Reaction of cyanide and alcohol to give imino ester salt
Pinner reaction
Named after
Adolf Pinner
Reaction type
Coupling reaction
Identifiers
Organic Chemistry Portal
pinner-reaction
RSC ontology ID
RXNO:0000361
The Pinner reaction refers to the acid catalysed reaction of a nitrile with an alcohol to form an imino ester salt (alkyl imidate salt); this is sometimes referred to as a Pinner salt.[1]
The reaction is named after Adolf Pinner, who first described it in 1877.[2][3][4]
Pinner salts are themselves reactive and undergo additional nucleophilic additions to give various useful products:[5][6]
With an excess of alcohol to form an orthoester
With ammonia or an amine to form an amidine (di-nitriles may form imidines, for instance succinimidine from succinonitrile)[7]
With water to form an ester
With hydrogen sulfide to form a thionoester
Commonly, the Pinner salt itself is not isolated, with the reaction being continued to give the desired functional group (orthoester etc.) in one go. It should be appreciated that the Pinner reaction refers specifically to an acid catalyzed process, but that similar results can often be achieved using base catalysis. The two approaches can be complementary, with nitriles which are unreactive under acid conditions often giving better results in the presence of base, and vice versa.[8] The determining factor is typically how electron-rich or poor the nitrile is. For example: an electron-poor nitrile is a good electrophile (readily susceptible to attack from alkoxides etc.) but a poor nucleophile would typically be easier to protonate than to participate in the reaction and hence would be expected to react more readily under basic rather than acidic conditions.
^"Pinner Reaction". Comprehensive Organic Name Reactions and Reagents (504): 2237–2240. 2010. doi:10.1002/9780470638859.conrr504. ISBN 9780470638859.
^A. Pinner, F. Klein; Klein (1877). "Umwandlung der Nitrile in Imide". Berichte der deutschen chemischen Gesellschaft. 10 (2): 1889–1897. doi:10.1002/cber.187701002154.
^A. Pinner, Fr. Klein; Klein (1878). "Umwandlung der Nitrile in Imide". Berichte der deutschen chemischen Gesellschaft. 11 (2): 1475–1487. doi:10.1002/cber.18780110258.
^A. Pinner (1883). "Ueber die Umwandlung der Nitrile in Imide". Berichte der deutschen chemischen Gesellschaft. 16 (2): 1643–1655. doi:10.1002/cber.18830160235.
^Roger, R.; Neilson, D. G. (1961). "The Chemistry of Imidates". Chem. Rev.61 (2): 179–211. doi:10.1021/cr60210a003.
^Adams, Roger; Thal, A. F. (1922). "Ethyl Phenylacetate". Organic Syntheses. 2: 27. doi:10.15227/orgsyn.002.0027.
^Elvidge, J. A.; Linstead, R. P. (1954). "Heterocyclic imines and amines. Part III. Succinimidine". Journal of the Chemical Society (Resumed): 442. doi:10.1039/JR9540000442.
^Schaefer, F. C.; Peters, G. A. (1961). "Base-Catalyzed Reaction of Nitriles with Alcohols. A Convenient Route to Imidates and Amidine Salts". Journal of Organic Chemistry. 26 (2): 412. doi:10.1021/jo01061a034.
sometimes referred to as a Pinner salt. The reaction is named after Adolf Pinner, who first described it in 1877. Pinner salts are themselves reactive...
by a number of synthetic routes, but are in general formed by the Pinnerreaction. This proceeds via the acid catalyzed attack of nitriles by alcohols...
Pentamidine Paranyline A common route to primary amidines is the Pinnerreaction. Reaction of the nitrile with alcohol in the presence of acid gives an iminoether...
cannot be isolated. However, ortho esters can be synthesized by the Pinnerreaction, in which nitriles react with alcohols under acid catalysis: RCN +...
presence of base Baeyer–Villiger oxidation of ketones with peroxides Pinnerreaction of nitriles with an alcohol Nucleophilic abstraction of a metal–acyl...
prepared by the Pinnerreaction, in which nitriles react with alcohols in the presence of one equivalent of hydrogen chloride. The reaction proceeds by formation...
developed a number of compounds. Imidines may be prepared in a modified Pinnerreaction, by passing hydrogen chloride into an alcoholic solution of their corresponding...
obtained from reaction of an amide PhCONHPh with phosphorus pentachloride. Amide reduction Nitrile reduction Pinnerreaction – a similar reaction using alcohols...
proposed. Amidine substrates for the reaction can easily be formed from the corresponding nitriles via the Pinnerreaction. The halide substituent in the diazirine...
undergoes many reactions characteristic of nitriles. It can be hydrolyzed to give phenylacetic acid or it can be used in the Pinnerreaction to yield phenylacetic...
(1901–1906). "Adolf Pinner". In Singer, Isidore; et al. (eds.). The Jewish Encyclopedia. New York: Funk & Wagnalls. Adolf Pinner in the German National...
The Pinner triazine synthesis describes the preparation of 2-hydroxyl-4,6-diaryl-s-triazines by reaction of aryl amidines and phosgene. This reaction may...
addition reactions: with an organozinc compound in the Blaise reaction with alcohols in the Pinnerreaction. with amines, e.g. the reaction of the amine...
organozinc nucleophiles in the Blaise reaction alcohols in the Pinnerreaction. the (same) nitrile α-carbon in the Thorpe reaction. The intramolecular version is...
material have been developed: The first of these methods consists of a Pinnerreaction of benzyl cyanide, giving phenylacetic acid ethyl ester. Subsequently...
mechanism has never been proposed, although it is likely similar to the Pinnerreaction; preceding via an intermediate amidine. Limited research has been done...
The Overman rearrangement may also be used for asymmetric synthesis. Pinnerreaction Larry E. Overman (1976). "A general method for the synthesis of amines...
pyrimidines began in 1884 with Pinner, who synthesized derivatives by condensing ethyl acetoacetate with amidines. Pinner first proposed the name “pyrimidin”...
properties. The reaction of chloroacetonitrile (1) with methanol and hydrogen chloride leads to the corresponding iminoether (Pinnerreaction). Condensation...
nitriles: Kolbe nitrile synthesis Rosenmund-von Braun reaction For reactions of nitriles: Pinnerreaction Stephen aldehyde synthesis Letts, E. A. (1872). "Neue...
as a β-sulfonyl nitrile molecule. Its mechanism of action induces a Pinnerreaction which is initiated by reacting with thiols, alcohols and amines. Thus...
nuclear reactions take place and the heat is generated. Typically, the fuel will be low-enriched uranium contained in thousands of individual fuel pins. The...
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