Cyanine dyes based on vinyl derivatives of pyeidine and quinoline

Monomethylidynecyanine dyes containing vinyl groups were obtained by the reaction of the alkiodides of 2-methyl-5-vinylpyridine, 2-vinylquinoline, and 4-methyl-2-vinylquinoline with the appropriate alkiodides of quinoline derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1679–1680, December, 1971.     

Synthesis of tricyclic phospholene oxides by cycloaddition of phosphorus halides with heterocyclic analogs of 1-vinyl-3,4-dihydronaphthalenes

Replacement of C-4 with a hetero substituent (NR,O,S) in the 1-vinyl-3,4-dihydronaphthalene system has provided a new type of diene for participation in the McCormack cycloaddition reaction with P(III) halides. The tricyclic phospholene oxides so obtained are the first to bear an additional heteroatom in the ring system. 1,2-Dihydro-7-methoxy-1-(p-toluenesulfonyl)-4-vinylquinoline is a stable solid that reacts with methylphosphonous dichloride to give, after hydrolysis of the cycloadduct, the 1,2,4,5-tetrahydro-1H-phospholo-[2,3-c]quinoline ring system. The dihydroquinoline moiety was aromatized by detosylation with potassium t-butoxide. The tendency of 4-vinyl-2H-benzopyran to dimerize was a serious complication in its use, and the cycloaddition with methylphosphonous dichloride proceeded only in low yield. The product, a 2,3,3a,4-tetra-hydrobenzo[3,2-d]pyran derivative, was a stable, easily purified and characterized substance. 4-Vinyl-2H-benzo[b]thiopyran was more stable than the pyran, but the phospholo derivative from reaction with methylphosphonous dichloride was more difficult to purify. All products were characterized by ¹³C-nmr spectroscopy.     

Synthesis of derivatives of 7-iodo-4-aminoquinolines

7-Iodo- and 7,8-diiodo-4-(3-dimethylaminopropylamino)quinolines and 7-iodo-4-(3) dipropyl-aminopropylamlno)- and 7-iodo-4-(3-diallylaminopropylamino)quinoline were obtained by the reaction of 7-iodo- and 7,8-diodo-4-chloroquinolines with the corresponding diamines. The catalytic hydrogenation of 7-iodo-4-(3-diallylaminopropylamino)quinoline at normal pressure leads to 7-iodo-4-(3-dipropylaminopropylamino)quinoline.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 972–975, July, 1980.     

Synthesis and Transformations of 4-(4-Ethoxycarbonylphenylamino)- and 4-(2-Carboxyphenylamino)quinolines

Synthesis was performed of 4-(4-ethoxycarbonylphenylamino)- and 4-(2-carboxyphenylamino)-2-methylquinolines by reaction of 2-methyl-4-chloroquinoline with anesthesin and anthranilic acid. In concentrated sulfuric acid 4-(2-carboxyphenylamino)-2-methylquinoline underwent cyclization into 6-hydroxy-7-methylquinolino[3,2-c]quinoline, and the alkaline hydrolysis of 4-(4-ethoxycarbonylphenyl-amino)quinoline afforded 2-methyl-4-(4-carboxyphenylamino)quinoline.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 786–787.Original Russian Text Copyright © 2005 by Avetisyan, Aleksanyan, Ambartsumyan.     

Photochemical properties of amino and nitro derivatives of 2-and 4-styrylquinolines and their hydrochlorides

The trans-cis and cis-trans photoisomerization reactions of a double bond in nitro and amino derivatives of 2-and 4-styrylquinolines in the neutral and protonated (hydrochloride) forms were studied. Protonation in nitrostyrylquinolines was shown to have no effect on the photoisomerization quantum yields. In aminostyrylquinolines, the photoisomerization reaction is “switched off” for the monocationic form as a result of the competitive process of intramolecular charge transfer and is “switched on” again for the dication. In the latter case, the quantum yield of trans-cis photoisomerization decreases by a factor of 2–2.5 and the quantum yield of cis-trans photoisomerization remains practically unchanged as compared to that of the neutral compound. Upon long-term irradiation of 4-(4′-nitrostyryl)quinoline, the photocyclization reaction of the cis-isomer was observed.     

Reactions of methyl (E,Z)-2-(2-benzoyl-2-ethoxycarbonyl-1-ethenyl)-amino-3-dimethylaminopropenoate with heteroarylhydrazines. 2-(2-Benzoyl-2-ethoxycarbonyl-1-ethenyl)amino-3-heteroarylhydra-zonopropanoates and 1-heteroaryl-4-ethoxycarbonyl-3-phenylpyrazoles

In the reaction of methyl (E,Z)-2-(2-benzoyl-2-ethoxycarbonyl-1-ethenyl)amino-3-dimethylaminopro-penoate ( 1 ) with heteroarylhydrazines 2 in ethanol in the presence of catalytic amounts of hydrochloric acid two types of products were formed: methyl 2-(2-benzoyl-2-ethoxycarbonyl-1-ethenyl)amino-3-heteroaryl-hydrazonopropanoates 4 in 73-86% yield and 1-heteroaryl-4-ethoxycarbony-3-phenylpyrazoles 5 in 5-16% yield.     

Synthesis and antimycobacterial screening of new 4-(4-(1-benzyl-1H-1,2,3-triazol-4-yl)-1-phenyl-1H-pyrazol-3-yl)quinoline derivatives

A new series of 4-(4-(1-benzyl-1H-1,2,3-triazol-4-yl)-1-phenyl-1H-pyrazol-3-yl)quinoline ( 6a-t ) have been synthesized by a click reaction of 4-(4-ethynyl-1-phenyl-1H-pyrazol-3-yl)quinoline ( 4a-d ) with a substituted benzyl azide ( 5a-e ). The starting alkyne derivatives 4a-d are obtained from Bestmann-Ohira reaction of 1-phenyl-3-(quinolin-4-yl)-1H-pyrazole-4-carbaldehyde and dimethyl(1-diazo-2-oxopropyl)phosphonate. The newly synthesized compounds are screened against M. tuberculosis H37Ra dormant and active, Escherichia coli, Pseudomonas fluorescence, Staphylococcus aureus and Bacillus subtilis strains at 30 μg/mL concentration. Most of the screened compounds showed good to moderate antibacterial activity against S. aureus, B. subtilis, and Mycobacterium tuberculosis H37Ra strains. The synthesized derivatives of quinolinyl-pyrazole-4-carbaldehyde and quinolinyl-pyrazole-4-ethyne reportd good to moderate activity against both strains of M. tuberculosis H37Ra. Ten derivatives of quinolinyl-pyrazole presented good activity against B. subtilis. These results suggested that further optimization and development of quinolinyl-pyrazolyl-1,2,3-triazole moeity could serve as lead compounds for antimycobacterial activity.     

Total synthesis of (-)-martinellic acid via radical addition-cyclization-elimination reaction

The asymmetric total synthesis of martinellic acid, the first pyrrolo[3,2-c]quinoline alkaloid found in nature, is described. Three key steps in our synthesis of (-)-martinellic acid are the Bu(3)SnH-promoted radical addition-cyclization-elimination (RACE) reaction of an oxime ether with an alpha,beta-unsaturated ester to generate the pyrrolo[3,2-c]quinoline core, a chemoselective lactam carbonyl reduction, and guanidinylation under Mitsunobu reaction conditions. The key radical cyclization has also been investigated by using SmI(2). (-)-Martinellic acid was synthesized from commercially available methyl 4-bromo-3-methylbenzoate in fewer steps than previous syntheses and in an improved overall yield.     

Regioselective alkynylation of 2-aryl-4-chloro-3-iodoquinolines and subsequent arylation or amination of the 2-aryl-3-(alkynyl)-4-chloroquinolines

Palladium-CuI catalyzed Sonogashira coupling of 2-aryl-4-chloro-3-iodoquinolines with terminal acetylenes (1 equiv) in triethylamine afforded the 2-aryl-3-(alkynyl)-4-chloroquinolines as sole products. The 2-aryl-4-chloro-3-iodoquinolines coupled with excess terminal acetylenes (2.5 equiv) in dioxane/water to yield the 2-aryl-3,4-bis(alkynyl)quinoline derivatives in a one-pot operation. The 2-aryl-3-(alkynyl)-4-chloroquinolines were, in turn, subjected to arylation via Suzuki cross-coupling with arylboronic acid derivatives or amination with methylamine, respectively. The structures of the products of successive Sonogashira and Suzuki cross-couplings were also confirmed by X-ray crystallography.     

异色满酮-4及其衍生物的合成(Ⅳ)——辛可宁酸类似物的合成

由异色满酮-4(1)与邻氨基苯甲醛或邻氨基胡椒醛进行Friedlender缩合反应得到异色满并喹啉衍生物异色满并[4,3-b]喹啉(2)和9,10-亚甲二氧基异色满并[4,3-b]喹啉(3).     

Novel synthesis of substituted thiophenes by palladium-catalyzed cycloisomerization of (Z)-2-en-4-yne-1-thiols

[reaction: see text] The first example of palladium-catalyzed cycloisomerization of (Z)-2-en-4-yne-1-thiols 1 to give substituted thiophenes 2 is reported. Cycloisomerization reactions are carried out under nitrogen at 25-100 degrees C in N,N-dimethylacetamide as the solvent in the presence of catalytic amounts of PdI2 in conjunction with KI to give the corresponding thiophenes in 43-94% yield.     

Photosensitized cyclodimerizations of 4-vinylpyridine, 2-vinylpyridine,and 2-vinylquinoline

Irradiations of 4-vinylpyridine and of 2-vinylpyridine in either f-butyl alcohol or benzene, with benzophenone, yielded a single photodimer, which, on the basis of the nmr and mass spectral data, was assigned the trans-head-to-head structure (I). Upon irradiation in either t-butyl alcohol or benzene, in the presence of benzophenone, 2-vinylquinoline gave a single photodimer whose structure and stereochemistry were also determined from the nmr and mass spectral evidence as (V). Irradiation of 2-vinylquinoline in benzene, in the absence of benzophenone, also gave rise to the same photodimer, but, when t-butyl alcohol or methanol was used as a solvent, no dimer formation was observed.     

Synthesis and transformations of 2- and 4-(2-Methylquinolin-4-ylamino)benzoic acids and ethyl 4-(2-methylquinolin-4-ylamino)benzoates and their fluorescent properties

2- and 4-(2-Methylquinolin-4-ylamino)benzoic acids and ethyl 4-(2-methylquinolin-4-ylamino)-benzoates having a substituent in the 6(8)-position of the quinoline ring were synthesized by reaction of the corresponding substituted 4-chloro-2-methylquinolines with 2- and 4-aminobenzoic acids and ethyl 4-aminobenzoate. Intramolecular cyclization of 2-(2-methylquinolin-4-ylamino)benzoic acids in concentrated sulfuric acid gave 7-hydroxy-6-methyldibenzo[b,h][1,6]naphthyridines, and ethyl 4-(2-methylquinolin-4-ylamino)benzoates were converted into 4-(2-methylquinolin-4-ylamino)benzoic acids by alkaline hydrolysis.     

9,9-二[4-(4-羧基苯氧基)苯基]呫吨的合成

在碘化亚铜、四丁基溴化铵和磷酸钾存在下,9,9-二(4-羟基苯基)呫吨(1)和4-甲基碘苯(2)于N,N-二甲基甲酰胺溶剂中发生Ullmann偶联反应,加热回流反应24 h,以95%的产率合成了中间体--9,9-二[4-(4-甲基苯氧基)苯基]呫吨(3),继而加入催化量的N-溴代丁二酰亚胺并在光照条件下,将中间体3氧化得到一种新型芳香族二羧酸--9,9-二[4-(4-羧基苯氧基)苯基]呫吨(4),其产率为84%,二步反应总收率为79.8%。 目标化合物4经1H NMR、13C NMR、IR和元素分析测试技术确定了其结构。 该法具有原料易得,操作简单,反应条件温和,收率高等优点。     

Synthesis and modification of 4-hydroxy-2-methyl-3-(2-chloro-2-propenyl)quinoline

4-Hydroxy-2-methyl-3-(2-chloro-2-propenyl)quinoline was prepared by O-allylation of 4-hydroxy-2-methylquinoline followed by the Claisen rearrangement of the 2-methyl-4-(2-chloro-2-propenyloxy)quinoline obtained. Chemical modifications of 4-hydroxy-2-methyl-3-(2-chloro-2-propenyl)quinoline resulted in the synthesis of 4-amino-2-methyl-3-(2-methyl-3-indolyl)quinoline.     

An unexpected [2+2]-cycloaddition reaction of 4-methyldithieno-[3,4-b:3′,2′-d]pyridinium iodide with dimethyl acetylenedicarboxylate

An unexpected [2+2]-cycloaddition occured in the reaction of 4-methyldithieno-[3,4-6:3′,2′-d]pyridinium iodide (3)with two equivalents of DMAD, giving 4-(trans-1,2-dicarbomethoxy-2- iodovinyl)-5-methyl-6,7-dicarbomethoxy-4,5-dihydrothieno [23-c]quinoline (4) in 54% yield. 4 is formed via 4-methyl-5-(trans-1,2-dicarbomethoxy-2-iodo-4,5-dihydrothieno [3,4-b:3′,2′-d]pyridine (16), followed by [2+2]-cycloaddition. The primary adduct rearranges via a thiepin to an episulfide which eliminates sulfur to give 4.     

Ethynyl ketene-S,S-acetals: the highly reactive electron-rich dienophiles and applications in the synthesis of 4-functionalized quinolines via a one-pot three-component reaction

An efficient synthetic method for 4-functionalized quinoline derivatives, 4-((1,3-dithian-2-ylidene)methyl)quinolines, has been developed. Mediated by trifluoromethanesulfonic acid, ethynyl ketene-S,S-acetals can react in a one-pot procedure with various arylamines and aldehydes under mild conditions to give the corresponding quinoline derivatives in good to high yields via a consecutive arylimine formation, regiospecific aza-Diels-Alder (Povarov) reaction, and reductive amination.     

氯化锆催化芳胺和正丁醛合成喹啉衍生物

以ZrCl4为催化剂,芳胺和醛为原料,采用"一锅法"合成了喹啉衍生物;考察了空气、催化剂用量、原料比例以及芳胺的取代基等因素对反应收率的影响;利用高分辨质谱和核磁共振谱(1 H NMR、13 C NMR)表征了产物的分子结构.结果表明,以苯胺和正丁醛为原料时,3-乙基-2-丙基喹啉的收率可达65%,同时生成27%的N-丁基苯胺;工艺经改进后,反应条件温和、操作简便、催化剂用量少、产物收率高.     

The chemistry of 2H-3,1-benzoxazine-2,4(1H)-dione (isatoic anhydride). 10. Reactions with ester enolates. Synthesis of 4-hydroxy-1-methyl-3-prenyl-2(1H)-quinolinones,Crucial intermediates in the synthesis of quinoline alkaloids

N-Methylisatoic anhydride reacts with the lithium enolates of esters to produce β-ketoesters 4 in nearly quantitative yield. Thermal cyclization of these relatively unstable intermediates afford the corresponding 3-substituted-4-hydroxy-1-methyl-2(1H)-quinolinones (5) in good yields. The reaction of the lithium enolate of 5-methyl-4-hexenoic acid ethyl ester ( 14 ) with various nuclear substituted isatoic anhydrides gives 4-hydroxyl-methyl-3-prenyl-2(1H)-quinolinones 8, 9 , and 18 which are highly desirable intermediates in the synthesis of a variety of quinoline alkaloids. Treatment of 18 with DDQ furnishes oricine in 73% yield.     

Direct C-4 arylation of crotonaldehyde with arenediazonium tetrafluoroborates

Arenediazonium tetrafluoroborates react with crotonaldehyde (2-butenal) in methanol in the presence of catalytic amounts of Pd(OAc)₂ to yield mainly 4,4-dimethoxy-1-butenylarenes. In most of the examples studied, small amounts of an isomeric byproduct were formed, presumably 3,3-dimethoxy-1-methylenepropylarenes. Because crotonaldehyde and arenediazonium salts are cheap and readily available, this reaction is a convenient access to protected 4-arylbutenals.