Study of internal motions through N.Q.R. in 6-Chloropyridin-2-ol

Chlorine-35 n.q.r, has been observed for the first time in 6-chloropyridin-2-ol and its temperature dependence has been studied from 77 K to room temperature. The torsional frequencies and their temperature dependences have been calculated by using Bayer's theory with and without Tatsuzaki's modification.

Alterations in the activities of the enzymes of proline metabolism in Ragi (Eleusine coracana) leaves during water stress

Free proline content in Ragi (Eleusine coracana) leaves increased markedly (6 to 85 fold) as the degree of water stress, created by polyethylene gylcol treatment, was prolonged There was also a marginal increase in soluble proteins in the stressed leaves as compared to that in the controls. Water stress stimulated the activities of ornithine aminotransferase and pyrroline-5-carboxylate reductase, the enzymes of proline biosynthesis and markedly inhibited the enzymes involved in proline degradation viz., proline oxidase and pyrroline-5-carboxylate dehydrogenase. These results suggest that increase in free proline content of Ragi leaves could be due to enhanced activities of the enzymes synthesizing proline but more importantly due to severe inhibition of the enzymes degrading proline. These observations establish for the first time, the pathway of proline metabolism in plants by way of detection of the activities of all the enzymes involved and also highlight the role of these enzymes in proline accumulation during water stress.

Structure of (6S,13bR)-1,2,3,5,6,13b-hexahydro-6-isopropyl-8H-pyrrolo[1',2':1,2]pyrazino[3,4,-b]quinazoline-5,8-dione

C17H19N302, monoclinic, P21, a = 5.382 (1), b = 17.534(4), c = 8.198(1)/L ,8 = 100.46(1) °, Z= 2, d,, = 1.323, dc= 1.299 Mg m-3, F(000) = 316, /~(Cu .Ka) = 0.618 mm -1. R = 0.052 for 1284 significant reflections. The proline-containing cispeptide unit which forms part of a six-membered ring deviates from perfect planarity. The torsion angle about the peptide bond is 3.0 (5) ° and the peptide bond length is 1.313 (5)A. The conformation of the proline ring is Cs-Cf~-endo. The crystal structure is stabilized by C-H... O interactions.

Amide-catalysed isomerisation of 5,6-dihydroisoquinolines: a novel synthesis of 1,2-dihydroisoquinolines

Knoevenagel condensation of 2-acylcyclohexanones or 2-ethoxycarbonylcyclohexanone with either cyanoacetamide or malononitrile followed by silver salt alkylation gave the 5,6,7,8-tetrahydroisoquinolines (3a–i). Chromic acid oxidation of the 5,6,7,8-tetrahydroisoquinolines (3a–i) to the corresponding tetralones (4a–i) followed by sodium borohydride reduction and p-toluenesulphonic acid-catalysed dehydration of the resulting alcohols (5a–i) gave the 5,6-dihydroisoquinolines (6a–i). Reaction of 5,6-dihydroisoquinolines (6a–g) with potassium amide in liquid ammonia gave a mixture of the 1,3-dihydroisoquinolines (7a–g) and the isoquinolines (8a–g). The C-1 unsubstituted 1,2-dihydroisoquinoline (7c) was found to be very unstable. In the case of the 5,6-dihydroisoquinolines (6h and 6i), reaction of potassium amide in liquid ammonia resulted in a mixture of 1-aminoisoquinoline (9) and the isoquinolines (8h and 8i). All the above compounds have been characterised by spectral data. A probable pathway for the formation of the 1,2-dihydroisoquinolines (7a–g) and the isoquinolines (8a–i) is suggested.

Structure of 2-(2,6-Dimethoxyphenyl)-2,5-dimethylbicyclo[3.2. l]octane-6,8-dione

C18H2204, orthorhombic, P212~21, a = 7.343 (4), b = 11.251 (4), c = 19.357 (4)A, Z = 4, Dr, ' = 1.20, D e = 1.254 g cm -3, F(000) = 648, p(Mo Ka) = 0.94 cm -~. X-ray intensity data were collected on a Nonius CAD-4 diffractometer and the structure was solved by direct methods. Full-matrix least-squares refinement gave R = 0.052 (R w = 0.045) for 1053 observed reflections. The stereochemical configuration at C(2) has been shown to be 2-exo-methyl-2-endo- (2,6-dimethoxyphenyl), i.e. (3) in contrast to the structure (2) assigned earlier based on its ~H NMR data.

Intermolecular charge-transfer complexes of macrocyclic polyethers with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone

The interactions of benzo-15-crown-5, dibenzo-18-crown-6, and dibenzo-24-crown-8 with 2,3-dichloro-5,6-dicyano- 1,4-benzoquinone have been studied in methylene chloride by using spectroscopic methods. These crown ethers from 1:l molecular complexes with the acceptor. The magnitudes of association constants and thermodynamic parameters of complexation are indicative of cooperative interaction of oxygens with the acceptor.

Oxidation of Abel's ketone and similar spiroketones with 2,3-dichloro-5,6-dicyano-1,4- benzoquinone (DDQ). Synthesis of novel tropone derivatives

The structure of the novel product obtained from the oxidation of Abel's ketone (1a) and similar spiroketones (1b–d) with 2, 3-dichloro-5, 6-dicyano-1,4-benzoquinone has been determined on basis of spectral data (i.r., n.m.r., and mass)

Modulation of succinate dehydrogenase in response to environmental stress conditions of hypobaria and hypoxia

1. 1. An increase in the oxidation of succinate by hepatic mitochondria in rats exposed to hypoxia (O2-N2; 1:9, v/v) or hypobaria (0.5 atm) was observed which appears to be due to modification of the activity of the rate-limiting succinate dehydrogenase [succinate: (acceptor) oxidoreductase, EC 1.3.99.1].

Pressure dependence of 35Cl nuclear quadrupole resonance in 2,5-, 2,6- and 3,5-dichlorophenols

Pressure dependence of the 35Cl Nuclear Quadrupole Resonances (N.Q.R.) in 2,5-, 2,6- and 3,5-dichlorophenols (DCP) has been studied up to a pressure of about 6·5 kbar at room temperature. While the pressure dependence of the two resonance lines in 2,6-DCP is essentially similar, the lower frequency line in 2,5-DCP is almost pressure independent and the higher frequency line shows a linear variation with pressure upto about 3·5 kbar but shows a negative pressure coefficient beyond this pressure. The two lines in 3,5-DCP have a non-linear pressure dependence with the curvature changing smoothly with pressure. The pressure coefficient for both lines becomes negative beyond a pressure of 5 kbar. The pressure dependence of the N.Q.R. frequencies is discussed in relation to intra- and inter-molecular contacts. Also, a thermodynamic analysis of the data is carried out to determine the constant volume temperature derivative of the N.Q.R. frequency.

Structure of (4S)-2,4-dimethyl-1,2-dihydropyrazino[2,1-b]quinazoline-3(4H),6-dione

C13HI3N302, orthorhombic, P2~2121, a = 17.443 (5), b = 11.650 (4), c = 5.784 (1)/~, Z = 4, d m = 1.456, d c = 1.429 Mg m -3, F(000) = 512, g(Cu Ka) = 0.843 mm-L The R index is 0.040 for 1358 significant reflections. The structure is stabilized by C-H...O interactions. The N-methylated eis peptide group which forms part of a six-membered ring is non-planar. The torsion angle about the peptide bond is -6.1 (4) ° and the peptide bond length is 1.337 (3) A.

Amide catalysed facile isomerization of 5,6-dihydroisoquinolines: synthesis of stable 1,2-dihydroisoquinolines

Stable 1,2-dihydroisoquinolines have been synthesized by an amide catalysed novel isomerization reaction of 5,6-dihydroisoquinolines.

Synthesis of 4,6-(and 5,7-)dimethoxy-3,3-dimethyl-1-indanones

Grignard reaction of ethyl 3-(3,5-dimethoxyphenyl)-propionate (4) followed by cyclodehydration of the carbinol (5) with conc H2SO4 gave 4,6-dimethoxy-3,3-dimethylindane (6). Oxidation of the indane (6) with CrO3-pyridine complex in methylene chloride gave 4,6-dimethoxy-3,3-dimethylindan-1- one (1) in high yield. Conjugate addition of methyl magnesium iodide to methyl α-cyano-β-methyl-3,5-dimethoxycinnamate (11), prepared from 3,5-dimethoxyacetophenone (10) by Knoevenagel condensation, resulted in methyl 2-cyano-3-(3,5-dimethoxyphenyl)-3,3-dimethylpropionate (12). Refluxing the ester (12) with aq DMSO containing sodium chloride gave the corresponding nitrile (15) which underwent Höesch reaction to yield 5,7-dimethoxy-3,3-dimethylindan-1-one (2).

The structure of the monobarium salt of glucose 6-phosphate heptahydrate

C6H11o9P2-.Ba2+.7H2o, M, = 521.5, is monoclinic, space group P21, a = 11.881 (4), b = 8.616 (5), c = 8.350 (4) A,B = 102.95 (3)0, Z = 2, U = 833.0 A 3, d m = 2.09, d c = 2.08 Mg m -3, F(000) = 516. Mo Ka (u = 0.034 mm -1) intensity data. R is 0.068 for 1603 reflections. Of the two endocyclic C-O bonds in the glucose ring, C(5)-O(5) [1.463 (23)] is longer than C(1)-O(5) [1.395 (23)A]. The pyranose sugar ring takes a 4C1 chair conformation. The Cremer-Pople puckering parameters are, 0 = 6.69 o, Q = 0.619 A and 0 = 263.7o. The conformation about the exocyclic C(5)-C(6) bond is gauche-gauche, in contrast to gauche-trans observed in the structure of glucose 1-phosphate. The phosphate ester bond, P-O(6), is 1.61 (1)A. It is similar in length to the 'high-energy' P~O bond in phosphoenolpyruvate. The Ba 2÷ ion is surrounded by nine O atoms within a distance of 2.95 A, of which seven are from water molecules. There is an intramolecular hydrogen bond between the sugar hydroxyl 0(4) and phosphate oxygen O(12).

Structure of pentacyclo[7.4.2.02,6.06,15.011,14]pentadec-4-ene-7,13-dione, a novel pentacyclic C15 quinane system

C 15H 1602 (a synthetic precursor to dodecahedrane), monoclinic, P21/n, a = 12.171 (5), b = 6.976(5), c = 13.868 (3) A, B = 102.56 (3) ° , Z = 4, D m = 1.30, D c = 1.318 g cm -3, F(000) = 488, g(Mo K¢t) = 0.92 cm- 1. Intensity data were collected on a Nonius CAD-4 diffractometer and the structure was solved by direct methods. Full-matrix least-squares refinement gave R = 0.077 (R w = 0.076) for 1337 observed reflections. All the five-membered rings are cis fused and have envelope (C s symmetry) conformations.