Synthesis of novel 6-enaminopurines

Two different approaches have been used for the synthesis of 6-enaminopurines 6 from 5-amino-4-cyanoformimidoyl imidazoles. In the first approach imidazoles 1 were reacted with ethoxymethylenemalononitrile or ethoxymethylenecyanoacetate under mild experimental conditions and this led to 9-substituted-6-(1-amino-2,2-dicyanovinyl) purines 6a-f or 9-substituted-6-(1-amino-2-cyano-2-methoxycarbonylvinyl) purines 6g-k. These reactions are postulated to occur through an imidazo-pyrrolidine intermediate 7, which rapidly rearranges to the 6-enaminopurine 6. In the second approach 6-methoxyformimidoyl purines 3, prepared in two efficient steps from 5-amino-4-cyanoformimidoyl imidazoles 1, were reacted with malononitrile and methylcyanoacetate with a mild acid catalysis (ammonium acetate or piperidinium acetate) to give 6-enaminopurines 6a, 6d, 6f, 6g and 6k in very good yields. Only low yields were obtained for the 6-enaminopurine 6j, as competing nucleophilic attack on C-8 of either 3d or 6jcauses ring opening with formation of pyrimido-pyrimidines 11 and 10a respectively.     

Isolation of 6-mercaptopurine in human plasma by aluminum ion complexation for high-performance liquid chromatographic analysis

A sample preparation technique and a high-performance liquid chromatographic method for 6-mercaptopurine (6-MP) that is simple, sensitive and without interference from its metabolites is described. 6-Thioguanine (6-TG) is added as an internal standard to the plasma sample, which is then treated with an aqueous solution of aluminum perchlorate to denature the plasma proteins and form complexes with 6-TG, 6-MP and its major metabolite, 6-thiouric acid (6-TUA). These complexes coprecipitate with proteins on centrifugation. 6-MP and its analogues are then extracted from the precipitate with perchloric acid containing sodium hydrosulfite and the extract is chromatographed on an Ultrasphere ODS column eluted with 0.1 M phosphoric acid and 0.001 M dithiothreitol in deionized water. The eluate is monitored at 340 nm. No interfering peak was encountered in over 300 clinical plasma samples. 6-TUA was separated from 6-MP and was found to be present in much higher concentration than 6-MP itself throughout the sampling time (6 h) following oral administration of the drug.     

Mechanisms of cytotoxicity in human ovarian carcinoma cells exposed to free Mce6 or HPMA copolymer-Mce6 conjugates

It is essential to understand cellular responses on photodynamic therapy (PDT) to design delivery systems that maximize cytotoxic effects coupled with minimal induction of side effects or protective mechanisms (or both). Here, we investigated mechanisms of toxicity in human ovarian carcinoma A2780 cells treated with structurally diverse N-(2-hydroxypropyl)methacrylamide (HPMA) copolymer (P)-mesochlorin e6 monoethylenediamine (Mce6) conjugates that possessed differential subcellular accumulation or covalent attachments of photosensitizers (or both). Apoptosis and necrosis were observed after photoactivation, with increased apoptotic responses observed in cells exposed to conjugates possessing Mce6 linkage via a lysosomally degradable tetrapeptide spacer (HPMA copolymer-Mce6 conjugates containing Mce6 bound via glycylphenylalanylleucylglycine [GFLG] linker [P-GFLG-Mce6], HPMA copolymer-Mce6 conjugates containing Mce6 bound via a GFLG spacer and containing nuclear localization sequence, PKKKRKV132K(FITC)C [NLS(fluorescein-5-isothiocyanate [FITC])] bound via a thioether linkage [P-NLS(FITC)-GFLG-Mce6]). Furthermore, the induction of necrosis was more pronounced in cells exposed to conjugates containing both a nuclear localization sequence (NLS) and Mce6 bound by a degradable linker (P-NLS(FITC)-GFLG-Mce6). Caspase-independent mechanisms of cell death were identified in cells treated with nuclear-targeted conjugates possessing Mce6 attached using a nondegradable tether (HPMA copolymer-Mce6 conjugates containing Mce6 bound via a GG spacer and containing NLS(FITC) bound via a thioether linkage [P-NLS(FITC)-GG-Mce6]), whereas low levels of apoptosis and necrosis were detected in cells exposed to photoactivated nontargeted HPMA copolymer-Mce6 conjugates containing Mce6 coupled through a nondegradable spacer (HPMA copolymer-Mce6 conjugates containing Mce6 bound via GG linker [P-GG-Mce6]). Variations in gene expression were observed in cells on PDT. Specifically, HSP70 expression was solely detected in cells treated with P-GFLG-Mce6, whereas the loss of detection of several genes were observed in cells treated with P-NLS(FITC)-GFLG-Mce6. Variations in cellular responses on PDT using different HPMA copolymer-Mce6 conjugates will prove useful in the design of optimal HPMA copolymer PDT delivery systems.     

催化裂化干气与苯烷基化催化蒸馏制乙苯反应网络热力学研究

 高温气相反应条件下的催化裂化干气制乙苯过程中，容易生成甲苯和二甲苯等副产物；在该过程中采用催化蒸馏技术，使苯与乙烯在低温条件下进行反应，可大幅度降低产品中二甲苯的含量．通过对催化裂化干气与苯烷基化催化精馏过程中的各反应步骤进行分析与热力学计算，结合反应的实际产物组成，提出了苯与乙烯烷基化的反应网络，探讨了苯与乙烯烷基化反应过程中甲苯和二甲苯的形成机理及影响因素．结果表明，增大苯／乙烯比对提高乙烯平衡转化率及乙苯收率有利；在较低温度下进行烷基化反应，可大大减缓C－C键裂解速度，抑制甲苯和二甲苯生成，提高乙苯产品质量．     

Arachno, nido, and closo aromatic isomers of the Li6B6H6 molecule

We analyzed chemical bonding in low-lying isomers of the recently computationally predicted B(6)H(6)Li(6) molecule. According to our calculations the benzene-like B(6)H(6)Li(6) (D(2h), (1)A(1g)) arachno structure with the planar aromatic B(6)H(6)(6-) anion is the most stable one. A nido isomer with two aromatic B(6)H(6)(4-) (pentagonal pyramid) and Li(3)(+) (triangular) moieties, which can be considered as derived from the global minimum structure through a two-electron intramolecular transfer from B(6)H(6)(6-) to three Li(+) cations, was found to be 10.7 kcal/mol higher in energy. A closo isomer with three aromatic moieties (octahedral B(6)H(6)(2-) and two Li(3)(+)) was found to be 31.3 kcal/mol higher in energy than the global minimum. Another isomer with three aromatic moieties (two B(3)H(3)(2-) and Li(3)(+)) was found to be substantially higher in energy (74.4 kcal/mol). Thus, the intramolecular electron transfers from the highly charged B(6)H(6)(6-) anion to cations are not favorable for the B(6)H(6)Li(6) molecule, even when a formation of three-dimensional aromatic B(6)H(6)(2-) anion and two sigma-aromatic Li(3)(+) cations occurs in the closo isomer.     

Structures and Chemistry of Methanofullerenes: A Versatile Route into N-[(Methanofullerene)carbonyl]-Substituted Amino Acids

The reaction of C₆₀ with oxadiazole 13 afforded the dimethoxymethanofullerene 7 in 32% yield as a 6-6-ring-bridged isomer with a closed transannular bond. A literature survey showed that all 6-6-ring-bridged methanofullerenes are σ-homoaromatic with a closed transannular bond (6-6-closed) and all 6-5-ring-bridged are π-homoaromatic with an open transannular bond (6-5-open). The preference for 6-6-closed and 6-5-open structures is not due to substituent effects but is best explained with the conservation in these isomers of the favorable bonding seen in C₆₀ with higher double-bond character at 6-6 bonds and higher single-bond character at 6-5 bonds. Reaction of C₆₀ with diazo diester 15 gave the fullerene diester 14 which was hydrolyzed with BBr₃ in benzene to the methanofullerenecarboxylic acid 10 , a versatile synthon for the preparation of amphiphilic fullerene derivatives. Treatment of 10 with alcohols and amino acid esters under DCC coupling conditions afforded the esters 5 and 17 and the amino-acid derivatives 11 and 12 , respectively.     

Isolation of 6-mercaptopurine in human plasma by aluminum ion complexation for high-performance liquid chromatographic analysis

A sample preparation technique and a high-performance liquid chromatographic method for 6-mercaptopurine (6-MP) that is simple, sensitive and without interference from its metabolites is described. 6-Thioguanine (6-TG) is added as an internal standard to the plasma sample, which is then treated with an aqueous solution of aluminum perchlorate to denature the plasma proteins and form complexes with 6-TG, 6-MP and its major metabolite, 6-thiouric acid (6-TUA). These complexes coprecipitate with proteins on centrifugation. 6-MP and its analogues are then extracted from the precipitate with perchloric acid containing sodium hydrosulfite and the extract is chromatographed on an Ultrasphere ODS column eluted with 0.1 M phosphoric acid and 0.001 M dithiothreitol in deionized water. The eluate is monitored at 340 nm. No interfering peak was encountered in over 300 clinical plasma samples. 6-TUA was separated from 6-MP and was found to be present in much higher concentration than 6-MP itself throughout the sampling time (6 h) following oral administration of the drug.     

Ligand substitution reactions of W6S8L6 with tricyclohexylphosphine (L = 4-tert-butylpyridine or n-butylamine): 31P NMR and structural studies of W6S8(PCy3)n(4-tert-butylpyridine)6-n (0 < n < or = 6) complexes

The substitution reactions by bulky tricyclohexylphosphine (PCy3) ligands on W6S8L6 (L = 4-tert-butylpyridine or n-butylamine) clusters were investigated to prepare clusters with mixed axial ligands for low-dimensional cluster linking. When 4-6 equiv of PCy3 are used to react with W6S8(4-tert-butylpyridine)6 (4) in THF, cis-W6S8(PCy3)4(4-tert-butylpyridine)2 (1) is preferentially formed. But when starting with W6S8(n-butylamine)6 (2), only W6S8(PCy3)6 (3) is produced with 6 equiv of PCy3. Other conditions with fewer equivalents of PCy3 led to mixtures of partially substituted complexes in the W6S8L6-n(PCy3)n (0 < or = n < or = 6, L = 4-tert-butylpyridine or n-butylamine) series. A significantly distorted structure for 1 helps to explain its preferential formation. 1H NMR spectra were collected for clusters 1 and 2 and 31P NMR spectra for 1 and W6S8(4-tert-butylpyridine)6-n(PCy3)n complexes. P-P coupling through P-W-W-P is reported for the first time in octahedral metal clusters and shown to be very useful in identifying nearly all the W6S8L6-n(PR3)n complexes and their stereoisomers in the mixtures even before individual species are isolated.     

Purine N-oxides: XXXVII. Derivatives from 6-chloropurine 3-oxide

Interaction of 6-chloropurine 3-oxide with several amines led to 6-substituted purine 3-oxides. 6-Chloropurine 3-oxide and selenourea gave 6-selenopurine 3-oxide. 6-Mereaptopurine 3-oxide, prepared from the 6-chloro derivative and ammonium dithioearbonate, was transformed with chlorine and hydrogen fluoride into 6-purinesulfonyl fluoride 3-oxide which upon ammonolysis afforded purine-6-sulfonamide 3-oxide. Methanelhiol and 6-ehloropurint: 3-oxide yielded the known 6-methylthiopurine 3-oxide, which by treatment with chlorine was oxidized to 6-methyl-sulfonylpurine 3-oxide. Reaction of the latter with hydroxylamine led to an improved synthesis of 6-hydroxylaminopurine 3-oxide, which by interaction with manganese dioxide was transformed into 6-nitrosopurine 3-oxide.     

Interfacial behavior of chroman-6 and chroman-6 palmitoyl ester and their interaction with phospholipids

The surface activity of chroman-6 (CR-6) and chroman-6 palmitoyl ester (PCR-6) and the interactions with lipid membranes, using 1,2-dipamitoyl-sn-glycero-3-phosphocholine (DPPC) and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) monolayers, were determined. 8-Anilino-1-naphthalenesulfonic acid titration indicates that none of these molecules was able to form aggregates in aqueous media. The presence of a palmitoyl chain in PCR-6 increases strongly the surface activity of the parent compound (CR-6), rendering a molecule to form stable monomolecular layers. The interaction of both compounds with DPPC and DOPC, measured at constant area or in a compression isotherm model, follows the same trend. Miscibility studies performed with DPPC/CR-6 or PCR-6 indicate that the energies involved are small. The presence of CR-6 and PCR-6 has a soft influence on the compressibility of the Langmuir mixed films. Differential scanning calorimetry studies indicate that CR-6 and PCR-6 modify the temperature and cooperativity of the transition from gel to liquid crystal process in DPPC vesicles.     

Spectroscopic investigation of interaction of 6-methoxyflavanone and its β-cyclodextrin inclusion complex with calf thymus DNA

The interaction of 6-methoxyflavanone (6MF, 6-methoxy-2-phenyl-4H-1-benzopyran-4-one) with calf thymus DNA (ctDNA) was investigated by absorption spectroscopy, fluorescence spectroscopy, and cyclic voltammetry in the presence and absence of ??-cyclodextrin (??-CD) acting as capping agent. Molecular modelling was used to optimise the study of 6MF-??-CD and 6MF-DNA interactions. Enhancement in the fluorescence intensity of 6MF was observed due to the formation of 1 : 1 complex with ??-CD. In the presence and absence of DNA, 6MF showed different characteristics such as hyperchromic effect, red shift of absorption spectra and fluorescence quenching of 6MF due to binding between 6MF and ctDNA. The nature of the binding group was found to be different for the 6MF-ctDNA and 6MF-ctDNA-??-CD systems. An increase in fluorescence intensity was observed for the 6MF-ctDNA system while varying the concentration of ??-CD due to encapsulation of a part of 6MF in cyclodextrin. The results are compatible with the possibility of the interaction of dihydrobenzopyran-4-one moiety of 6MF with ctDNA as well as with ??-CD. Cyclic voltammetric studies confirmed the binding interaction between 6MF and ctDNA in the absence and presence of ??-CD and molecular modelling explains the site of the interaction of 6MF with cyclodextrin and ctDNA.     

Preparation of 6-styrylphenanthridines

(6-Phenanthridinylmethyl)magnesium halides do not react with aromatic and aliphatic aromatic ketones but do react with aromatic aldehydes to give the corresponding carbinols. The latter are readily dehydrated to the corresponding 6-styrylphenanthridines. 6-Cyanomethylphenanthridine reacts with aromatic aldehydes in the presence of sodium ethoxide to give 6-(α-cyanostyryl)phenanthridines and is converted to 5-acyl-6-cyanomethylene-5,6-dihydrophenanthridine on heating with acetic anhydride or benzoyl chloride.     

The reactivity of Mo(PMe3)(6) towards heterocyclic nitrogen compounds: transformations relevant to hydrodenitrogenation

The reactions of Mo(PMe3)6 towards a variety of five- and six-membered heterocyclic nitrogen compounds (namely, pyrrole, indole, carbazole, pyridine, quinoline, and acridine) have been studied to provide structural models for the coordination of these heterocycles to the molybdenum centers of hydrodenitrogenation catalysts. Pyrrole reacts with Mo(PMe3)6 to yield the eta5-pyrrolyl derivative (eta5-pyr)Mo(PMe3)3H, while indole gives sequentially (eta1-indolyl)Mo(PMe3)4H, (eta5-indolyl)Mo(PMe3)3H, and (eta6-indolyl)Mo(PMe3)3H, with the latter representing the first example of a structurally characterized complex with an eta6-indolyl ligand. Likewise, carbazole reacts with Mo(PMe3)6 to give (eta6-carbazolyl)Mo(PMe3)3H with an eta6-carbazolyl ligand. The reactions of Mo(PMe3)6 with six-membered heterocyclic nitrogen compounds display interesting differences in the nature of the products. Thus, Mo(PMe3)6 reacts with pyridine to give an eta2-pyridyl derivative [eta2-(C5H4N)]Mo(PMe3)4H as a result of alpha-C-H bond cleavage, whereas quinoline and acridine give products of the type (eta6-ArH)Mo(PMe3)3 in which both ligands coordinate in an eta6-manner. For the reaction with quinoline, products with both carbocyclic and heterocyclic coordination modes are observed, namely [eta6-(C6)-quinoline]Mo(PMe3)3 and [eta6-(C5N)-quinoline]Mo(PMe3)3, whereas only carbocyclic coordination is observed for acridine.     

Infrared absorption of C6H5SO2 detected with time-resolved Fourier-transform spectroscopy

C6H5SO2 radicals were produced upon irradiation of three flowing mixtures: C6H5SO2Cl in N2, C6H5Cl and SO2 in CO2, and C6H5Br and SO2 in CO2, with a KrF excimer laser at 248 nm. A step-scan Fourier-transform spectrometer coupled with a multipass absorption cell was employed to record the time-resolved infrared (IR) absorption spectra of reaction intermediates. Two transient bands with origins at 1087.7 and 1278.2 cm-1 are assigned to the SO2-symmetric and SO2-antisymmetric stretching modes, respectively, of C6H5SO2. Calculations with density-functional theory (B3LYP/aug-cc-pVTZ and B3P86/aug-cc-pVTZ) predict the geometry and vibrational wave numbers of C6H5SO2 and C6H5OSO. The vibrational wave numbers and IR intensities of C6H5SO2 agree satisfactorily with the observed new features. Rotational contours of IR spectra of C6H5SO2 simulated based on predicted molecular parameters agree satisfactorily with experimental results for both bands. The SO2-symmetric stretching band is dominated by a- and c-type rotational structures and the SO2-antisymmetric stretching band is dominated by a b-type rotational structure. When C6H5SO2Cl was used as a precursor of C6H5SO2, C6H5SO2Cl was slowly reproduced at the expense of C6H5SO2, indicating that the reaction Cl+C6H5SO2 takes place. When C6H5Br/SO2/CO2 was used as a precursor of C6H5SO2, features at 1186 and 1396 cm-1 ascribable to C6H5SO2Br were observed at a later period due to secondary reaction of C6H5SO2 with Br. Corresponding kinetics based on temporal profiles of observed IR absorption are discussed.     

Reactivity of 4-hydroxy-2-methyl-7,8,9,10-tetrahydrobenzo[h] quinoline towards base-catalyzed cyclization,mannich and turpin reactions

Mannich reaction upon 4-hydroxy-2-methyl-7,8,9,10-tetrahydrobenzo[h]quinoline ( 1 ) as well as its nitration were studied. Condensation of the chloroquinoline 6b with sodium azide, benzylamine and ethanolamine gave the quinoline derivatives 6c, 6f and 6g , respectively. Phenylhydrazine and sodium borohydride effected reduction of the azidoquinoline 6c to the corresponding amino- and hydroxyamino derivatives 6d and 6e , respectively. Also, Turpin's reaction gave the benzoquinobenzoxazines 7a-d when applied to 6b . Treatment of 6f, 6g with alkali and the condensation of 6b with glycine in alcoholic sodium carbonate solution afforded the imidazo[4,5-c]quinoline derivatives 9a-c , respectively.     

Liquid-phase force field and dipole moment derivatives with respect to internal coordinates of benzene

This paper presents an analysis of the infrared vibrational intensities found for C(6)H(6), C(6)D(6) and C(6)H(5)D in the liquid phase, motivated in part by the quite marked intensity differences between the fundamentals of C(6)H(6) and C(6)D(6) in the liquid, and between corresponding vibrations in the liquid and gas phases. The analysis is carried out under the harmonic approximation and results from a determination of the force field for liquid C(6)H(6), C(6)D(6) and C(6)H(5)D. The force constants for the liquid-phase are presented and compared to those in the literature for the gas-phase. Previously reported experimental intensities are used along with the eigenvectors of the force field analysis to determine the dipole moment derivatives with respect to symmetry and internal coordinates. The dipole moment derivatives with respect to internal coordinates obtained are partial differentialmicro/ partial differentials=0.38+/-0.02DebyeA(-1), partial differentialmicro/ partial differentialt=0.24+/-0.01, partial differentialmicro/ partial differentialbeta=0.26+/-0.01, and partial differentialmicro/ partial differentialgamma=0.64+/-0.03DebyeA(-1). There is very little difference between the dipole moment derivatives with respect to internal coordinates obtained from non-linear least squares fitting of the two D(6h) isotopomers and those obtained from non-linear least squares fitting of the three isotopomers. The results show that there is significant intensity sharing in the CH stretch region of C(6)H(5)D between the fundamental and combination bands.     

Synthesis,Characterization, and In Vitro Antimicrobial Activity of a New Class of 7‐Substituted Amino‐2‐phenyl‐3H‐pyrimido[4,5‐d]pyrimidin‐4‐one

A new class of pyrimido pyrimidine derivatives that exhibits in vitro antimicrobial activity was synthesized. The protection of amino group in the compound 1 with acetic anhydride, followed by the reaction with POCl₃, gave 3 . The reaction of 3 with different substituted phenyl methanediamine in dry TEA under inert atmosphere led to the formation of 4 . Deprotection of 4 followed by refluxion with different acid chlorides yielded title compounds 6a , 6b , 6c , 6d , 6e , 6f , 6g , 6h , 6i , 6j , 6k , 6l , 6m in good yields. The identities of these compounds were confirmed following elemental analysis, IR, ¹H, ¹³C NMR, and mass spectral studies. All the title compounds exhibited pronounced in vitro antibacterial and antifungal activities.     

Hexanuclear cobalt carbonyl carbide clusters: the interplay between octahedral and trigonal prismatic structures

The six-vertex cobalt carbonyl clusters [Co6C(CO)n](2-) (n = 12, 13, 14, 15, 16) with an interstitial carbon atom have been studied by density functional theory (DFT). These DFT studies indicate that the experimentally known structure of [Co6C(CO)15](2-) consisting of a Co6 trigonal prism with each of its edges bridged by carbonyl groups is a particularly stable structure lying more than 20 kcal/mol below any other [Co6C(CO)15](2-) structure. Addition of a CO group to this [Co6C(CO)15](2-) structure gives the lowest energy [Co6C(CO)16](2-) structure, also a Co6 trigonal prism with one of the vertical edges bridged by two CO groups and the remaining eight edges each bridged by a single CO group. However, this [Co6C(CO)16](2-) structure is thermodynamically unstable with respect to CO loss reverting to the stable trigonal prismatic [Co6C(CO)15](2-). This suggests that 15 carbonyl groups is the maximum that can be attached to a Co6C skeleton in a stable compound. The lowest energy structure of [Co6C(CO)14](2-) has a highly distorted octahedral Co6 skeleton and is thermodynamically unstable with respect to disproportionation to [Co6C(CO)15](2-) and [Co6C(CO)13](2-). The lowest energy [Co6C(CO)13](2-) structure is very similar to a known stable structure with an octahedral Co6 skeleton. The lowest energy [Co6C(CO)12](2-) structure is a relatively symmetrical D3d structure containing a carbon-centered Co6 puckered hexagon in the chair form.     

Analysis of oxycodol and noroxycodol stereoisomers in biological samples by capillary electrophoresis

A capillary electrophoresis (CE) method for the separation of the diastereoisomers of 6-oxycodol (6OCOL) and nor-6-oxycodol (N6OCOL), the 6-keto-reduced metabolites of oxycodone (OCOD) and noroxycodone (NOCOD), respectively, is reported and employed to assess the stereoselectivity of these metabolic steps in vivo, in vitro, and in chemical synthesis. CE in an untreated fused-silica capillary with acidic buffers containing 2-hydroxypropyl-beta-cyclodextrin, randomly sulfated beta-cyclodextrin, or single isomer heptakis(2,3-diacetyl-6-sulfato)-beta-cyclodextrin (HDAS-beta-CD) is shown to permit the simultaneous separation of the stereoisomers of 6OCOL and N6OCOL. A 100 mM phosphate buffer of pH 2.0 containing 2.05% w/v HDAS-beta-CD provides a medium for rapid analysis and unambiguous identification of these stereoisomers in solid-phase extracts of (i) urines stemming from patients under pharmacotherapy with OCOD, (ii) incubations of OCOD and NOCOD with human liver cytosol and the human liver S9 fraction, and (iii) after chemical synthesis from OCOD and NOCOD using NaBH(4). In all cases, alpha-N6OCOL is shown to be the predominant stereoisomer of N6OCOL. For 6OCOL, the same is true for in vitro formation and for chemical synthesis. In urine, however, beta-6OCOL is observed to be excreted in a higher amount than alpha-6OCOL. For the urinary alpha-/beta-isomer ratio of 6OCOL and N6OCOL, there are no differences between the data obtained for nonhydrolyzed and enzymatically hydrolyzed urines. The data document the stereoselectivity of the 6-keto-reduction of OCOD and NOCOD in man.     

五氯代-12H-双苯并[1, 3, 2]二氧磷杂八环的合成与化学

以双(2-羟基-3,5-二氯苯基)甲烷(4)与PSCl3关环,高收率地得到2,4,6,8,10-五氯-6-硫-12H-双苯并[d,g][1,3,2]二氧磷杂八环(5)。5与酚在无水K2CO3及铜粉存在下,或与醇在醇钠存在下反应,生成2,4,8,10-四氯-6-硫-6-芳氧基-12H-双苯并[1,3,2]二氧磷杂八环(6),或6-烷氧基的类似物(7)。5与醇在三乙胺存在下反应的产物为2,4,8,10-四氯-6-硫-6-羟基-12H-双苯并[1,3,2]二氧磷杂八环三乙胺盐(8)。8在DMSO中回流则氧化为它的氧类似物9。