六乙酰基六氮杂异伍兹烷的合成

从苄胺和乙二醛出发 ,通过缩合、氢解脱苄等反应合成了高张力高密度笼形化合物——六乙酰基六氮杂异伍兹烷 ( HAIW) ,并经 FTIR、1H NMR、MS( CI)及元素分析等证实该化合物的结构。HAIW是合成六硝基六氮杂异伍兹烷 ( HNIW)的一种极佳中间体 ,而 HNIW是迄今为止密度和能量水平很高的高能量密度化合物。     

氧化法合成六硝基六氮杂异伍兹烷

研究了用氧化方法合成六硝基六氮杂异伍兹烷的无氢解合成路线。采用70％的HNO3／AN体系水解硝化六苄基六氮杂异伍兹烷的中间氧化产物,以21％的收率得到六硝基六氮杂异伍兹烷,讨论了六氮杂异伍兹烷母体环上苯甲酰基的硝解机理。     

四乙酰基二亚硝基六氮杂异伍兹烷的合成与表征

采用无机亚硝解试剂由六苄基六氮杂异伍兹烷(HBIW)的一次氢解产物四乙酰基二苄基六氮杂异伍兹烷(TADBIW)合成四乙酰基二亚硝基六氮杂异伍兹烷(TADNSIW),维持温度25℃,反应1h,TADNSIW得率为81 0%。对产物进行了分离、提纯,目标产物熔点为288～290℃。并用FT-IR、1HNMR、MS及元素分析法对目标产物进行了结构鉴定。定量地分离出副产物苯甲醛,并由此证明该文所提反应机理的合理性。     

六苄基六氮杂异伍兹烷氢解工艺的改进

提出了使用溴甲基（o,m,p-混合物）代替文献所使用溴苯等在六苄基六氮杂异伍兹烷（HBIW）一次氢解中为溴源物质，其结果提高了氢解收率，降低了溴源物质的用量和毒性，溴甲苯制造简单，有利于放大制备。     

四乙酰基二氯乙酰基六氮杂异伍兹烷硝解产物中副产物的分离和鉴定

硝解四乙酰基二氯乙酰基六氮杂异伍兹烷 (TADCIW)制备四硝基二氯乙酰基六氮杂异伍兹烷 (TNDCIW)时 ,所得产物经薄层色谱 (TL C)检测发现含有少量副产物。采用柱色谱分离出了该副产物 ,经 FTIR、1H- NMR、MS(CI)及元素分析对副产物的结构进行鉴定 ,确定它为五硝基一氯乙酰基六氮杂异伍兹烷 (PNMCIW) ,这为改进 TADCIW的硝解条件提供了依据。     

六氮杂异伍兹烷衍生物的选择性硝解

以六氮杂异伍兹烷衍生物：四乙酰基-二(对氯苯甲酰基)六氮杂异伍兹烷（TABIW）为基质,经选择性硝解合成了四硝基-二(3,5-二硝基-4-氯苯甲酰基)六氮杂异伍兹烷（TANIW）,分别用FTIR、1H NMR及元素分析对产物TANIW进行了结构表征,并讨论了硝解剂、硝解温度、硝解时间、加料方式对反应的影响。结果表明：冰浴下,在搅拌作用下分批把反应物TABIW加入到发烟硝酸[m(HNO3)=98%]中,使之溶解。待溶解完全后,慢慢滴加发烟硫酸[m(SO3)=20%],待滴加完毕后首先升温至70 ℃并恒温反应1h,然后再升温至90 ℃并恒温反应3 h使反应完全,直接过滤得到产物,熔点为242～244 ℃,收率为71.4%。     

四乙酰基二硝基六氮杂异伍兹烷分子结构研究

四乙酰基二硝基六氮杂异伍兹烷(TADNIW)是合成六硝基六氮杂异伍兹烷(HNIW)的中间体。该文用Gaussian 98软件包,采用密度泛函理论B3LYP和标准基组6-31G对所选构型进行了全优化计算,在结构上对TADNIW的键长、键角、二面角、Mu lliken电荷及集居数进行了理论分析,发现笼形化合物的六元环成船式构象,硝基处于桥头,骨架以亚稳态存在。结构分析表明,六元环上N—NO2键相对较稳定,采用一般的硝解条件反应不能进行,作者提出了新的反应机理,即水解-硝化假设:含有酰胺基团的一类化合物在含水的硝化介质中首先发生水解生成相应的仲胺,碱性较强的仲胺再在氮硝化催化剂的作用下,迅速硝化成硝胺。计算得到TADNIW分子总能量为-1 583.375 682 a.u.,前线轨道能量差ΔE(ELUMO-EHOMO)为4.123 eV。计算IR谱图与实验IR谱图对比,误差小于20 cm-1。     

3，9-二（4-甲基苯）-2，4，8，10-四氧杂螺[5．5]十一烷的NMR研究

对含有手性轴的螺环化合物3,9-二（4-甲基苯）-2,4,8,10-四氧杂螺[5．5]十一烷的一维、二维核磁共振谱（^1HNMR,^13CNMR,DEPT,2D^1H—^1HCOSY,HSQC,HMBC）进行了解析和报道。认真的分析了两个六元杂环上四个亚甲基出现的信号,对其所有的NMR谱信号进行了全归属,为研究含杂原子的手性螺环化合物提供了参考数据。     

咪唑啉酮类除草剂的定性分析

咪唑啉酮类除草剂的定性分析。以甲基咪草烟和咪唑烟酸为例,采用KBr压片法测得两种除草剂的红外吸收光谱图,1650 cm~(-1);1690 cm~(-1);1750 cm~(-1);2500 cm~(-1);3250~3270 cm~(-1)附近强且尖锐的吸收峰是鉴别咪唑啉酮类除草剂的特征吸收峰;以氘代丙酮和氘代氯仿为溶剂采集核磁共振信号,~1H-NMR共同特征峰为:δH=0.90~1.18 ppm(-CH_3氢);δH=2.06~2.27 ppm(次甲基氢);δH=7.72~9.05 ppm(吡啶环氢);液-质联用仪获得的质谱图显示,优先丢失与吡啶环相连的质荷比为m/z 45的羧基,并产生m/z 231或m/z 217的特征碎片离子。     

一乙酰基五硝基六氮杂异伍兹烷的晶体结构

为进一步研究四乙酰基六氮杂异伍兹烷(TAIW)硝化制备六硝基六氮杂异伍兹烷(CL-20)反应中副产物一乙酰基五硝基六氮杂异伍兹烷(MPIW)的性质和结构,用硅胶柱层析技术从CL-20产品中分离得到MPIW,对其进行了旋光度测定,并用冷却饱和溶液法得到单晶,以X射线衍射仪测定单晶结构。晶体C8H9N11O11 /1 5C4H8O2 属三斜晶系,空间群为P-1,晶胞参数为a=0 81677(16)nm,b=1 0139(2)nm,c=1 5046(3)nm,β=89 09(3)°,V=1 1720(4)nm3,Z=2,dc=1 608g/cm3,μ=0 144mm-1,F(000) =588。结果表明,晶体中有一个对称中心,存在一对对映异构体,是外消旋化合物。     

Microstructure analysis of poly(styrene‐co‐vinylidene chloride) copolymers by NMR spectroscopy

Poly(styrene‐co‐vinylidene chloride) (S/V) copolymers were prepared by free‐radical photopolymerization using uranyl nitrate as an initiator. The microstructure of the copolymer S/V was investigated by ¹H‐ and ¹³C{¹H}‐NMR, ¹H–¹³C‐heteronuclear shift quantum correlation (HSQC) NMR, and homonuclear total correlated spectroscopy (TOCSY). The ¹H‐NMR spectra of the copolymers is complex due to overlapping resonance signals of the various triad configurations. Assignments were made up to the triad and tetrad levels for the methylene and methine regions using two‐dimensional HSQC experiments. A ¹³C‐distortionless enhancement by polarization transfer (DEPT) spectrum was used to differentiate between the carbon resonance signals of methine and the methylene units. The geminal couplings in the methylene protons and vicinal coupling between the methine and methylene protons were detected from the TOCSY spectra. Monte Carlo simulations were used to investigate the effect of the degree of polymerization on the triad fractions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 544–554, 2001     

Microstructure analysis of methyl acrylate/methyl methacrylate copolymers by two‐dimensional NMR spectroscopy. II

In the present article, a comprehensive two‐dimensional heteronuclear multi bond correlation (HMBC) spectral analysis of methyl acrylate (A)/methyl methacrylate (B) copolymers is reported. The methylene carbon and methine carbon resonances assigned from the 2D HSQC spectroscopy were established by analyzing the two and three bond order couplings with α‐methyl protons, methylene protons, and methine protons. Quaternary carbon resonances of the B unit were assigned by investigating the two bond order couplings with α‐methyl protons and methylene protons. Assignments of carbonyl carbon resonances based on the analysis of three bond couplings with α‐methyl protons and methylene protons are reported. The analyses present comprehensive assignments of the carbonyl carbon resonances showing the critical contribution of 2D HMBC spectroscopy in the indirect analysis of carbon resonances. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

NMR characterization of dihydrosterculic acid and its methyl ester

Cyclopropane FA occur in nature in the phosphoplipids of bacterial membranes, in oils containing cyclopropene FA, and in Litchi sinensis oil. Dihydrosterculic acid (2-octyl cyclopropaneoctanoic acid) and its methyl ester were selected for ¹H and ¹³C NMR analysis as compounds representative of cyclopropane FA. The 500 MHz ¹H NMR spectra acquired with CDCl₃ as solvent show two individual peaks at −0.30 and 0.60 ppm for the methylene protons of the cyclopropane ring. Assignments were made with the aid of 2D correlations. In accordance with previous literature, the upfield signal is assigned to the cis proton and the downfield signal to the trans proton. This signal of the trans proton is resolved from the peak of the two methine protons of the cyclopropane ring, which is located at 0.68 ppm. The four protons attached to the two methylene carbons α to the cyclopropane ring also show a split signal. Two of these protons, one from each methylene moiety, display a distinct shift at 1.17 ppm, and the signal of the other two protons is observed at 1.40 ppm, within the broad methylene peak. The characteristic peaks in the ¹³C spectra are also assigned.     

Investigation of microstructure of the acrylonitrile‐styrene‐glycidyl methacrylate terpolymers by 1D and 2D NMR spectroscopy

Acrylonitrile‐styrene‐glycidyl methacrylate (N/S/G) terpolymers were prepared by bulk polymerization by using benzoyl peroxide as initiator and analyzed by NMR spectroscopy. The compositions of terpolymers were determined by quantitative ¹³C{¹H}‐NMR spectra and compared with those calculated by Goldfinger's equation by using comonomer reactivity ratios: r_NS = 0.04, r_SN = 0.40; r_NG = 0.22, r_GN = 1.37; r_SG = 0.44, r_GS = 0.53. The ¹³C{¹H}‐ and ¹H‐NMR spectra were overlapping and complex. The spectral assignments were done with the help of distortionless enhancement by polarization transfer and two‐dimensional ¹³C‐¹H heteronuclear single quantum correlation experiments. 2D total correlated spectroscopy was used to ascertain the various coupling between the protons. The methyl, methine, methylene, and oxymethylene carbon resonances showed compositional sensitivity. 2D nuclear Overhauser enhancement spectroscopy (NOESY) experiment was used to ascertain the spatial proton–proton couplings. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1779–1790, 2003     

Stereochemical assignments of the nuclear magnetic resonance spectra of isobornyl acrylate/methacrylonitrile copolymers

Isobornyl acrylate (B)/methacrylonitrile (N) copolymers with different compositions were synthesized by the free‐radical bulk polymerization with azobisisobutyronitrile as the initiator under a nitrogen atmosphere at 70°C. The copolymer compositions were calculated from quantitative ¹³C(¹H)NMR spectra. The reactivity ratios of the comonomers in the B/N copolymers determined from the linear Kelen–Tudos method and nonlinear error‐in‐variable method were r_B = 0.66 ± 0.11 and r_N = 1.54 ± 0.22 and r_B = 0.74 and r_N = 1.65, respectively. The complete spectral assignments of the ¹H‐NMR and ¹³C(¹H)‐NMR spectra were carried out with the help of distortionless enhancement by polarization transfer, two‐dimensional (2D) heteronuclear single quantum coherence, and 2D total correlation spectroscopy. The nitrile carbon of the N unit and the methine and OCH carbons of the B unit were assigned to triad compositional sequences, whereas the β‐methylene carbons of the B and N units were assigned to the tetrad compositional and configurational sequences. The α‐methyl carbon of the N unit was also assigned to the triad level of configurational and compositional sequences. Similarly, the nitrile and quaternary carbon resonances with the methine, methylene, and methyl protons were studied in detail with 2D heteronuclear multiple‐bond correlation spectra. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Conventional Study on Novel Dicationic Ionic Liquid Inclusion with β-Cyclodextrin

This study focuses on the synthesis and characterization of the inclusion complex of β-Cyclodextrin (β-CD) with dicationic ionic liquid, 3,3'-(1,4-Phenylenebis [methylene]) bis(1-methyl-1H-imidazol-3-ium) di(bromide) (PhenmimBr). The inclusion complex was prepared at room temperature utilizing conventional kneading technique. Proton ((1)H) NMR and 2D ((1)H-(1)H) COSY NMR were the primary characterization tools employed to verify the formation of the inclusion complex. COSY spectra showed strong correlations between protons of imidazolium and protons of β-CD which indicates that the imidazolium ring of PhenmimBr has entered the cavity of β-CD. UV absorption indicated that β-CD reacts with PhenmimBr to form a 2:1 β-CD-PhenmimBr complex with an apparent formation constant of 2.61 × 10(5) mol&(-2) L(2). Other characterization studies such as UV, FT-IR, XRD, TGA, DSC and SEM studies were also used to further support the formation of the β-CD-PhenmimBr inclusion complex.     

Stereochemical elucidation of complex α‐methyl and β‐methylene carbon resonances in poly(2‐hydroxy ethyl methacrylate‐co‐methacrylonitrile) by 2D NMR

Copolymers of 2‐hydroxy ethyl methacrylate and methacrylonitrile (H/M) of different composition were synthesized by free radical bulk polymerization using azobisisobutyronitrile (AIBN) as an initiator under nitrogen atmosphere. The copolymers composition were calculated from ¹H and quantitative ¹³C{¹H}NMR spectra. The complete spectral assignment of complex and overlapped α‐methyl and β‐methylene carbon regions in ¹³C{¹H} NMR spectrum in term of compositional and configurational sequences of H/M copolymers were done with the help of two‐dimensional heteronuclear single quantum coherence (HSQC) and total correlation spectroscopy (TOCSY). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Microstructure determination and thermal studies of n‐acryloylcarbazole/vinyl acetate copolymers

Copolymers of N‐acryloylcarbazole (A) and vinyl acetate (V) were synthesized by bulk polymerization using benzoyl peroxide (BPO) as free‐radical initiator at 65°C in different in‐feed ratios. The composition of the copolymer was determined by ¹H‐NMR spectrum. The comonomer reactivity ratios, determined by Kelen–Tudos (KT) and nonlinear error‐in‐variables (EVM) methods, were r_A= 16.75 ± 1.38, r_V = 0.015 ± 0.002, and r_A = 16.36, r_V = 0.015, respectively. Complete spectral assignments of the ¹H and ¹³C{¹H} NMR spectra of the copolymers were done by the help of distortionless enhancement by polarization transfer (DEPT) and two‐dimensional NMR techniques such as heteronuclear single quantum coherence (HSQC) and total correlation spectroscopy (TOCSY). The methine and methylene carbon resonances were found to be compositional as well as configurational sensitive. The signals obtained were broad pertaining to the restricted rotation of bulky carbazole group. The thermal stability and glass‐transition temperatures (T_g) of the copolymers were found to be dependant on polymer composition and characteristic of rotational rigidity of the polymer chain. Variation in the values of T_g with the copolymer composition was found to be in good agreement with theoretical values obtained from Johnston and Barton equations. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2720–2733, 2007     

In situ fourier‐transform infrared spectra analysis of hydrogen bond in polypropylene/chlorinated polypropylene/polyaniline composite

The previous studies suggest that hydrogen bond between chlorinated polypropylene (CPP) and polyaniline (PANI) plays a prominent role in the decision of polypropylene/CPP/PANI composites' electric property. In situ Fourier‐transform infrared spectra were employed to detect and identify the relationship between the hydrogen bond and the temperature. Two kinds of hydrogen bond were carefully studied in the nitrogen–hydrogen bond (N? H) stretching, sulfur–oxygen double bond (S?O) stretching, and carbon–chlorine bond (C? Cl) stretching regions, using an iterative least‐squares computer program to obtain the best fit of spectra. The ratio of absorptivity coefficients and the mole fraction of the “free” and two kinds of H‐bonded N? H were calculated. There exists an apparent turning point in the curves of the relationship between the fraction of two kinds of H‐bonded N? H and temperature. This phenomenon also exists in the S?O stretching region, and the turning point is at about 60°C. The mole fraction of H‐bonded C? Cl decreases, and that of “free” C? Cl increases with increasing temperature. The enthalpy gap between the H‐bonded N? H…O?S and the H‐bonded N? H…Cl?C dissociation was also obtained as 23.2 KJ/mol. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers