Nucleophilic Substitution in 4-Bromo-5-nitrophthalodinitrile: IV. 5-Nitro-4-(phenylthio)phthalodinitrile and Octa-substituted Metal Phthalocyanines Based Thereon

5-Nitro-4-(phenylthio)phthalodinitrile was obtained by nucleophilic substitution of the bromine atom in 4-bromo-5-nitrophthalodinitrile. The product was used to prepare copper(II) and cobalt tetra(5-nitro-4-phenylthio)phthalocyanines, and their spectral properties were studied.     

Nucleophilic Substitution in 4-Bromo-5-nitrophthalodinitrile: VI. 4-Dimethylphenoxy-5-nitrophenoxyphthalodinitrile and the Copper Phthalocyanine Derived from It

4-(3,4-Dimethylphenoxy)-5-(4-nitrophenoxy)phthalodinitrile was prepared by stepwise nucleophilic substitution of bromine and then the nitro group in 4-bromo-5-nitrophthalodinitrile by the substituted phenoxy groups and was converted to the corresponding octasubstituted copper phthalocyanine by the reaction with copper acetate. The spectroscopic and mesomorphic properties of the resulting complex were studied. It exhibits thermotropic mesomorphism and forms an M phase in the range 85-155°C.     

Nucleophilic Substitution of 4-Bromo-5-nitrophthalodinitrile: XVII. Synthesis and Properties of Bifunctionally Substituted Metal Phthalocyanines with Aryloxy and Nitro Groups

By substitution of bromine in 4-bromo-5-nitrophthalonitrile 4-(aryloxy)-5-nitrophthalonitriles were synthesized and, on their basis, cobalt and copper tetra(4-aryloxy-5-nitro)phthalo-cyanines were prepared. Spectral properties of the obtained octasubstituted phthalocyanines were investigated.     

Nucleophilic Substitution in 4-Bromo-5-nitrophthalodinitrile: VII. Synthesis and Properties of Phenylthio-substituted Phthalocyanine Metal Complexes

New phenylthio-substituted phthalodinitriles have been synthesized: 5-amino-4-phenylthio-, 5-acetylamino-4-phenylthio-, 5-octanoylamino-4-phenylthio-, 5-phenoxy-4-phenylthio-, 5-(4-carboxyphenoxy)-4-phenylthio-, 5-(4-tert-butylphenoxy)-4-phenylthio-, and 4,5-bis(phenylthio)phthalodinitriles. Their complexes with metals have been prepared and examined by spectral methods.     

Nucleophilic substitution in 4-bromo-5-nitrophthalodinitrile: IX. Synthesis of 4-(morpholin-4-yl)-5-aryloxyphthalodinitriles and copper phthalocyanines based thereon

Nucleophilic aromatic substitution of bromine in 4-bromo-5-nitrophthalodinitrile with the morpholine residue and the subsequent substitution of nitro group with the aryloxy one yielded 4-morpholyl-5-aryloxyphthalodinitriles. From these substances octasubstituted copper phthalocyanines were synthesized, and their physicochemical properties were studied.

     

Nucleophilic substitution in 4-bromo-5-nitrophthalodinitrile: X. Synthesis of 4-(1-benzotriazolyl)-5-(1(2)-naphthyloxy)-phthalodinitriles and related phthalocyanines

4-(1-Benzotriazolyl)-5-[1(2)-naphthyloxy]phthalodinitriles were obtained by nucleophilic substitution of bromine and nitro group in 4-bromo-5-nitrophthalodinitrile. These compounds were used for the synthesis of the corresponding octa-substituted phthalocyanines. Spectral data of the compounds obtained were examined.     

Nucleophilic substitution of 4-bromo-5-nitrophthalodinitrile: XIII. Synthesis and properties of 4-(1-benzotriazolyl)-5-(4-tritylphenoxy)phthalonitrile and phthalocyanines based thereon

4-(1-Benzotriazolyl)-5-(4-tritylphenoxy)phthalonitrile was synthesized by nucleophilic substitution of bromine and nitro group of 4-bromo-5-nitrophthalonitrile, and on its basis the corresponding octa-substituted phthalocyanines were obtained. Spectral properties of the synthesized compounds were investigated.     

Nucleophilic Substitution in 4-Bromo-5-nitrophthalodinitrile: XVI.<Superscript>1</Superscript> 4-(1<Emphasis Type="Italic">H</Emphasis>-Benzotriazol-1-yl)-5-[(4-carboxyphenyl)oxy/sulfanyl]- phthalonitriles and Cobalt Phthalocyanines Thereof

A method of synthesis of 4-(1H-benzotriazol-1-yl)-5-[(4-carboxyphenyl)oxy]- and -5-[(4-carboxyphenyl) sulfanyl]phthalonitriles starting with 4-bromo-5-nitrophthalonitriles was developed. The synthesized phthalonitriles were used to prepare cobalt tetra-4-(1H-benzotriazol-1-yl)-tetra-5-[(4-carboxyphenyl)oxy/sulfanyl]phthalocyanines. The spectral and catalytic properties of the resulting octasubstituted phthalocyanines were studied.     

Nucleophilic substitution in 4-bromo-5-nitrophthalodinitrile: VIII. Synthesis of 4-(benzotriazol-1-yl)-5-[4-(1-methyl-1-phenylethyl)phenoxy]phthalodinitrile and phthalocyanines on its basis

Nucleophilic aromatic substitution of the bromine atom in 4-bromo-5-nitrophthalodinitrile by a 2-aminophenylamine residue followed by conversion of the resulting compound to 4-(1-benzothiazol-1-yl)-5-nitrophthalodinitrile and nucleophilic substitution of the nitro group by a 4-(1-methyl-1-phenylethyl)-phenoxy group gave 4-(benzotriazol-1-yl)-5-[4-(1-methyl-1-phenylethyl)phenoxy]phthalodinitrile. The latter product was reacted with certain metal acetates and chlorides to obtain the corresponding metal complexes of octasubstituted phthalocyanines. Spectral properties of the complexes were studied.     

Synthesis and Properties of 4-Acyloxy-5-nitrophthalodinitriles and Copper(II) Phthalocyanines Derived Thereof

Acylation of 4-hydroxy-5-nitrophthalonitrile gave 4-acetoxy-5-nitro- and 4-benzoyloxy-5-nitrophthalonitriles. The products were reacted with copper(II) acetate to obtain the corresponding octasubstituted phthalocyanines.     

Nucleophilic substitution in 4-bromo-5-nitrophthalodinitrile: XV. Synthesis of bis-4,5-(phenylsulfanyl)phthalonitrile,octakis-4,5-(phenylsulfanyl)phthalocyanines,and their sulfo and alkylsulfamoyl derivatives

Novel water- and organic-soluble derivatives of octakis-4,5-(sulfanylphenyl)phthalocyanine and its magnesium and aluminum complexes were synthesized starting from 4,5-bis(phenylsulfanyl)phthalonitrile obtained by nucleophilic substitution of the bromine and nitro group in 4-bromo-5-nitrophthalonitrile. Spectral and luminescence characteristics of the newly synthesized compounds were studied.     

Novel Substitution Reactions of 5-(4-Nitrophenyl)-10,15,20-triphenyl porphyrin with Nucleophilic Reagents

Substitution reactions of 5-(4-nitrophenyl)-10,15,20-triphenylporphyrin (1)and its Ni(Ⅱ) complexe 2 with different nucleophilic reagents were studied for preparing asymmetric porphyrin. The reaction products are different with the nucleophilic reagents changing. Diporphyrin (3) was obtained when compound 1 reacted with sodium phenoxide or diphenoxide ion in DMF solution. Whereas the nitro group was reduced and 5-(4-amino-phenyl)-10,15,20-triphenylporphyrinato Nickel(Ⅱ) (4) was achieved when compound 2 reacted with above nuleophilic reagents in the same condition. The reductive product 5-(4-aminophenyl)-10,15,20-triphenylporphyrin (5) was also achieved when 1 reacted with mercaptoethanol or thiophene and lithium hydroxide. While the nitro group was substituted by cyanide anion and 5-(4-nitrilephenyl)-10,15,20-triphenylporphyrin (6) was achieved when 1 reacted with sodium cyanide.     

4-(5-硝基-6-羟基-2-苯并(噁)唑基)苯甲酸甲酯的合成

研究了以关键中间体4-氨基-6-硝基间苯二酚盐酸盐(ANR·HCl)和对苯二甲酸单甲酯(MTA)为原料,分别经酰氯化、缩合、环合分步或原位合成AB型新单体前体-4-(5-硝基-6-羟基-2-苯并唑基)苯甲酸甲酯(MNB)的技术. 反应优化条件为:在甲基异丁基酮溶剂中,n(ANR·HCl)∶ n(MTA)=1.00∶ 1.03,115 ℃缩合反应2.5 h,m(ANR·HCl)∶ m(PPA)=1.00∶ 3.25的多聚磷酸(PPA),120 ℃环合8.5 h,MNB收率75.68%(以ANR·HCl计),HPLC测定ω(MNB)=96.32%. 产物结构经1H NMR和IR测试技术得以确证.     

Nucleophilic Vinyl Substitution in the Synthesis of Heterocycles. (Review)

Published data on the synthesis of various heterocyclic compounds by the reaction of nucleophiles with electrophilic olefins containing a nucleophilic group are reviewed and analyzed.     

Facile Synthesis of Enantiomerically Pure 1-（5-Bromo-2-chlorophenyl）-1-（4-ethoxyphenyl）ethane

A facile 7-step procedure for the synthesis of enantiomerically pure 1-（5-bromo-2-chlorophenyl）-1-（4-ethoxyphenyl）ethanes[（R）-2 and（S）-2] that started from （5-bromo-2-chlorophenyl）（4-ethoxyphenyl）methanone 3 was developed.The key step was the resolution of 2-（5-bromo-2-chlorophenyl）-2-（4-ethoxyphenyl）acetic acid 6 by crystallizations of its L-and D-menthyl esters 7 and 8 from petroleum ether to give optically pure enantiomers 9 and 10,respectively.The absolute configurations of the products were unambiguously determined by single-crystal X-ray diffractions of four key intermediates,9,10,13 and 14.This procedure is characterized by inexpensiveness,scalability and ability to produce two individual enantiomers of a diarylethane with unambiguously determined absolute configurations and high enantiomeric purities.     

Synthesis of 2-Amino-5(6)-(4-aminophenyl)benzimidazole Derivatives: II. Reaction of 2-Nitro-4-thiocyanatoaniline with 4-Nitrochlorobenzene

The reaction of 2-nitro-4-thiocyanatoaniline with 4-nitrochlorobenzene in aqueous alkaline medium in the presence of phase-transfer catalyst at 95-100°C was studied with a view to obtain 4-amino-3,4'-dinitrodiphenyl sulfide. Optimal conditions for the synthesis and isolation of the product were found.     

3-(5-Substituted 2-Methoxyphenyl)-4-Nitro-2-Phenyl-5-Thiophene-2-yl-Isoxazolidines - Synthesis and Conformational Studies

Abstract

The synthesis of a new set of 2,3,4,5-substituted isoxazolidines having a sulfur containing heterocyclic moiety has been described. The structural features of the compounds have been analyzed by ¹H and ¹³C NMR spectroscopy as well as by single crystal X-ray studies.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: .cif file.]     

新显色剂4-(5-硝基-2-吡啶偶氮)-1,3-二氨基苯的合成及其与钯显色反应的研究

合成并用红外光谱和元素分析鉴定了吡啶偶氮氨类试剂：4-（5-硝基-2-吡啶偶氮）-1,3-二氨基苯（5-NO2-PADAB）,研究了该试剂与钯的显色反应。在0.36-2.04 mol/L HClO4介质中,钯与试剂形成1∶1的蓝色配合物,其最大吸收波长位于586 nm处。表观摩尔吸光系数为1.04&#215;10^5L.mol-1.cm^-1,钯的质量浓度在0-1.2μg/mL范围内符合比尔定律。方法是目前测定钯的高灵敏和高选择性体系之一。     

新显色剂4-(5-硝基-2-吡啶偶氮)-1,3-二氨基苯的合成及其与钯显色反应的研究

合成并用红外光谱和元素分析鉴定了吡啶偶氮氨类试剂:4-(5-硝基-2-吡啶偶氮)-1,3-二氨基苯(5-NO2-PADAB),研究了该试剂与钯的显色反应.在0.36～2.04 mol/L HClO4介质中,钯与试剂形成1:1的蓝色配合物,其最大吸收波长位于586 nm处.表观摩尔吸光系数为1.04×105 L·mol-1·cm-1,钯的质量浓度在0～1.2μg/mL范围内符合比尔定律.方法是目前测定钯的高灵敏和高选择性体系之一.