Reactions of 9-chloro-1,10-anthraquinone 1-dichlorophosphorylimine with N- and C-nucleophiles

9-Chloro-1,10-anthraquinone 1-dichlorophosphorylimine formed in the reaction of 1-amino-9,10-anthraquinone with PCl₅ followed by dehydrochlorination reacts with primary amines with substitution of chlorine atoms. In the case of aliphatic amines, the reaction occurs further concurrently in two directions: the addition of the amine molecule with the formation of 9,9-di(alkylamino) derivatives of the anthrone and the substitution of hydrogen atom at position 4 with the formation of 4,9-di(alkylamino) derivatives of 1,10-anthraquinone 1-imine. In the case of aromatic amines, 1-amino-9,10-anthraquinone 9-arylimines are the end products. Reactions with the anions of CH-acids containing an alkoxycarbonyl or cyano group occur with substitution in position 9 followed by intramolecular cyclization with the formation of 2-alkoxy- or 2-amino-7H-dibenzo[f,ij]isoquinolin-7-one derivatives, respectively. For preliminary communication, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1179–1184, June, 1998.     

Quinones VIII. Synthesis of 3-t-butyl-5,8-dimethyl-1,10-anthraquinone

An 1,10-anthraquinone - stabilized only by alkylgroups - is prepared (in a four step synthesis) and described for the first time.     

Synthesis of 2-chloro-2-imidazoline and its reactivity with aromatic amines,phenols, and thiophenols

2-Chloro-2-imidazoline has been synthesized by the reaction of ethylene-thiourea with chlorine in aqueous solution at 50°. The compound was reacted with aromatic amines, phenols, and thiophenols.     

2-Substituted hexahydroacylanthranils: Synthesis and selective reactions with amines

Summary In contrast to their aromatic analogues, the corresponding saturated diamides5–9 are formed exclusively when hexahydro-3,1,4-benzoxazinones (3,4) are reacted with amines. The cyclodehydration reaction of the diamides5–9 cannot be carried out at arbitrarily high temperatures.Saturated Heterocycles, Part 217. Part 216: L. Simon, S. G. Talpas, F. Fülöp, G. Bernáth, G. Argay, A. Kálmán, P. Sohár (1995) J Heterocyclic Chem32: 161     

Synthesis and reactions of 2-chloro-3,4-dihydrothienopyrimidines and -quinazolines

Reaction of 2,4-dichlorothienopyrimidines and -quinazolines 1 with sodium borohydride gave the corresponding 2-chloro-3,4-dihydro derivatives 2. Some nucleophilic substitutions of 2b afforded 2-substituted derivatives 3b-7b and reaction of 2g,h with ethyl bromoacetate yielded selectively the corresponding 3-substituted compounds 8g,h which were derived to imidazo[2,1-b]quinazolin-2-ones 9g,h .     

Displacement reactions of 2-chloro- and 2,9-dichloro-1,10-phenanthroline: synthesis of a sulfur-bridged bis-1,10-phenanthroline macrocycle and a 2,2′-amino-substituted-bis-1,10-phenanthroline

The synthesis and structural assignments of 9-chloro-1,1-phenanthroline-2(1H)-thione and 1,10-dihydro-1,10-phenanthroline-2,9-dithione have been accomplished. The sulfur-bridged bis-1,10-phenanthroline macrocycle was readily prepared by heating the thione or equimolar amounts of the dithione and 2,9-dichloro-1,10-phenanthroline in diphenyl ether. Displacements of 2-chloro- or 2,9-dichloro-1,10-phenanthroline with N,N-dimethylethylenediamine afforded the corresponding amine and diamino analogues. An amino-substituted-2,2′-bis-1,10-phenanthroline has been prepared.     

Doubly hydrogen-bridged 1,2-diphenylenediboranes derived from 9-chloro-9-borafluorene and ligand exchange reactions

Cyclic 1,2-diphenylenediboranes containing a doubly hydrogen-bridged structure, including 1,2-(2,2^′biphenylylene)diborane(I) and 1,2-(2,2^′biphenylylene)-1,2-diethyldiborane (II), are conveniently prepared by treating 9-chloro-9-borafluorene with NaBH₄ and Na(Et)₃BH, respectively. The reaction mechanism involves an initial Cl-H exchange to form 9-borafluorene containing a reactive 5-member ring diarylborane moiety, which subsequently engages in a facile ring expansion with the in situ formed B-H containing residue (BH₃ or HBEt₂) to result in cyclic 1,2-diphenylenediboranes compounds. The doubly hydrogen-bridged structure shows good thermal stability up to 50 °C. Upon thermal cleavage at higher temperature, all free B-H groups become very reactive involving hydroboration with α-olefin. The complexization study also reveals that this intradiborane moiety forms a 1:2 complex with a strong base, such as pyridine.     

Reactions of 4-chloro-3-formyl-coumarin with primary amines

The reaction of 4-chloro-3-formylcoumarin with primary amines in the presence of triethylamine was studied. The reaction with aliphatic and aromatic amines leads to N-substituted 4-amino-3-formylcoumarins, whereas hetarylamines react primarily with the formyl group to form a mixture of the Z-and E-isomers of N-substituted 3-aminomethylenechroman-2,4-diones. Replacement of the triethylamine by anhydrous sodium acetate in the reaction of chlorocoumarin with 2-aminopyridines leads to the formation of the condensed benzopyranopyridopyrimidine system as a result of nucleophilic attack of the amino group by the chlorine atom at position 4. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 660–668, May, 2006.     

Ynaziridines and their reactions with amines

On the basis of the results of IR and UV spectroscopy, a considerable decrease in the efficacy of the conjugation of the unshared pair of the nitrogen atom with a carbonyl group in ynaziridines as compared with ynamines has been shown. The difference in the electronic structures of these compounds finds its reflection in their chemical behavior: the electrophilicity of the triple bond in an ynaziridine is higher than that in the analogous ynamine in reactions with amines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 618–622, May, 1985.     

Synthesis and reactions of 2-chloro- and 2-tosyloxy-2'-deoxyinosine derivatives

Convenient syntheses of 2-chloro- and 2-tosyloxy-2'-deoxyinosine as their tert-butyldimethylsilyl ethers are described. Both compounds can be synthesized via a common route and rely on commercially available 2'-deoxyguanosine. The present method leading to the chloro nucleoside is operationally simpler compared to previously reported glycosylation techniques where isomeric products were obtained. Both electrophilic nucleosides can be used for the preparation of N-substituted 2'-deoxyguanosine analogues via displacement of the leaving groups, and a comparison of their reactivities shows the chloro analogue to be superior. Interestingly, a Pd catalyst-mediated, two-step, one-pot conversion of an allyl-protected chloro nucleoside intermediate to the final modified 2'-deoxyguanosine derivatives is also feasible. On the basis of these observations, initial assessments of Pd-catalyzed aryl amination as well as a C-C cross-coupling have also been performed with the chloro and tosyloxy nucleoside substrates. Results indicate a potentially high synthetic utility of 2-chloro-2'-deoxyinosine and in many instances this derivative can supplant the bromo and fluoro analogues that are more cumbersome to prepare or are not readily available.     

One-electron reduction of 9, 10-anthraquinone, 1-amino-9, 10-anthraquinone and 1-hydroxy-9, 10-anthraquinone in aqueous-isopropanol-acetone mixed solvent: A pulse radiolysis study

The semiquinone radicals produced by one-electron reduction of 9, 10-anthraquinone, 1-amino-9, 10-anthraquinone and 1-hydroxy-9, 10-anthraquinone have been characterized in aqueous-organic mixed solvent comprising of 30.2 mol dm⁻³ water, 5 mol dm⁻³ isopropanol and 1 mol dm⁻³ acetone, using the pulse radiolysis technique. Spectroscopic characteristics, the kinetic parameters of formation and decay and one acid dissociation constants of the semiquinones and one-electron reduction potentials of the quinones have been estimated. The characteristics of the present semiquinone systems have been compared with those of other similar systems. The observed differences in characteristics of the semiquinones due to different substitutions have been analysed.     

Regioselective Sonogashira cross-coupling reactions of 6-chloro-2,8-diiodo-9-THP-9H-purine with alkyne derivatives

Lithiation of 6-chloro-9-(tetrahydro-2H-pyran-2-yl)-9H-purine with LiTMP, gave access to 6-chloro-2,8-dihalogenated purine derivatives. In particular, the 6-chloro-2,8-diiodopurine derivative is an interesting new intermediate which gave regioselectively various 2-alkynylated compounds or 2,8-dialkynylated purines by using an excess of alkyne.     

Synthesis of 2-oxooxazolo[5,4-b]pyridines and their reactions with amines

Riga Technical University, Riga, LV-1658. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 271–272, February, 1995. Original article submitted December 29, 1994.     

2-吡唑啉9-芳基邻菲咯啉镍配合物的合成及催化乙烯齐聚的研究

利用1-苯基-3-(2,4,6-三甲基苯基)丙烯酮和2-肼-9-芳基邻菲咯啉的缩合反应合成了一系列2-[N-(3-笨基-5(2,4,6-三甲基笨基)吡唑啉)]-9-芳基邻菲咯啉类配体(L_1-L_4),分别与NiCl_2反应得到了相应的配合物[NiCl_2](1-4), 对配体和配合物进行了表征, 并用X-单晶衍射分析了配合物4的晶体结构, 表明Ni中心为五配位的四方锥构型. 化合物l-4在MAO存在下对乙烯齐聚表现出良好的催化活性. 在1 Mpa 乙烯压力下, 化合物4的催化活性最好, 高达2.52×10~5g mol~(-1) h~(-1). 讨论了配体空间位阻及反应条件对乙烯齐聚活性的影响, 发现邻菲咯啉的9-位位阻对催化活性影响更明显.     

Reaction of 3-chloro-3-sulfolene and 3-chloro-2-sulfolene with alkyl(aryl)amines

The corresponding 3-alkylamino-2-sulfolenes are formed in the reaction of 3-chloro-3-sulfolene and 3-chloro-2-sulfolene with aliphatic amines. It was established that under the influence of the amines 3-chloro-3-sulfolene initially undergoes isomerization to 3-chloro-2-sulfolene with subsequent replacement of the chlorine atom by the amine component. 3-Chloro-3-sulfolene and 3-chloro-2-sulfolene are inert in the reaction with aromatic amines that have low basicities.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 892–894, July, 1979.     

Pyridoxal reactions with amines and aliphatic diamines

Interaction of pyridoxal (3-hydroxy-5-hydroxymethyl-2-methylisonicotinaldehyde) with amines, mono- and disubstituted diamines led to the formation of compounds having in their structure imine, imidazolidine, and pyrimidine moieties. Structure of the obtained compounds was proved by IR data, ¹H NMR spectroscopy, mass spectrometry, and X-ray diffraction analysis.