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).     

Migrating simulation of novel high-energy SMX-based propellants based on molecular dynamics

Structural Chemistry - Three 2,3-bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol tetranitrate (SMX)–based propellants were firstly reported, then the specific impulses of SMX-based propellants...     

Electronic absorption spectra and kinetics of the photochemical conversions of 2,3-dihydroxymethylquinoxaline 1,4-di-N-oxide in solutions

Conclusions The electronic absorption spectra of 2,3-dihydroxymethylquinoxaline 1,4-di-N-oxide (di-oxidine) in water, ethanol, and chloroform have been measured; the kinetics have been studied; and the absolute quantum yields of the photochemical decomposition of dioxidine in the solutions have been determined.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 806–810, April, 1986.     

Donor-acceptor complexes of heteroaromatic N-oxides. A review

Petrozavodsk State University, 185640 Petrozavodsk and St. Petersburg State University, 198904 St. Petersburg. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 760–773, June, 1995. Original article submitted December 24, 1994.     

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.     

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.     

Conformational analysis of trans-2,3-diaryloxy-1,4-dioxanes. A tool for discriminating between steric and electronic effects in the position of

The conformation of several $\text{trans}$-2,3-diaryloxy-1,4-dioxanes has been studied using ¹H NMR techniques. $\text{Trans}$-2,3-bis(4-nitrophenoxy)-1,4-dioxane and $\text{trans}$-2,3-bis(4-methoxyphenoxy)-1,4-dioxane have been found to be predominantly ( ≈98%) in diaxial conformation in CDCl₃). On the other hand, $\text{trans}$-2,3-bis(2,6-dimethylphenoxy)-1,4-dioxane exists in the same conditions as a 66:33 mixture of diaxial and diequatorial conformers. An explanation based on the fulfilment of the exo-anomeric effect is provided.     

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.     

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.     

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.     

Synthesis, molecular structure, spectral properties and antifungal activity of polymethylene-α,ω-bis(N,N- dimethyl-N-dodecyloammonium bromides)

Hexamethylene-1,6-bis-(N,N-dimethyl-N-dodecylammonium bromide), pentamethylene-1,5-bis(N,N-dimethyl-N-dodecylammonium bromide), tetramethylene-1,4-bis(N,N-dimethyl-N-dodecylammonium bromide), trimethylene-1,3-bis(N,N-dimethyl-N-dodecylammonium bromide) and ethylene-1,2-bis(N,N-dimethyl-N-dodecylammonium bromide) have been obtained and characterized by FTIR and NMR spectroscopy. DFT calculations have also been carried out. The optimized bond lengths, bond angles and torsion angles calculated by Hartree-Fock/3-21G(d,p) approach have been presented. MIC values for A. niger, P. chrysogenum, C. albicans have been determined and the relationship between MIC and spacer length has been discussed.     

Cubane derivatives

An efficient procedure for the preparation of 1,4-bis(hydroxymethyl)cubane by reduction of cubane-1,4-dicarboxylic acid or its dimethyl ester with aluminum hydride was developed. The molecular structure of 1,4-bis(hydroxymethyl)cubane was established by X-ray diffraction analysis. For Part 3, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1387–1390, July, 1998.     

两种含杂环的氨基萘醌化合物的合成

以2,3-二氯-1,4-萘醌为主要原料,分别与吗啡啉和糠胺在一定条件下反应生成2种含杂环的氨基萘醌类化合物。2,3-二氯-1,4-萘醌与吗啡啉及2,3-二氯-1,4-萘醌与糠胺物质的量比均为1∶2,反应温度为60℃,溶剂为乙醇。2,3-二氯-1,4-萘醌与吗啡啉反应时间为1 h,产物2-氯-3-吗啡啉基萘-1,4-二酮(a)收率为93.5%;2,3-二氯-1,4-萘醌与糠胺反应时间为4 h,产物N~2,N~3-二(2-呋喃甲基)-1,4-二((2-呋喃甲基)亚胺)-1,4-二氢化萘-2,3-二氯化铵(d)收率为46.7%。对产物进行IR、Uv、MS和H-NMR等分析表征。     

Derivatives of 1,1,2,2-tetraaminoethane: II. Condensation of 4,5-diacetoxy-1,3-diacetylimidazolidine and 2,3-diacetoxy-1,4-diacetylpiperazine with nitrogen-containing nucleophiles

Reactions of 4,5-diacetoxy-1,3-diacetylimidazolidine and 2,3-diacetoxy-1,4-diacetylpiperazine with acetamide and ethyl carbamate gave 1,3-diacetyl-4,5-bis(acetylamino)imidazolidine, 1,4-diacetyl-2,3-bis(acetylamino)piperazine, 1,3-diacetyl-4,5-bis(ethoxycarbonylamino)imidazolidine, and 1,4-diacetyl-2,3-bis(ethoxycarbonylamino)piperazine, respectively. Condensation products of 4,5-diacetoxy-1,3-diacetylimidazolidine and 2,3-diacetoxy-1,4-diacetylpiperazine with urea, furazan-3,4-diamine, and 4-phenylfurazan-3-amine were isolated.     

Novel chiral water soluble phosphines I. Preparation and characterization of amine functionalized DIOP, Chiraphos, and BDPP derivatives and quaternization of their rhodium complexes

Synthetic details for the preparation of tetra-amine functionalized derivatives of the ligands BDPP, Chiraphos, and DIOP (2,4-bis(-bis(-p-N,N-dimethylaminophenyl)phosphino)pentane; 2,3-bis(-bis(-p-N,N-dimethylaminophenyl)-phosphino)butane; and 2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(-bis(-p-N,N-dimethylaminophenyl)phosphino)butane; respectively). The ligands are conveniently quaternized in their rhodium diene complexes with (CH₃)₃OBF₄. Both the methyl quaternized and proton quaternized versions of the rhodium complexes have unlimited water solubility.     

Synthesis of benzo[f]isoindole-4,9-diones

A synthesis of benzo[f]isoindole-4,9-diones 1 is presented starting from the reaction of 2,3-bis(bromomethyl)-1,4-dimethoxynaphthalene 15 with primary amines affording 2,3-bis(aminomethyl)-1,4-dimethoxynaphthalenes 14, which could be converted by CAN-mediated oxidation in one step to benzo[f]isoindole-4,9-diones 1. An alternative synthesis of benzo[f]isoindole-4,9-diones 1 starts from 2,3-bis(bromomethyl)-1,4-naphthoquinone 9 via 2,3-dihydrobenzo[f]isoindoles 10 which spontaneously oxidize.     

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.     

Effektive Synthese von 3,1′-Spiro[3,4-dihydro-2H-[1,3]oxazino[3,2-a]benzimidazol] cyclo- bzw. benzocycloalkanen sowie ihrer Thia-Analogen Über Spirane, 23. Mitt.

Ten new constitutionally unsymmetrical azaspiran systems were synthesized upon condensation of Na-derivatives of 2,3-dihydro-1H-benzimidazol-2-one and 2,3-dihydro-1H-benzimidazol-2-thione, respectively, with 1,1-bis(bromomethyl)-and 1,1-bis(iodomethyl)- and ditosylate of 1,1-bis(hydroxymethyl) cycloalkanes.

Vorgetragen auf dem 28. IUPAC-Kongreß in Vancouver (August 1981).     

Quinoxaline-2,3-dithiol in reactions with propargyl bromide and 1,3-dibromopropyne

Propargyl bromide with quinoxaline-2,3-dithiol in DMSO in the presence of K₂CO₃ affords 2,3-bis-(2-propynylsulfanyl)quinoxaline in good yield whereas in absolute methanol in the presence of sodium methoxide at 20°C a 1:2 mixture of 2,3-bis(2-propynylsulfanyl)quinoxaline and 3-(2-propynylsulfanyl)-2(1H)-quinoxalinethione is formed. Individual 3-(2-propynylsulfanyl)-2(1H)-quinoxalinethione was obtained by crystallization of this mixture from ether. The reaction of 1,3-dibromopropyne with quinoxaline-2,3-dithiol in ethanol in the presence of NaOH at heating results in 2-bromomethylidene-1,4-(3H)-dithiino[2,3-b]quinoxaline in 77% yield. Performing this reaction in methanol in the presence of sodium methoxide during long heating (16 h) led to 2,3-bis[(3-bromo-2-propynyl)sulfanyl]quinoxaline in 72% yield.     

Development of new methods for the synthesis of 2,3-bis(nitroxymethyl)-2,3-dinitrobutane-1,4-diol dinitrate and its intermediates

Known methods for the synthesis of 2,3-bis(nitroxymethyl)-2,3-dinitrobutane-1,4-diol dinitrate and its intermediates were investigated. New procedures were developed for the preparation of these compounds. 2,3-Bis(nitroxymethyl)-2,3-dinitrobutane-1,4-diol dinitrate was studied by X-ray diffraction.