Synthesis of chlorinated 2-(aminomethyl)- and 2-(alkoxymethyl)pyrroles

The synthesis of chlorinated 2-(hydroxymethyl)-, 2-(alkoxymethyl)- and 2-(aminomethyl)pyrroles via aromatization of 2-aryl-3,3-dichloro-5-(bromomethyl)pyrrolines and via reduction of 2-formyl- and 2-cyanopyrroles is described. The former methodology also provided new 2-[(alkyl- or phenylamino)methyl]pyrroles and a 2-(phosphonomethyl)pyrrole. Halogenated and methylene-spaced functionalized pyrroles are of particular interest for their pronounced physiological activities.     

Preparation,molecular structures,and characteristic properties of (E)-1-(2-furyl)- and (E)-1-(2-thienyl)-2-(3-guaiazulenyl)ethylenes and (E)-1-(3-furyl)- and (E)-1-(3-thienyl)-2-(3-guaiazulenyl)ethylenes

Wittig reactions of 2-furaldehyde (20) [and thiophene-2-carbaldehyde (21)] with (3-guaiazulenylmethyl)triphenylphosphonium bromide (19) in ethanol containing NaOEt at 25 °C for 24 h under argon give (E)-1-(2-furyl)-2-(3-guaiazulenyl)ethylene (22E) and (E)-1-(2-thienyl)-2-(3-guaiazulenyl)ethylene (23E) in 53 and 36% yields. Similarly, Wittig reactions of 3-furaldehyde (29) [and thiophene-3-carbaldehyde (30)] with 19 under the same reaction conditions as for 20 and 21 afford (E)-1-(3-furyl)-2-(3-guaiazulenyl)ethylene (31E) and (E)-1-(3-thienyl)-2-(3-guaiazulenyl)ethylene (32E) in 32 and 46% yields. Molecular structures and characteristic properties as well as preparation of the title E (i.e., one of the geometrical isomers) forms, with a view to comparative study, are reported. Moreover, reactions of those conjugated π-electron systems with TCNE (=tetracyanoethylene) in benzene [and in DMF (=N,N-dimethylformamide)] at 25 °C for 24 h under argon yield unique products, possessing interesting molecular structures, respectively, whose characteristic properties and crystal structures are documented, also.     

Synthesis of 2-(2-methoxyethyl)- and 2-(2-thiomethoxyethyl)-aniline and related compounds

Summary 2-(2-Nitrophenyl)-ethanol (2) was methylated with dimethyl sulfate to give 2-(2-methoxyethyl)-1-nitrobenzene (3a) which then was reduced with hydrazine hydrate in the presence ofRaney nickel to 2-(2-methoxyethyl)-aniline (1a). Compound1a can be transformed into the N-monosilylated derivative4 by lithiation withn-butyllithium and subsequent reaction with chlorotrimethylsilane. Reaction of2 withp-toluenesulfonyl chloride yields 2-(2-nitrophenyl)-ethylp-toluenesulfonate (5), which reacts with sodium thiomethoxide to give 2-(2-nitrophenyl)-ethylp-toluenesulfonate (5), which reacts with sodium thiomethoxide to give 2-(2-thiomethoxyethyl)-1-nitrobenzene (3b).3b was reduced with hydrazine hydrate in the presence ofRaney nickel to yield 2-(2-thiomethoxyethyl)-aniline (1b). Ethyl (2-nitrophenyl)-acetate (6) could be dimethylated with methyl iodide in the presence of potassiumtert-butoxide and 18-crown-6 to give ethyl 2-methyl-2-(2-nitrophenyl)-propionate (7). Reduction of7 with lithium borohydride yields 2,3-dihydro-3,3-dimethyl-1H-indole (9) and 2-[(1-hydroxy-2-methyl)-2-propyl]-aniline (10).

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Synthese von 2-(2-Methoxyethyl)- und 2-(2-Thiomethoxyethyl)-anilin und verwandten Verbindungen

Zusammenfassung 2-(2-Nitrophenyl)-ethanol (2) wurde mit Dimethylsulfat zu 2-(2-Methoxyethyl)-1-nitrobenzol (3a) methyliert, das sich mit Hydrazinhydrat in Gegenwart vonRaney-Nickel zu 2-(2-Methoxyethyl)-anilin (1a) reduzieren läßt. Verbindung1a kann durch Metallierung mitn-Butyllithium und anschließende Reaktion mit Chlortrimethylsilan in dasN-monosilylierte Derivat4 umgewandelt werden. Reaktion von2 mitp-Toluolsulfonylchlorid ergab 2-(2-Nitrophenyl)-ethyl-p-Toluolsulfonat (5), das mit Natriumthiomethanolat zu 1-Nitro-2-(2-thiomethoxyethyl)-benzol (3b) reagiert.3b wurde mit Hydrazinhydrat in Gegenwart vonRaney-Nickel zu 2-(2-Thiomethoxyethyl)-anilin (1b) reduziert. Ethyl-2-(nitrophenyl)-acetat (6) kann mit Methyliodid in Gegenwart von Kalium-tert-butoxid und 18-Krone-6 zu Ethyl-2-methyl-2-(2-nitrophenyl)-propionat (7) dimethyliert werden. Reduktion von7 mit Lithiumborhydrid lieferte 2,3-Dihydro-3,3-dimethyl-1H-indol (9) und 2-[(1-Hydroxy-2-methyl)-2-propyl]-anilin (10).

     

Synthesis and properties of 2-(2-furyl)-and 2-(2-Thienyl)-1,3-benzoxazoles

Condensation of o-aminophenol with furoyl and thenoyl chlorides in 1-methylpyrrolidin-2-one gave, respectively, 2-(2-furyl)- and 2-(2-thienyl)-1,3-benzoxazoles in which the furan and thiophene rings showed no acidophobic properties. Reactions of 2-(2-furyl)- and 2-(2-thienyl)-1,3-benzoxazoles with electrophilic reagents (acylation, bromination, nitration, and sulfonation) afforded products of hydrogen replacement in both hetaryl and benzene rings, depending on the conditions.     

1-(Fluoren-2-yl)-2-(2-azafluoren-3-yl)ethene and 1-(fluoren-2-yl)-2-(2H,2-methylindeno[2,3-c]pyridine)ethene

Condensation of 3-methyl-2-azafluorene with 2-formylfluorene results in the formation of a compound containing a polyconjugated system and two acidic CH centers, namely, 1-(fluoren-2-yl)-2-(2-azafluoren-3-yl)ethene. The conversions of this compound upon treatment with alkali have been studied by electronic absorption spectroscopy. The methyl iodide derivative of this base was used as an intermediate in the preparation of a pseudo-azulene, 1-(fluoren-2-yl)-2-(2H, 2-methylindeno[2,3-c]pyridine)ethene.Translated from Khimiya Geterotsiklicheskikh Soedinenii No. 5, pp. 657–659, May, 1987.     

An equilibrium analysis of the aqueous H+-MoO4(2-)-(HP)O(3)2- and H+-MoO4(2-)-(HP)O(3)2--HPO4(2-) systems

The speciation in the phosphitomolybdate system, H+-MoO4(2-)-(HP)O(3)2-, has been determined from combined potentiometric and 31P NMR measurements in 0.600 M Na(Cl) medium at 298(1) K. Potentiometric titration data were collected in the ranges 2.5<-log[H+]<6.2, 40.0相似文献   

A facile preparation of 2-(2-arylethyl)- and 2-(aminomethyl)indoles

An important process for the acid catalyzed cleavage of the benzoyl group from 3-benzoylindoles in high yield is identified and its application for the facile syntheses of 2-substituted indoles is demonstrated by preparing some 2-(2-arylethyl)- and 2-(aminomethyl)indoles from 1,3-dibenzoyl-2-bromomethylindole (7).     

Synthesis and Crystal Structure of（E）-Ethyl 2-（5-（3-methyl-2-butenyloxy）-2-（3-（4-（3-methyl-2-butenyloxy）phenyl）acryloyl）phenoxy）acetate

The title compound,(E)-ethyl 2-(5-(3-methyl-2-butenyloxy)-2-(3-(4-(3-methyl-2-butenyloxy)phenyl) acryloyl) phenoxy)acetate(1),has been synthesized and characterized by FT-IR and 1H-NMR spectroscopy,ESI-MS,and X-ray single-crystal diffraction.FT-IR,1H-NMR and ESI-MS confirm the functional groups,particularly the ethyl groups in the ester moiety,of the compound.The single-crystal X-ray diffraction has revealed a monoclinic structure,space group P21/n with a = 14.6832(14),b = 7.7581(7),c = 23.075(2),β = 101.670(2)o,V = 2574.2(4) ?3,Z = 4,Dc = 1.235 g/cm,μ = 0.085 mm-1,and F(000) = 1024.The skeleton of chalcone in the molecular structure is coplanar.     

2-(2-thiazolylazo)-4-methoxyphenol and 2-(2-thiazolylazo)-5-methoxyphenol as metal-ion indicators

2-(2-Thiazolylazo)-5-methoxyphenol (TAMR) and 2-(2-thiazolylazo)-4-methoxyphenol (TAMH) are shown to be good indicators for the titration of many metal ions with EDTA. TAMH is better and more widely applicable than TAMR. The acid dissociation constants have been determined by spectrophotometry. The effect of pH on the absorbance of the indicators and metal-indicator complexes is reported.     

苯乙烯基氮氧杂芳烃间的交叉光二聚反应

用中压汞灯(λ > 300 nm)照射4-苯乙烯基吡啶、2-苯乙烯基苯并噁唑和5-苯基-2-苯乙烯基噁唑三种杂芳基乙烯单体中任意两种的硫酸水溶液，得到三种交叉二聚体.用高效液相色谱跟踪研究了交叉光二聚反应，发现每组反应生成三种光二聚体，其中二种为单体自身的光二聚体，而另外一种是两种不同单体的交叉光二聚体.交叉二聚体通过柱色谱分离得到，其顺式头对尾结构经紫外、红外、氢谱、碳谱和元素分析确定.用紫外光谱和高效液相色谱跟踪研究了交叉光二聚体的稀溶液在低压汞灯（λmax=254 nm）照射下的光解反应.研究发现交叉二聚体能够彻底发生光解，首先生成原来的反式单体，所生成的反式单体容易发生异构化而生成顺式单体，最终建立起反顺异构化平衡.     

2-(Acylmethylmercapto)-3-amino- and 2-(acylmethylmercapto)-3-acetamidopyridines

The reaction of 2-mercapto-3-acetamido-5-(or 6-)chloropyridines with phenacyl bromide and substituted phenacyl bromides yielded 2-(phenacylmercapto)-3-acetamidopyridines, while the reaction of the former with -chloroacetoacetic ester yielded 2-(carbethoxyacyl-methylmercapto)-3-acetamidopyridlnes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1391–1394, October, 1971.     

Synthesis of 1-(2-naphthyl)dihydro- and 1-(2-naphthyl)-2-thiodihydrouracils and their transformations

1-(2-Naphthyl)dihydro- and 1-(2-naphthyl)-2-thiodihydrouracils were obtained from N-(2-naphthyl)--alanine derivatives. The thiodihydrouracil was converted to a dihydrouracil. Bromination of 1-(2-naphthyl)dihydrouracil gave (1-bromonaphthyl)dihydrouracil. 1-(2-Naphthyl)-2-oxo-, 1-(2-naphthyl)-2-thio-. and 1-(1-bromo-2-naphthyl)-2-oxohexahydro-pyrimidines were obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii. No. 12, pp. 1695–1697, December, 1971.     

Reactions of 3-(4-Aryl-2-thiazolyl)- and 3-(2-Benzothiazolyl)-2-iminocoumarins with N-Nucleophiles

The reaction of 3-(4-aryl-2-thiazolyl)- and 3-(2-benzothiazolyl)-2-iminocoumarins with N-nucleophiles was studied. This reaction gives 2-N-substituted 3-(4-aryl-2-thiazolyl)- and 3-(2-benzothiazolyl)iminocourmarins. N-Nucleophiles such as arylamines, heterocyclic amines, and hydrazine derivatives undergo this reaction.     

Synthesis and deprotonation of 2-(pyridyl)phenols and 2-(pyridyl)anilines

2-(2- and 3-Pyridyl)anilines (1, 2), 2,2-dimethyl-N-[2-(2- and 3-pyridyl)phenyl]propanamides (3, 4), and 2-, 3- and 4-(2-methoxyphenyl)pyridines (7-9) are readily synthesized using cross-coupling reactions. Whereas the amines 1, 2 undergo side reactions, the corresponding amides 3, 4 are deprotonated with lithium 2,2,6,6-tetramethylpiperidide (LTMP): the compound 3 at C6' under in situ quenching, and the compound 4 at C4'. When the ether 7 is subjected to the same reagent, lithiation occurs at C6'.     

Synthesis and Properties of 2-(2-Furyl)- and 2-(2-Thienyl)-1-methylphenanthro[9,10-d]imidazoles

Condensation of 9,10-phenanthrenequinone with 2-furaldehyde and 2-thiophenecarbaldehyde in glacial acetic acid in the presence of ammonium acetate gave 2-(2-furyl)- and 2-(2-thienyl)phenanthro[9,10-d]imidazoles which were converted into the corresponding 1-methyl derivatives. The furan and thiophene rings in the products lose their acidophobic properties. Depending on the conditions, electrophilic substitution reactions in 2-(2-furyl)- and 2-(2-thienyl)phenanthro[9,10-d]imidazoles occur both at the furan (thiophene) and phenanthrene moieties.     

2-(5-Bromo-2-furyl)quinoxaline and 3-(5-bromo-2-furyl)-2-quinoxalone

2-(5-Bromo-2-furyl)quinoxaline and 3-(5-bromo-2-furyl)-2-quinoxalone were obtained by the action of bromine on the corresponding quinoxaline derivatives and also by condensation of o-phenylenediamine with, respectively, (5-bromo-2-furyl)glyoxal or (5-bromo-2-furyl)glyoxylic acid esters.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 404–406, March, 1973.     

Synthesis and properties of 1-(2-bromoethyl)-, 1-(2-alkoxyethyl)- and 1-(2-dialkylaminoethyl)2-alkylpyrroles

The reaction of 3-chloropropenyl alkyl ketones or 2,3-dichloropropyl alkyl ketones with 2-substituted ethylamine derivatives leads to the formation of the hitherto unknown 1-(2-R-ethyl)-2-alkylpyrroles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1047–1049, August, 1990.     

3-(2-Quinolyl)- and 3-(5-carbethoxyfuryl-2)coumarins

3-(2-Quinolyl)- and 3-(5-carbethoxyfuryl-2)coumarins were prepared by reaction of substituted salicylaldehydes and hetarylacetonitriles. Alkylation and acylation of 3-hetaryl-7-hydroxycoumarins were studied. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 432–434, September–October, 2005.     

1-(Triorganylsilyl)-2-(triethoxysilyl)ethanes

Conclusions The conditions were found for the hydrosilylation of CH₂=CHSi(OC₂H₅)₃ with triorganylsilanes in the presence of H₂PtCl₆ · 6H₂O in isopropanol, which assured a high yield (>90%) of the 1-(triorganylsilyl)-2-(tri-ethoxysilyl)ethanes. These conditions were used to synthesize 27 new 1-(triorganylsilyl)-2-(triethoxysilyl)-ethanes.The addition of (C₂H₅O)₃SiH to (CH₂=CHSi(CH₃)₃ in the presence of the same catalyst gave 1-(trimethyl-silyl)-2-(triethoxysilyl)ethane in 98.6% yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1622–1625, July, 1976.     

Complexation of uranium by 2-(2-thiazolylazo)-4-methoxyphenol and 2-(2-thiazolylazo)-5-methoxyphenol

A comparative study has been made of the complexation of uranium(VI) by 2-(2-thiazolyl)-4-methoxyphenol (TAMH) and 2-(2-thiazolylazo)-5-methoxyphenol(TAMR). The complexes are less stable and have lower molar absorptivities than the PAR and TAR complexes but are still useful for determination of uranium. The TAMH chelate can be extracted into isobutyl methyl ketone. Both complexes are 1:1 metal :ligand. For the TAMH complex log beta(1) = 8.8, = 1.4 x 10(4) at 610 mmu; for the TAMR complex log beta(1) = 8.1, = 2.0 x 10(4) at 530 mmu.