Reissert aldehyde synthesis

Aldehyde synthesis from the corresponding acid chloride, quinoline, and KCN. 

Reissert, A. Ber. Dtsch. Chem. Ges. 1905, 38, 1603, 3415. Carl Arnold Reissert was bom in 1860 in Powayen, Germany. He received his Ph.D. in 1884 at Berlin, where he became an assistant professor. He collaborated with Tiemann. Reissert later joined the faculty at Marburg in 1902. 

---

Reissert Reaction (Grosheintz-Fischer-Reissert Aldehyde Synthesis)... 

This reaction was initially reported by Reissert in 1905 and extended by Grosheintz and Fischer in 1941 It is the synthesis of aldehyde involving the formation of 1 -acyl-2-cyano-1,2-dihydroquinoline derivatives from acyl chlorides, quinoline, and potassium cyanide and the subsequent hydrolysis of said dihydroquinoline derivatives under acidic conditions to produce quinaldic acid and aldehydes. The original procedure occurs smoothly for aroyl or cinnamoyl chloride in liquid SO2 but not in benzonitrile, ether, dioxane, acetone, or CHCb. However, the modification from Grosheintz and Fischer using hydrogen cyanide and 2 eq. quinoline in absolute benzene is also adaptable for aliphatic acid chlorides. This is one of the methods that converts acyl chlorides into aldehydes and is found to be superior to the normal Rosenmund Reduction. For example, o-nitrobenzoyl chloride has been converted into o-nitrobenzaldehyde in 60% yield by the current reaction, whereas the Rosenmund Reduction is not suitable for such conversion. Therefore, this reaction is referred to as the Grosheintz-Fischer-Reissert aldehyde synthesis or Reissert aldehyde synthesis. ... 

Other references related to the Grosheintz-Fischer-Reissert aldehyde synthesis are cited in the literature. ... 

In the light of the foregoing, it is perhaps not surprising that interest has lapsed in the hydrolysis of Reissert compounds as a method of aldehyde synthesis. However, the value of the compounds in hetero-... 

Except for a demonstration that the phthalazine Reissert compound (3 R = Ph) behaves normally in giving benzaldehyde on acid-catalyzed hydrolysis, no new reports have appeared of Reissert compounds being used in aldehyde synthesis. Acid-catalyzed hydrolysis has been used, however, in some cases to prepare heterocyclic carboxylic acids. Thus in addition to the preparation of isoquinaldic acid, phthalazine-1-carboxyIic acid and 15 have been prepared from 3(R = Ph) and 11, respectively. Acid-catalyzed hydrolysis of 16 occurs with cyclization to give 17. A series of Reissert compounds derived from substituted 3-aminoquinolines have been converted to the corresponding quinaldic acids by acid-catalyzed hydrolysis. ... 

The formation of a Reissert anion (intermediate of type 16) is usually the introductory step in a great number of synthetic routes leading to isoquinoline as well as indole alkaloids and related compounds. On the one hand, the alkylation of a Reissert anion with alkyl halide followed by alkaline hydrolysis is the most frequently used method for the synthesis of 1-alkyl- or 1-arylalkylisoquinolines (20) (Scheme 4). On the other hand, Reissert anions react with aldehydes to form... 

The Reissert reaction exemplifies the B pathway (equation 73), and is of course a notable method for aldehyde and alkaloid synthesis. The Fujiwara reaction (81JOC3175), a colour test, provides an example of Type D behavior (Scheme 50). 

A new synthesis of dibenzo[a,g]quinolizinium derivatives also makes use of an aldehyde cyclization (Scheme 80) (75JAP(K)7596599). In one example, a benzyl bromide bearing an acetal-masked aldehyde group in the ortho position (126) was allowed to react with the anion (127) generated by the action of phenyllithium on a Reissert compound. The condensation product was heated with alkali to cleave the benzoyl and cyano groups to yield the isoquinoline (128), then the acetal was cleaved and the resulting aldehyde cyclized to (129), presumably under acid conditions. 

A solid-phase Ugi-Reissert reaction on chloroformate resin, has been reported. The product, the ot-carbamoylated isoquinoline 230, is released by oxidative cleavage (Scheme 33a). Interestingly, the enamide moiety in the adduct can be exploited to perform this process in tandem with a Povarov MCR [189, 190]. In this way, by interaction of dihydroisoquinoline 231 with aldehydes, anilines and a suitable Lewis acid catalyst, the polyheterocyclic system 232 was prepared (Scheme 33b). The Zhu group devised an innovative approach for the synthesis of this class of compounds. They employed the heterocyclic amine 233, which was oxidized in situ to the dihydroisoquinoline 234 with IBX, to undergo the classic Ugi reaction. Remarkably, all the components are chemically compatible, allowing the sequence to proceed as a true MCR (Scheme 33c) [191]. 

A novel method for the synthesis of 2-alkylpyridines and 2-pyridine-carbinols starts from pyridine and involves the pyridine Reissert analog 175. Anion formation with sodium hydride and alkylation with alkyl halides afford the 2-alkyl-l-ethoxycarbonyl-2-cyano-1,2-dihydropyridines 176, which on heating with HMPT/Nal (HMPT = hexamethylphosphorous triamide) give 2-alkylpyridines 177. Condensation of the anion with benzaldehyde or o-tolualdehyde leads to 2-pyridinecarbinols (85CI(L)125). The reaction of 1,4-bis(trimethylsilyl)-1,4-dihydropyridine (178) with aldehydes (and ketones) in... 

Several of the condensations with aromatic aldehydes have been used in the synthesis of alkaloid systems. 2-Nitrobenzaldehydes have been used in synthetic routes to 7-hydroxyaporphines/°° and 2-iodobenzaldehydes have been used in oxidative photochemical routes to the aporphines and oxoapor-phines caaverine, isoboldine, corunnine, and nandazurine. ° The aldehyde 46 has been used with the anion of the Reissert compound derived from... 

REISSERT - GROSHEINTZ - FISCHER CyanoamineReaction Synthesis of aldehydes or alkaloids from acid chlorides via 1 cyano-2-acylisoquinoime or 2-... 

REISSERT GROSHEINTZ - FISCHER Cyanoamine Reaction Synthesis ot aldehydes or alkaloids frem acid chiondes via 1 -cyano-2-acylisoquinoline or 2-cyanoquinoline intermediates... 

---