Reactivity of N-arylsulfonyl-1,4-benzoquinone imines. Reaction with hydrazoic acid

N-Arylsulfonyl-2-halo-1,4-benzoquinone imines react with hydrazoic acid in boiling acetic acid via two pathways: the 1,4-addition and nucleophilic replacement of the halogen atom by an azido group, followed by the 1,4-addition of HN₃. In the reaction of N-arylsulfonyl-2,6-dihalo-1,4-benzoquinone imines with hydrazoic acid, both halogen atoms are replaced by azido groups, while N-p-tolylsulfonyl-2-methyl-1,4-benzoquinone imine takes up HN₃ molecule according to the 1,4-addition pattern.     

Hydrohalogenation of N-acetyl(aroyl)-1,4-benzoquinone monoimines

New N-acetyl-1,4-benzoquinone monoimines alkyl-substituted in the quinoid ring were synthesized. The hydrohalogenation of N-acetyl(aroyl)-1,4-benzoquinone monoimines proceeds exclusively in keeping with the 1,4-addition. The hydrochlorination occurs along the ionic mechanism, in the hydrobromination grows the role of the radical mechanism.     

Reaction of N-acetyl- and N-[1-(arylsulfonylimino)ethyl]-1,4-benzoquinone imines with sodium arenesulfinates

N-Acetyl- and N-[1-(arylsulfonylimino)ethyl]-1,4-benzoquinone imines having no substituent in the 2- and/or 6-position of the quinoid ring react with sodium arenesulfinates preferentially according to the 1,4-addition pattern. The presence of an ArSO₂N group favors radical ion reaction with formation of 1,6-addition products.     

Reaction of N-[aryl(benzylidene,phenoxy)acetyl]-1,4-benzoquinone imines with sodium 4-methylbenzenesulfinate

The reaction of N-[aryl(phenoxy, benzylidene)acetyl]-1,4-benzoquinone imines with sodium 4-methylbenzenesulfinates takes different addition patterns, depending on the LUMO energy and charge distribution over the quinoid ring of the initial quinone imine.     

Halogenation of N-substituted p-quinone monoimines and p-quinone monooxime ethers: XIV. Halogenation of N-[arylsulfonylimino(phenyl)methyl]-2,5-dialkyl-1,4-benzoquinone monoimines and their reduction products

Despite steric hindrances created by the bulky substituent on the nitrogen atom, halogenation of 2,5-dialkyl-N-[arylsulfonylimino(phenyl)methyl]-1,4-benzoquinone monoimines fairly readily gives their derivatives having two halogen atoms in the quinoid ring.     

Activated Sterically Strained C = N Bond in N-Substituted p-Quinonemono- and -diimines: X. Reactions of N-[N-Arylsulfonylbenz(acet)imidoyl]-3,5-dimethyl-1,4-benzoquinonimines with Alcohols

N-[N-Arylsulfonylbenz(acet)imidoyl]-3,5-dimethyl-1,4-benzoquinonimines react with alcohols to give the corresponding adducts at the activated CÍN bond. The adducts lose alcohol molecule on heating to afford initial quinonimines. Hydrolysis of the title compounds leads to formation of the corresponding quinones and N-arylsulfonylamidines.     

Comparison of preparation methods of N-arylsulfinyl-1,4-benzoquinone monoimines

Advantages and shortcomings were discussed of three procedures for preparation N-arylsulfinyl-1,4-benzoquinone imines: the reaction of arenesulfenyl chlorides with 1,4-benzoquinone oximes, the oxidation of N-arylthio-1,4-benzoquinone imines, and the reaction of arylsulfinyl chlorides with p-aminophenols followed by oxidation. A series of new N-arylsulfinyl-1,4-benzoquinone imines was obtained.     

Synthesis and structure of N-aryl(phenoxy, benzylidene)acetyl-1,4-benzoquinone monoimines

New N-aryl(phenoxy, benzylidene)acetyl-1,4-benzoquinone monoimines were synthesized by reaction of aminophenols with arylacetyl, phenoxyacetyl, and cinnamoyl chlorides in dimethylformamide-acetic acid (1: 3) in the presence of anhydrous sodium acetate. Structural parameters of the products and their probable biological activity were determined.     

Chlorination of N-(N-Arylsulfonylarylimidoyl)-1,4-benzoquinone Imines and Their Reduced Forms

The study of chlorination of N-(N-arylsulfonylarylimidoyl)-1,4-benzoquinone imines and of N-(N-arylsulfonylarylimidoyl)-1,4-aminophenols revealed that the dominant stage in the process was the formation of cyclohexene structures, 4-(N-arylsulfonylarylimidoyl)imino-2,5,6-trichloro-2-cyclohexene-1- ones, resulting from addition of a Cl₂ molecule across the C = C bond of the quinoid ring. These substances suffer a prototropic rearrangements yielding N-(N-arylsulfonylarylimidoyl)-2,3,6-trichloro-4-aminophenols. The latter are the most common reaction products. The products of deeper chlorination were also obtained.     

Thiocyanation of N-aryl,N-acetyl,and N-[arylsulfonylimino(methyl)methyl] derivatives of 1,4-benzoquinone monoimine

N-[arylsulfonylimino(methyl)methyl] derivatives of 1,4-benzoquinone monoimine with alkyl substituents in the quinoid ring have been synthesized and their spectral characteristics were determined. The thiocyanation of N-aryl, N-acetyl, and N-[arylsulfonylimino(methyl)methyl] derivatives of 1,4-benzoquinone monoimine depending on the LUMO energy of the initial quinone monoamine affords derivatives of benzo[d][1,3]oxathiol-2-ones and benzo[d]oxazole-2(3H)-thiones.     

Reaction of 3-[N-(2-naphthyl)formimidoyl]pyridine with substituted acetophenones

The reaction of 3-[N-(2-naphthyl)formimidoyl]pyridine with substituted acetophenones in the presence of a proton catalyst leads to 1-aryl-3-(3-pyridyl)benzo[f]quinolines. Noncyclic amino ketones — [1-aryl-3-(3-pyridyl)-3-(2-naphthylamino)]-1-propanones — precede the formation of the cyclic products. The IR, UV, PMR, and mass spectra of the synthesized compounds are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 351–354, March, 1989.     

Reaction of <Emphasis Type="Italic">N</Emphasis>-alkyl(aryl)aminocarbonyl-1,4-benzoquinone monoimines with alcohols

Reactions of N-alkyl(aryl)aminocarbonyl-3,5-dimethyl-1,4-benzoquinone monoimines with alcohols led to the formation of products of 1,2-addition, quinolide compounds. They are the final products in reactions with alkyl derivatives, but in event of aryl derivatives they underwent cyclization with the subsequent elimination of the alcohol molecule to provide 4,7a-dimethyl-1-aryl-7,7a-dihydro-1H-benzimidazole-2,6-diones.     

新树型配体N,N′,N″-(三苯甲酰)-三乙氨基胺与镍的络合反应

1　引　　言树形分子是一类三维结构的新型有机配体 ,这类配体具有 2个或 2个以上可摆动的“臂”(饱和碳链 ) ,根据“臂”上所连的基团不同 ,可以与不同半径的金属离子配位 ,具有很高的选择性。三乙氨基胺类化合物是树型配体中的一类 ,该类配体与过渡金属离子形成的络合物可以作为选择性磁共振显影剂和超氧化物净氧剂。因而倍受化学研究者的关注。我们合成的新配体Ｎ ,Ｎ′,Ｎ″ (三苯甲酰 ) 三乙氨基胺 (ＴＢＯＡＡ) ,在显色剂二甲酚橙中 ,ｐＨ =3 .2～ 5 .8之间能与Ｎｉ2 + 形成橙红色络合物 ,其检测Ｎｉ2 + 下限达到 8.5× 1 0 - 8ｍｏ…     

Hydrohalogenation of <Emphasis Type="Italic">N</Emphasis>-[arylsulfonylimino(phenyl)methyl]-1,4-benzoquinone monoimines having alkyl substituents in the quinoid ring

Hydrohalogenation of N-[arylsulfonylimino(phenyl)methyl]-2,5(3,5)-dimethyl-1,4-benzoquinone monoimines follows exclusively the 1,4-addition pattern, whereas N-[arylsulfonylimino(phenyl)methyl]-2,6-dimethyl-1,4-benzoquinone monoimines take up hydrogen halides according to the 6,3-addition scheme.     

The Reaction of [N-(p-Toluenesulfonyl)Imino]-Phenyliodinane with Enol Silanes

[N-(p-Toluenesulfonyl)imino]phenyliodinane reacts with enol silanes to provide α-tosylamino carbonyl compounds.     

Reaction of N-arylcarbamoyl-1,4-benzoquinone imines with sodium azide

N-Arylcarbamoyl-1,4-benzoquinone imines reacted with sodium azide in completely regioselective fashion according to the 1,4-addition pattern with formation of 1-(3-azido-4-hydroxyphenyl)-3-arylureas. The reaction of N-arylcarbamoyl-2,6-dichloro-3,5-dimethyl-1,4-benzoquinone imines with sodium azide afforded N-arylcarbamoyl-2,6-diazido-3,5-dimethyl-1,4-benzoquinone imines as a result of nucleophilic substitution of the chlorine atoms.     

新树型配体 TBOAA 与钴配合物的研究

研究了新配体N，N’，N”－（三苯甲酰）－三乙氨基胺（TOBAA）与二价钴离子生成配合物的光度特征和电化学特征。在较宽的pH范围内，新试剂和钴离子形成2：1的配合物，并且在一定范围内其吸光度与浓度具有良好的线性关系。