Friedel-Crafts acylation of ferrocene with alkynoic acids

Ferrocene reacts with alkynoic acids (conjugated or nonconjugated terminal), trifluoroacetic anhydride and triflic acid (or boron trifluoride etherate) to afford the corresponding ferrocenyl ynones in good yields. Only in the case of propynoic- and 3-butynoic acid complex, untreatable reaction mixtures were obtained. However, propynoilferrocene was obtained by desilylation of (trimethylsilyl)propynoilferrocene with KF/18-crown-6. Reaction with nonconjugated terminal alkynoic acids, carried out in the presence of a large excess of triflic acid (4 equiv.) results in formation of complex mixtures of products (in the reaction with 4-pentynoic acid enol triflate of ferrocenyl 1,4-diketone and 2-ferrocenyl-5-methylfuran were isolated). Ferrocenyl ynones obtained in this work can be used for synthesis of more complex ferrocenyl systems by “click” chemistry.     

Sulfur-containing carboxylic acids. 6. The syntheses of 3,3"-sulfinyldipropionic and 2,2"-sulfinyldiacetic acids

Pure sulfoxides of thiodialiphatic acids were obtained in high yields by oxidation of the corresponding sulfides in organic solvents. 3,3"-Sulfinyldipropionic acid was obtained by the reaction of hydrogen peroxide with thiodipropionic acid in acetone. 2,2"-Sulfinyldiacetic acid was synthesized by the reaction of thiodiglycolic acid with H₂O₂ in acetone containing acetic acid (26 mol. %). Pure 2,2"-sulfinyldiacetic acid was found to be stable in storage rather than labile as reported previously.     

Pentaatomie heteroaromatic cations. Note III . A Convenient Synthesis of Aldehydes from Carboxylic Acids via 2-Substituted 1,3-Benzoxathiolium Perchlorates

A convenient method for the preparation of aldehydes from the corresponding carboxylic acids is presented. By reaction of the carboxylic acids with o-mercaptophenol and perchloric acid in phosphorus oxychloride, the corresponding 2-substituted 1,3-benzoxathiolium perehlorates were obtained. Reduction of the salts with lithium aluminium hydride in dry ether gave 2-substituted 1,3-benzoxathioles, which, when hydrolyzed by mercuric chloride, gave the corresponding aldehydes. Twenty five aldehydes of different structure were obtained in good yields, by a fast and simple procedure.     

Benzazoles. 4. Synthesis and chemical reactions of 6-chlorosulfonylbenzoxazolin-2-ones

The corresponding 6-chlorosulfonyl derivatives were synthesized from benzoxazolin-2-one and its 3-methyl derivative by treatment with chlorosulfonic acid. By treatment of the compounds obtained with water and other nucleophilic reagents (aliphatic and heterocyclic amines) 2-oxobenzoxazoline-6-sulfonic acids and a series of their amides were obtained, while reduction with SnCl₂·2H₂O gave 6-mercaptobenzoxazolin-2-ones.     

Studies on Reactions of Cyclic Oxalyl Compounds with Hydrazines or Hydrazones. 2. Synthesis and Reactions of 4-Benzoyl-1-(4-nitrophenyl)-5-phenyl-1H-pyrazole-3-carboxylic Acid

4-Benzoyl-1-(4-nitrophenyl)-5-phenyl-1H-pyrazole-3-carboxylic acid, obtained from the corresponding furan-2,3-dione and N-benzylidene-N'-(4-nitrophenyl)hydrazine, was converted via reactions of its acid chloride with various alcohols or N-nucleophiles into the corresponding ester or amide derivatives. The nitrile of the starting acid and 1-(4-aminophenyl)-4-benzoyl-5-phenyl-1H-pyrazole-3-carboxylic acid were also obtained. While cyclocondensation reactions of the two acids and the nitrile mentioned with hydrazines lead to pyrazolo[3,4-d]pyridazine derivatives, the reaction of starting acid with 2-hydrazinopyridine provided the hydrazonopyrazole acid derivative.     

Investigation of phenanthridone and dioxotetrahydrodiazapyrene. 4. Synthesis of amino-substituted phenanthridones and dioxotetrahydrodiazapyrenes

The corresponding mono-, di-, and triamino derivatives substituted in the 2, 4, and 8 positions of the phenanthridone ring were obtained by reduction of mono-, di-, and trinitro-substituted phenanthridone (I), phenanthridone-10-carboxylic acid (II), phenanthridone-1-carboxylic acid (III), 4H-cyclopenta[k,l,m]phenanthridine-5,9-dione (IV), 4H-cyclopenta[k,l,m]phenanthridin-5-one (V), 5,10-dioxo-4,5,9,10-tetrahydro-4,9-diazapyrene (VI), and 5,9-dioxo-4,5,9,10-tetrahydro-4,10-diazapyrene (VII) with powdered iron in an electrolyte medium, with hydrogen in the presence of a nickel catalyst, or with stannous chloride. The 2,4,7,9-tetraamino derivative of VI was similarly obtained. 1-Amino-, 7-amino-, and 10-amino-phenanthridones were obtained by the Schmidt reaction from the corresponding carboxylic acids. 1,10-Diamino-, and 3,8-diaminophenanthridones were similarly obtained from the corresponding aminofluorenones.See [1] for Communication 3.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 394–397, March, 1981.     

Synthetic analogues of Peganum alkaloids. III. Pentamethylenequinazolones

Monosubstituted 5-, 6-, and 8-methoxy-3,4-dihydro-2,3-pentamethylenequinazolones (1–3) have been syntehsized by the condensation of monosubstituted methoxyanthranilic acids with caprolactam. Demethylation with hydrobromic acid gave the corresponding hydroxy compounds [4–6]. When the 6- and 8-methoxy- and 6- and 8-hydroxy-3,4-dihydro-2,3-pentamethylenequinazolones (2, 3, 5, and 6) were reduced with zinc in hydrochloric acid, the corresponding quinazoline derivatives (7–10) were obtained. The melting points of the basis and their hydrochlorides are given. Some features of their UV, mass, and PMR spectra are reported.     

The synthesis of benzofuroquinolines. V. Some benzofuro[3,2-B]quinoline derivatives

Some benzofuro[3,2-b]quinoline derivatives 1a-d and 3a were synthesized by condensation of 2-amino-benzaldehyde, 2-aminoacetophenone, 2-aminobenzophenone, isatin, or 2-aminobenzoic acid with 3(2H)-benzofuranone. The benzofuroquinolinone 3a was also obtained from 2-aminobenzoic acid and phenoxy-acetyl chloride in two steps and converted to 10-chloro derivative 1e . Similarly, some 8-halobenzofuro[3,2-b]-quinoline derivatives 1d,e and 3a (X = F, Cl, Br, I) were synthesized from 5-haloisatin or 2-amino-5-halo-benzoic acid. And benzofuro[3,2-b]quinolines 1a-e thus obtained were converted to corresponding N-oxides 2 .     

Umlagerung und Spaltung von α, β-Dioxopropionsäureestern in alkalischem Milieu. 28. Mitt. über Reduktone und Tricarbonylverbindungen [1]

The behaviour of α,β-dioxopropionic acid derivatives of the type R? CO? CO? COX (R = phenyl, p-substituted phenyls, CF₃, mesityl; X = OC₂H₅, NH₂) was investigated under benzilic acid rearrangement conditions. Nearly all compounds were cleaved by alkali to give the corresponding acids R? COOH and glyoxylic acid. Only the sterically hindered ethyl β-mesityl-α,β-dioxopropionate underwent rearrangement (after hydrolysis of the ester group); it was shown by ¹⁴C-labelling that the carboxylate group migrates to the β-carbonyl group.     

Entzündungshemmende wirkstoffe. III. Synthese und entzündungshemmende wirksamkeit aromatisch substituierter benztriazole

The I-acylbenzotriazoles 3a-3j were obtained by interaction of the corresponding carboxylic acid chlorides 2a-2j with benzotriazole (1). Among the new compounds 3a-3j , I-(3,4,5-trimethoxy-benzoyl)-( 3c )and I-phenoxycarbonyl-benzotriazole ( 3d ) exhibit the strongest antiinflammatory activity.     

Synthetic transformations of higher terpenoids: XV. Transformations of azlactone derived from 16-formyllambertianic acid methyl ester

Condensation of 16-formyllambertianic acid methyl ester with hippuric acid gave methyl 15,16-epoxy-16-[(4Z)-5-oxo-2-phenyl-4,5-dihydrooxazol-4-ylidenemethyl]labda-8(20),13(16),14-trien-19-oate which underwent ready transformation into 2-benzoylamino-3-(2-furyl)acrylic acid of the labdanoid series. Reactions of the diterpenoid azlactone with amines and α-amino acid esters led to the formation of the corresponding carbamoylvinylbenzamides and N-(2-benzoylaminoacryloyl) amino acid esters, and furylacrylic acid hydrazides were formed in reactions with hydrazines. Cyclization of the N′-phenylhydrazide by the action of 1 M aqueous sodium hydroxide gave the corresponding 1,2,4-triazin-6-one. By treatment of the azlactone with aqueous ammonia on heating, 4-substituted 2-phenyl-4,5-dihydroimidazol-5-one was obtained.     

Condensed imidazo-1,2,4-azines. 15. Reaction of 1,2-diaminobenzimidazole with 5-phenyl-2,3-dihydrofuran-2,3-dione

The reaction of 1,2-diaminobenzimidazole with 5-phenyl-2,3-dihydrofuran-2,3-dione in acetic acid gave a mixture of 2-benzoylmethyl-1,2,4-triazino [2,3-a]-benzimidazol-4H-3-one and 3-benzoylmethyl-1,2,4-triazino[2,3-a]benzimidazol-1H-2-one, the intramolecular cyclization of which gave isomeric 2-phenylfuro-[5,4-e]- and 2-phenylfuro[4,5-e]-1,2,4-triazino[2,3-a]benzimidazoles. Only the corresponding furo[4,5-e]-1,2,4-triazino[2,3-a]benzimidazole was isolated when the reaction was carried out in sulfuric acid.See [1] for Communication 14.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 533–535, April, 1987.     

Synthetic analogues of Peganum alkaloids. III. Pentamethylenequinazolones

Monosubstituted 5-, 6-, and 8-methoxy-3,4-dihydro-2,3-pentamethylenequinazolones (1–3) have been syntehsized by the condensation of monosubstituted methoxyanthranilic acids with caprolactam. Demethylation with hydrobromic acid gave the corresponding hydroxy compounds [4–6]. When the 6- and 8-methoxy- and 6- and 8-hydroxy-3,4-dihydro-2,3-pentamethylenequinazolones (2, 3, 5, and 6) were reduced with zinc in hydrochloric acid, the corresponding quinazoline derivatives (7–10) were obtained. The melting points of the basis and their hydrochlorides are given. Some features of their UV, mass, and PMR spectra are reported.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 465–469, July–August, 1986.     

Acetals of acid lactams and amides. 70. Reactions of 2-aminomethyleneindolin-3-one with CH-acids. Synthesis of substituted pyrrolo[1,2-a]indoles

The reaction of enaminoketones, 2-dimethylamino- and piperidinomethyleneindolin-3-ones with dimedone and Meldrum acid, gave the corresponding cyclic derivatives of 2-vinylindolin-3-one, while with cyanoacetic ester and cyanoacetamide — the derivatives of 3-amino-9-oxopyrrolo[1,2-a]indole were obtained.For Communication 69, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1199–1204, September, 1991.     

Pyridazines. XV. Synthesis of 6-aryl-5-amino-3(2H)-pyridazinones as potential platelet aggregation inhibitors

Several 3(2H)-pyridazinones with amino groups at the 5-position of the pyridazine nucleus have been prepared. The 6-aryl-5-halo-3(2H)-pyridazinones obtained from mucochloric and mucobromic acid lead to the corresponding 5-alkylamino-3(2H)-pyridazinones, which were tested as platelet aggregation inhibitors.     

Ferrocene compounds XXIII. Synthesis and reactions of the new type of methyl ferrocyloxyalkanoates

The new types of ferrocenyloxaaliphatic acid ester, FcCHROCHR′COOMe (R = H, Me, Ph; R′ = H, Me) (7) have been prepared by the action of alkoxides derived from methyl glycolate or methyl lactate on the corresponding ferrocenylcarbinyl acetates (2) or N,N,N-trimethylferrocylammonium iodides (4). The esters obtained were accompanied by a small quantity of oligomeric esters, FcCHR(OCHR′CO)_n OMe (9), and with more or less ferrocyl methyl ethers (8). As opposed to the alkaline hydrolysis of the analogous methyl benzoxyacetate (6) into benzoxyacetic acid (5) the acidification of sodium alkanoates 10 obtained by saponification of esters 7 gave unexpectedly the corresponding ferrocenylcarbinols 1. In a similar way the esters 7 were converted into mixtures of the mentioned carbinols and diferrocyl ethers 11 under action of aqueous hydrochloric acid. The mechanisms of the reactions 10 → 1 and 7 → 1, 11 are discussed.     

Sulfides,sulfones, and sulfoxides of the furan-2(5H)-one series. synthesis and structure

A number of 4- and 5-R-sulfanylfuran-2(5H)-one derivatives were synthesized, and their oxidation with various reagents was studied. The corresponding sulfones were obtained using hydrogen peroxide in acetic acid. 4-R-sulfanyl derivatives were selectively oxidized to sulfoxides with m-chloroperoxybenzoic acid. The molecular and crystal structures of some new sulfones and sulfoxides were determined by X-ray analysis.     

Synthesis based on furancarboxylic acid amides. 2. Synthesis of diamides of the furan series

The corresponding furancarboxylic acid diamides were obtained by the addition of primary amides of furancarboxylic acids to the double bond of vinyl butyl ether and the carbonyl group of various aldehydes..See [2] for Communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1316–1318, October, 1990.     

Indole derivatives 138. Synthesis of some new sulfur-containing derivatives of indole

2-Ethoxycarbonyl-5-(p-nitrophenylthio)indole and the corresponding acid were obtained by the E. Fischer reaction. Decarboxylation of the acid gave 5-(p-nitrophenylthio)indole. The geometric isomers of the initial hydrazone of ethyl pyruvate were isolated and characterized.For Communication 137, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1508–1511, November, 1991.     

The acid-base properties of Fast Grey R. A.

Summary The acid-base properties of Fast Grey R. A. have been studied with reference to the mode of chelation of the dye with different valent metals. The pK values of 3.83, 10.53 and 10.70 corresponding to the three steps of ionization of the free acid were evaluated by the aid of the relation between log [acid]/[salt] and p_H values obtained during the course of the potentiometric titration of the free acid with a free base.