Novel Phosphonoacetic Acid Derivatives.Synthesis of N-(Ethoxycarbonylmethylphosphonyl)-α-Amino Esters and-α-Amino Phosphonic Acid Esters and Their Bioactivities

A series of novel phosphonoacetic acid derivatives, N-(ethoxycarbonylmethy-ethoxyphosphonyl)-α-amino acid esters and α-amino phosphonates, were synthesized via the reaction of the corresponding phosphonyl chloride with amino acid ester hydrochlorides or amino phosphonates in the presence of a base. The preliminary bioassay shows that some compounds show significant anti-viral activity against tobacco mosaic virus (TMV)

A Novel Method for the Synthesis of Bioactive Benzimidazolyl-Phenoxyacetic Acid O-Acetylglucosyl Saccharide Esters

A novel method of synthesis of nitro or trifluoromethyl substituted benzimidazolyl phenoxyacetic acid O-acetylglucosyl saccharide esters by the reaction of O-acetylglucosyl bromide with substituted benzimidazolyl phenoxyacetic acid at room temperature was developed. 4 dimethylaminopyridine （DMAP） was used as catalyst, triethylamine （Et3N） was used as deacid reagent, three saccharide esters were synthesized in the system of DMAP/ Et3 N. The catalytic mechanism of DMAP/Et3N was discussed. The results show that DMAP is an effective catalyst, the yields can reach 50%. The test indicates that the title compounds show better antiplantviral activity.

Microwave-promoted solvent-free synthesis of N-(diphenylmethylene)glycine alkyl esters

The efficient synthesis of N-（diphenylmethylene） glycine alkyl esters was achieved for the first microwave irradiation under solvent-free condition, using PEG or quaternary ammonium salts as phase transfer catalysts （PTCs）. Under the optimum conditions, N-（diphenylmethylene） glycine alkyl esters were obtained in excellent yields in most cases.

Pyrolysis-GC/MS of Menthyl Esters of N-Benzoxycarbonyl Amino Acid

With the aid of a Pyrolysis-GC/TOF MS technique, the pyrolysis behaviour of two menthyl esters of N-benzoxycarbonyl amino acid was investigated. A clear pattern emerges involving the cleavage of the bond linking the menthyl ring to the carboxy group, followed by further degradation of the fragments. The major pyroproducts were p-menth-l-ene pyrolysed at a higher temperature or p-menth-2-ene pyrolysed at a lower temperature, and various derivatives of cyclohexene pyrolyzed from the menthyl ring. In addition, some of the products were also iden- tified as derivatives of benzene from the pyrolysis of benzyloxyl moiety.

Simple Detection Method of Biogenic Amines in Decomposed Fish by Intramolecular Excimer Fluorescence

Biogenic amines are known to have various biological functions such as not only neurotransmitter and cell proliferation but also food poisoning. Bacterially-decomposed amines such as histamine, agmatine, putrescine, cadaverine, spermidine and spermine cause allergic symptoms. We developed simple method for measurement of polyamine as indicator of food decomposition with a fluorometer by using 4-(1-Pyrene)butyric acid N-hydroxysuccinimide ester (PSE). PSE reacts with primary and secondary amino moieties of polyamines and produces the intramolecular excimer fluorescence. Excimer fluorescence with broad peak at around 470 nm was clearly detected in linear type biogenic amines such as putrescine, cadaverine, spermidine and spermine at 10 mM. However neither histamine nor trimethylamine altered the fluorescence. Decomposed sardine and mackerel by improper storage showed stronger intensity than fresh ones. Comparing with OPA-method, PSE method was useful for screening biogenic amines present in food, esp. fish since the analysis was simple after one-step purification procedure. An inexpensive system which can rapidly detect biogenic amines from food is necessary in a medium and small-sized food business. The technique using excimer has potential to realize the high through-put screening system for evaluation of food freshness and is expected to bring the public interests such as food security and safety of consumer.

An Alternative Synthesis and Crystal Structure Characterization of Nutrient Fortifier N-(1-(Phenylacetyl)-L-prolyl) Glycine Ethyl Ester

A nutritional fortifier N-(1-(phenylacetyl)-L-prolyl)glycine ethyl ester(4)was successfully synthesized through two synthetic schemes and characterized by IR,^1H-NMR,^13C-NMR,elemental analysis and X-ray single-crystal diffraction.The intermediate N-phenylacetyl-L-proline(2)was synthesized by the solid-liquid reaction of L-proline and phenylacetyl chloride directly.Compound 2(C13 H15 NO3,Mr=233.26)belongs to the orthorhombic system,space group P212121 with a=8.9468(3),b=9.3190(3),c=14.0453(4)A,V=1171.03(6)A^3,Z=4,Dc=1.323 g/cm^3,μ=0.773 mm^-1,F(000)=496.0,the final R=0.0313 and wR=0.0797 for all data.Compound 4(C17 H22 N2 O4,Mr=318.36)is of orthorhombic system,space group P212121 with a=6.5831(2),b=8.5536(2),c=28.9138(9)A,V=1628.11(8)A^3,Z=4,Dc=1.299 g/cm3,μ=0.763 mm-1,F(000)=680.0,the final R=0.0353 and wR=0.0816 for all data.

Chiral Separation of N-Benzoyl Phenylalanine Methyl Ester by Nonaqueous Capillary Electrophoresis

A successful chiral separation of N-benzoyl phenylalanine methyl ester has been achieved by nonaqueous capillary electrophoresis (NACE) using P-CD as chiral selector in formamide (FA). Some experimental parameters influencing the chiral separation such as concentration of P-CD, ionic strength and apparent pH (pH*) are discussed.

Total synthesis and anticancer activity studies of the stereoisomers of asperphenamate and patriscabratine

All stereoisomers of asperphenamate 1a and patriscabratine 2a were achieved with a high yield,and total synthesis of 2a is firstly described here.The absolute configuration of patriscabratine was determined as(S,S).The compounds 1a-d and 2a-d have been tested by MTT assay in T47D,MDA-MB231,HL60,Hela and SGC-7901 cell lines in vitro.Among them,the(R,S) stereoisomer shows the strongest anticancer effects,while the(S,R) shows the weakest one.

Synthesis and Characterization of 2-cetyl-3-20 keto acid(N-ethyl perfluorinated octyl sulfonamide) N-ethyl ester

2-Cetyl-3-20 keto acid（N-ethyl perfluorinated octyl sulfonamide） N-ethyl ester was synthesized by the reaction of N-ethyl-N-hydroxyethyl perfluorinated octyl sulfonamide and alky ketene dimer. The experimental results show that the yield of products can be 89% when the molar ratio of perfluorinated octyl sulfonamide to ketene dimer is 1 ： 1.1 and the reaction lasts about four hours at 80 ℃. The structure of the product was characterized by FTIR and ^1HNMR. The product can dissolve in polar solvents such as NMP, DMAC, THF, DMSO, CHCl3, and 10% weight-loss temperature measured by TGA is 202℃.

Chloroquine Relieves Acute Lung Injury in Rats with Acute Hemorrhagic Necrotizing Pancreatitis

Summary： This study preliminarily investigated the mechanism by which chloroquine （CQ） relieves acute lung injury （ALI） complicated in acute hemorrhagic necrotizing pancreatitis （AHNP）. Sixty male Wistar rats were randomized into sham-operated group （group A, n=10）, AHNP group （group B, n=10）, L-arginine-treated group （group C, n=10）, L-N-nitro-L-arginine methyl ester （NAME）-treated group （group D, n=10）, CQ-treated group （group E, n=10） and CQ＋L-NAME-treated group （group F, n=10）. TLR4 expression was measured by using real time-PCR and Western blotting respectively. The results showed that, in the group B, the expression of TLR4 and the levels of TNF-α and IL-6 in the lungs were significantly increased, and the nitric oxide （NO） concentration was reduced, as compared with those in the group A （P〈0.05 or P〈0.01）. Lung injury was aggravated with the increased expression of TLR4. When the inhibitor and stimulator of TLR4, namely L-Arg and L-NAME, were added respectively, lung injury was correspondingly relieved or aggravated （P〈0.05 or P〈0.01）. In the group E, TLR4 expres- sion was substantially lower and NO concentration higher than those in the group B （P〈0.05 or P〈0.01）. However, in the group F, NO concentration was markedly decreased, and the inhibitory effect of CQ on TLR4 expression and the relief of lung injury were weakened when compared with those in the group E （P〈0.05 or P〈0.01）. It was concluded that TLR4 may play an important role in the pathogenesis and development of ALl complicated in AHNP. CQ could relieve ALl by decreasing the TLR4 expression and increasing the NO release.

Studies on the esterifications of 9-(hydroxyimino)-4-methyl-8,9-dihydrofuro[2,3-h]chromen-2-one with acid chlorides under different conditions

The esterifications of 9-（hydroxyimino）-4-methyl-8,9-dihydrofuro[2,3-h]chromen-2-one （4） with acid chlorides afforded normal oxime-esters 3a-e in 35-78% yields in presence of excessive 4-dimethylaminopyridine as the acid scavenger, whereas the reactions gave unexpected 8-substituted products N-（8-chloro-4-methyl-2-oxo-2H-furo-[2,3-h]chromen-9-yl）amides （5a-c） and 4-methyl-2,9-dioxo-8,9-dihydro-2H-furo[2,3-h]chromen-8-ylcarboxyloates （6d-e） by using excessive acid chlorides. The structures of 10 new compounds were determined by 1H NMR, 13C NMR, MS and HRMS, and the possible mechanism for the formation of unexpected products 5a--c and 6d-e was also proposed.

Synthesis and characterization of 2-hydroxy-N-methyl-N-phenyl-acetamide

2-hydroxy N methyl N phenyl acetamide was synthesized by using N methylaniline, chloracetyl chloride, anhydrous sodium acetate and methanol through the acetylation, esterfication and ester interchange steps. The acetylation of N methylaniline with chloracetyl chloride, catalyzed by triethylamide with mole ratio n (C 6H 5NHCH 3)∶ n (ClCH 2C(O)Cl)∶ n (N(C 2H 5) 3)=1∶1.05∶1, the yield of 2 chloro N methyl N phenyl acetamide(Ⅰ) was 93.8%; Then the esterification of Ⅰ with anhydrous sodium acetate in the presence of phase transfer catalyst tetrabutyl ammonia bromide gave 97.3% yield of 2 acetoxyl N methyl N phenyl acetamide (Ⅱ); The ester interchange of with methanol catalyzed by potassium hydroxide gave 2 hydroxy N methyl N phenyl acetamide (Ⅲ) in 96.4% yield. And the total yield was 88.0%. IR and MS spectroscopy of products were analyzed and their characteristic peaks were assigned. Combining the results of elemental analysis, the molecular structure of Ⅰ, Ⅱ and Ⅲ was identified.

STUDY ON THE SYNTHESIS AND PROPERTIES OF POLY(ESTER-IMIDEETHER)MULTIBLOCK COPOLYMERS

A new class of poly(ester-imide-ether) multiblock copolymers was synthesized by transes-terification and melt copolymerization of dimethyl terephthalate (DMT) and N-(4-carbomethoxyphenyl)-4-(carbomethoxy)-phthalimide with ethylene glycol (EG) and polytetramethylene glycol (PTMG). The structure of the above copolymers was characterized by H-1-NMR and IR spectroscopy. Some properties of the coplymers were also examined. It was found that their mechanical properties and heat stability, compared with poly(ether-ester) copolymers, were obviously improved.

N-羟基邻苯二甲酰亚胺酯(NHP酯)的合成方法研究

报道了一种N-羟基邻苯二甲酰亚胺酯(NHP酯)的合成方法,我们采用商业化的氨基酸为原料,对氨基酸上的氨基进行修饰,然后与N-羟基邻苯二甲酰亚胺发生酯化反应,可以得到具有不同取代基的NHP酯,该方法操作简单,安全可靠,是一种可以用于有机合成的新策略。

A new triterpene saponin from Panax japonicus C.A.Meyer var major(Burk.) C.Y.Wu et K.M.Feng

One new Iriterpene saponin was isolated from Panaxjaponicus C. A. Meyer var major （Burk.） C. Y. Wu et K. M. Feng, and established as oleanolic acid 3-O-[β-D-glucopyranosyl-（1 →2）-β-D-glucuronopyranosyl-6＇-O-n-butyl ester] which showed mod- erate antitumor activities against the A2780 cells and OVCAR-3 cells. Its structure was established by means of spectral data, particularly NMR, including HSQC and HMBC techniques.

Synthesis, Crystal Structure and Inhibition of N-2-Thiophenesulfonyl-α-L-phenylalanine Ethyl Ester on K562 Cell Proliferation

The title compound N-2-thiophenesulfonyl-a-L-phenylalanine ethyl ester has been synthesized. Complete assignments were achieved by IR, MS, ^1H NMR and single-crystal X-ray diffraction analyses. Using MTT assay, the inhibitory rate of the title compound on K562 cells （chronic myeloid leukemic cells） was measured and the result of preliminary bioassay showed that the title compound possesses antiproliferation effects on K562 cells. In order to investigate the relationship between structure and activity of the target compound, we report its crystal structure and biological behavior in the present paper. Crystallographic data： C15H17NO4S2, Mr = 339.42, monoclinic, space group P21, flack = -0.15（12）, a = 5.7916（10）, b = 11.5078（19）, c = 12.924（2） A, β = 97.781（3）°, Z = 2, V = 853.4（2） A^3, De = 1.321 g/cm^3, F（000） = 356, -7≤h≤7, -10≤k≤14, -15 ≤ l≤15, R = 0.0628, wR = 0.1540 and μ（MoKa） = 0.327 mm^-1. The molecule comprises a benzene and a thiofuran rings, and the intramolecular N（1）-H（1A）…O（1） makes a five-membered ring of O（1）--C（6）-C（5）--N（1）--H（1A）.

SnCl_2催化合成N,N-二乙基甘氨酸酯

对9种N,N-二乙基甘氨酸酯的合成进行了研究.以SnCl2作催化剂,N,N-二乙基甘氨酸分别与正己醇、正辛醇、正癸醇、正十二烷醇、正十四烷醇、正十六烷醇、香叶醇、香茅醇和1,6-己二醇在环己烷中回流反应合成了N,N-二乙基甘氨酸正己酯、N,N-二乙基甘氨酸正辛酯、N,N-二乙基甘氨酸正癸酯、N,N-二乙基甘氨酸正十二烷醇酯、N,N-二乙基甘氨酸正十四烷醇酯、N,N-二乙基甘氨酸正十六烷醇酯、N,N-二乙基甘氨酸香叶醇酯、N,N-二乙基甘氨酸香茅醇酯和N,N-二乙基甘氨酸-6-羟基-1-己酯,其结构经IR谱、1HNMR谱和ESI-MS谱确证.并考察了各因素对产物收率的影响,较佳的反应条件是:n(脂肪醇):n(N,N-二乙基甘氨酸):n(氯化亚锡)=1:1.2:0.09,在环己烷中回流2.5 h,产物的收率为89.3%～97.6%.

手性磷酸催化非环状N,N′-缩酮的不对称合成

手性N,N′-缩酮是药物分子和生物活性化合物最重要的核心结构之一,也是有机合成中重要的催化剂或配体。因此,不对称合成N,N′-缩酮具有重要意义。通过手性磷酸、溶剂、催化剂负载量和投料比的筛选,确定了最佳的反应条件:在手性磷酸的催化下,以1,4-二氧六环作为溶剂,5-氨基异噁唑与β,γ-炔基-α-酮亚胺酯在室温下发生区域选择性的氮杂-曼尼希反应,实现异噁唑的不对称N—H烷基化,以中等至良好的收率(46%~83% yield)和较好的对映选择性(82%~92%ee)合成非环状的N,N′-缩酮。所有产物结构由^(1)H NMR,^(13)C NMR和HR-MS(ESI)确证,绝对构型通过X-射线晶体结构分析确定。

Lipid Distribution in Marine Sediments from the Northern South China Sea and Association with Gas Hydrate

The distributions of lipids in surface and subsurface sediments from the northern South China Sea were determined. The n-alkanes were in bimodal distribution that is characterized by a centre at n-C16 –n-C20 with maximum at C18（or C19） and n-C27 –n-C31 as well as at C29（or C31）. The short-chain alkanes suffered from significant losses due to their slow deposition in the water column, and their presence with a slight even carbon predominance in shallow seafloor sediments was ascribed mainly to the direct input from the benthos. The long-chain alkanes with odd predominance indicate transportion of terrigenous organic matter. Immature hopanoid biomarkers reflect the intense microbial activity for bacteria–derived organic matter and the gradual increase of maturity with burial depth. Abundant n-fatty acid methyl esters（n-FAMEs） that are in distributions coincident with fatty acids were detected in all samples. We proposed that the observed FAMEs originated from the methyl esterification of fatty acids; methanol production by methanotrophs and methanogenic archaea related to the anaerobic oxidation of methane, and sulfate reduction provided an O–methyl donor for methylation of fatty acids. The CH4 released from hydrate dissociation at oxygen isotope stage II of Cores ZD3 and ZS5, which had been confirmed by the occurrence of negative δ13C excursion and spherical pyrite aggregates, could have accelerated the above process and thus maximized the relative content of FAMEs at ZD3-2（400–420 cm depth） and ZS5-2（241–291 cm depth）.

N-芳基氨基甲酸苄酯的合成及抗真菌活性研究

为发现更多抗真菌药物分子,设计合成16种N-芳基氨基甲酸苄酯类目标化合物,并进行结构鉴定;以醚菌酯为阳性对照,采用菌丝线性生长速率法,测定目标化合物对常见的10种植物病原真菌的体外抑制活性,以及5种高抗菌活性的目标化合物对苹果轮纹病原菌和番茄早疫病原菌的毒力。结果发现,所有目标化合物对10种供试真菌都有不同程度的抑制活性,其中,化合物B11抗菌活性最高,对9种供试真菌的抑制率均超过80%,对马铃薯干腐病原菌的抑制率为98.1%,对番茄早疫病原菌的EC50为7.6μg/mL。构效关系研究表明,-F和-Me的引入有利于提高活性,是该类化合物的优势基团;-F和-Me的组合可大幅度提高活性,是优势基团叠加效应的结果。