Synthesis of quinoline from aniline and glycerol pdf

In 1880, czech chemist zdenko hans skraup heated aniline and glycerol with an oxidant in concentrated sulfuric acid, a method that is still. In the archetypal skraup reaction, aniline is heated with sulfuric acid, glycerol. Influence of reaction parameters on the catalytic performance. In conclusion, efficient synthesis of quinoline derivatives has been achieved by a onepot coupling reaction of carbonyl compounds and aminobenzophenone using catalytic amounts of nbcl 5 in glycerol. Skraup synthesis article about skraup synthesis by the free. Vapour phase synthesis of quinoline from aniline and glycerol over mixed oxide catalysts. The same idea works well in probably the most famous quinoline synthesis, the skraup reaction. Proficient procedure for preparation of quinoline derivatives. His other works were in the fields of natural products like the structure of alkaloids, synthesis of isoquinolines etc. The quinoline substructure is an important heterocyclic motif which is found in many natural products, pharmaceuticals and functional materials.

Novel aniline trimers are prepared using glycerol, and substituted anilines under pressure, in acidic medium and water. Highefficiency catalytic performance over mesoporous nibeta zeolite for the synthesis of quinoline from glycerol and aniline. Quinoline is a heterocyclic aromatic organic compound with the chemical formula c9h7n. Vapour phase synthesis of quinoline from aniline and glycerol. The skraup synthesis is very energy intensive, and many modifications have been introduced batista et al. We shall describe two more important variants on the same theme, one for quinolines and one for quinolones. Glycerol was employed as a catalyst and a green solvent in the synthesis of novel pyridazines ac. Pdf vapour phase synthesis of quinoline from aniline and.

Quinoline is a heterocyclic aromatic organic compound with the chemical formula c 9 h 7 n. Method for the preparation of quinoline and aniline. It is the best reaction for synthesis of quinoline17 nh2 h o. Nov 03, 2012 this reaction was first studied in 1880 by zdenko hans skraup 18501910, a czech scientist born in prague city of czech republic. Its derivatives represent the major class of heterocycles and a number of preparations have been known for a. Aged samples, if exposed to light,become yellow and later brown. Important green metrics were analyzed and will allow the choice of the best sustainable approaches toward quinoline synthesis. This synthesis involves a series of reactions brought about by heating a primary aromatic amine, in which at least one position ortho to the amino group is unsubstituted, with glycerol, sulfuric acid. Quinoline and aniline compounds have been synthesized from aromatic nitro compounds and ethylenically unsaturated hydrocarbons in the presence of complexes of group viii metals used as catalysts. Quinoline is readily obtained by the skraup synthesis in which a mixture of aniline, glycerol and concentrated sulphuric acid is heated with a suitable oxidising agent. Grace and pandian reported the synthesis of spherical and prism shaped au nps in gly cerol at both reflux and microwave conditions 16. Synthesis of quinolines from aniline and propanol over. Reaction mechanism of the skraup quinoline synthesis.

These include antiinflammatory and antitumor agents, the antimalarial drugs quinine and chloroquine, and organic lightemitting diodes. Quinoline is readily obtained by the skraup synthesis in which a mixture of aniline, glycerol and concentrated. The quinoline scaffold is present in a vast number of natural compounds and pharmacologically active substances, comprising a significant segment of the pharmaceutical market. Methylindole from glycerol cyclization with aniline over cucral 2 o 3 catalysts modified by alkali earth oxides, heteroatom chemistry on deepdyve, the largest online rental service for scholarly research with thousands of academic publications available at your fingertips.

Find, read and cite all the research you need on researchgate. Itis a colorless hygroscopic liquid with a strong odor. This reaction was first studied in 1880 by zdenko hans skraup 18501910, a czech scientist born in prague city of czech republic. Synthesis from solketal continuous niobium phosphate. When glycerol is used as an in situ source of acrolein, quinolines carrying no substituents on the heterocyclic ring are produced. Studies on potential antimicrobial agents page 59 brief introduction to quinoline. Approximately 10% in weight of crude glycerol is created for every 1 kg of biodiesel production. The skraup synthesis26 in this extraordinary reaction, quinoline is produced when aniline, concentrated sulphuric acid, glycerol and mild oxidizing agent are heated together. General description quinoline is a heterocyclic aromatic organic compound with the chemical formula c 9 h 7 n. One of the most well known methods for the preparation of quinoline is the skraup synthesis which consists of heating a primary aromatic amine, such as, aniline with glycerol, concentrated sulphuric acid and an oxidizing agent such as nitrobenzene, ferric chloride or arsenic acid. In the original procedure the oxidant was nitrobenzene, but since this often leads to a violent reaction, arsenic pentoxide or iodine is preferred. Pdf vapour phase synthesis of quinoline from aniline and glycerol.

The skraup synthesis is a chemical reaction used to synthesize quinolines. The reaction proceeds via dehydration of glycerol to acrolein. An effective reductive alkylation of electrondeficient ochloroarylamines was developed. Synthesis of quinolines from anilines, acetophenones and. Request pdf skraup quinoline synthesis quinoline from aniline, glycerol, sulfuric acid and oxidizing agent e. In this work, we reported a green and economic route for vaporphase synthesis of quinoline from glycerol and aniline, for the rst time, using modi ed mesoporous beta zeolite as catalyst. It is a mancude organic heterobicyclic parent, a member of quinolines, an azaarene and an orthofused heteroarene. Highefficiency catalytic performance over mesoporous ni. Green synthesis of gold nanoparticles using glycerol as a. Activity relationship of 4substituted 22acetyloxyethyl8morpholine 4sulfonylpyrrolo3,4cquinoline 1,3diones as potent caspase3 inhibitors dmitri v. The skraup synthesis 10 in this extraordinary reaction, quinoline is produced when aniline, concentrated sulfuric acid, glycerol and a mild oxidising agent are heated together. Synthesis and biological activity investigation of some. Vapour phase synthesis of quinoline from aniline and.

Supporting information quinoline from glycerol and aniline. The resulting intermediate is cyclised, oxidized and dehydrated to give quinoline 16. The compound ii was treated with hydrazine hydrate 80% in pyridine to give n amino4,7dimethy 6nitroquinoline2one iv. The quinoline ring system is one of the most ubiquitous heterocycles in the fields of medicinal and industrial chemistry, forming the scaffold for compounds of great significance. Nov 09, 2012 quinoline is a heterocyclic aromatic organic compound with the chemical formula c9h7n. Quinoline from aniline, glycerol, sulfuric acid and oxidizing agent e. The synthesis of a series of indole and carbazole derivatives from 2fluorophenyl imines is reported. This work describes the synthesis of new heterocyclic compounds from quinoline derivatives and amines. Pdf mesoporous tungstic acid functionalized kit6 has been synthesized through a condensation of 3chloropropyl triethoxysilane and. Over the past few years, various methods have been established for the synthesis of quinolines, which has greatly enriched the development of quinoline chemistry. The productivity of quinoline in terms of weight time yield. A practicable quinoline synthesis from aniline and two amino acids provides a wide range of quinolines with high efficiency and diversity including pharmaceutical derivatives, photochemical active compounds, and challenging scaffolds. Theliteraturehowever,givesthenameoftheproduct derivedfrom the above reaction as anhydroformaldehydeaniline andrepresents it by the follovin structures. Part i studies on compounds consisting quinoline and 2.

Ill the reaction has been shown to proceed via dehydration of the glycerol to acrolein, to which aniline then adds in a conjugate fashion. Quinoline may be prepared by the classical skraup synthe sis from 1880 of heating aniline with glycerol in the presence of sulfuric acid and an oxidising agent such as nitrobenzene oneil, 2006. Sulfuric acid,glycerol and mild oxidising agent are heated together 16. Us6103904a us08896,556 us89655697a us6103904a us 6103904 a us6103904 a us 6103904a us 89655697 a us89655697 a us 89655697a us 6103904 a us6103904 a us 6103904a authority us united states prior art keywords temperature reaction quinolones skraup substituted prior art date 19970717 legal status the legal status is an assumption and is not a legal conclusion. Quinoline is the simplest member of the quinoline class of compounds, comprising a benzene ring ortho fused to c2 and c3 of a pyridine ring. Synthesis of quinolines from glycerol over tungstic acid. In this work, quinoline derivatives were synthesized from reaction of aniline, benzylaldehyde and dimethylacetylene dicarboxylate dmad in sequent steps to provide quinoline derivative dimethyl 2r, 3s, 4r2phenyl4phenylamino1, 3, 4trihydroquinoline2,3dicarboxylate 12. The classical methods for the synthesis of this heterocyclic skeleton require. Catalysts, mesoporous catalysts, functionalized catalysts, skraup synthesis, wkit6, quinoline, glycerol glycerol is produced as a major byproduct of biodiesel manufacturing process. Skraups synthesis is a chemical reaction used to synthesize quinolines by the condensation of glycerine. Skraup synthesis using ferrous sulfate, glycerol, aniline, nitrobenzene, and sulfuric acid. Jun 25, 2009 quinoline from aniline, glycerol, sulfuric acid and oxidizing agent e. The vapour phase synthesis of quinoline from aniline and glycerol 1. However, many of the existing methods utilise expensive transition metals, pre.

Sulfuric acid, glycerol and mild oxidising agent are heated together 16. Quinoline and its derivatives are important heterocyclic systems which have great significance as a biologically active compounds as well as being useful synthon for synthesis of many heterocyclic compounds. Shortly after he prepared quinoline by heating the condensation product of aniline and acrolein, thus anticipating the classical skraup synthesis. New quinoline2one derivatives were synthesized by reaction of 4,7dimethyl coumarin i with nitric acid in the presence of concentrated sulfuric acid to afford 4,7dimethyl6nitrocoumarin ii and 4,7dimethyl8nitrocoumarin iii. Skraup synthesis involves heating aniline derivatives with glycerol, sulfuric acid and oxidizing agents. As water is the most beneficial solvent it will be of interest to study the effect of water in glycerol on the formation of nps. Pdf synthesis of quinolines from glycerol over tungstic acid. Synthesis of derivatives of 2 phenyl quinoline 4 carboxylic acid. In the archetypal skraup reaction, aniline is heated with sulfuric acid, glycerol, and an oxidizing agent such as nitrobenzene to yield quinoline. Quinoline appears as a colorless liquid with a peculiar odor. Quinolines were first synthesized in 1879, and since then a multitude of. Simple reaction procedures, inexpensive catalysts, and single product formation make this an attractive protocol over the existing procedures.

In the synthesis of pyridines it proved advantageous to make a dihydropyridine and oxidize it to a pyridine afterwards. Doebnermiller synthesis the doebnermiller reaction is the organic reaction of an aniline with. Glycerol 11 is dehydrated with sulfuric acid to acrolein 12, which then reacts with aniline by conjugate addition scheme 1. Quinoline 1azanaphthalene or benzobpyridine is a stable base. Us4157445a method for the preparation of quinoline and. Novel aniline trimers are prepared using glycerol, and substituted anilines under. Us6103904a skraup reaction process for synthesizing. Quinolines have antiseptic, antipyretic, and antiperiodic properties and are used as antimalarials and for preparing other antimalarial drugs. Camps quinoline synthesis using an oacylaminoacetophenone and hydroxide. Table 1 skraup reaction of glycerol with substituted aniline over. Synthesis of 7nitrobenzohquinoline has been achieved by heating. Highefficiency catalytic performance over mesoporous nibeta. Quinoline is only slightly soluble in cold water but dissolvesreadily in hot water and most organic solvents.

Quinoline derivatives are prevalent in a variety of pharmacologically active synthetic and natural compounds. Recent advances in metalfree quinoline synthesis ncbi. Quinoline reagent grade, 98% 2,3benzopyridine sigma. A green route for the vaporphase synthesis of quinoline from glycerol and aniline was developed in this work, employing nimesoporous beta zeolite denoted as nih. Quinoline reagent grade, 98% 2,3benzopyridine sigmaaldrich. It is named after the czech chemist zdenko hans skraup 18501910. Microwaveassisted synthesis of phenothiazine and quinoline. Among these catalysts investigated, the cuoznoal 2 o 3 combination effectively performed this. For an alternative mechanism, see that of the doebnervon miller reaction.