Reaction of 2-chloro-3-(4-N,N-dimethylaminoanilino)-1,4-naphthoquinone with cyclic amines (piperidine,morpholine, and pyrrolidine)

It was shown that the reaction of 2-chloro-3-(4-N,N-dimethylaminoanilino)-1,4-naphthoquinone with piperidine in the absence of a solvent gives not only a product of replacement of the chlorine atom by a piperidino group, 3-(4-N,N-dimethylaminoanilino)-2-piperidino-1,4-naphthoquinone, but also 2-(4-N,N-dimethylaminoanilino)-1,4-naphthoquinone and 2-(4-N,N-dimethylaminoanilino-2-piperidino)-1,4-naphthoquinone. The latter compounds are the only reaction products formed in dimethyl sulfoxide. The reaction with morpholine occurs in a similar way, whereas that with pyrrolidine gives only a product of replacement of the chlorine atom by hydrogen.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2451–2454, December, 1995.     

Chemistry of naphthazarin derivatives 13. Conformational analysis of 3-(alk-1-enyl)-2-hydroxy-1,4-naphthoquinones by quantum chemistry methods

The molecular structures of various conformers of 2-hydroxy-1,4-naphthoquinone; 3-(alk-1-enyl)-2-hydroxy-1,4-naphthoquinones; 2,5,8-trihydroxy-1,4-naphthoquinone; and 3-(alk-1-enyl)-2,5,8-trihydroxy-1,4-naphthoquinones were studied by density functional theory (B3LYP/6-31(d), B3LYP/6-31(d, p)) and ab initio (MP2/6-31G, MP2/6-31(d)) methods. The strengths of the intramolecular hydrogen bonds formed by the β-hydroxy group with the O atom at C(1) and with the double bond π-electrons of the alkenyl substituents in the quinonoid rings were estimated. The compounds studied mainly exist as rotamers with the former-type hydrogen bonds. The splitting of the quinonoid bands of the stretching vibrations of the β-hydroxy group in the IR spectra of 3-(alk-1-enyl)-2-hydroxy-1,4-naphthoquinones and 3-(alk-1-enyl)-2,5,8-trihydroxy-1,4-naphthoquinones in hexane solutions is due to the existence of rotamers formed upon internal rotation of the alkenyl substituent. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1667–1673, October, 2006.     

Synthesis of benzo[<Emphasis Type="Italic">g</Emphasis>]quinoline-5,10-diones

Addition of HCl to 2-amino-3-(4-methyl-3-oxopentynyl)-1,4-naphthoquinone in CHCl₃ at 20 °C is followed by its cyclization to 4-chloro-2-isopropylbenzo[g]quinoline-5,10-dione. Chlorine atom in this compound can be easily replaced by dialkylamino group upon treatment with secondary amines. 4-Dialkylamino-2-isopropylbenzo[g]quinoline-5,10-dione is also formed by the direct reaction of the starting ketone with secondary amines. Syntheses of 2-amino-3-(4-methyl-3-oxopentynyl)-1,4-naphthoquinone from 2-bromo-and 2-amino-3-iodo-1,4-naphthoquinones are also described. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2381–2385, December, 2007.     

两种含杂环的氨基萘醌化合物的合成

以2,3-二氯-1,4-萘醌为主要原料,分别与吗啡啉和糠胺在一定条件下反应生成2种含杂环的氨基萘醌类化合物。2,3-二氯-1,4-萘醌与吗啡啉及2,3-二氯-1,4-萘醌与糠胺物质的量比均为1∶2,反应温度为60℃,溶剂为乙醇。2,3-二氯-1,4-萘醌与吗啡啉反应时间为1 h,产物2-氯-3-吗啡啉基萘-1,4-二酮(a)收率为93.5%;2,3-二氯-1,4-萘醌与糠胺反应时间为4 h,产物N~2,N~3-二(2-呋喃甲基)-1,4-二((2-呋喃甲基)亚胺)-1,4-二氢化萘-2,3-二氯化铵(d)收率为46.7%。对产物进行IR、Uv、MS和H-NMR等分析表征。     

Spinazarin and ethylspinazarin,pigments of the sea urchin <Emphasis Type="Italic">Scaphechinus mirabilis</Emphasis>

2,3,5,8-Tetrahydroxy-1,4-naphthoquinone (spinazarin) and 6-ethyl-2,3,5,8-tetrahydroxy-1,4-naphthoquinone (ethylspinazarin) were first isolated from the sea urchin Scaphechinus mirabilis. The structures of spinazarins were established based on analysis of spectroscopic data. A preparative synthetic route to ethylspinazarin was proposed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 788–791, April, 2007.     

Oxidative arylamination of 1,7-dihydroxynaphthalene

1,7-Dihydroxynaphthalene reacts with aniline orp-toluidine in the presence of oxidants to give the correspondingN-aryl-7-hydroxy-1,4-naphthoquinone 4-imines, 2-arylamino- and 2,8-diarylamino-N-aryl-7-hydroxy-1,4-naphthoquinone 4-imines, and benzo[a]oxophenoxazinimine derivatives. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 347–350, February, 1999.     

Synthesis of 2-(3-amino-2-oxoindolin-3-yl)-3-hydroxynaphthalene-1,4-dione derivatives via a one-pot,three-component reaction under catalyst-free conditions

A concise, facile and straightforward synthetic method has been described for the synthesis of 2-(3-amino-2-oxoindolin-3-yl)-3-hydroxynaphthalene-1,4-dione derivatives by a one-pot, three-component reaction of isatins, 2-hydroxy-1,4-naphthoquinone and ammonium acetate under catalyst-free conditions in ethanol. This protocol becomes highly efficient due to its mild reaction conditions, operational simplicity, and overall good to excellent yields (80–99%).     

Synthesis and efficiency of photolysis of methylated 2-dialkylamino- and 2-piperidino-1,4-naphthoquinones

2-Dialkylamino- and 2-piperidino-1,4-naphthoquinones with a methyl group in position 3 or 5(8) of the naphthoquinone were synthesized by reacting dimethyl- and diethylamines and piperidine with 2- and 5-methyl-1,4-naphthoquinones. The quantum yields of photoconversion of the synthesized compounds in benzene were determined. A 1.2- to 6.5-fold increase of the quantum yield over that of 2-dimethylamino-1,4-naphthoquinone was established. A comparison of the quantum yields with the calculated charges on the reaction centers in the excited (T ₁) state showed that there is not a linear relationship between them.Institute of Organic Chemistry, Russian Academy of Sciences, Siberian Branch, 630090 Novosibirsk. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 707–714, March, 1992.     

Comparative Sites for Coordination of Naphthoquinones and its Derivatives: Studies on the Synthesis of a Series of 1,4-Naphthoquinone Derivatives and Their Ni(II) Complexes

Abstract

New derivatives (5–8) of 5-amino-8-hydroxy-1,4-naphthoquinone (1) have been synthesized and characterized by IR, UV-Vis, ¹H NMR, mass spectra and CNH. These new ligands and the 5-amino-8-hydroxy-l,4-naphthoquinone (1), the 5-amino-6-bromo-8-hydroxy-1,4-naphtho-quinone (2), the 5-acetylamino-8-hydroxy-1,4-naphthoquinone (3) and the 5-dodecanoylamino-8-hydroxy-1,4-naphthoquinone (4), were complexed with Ni(II) giving the chelates (1a–8a). The structure and site of coordination of these complexes are discussed in relation to their spectroscopic data and thermal analysis.     

Copper Bromide–Catalyzed C-Alkylation of 2-Amino-1,4-Naphthoquinone: New Synthesis of 1-Azaanthraquinones

Copper(I) bromide catalyzes the regioselective Michael addition reaction of 2-amino-1,4-naphthoquinone (5) with methyl vinyl ketone and 2-propenal to provide easy access to C-alkylated quinone derivatives, useful precursors of 1-azaanthraquinones.     

Condensation of Ethyl 2-Oxoindoline-3-glyoxylate with o-Aminophenol and o-Phenylenediamine

A method is presented for the synthesis of 3-(2-oxo-1,2-dihydro-3H-indol-3-ylidene)-1,4-dihydroquinoxalin-2-one and 2-(2-oxo-1,2-dihydro-3H-indol-3-ylidene)-2H-1,4-benzoxazin-3(4H)-one by the reaction of ethyl 2-oxoindoline-2-glyoxylate with o-aminophenol and o-phenylenediamine. Proposed reaction mechanisms are presented.     

Synthesis and structure elucidation of oxidative coupling products of 2-hydroxy-1,4-naphthoquinones

2,3-Dihydro-3-O-(1,4-naphthoquinon-2-yl)-2-oxo-1,4-naphthoquinones are the products of oxidative coupling of substituted 2-hydroxy-1,4-naphthoquinones (regardless of the presence of peri-hydroxy groups in their structures) under the action of lead dioxide. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 294—298, February, 2006.     

Reaction of 2,3-Dichloro-1,4-naphthoquinone with Some Active Methylene Compounds in Different Basic Media

Reaction of 2,3-dichloro-1,4-naphthoquinone with some active methylene compounds, such as malononitrile and cyanoacetamide, under various basic conditions has been investigated. A mechanism for these reactions is proposed.     

Aminodefluorination of 2-X-pentafluoro-1,4-naphthoquinones (X = NHBu, NEt2, and OMe)

Aminodefluorination of 2-n-butylamino- and 2-diethylaminopentafluoro-1,4-naphthoquinone by alkylamines HNR¹R² (NR¹R² = NHEt, NHⁿBu and NEt₂) occurs at the 6- or 8-position and further, accordingly, at the 8- or at one of the 5- and 6-sites. The isomer ratio changes significantly in favor of a β-replacement product with solvent variation in the sequence: toluene < 1,4-dioxane < DMSO. n-Butylaminodefluorination of 2-methoxypentafluoro-1,4-naphthoquinone gives mixtures of fluorine substitution products both on the benzene and quinone rings.     

Synthesis of lomazarin and norlomazarin, pigments from Lomandra hastilis

5,8-Dihydroxy-2,3,6-trimethoxy-7-ethyl-1,4-naphthoquinone (1) was used to synthesize in high yield 5,8-dihydroxy-7(1′-hydroxyethyl)-2,3,6-trimethoxy-1,4-naphthoquinone (lomazarin, 3), a pigment from Lomandra hastilis. Alkaline hydrolysis of lomazarin produced mainly 5,6,8-trihydroxy-2,3-dimethoxy-1,4-naphthoquinone (9) through a retro-aldol decomposition of the 6-keto-form of 5,6,8-trihydroxy-7(1′-hydroxyethyl)-2,3-dimethoxy-1,4-naphthoquinone (13b) formed during the reaction. 2,5,8-Trihydroxy-7(1′-hydroxyethyl)-3,6-dimethoxy-1,4-naphthoquinone (norlomazarin, 4a), a pigment of L. hastilis, and its 3,5,8-trihydroxy-7(1′-hydroxyethyl)-2,6-dimethoxy isomer 4b were formed as a difficultly separable mixture in addition to quinone 9. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 581–584, November–December, 2008.     

Synthesis, spectral and electrochemical characterization of novel 2-(fluoroanilino)-1,4-naphthoquinones

The preparation of novel 2-(fluoroanilino)-1,4-naphthoquinones is presented. It takes place under mild conditions by reacting the corresponding fluoroaniline and 1,4-naphthoquinone in the presence of a Lewis acid catalyst with strong oxidation properties such as CeCl₃·7H₂O. This preparation was also investigated under microwave irradiation. All 1,4-naphthoquinone derivatives were characterized by UV-Vis, IR, ¹H and ¹⁹F NMR, MS and cyclic voltammetry, to investigate the effect of the fluoro-substituents on their electronic properties.     

Iodinated 1,4-naphthoquinones

Iodination of 5-amino- and 6-amino-1,4-naphthoquinones with I₂ and HIO₃ in aqueous dioxane occurs only at the benzoid ring. Depending on the reaction conditions, either aminoiodo- or aminodiiodonaphthoquinones are produced. Diazotization of these compounds followed by reduction or replacement of the diazo group with iodine affords mono- or polyiodo derivatives of 1,4-naphthoquinone. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1465–1469, June, 2005.     

Phase-transfer oxidation of 2-methyl-1-naphthol into 2-methyl-1,4-naphthoquinone in the presence of vanadomolybdophosphoric heteropolyacids

2-Methyl-1-naphthol is oxidized into 2-methyl-1,4-naphthoquinone (menadione) by air in the presence of vanadomolybdophosphoric heteropolyacids and their salts. The reaction proceeds in a biphasic system, and the yield of menadione is up to 85 %. The influence of the composition of the heteropolyacids on the rate and the selectivity of the reaction was studied, and the reaction mechanism was proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1208–1211, July, 1994.     

Synthesis and Spectroscopic Properties of S-,O-Substituted Naphthoquinone Dyes

New S-,O-substituted naphthoquinone compounds (3a, 4b, 6, 7c, 9d, 10, 12, 13c, 14d, 15) were synthesized via vinilic substitution. 2,3-Dichloro-1,4-naphthoquinone gave 3a and 4b with 4,4′-thiobisbenzenethiol, respectively. Compounds 6 and 7c were obtained from the reaction of 2,3-dichloro-1,4-naphthoquinone with cyclohexylmercaptane. The compounds 9d and 10 were prepared from the reaction of 2,3-dichloro-1,4-naphthoquinone with 6-mercapto-1-hexanol. Compounds 12, 13c, 14d, and 15 were synthesized from the reaction of 2,3-dichloro-1,4-naphthoquinone with 1,6-hexanedithiol. Their structures were characterized by micro analysis, FT-IR, ¹H NMR, ¹³C NMR, MS, UV-Vis, and fluorescence spectroscopy.     

New NH-substituted 1,4-naphtho- and 1,4-benzo- quinones: Synthesis,characterization and potential antiproliferative effect against MDA-MB-231 cells

Abstract

Eleven new alkyl and aryl amino quinones were synthesized from quinones (2,3-dibromo-1,4-naphthoquinone 1, 2-bromo-1,4-naphthoquinone 2, p-benzoquinone 3 or 2,6-dichloro-1,4-benzoquinone 8) with primary amines. The structures of all compounds were characterized by spectroscopic technics and elemental analysis. The structure of 2-((6,6-Dimethylbicyclo[3.1.1]heptan-2-yl)methylamino)-3-bromonaphthalene-1,4-dione (5a) was established by single crystal diffraction. 2-(2-(Ethylthio)ethylamino)naphthalene-1,4-dione (6b) was found to have noteworthy antiproliferative effect against MDA-MB-231 cells.