangement is degenerate), or alkylating agents that yield stabilized carbocations (e.g., benzylic or allylic ones). In the case of primary alkyl halides, the carbocation-like complex (R(+)\
X
Al(-)Cl3) will undergo a carbocation rearrangement reaction to give almost exclusively the rearranged product derived from a secondary or tertiary carbocation.[8]

Protonation of alkenes generates carbocations, the electrophiles. A laboratory-scale example by the synthesis of neophyl chloride from benzene and methallyl chloride using sulfuric acid catalyst.[9]

#### Mechanism

[edit]

The general mechanism for primary alkyl halides is shown in the figure below.[8]

Mechanism of Friedel–Crafts alkylation.For primary (and possibly secondary) alkyl halides, a carbocation-like complex with the Lewis acid, [R(+)\
(X
MXn)(–)] is more likely to be involved, rather than a free carbocation.

### Friedel–Crafts dealkylation

[edit]

Friedel–Crafts alkylations can be reversible. Although this is usually undesirable it can be exploited; for instance by facilitating transalkylation reactions.[10]

1,3-Diisopropylbenzene is produced via transalkylation, a special form of Friedel–Crafts alkylation.

It also allows alkyl chains to be added reversibly as protecting groups. This approach is used industrially in the synthesis of 4,4'-biphenol via the oxidative coupling and subsequent dealkylation of 2,6-di-tert-butylphenol.[11][12]

## Acylation

[edit]

Friedel-Crafts acylation

Named after  | Charles Friedel
James Crafts
Reaction type  | Coupling reaction
Reaction
| Aromatic Ring

Acylating agents

Friedel-Crafts aromatic addition product

HCl (reaction type dependent)
Conditions
Catalyst |

Strong lewis acid:
Zeolite, AlCl3

Identifiers
Organic Chemistry Portal  | friedel-crafts-acylation
RSC ontology ID  | RXNO:0000045

Friedel–Crafts acylation involves the acylation of aromatic rings. Typical acylating agents are acyl chlorides. Acid anhydrides as well as carboxylic acids are also viable. A typical Lewis acid catalyst is aluminium trichloride. Because, however, the product ketone forms a rather stable complex with Lewis acids such as AlCl3, a stoichiometric amount or more of the "catalyst" must generally be employed, unlike the case of the Friedel–Crafts alkylation, in which the catalyst is constantly regenerated.[13] Reaction conditions are similar to the Friedel–Crafts alkylation. This reaction has several advantages over the alkylation reaction. Due to the electron-withdrawing effect of the carbonyl group, the ketone product is always less reactive than the original molecule, so multiple acylations do not occur. Also, there are no carbocation rearrangements, as the acylium ion is stabilized by a resonance structure in which the positive charge is on the oxygen.

The viability of the Friedel–Crafts acylation depends on the stability of the acyl chloride reagent. Formyl chloride, for example, is too unstable to be isolated. Thus, synthesis of benzaldehyde through the Friedel–Crafts pathway requires that formyl chloride be synthesized in situ. This is accomplished by the Gattermann-Koch reaction, accomplished by treating benzene with carbon monoxide and hydrogen chloride under high pressure, catalyzed by a mixture of aluminium chloride and cuprous chloride. Simple ketones that could be obtained by Friedel–Crafts acylation are produced by alternative methods, e.g., oxidation, in industry.

### Reaction mechanism

[edit]

The reaction proceeds through generation of an acylium center. The reaction is completed by deprotonation of the arenium ion by AlCl4−, regenerating the AlCl3 catalyst. However, in contrast to the truly catalytic alkylation reaction, the formed ketone is a moderate Lewis base, which forms a complex with the strong Lewis acid aluminum trichloride. The formation of this complex is typically irreversible under reaction conditions. Thus, a stochiometric quantity of AlCl3 is needed. The complex is destroyed upon aqueous workup to give the desired ketone. For example, the classical synthesis of deoxybenzoin calls for 1.1 equivalents of AlCl3 with respect to the limiting reagent, phenylacetyl chloride.[14] In certain cases, generally when the benzene ring is activated, Friedel–Crafts acylation can also be carried out with catalytic amounts of a milder Lewis acid (e.g. Zn(II) salts) or a Brønsted acid catalyst using the anhydride or even the carboxylic acid itself as the acylation agent.

If desired, the resulting ketone can be subsequently reduced to the corresponding alkane substituent by either Wolff–Kishner reduction or Clemmensen reduction. The net result is the same as the Friedel–Crafts alkylation except that rearrangement is not possible.[15]

## Hydroxyalkylation

[edit]

Arenes react with certain aldehydes and ketones to form the hydroxyalkylated products, for example in the reaction of the mesityl derivative of glyoxal with benzene:[16]

As usual, the aldehyde group is more reactive electrophile than the phenone.

## Scope and variations

[edit]

Alkylation of benzene & ethylene, one of the largest scale reactions practiced commercially.

This reaction is related to several classic named reactions:

* The acylated reaction product can be converted into the alkylated product via a Clemmensen or a Wolff-Kishner reduction.[17]
* The Gattermann–Koch reaction can be used to synthesize benzaldehyde from benzene.[18]
* The Gatterman reaction describes arene reactions with hydrocyanic acid.[19][20]
* The Houben–Hoesch reaction describes arene reactions with nitriles.[21]
* A reaction modification with an aromatic phenyl ester as a reactant is called the Fries rearrangement.
* In the Scholl reaction two arenes couple directly (sometimes called Friedel–Crafts arylation).[22]
* In the Blanc chloromethylation a chloromethyl group is added to an arene with formaldehyde, hydrochloric acid and zinc chloride.
* The Bogert–Cook synthesis (1933) involves the dehydration and isomerization of 1-β-phenylethylcyclohexanol to the octahydro derivative of phenanthrene[23]

* The Darzens–Nenitzescu synthesis of ketones (1910, 1936) involves the acylation of cyclohexene with acetyl chloride to methylcyclohexenylketone.
* In the related Nenitzescu reductive acylation (1936) a saturated hydrocarbon is added making it a reductive acylation to methylcyclohexylketone
* The Nencki reaction (1881) is the ring acetylation of phenols with acids in the presence of zinc chloride.[24]
* In a green chemistry variation aluminium chloride is replaced by graphite in an alkylation of p-xylene with 2-bromobutane. This variation will not work with primary halides from which less carbocation involvement is inferred.[25]

### Dyes

[edit]

Friedel–Crafts reactions have been used in the synthesis of several triarylmethane and xanthene dyes.[26] Examples are the synthesis of thymolphthalein (a pH indicator) from two equivalents of thymol and phthalic anhydride:

A reaction of phthalic anhydride with resorcinol in the presence of zinc chloride gives the fluorophore fluorescein. Replacing resorcinol by N,N-diethylaminophenol in this reaction gives rhodamine B:

### Haworth synthesis

[edit]

The Haworth synthesis is a classic method for the synthesis of polycyclic aromatic hydrocarbons. In this reaction, an arene is reacted with succinic anhydride, the subsequent product is then reduced in either a Clemmensen reduction or a Wolff-Kishner reduction. Lastly, a second Friedel-Crafts acylation takes place with addition of acid.[27]

The product formed in this reaction is then analogously reduced, followed by a dehydrogenation reaction (with the reagent SeO2 for example) to extend the aromatic ring system.[28]

### Friedel–Crafts test for aromatic hydrocarbons

[edit]

Reaction of chloroform with aromatic compounds using an aluminium chloride catalyst gives triarylmethanes, which are often brightly colored, as is the case in triarylmethane dyes. This is a bench test for aromatic compounds.[29]

## See also

[edit]

* Friedel family, lineage of French scientists
* Hydrodealkylation
* Transalkylation

## References

[edit]

1. ^ Friedel, C.; Crafts, J. M. (1877) "Sur une nouvelle méthode générale de synthèse d'hydrocarbures, d'acétones, etc.," Compt. Rend., 84: 1392 & 1450.
2. ^ Price, C. C. (1946). "The Alkylation of Aromatic Compounds by the Friedel-Crafts Method". Org. React. 3: 1. doi:10.1002/0471264180.or003.01. ISBN 0471264180. `{{cite journal}}`: ISBN / Date incompatibility (help)
3. ^ Groves, J. K. (1972). "The Friedel–Crafts acylation of alkenes". Chem. Soc. Rev. 1: 73. doi:10.1039/cs9720100073.
4. ^ Eyley, S. C. (1991). "The Aliphatic Friedel–Crafts Reaction". Compr. Org. Synth. 2: 707–731\. doi:10.1016/B978-0-08-052349-1.00045-7. ISBN 978-0-08-052349-1.
5. ^ Heaney, H. (1991). "The Bimolecular Aromatic Friedel–Crafts Reaction". Compr. Org. Synth. 2: 733–752\. doi:10.1016/B978-0-08-052349-1.00046-9. ISBN 978-0-08-052349-1.
6. ^ Rueping, M.; Nachtsheim, B. J. (2010). "A review of new developments in the Friedel–Crafts alkylation – From green chemistry to asymmetric catalysis". Beilstein J. Org. Chem. 6 (6): 6. doi:10.3762/bjoc.6.6. PMC 2870981. PMID 20485588.
7. ^ L., Williamson, Kenneth (4 January 2016). Macroscale and microscale organic experiments. Masters, Katherine M. (Seventh ed.). Boston, MA, USA. ISBN 9781305577190. OCLC 915490547.`{{cite book}}`: CS1 maint: location missing publisher (link) CS1 maint: multiple names: authors list (link)
8. ^ a b Smith, Michael B.; March, Jerry (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience, ISBN 978-0-471-72091-1
9. ^ Smith, W. T. Jr.; Sellas, J. T. (1952). "Neophyl Chloride". Organic Syntheses. 32: 90. doi:10.15227/orgsyn.032.0090.
10. ^ Tsai, Tseng-Chang "Disproportionation and Transalkylation of Alkylbenzenes over Zeolite Catalysts". Elsevier Science, 1999
11. ^ Helmut Fiege; Heinz-Werner Voges; Toshikazu Hamamoto; et al. (2002). "Phenol Derivatives". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_313. ISBN 3527306730.
12. ^ Hay, Allan S. (1969). "p,p'-Biphenols". The Journal of Organic Chemistry. 34 (4): 1160–1161\. doi:10.1021/jo01256a098.
13. ^ Somerville, L. F.; Allen, C. F. H. (1933). "β-Benzoylpropionic acid". Organic Syntheses. 13: 12. doi:10.15227/orgsyn.013.0012.
14. ^ "Desoxybenzoin". orgsyn.org. Retrieved 26 January 2019.
15. ^ Friedel-Crafts Acylation. Organic-chemistry.org. Retrieved 2014-01-11.
16. ^ Fuson, R. C.; Weinstock, H. H.; Ullyot, G. E. (1935). "A New Synthesis of Benzoins. 2′,4′,6′-Trimethylbenzoin". J. Am. Chem. Soc. 57 (10): 1803–1804\. Bibcode:1935JAChS..57.1803F. doi:10.1021/ja01313a015.′,4′,6′-Trimethylbenzoin&rft.volume=57&rft.issue=10&rft.pages=1803-1804&rft.date=1935&rft_id=info:doi/10.1021/ja01313a015&rft_id=info:bibcode/1935JAChS..57.1803F&rft.au=Fuson,+R.+C.&rft.au=Weinstock,+H.+H.&rft.au=Ullyot,+G.+E.&rfr_id=info:sid/en.wikipedia.org:Friedel–Crafts+reaction" class="Z3988">
17. ^ Smith & March 2001, p. 1835.
18. ^ Smith & March 2001, p. 745.
19. ^ Smith, Michael B.; March, Jerry (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience, p. 725, ISBN 978-0-471-72091-1
20. ^ Smith, M.B.; March, J (2001). March's Advanced Organic Chemistry. p. 725\. ISBN 0-471-58589-0.
21. ^ Smith & March 2001, p. 732.
22. ^ Grzybowski, M.; Skonieczny, K.; Butenschön, H.; Gryko, D. T. (2013). "Comparison of Oxidative Aromatic Coupling and the Scholl Reaction". Angew. Chem. Int. Ed. 52 (38): 9900–9930\. doi:10.1002/anie.201210238. PMID 23852649.
23. ^ This reaction with phosphorus pentoxide: Kamp, J. V. D.; Mosettig, E. (1936). "Trans- and Cis-As-Octahydrophenanthrene". Journal of the American Chemical Society. 58 (6): 1062–1063\. doi:10.1021/ja01297a514.
24. ^ Nencki, M.; Sieber, N. (1881). "Ueber die Verbindungen der ein- und zweibasischen Fettsäuren mit Phenolen". J. Prakt. Chem. (in German). 23: 147–156\. doi:10.1002/prac.18810230111.
25. ^ Sereda, Grigoriy A.; Rajpara, Vikul B. (2007). "A Green Alternative to Aluminum Chloride Alkylation of Xylene". J. Chem. Educ. 2007 (84): 692. Bibcode:2007JChEd..84..692S. doi:10.1021/ed084p692.
26. ^ McCullagh, James V.; Daggett, Kelly A. (2007). "Synthesis of Triarylmethane and Xanthene Dyes Using Electrophilic Aromatic Substitution Reactions". J. Chem. Educ. 84 (11): 1799. Bibcode:2007JChEd..84.1799M. doi:10.1021/ed084p1799.
27. ^ Li, Jie Jack (2003) Name Reactions: A Collection of Detailed Reaction Mechanisms, Springer, ISBN 3-540-40203-9, p. 175.
28. ^ Menicagli, Rita; Piccolo, Oreste (June 1980). "Optically active .alpha.- and .beta.-naphthalene derivatives. 5. Stereochemical course of the Haworth-type synthesis of optically active 2-(1-methylpropyl)naphthalene". The Journal of Organic Chemistry. 45 (13): 2581–2585\. doi:10.1021/jo01301a007. ISSN 0022-3263.
29. ^ John C. Gilbert., Stephen F. Martin. Brooks/Cole CENGAGE Learning, 2011. pp 872. 25.10 Aromatic Hydrocarbons and Aryl Halides – Classification test. ISBN 978-1-4390-4914-3

### Friedel–Crafts reactions published on Organic Syntheses

[edit]

* Alkylations:
* Everett M. Schultz; Sally Mickey (1949). "Diphenylacetone" (PDF). Organic Syntheses. 29: 38.
* Lee Irvin Smith (1930). "Durene" (PDF). Organic Syntheses. 10: 32.
* C. S. Marvel; W. M. Sperry (1928). "Benzophenone" (PDF). Organic Syntheses. 8: 26.
* Acylations:
* R. E. Lutz (1940). "trans-dienzoethylene" (PDF). Organic Syntheses. 20: 29.
* L. F. Fieser (1940). "β-(3-Acenaphthoyl)Propionic acid" (PDF). Organic Syntheses. 20: 1.
* C. F. H. Allen; W. E. Barker (1932). "Desoxybenzoin" (PDF). Organic Syntheses. 12: 16.
* Kamil Paruch; Libor Vyklicky; Thomas J. Katz (2003). "Preparation of 9,10-dimethoxyphenanthrene and 3,6-diacetyl-9,10-dimethoxyphenanthrene" (PDF). Organic Syntheses. 80: 227.
* Roger Adams; C. R. Noller (1925). "p-bromoacetophenone" (PDF). Organic Syntheses. 5: 17.
* L. F. Fieser (1925). "β-methyanthraquinone" (PDF). Organic Syntheses. 4: 43.
* Perry C. Reeves (1977). "Carboxylation of aromatic compounds: ferrocenecarboxylic acid" (PDF). Organic Syntheses. 56: 28.

* v
* t
* e

Alcohols

By consumption|

| Alcohols found in
alcoholic drinks|

* 1-Propanol
* 2-Methyl-1-butanol
* Ethanol
* Isoamyl alcohol
* Isobutanol
* Phenethyl alcohol
* tert-Amyl alcohol
* tert-Butyl alcohol
* Tryptophol

|

Medical alcohol|

* Ethchlorvynol
* Methylpentynol
* Methanol poisoning
* Ethanol

Toxic alcohols|

* Isopropyl alcohol
* Methanol

Primary
alcohols (1°)|

| Methanol|

* 4-Methylcyclohexanemethanol
* Aminomethanol
* Cyclohexylmethanol
* Methoxymethanol
* Methylazoxymethanol
* Trifluoromethanol

|

Ethanol|

* 1-Aminoethanol
* 2,2,2-Trichloroethanol
* 2,2,2-Trifluoroethanol
* 2-(2-Ethoxyethoxy)ethanol
* 2-(2-Methoxyethoxy)ethanol
* 2-(2-Methoxyethoxy)ethanol
* 2-Butoxyethanol
* 2-Chloroethanol
* 2-Ethoxyethanol
* 2-Fluoroethanol
* 2-Mercaptoethanol
* 2-Methoxyethanol
* Aminoethylethanolamine
* Diethylethanolamine
* Dimethylethanolamine
* Ethanol
* Ethanolamine
* N,N-Diisopropylaminoethanol
* N-Methylethanolamine
* Phenoxyethanol
* Tribromoethanol

Butanol|

* 2-Methyl-1-butanol
* Isobutanol
* n-Butanol

Straight-chain
saturated
C1 — C9|

* Methanol
* Ethanol
* 1-Propanol
* 1-Butanol
* 1-Pentanol
* 1-Hexanol
* 1-Heptanol
* 1-Octanol (capryl)
* 1-Nonanol (pelargonic)

Straight-chain
saturated
C10 — C19|

* 1-Decanol (capric)
* 1-Undecanol (hendecyl)
* 1-Dodecanol (lauryl)
* 1-Tridecanol
* 1-Tetradecanol (myristyl)
* 1-Pentadecanol
* 1-Hexadecanol (cetyl / palmityl)
* 1-Heptadecanol
* 1-Octadecanol (stearyl)
* 1-Nonadecanol

Straight-chain
saturated
C20 — C29|

* 1-Icosanol (arachidyl)
* 1-Heneicosanol
* 1-Docosanol (behenyl)
* 1-Tricosanol
* 1-Tetracosanol (lignoceryl)
* 1-Pentacosanol
* 1-Hexacosanol (ceryl)
* 1-Heptacosanol
* 1-Octacosanol (cluytyl / montanyl)
* 1-Nonacosanol

Straight-chain
saturated
C30 — C39|

* 1-Triacontanol (melissyl / myricyl)
* 1-Hentriacontanol
* 1-Dotriacontanol (lacceryl)
* 1-Tritriacontanol
* 1-Tetratriacontanol (geddyl)
* 1-Pentatriacontanol
* 1-Hexatriacontanol
* 1-Heptatriacontanol
* 1-Octatriacontanol
* 1-Nonatriacontanol

Straight-chain
saturated
C40 — C49|

* 1-Tetracontanol
* 1-Hentetracontanol
* 1-Dotetracontanol
* 1-Tritetracontanol
* 1-Tetratetracontanol
* 1-Pentatetracontanol
* 1-Hexatetracontanol
* 1-Heptatetracontanol
* 1-Octatetracontanol
* 1-Nonatetracontanol

* 2-Ethylhexanol
* Allyl alcohol
* Anisyl alcohol
* Benzyl alcohol
* Cinnamyl alcohol
* Crotyl alcohol
* Furfuryl alcohol
* Isoamyl alcohol
* Neopentyl alcohol
* Nicotinyl alcohol
* Perillyl alcohol
* Phenethyl alcohol
* Prenol
* Propargyl alcohol
* Salicyl alcohol
* Tryptophol
* Vanillyl alcohol
* Veratrole alcohol

Secondary
alcohols (2°)|

* 1-Phenylethanol
* 2-Butanol
* 2-Deoxyerythritol
* 2-Heptanol
* 3-Heptanol
* 2-Hexanol
* 3-Hexanol
* 3-Methyl-2-butanol
* 2-Nonanol
* 2-Octanol
* 2-Pentanol
* 3-Pentanol
* Cyclohexanol
* Cyclopentanol
* Cyclopropanol
* Diphenylmethanol
* Isopropanol
* Pinacolyl alcohol
* Pirkle's alcohol
* Propylene glycol methyl ether

Tertiary
alcohols (3°)|

* 2-Methyl-2-pentanol
* 2-Methylheptan-2-ol
* 2-Methylhexan-2-ol
* 3-Methyl-3-pentanol
* 3-Methyloctan-3-ol
* Diacetone alcohol
* Ethchlorvynol
* Methylpentynol
* Nonafluoro-tert-butyl alcohol
* tert-Amyl alcohol
* tert-Butyl alcohol
* Triphenylethanol
* Triphenylmethanol

Hydric alcohols|

| Monohydric alcohols|

* Methanol (C1)
* Ethanol (C2)
* Isopropanol (C3)
* 1-Butanol (C4)
* 1-Pentanol (C5)
* Cetyl alcohol (C16)

|

Dihydric alcohols|

* Ethylene glycol
* Propylene glycol

Trihydric alcohols|

* Glycerol

Polyhydric alcohols (sugar alcohols)|

* Pentaerythritol
* Ethylene glycol (C2)
* Glycerol, Propylene glycol (C3)
* Erythritol, Threitol (C4)
* Xylitol (C5)
* Mannitol, Sorbitol (C6)
* Volemitol (C7)

Amyl alcohols|

* 2,2-Dimethylpropan-1-ol
* 2-Methylbutan-1-ol
* 2-Methylbutan-2-ol
* 3-Methylbutan-1-ol
* 3-Methylbutan-2-ol
* Pentan-1-ol
* Pentan-2-ol
* Pentan-3-ol

Aromatic alcohols|

* Benzyl alcohol
* 2,4-Dichlorobenzyl alcohol
* 3-Nitrobenzyl alcohol

Saturated
fatty alcohols|

* Cetostearyl alcohol
* Decanol
* Lauryl alcohol
* Myristyl alcohol
* Nonanol
* Octanol
* Tridecanol
* Undecanol

Branched and
unsaturated
fatty alcohols|

* 3-Methyl-3-pentanol
* Erucyl alcohol
* Linolenyl alcohol
* Linoleyl alcohol
* Oleyl alcohol
* Palmitoleyl alcohol
* tert-Amyl alcohol
* tert-Butyl alcohol

Sugar alcohols|

| C1 — C7|

* Methylene glycol (C1)
* Ethylene glycol (C2)
* Glycerol (C3)
* Erythritol (C4)
* Threitol (C4)
* Arabitol (C5)
* Ribitol (C5)
* Xylitol (C5)
* Mannitol (C6)
* Sorbitol (C6)
* Galactitol (C6)
* Iditol (C6)
* Volemitol (C7)

|

Deoxy sugar
alcohols|

* Fucitol

Cyclic sugar
alcohols|

* Inositol

Glycylglycitols|

* Maltitol
* Lactitol
* Isomalt
* Maltotriitol
* Maltotetraitol
* Polyglycitol

Terpene alcohols|

| Monoterpene
alcohols|

* Borneol
* Citronellol
* Geraniol
* Linalool
* Menthol
* Nerol
* Rhodinol
* Terpineol

|

Sesquiterpene
alcohols|

* Bisabolol
* Farnesol
* Nerolidol
* Patchoulol

Diterpene
alcohols|

* Phytol

Dialcohols|

* 1,4-Butanediol
* 1,5-Pentanediol
* 2-Methyl-2-propyl-1,3-propanediol
* Diethylpropanediol
* Ethylene glycol

Trialcohols|

* Glycerol

Sterols|

* Cholesterol
* Ergosterol
* Lanosterol
* β-Sitosterol
* Stigmasterol

Fluoroalcohols|

* 1,3-Difluoro-2-propanol
* 2,2,2-Trifluoroethanol
* 2-Fluoroethanol
* Nonafluoro-tert-butyl alcohol
* Trifluoromethanol

Preparations|

* Substitution of haloalkane
* Carbonyl reduction
* Ether cleavage
* Hydrolysis of epoxide
* Hydration of alkene
* Ziegler process

Reactions|

* Deprotonation
* Protonation
* Alcohol oxidation
* Glycol cleavage
* Nucleophilic substitution
* Fischer–Speier esterification
* Williamson ether synthesis
* Elimination reaction
* Nucleophilic substitution of carbonyl group
* Friedel-Crafts alkylation
* Nucleophilic conjugate addition
* Transesterification

* Category

* v
* t
* e

Topics in organic reactions

* Addition reaction
* Elimination reaction
* Polymerization
* Reagents
* Rearrangement reaction
* Redox reaction
* Regioselectivity
* Stereoselectivity
* Stereospecificity
* Substitution reaction

* A value
* Alpha effect
* Annulene
* Anomeric effect
* Antiaromaticity
* Aromatic ring current
* Aromaticity
* Baird's rule
* Baker–Nathan effect
* Baldwin's rules
* Bema Hapothle
* Beta-silicon effect
* Bicycloaromaticity
* Bredt's rule
* Bürgi–Dunitz angle
* Catalytic resonance theory
* Charge remote fragmentation
* Charge-transfer complex
* Clar's rule
* Conformational isomerism
* Conjugated system
* Conrotatory and disrotatory
* Curtin–Hammett principle
* Dynamic binding (chemistry)
* Edwards equation
* Effective molarity
* Electromeric effect
* Electron-rich
* Electron-withdrawing group
* Electronic effect
* Electrophile
* Evelyn effect
* Flippin–Lodge angle
* Free-energy relationship
* Grunwald–Winstein equation
* Hammett acidity function
* Hammett equation
* George S. Hammond
* Hammond's postulate
* Homoaromaticity
* Hückel's rule
* Hyperconjugation
* Inductive effect
* Kinetic isotope effect
* LFER solvent coefficients (data page)
* Marcus theory
* Markovnikov's rule
* Möbius aromaticity
* Möbius–Hückel concept
* More O'Ferrall–Jencks plot
* Negative hyperconjugation
* Neighbouring group participation
* 2-Norbornyl cation
* Nucleophile
* Kennedy J. P. Orton
* Passive binding
* Phosphaethynolate
* Polar effect
* Polyfluorene
* Ring strain
* Σ-aromaticity
* Spherical aromaticity
* Spiroaromaticity
* Steric effects
* Superaromaticity
* Swain–Lupton equation
* Taft equation
* Thorpe–Ingold effect
* Vinylogy
* Walsh diagram
* Woodward–Hoffmann rules
* Woodward's rules
* Y-aromaticity
* Yukawa–Tsuno equation
* Zaitsev's rule
* Σ-bishomoaromaticity

List of organic reactions

Carbon-carbon
bond forming
reactions|

* Acetoacetic ester synthesis
* Acyloin condensation
* Aldol condensation
* Aldol reaction
* Alkane metathesis
* Alkyne metathesis
* Alkyne trimerisation
* Alkynylation
* Allan–Robinson reaction
* Arndt–Eistert reaction
* Auwers synthesis
* Aza-Baylis–Hillman reaction
* Barbier reaction
* Barton–Kellogg reaction
* Baylis–Hillman reaction
* Benary reaction
* Bergman cyclization
* Biginelli reaction
* Bingel reaction
* Blaise ketone synthesis
* Blaise reaction
* Blanc chloromethylation
* Bodroux–Chichibabin aldehyde synthesis
* Bouveault aldehyde synthesis
* Bucherer–Bergs reaction
* Buchner ring expansion
* Cadiot–Chodkiewicz coupling
* Carbonyl allylation
* Carbonyl olefin metathesis
* Castro–Stephens coupling
* Chan rearrangement
* Chan–Lam coupling
* Claisen condensation
* Claisen rearrangement
* Claisen-Schmidt condensation
* Combes quinoline synthesis
* Corey–Fuchs reaction
* Corey–House synthesis
* Coupling reaction
* Cross-coupling reaction
* Cross dehydrogenative coupling
* Cross-coupling partner
* Dakin–West reaction
* Darzens reaction
* Diels–Alder reaction
* Doebner reaction
* Wulff–Dötz reaction
* Ene reaction
* Enyne metathesis
* Ethenolysis
* Favorskii reaction
* Ferrier carbocyclization
* Friedel–Crafts reaction
* Fujimoto–Belleau reaction
* Fujiwara–Moritani reaction
* Fukuyama coupling
* Gabriel–Colman rearrangement
* Gattermann reaction
* Glaser coupling
* Grignard reaction
* Grignard reagent
* Hammick reaction
* Heck reaction
* Henry reaction
* Heterogeneous metal catalyzed cross-coupling
* High dilution principle
* Hiyama coupling
* Homologation reaction
* Horner–Wadsworth–Emmons reaction
* Hydrocyanation
* Hydrovinylation
* Hydroxymethylation
* Ivanov reaction
* Johnson–Corey–Chaykovsky reaction
* Julia olefination
* Julia–Kocienski olefination
* Kauffmann olefination
* Knoevenagel condensation
* Knorr pyrrole synthesis
* Kolbe–Schmitt reaction
* Kowalski ester homologation
* Kulinkovich reaction
* Kumada coupling
* Liebeskind–Srogl coupling
* Malonic ester synthesis
* Mannich reaction
* McMurry reaction
* Meerwein arylation
* Methylenation
* Michael reaction
* Minisci reaction
* Mizoroki-Heck vs. Reductive Heck
* Nef isocyanide reaction
* Nef synthesis
* Negishi coupling
* Nierenstein reaction
* Nitro-Mannich reaction
* Nozaki–Hiyama–Kishi reaction
* Olefin conversion technology
* Olefin metathesis
* Palladium–NHC complex
* Passerini reaction
* Peterson olefination
* Pfitzinger reaction
* Piancatelli rearrangement
* Pinacol coupling reaction
* Prins reaction
* Quelet reaction
* Ramberg–Bäcklund reaction
* Rauhut–Currier reaction
* Reformatsky reaction
* Reimer–Tiemann reaction
* Rieche formylation
* Ring-closing metathesis
* Robinson annulation
* Sakurai reaction
* Seyferth–Gilbert homologation
* Shapiro reaction
* Sonogashira coupling
* Stetter reaction
* Stille reaction
* Stollé synthesis
* Stork enamine alkylation
* Suzuki reaction
* Takai olefination
* Thermal rearrangement of aromatic hydrocarbons
* Thorpe reaction
* Ugi reaction
* Ullmann reaction
* Wagner-Jauregg reaction
* Weinreb ketone synthesis
* Wittig reaction
* Wurtz reaction
* Wurtz–Fittig reaction
* Zincke–Suhl reaction

| Homologation reactions|

* Arndt–Eistert reaction
* Hooker reaction
* Kiliani–Fischer synthesis
* Kowalski ester homologation
* Methoxymethylenetriphenylphosphorane
* Seyferth–Gilbert homologation
* Wittig reaction

|

Olefination reactions|

* Bamford–Stevens reaction
* Barton–Kellogg reaction
* Boord olefin synthesis
* Chugaev elimination
* Cope reaction
* Corey–Winter olefin synthesis
* Dehydrohalogenation
* Elimination reaction
* Grieco elimination
* Hofmann elimination
* Horner–Wadsworth–Emmons reaction
* Hydrazone iodination
* Julia olefination
* Julia–Kocienski olefination
* Kauffmann olefination
* McMurry reaction
* Peterson olefination
* Ramberg–Bäcklund reaction
* Shapiro reaction
* Takai olefination
* Wittig reaction

Carbon-heteroatom
bond forming
reactions|

* Azo coupling
* Bartoli indole synthesis
* Boudouard reaction
* Cadogan–Sundberg indole synthesis
* Diazonium compound
* Esterification
* Grignard reagent
* Haloform reaction
* Hegedus indole synthesis
* Hurd–Mori 1,2,3-thiadiazole synthesis
* Kharasch–Sosnovsky reaction
* Knorr pyrrole synthesis
* Leimgruber–Batcho indole synthesis
* Mukaiyama hydration
* Nenitzescu indole synthesis
* Oxymercuration reaction
* Reed reaction
* Schotten–Baumann reaction
* Ullmann condensation
* Williamson ether synthesis
* Yamaguchi esterification

Degradation
reactions|

* Barbier–Wieland degradation
* Bergmann degradation
* Edman degradation
* Emde degradation
* Gallagher–Hollander degradation
* Hofmann rearrangement
* Hooker reaction
* Isosaccharinic acid
* Marker degradation
* Ruff degradation
* Strecker degradation
* Von Braun amide degradation
* Weerman degradation
* Wohl degradation

Organic redox
reactions|

* Acyloin condensation
* Adkins–Peterson reaction
* Akabori amino-acid reaction
* Alcohol oxidation
* Algar–Flynn–Oyamada reaction
* Amide reduction
* Andrussow process
* Angeli–Rimini reaction
* Aromatization
* Autoxidation
* Baeyer–Villiger oxidation
* Barton–McCombie deoxygenation
* Bechamp reduction
* Benkeser reaction
* Bergmann degradation
* Birch reduction
* Bohn–Schmidt reaction
* Bosch reaction
* Bouveault–Blanc reduction
* Boyland–Sims oxidation
* Cannizzaro reaction
* Carbonyl reduction
* Clemmensen reduction
* Collins oxidation
* Corey–Itsuno reduction
* Corey–Kim oxidation
* Corey–Winter olefin synthesis
* Criegee oxidation
* Dakin oxidation
* Davis oxidation
* Deoxygenation
* Dess–Martin oxidation
* DNA oxidation
* Elbs persulfate oxidation
* Emde degradation
* Eschweiler–Clarke reaction
* Étard reaction
* Fischer–Tropsch process
* Fleming–Tamao oxidation
* Fukuyama reduction
* Ganem oxidation
* Glycol cleavage
* Griesbaum coozonolysis
* Grundmann aldehyde synthesis
* Haloform reaction
* Hydrogenation
* Hydrogenolysis
* Hydroxylation
* Jones oxidation
* Kiliani–Fischer synthesis
* Kolbe electrolysis
* Kornblum oxidation
* Kornblum–DeLaMare rearrangement
* Leuckart reaction
* Ley oxidation
* Lindgren oxidation
* Lipid peroxidation
* Lombardo methylenation
* Luche reduction
* Markó–Lam deoxygenation
* McFadyen–Stevens reaction
* Meerwein–Ponndorf–Verley reduction
* Methionine sulfoxide
* Miyaura borylation
* Mozingo reduction
* Noyori asymmetric hydrogenation
* Omega oxidation
* Oppenauer oxidation
* Oxygen rebound mechanism
* Ozonolysis
* Parikh–Doering oxidation
* Pinnick oxidation
* Prévost reaction
* Reduction of nitro compounds
* Reductive amination
* Riley oxidation
* Rosenmund reduction
* Rubottom oxidation
* Sabatier reaction
* Sarett oxidation
* Selenoxide elimination
* Shapiro reaction
* Sharpless asymmetric dihydroxylation
* Epoxidation of allylic alcohols
* Sharpless epoxidation
* Sharpless oxyamination
* Stahl oxidation
* Staudinger reaction
* Stephen aldehyde synthesis
* Swern oxidation
* Transfer hydrogenation
* Wacker process
* Wharton reaction
* Whiting reaction
* Wohl–Aue reaction
* Wolff–Kishner reduction
* Wolffenstein–Böters reaction
* Zinin reaction

Rearrangement
reactions|

* 1,2-rearrangement
* 1,2-Wittig rearrangement
* 2,3-sigmatropic rearrangement
* 2,3-Wittig rearrangement
* Achmatowicz reaction
* Alkyne zipper reaction
* Allen–Millar–Trippett rearrangement
* Allylic rearrangement
* Alpha-ketol rearrangement
* Amadori rearrangement
* Arndt–Eistert reaction
* Aza-Cope rearrangement
* Baker–Venkataraman rearrangement
* Bamberger rearrangement
* Banert cascade
* Beckmann rearrangement
* Benzilic acid rearrangement
* Bergman cyclization
* Bergmann degradation
* Boekelheide reaction
* Brook rearrangement
* Buchner ring expansion
* Carroll rearrangement
* Chan rearrangement
* Claisen rearrangement
* Cope rearrangement
* Corey–Fuchs reaction
* Cornforth rearrangement
* Criegee rearrangement
* Curtius rearrangement
* Demjanov rearrangement
* Di-π-methane rearrangement
* Dimroth rearrangement
* Divinylcyclopropane-cycloheptadiene rearrangement
* Dowd–Beckwith ring-expansion reaction
* Electrocyclic reaction
* Ene reaction
* Enyne metathesis
* Favorskii reaction
* Favorskii rearrangement
* Ferrier carbocyclization
* Ferrier rearrangement
* Fischer–Hepp rearrangement
* Fries rearrangement
* Fritsch–Buttenberg–Wiechell rearrangement
* Gabriel–Colman rearrangement
* Group transfer reaction
* Halogen dance rearrangement
* Hayashi rearrangement
* Hofmann rearrangement
* Hofmann–Martius rearrangement
* Ireland–Claisen rearrangement
* Jacobsen rearrangement
* Kornblum–DeLaMare rearrangement
* Kowalski ester homologation
* Lobry de Bruyn–Van Ekenstein transformation
* Lossen rearrangement
* McFadyen–Stevens reaction
* McLafferty rearrangement
* Meyer–Schuster rearrangement
* Mislow–Evans rearrangement
* Mumm rearrangement
* Myers allene synthesis
* Nazarov cyclization reaction
* Neber rearrangement
* Newman–Kwart rearrangement
* Overman rearrangement
* Oxy-Cope rearrangement
* Pericyclic reaction
* Piancatelli rearrangement
* Pinacol rearrangement
* Pummerer rearrangement
* Ramberg–Bäcklund reaction
* Ring expansion and contraction
* Ring-closing metathesis
* Rupe reaction
* Schmidt reaction
* Semipinacol rearrangement
* Seyferth–Gilbert homologation
* Sigmatropic reaction
* Skattebøl rearrangement
* Smiles rearrangement
* Sommelet–Hauser rearrangement
* Stevens rearrangement
* Stieglitz rearrangement
* Thermal rearrangement of aromatic hydrocarbons
* Tiffeneau–Demjanov rearrangement
* Vinylcyclopropane rearrangement
* Wagner–Meerwein rearrangement
* Wallach rearrangement
* Weerman degradation
* Westphalen–Lettré rearrangement
* Willgerodt rearrangement
* Wolff rearrangement

Ring forming
reactions|

* 1,3-Dipolar cycloaddition
* Annulation
* Azide-alkyne Huisgen cycloaddition
* Baeyer–Emmerling indole synthesis
* Bartoli indole synthesis
* Bergman cyclization
* Biginelli reaction
* Bischler–Möhlau indole synthesis
* Bischler–Napieralski reaction
* Blum–Ittah aziridine synthesis
* Bobbitt reaction
* Bohlmann–Rahtz pyridine synthesis
* Borsche–Drechsel cyclization
* Bucherer carbazole synthesis
* Bucherer–Bergs reaction
* Cadogan–Sundberg indole synthesis
* Camps quinoline synthesis
* Chichibabin pyridine synthesis
* Cook–Heilbron thiazole synthesis
* Cycloaddition
* Darzens reaction
* Davis–Beirut reaction
* De Kimpe aziridine synthesis
* Debus–Radziszewski imidazole synthesis
* Dieckmann condensation
* Diels–Alder reaction
* Feist–Benary synthesis
* Ferrario–Ackermann reaction
* Fiesselmann thiophene synthesis
* Fischer indole synthesis
* Fischer oxazole synthesis
* Friedländer synthesis
* Gewald reaction
* Graham reaction
* Hantzsch pyridine synthesis
* Hegedus indole synthesis
* Hemetsberger indole synthesis
* Hofmann–Löffler reaction
* Hurd–Mori 1,2,3-thiadiazole synthesis
* Iodolactonization
* Isay reaction
* Jacobsen epoxidation
* Johnson–Corey–Chaykovsky reaction
* Knorr pyrrole synthesis
* Knorr quinoline synthesis
* Kröhnke pyridine synthesis
* Kulinkovich reaction
* Larock indole synthesis
* Madelung synthesis
* Nazarov cyclization reaction
* Nenitzescu indole synthesis
* Niementowski quinazoline synthesis
* Niementowski quinoline synthesis
* Paal–Knorr synthesis
* Paternò–Büchi reaction
* Pechmann condensation
* Petrenko-Kritschenko piperidone synthesis
* Pictet–Spengler reaction
* Pomeranz–Fritsch reaction
* Prilezhaev reaction
* Pschorr cyclization
* Reissert indole synthesis
* Ring-closing metathesis
* Robinson annulation
* Sharpless epoxidation
* Simmons–Smith reaction
* Skraup reaction
* Urech hydantoin synthesis
* Van Leusen reaction
* Wenker synthesis

| Cycloaddition|

* 1,3-Dipolar cycloaddition
* 4+4 Photocycloaddition
* (4+3) cycloaddition
* 6+4 Cycloaddition
* Alkyne trimerisation
* Aza-Diels–Alder reaction
* Azide-alkyne Huisgen cycloaddition
* Bradsher cycloaddition
* Cheletropic reaction
* Conia-ene reaction
* Cyclopropanation
* Diazoalkane 1,3-dipolar cycloaddition
* Diels–Alder reaction
* Enone–alkene cycloadditions
* Hexadehydro Diels–Alder reaction
* Intramolecular Diels–Alder cycloaddition
* Inverse electron-demand Diels–Alder reaction
* Ketene cycloaddition
* McCormack reaction
* Metal-centered cycloaddition reactions
* Nitrone-olefin (3+2) cycloaddition
* Oxo-Diels–Alder reaction
* Ozonolysis
* Pauson–Khand reaction
* Povarov reaction
* Prato reaction
* Retro-Diels–Alder reaction
* Staudinger synthesis
* Trimethylenemethane cycloaddition
* Vinylcyclopropane (5+2) cycloaddition
* Wagner-Jauregg reaction

|

Heterocycle forming reactions|

* Algar–Flynn–Oyamada reaction
* Allan–Robinson reaction
* Auwers synthesis
* Bamberger triazine synthesis
* Banert cascade
* Barton–Zard reaction
* Bernthsen acridine synthesis
* Bischler–Napieralski reaction
* Bobbitt reaction
* Boger pyridine synthesis
* Borsche–Drechsel cyclization
* Bucherer carbazole synthesis
* Bucherer–Bergs reaction
* Chichibabin pyridine synthesis
* Cook–Heilbron thiazole synthesis
* Diazoalkane 1,3-dipolar cycloaddition
* Einhorn–Brunner reaction
* Erlenmeyer–Plöchl azlactone and amino-acid synthesis
* Feist–Benary synthesis
* Fischer oxazole synthesis
* Gabriel–Colman rearrangement
* Gewald reaction
* Hantzsch ester
* Hantzsch pyridine synthesis
* Herz reaction
* Knorr pyrrole synthesis
* Kröhnke pyridine synthesis
* Lectka enantioselective beta-lactam synthesis
* Lehmstedt–Tanasescu reaction
* Niementowski quinazoline synthesis
* Nitrone-olefin (3+2) cycloaddition
* Paal–Knorr synthesis
* Pellizzari reaction
* Pictet–Spengler reaction
* Pomeranz–Fritsch reaction
* Prilezhaev reaction
* Robinson–Gabriel synthesis
* Stollé synthesis
* Urech hydantoin synthesis
* Wenker synthesis
* Wohl–Aue reaction

Authority control databases: National |

* Japan
* Latvia

|

*[v]: View this template
*[t]: Discuss this template
*[e]: Edit this template