四氯蔗糖及其衍生物的NMR碳氢化学位移完全解析及结构研究

4,6,1′,6′-四氯蔗糖及其两个单酯化衍生物4,6,1′,6′-四氯蔗糖-3-乙酯和4,6,1′,6′-四氯蔗糖-2-乙酯是在合成三氯蔗糖的过程中得到的3种副产物，应用质谱（MS）和核磁共振（NMR）中的¹H-¹H COSY、HSQC等多种二维谱技术对它们的结构进行了研究，报道了四氯蔗糖及其两个单酯衍生物的合成及NMR碳氢化学位移完全解析，并对其氯化产物的立体化学进行了讨论.     

含手性轴的季戊四醇双缩醛的NMR研究

采用1D和2D梯度场NMR技术(包括1D ¹H NMR, ¹³C NMR, DEPT, 2D ¹H-¹H COSY, HSQC, HMBC),对3,3′-二（2,4-二氯苯基）-2,4,2′,4′-四氧杂螺[5.5]十一烷的4个亚甲基呈现的4组裂分峰进行了明确的归属,也对化合物中其它¹H和¹³C NMR谱信号进行了全归属,为四氧杂螺双缩醛类化合物的结构鉴定提供了充分依据.     

新的4′-去甲表鬼臼衍生物的2D NMR研究

采用¹H-¹H COSY、NOESY、¹H-¹³C HMQC及HMBC二维NMR技术鉴定了2个新合成的4β-5- 氟尿嘧啶取代-4′-去甲表鬼臼毒衍生物, 并对它们的¹H和¹³C NMR 谱峰进行了全归属.     

一个A环开环型芳基萘内酯类木脂素2D NMR全归属

采用二维核磁共振技术(¹H-¹H COSY, DEPT, HSQC, HMBC, NOESY)和CD光谱,确定了A环开环型芳基萘内酯类木脂素3′, 4′-O, O-demethylene-4-O- demethylpodophyllotoxin (1)的结构. 首次对化合物1的¹³C NMR数据进行了全归属.     

单甲基酯亚磺酸帕珠沙星盐的波谱学研究

帕珠沙星(Pazufloxacin), (S)-7-(1′-氨基环丙基)[N,8-缩-(2″-甲基)乙氧基]-3-羧酸-6-氟-喹啉-[4]酮-(S)-7-(1′-Aminocyclopropy1)-[N,8-de]-(2″-methy1)-epoxyethane-3-Carbony1ic acid-6-fluoro-quino1-[4]-one,及其单甲基酯亚磺酸盐是一种可望用于抗革兰氏阳性菌和阴性菌的防治药物. 本文采用¹H NMR、¹³C NMR、DEPT及二维谱¹H-¹H COSY、HMQC、HMBC和IR、MS推证了单甲基酯亚磺酸帕珠沙星盐分子结构的正确性,并进行了¹H、¹³C NMR谱峰的全归属. 对其IR、MS各主要峰也进行了归属.     

2-甲基重氮萘醌在环醚中光解产物的2D NMR研究

应用二维核磁共振对2-甲基重氮萘醌在四氢呋喃和二氧六环中光解反应的产物：2-甲基-4-螺(2′-四氢吡喃)萘-1-酮 (3)、2-甲基-4-(2′-四氢呋喃基)-1- 萘酚 (4)、2-甲基-4-螺［7′-(1′,4′-二氧杂环庚烷)萘-1-酮 (5)、2-甲基-4 -［2′-(1′,4′-二氧杂环己基)］-1-萘酚 (6)和二(2-甲基-萘 -22-冠-6) (7)的¹H和¹³C NMR谱进行了全归属.     

新型β-氨基醇及其中间体的合成与波谱研究

由D-木糖出发，经过杂D-A 反应、Henry反应、合成了中间体(1αS，2αR， 3αS，4S，7E，9αR，10αR)-1，2∶9，10-O-二异丙叉基-3-硝甲基-5，6-二脱氧-7-烯-4-氧化-1，4∶7，10-二呋喃-4，8-吡喃糖（化合物1），再经催化氢化，立体选择性地得到了含高碳糖结构片断的β-氨基醇(1αS，2αR， 3αS，4S，7αS，8βR，9αR，10αR)-1，2∶9，10-O-二异丙叉基-3-氨甲基-5，6-二脱氧-4-氧化-1，4∶7，10-二呋喃-4，8-吡喃糖（化合物2）， 通过DEPT和¹H-¹H COSY，HMQC，HMBC等2D NMR 技术对化合物1的¹H和¹³C NMR数据进行了全归属和较详细的解析并探讨了其ESI-MS/MS质谱裂解规律. 同时得到化合物1的还原产物化合物2的¹H，¹³C NMR归属.     

呋喃阿洛糖衍生物水解产物的结构确定

1,2;5,6-双-O-异丙叉基-3-C-硝甲基-α-D-呋喃阿洛糖（化合物1）在酸性条件下选择性脱除5,6-异丙叉基得到C-3位构型保持的水解产物1,2-O-异丙叉基-3-C-硝甲基-α-D-呋喃阿洛糖（化合物2）;化合物1先经过Moffatt脱水生成C-3硝基烯产物1,2;5,6-双-O-异丙叉基-3-脱氧-亚甲基硝基-α-D-呋喃木糖（化合物3）,然后在酸性条件下选择性脱除5,6-异丙叉基过程中协同发生氧杂-Michael加成反应得到C-3位构型反转的水解产物1,2-O-异丙叉基-3-C-硝甲基-α-D-呋喃葡萄糖（化合物2′）,两种产物化合物2和2′互为C-3差向异构体.通过¹H NMR、¹³C NMR、DEPT-135、¹H-¹H COSY、gHSQC和gHMBC等核磁共振（NMR）技术,对化合物2′的¹H和¹³C NMR数据进行了全归属．     

天然结晶辣椒碱的NMR谱研究

用一维¹H NMR谱、¹H-¹H COSY谱和一维¹³C NMR谱、DEPT谱研究辣椒碱分子和二氢辣椒碱分子及其混合物,得到¹H和¹³C的化学位移,采用¹H NMR谱测定天然辣椒碱中辣椒碱和二氢辣椒碱的相对含量.     

南海海绵Dysidea fragilis中两个倍半萜内酯的NMR研究

用一维¹H、¹³C NMR谱、DEPT ¹³C NMR谱、选择性远程DEPT ¹³C NMR、¹H-¹H COSY和¹³C-¹H COSY二维核磁共振技术研究了南海海绵Dysidea fragilis中的两个倍半萜herbadysidolide(1)和furodysinin lactone(2),确认了化学结构,并对其¹³C NMR和¹H NMR谱进行了归属.药理活性试验表明:1和2具有一定的心血管活性.     

NMR Analysis of a Complex Spin System from a Siruo-Chamigrene

The compound 2,10-dibromo-3-chloro-8-hydroxy-β-chamigrene was analysed in detail by NMR Spectroscopy. the complete assignment of the signals in the ¹H and ¹³C NMR spectra and the determination of the relative configurations were achieved by 2D NMR techniques, AM1 data and ¹H spectrum simulation. Comparisons of the results with related spiro chamigrene systems are also presented.     

Molecular structure,experimental and theoretical 1H and 13C NMR chemical shift assignment of cyclic and acyclic α,β‐unsaturated esters

The experimental ¹H and ¹³C NMR spectra of 13 phenyl cinnamates and four 4‐methylcoumarins were investigated and their chemical shifts assigned on the basis of the two‐dimensional spectra. For the unsubstituted cinnamic acid phenyl ester, optimized molecular structures were calculated at a B3LYP/6‐311++G(d,p) level of theory. ¹H and ¹³C NMR chemical shifts were also calculated with the GIAO method at the B3LYP/6‐311 + G(2d,p) level of theory. The comparison between experimental and calculated NMR chemical shift suggests that the experimental spectra are formed from the superposition spectra of the two lowest energy conformers of the compound in solution. The most stable s‐cis configuration found in our studies is also the conformation adopted for a related phenyl cinnamate in solid state. The experimental results were analyzed in terms of the substituent effects. Copyright © 2013 John Wiley & Sons, Ltd.     

Structural Elucidation of the Hitherto 2,3-Dihydro-1,2,3,5-Benzothiatriazepine-1,1-Dioxide Ring System1,2

The structure of the product from the successive reaction of pyridinium 2-benzamido-5-chloro-4-methylbenzenesulfonate with PCl₅ and excess anhydrous hydrazine has been established as 8-chloro-4-phenyl-7-methyl-2,3-dihydro-1,2,3,5-benzothiatriazine-1,1-dioxide, 1. MS, IR, ¹H and ¹³C NMR have provided definite proof of 1.     

滇黄精中两个呋甾皂苷的NMR研究

从滇黄精新鲜根茎中分离得到一对立体异构的呋甾皂苷, 利用1D、2D NMR鉴定其结构为: 26-O-β-D-吡喃葡萄糖基25(S)-呋甾-△^5（6）-烯-3β, 22, 26-三羟基-12酮基-3-O-β-D-吡喃葡萄糖基(1→4)-β-D-吡喃呋糖苷(1, 25S-kingianoside D)和26-O-β-D-吡喃葡萄糖基25(R)-呋甾-△^5（6）-烯-3β-, 22, 26-三羟基-12酮基-3-O-β-D-吡喃葡萄糖基(1→4)-β-D-吡喃呋糖苷(2, kingianoside D). 利用1D、2D NMR对两个呋甾皂苷25位的立体构型进行了确定, 并对其碳、氢信号进行了全归属.      

扁枝藓中锯齿石松烷型三萜的NMR化学位移全归属

从扁枝藓(Homalia trichomanoides)中分得了三个锯齿石松烷型三萜化合物: 3α-甲氧基-锯齿石松-14-烯-21β-醇(1)、3β-甲氧基-锯齿石松-14-烯-21β-醇(2)和3β-甲氧基-锯齿石松-14-烯-21-酮(3), 应用1D和各种2D NMR实验技术(包括¹H-¹H COSY, HMQC和HMBC)对化合物结构进行了研究, 对¹H和¹³C化学位移进行了完全归属, 并根据¹H NMR中信号的裂分对三个化合物C-3位与1和2的C-21位的立体构型作出了判断     

TOTAL ASSIGNMENT OF 1H AND 13C NMR SPECTRA OF A BRIDGED TRIRUTHENIUM CLUSTER-POLYPYRIDINE DIMER BASED ON 2D (COSY,HMQC, AND HMBC) TECHNIQUES

The bridged ruthenium cluster-polypyridine dimer [Ru₃O(CH₃COO)₆(py)₂(tmbpy)Ru(bpy)₂(Cl)](PF₆)₂ (py = pyridine, = 2, 2′-bipyridine and tmbpy = 4, 4′-trimethylenedipyridine) has been synthesized and structurally characterized based on ¹H and ¹³C NMR spectroscopy. This species exhibits a complex pattern of NMR signals due to the presence of a paramagnetic [Ru₃O] core and seven non-equivalent aromatic rings. 2D NMR (COSY, HMQC and HMBC) correlation techniques have been required for the total assignment of the ¹H and ¹³C NMR spectra.     

对氯苯氧基氯苯乙酮异构体的NMR分析

2-氯-4-(4-氯苯氧基)苯乙酮和2-(4-氯苯氧基)-4-氯苯乙酮互为同分异构体,它们的核磁共振谱十分相似,只通过一维核磁共振谱对其结构确定有很大的困难. 本文借助2-(4-氯苯氧基)-4-氯苯乙酮的分子晶体结构信息,利用二维核磁共振方法,对两个化合物的¹H NMR和¹³C NMR进行了指认,为这两种化合物的结构鉴定提供了重要依据.     

Spectral Data of Chemical Modification Products of Costunolide

Epoxidation of costunolide (1) yielded parthenolide (3), 1, 10-epoxycostunolide (4), and the cyclization products of 4, santamarin (5), reynosin (6), magnolialide (7) and a 1, 4-epoxyeudesmanolide (8). Reduction of santamarin (5) with sodium borohydride afforded 11, 13-dihydrosantamarin (9) and an eudesmen-triol (10). Reduction of reynosin (6) provided 11, 13-dihydroreynosin (11) and the two eudesman-triols 12 and 13. The structures of the new compounds were elucidated by ID and 2D ¹H and ¹³C NMR spectral methods.     

1H and 13C NMR Spectra of Alditolyl Derivatives of 3-Hydrazino-5-Methyl[1,2,4]triazino[5,6-b]indole and Their Cyclized Products.

The ¹H and ¹³C NMR spectra of sugar (5-methyl [1, 2, 4]-triazino [5, 6-b] indol-3-yl) hydrazones (1), per-0-acetyl aldehydo sugar 1-acetyl-1-(5-methyl [1, 2, 4] triazino [5, 6-b]-indol-3-yl) hydrazones (2), l- (penta-0-acetyl-pentitol-1-yl)-10-methyl [l, 2, 4] triazolo [3′, 4′:3, 4] [l, 2, 4] triazino [5, 6-b]-indoles (3) have been investigated. The 2 D NMR (H, C COSY) spectrum of 2a has been studied.