Preparation,X-ray crystal structure and 13C- and 1H-NMR study of 1-methyl-2-(N-methyl-N-phenylglycyl)-3-(N-methylanilino)indole

Reaction of N-methylaniline with 40% glyoxal yields 1-methyl-2-(N-methyl-N-phenylglycyl)-3-(N-methylanilino)indole ( 1a ) as the main product together with 1-methyl-3-(N-methylanilino)indole ( 1b ). The reaction appears to be general for aromatic secondary amines since N-ethylaniline and N-phenylbenzylamine yield the corresponding indoles. The structure of 1a has been verified by single crystal X-ray diffraction. Compound 1a (C₂₅H₂₅N₃O) crystallized in the triclinic space group Pl? with cell dimensions a = 10.085(3)Å, b = 10.371(3)Å, c = 11.908(5)Å, α = 74.2(3)°, β = 74.7(3)° and γ = 60.7(2)° with Z = 2. The complete ¹H and ¹³C nmr assignment of indoles 1a and 1b was achieved from two-dimensional HETCOR and COSY spectra with the aid of homonuclear and heteronuclear double resonance experiments.     

Internal rotation around the isopropyl-nitrogen bond and stable conformations of S-methyl-N,N-di-isopropyldithiocarbamate,dichlorotin(IV) bis(N,N-di-isopropyldithiocarbamate) and related compounds

Temperature dependent proton magnetic resonance spectra of dichloro- and dimethyltin(IV) bis(N,N-di-isopropyl-dithiocarbamate) ( 1 and 2 , respectively), dimethylchlorotin(IV) N,N-di-isopropyldithiocarbamate ( 3 ), dimethyltin(IV) bis(N-isopropyldithiocarbamate) ( 4 ), S-methyl-N,N-di-isopropyldithiocarbamate ( 5 ) and S-methyl-N-isopropyldithiocarbamate ( 6 ) were measured in halogenated hydrocarbons or CS₂. The internal rotation around the isopropyl–nitrogen bond of 1, 2, 3 and 5 is restricted below ?30°C, and that of 4 and 6 below ?70°C; 1, 2 and 3 exist as only one conformer in dichloromethane, while 5 exists as two rotational isomers with respect to the isopropyl–nitrogen bond with a mole ratio of about 2·7:1·0 in CS₂ below ?30°C. At this temperature, 6 exists as two stereoisomers in CS₂ with a mole ratio of about 1·2:1·0, although there is no stereoisomer in 4 . From these results, possible conformations of the compounds at low temperature are proposed and the assignments of each proton signal are described.     

New Discoveries of Heating Effect on Trimethylsilyl Derivatization for Simultaneous Determination of Steroid Endocrine Disrupting Chemicals by GC–MS

Most previously described derivatization procedures with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) or N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) for the GC–MS analysis of steroids, such as estrone (E1), 17β-estradiol (E2), estriol (E3) and 17α-ethynylestradoil (EE2), used a heating process of 45–80 °C (typically 70 °C) for 25–60 min, usually in combination with a catalyst. However, we found that it is not necessary to heat and add catalyst for the derivatization with BSTFA. Best reaction conditions for MSTFA are heating at 70 °C for 10 min. Derivatization of EE2 using MSTFA without heating results in three products: TMS-E1, mono-TMS-EE2 and di-TMS-EE2.

     

Nitrogen-15 nuclear magnetic resonance spectroscopy. N?H proton exchange reactions of urea and substituted ureas

Proton-coupled nitrogen-15 NMR spectra of urea, N-methylurea, N,-N′-dimethylurea, N-methyl-N′-benzylurea and N-phenylurea have been obtained at natural abundance level in neutral, basic and acidic solutions at 25°C. Base-catalyzed N? H proton exchange of the ? NH₂ group of N-methylurea in water was found to be 1.5 times faster than that for the -NH- group, while the corresponding acid-catalyzed exchange is 7.5 times faster. Comparison of urea and N,-N′-dimethylurea in water shows urea to be 10 times faster in base but 2 times slower in acid. The ratio of the base-catalyzed N? H proton exchanges of the two -NH- groups of N-methyl-N′-benzylurea in dimethyl sulfoxide is close to unity, whereas the CH₃NH- group exchanges 4 times faster in acid. Similarly, the C₆H₅NH- group of N-methyl-N′-phenylurea exchanges 50 times faster than the CH₃NH- group in base and about 3 orders of magnitude slower in acid. The results are rationalized by consideration of steric and electronic effects.     

4,4-Disubstituierte Imidazol-Derivate aus der Umsetzung von 3-Amino-2H-azirinen mit Salicylamid

4,4-Disubstituted Imidazole Derivatives from the Reaction of 3-Amino-2H-azirines with Salicylamide Reaction of 3-amino-2H-azirines 1a–c with salicylamide ( 7 ) in MeCN leads to imidazoles 10 and 11 in different rates, depending on the conditions. In the case of 1a and 1b, 11a and 11b , respectively, have been obtained as the main product at 50°; in reactions at 80°, 10a and 10b are the favored products (Tables 1 and 2). 2,2-Dimethyl-3-(N-methyl-N-phenylamino)-2H-azirine ( 1c ) reacts with 7 in MeCN mainly to 2-(2-hydroxyphenyl)-5,5-dimethyl-3,5-dihydroimidazol-4-one ( 10a ); in boiling toluene, 11c is formed with low preference (Table 3). The structure of the products has been established by spectroscopic means, and in the case of 10b and 11c , by X-ray crystallography. Two different reaction mechanisms for the formation of the products are discussed (Scheme 2).     

Homopolymerization of <Emphasis Type="Italic">N</Emphasis>-vinylamides in the presence of water-soluble initiators and preparation of polyelectrolytes from the polymerization products

Homopolymerization of vinylformamide and N-methyl-N-vinylacetamide in water in the presence of 2,2′-azobis(2-methylpropanediamine) dihydrochloride and of the hydrogen peroxide-ammonium hydroxide system was examined. Hydrolysis of polyvinylformamide, poly-N-methyl-N-vinylacetamide, and poly-N-vinylacetamide with hydrochloric acid at 100°C was studied.     

Synthesis, properties, and molecular structure of nitro-substituted N-methyl-N-nitroanilines

Ten mono-, di-, and trinitro derivatives of N-methyl-N-nitroaniline were synthesized and studied by spectral, electrooptical, and quantum-chemical methods. Three of these derivatives, N-methyl-N,2,3-trinitroaniline, N-methyl-N,2,5-trinitroaniline, N-methyl-N,3,5-trinitroaniline, were also examined by the X-ray diffraction method. The N-nitroamino group in their molecules is almost planar, the N⁷-N⁸ bond is shortened, and the N⁸ atom is characterized by a strong deficit of electron density. The dihedral angle between the planes of the N-nitroamino group and the benzene ring is 56°–92°, which makes conjugation between these fragments impossible. The N-nitroamino group in the examined compounds acts as a weak electron donor with respect to the nitro groups in the aromatic ring; the mechanism of this effect is inductive.     

Synthesis of pyrrolidine and tetrahydroazonine derivatives from <Emphasis Type="Italic">N</Emphasis>-[bis(ethoxycarbonyl)methyl]tetrahydropyridinium bromide and methyl acetylenedicarboxylate

The reaction of N-methyl-N-(diethoxycarbonyl)methyltetrahydropyridinium bromide with dimethyl acetylenedicarboxylate in the presence of triethylamine at room temperature afforded 1,2-dimethyl 1-ethyl 2-[(3-vinyl-1-methyl-3-phenyl-2-ethoxycarbonyl)pyrrolidin-2-yl]-ethene-1,1,2-tricarboxylate in 25% yield. Its structure was proved by XRD analysis. At cooling to −20°C the pyrrolidine yield signifi cantly decreased and 3,4-dimethyl 2,2-diethyl 1-methyl-7-phenyl-1,5,8,9-tetrahydro-2H-azonine-2,2,3,4-tetratcarboxylate was obtained in 31% yield.     

1,2-fused pyrimidines. V. Synthesis of 1-alkyl or phenyl-2H-dipyrido-[1,2-a:2′,3′-d]pyrimidine-2,5(1H)-diones

The reaction of 2-[(N-acyl, N-alkyl or phenyl)amino]-4H-pyrido[1,2-a]pyrimidin-4-ones 8a-g with the N,N-dimethylformamide/phosphorus oxychloride Vilsmeier reagent 1 (95°, 90 minutes) afforded 1-alkyl or phenyl-2H-dipyrido[1,2-a:2′,3′-d]pyrimidine-2,5(1H)^?diones, 3-alkyl substituted or not, 10a-g . The starting compounds 8 were prepared by treating 2-amino-4H-pyrido[1,2-a]pyrimidin-4-ones N-alkyl substituted 7a,b or N-phenyl substituted 4 with excess anhydrides (130°, 7 hours) when the 2-(alkylamino) derivatives 7 were used in the reaction, compounds 8 were obtained along with very small amounts of 3-acyl-2-(alkylamino)-4H-pyrido[1,2-a]pyrimidin-4-ones 9 .     

N,N′-(1,2-phenylene)bis­(pyridine-2-carboxamide) and N,N′-(1,2-cyclohexanediyl)bis(pyridine-2-carbox­amide) toluene hemisolvate

The crystal structures of N,N′-(1,2-phenyl­ene)­bis­(pyridine-2-carbox­amide), C₁₈H₁₄N₄O₂, (I), and N,N′-(1,2-cyclo­hexane­diyl)­bis­(pyridine-2-carbox­amide) have been determined, the latter compound as the toluene hemisolvate, C₁₈H₂₀N₄O₂·0.5C₇H₈, (II). In (I), the benzene ring is nearly coplanar with one of the pyridine rings and forms a dihedral angle of 59.4 (1)° with the other. However, in (II), the dihedral angle of the two pyridine rings is 70.0 (1)°.     

Base Hydrolysis of Pentaaminecobalt(III) Complexes: The [CoX(dien) (dapo)]n+ system. Part 1. Syntheses,structures, configuration,and spectroscopy

Oxygentation of aqueous solutions of Co^III in presence of stoichiometric amounts of N-(2-aminoethyl)ethane-1,2-diamine (dien) and 1,3-diaminopropan-2-ol (dapo) produces μ-peroxocobalt(III) dimers. Acid cleavage (HCI) yields mer-exo(H)-, mer-endo (H)-, unsym-fac-exo(OH)-, and unsym-fac-endo(OH)-[CoCl(dien)(dapo)]²⁺ ( A–D )(X = Cl), resp. and unsym-fac-[Co-(dien)(dapo-N,N′,O)]³⁺ ( G ). Isomer seperation was achieved by fractional crystallization as ZnCl and ClO salts and by ion-exchange chromatography. The corresponding bromo, azido, nitrito-O, nitro-N, thiocyanato, hydroxo, and aqua complexes were also synthesized. Optically resolved samples were prepared for chiral compounds, and the complexes were structurally characterized by X-ray analyses ($ \mathop {\it \Lambda} \limits^ \to $(?)_436(CD) -A (X = N₃)), ($ \mathop {\it \Delta} \limits^ \to $(?)₄₃₆(CD) -B ). (X = N₃), $ \mathop {\it \Delta} \limits^ \to $ (+)₄₃₆(CD) -B by their chiroptical properties, and by ¹³C-NMR spectroscopy supported by ¹H-NMR, IR, CD, and UV/VIS spectroscopy. $ \mathop {\it \Lambda} \limits^ \to $(?)_436(CD)-mer-exo(H)-[Co(N₃)(dien)(dapo)](hydrogen di-O-benzoyl-L-tartrate)₂.4 H₂O crystallizes in the orthorhombic space group P2₁2₁2₁, a = 7.676(1) Å, b = 19.457(1) Å, c = 34.702(2) Å. $ \mathop {\it \Lambda} \limits^ \to $(?)_436(CD)-mer-endo(H)-[Co(N₃)(dien)(dapo)] (hydrogen di-O-benzoyl-L-tartrate)₂.2.75 H₂O crystallizes in the triclinic space group P1, a = 8.062(3) Å b = 10.296(1) Å, c = 15.056(2) Å, alpha = 80.55(1)°, β = 85.18(2)°, γ = 89.10(2)°. $ \mathop {\it \Delta} \limits^ \to $(+)_436(CD)-mer-endo(H)-[Co(N₃)(dien)(dapo)](hydrogen di-O-benzoyl-L-tartrate)₂. 5.75 H₂O crystallizes in the triclinic space group P1, a = 7.742(1) Å, b = 10.014(1) Å, c = 18.045(2) Å, α = 99.57(1)°, β = 92.87(1)°, γ = 102.56(1)°. The absolute configurations of the three cations were determined unambiguously. Interconversions of the various isomers and derivatives and structural, configurational, and spectroscopic aspects are discussed in detail.     

Some reactions of 2-(4-substitutedphenyl)-2-(N-methyl-N-4-substitutedbenzamido) acetic acids

In situ generated 2,4-diaryl substituted münchnones from 2-(4-substitutedphenyl)-2-(N-methyl-N-4-substitutedbenzamido)acetic acids react with acetic anhydride in the presence of 2-nitromethylene thiazolidine, which is most likely acting as a base, and unexpectedly undergo a Dakin–West type reaction and a concurrent autoxidation reaction leading to the formation of (E)-1-(N,4-dimethylbenzamido)-1-(4-fluorophenyl)prop-1-en-2-yl acetate, 4-substitutedphenyl-N-methyl-N-(4-substitutedbenzoyl) benzamides and p-substituted benzoic acids. In addition, a novel and efficient access to N-acyl urea derivatives is described by the reaction between 2-(4-substitutedphenyl)-2-(N-methyl-N-4-substitutedbenzamido)acetic acids and cyclohexyl, isopropyl carbodiimides in the presence of a base. The structures of all new products were identified on the basis of NMR and IR spectra, along with X-ray diffraction data and HRMS measurements.     

Organometallic compounds : LXIX. Synthesis and properties of the first chiral triorganostannyl-manganese complex

Methyl-1-naphthylphenylstannyltetracarbonyl(diphenyl-N-methyl-N-(S)-1-phenylethylaminophosphine)manganese (I) has been prepared by two different routes from racemic methyl-1-naphthylphenyltin chloride. Fractional recrystallizations yielded two diastereomeric fractions with fx205-1 = +40.3° and —71.4°, respectively, which have identical NMR and IR spectra.     

Study on side-chain second-order nonlinear optical polyimides based on novel chromophore-containing diamines. I. Synthesis and characterization

Side-chain second-order nonlinear optical polyimides were prepared from four novel chromophore-containing diamines and 4,4′-(hexafluoroisopropylidene) diphthalic anhydride by a traditional two-step process that included a solution polycondensation followed by a chemical imidization. The four diamines were 2,4-di-β-aminoethylamino-6-p-nitrophenylamino-1,3,5-triazine (M1), 4-nitro-4′-[N-(4,6-di-β-aminoethylamino)-1,3,5-triazin-2-yl]amino azobenzene (M2), 2,4-di-p-aminophenylamino-6-p-nitrophenylamino-1,3,5-triazine (M3), and 4-nitro-4′-[N-(4,6- di-4-aminophenylamino)-1,3,5-triazin-2-yl]amino azobenzene (M4). All the polyimides exhibited maximum ultraviolet-visible absorption peaks or shoulders of chromophores at wavelengths below 400 nm, and those based on M1 and M3 were transparent at wavelengths above 450 nm, whereas those based on M2 and M4 were transparent at wavelengths above 550 nm. The polyimides possessed high glass-transition temperatures (T_g's; 218–247 °C) and thermal decomposition temperatures. They were soluble in aprotic solvents such as N-methyl-2-pyrrolidone, N,N-dimethyl acetamide, N,N-dimethyl formamide, and dimethylsulfone. Some were even soluble in common low-boiling-point solvents such as tetrahydrofuran. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4330–4336, 1999     

A Modified Water-Gas Shift Reaction. The Decomposition of Alkyl Formate in the Presence of Water Using a Ruthenium Carbonyl

Alkyl formates in the presence of water were rapidly decomposed to H₂, CO₂ and the corresponding alcohols using Ru₃(CO)₁₂ and KOAc as catalyst. Based on the hydrogen gas produced, a turnover rate as fast as 8446/h for ethyl formate at 140°C was observed. The catalyst system was also active for the decomposition of other alkyl formates. The rate of decomposition increased both with increasing amount of KOAc and with decreasing number of carbon atom in the alkyl group of the formate. In addition to Ru₃(CO)₁₂, several other transition metal complexes RuCl₃, RuCl₂(PPh₃)₃, Os₃(CO)₁₂, H₂Os₃(CO)₁₀, RhCl₃, and RhCl(PPh₃)₃, were active in the catalytic decomposition of alkyl formates, although their activities varied greatly. The Ru₃(CO)₁₂-KOAc system also catalyzed the reduction of nitrobenzene by HCOOEt-H₂O to aniline in EtOH and to a mixture of N-phenylformamide and N-methyl-N-phenylformamide in HCOOEt. Under coditions the same as for the hydrogenation of nitrobenzene, ethylene styrene and cyclohexenone were reduced to the corresponding alkanes, whereas 1-hexene and 1-octene were isomerized to the corresponding 2-alkene products.     

Anionic synthesis of aromatic amide and carboxyl functionalized polymers. Chain-end functionalization of poly(styryl)lithium with N,N-diisopropyl-4-(1-phenylethenyl)benzamide

The novel syntheses of N,N-diisopropyl-4-benzoylbenzamide, N,N-diisopropyl-4-(1-hydroxy-1-phenylethyl)benzamide, and N,N-diisopropyl-4-(1-phenylethenyl)benzamide ( 1 ) are described. ω-Amidopolystyrene ( 2 ) was synthesized in quantitative yields by the reaction of poly(styryl)lithium with stoichiometric amounts of N,N-diisopropyl-4-(1-phenylethenyl)benzamide ( 1 ) in toluene/tetrahydrofuran (4 : 1 v/v) at −78°C. Deblocking of the amide protecting group by acid hydrolysis quantitatively provides the corresponding aromatic carboxyl chain-end functionalized polystyrene ( 3 ). The functionalization agent and functionalized polymers were characterized by HPLC, thin-layer chromatography, size exclusion chromatography, vapor phase osmometry, spectroscopy (¹H-NMR, ¹³C-NMR, and FTIR), potentiometry, and elemental analysis. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1233–1241, 1998     

(N-methyl-N-alkoxymethylaminomethyl)dialkoxysilanes and bis[N-methyl-N-(dialkoxysilylmethyl)amino]methanes

(N-methyl-N-alkoxymethylaminomethyl)-dialkoxysilanes and bis[N-methyl-N-(dialkoxymethyl)amino]methanes were first obtained by the interaction of (N-methylaminomethyl) dialkoxy-R-silanes with chloromethyl alkyl ethers in yields of 40–67% and 10–25 %, respectively.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 382–383, February, 1995.     

Studies on the hydrolysis of cyclophosphamide II. Isolation and characterization of intermediate hydrolytic products

Two new products of hydrolysis of cyclophosphamide in water at 100°, N-(2-chloroethyl)-N' -(3-phosphatopropy l)ethylenediamine and N-(2-hydroxyethyl)-N -(3-phosphatopropyl)ethylene-diamine, have been isolated after 30 minutes, and 6 hours of reaction times, respectively. These products have been shown to be intermediates leading to the formation of N-(2-hydroxyethyl)-N'-(3-hydroxypropyl)ethylenediamine, the principal ultimate product of cyclophosphamide hydrolysis. The nature of these new products supports the previously postulated mechanism involving an intramolecular alkylation as the initial step in the hydrolytic process although the pathway appears to be an unlikely model for the metabolic transformations of cyclophosphamide in vivo.     

[1-芳基甲羰基-2-(1,2,4-三唑-1-基)]乙基-N,N-二烷基二硫代氨基甲酸酯衍生物的合成、结构表征及生物活性研究

以芳香基三唑类杀菌剂三唑酮为先导物设计并合成了5个含N,N-二烷基二硫代氨基甲酸酯的芳香三唑类化合物, 通过元素分析、红外光谱、核磁共振氢谱和质谱对其结构进行了表征. 用X射线单晶衍射测定了[α-(4-甲氧基苯甲酰基)-2-(1,2,4-三唑-1-基)]乙基-N,N-二甲基二硫代氨基甲酸酯的晶体结构, 晶体属于三斜晶系, 空间群, 晶胞参数为: a＝0.73482(15) nm, b＝1.1051(2) nm, c＝1.1209(2) nm, α＝90.32(3)°, β＝101.97(3)°, γ＝105.13(3)°, V＝0.8578(3) nm³, Z＝2, D_c＝1.357 g/cm³, F(000)＝368, µ＝0.324 mm^－1. 生物测试结果显示这5种有机化合物都具有杀菌性和植物生长调节活性     

Synthesis and characterization of N -(alky(aryl)carbamothioyl)cyclohexanecarboxamide derivatives and their Ni(II) and Cu(II) complexes

N-(R-carbamothioyl)cyclohexanecarboxamides (R: diethyl, di-n-propyl, di-n-butyl, diphenyl and morpholine-4) and their Ni(II) and Cu(II) complexes have been synthesized and characterized by elemental analyses, FT-IR and NMR methods. N-(diethylcarbamothioyl)cyclohexanecarboxamide, HL¹, C₁₂H₂₂N₂OS, crystallizes in the orthorhombic space group P2₁2₁2₁, with Z = 4, and unit cell parameters, a = 6.6925(13) Å, b = 9.0457(18) Å, c = 22.728(5) Å. The conformation of the HL¹ molecule with respect to the thiocarbonyl and carbonyl moieties is twisted, as reflected by the torsion angles O1–C6–N2–C5, C6–N2–C5–N1 and S1–C5–N2–C6 of 1.68°, ?67.47° and 115.50°, respectively. The structure of HL¹ also shows a delocalization of the π electrons of the thiocarbonyl group over the C–N bonds. The ring puckering analysis shows that the cyclohexane ring has a chair conformation. The bis(N-(morpholine-4-carbonothioyl)cyclohexane carboxamido)nickel(II) complex, Ni(L⁵)₂, C₂₄H₃₈N₄NiO₄S₂, crystallizes in the monoclinic space group P2₁/c, with Z = 4, and unit cell parameters, a = 16.919(3) Å, b = 8.3659(17) Å, c = 19.654(4) Å, β = 107.43(3)°. Ni(L⁵)₂ is a cis-complex with a slightly distorted square-planar coordination of the central nickel by two oxygen and two sulfur atoms.