Ethyl 4-(3-hydroxyphenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate

In the molecular structure of the title compound, C21H25NO4, the dihydropyridine ring adopts a flattened boat conformation while the cyclohexenone ring is in an envelope conformation. In the crystal structure, molecules are linked into a two-dimensional network parallel to (10 (1) over bar) by N-H center dot center dot center dot O and O-H center dot center dot center dot O hydrogen bonds. The network is generated by R-4(4)(30) and R-4(4)(34) graph-set motifs.

Ethyl 6-chloro-2-oxo-4-phenyl-1,2-dihydroquinoline-3-carboxylate

In the title compound,C18H14ClNO3,the dihydroquinolin-2-one ring system is almost planar (r.m.s.deviation = 0.033 angstrom).The carboxylate plane and the phenyl group are twisted away from the dihydroquinolin-2-one ring system by 50.3(1) and 64.9(1)degrees,respectively.In the crystal structure, inversion-related molecules form R-2(2)(8)dimers via pairs of N-H center dot center dot center dot O hydrogen bonds.

Ethyl 6-chloro-2-methyl-4-phenylquinoline-3-carboxylate

In the title compound, C19H16ClNO2, the quinoline ring system is planar (r.m.s. deviation = 0.008 angstrom). The phenyl group and the -CO2 fragment of the ester unit form dihedral angles of 60.0 (1) and 60.5 (1)degrees, respectively, with the quinoline ring system.

Effect of substitution on molecular conformation and packing features in a series of aryl substituted ethyl-6-methyl-4-phenyl-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylates

The supramolecular structures of eight aryl protected ethyl-6-methyl-4-phenyl-2-thioxo-1,2,3,4 tetrahydropyrimidine-5-carboxyl ates were analyzed in order to understand the effect of variations in functional groups on molecular geometry, conformation and packing of molecules in the crystalline lattice. It is observed that the existence of a short intra-molecular C-H center dot center dot center dot pi interaction between the aromatic hydrogen of the aryl ring with the isolated double bond of the six-membered tetrahydropyrimidine ring is a key feature which imparts additional stability to the molecular conformation in the solid state. The compounds pack via the cooperative involvement of both N-H center dot center dot center dot S=C and N-H center dot center dot center dot O=C intermolecular dimers forming a sheet like structure. In addition, weak C-H center dot center dot center dot O and C-H center dot center dot center dot pi intermolecular interactions provide additional stability to the crystal packing.

Ethyl 6-chloro-2-[(2-chloro-7,8-dimethylquinolin-3-yl)methoxy]-4-phenylquino line-3-carboxylate

In the title compound, C30H24Cl2N2O3, the two quinoline ring systems are almost planar [maximum deviations = 0.029 (2) and 0.018 (3) angstrom] and the dihedral angle between them is 4.17 (8)degrees. The dihedral angle between the phenyl ring and its attached quinoline ring is 69.06 (13)degrees. The packing is stabilized by C-H center dot center dot center dot O, C-H center dot center dot center dot N, weak pi-pi stacking [centroid-centroid distances = 3.7985 (16) and 3.7662(17) angstrom] and C-H center dot center dot center dot pi interactions.

Isomerisations of substituted β-keto-esters - Part II. Isomerisation of ethyl 1-ethoxycarbonyl 2oxocyclopentyl acetate into 2, 3-diethoxycarbonylcyclohexanone

A mechanism for the isomerisation of ethyl 1-ethoxycarbonyl-2-oxocyclopentylacetate (I) into a cyclohexane β-keto-ester as proceeding through an intermediate bicyclic /gb-diketone (VII) has been considered as an alternative mechanism to one earlier suggested.1 The determination of the structure of the isomerised β-keto-ester as 2, 3-diethoxycarbonylcyclohexanone (V) has provided support for the earlier mechanism.

Insights into conformational and packing features in a series of aryl substituted ethyl-6-methyl-4-phenyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate

The supramolecular structures of eight aryl protected ethyl-6-methyl-4-phenyl-2-oxo-1,2,3,4-tetrahydropyrimidine- 5-carboxylates have been analyzed to determine the role of different functional groups on the molecular geometry, conformational characteristics and the packing of these molecules in the crystal lattice. Out of these the para fluoro substituted compound on the aryl ring exhibits conformational polymorphism, due to the different conformation of the ester moiety. This behaviour has been characterized using both powder and single-crystal X-ray diffraction, optical microscopy and differential scanning calorimetry performed on both these polymorphs. The compounds pack via the cooperative interplay of strong N-H center dot center dot center dot O=C intermolecular dimers and chains forming a sheet like structure. In addition, weak C-H center dot center dot center dot O=C and C-H center dot center dot center dot pi interactions impart additional stability to the crystal packing.

Structure of Ethyl 5-Methoxy-3-phenyl-2-indolecarboxylate

C18H17NO3, M r = 295"34, monoclinic, C2/c, a = 11.689 (2), b = 22.934 (4), c = 11.592 (2) A, fl=100.16(3) ° , V =3058.8(8) A 3, Z=8, D,n= 1.30 (5), Dx = 1.28 Mg m -3, A(Mo Ka) = 0.7107 A, tz(Mo Ka) = 0.094 mm- 1, F(000) = 1248, T = 300 K, final R = 0.046 for 1849 observed reflections [I > 30"(/)]. The indole nucleus is slightly bent along the C(8)---C(9) bond. The phenyl ring connected to the indole moiety is rotated about the C(3)---C(10) bond by 45.8 (3) °. The carboxyl group makes a dihedral angle of 8.1 (4) ° with the mean plane of the indole moiety. Centrosymmetrically related pairs of molecules are linked through hydrogen bonds across the centre of symmetry and form dimers.

3-Ethyl-4-methyl-1H-pyrazol-2-ium-5-olate

The title compound, C(6)H(10)N(2)O, is a zwitterionic pyrazole derivative. The crystal packing is predominantly governed by a three-center iminium-amine N(+)-H center dot center dot center dot O(-)center dot center dot center dot H-N interaction, leading to an undulating sheet-like structure lying parallel to (100).

Ethyl 6-methyl-2-sulfanylidene-4-[4(trifluoromethyl)phenyl]-1,2,3,4-tetrahyd ropyrimidine-5-carboxylate

The title compound, C(15)H(15)F(3)N(2)O(2)S, adopts a conformation with an intramolecular C-H center dot center dot center dot pi interaction. The dihedral angles between the planes of the 4-(trifluoromethyl) phenyl and ester groups with the plane of the six-membered tetrahydropyrimidine ring are 81.8 (1) and 16.0 (1)degrees, respectively. In the crystal structure, intermolecular N-H center dot center dot center dot S hydrogen bonds link pairs of molecules into dimers and N-H center dot center dot center dot O interactions generate hydrogen-bonded molecular chains along the crystallographic a axis.

Analysis of aromatic amines by high-performance liquid chromatography with pre-column derivatization by 2-(9-carbazole)-ethyl-chloroformate

2-(9-Carbazole)-ethyl-chloroformate (CEOC), a novel pre-column fluorescence derivatization reagent, has been developed for the analysis of aromatic amines. Taking five monocyclic aromatic amines (o-toluidine, aniline, 3,4-dimethylaniline, N-ethyl-p-toluidine, and p-phenylenediamine) as testing compounds, derivatization conditions such as pH of borate buffer, reaction time and fluorescent tagging reagent concentration have been investigated. By a one-step procedure, CEOC reacts readily with the aromatic amines to form stable derivatives with excitation and emission wavelengths, respectively, at 293 and 360 nm. This derivatization reaction could be finished within 20 min even at room temperature. The peak shapes of the derivatized aromatic amines can be improved greatly without any addition of competition amines into the mobile phase. Furthermore, this method can offer excellent quantitative precision with high tolerance of the matrix of samples. (C) 2003 Elsevier B.V. All rights reserved.

Determination of peptides and amino acids from wool and beer with sensitive fluorescent reagent 2-(9-carbazole)-ethyl chloroformate by reverse phase high-performance liquid chromotography and liquid chromotography mass spectrometry

A new method for the sensitive determination of amino acids and peptides using the tagging reagent 2-(9-carbazole)-ethyl chloroformate (CEOC) with fluorescence (FL) detection has been developed. Identification of derivatives was carried out by liquid chromotography mass spectrometry. The chromophore in the 2-(9-fluorenyl)-ethyl chloroformate (FMOC) reagent was replaced by carbazole, which resulted in a sensitive fluorescence lerivatizing agent CEOC. CEOC can easily and quickly label peptides and amino acids. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography. Studies on derivatization demonstrate excellent derivative yields over the pH range 8.8-10.0. Maximal yields close to 100% are observed with three- to fourfold molar reagent excess. Derivatives exhibit strong fluorescence and allow direct injection of the reaction mixture with no significant disturbance from the major fluorescent reagent degradation by-products, such as 2(9-carbazole)-ethanol and bis-(2-(9-carbazole)-ethyl) carbonate. In addition, the detection responses for CEOC derivatives are compared to those obtained with FMOC. The ratios AC(CEOC)/AC(FMOC) = 1.00-1.82 for fluorescence (FL) response and AC'(CEOC)/AC'(FMOC) = 1.00-1.21 for ultraviolet (UV) response are observed (here, AC and AC' are, respectively, FL and UV F response). Separation of the derivatized peptides and amino acids has been optimized on a Hypersil BDS C18 column. Excellent linear responses are observed. This method was used successfully to analyze protein hydrolysates from wool and from direct-derivatized beer. (C) 2003 Elsevier Science (USA). All rights reserved.