N-(17-Acyloxy-acyl)-glutamines: novel surfactants from oral secretions of lepidopteran larvae

N-(17-Acyloxy-acyl)-glutamine conjugates such as N-(17-linolenoyloxy-linolenoyl)-glutamine (6), N-(17-linolenoyloxy-linoleoyl)-glutamine (7), N-(17-linoleoyloxy-linolenoyl)-glutamine (8), and N-(17-linoleoyloxy-linoleoyl)-glutamine (9) were identified as novel surfactants in the oral secretion of several lepidopteran larvae (S. exigua, S. littoralis, S. frugiperda, and H. virescens) by LC-MS/MS and chemical degradation. Authentic reference compounds were synthesized via a dissymmetric bis-Wittig approach and confirmed the assigned structures.     

The crystal and molecular structure of N-(17-methoxy-phenyl)-2-chloropyrrolo (2,3- b ) quinoline

N-(17-methoxy-phenyl)-2-chloropyrrolo (2,3-b) quinoline was solved by direct methods and refined to anR of 0.104 for 950 observed reflections. The intensity data were collected by the multiple film equi-inclination Weissenberg technique and estimated visually. The packing of the molecule is stabilised by van der Waals interaction. The pyrrolo (2,3-b) quinoline ring system is planar and the methoxy phenyl ring is approximately perpendicular to the plane of this ring system with a dihedral angle of 86.5°.     

Synthesis of N-(Hydroxy)amide- and N-(Hydroxy)thioamide-containing peptides

Methods developed with N-(benzoyloxy)amines and hydroxamic acids were used in the synthesis of N-(hydroxy)amide-containing pseudopeptides. Acylation of N-(benzoyloxy)phenethylamine with the acid chloride of N(alpha)-Fmoc-L-leucine provided a N(alpha)-Fmoc-N-(benzoyloxy)-L-leucinamide in 90% yield. Deprotection of the benzoyl group (using 10 vol % NH(4)OH/MeOH) provided the N(alpha)-Fmoc-N-(hydroxy)-L-leucinamide in 87% yield. In general, the appended Fmoc group allowed for further elaboration of the N-hydroxy-N-(alkyl)amides using classic peptide-coupling methods. A practical synthetic strategy was developed, and racemization issues were addressed using diastereomeric Val-Leu derivatives. In addition, N-(hydroxy)thioamides were generated from the corresponding N-(benzoyloxy)thioamides. N-(Benzoyloxy)thioamides were obtained in moderate yields (53-76%) from the reaction of the corresponding N-(benzoyloxy)amides with Lawesson's reagent (i.e., 2, 4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disu lfide). In summary, this new technology allows for the introduction of either N-hydroxyamide or N-(hydroxy)thioamide linkages into pseudopeptide chains without racemization.     

The electrochemical fluorination of N-(ω-chloroalkyl)pipecolines and N-(ω-chloroalkyl)hexamethyleneimines

Electrochemical fluorinations of six kinds of N-(ω-chloroalkyl)pipecolines [N-(2-chloroethyl)-2-, N-(3-chloropropyl)-2-, N-(2-chloroethyl)-3-, N-(3-chloropropyl)-3-, N-(2-chloroethyl)4- and N-(3-chloropropyl)-4-pipecolines] and two kinds of N-(ω- chloroalkyl)-substituted hexamethyleneimines [N-(2-chloroethyl)- and N-(3-chloropropyl)hexamethyleneimines] were conducted. From these starting materials, corresponding chlorine-retained fully fluorinated amines together with ring isomerized products were formed in yields of 7.6～14.8% from the former and 5.4～5.5% from the latter, respectively. New chloropolyfluoroamines obtained in the present investigation have been isolated and characterized by spectroscopic (infrared, ¹⁹F nmr and mass) and elemental analysis.     

Untersuchungen zur Silicationenkonstitution in N-(2)Hydroxyethyl- und N-(2)Hydroxypropylpyridiniumsilicatlösungen. Bildung von N-(2)Hydroxypropylpyridiniumsilicathydrat

Investigations on the Silicate Ion Constitution in N-(2)hydroxyethyl- and N-(2)hydroxypropylpyridinium Silicate Solutions Crystallization of N-(2)hydroxypropylpyridinium Silicate Hydrate In N-(2)hydroxyethyl- and N-(2)hydroxypropylpyridinium silicate solutions are present mainly double three-ring and double four-ring silicate ions. With increasing concentration their molar ratio shifts in direction to double four-ring silicate. Simultaneously the amount of the low-condensed silicates decreases. An increasing concentration of the alkali hydroxide destroys the double ring cages. From solutions of N-(2)hydroxypropylpyridinium silicate with molar ratios of the pyridinium base to silicon dioxide of 0.5 to 2 and from solutions with a certain amount of alkali hydroxide an acid- N-(2)hydroxypropylpyridinium-double-four-ring silicate hydrate is obtained by crystallization.     

N-(P-羟甲基苯基)咔唑丙烯酸酯的合成和聚合

<正> 为了深入认识含咔唑基单体的光敏性与聚合性的关系,在本系列含咔唑基化合物的基础上,合成了两个新单体:N-(p-羟甲基苯基)咔唑丙烯酸酯和N-(P-羟甲基苯基)咔唑甲基丙烯酸酯,并研究了其聚合行为。 化合物Ⅰ、Ⅱ、Ⅲ和聚合物的合成,反应式如下:     

Synthesis of new azo compounds based on N-(4-hydroxypheneyl)maleimide and N-(4-methylpheneyl)maleimide

Maleic anhydride was reacted with p-aminophenol and p-toluidine in the presence of di-phosphorus pentoxide (P?O?) as a catalyst to produce two compounds: N-(4-hydroxy-phenyl)maleimide (I) and N-(4-methylphenyl)maleimide (II). The new azo compounds I(a-c) and II(a-c) were prepared by the reaction of I and II with three different aromatic amines, namely aniline, p-aminophenol and p-toluidine. The structures of these compounds were confirmed by CHN, FT-IR, 1H-NMR, 13C-NMR, mass spectrum and UV/Vis spectroscopy.     

Synthesis of N-(fluoro phenyl) maleamic acids and N-(fluoro phenyl) maleimides

A series of seven N-(fluoro phenyl) maleamic acids and their N-(fluoro phenyl) maleimides were prepared by the reaction of fluoro phenyl amines ( o-, m-, and p-fluoro, 2.4-, 2.5-difluoro, 2.3.5.6-tetrafluoro and 2.3.4.5.6.-pentafluoro anilines) with maleic anhydride according to substantial modifications made to the reaction conditions used by Searle for the preparation of normal N-aryl maleimides.     

N─苯基邻苯二甲酰亚胺和N─对甲苯基邻苯二甲酰亚胺的晶体和分子结构

报道一种新类型的有机电子晶体Ｎ－苯基邻苯二甲酰亚胺（１）（Ｃ＿（１４）Ｈ＿９ＮＯ＿２）和Ｎ－对甲苯基邻苯二甲酰亚胺（２）（Ｃ＿（１５）Ｈ＿（１１）ＮＯ＿２）的晶体和分子结构，（１）属正交晶系，空间群为Ｐｃａｂ，ａ＝７．６４９（４），ｂ＝１１．６５９（２），ｃ＝２３．７３９（３）Ａ，Ｖ＝２１１７．０Ａ￣３，Ｚ＝８，Ｄ＿ｃ＝１．４０１ｇ／ｃｍ￣３，Ｍ＿ｒ＝２２３．２３，μ＝０．８８５ｃｍ￣（－１），最终偏离因子Ｒ＝０．０５３，Ｒ＿ω＝０．０４８；（２）属正交晶系，空间群为Ｐｎａ２＿１，ａ＝７．６２４（２），ｂ＝１１．２３７（１），ｃ＝１３．８５６（２）Ａ，Ｖ＝１１８７．０　Ａ３，Ｚ＝４，Ｄ＿ｃ＝１．３２８ｇ／ｃｍ￣３，Ｍｒ＝２３７．２６，μ＝２．７６４ｃｍ－１，最终偏离因子Ｒ＝０．０３６，Ｒ＿ω＝０．０３２。晶体结构测定结果表明，邻苯二甲酰亚胺的内酰亚胺碳、氮、氧原子与其苯并环共平面。化合物（２）中的甲基碳原子与取代基苯环共平面，苯并酰亚胺平面与取代苯环平面间的夹角分别为５８．４°（化合物１）和５６．２°（化合物２）。     

N-(2-苦胺基乙基)单氮杂冠醚的合成

研究并比较了氮支套索型生色冠醚1a和1b两条不同的合成路线, 结果表明, 由N-苦基乙二胺(2)与1,11-二碘-3,6,9-三氧杂十一烷进行N-烷基化环化反应, 可方便地制备N-(2-苦胺基乙基)单氮杂-12-冠-4(1a), 但按此法未能获得更大环的-15-冠-5(1b);若从N-对甲苯磺酰基乙二胺(6)或N-(2-对甲苯磺酰胺基乙基)二乙醇胺(7)出发, 经环化, 脱除对甲苯磺酰基而制得的N-(2-氨基乙基)单氮杂冠醚5a和5b分别与苦基氯反应, 则可获得高产率的生色生色冠醚11a和1b.     

N-(Arylaminosulfonyl)benzamide

N-(Arylaminosulfonyl)benzamides3 were prepared by reaction of N-chlorosulfonylbenzamide or 4-chloro-N-chlorosulfonylbenzamide, resp., with isocyclic and heterocyclic amines.

     

Synthesis and 15N- and 17O-NMR Spectra of 5-Methyl(15N2)[O2,O4-17O2]uridine (= (15N2)[O2,O4-17O2]Ribosylthymine)

The 5-methyl(¹⁵N₂)[O²,O⁴-¹⁷O₂]uridine (= (¹⁵N₂)[O²,O⁴-¹⁷O ₂]ribosylthymine; 15 ) was synthesized and analyzed by ¹⁵N- and ¹⁷O-NMR spectroscopy. (¹⁵N₂)Urea was condensed with 2,3-dibromo-2-methylpropanoyl chloride ( 3 ) and cyclized to form (¹⁵N₂)thymine ( 5 ). After glycosidation, the ¹⁷O isotopes were introduced in two separate steps: hydrolytic ring opening of 2,5′-anhydro derivative 9 and hydrolysis of 3-nitro-1H-1,2,4-triazole derivative 12 with labelled water in the presence of a strong base. The ¹⁵N- and ¹⁷O-NMR spectra (Fig.) of 15 in phosphate-buffered water serve as references for heteronuclear NMR spectra of labelled RNA fragments.     

N-(R-cyclopropyl)fluorobenzimidoyl phosphonates

Russian Journal of General Chemistry - Reaction of N-(R-cyclopropyl)benzimidoyl chloride with triethyl phosphite has yielded the corresponding N-(R-cyclopropyl)-substituted benzimidoyl phosphonates...     

Darstellung und Strukturen einiger N-(Tri-t-butoxysilyl)anilin-Derivate

Formation and Structures of N-(tri-t-butoxysilyl)aniline Compounds Para-substituted N-(tri-t-butoxysilyl)anilines (t-BuO)₃SiNRC₄H₄X-p, R = H, CH₃, with substituents of high electron affinity (X = CN, NO₂) were prepared by a one-pot reaction of tri-t-butoxychlorsilane, potassium t-butanolate and substituted anilines. Corresponding compounds with substituents of low electron affinity (X = OMe, H) preferably were prepared by metalation of anilines with sodium amide. Four crystal structures were determined. N-(tri-t-butoxysilyl)-p-nitro-aniline, N-methyl-(N-tri-t-butoxysilyl)-p-nitroaniline and N-(tri-t-butoxysilyl)-p-cyanoaniline crystallize at 298 K monoclinically, N-(tri-t-butoxysilyl)aniline crystallizes orthorhombically.     

Synthesis of N-(1H)-tetrazole sulfoximines

N-(1H)-Tetrazole sulfoximines are readily available by addition of sodium azide to the corresponding N-cyano derivatives in the presence of ZnBr2. The use of these N-(1H)-tetrazoles as intermediates in the synthesis of other N-heterocyclic sulfoximines is demonstrated.     

N-(11-羧基十一烷基)马来酰亚胺及其三聚体的合成

以顺丁烯二酸酐和12-氨基十二酸为原料,硫酸、三乙胺为脱水催化剂,经两步反应合成了N-(11-羧基十一烷基)马来酰亚胺.再在三苯基膦和苯酚作用下,N-(11-羧基十一烷基)马来酰亚胺进一步发生三聚反应合成了相应的马来酰亚胺三聚体.采用红外光谱和核磁共振谱对三聚体的结构进行了表征.     

N-(2,2,2-trinitroethyl)-N-polynitrohexaazaisowurtzitanes

Russian Chemical Bulletin - Synthetic procedures towards a series of new high energy N-(2,2,2-trinitroethyl) derivatives of polynitrohexaazaisowurtzitanes were elaborated; the properties of the...     

N-(amino-thiocarbonyl)-benzimidchloride

The reaction of nickel(II) chelates of N′,N′-disubstituted N-benzoylthioureas with thionylchloride in a non polar solvent yields N-(amino-thiocarbonyl)-benzimide chlorides.     

Zur Komplexbildung von N-(Thiocarbamoyl)benzamidinen

Complex Formation of N-(Thiocarbamoyl) benzamidines N-(Thiocarbamoyl)benzamidines 1 and N-(Thiocarbamoyl)-N′-phenyl-benzamidines 2 form in alcoholic solutions with Ni²⁺, Cu²⁺, Pd²⁺, Co³⁺, and Ag⁺ ions well crystallized chelates 1a ? h and 2a? h , respectively, with N/S coordination. The X-ray photoelectron spectra evidence the NH group as ligator in the case of chelates of 1 and the increased donor capacity compared with the isosteric oxygen ligator atom bound to nickel. This is confirmed by d-¹H-n.m.r. spectroscopy analyzing the value of ΔG_c^≠ for the rotational barrier for the Et₂N group of 1a     

Thermochemical and thermal analysis on N-(p-methylphenyl)-N'-(2-pyridyl)urea

Low temperature heat capacities of N-(p-methylphenyl)-N'-(2-pyridyl)urea were determined by adiabatic calorimetry method in the temperature range from 80 to 370 K. It was found that there was not any heat anomaly in this temperature region. Based on the experimental data, some thermodynamic function results were obtained. Thermal stability and decomposition characteristics analysis of N-(p-methylphenyl)-N'-(2-pyridyl)urea were carried out by DSC and TG. The results indicated that N-(p-methylphenyl)-N'-(2-pyridyl)urea started to melt at ca. 426 K (153°C) and the melting peak located at 447.01 K (173.86°C). The melting enthalpy was 204.445 kJ mol^-1 (899.6 J g^-1). The decomposition peak of N-(p-methylphenyl)-N'-(2-pyridyl)urea was found at 499.26 K (226.11°C) from DSC curve. This result was similar with that from TG and DTG experiment, in which the mass loss peak was determined as 500.4 K (227.2°C). This revised version was published online in August 2006 with corrections to the Cover Date.