Preparation of Amide-Containing Insecticidal Derivatives from the Renewable Natural Productβ-Pinene

The preparation of bioactive derivatives from the renewable natural product pinene is a hot research topic in the deep processing and utilization of pinene.In this study,β-pinene was used to develop novel molecules as a promising new precursor of insecticide.A series of amide-containing derivatives ofβ-pinene were synthesized and characterized.The insecticidal activities of these derivatives against Mythimna separate and Semiaphis heraclei were tested.The structure characterization results showed that the characterization data of amide-containing derivatives were in full agreement with their proposed structures.The insecticidal activities evaluation results indicated that amide-containing derivatives exhibited weak insecticidal activity against Mythimna separate,but exhibited moderate to good insecticidal activity against Semiaphis heraclei.After testing for 72 h,the corrected mortality against Semiaphis heraclei of compounds 5c,5e,5f,5 h,5j,and 5 m was 100%at 1000 mg/L.The structure-activity relationship analysis results showed that the introduction of an amide group into the structure of derivatives improved their insecticidal activity against Semiaphis heraclei.Meanwhile,the amide-containing derivatives containing the F and NO_(2) substituted benzene ring might improve their insecticidal activity against Semiaphis heraclei.This study will be helpful for the high value-added utilization of the natural renewable resourceβ-pinene and the development of novel insecticides.

Methanolysis of amides under high-temperature and high-pressure conditions with a continuous tubular reactor

The methanolysis of amides,which is widely employed in the synthetic organic chemistry,hardly occurs under mild conditions.To safely and controllably intensify the methanolysis reaction with hightemperature and high-pressure environment,a continuous tubular reaction technology is developed,whose space-time yield is over twice of that of the conventional batch reaction.The methanolysis of acetanilide is selected as the representative reaction,and the influences of temperature,pressure,reactant and catalyst concentration,and residence time on the reaction performances are systematically investigated.Taking the advantages of precise temperature and reaction time control by the tubular reactor,the kinetics of acetanilide methanolysis are determined and compared to the kinetics of acetanilide hydrolysis reaction.The tubular reaction method is also employed to test a variety of other amides to show the effects of substituents,steric hindrance,and alkalinity on the reaction rate of methanolysis.

Three new amide derivatives from the fungus Alternaria brassicicola

Three new amide derivatives(alteralkaloids A-C,1-3)and three known alkaloids(4-6)were afforded after phytochemical investigation of fungus Alternaria brassicicola.The structures of these compounds were confirmed by NMR spectroscopic and HRESIMS data.Furthermore,the absolute configuration of 1 was determined using the single-crystal X-ray diffraction analysis.Compounds 1-3 belong to a class of amide derivatives that have not been found in nature before,sharing the same characteristic signals of the butyl moiety and amide group.These isolated compounds mentioned above were tested for the cytotoxic activity.

Amide proton transfer imaging of Alzheimer's disease and Parkinson's disease

Amide proton transfer (APT) magnetic resonance imaging (MRI) is an important molecularimaging technique at the protein level in tissue. Neurodegenerative diseases have a highlikelihood of causing abnormal protein accumulation in the brain, which can be detectedby APT MRI. This article briefly introduces the principles and image processing technologyof APT MRI, and reviews the current state of research on Alzheimer's disease and Parkinson's disease using this technique. Early applications of this approach in these twoneurodegenerative diseases are encouraging, which also suggests continued technicaldevelopment and larger clinical trials to gauge the value of this technique.

大位阻氨基酸Fmoc-Arg(Pbf)-OH与Rink Amide-AM树脂的高效缩合

采用集自动搅拌、过滤、鼓泡等多重功能于一体的自制多肽固相合成反应器,以对称酸酐法、活化酯法、2,6-二氯苯甲酰氯(DCB)法研究了大位阻氨基酸Fmoc-Arg(Pbf)-OH与Rink Amide-AM树脂的连接反应工艺。探讨了催化体系、溶剂体系、反应时间、反应物配比以及搅拌方式对合成Fmoc-Arg(Pbf)-Rink Amide-AM树脂反应的影响。结果表明,采用活化酯法(DIC/HOBt/DMAP)时连接率最高,最佳反应条件为:在采用N2辅助磁力拌系统,以体积比为1∶1的DMA/DCM为反应溶剂,氨基酸与树脂物质的量的比为3∶1,反应时间为3 h时,连接率高达93%。

天然产物Trichodermamide类似物的合成

以8a-甲氧基-4,4a,5,8-四氢-1,2-苯并口恶嗪-3-羧酸乙酯(1a)为起始原料,经NaOH醇溶液和酸处理,在4-pyrrolidinopyridine和碳化双(环己基亚胺)(DCC)的存在下与3-氨基-7,8-二甲氧基香豆素(2)进行了酰胺化反应,合成了天然产物Trichodermamides的类似物T-1,总收率为61.6%,T-1通过了1HNMR,13CNMR,IR和元素分析等光谱学的结构表征;同时水解反应研究发现,含苯并口恶嗪双环结构的化合物1a可水解脱去酯基,而口恶嗪双环8a位上连有两个O的缩酮类似结构可稳定地保留。

Research Status of Amide Herbicides and Their Safeners

The widespread use of chemical herbicides especially amide herbicides has promoted the innovation of chemical weeding in farmland, but amide herbicides have brought invisible chemical injuries to crops in addition to weeding. Herbi-cidesafeners should be applied at the same time with herbicides to ensure herbi- cides will not injure crops while controlling weeds. The research and application of safeners is of great significance to resolving or alleviating the negative effects of herbicides on crop growth. The overview, mechanism, applied research progress and existing problems of amide herbicides and their safenars are summarized.

In situ Detection of Amide A Bands of Proteins in Water by Raman Ratio Spectrum

The amide A band of protein is sensitive to the hydrogen bands of amide groups of proteins. However, it is hard to distinguish the amide A band of aqueous protein in situ directly, since it overlaps with O-H stretching vibration of water. In this work, we presented a new analytical method of Raman ratio spectrum, which can extract the amide A band of proteins in water. To obtain the Raman ratio spectrum, the Raman spectrum of aqueous protein was divided by that of pure water. A mathematical simulation was employed to examine whether Raman ratio spectrum is effective. Two kinds of protein, lysozyme and （^-chymotrypsin were employed. The amide A bands of them in water were extracted from Raman ratio spectra. Additionally, the process of thermal denaturation of lysozyme was detected from Raman ratio spectrum. These results demonstrated the Raman ratio spectra could be employed to study the amide A modes of proteins in water.

L-theanine: A potential multifaceted natural bioactive amide as health supplement

Natural bioactive compounds from plants are of great importance in modern therapeutics,which are used to prepare antibiotics, growth supplements or some other therapeutics. Ltheanine is such a bioactive amide amino acid presented in different plants and fungi,especially in tea. Theanine has influential effects on lifestyle associated diseases, such as diabetes, cardiovascular disorders, hypertension, stress relief, tumor suppression,menstruation and liver injury. This amino acid can maintain normal sleep and improve memory function and nullify effect of the neurotoxins. The rate of bioavailability and its medium of ingestion in the body is one of the great concerns for its additional antioxidant properties. Pharmacokinetics of the bioactive compound and its mode of action are described herewith. The biosynthesis and industrial synthesis are also reviewed to promote accelerated production of this bioactive compound in the pharmaceutical industries.

Synthesis and Anti-tumor Activity of Novel Amide Derivatives of Ursolic Acid

Ursolic acid was modified at C3 and C28 position to obtain fourteen derivatives including twelve novel compounds, and their chemical structures were characterized by IR, ^1H NMR and MS. Cell growth inhibitory effects of the derivatives against Hela cell were evaluated by MTT assay. All these derivatives were found to have stronger cell growth inhibitory than their parent compound, ursolic acid. The derivatives with a substituted acetyl group at C3 hydroxyl group show better activities than those with an unsubstituted hydroxyl group.

Synthesis of 2, 6-(substituded)pyridine Derivatives Using Amide and Imine Groups

A new wo-armed?acyclic diamide Ia 2, 6-bis(1-ethanecarbozamido-2-amino)pyridine, and a new series of aromatic aldehyde schiff bases containing pyridine ring and amide bridge, IIa-f, were prepared. The compounds were characterized by elemental analysis, IR, 1HNMR and MS. The bioactivity half inhibitory concentration C1/2 is given.

Amide-AlCl_(3)类离子液体催化苯与苯酐酰基化反应

采用催化剂筛选和单因素实验及红外光谱、紫外光谱、拉曼光谱等表征手段,对Amide-AlCl_(3)类离子液体催化苯与苯酐(PHA)酰基化合成邻苯甲酰苯甲酸(BBA)的反应性能及机理进行了研究。结果表明,类离子液体N,N-二甲基乙酰胺-2AlCl_(3)(DMA-2AlCl_(3))为苯与苯酐酰基化反应的较优催化剂,其制备条件为n(AlCl_(3))∶n(DMA)=2∶1、100℃下反应3 h。DMA-2AlCl_(3)催化合成BBA反应的较优条件为n(Benzene)∶n(DMA-2AlCl_(3))∶n(PHA)=10∶2∶1、40℃、反应5 h,该条件下BBA收率达98.2%。DMA-2AlCl_(3)催化苯与苯酐酰基化反应机理为:DMA-2AlCl_(3)中的Al_(2)Cl_(7)^(-)进攻苯酐中的醚键氧及一个羰基氧得到酰基正离子;DMA-2AlCl_(3)中的[AlCl_(2)·n(DMA)]^(+)与苯环的π-环电子相互作用,使苯环上的π电子活化;酰基正离子作为亲电试剂进攻活化的苯环大π键,从而完成亲电取代反应生成BBA。

Measurement and Correlation for Solubility of (S)-(+)-2,2-Dimethyl-cyclopropane Carbox Amide in Different Solvents

(S)-(+)-2,2-dimethylcyclopropane carbox amide is a key intermediate of Cilastatin, an inhibitor of de- hydropeptidase-I. Its corresponding solid-liquid equilibrium data will provide essential support for industrial design and further theoretical studies. The solubilities of (S)-(+)-2,2-dimethylcyclopropane carbox amide in toluene, di- chloromethane, trichloromethane, ethyl acetate, ethanol and pure water at different temperature were measured us- ing the synthetic method by a laser monitoring observation technique. The solubility data were correlated with the modified Apelblat equation. The calculated values were good in agreement with the experimental values.

Synthesis and Properties of Gemini Cationic Surfactants with Amide Spacers

Four gemini cationic surfactants {N,N′-di[2-(lauryldimethylamino)acetyl]polymethylenediamine dichloride, LAA-s-LAA, s=2,3,4,6} were synthesized by using four bis(α-chloroacetamide)s and N,N-dimethyllaurylamine, respectively. The molecular structures were characterized by means of IR, ~ 1H NMR, \{~ ~13 C NMR\} and MS, and the behavior of their aqueous solutions was studied. The critical micell concentrations(CMC) of LAA-s-LAA were one order of magnitude lower than that of dodecyltrimethyl ammonium chloride(DTAC). With the change of the length of spacer chain(s), their CMC values change, and CMC reaches the top value at s=4.

Amide Ionic Liquids(AILs)/L-Proline Synergistic Catalyzed Asymmetric Mannich Reactions

Amide ionic liquids （MLs）/L-proline synergistic catalyzed Mannich reactions of isovaleraldehyde, methyl ketones, and aromatic amines were carried out in moderate to high yields （ up to 96% ） and high stereo selectivities （ 〉99% e. e. ）. The products were easily isolated by extraction; and the catalyst system was readily recycled at least thrice without significant loss of efficiency. The scope of the substrates was studied and the interpretation of the manifest improvement of the reaction rates and enantio-selectivity of the novel catalyst system was speculated.

Synthesis of Novel Poly(aryl ether amide)s Containing the Phthalazinone Moiety

Two novel heterocyclic diamine monomers: 1,2-dihydro-2-(4-aminophenyl)-4-[4-(4-aminophenoxy)phenyl] (2H)phthalazin-1-one and 1,2-dihydro-2-(4-aminophenyl)-4-[4-(4-aminophenoxy)-3,5-dimethylphenyl](2H)phthalazin-1-one were successfully synthesized from readily available heterocyclic bisphenol-like monomers in two steps in high yield. A series of novel poly(aryl ether amide)s containing the phthalazinone moiety were successfully prepared by the direct polymerization of the novel diamines and aromatic dicarboxylic acids using triphenyl phosphite and pyridine as condensing agents.

Reinvestigation on the Reaction of Salicylic Chloride with Salicylic Amide and X-ray Crystal Structure of a New Macrocyclic Polyester

The reaction of salicylic chloride and salicylic amide at 170 ℃ gave benzoxazine and a new macrocyclic polyester 3, whose crystal structure has been determined by single-crystal X-ray diffraction analysis. Compound 3: C28H16O8, Mr = 480.41, monoclinic, space group P21/n, a = 15.353(3), b = 14.196(3), c = 21.147(4) ? b = 103.32(3), V = 4485(2) ?, Z = 8, F(000) = 1984, Dc = 1.423 g/cm3 and m = 0.106 mm-1. The final R = 0.0535 and wR = 0.1275 for 7903 observed reflections (I ≥ 2(I)). In the asymmetric unit of the compound there exist two independent molecules which are connected by weak aromatic CH…O hydrogen bonding between C(47)?H(47) and atom O(7) of the carbonyl group.

Synthesis and Evaluation of Aromatic DTPA-bis(amide)Gadolinium Complexes as Magnetic Resonance Imaging Contrast Agents

Five DTPA bis(amide)s have been synthesized and characterized by means of 1 H NMR , FT IR and elemental analyses. The stability constants of their Gd 3+ complexes have been measured using a simple spectrophotometric method. The results show that the complexing properties of the ligands in comparison with those of DTPA are affected by converting two carboxyl groups to amide groups. The relaxation studies have shown that the relaxivity of the chelates is similar to that of Gd DTPA, indicating that in solution all the chelates have one water molecule directly coordinated to the metal ion. Only one water molecule in inner coordination sphere suggests the coordination of the carboxamide oxygen to gadolinium ion, which agrees with the FT IR results.

Synthesis of Methyl-substituted Phthalazinone-based Aromatic Poly(amide imide)s

A series of novel aromatic poly ( amide imide)s containing phthalazinone moieties were prepared from 2-(4-aminophenyl)-4-[3-methyl-4-(4-aminophenoxy)-2,3-phthalazinone-1], a novel diamine 1 with four diimide-dicarboxylic acids by Yamazaki phosphorylation method with the inherent viscosity of 0.36~0.65 dL/g. These polymers had high glass transition temperatures above 300C and they lost 10% weight between 426~475C in N2. The structure of diamine 1 and the polymers was confirmed by IR, 1H NMR and MS. The obtained polymers were readily soluble in polar solvents such as NMP, m-cresol etc. and easily cast into tough, flexible films. The X-ray indicated that they are all amorphous.

Synthesis of Eu(Ⅲ) and Tb(Ⅲ) Complexes with New Aryl Amide Type Tetrapodal Ligand and Their Luminescence Properties

A new aryl amide type tetrapodal ligand L (1, 1, 1, 1 tetrakis-{[(2 benzylaminoformyl) phenoxyl]methyl}methane) and its europium and terbium nitrate complexes were synthesized. The luminescence properties of these complexes were also studied.