| von Braun reaction | |||||||||
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| Named after | Julius von Braun | ||||||||
| Reaction type | Substitution reaction | ||||||||
| Reaction | |||||||||
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The von Braun reaction is an organic reaction in which a tertiary amine reacts with cyanogen bromide to an organocyanamide. [1] An example is the reaction of N,N-dimethyl-1-naphthylamine: [2]
These days, most chemist have replaced cyanogen bromide reagent with chloroethyl chloroformate reagent instead. It appears as though Olofson et al. was the first chemist to have reported this. [3]
The reaction mechanism consists of two nucleophilic substitutions: the amine is the first nucleophile displacing the bromine atom which then acts as the second nucleophile. [4] [5] In following the mechanism is described using trimethylamine as example: [6]
First, the trimethylamine reacts with the cyanogen bromide to form a quaternary ammonium salt, which in the next step reacts by splitting off bromomethane to give the dimethylcyanamide. This is a second-order nucleophilic substitution (SN2).
In chemistry, a nucleophile is a chemical species that forms bonds by donating an electron pair. All molecules and ions with a free pair of electrons or at least one pi bond can act as nucleophiles. Because nucleophiles donate electrons, they are Lewis bases.
In chemistry, a nucleophilic substitution is a class of chemical reactions in which an electron-rich chemical species replaces a functional group within another electron-deficient molecule. The molecule that contains the electrophile and the leaving functional group is called the substrate.
Bimolecular nucleophilic substitution (SN2) is a type of reaction mechanism that is common in organic chemistry. In the SN2 reaction, a strong nucleophile forms a new bond to an sp3-hybridised carbon atom via a backside attack, all while the leaving group detaches from the reaction center in a concerted fashion.
In chemistry, an electrophile is a chemical species that forms bonds with nucleophiles by accepting an electron pair. Because electrophiles accept electrons, they are Lewis acids. Most electrophiles are positively charged, have an atom that carries a partial positive charge, or have an atom that does not have an octet of electrons.
An enamine is an unsaturated compound derived by the condensation of an aldehyde or ketone with a secondary amine. Enamines are versatile intermediates.
In organic chemistry, a nucleophilic addition reaction is an addition reaction where a chemical compound with an electrophilic double or triple bond reacts with a nucleophile, such that the double or triple bond is broken. Nucleophilic additions differ from electrophilic additions in that the former reactions involve the group to which atoms are added accepting electron pairs, whereas the latter reactions involve the group donating electron pairs.
The Hofmann rearrangement is the organic reaction of a primary amide to a primary amine with one less carbon atom. The reaction involves oxidation of the nitrogen followed by rearrangement of the carbonyl and nitrogen to give an isocyanate intermediate. The reaction can form a wide range of products, including alkyl and aryl amines.
In organic chemistry, the Michael reaction or Michael 1,4 addition is a reaction between a Michael donor and a Michael acceptor to produce a Michael adduct by creating a carbon-carbon bond at the acceptor's β-carbon. It belongs to the larger class of conjugate additions and is widely used for the mild formation of carbon-carbon bonds.
The Corey–House synthesis (also called the Corey–Posner–Whitesides–House reaction and other permutations) is an organic reaction that involves the reaction of a lithium diorganylcuprate () with an organic halide or pseudohalide () to form a new alkane, as well as an ill-defined organocopper species and lithium (pseudo)halide as byproducts.
Cyanogen bromide is the inorganic compound with the formula (CN)Br or BrCN. It is a colorless solid that is widely used to modify biopolymers, fragment proteins and peptides, and synthesize other compounds. The compound is classified as a pseudohalogen.
The Weinreb ketone synthesis or Weinreb–Nahm ketone synthesis is a chemical reaction used in organic chemistry to make carbon–carbon bonds. It was discovered in 1981 by Steven M. Weinreb and Steven Nahm as a method to synthesize ketones. The original reaction involved two subsequent nucleophilic acyl substitutions: the conversion of an acid chloride with N,O-Dimethylhydroxylamine, to form a Weinreb–Nahm amide, and subsequent treatment of this species with an organometallic reagent such as a Grignard reagent or organolithium reagent. Nahm and Weinreb also reported the synthesis of aldehydes by reduction of the amide with an excess of lithium aluminum hydride.
In inorganic chemistry, sulfonyl halide groups occur when a sulfonyl functional group is singly bonded to a halogen atom. They have the general formula RSO2X, where X is a halogen. The stability of sulfonyl halides decreases in the order fluorides > chlorides > bromides > iodides, all four types being well known. The sulfonyl chlorides and fluorides are of dominant importance in this series.
Radical-nucleophilic aromatic substitution or SRN1 in organic chemistry is a type of substitution reaction in which a certain substituent on an aromatic compound is replaced by a nucleophile through an intermediary free radical species:
In organic chemistry, the Smiles rearrangement is an organic reaction and a rearrangement reaction named after British chemist Samuel Smiles. It is an intramolecular, nucleophilic aromatic substitution of the type:
The Zincke reaction is an organic reaction, named after Theodor Zincke, in which a pyridine is transformed into a pyridinium salt by reaction with 2,4-dinitro-chlorobenzene and a primary amine.
The Willgerodt rearrangement or Willgerodt reaction is an organic reaction converting an aryl alkyl ketone, alkyne, or alkene to the corresponding amide by reaction with ammonium polysulfide, named after Conrad Willgerodt. The formation of the corresponding carboxylic acid is a side reaction resulting from hydrolysis of the amide. When the alkyl group is an aliphatic chain, multiple reactions take place with the amide group always ending up at the terminal end. The net effect is thus migration of the carbonyl group to the end of the chain and oxidation.
Electrophilic amination is a chemical process involving the formation of a carbon–nitrogen bond through the reaction of a nucleophilic carbanion with an electrophilic source of nitrogen.
Electrophilic fluorination is the combination of a carbon-centered nucleophile with an electrophilic source of fluorine to afford organofluorine compounds. Although elemental fluorine and reagents incorporating an oxygen-fluorine bond can be used for this purpose, they have largely been replaced by reagents containing a nitrogen-fluorine bond.
Reactions of organocopper reagents involve species containing copper-carbon bonds acting as nucleophiles in the presence of organic electrophiles. Organocopper reagents are now commonly used in organic synthesis as mild, selective nucleophiles for substitution and conjugate addition reactions.
In organic chemistry, the Baylis–Hillman, Morita–Baylis–Hillman, or MBH reaction is a carbon-carbon bond-forming reaction between an activated alkene and a carbon electrophile in the presence of a nucleophilic catalyst, such as a tertiary amine or phosphine. The product is densely functionalized, joining the alkene at the α-position to a reduced form of the electrophile.