Synthesis of 4-bromocubane-1-carbaldehyde

Oxidation of 4-bromo-1-hydroxymethylcubane and 1,4-bis(hydroxymethyl)cubane with the 2,2,6,6-tetramethylpiperidine-N-oxyl-trichloroisocyanuric acid-sodium bicarbonate system afforded the corresponding aldehydes. 4-Bromocubanecarbaldehyde was also obtained in high yield by reduction of 4-bromocubanecarboxylic acid and its methyl ester with bis(N-methylpiperazinyl)aluminum hydride. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1256–1258, July, 2006.     

POLYROTAXANE WITH π-CONJUGATED PORPHYRIN AND POLYAZOMETHINE SYSTEMS PREPARED FROM A TYPE OF PORPHYRIN-DIALDEHYDE AND COMPLEX OF β-CYCLODEXTRIN WITH 1,4-PHENYLENEDIAMINE

The synthesis of 5,15-bis[4-(methoxycarbonyl)phenyl]-10,20-diphenylporphyrin (2) and its reduction to 5,15-bis[4-(hydroxymethyl)phenyl]-10,20-diphenylporphyrin (3), and so its oxidation to provide 5,15-bis(4-formylphenyl)-10,20-diphenylporphyrin (4) are reported. The copolymer possessing β-cyclodextrin (β-CD), π-conjugated porphyrin and polyazomethine systems was synthesized by the polycondensation of porphyrin-dialdehyde monomer (4) and β-cyclodextrin/1,4-phenylenediamine complex (5). The monomers and the copolymer were characterized by UV-Vis, 1H-NMR and IR spectra. Furthermore, 1H-NMR and FT-IR spectra confirmed locating the aromatic ring of 1,4-phenylenediamine molecule in the center of β-cyclodextrin cavity.     

Synthesis of 1,4-annulated cyclooctatetraenophanes based on a novel cubane building block approach

A general synthetic approach to strained 1,4-annulated cyclooctatetraene-based cyclophanes is described. A key feature in this approach is exploitation of the cubane core as a masked cyclooctatetraene synthon. Thus, 1,4-disubstituted cubanes 3 and 4 used as precursors to cyclooctatetraenophanes have been prepared in four steps from the readily available 1,4-cubanedicarboxaldehyde (5). The synthesis of 3 was effected by palladium/copper-mediated coupling of 1,4-bis[(Z,Z)-2-iodovinyl]cubane (6) and 1,4-bis[(Z,Z)-but-1-en-3-ynyl]cubane (8). For the synthesis of 4, on the other hand, modified Eglington-Glaser coupling was applied for the macrocyclization step. The general characteristic of Rh(I) to induce [2 + 2] cycloreversion of the cubane core to syn-tricyclo[4.2.0.0(2,5)]octa-3,7-diene followed by thermal rearrangement to cyclooctatetraene was applied as a key structural transformation toward targeted cyclooctatetraenophanes 1 and 2.     

Synthesis of segmented polyurethanes based on furazan units

Linear polyurethane thermoplastics comprising furazan blocks soluble in organic solvents and having low melting points were obtained by nonequilibrium polycondensation of 3,4-bis(hydroxymethyl)furazan, butane-1,4-diol and 2,4-di-isocyanatotoluene. The thermal behavior of some copolymers was studied by DSC and TGA methods.     

Phosphorylation of 1,4-bis(hydroxymethyl)benzene with trivalent phosphorus derivatives

Phosphorylation of 1,4-bis(hydroxymethyl)benzene with complete phosphorous acid amides and phenyl phosphorodichloridite is studied. Some phosphorus-containing linear systems, the phosphamacrocycle precursors, are synthesized. The possibility of synthesis of phosphamacrocyclic systems based on 1,4-bis(hydroxymethyl)benzene is considered; it was shown that this compound does not tend to form macrocycles.     

Cubane derivatives

NewN,N′-bis- andN,N,N′, N′-tetrakis-hydroxyalkyl-substituted 1,4-cubanedicarboxamides were synthesized. Nitration of these compounds yielded the corresponding nitrates. The reaction of 1,4-cubanedicarboxylic acid dichloride with ethylene glycol mononitrate and glycerol dinitrate gave ester 1,4-[R¹R²CHOC(O)]₂C₈H₆, where R¹=H and R²=CH₂ONO₂; and R¹=R²=CH₂ONO₂, respectively. The cardiopharmacological activity of some of the synthesized compounds was determined. This allowed us to find for the first time cubane derivatives that exhibit this kind of biological activity. The antiischemic activity of one of these compounds,N,N′-bis(2-nitroxythyl)-1,4-cubanedicarboxdiamide, is higher than that of the well-known Nicorandil. For Part 2, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1169–1172, June, 1998.     

2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯的合成、晶体结构及性能研究

以硝基甲烷为起始原料,经缩合、环化、氧化耦合、脱缩酮及硝化等5步反应合成了2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯(BHDBT),总收率为36.1％,并采用核磁共振谱、红外光谱以及元素分析等进行了结构表征.用浓盐酸代替氯化氢气体,改进了关键中间体2,3-二羟甲基-2,3-二硝基-1,4-丁二醇(BHDB)的合成方法,并确定最佳反应条件为:刀(浓盐酸):n(BDND)=1.1∶1,反应温度55℃,时间4h,收率为94.8％.首次发现了BHDB和BHDBT的亚甲基质子具有磁不等价性,并从理论上分析其产生的原因.培养了BHDBT单晶,四元衍射晶体结构解析表明:BHDBT属于单斜晶系,空间群P2(1)/n,晶胞参数:a=0.81944(11) nm,b=2.3365(3) nm,c=0.85838(11) nm,a=90°,β=113.501(2)°,y=90°,V=1.5072(3) nm3,Z=4,Dc=1.852 g·cm-3,μ=0.189 mm-1,F(000)=856.BHDBT熔点为86.37℃,分解峰温度为185.79℃(DSC),摩擦感度为100％ (3.92 MPa,90°),特性落高H50为10.0 cm(5 kg).     

Simons electrochemical fluorination of substituted homopiperazines(hexahydro-1,4-diazepines) and piperazines

Simons electrochemical fluorination (ECF) of 1,4-dimethyl-1,4-homopiperazine, methyl 4-ethylhomopiperazin-1-ylacetate and 1,4-bis(methoxycarbonylmethyl)-1,4-homopiperazine was studied. For comparison, ECF of three piperazines with a N-(methoxycarbonylmethyl) group(s) was also studied. ECF of 1,4-dimethyl-1,4-homopiperazine gave a low yield of corresponding perfluoro(1,4-dimethyl-1,4-homopiperazine) together with perfluoro(2,6-diaza-2,6-dimethylheptane) as the major product. Corresponding perfluoro(homopiperazines) with mono- and/or di-(fluorocarbonyldifluoromethyl) groups [CF₂C(O)F] at the 1- and/or 4-position were formed in low yields from methyl 4-ethylhomopiperazin-1-ylacetate and 1,4-bis(methoxycarbonylmethyl)-1,4-homopiperazine, respectively. These new seven-membered perfluoro(1,4-dialkyl-1,4-homopiperazines) were accompanied by the formation of mono- and/or di-basic linear perfluoroacid fluorides resulting from the CC bond scission at the 2- and 3-positions of the ring. From mono- and/or di-N-(methoxycarbonylmethyl)-substituted piperazines, corresponding perfluoropeperazines having the acid fluoride group(s) were formed in low yields.     

Transformations of 4,5-Substituted (4S,5S)-2,2-Dimethyl-1,3-dioxolanes

(4S,5S)-4,5-Bis(hydroxymethyl)-2,2-dimethyl-1,3-dioxolane treated with trifluoromethanesulfonyl chloride in pyridine undergoes tandem substitution of one hydroxy group by a triflate group, and the other by pyridinium moiety. In neutral solvents the (4S,5S)-4,5-bis(hydroxymethyl)-2,2-dimethyl-1,3-dioxolane dilithium salt reacts with trifluoromethanesulfonyl chloride affording both triflates and chlorides and also suffers a cleavage of the dioxolane ring followed by transformations of acyclic products. A triflate cationic complex rhodium cyclooctadiene (4S,5S)-2,3-dihydroxy-1,4-bis(dimethylamino)-2,3-O-isopropylidenebutane was prepared and used as catalyst for hydrogenation of -acetamidocinnamic and itaconic acids.     

Synthesis and investigation of cytotoxicity of new N- and S,S-substituted-1,4-naphthoquinone (1,4-NQ) derivatives on selected cancer lines

1,4-Naphthoquinones (1,4-NQ) have been reported to possess a variety of pharma-cological properties including antibacterial, antifungal, antiviral, anti-inflammatory, anti-artherosclerotic, and anticancer effects. In this study, new N- and S,S-substituted-1,4-NQ derivatives were synthesized in excellent yields and were completely characterized by spectroscopic analysis IR, NMR (¹H and ¹³C), MS and microanalysis. The cytotoxic activities of 1,4-NQ derivatives were examined against to A-549, DU145, HCT-116 and MDA-MB-231 cancer cells. Among these compounds, 2-[4-(2-furoyl)piperazine-1-yl]-3-chloro-1,4-NQ 5 and 2,3-bis(cyclobuthylsulfanyl)-1,4-NQ 17 were identified as the most potent anticancer agents with cytotoxic activity against three cell lines (breast (MDA-MB-231), prostate (DU145), colorectal (HCT-116).     

Synthesis and characterization of some copolycarbonates of 2,2-bis (4-hydroxyphenyl)propane (bisphenol-A) and 1,4-bis(hydroxymethyl) cyclohexane

Copolycarbonates of Bisphenol-A (BPA) and 1,4-bis(hydroxymethyl)cyclohexane have been prepared. The resulting copolymers have slightly lower glass-transition temperatures than BPA polycarbonate homopolymers. Crystallisation and annealing effects are also reduced. The results are generally similar to those obtained with copolymers of BPA and 1,4-bis(hydroxymethyl)decafluorobicyclo(2,2,1)-heptane [1] but the differences are less marked.     

二代螺环树形化合物1,2,3,4,5,6,7,8,9,10,11,12-十二氢-2,2;6,6;10,10-三[3,3-二(烷氧羰基)-1,1-环亚丁基二甲氧基]三亚苯基的合成

以1,4-环己二酮、丙二酸二乙酯及多元醇等为原料, 经过两次“一锅煮”法合成了六种二代螺环树形化合物1,2,3,4,5,6,7,8,9,10,11,12-十二氢-2,2;6,6;10,10-三[3,3-二(烷氧羰基)-1,1-环亚丁基二甲氧基]三亚苯基螺环树形化合物, 其中烷氧基为异戊氧基、三羟甲基甲氧基、2,2-二溴甲基-3-羟丙氧基、2,2-二羟甲基丙氧基、二羟甲基膦甲氧基和(N-羟甲基-N-二羟甲基氨基乙基)甲氧基. 利用IR, NMR, MS和元素分析对合成的化合物进行了结构认证, 对影响反应的因素进行了讨论.     

Synthesis of ethers and esters of 1,4-di-N-oxide of 2,3-bis(hydroxymethyl)quinoxalm under conditions of interfacial catalysis

Esters and ethers of the 1,4-di-N-oxide of 2,3-bis(hydroxymethyl)quinoyaline have been obtained under conditions of interfacial catalysis in a chloroform-water system. The catalytic activities of tetrabutylammonium bromide and cetyltriethylammonium bromide have been compared in the synthesis of the acetate, benzoate, and 4-nitrobenzoate of the 1,4-di-N-oxide of 2,3-bis(hydroxymethyl)quinoxaline.St. Petersburg State Technological Institute, St. Petersburg 198013. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 816–820, June, 1994. Original article submitted June 29, 1994.     

Synthesis of tetrachloroisophthalic and-terephthalic aldehydes and stable bis(nitrile oxides) based on them

A new route for the synthesis of 2,4,5,6-tetrachloroisophthalic and 2,3,5,6-tetrachloroterephthalic aldehydes from the corresponding tetrachlorobenzenes was developed. The method involves dichloromethylation of the initial compounds with chloroform in the presence of aluminum chloride and subsequent hydrolysis of the resulting 1,3-bis(dichloromethyl)-2,4,5,6-tetrachlorobenzene and 1,4-bis(dichloromethyl)-2,3,5,6-tetrachlorobenzene. Stable 2,4,5,6-tetrachlorobenzene-1,3-dicarbonitrile oxide and 2,3,5,6-tetrachlorobenzene-1,4-dicarbonitrile oxide were obtained for the first time from the above aldehydesvia the corresponding oximes. The products were characterized by IR and¹³C NMR spectra, and were converted into substituted 1,3- and 1,4-phenylenebis(isoxazolines) using 1,3-dipolar cycloaddition with styrene. Translated fromIzvestiya Akademit Nauk. Seriya Khimicheskaya, No. 1, pp. 106–109, January. 1997.     

Novel bridged anthracene derivatives and polyesters and copolyesters therefrom

9,10-Bis(hydroxymethyl)triptycene, 9,10-dihydro-9,10-bis(hydroxymethyl)-9,10-ethanoanthracene, 9,10-dihydro-9,10-bis(hydroxymethyl)-9,10-(2,3-bicyclo[2.2.1] heptano)-anthracene, 9,10-dihydro-9,10-bis(hydroxymethyl)-N-phenyl-9,10-ethanoanthracene-11,12-dicarboximide, and 9,10-bis(carbethoxy)triptycene have been prepared and employed as modifying agents to improve the physical properties of polyesters such as poly(ethylene terephthalate). Especially noteworthy are the high glass transition temperatures (T_g) which can be obtained.     

Polyesters containing bicyclo[2.2.2]octane and bicyclo[3.2.2]nonane rings

Polyesters containing bicyclo[2.2.2]octane and bicyclo[3.2.2]nonane rings are prepared from 1,4-bis(carboethoxy)bicyclo[2.2.2]octane, 1,4-bis(hydroxymethyl)bicyclo[2.2.2]-octane and the 1,5-disubstituted bicyclo[3.2.2]nonane analogs. These polyesters are compared to the related polymers containing 1,4-phenylene and trans-1,4-cyclohexylene rings in terms of their melting point, thermal stabilities and oxidative stabilities. The lower symmetry of the bicyclo[3.2.2]nonane ring produces lower-melting polymers than the other ring systems. The remaining three rings are approximately equivalent in their effect on the melting point of a polymer provided that no more than one bicyclo[2.2.2]octane ring is present per polymer repeat unit. Two such rings produce a highermelting polymer than any other combination. Both the thermal and oxidative stabilities of the polyesters is improved by the presence of the bicyclo rings. This is attributed to the rings providing an approximation of a ladder polymer.     

Synthesis of new unsymmetrical polyarylester dendrimers

Preparation of polyarylester dendrimers containing 2-(hydroxymethyl)-1,4-butanediol and 2,2-bis(hydroxymethyl)-1,4-butanediol cores is described. These polyarylester dendrimers are unsymmetrical with respect to chain lengths and function as model systems for studying in vitro controlled drug release systems. Reaction conditions for deprotection of trichloroethyl group of the dendritic wedges have been improved.     

Cross-coupling of E,E-1,4-diiodobuta-1,3-diene with nucleophiles catalyzed by Pd or Ni complexes: a new route to functionalized dienes

E,E-1,4-Diiodobuta-1,3-diene can enter into cross-coupling reactions with carbon- or other element-centered nucleophiles in the presence of Pd or Ni complexes as catalysts. Convenient procedures were developed for the stereoselective synthesis of E,E-1,4-dialkenylbuta-1,3-dienes, dienyl-1,4-bisphosphonates, E,E-1,4-bis(diphenylphosphino)buta-1,3-diene, E,E-1,4-diphenylbuta-1,3-diene, and E,E-1,4-bis(thiophenyl)buta-1,3-diene.     

“黑洞型”缺电子联吡啶环蕃的合成

利用2,3,5,6-四氟-1,4-苯二甲酸为原料, 经过酯化、还原及溴代, 合成1,4-二溴甲基-2,3,5,6-四氟苯. 以其为原料在低温下利用模板效应合成高度缺电子的“黑洞型”缺电子联吡啶环蕃化合物, 经过连续液液萃取及离子交换得到“黑洞型”缺电子联吡啶环蕃单体. 产品经¹H NMR, ¹³C NMR, MS表征. 利用变温核磁共振技术研究“黑洞型”缺电子联吡啶环蕃与经典的双环(百草枯-对苯撑)型缺电子联吡啶环蕃在溶液中的变化.     

Novel syntheses of symmetrical 2,5-diaryl-1,3,4-oxadiazoles and 1,4-phenylenebis-1,3,4-oxadiazoles

The reactions of trichloromethylarenes with excess hydrazine hydrate in ethanol gives symmetrical 2,5-diaryl-1,3,4-oxadiazoles in 68–96% yields. The reaction of 1,4-bis(trichloromethyl)benzene with acylhydrazines in an ethanol-pyridine mixture gives the corresponding substituted or unsubstituted 1,4-phenylenebis-1,3,4-oxadiazoles in 35–51% yields. The mass spectra of 2,5-diaryl-1,3,4-oxadiazoles and 1,4-phenylenebis-1,3,4-oxadiazoles were studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2309–2316, November, 1998.