jeanflop/post_ocr_correction2 huggingface dataset:
réduite en dérivé tetrahydroisoquinolique 4 par le borohydrure de sodium en milieu méthanolique. La N-méthylation de l'isoquinoléine 4 en 1-(3'-benzyloxybenzyl)-2-méthyl-6-méthoxy-7-benzyloxy-1,2,3,4-tetrahydroisoquinolène 5 est réalisée par réaction avec l'acide formique en solution dans un mélange (1/1) de méthanol et de dichlorométhane; après refroidissement à -5°C du mélange réactionnel, l'intermédiaire iminium est réduit en 5. La 1-(3'-hydroxybenzyl)-2-méthyl-6-méthoxy-7-hydroxy-1,2,3,4-tetrahydroisoquinolène 6 ou canelilline est isolée par débenzylation de 5 par chauffage à 100°C dans un mélange (1/1) d'acide acétique et d'acide chlorhydrique. Dans les mêmes conditions, la débenzylation de l'amine 4 conduit à la 3'-hydroxybenzyl)-6-méthoxy-7-hydroxy-1,2,3,4-tetrahydroisoquinolène 7 ou norcanelilline. Une réaction de Mannich, en présence d'aldehyde formique dans un mélange (1/1) de méthanol et de dichlorométhane appliquée à la norcanelilline 7, fournit un mélange équimolinique de 2,9-dihydroxy-3-méthoxy-tetrahydroprotoberberine 8 et de 2,11-dihydroxy-3-méthoxy-tetrahydroprotoberberine 9. Dans des conditions réactionnelles identiques, le composé benzyl 4 conduit au seul dérivé 9 avec un très faible rendement. Suite à la synthèse déjà décrite (Oger, 1992) de la noranicanine 10 nous avons utilisé cette matière première pour obtenir deux autres protoberbérines originales isolées chez Aniba canelilla [Oger (à paraître)], la manibacanine 11 et la pseudomanibacanine 12. La cyclisation intramoléculaire de la 1-(3'-hydroxybenzyl)-6,7-diméthoxy-1,2,3,4-tetrahydroisoquinolène 10, selon la réaction de Mannich, dans les conditions décrites ci-dessus, conduit aux mélanges (1/4) de la 9-hydroxy-2,3-diméthoxy-tetrahydroprotoberberine 11 et de 11-hydroxy-2,3-diméthoxy-tetrahydroprotoberberine 12. Cette méthode nous a donné permis d'obtenir, avec des rendements importants, l'ensemble des nouveaux dérivés isolés d'Aniba canelilla. Les potentialités pharmacologiques pourront dorénavant être évaluées in vivo. En ce qui concerne l'origine des composés 6-9 et 11-12, une étude biosynthétique approfondie impliquant la recolte des graines de cette espèce andine pourrait révéler chez Aniba canelilla les fonctions d'un système enzymatique inédit impliqué dans la biosynthèse des isoquinolines. Note remise le 2 décembre 1992, acceptée le 8 janvier 1993. Références bibliographiques A. FOURNET, B. VAGNEUR, P. RICHOMME et J. BRUNETON, Aryl-2 et alkyl-2 quinolines nouvelles isolées d'une Rutacée bolivienne : Galipea longiflora, Can. J. Chem., 67, 1989, p. 2116-218. M. LEBÈUF, A. RANAIVO, A. CAVÉ et H. MOSKOWITZ, La velutécryptine, nouvel alcaloïde isoquinolique isolé de Cryptocarya velutina, J. Nat. Prod., 52, 1989, p. 516-521. J.-M. OGER, O. DUVAL, P. RICHOMME,
aux mélanges (1/4) de la 9-hydroxy-2,3-diméthoxy-tetrahydroprotoberberine 11 et de 11-hydroxy-2,3-diméthoxy-tetrahydroprotoberberine 12. Cette méthode nous a donné permis d'obtenir, avec des rendements importants, l'ensemble des nouveaux dérivés isolés d'Aniba canelilla. Les potentialités pharmacologiques pourront dorénavant être évaluées in vivo. En ce qui concerne l'origine des composés 6-9 et 11-12, une étude biosynthétique approfondie impliquant la recolte des graines de cette espèce andine pourrait révéler chez Aniba canelilla les fonctions d'un système enzymatique inédit impliqué dans la biosynthèse des isoquinolines. Note remise le 2 décembre 1992, acceptée le 8 janvier 1993. Références bibliographiques A. FOURNET, B. VAGNEUR, P. RICHOMME et J. BRUNETON, Aryl-2 et alkyl-2 quinolines nouvelles isolées d'une Rutacée bolivienne : Galipea longiflora, Can. J. Chem., 67, 1989, p. 2116-218. M. LEBÈUF, A. RANAIVO, A. CAVÉ et H. MOSKOWITZ, La velutécryptine, nouvel alcaloïde isoquinolique isolé de Cryptocarya velutina, J. Nat. Prod., 52, 1989, p. 516-521. J.-M. OGER, O. DUVAL, P. RICHOMME, J. BRUNETON et H. GUINAUDEAU, (R)-(+)-noranicanine, a new type of trioxygenated benzylisoquinoline, isolation and synthesis, Heterocycles, 34, 1992, p. 17-20. J.-M. OGER, A. FARDEAU, P. RICHOMME, A. FOURNET et H. GUINAUDEAU, Nouveaux alcaloïdes isoquinoliques isolés d'une Lauracée bolivienne : Aniba canelilla H.B.K. (à paraître). S. TEITEL et A. BROSSI, An improved synthesis of various racemic polyphenolic tetrahydroisoquinoline alkaloids, J. Heterocycl. Chem., 5, 1968, p. 825-829. CEPM, UFR des Sciences Médiques et Pharmaceutiques, 16, boulevard Daviers, 49045 Angers Cedex, France. 1/2 H2O has been prepared through a metathesis reaction using AgH3PO4 as starting material. This salt is orthorhombic, Pnam, with Z = 8 and the following unit-cell dimensions: a= 19.568(10), b= 10.545(7), c = 7.773 (5) Å. The crystal structure was performed by using 2,220 reflections with a final R value of 0.037. As previously observed in all atomic arrangements of acidic diphosphates, the anions interconnected by strong hydrogen bonds assemble themselves as to build an infinite network. In the title compound, one observes the formation of layers or [H2P2O7]2 entities, perpendicular to the a direction. The two independent phosphoric groups have an internal mirror symmetry. Abridged English Version — INTRODUCTION. — Larbot, Norbert and Cot described chemical preparation and reported
improved synthesis of various racemic polyphenolic tetrahydroisoquinoline alkaloids, J. Heterocycl. Chem., 5, 1968, p. 825-829. CEPM, UFR des Sciences Médiques et Pharmaceutiques, 16, boulevard Daviers, 49045 Angers Cedex, France. 1/2 H2O has been prepared through a metathesis reaction using AgH3PO4 as starting material. This salt is orthorhombic, Pnam, with Z = 8 and the following unit-cell dimensions: a= 19.568(10), b= 10.545(7), c = 7.773 (5) Å. The crystal structure was performed by using 2,220 reflections with a final R value of 0.037. As previously observed in all atomic arrangements of acidic diphosphates, the anions interconnected by strong hydrogen bonds assemble themselves as to build an infinite network. In the title compound, one observes the formation of layers or [H2P2O7]2 entities, perpendicular to the a direction. The two independent phosphoric groups have an internal mirror symmetry. Abridged English Version — INTRODUCTION. — Larbot, Norbert and Cot described chemical preparation and reported crystal data for a rubidium dihydrogen diphosphate, given as anhydrous, Rb2H2P2O7. The authors reported for this compound an orthorhombic unit cell: a= 19.55(4), b= 10.534(3), c = 7.784 (3) Å and assigned Pnma as space group. No structural investigation was performed at this time. During an investigation at 298 K of the NH3-K2O-H3PO4-H4P2O7-H2O system, Frazier, Dillard, Thrasher and Waerstad characterized three acidic diphosphates, (NH4)1.6K2.4(H2P2O7)2.H2O, (NH4)3K(H2P2O7)2 and (NH4)3K3(HP2O7)2. Crystal data for these three salts were later on reported by Waerstad and Frazier. The unit-cell dimensions measured for the first one: a = 19.22 (2), b= 10.39(1), c = 7.64 (1) Å as well as the two possible space groups, Pnma or Pnam, show its very probable isotypy with Rb2H2P2O7, but suggest this last compound may be a hemihydrate. The basic purpose of the present investigation was to investigate the network built by the [H2P2O7] groups in the rubidium salt. In all previously determined atomic arrangements of diphosphates including acidic anionic entities, [H3P2O7], [H2P2O7]2 or [HP2O7]3, these groups are always interconnected by strong hydrogen bonds as to build infinite networks having various geometries, chains, ribbons, layers or 3D-arrangements. The hydrogen bonds responsible for the cohesion of such networks are strong ones, corresponding
of the NH3-K2O-H3PO4-H4P2O7-H2O system, Frazier, Dillard, Thrasher and Waerstad characterized three acidic diphosphates, (NH4)1.6K2.4(H2P2O7)2.H2O, (NH4)3K(H2P2O7)2 and (NH4)3K3(HP2O7)2. Crystal data for these three salts were later on reported by Waerstad and Frazier. The unit-cell dimensions measured for the first one: a = 19.22 (2), b= 10.39(1), c = 7.64 (1) Å as well as the two possible space groups, Pnma or Pnam, show its very probable isotypy with Rb2H2P2O7, but suggest this last compound may be a hemihydrate. The basic purpose of the present investigation was to investigate the network built by the [H2P2O7] groups in the rubidium salt. In all previously determined atomic arrangements of diphosphates including acidic anionic entities, [H3P2O7], [H2P2O7]2 or [HP2O7]3, these groups are always interconnected by strong hydrogen bonds as to build infinite networks having various geometries, chains, ribbons, layers or 3D-arrangements. The hydrogen bonds responsible for the cohesion of such networks are strong ones, corresponding to O-O distances in many cases shorter than the O-O distances observed in the constituting P2O4 tetrahedra. Note présentée par Bernard RAVEAU. In the case of the title compound, one observes the existence of layers we describe below. Another valuable result of the present investigation is to remove the ambiguity between the results obtained by the previous investigators concerning the state of hydration since our study shows clearly the existence of a hemihydrate. PREPARATION. — Recently we described chemical preparation and crystal structure of Ag2H2P2O7. This salt, now well characterized and rather easy to produce, was used as starting material in the present investigation for the preparation of Rb2H2P2O7.1/2 H2O according to the following reaction: 2RbCl + Ag2H2P2O7 → Rb2H2P2O7 + 2 AgCl A slurry, in water, of the sparingly water soluble silver salt was slowly added with an aqueous solution of rubidium chloride in the stoichiometric ratio. After removing silver chloride by filtration, the solution was slowly evaporated at room temperature till the crystallization of Rb2H2P2O7.1/2 H2O. Crystals appear as elongated orthorhombic prisms. DETERMINATION OF THE STRUCTURE. — An irregular prism fragment (0.48 x 0.32 x 0.38 mm) was used for the intensity data collection performed with a Nonius
between the results obtained by the previous investigators concerning the state of hydration since our study shows clearly the existence of a hemihydrate. PREPARATION. — Recently we described chemical preparation and crystal structure of Ag2H2P2O7. This salt, now well characterized and rather easy to produce, was used as starting material in the present investigation for the preparation of Rb2H2P2O7.1/2 H2O according to the following reaction: 2RbCl + Ag2H2P2O7 → Rb2H2P2O7 + 2 AgCl A slurry, in water, of the sparingly water soluble silver salt was slowly added with an aqueous solution of rubidium chloride in the stoichiometric ratio. After removing silver chloride by filtration, the solution was slowly evaporated at room temperature till the crystallization of Rb2H2P2O7.1/2 H2O. Crystals appear as elongated orthorhombic prisms. DETERMINATION OF THE STRUCTURE. — An irregular prism fragment (0.48 x 0.32 x 0.38 mm) was used for the intensity data collection performed with a Nonius CAD 4 diffractometer operating with silver radiation (0.5608 Å) monochromatized with a graphite plate. 5,344 reflections were explored with a 3°/40 scan of 1.40° with a maximum scan time of 90 sec. in a theta range: 2 < θ < 30.0°. Among them, 4,825 were non-zero reflections. Intensity reference reflections have no significant variation during the data collection. Crystal structure was solved using a direct method for the location of heavy atoms (Rb and P) and successive difference-Fourier for oxygen and hydrogen atoms. In the early stages of the structure determination, it appears clearly that this salt was in fact an hemihydrate, Rb2H2P2O7.1/2 H2O and that in one of the two independent H2P2O7 groups, the bonding oxygen atom, O (L 2), is disordered and occupies in fact two different positions in the mirror plane with occupancy rates refined to the values of 0.215 and 0.285. The final refinements of this arrangement show clearly that the proper space group is the centrosymmetric Pnma. Hydrogen atoms of the anionic entities were easily located but those of the water molecule could not be localized with a sufficient degree of certainty. The final refinements (on F) were performed using 2,220 reflections corresponding to I
have no significant variation during the data collection. Crystal structure was solved using a direct method for the location of heavy atoms (Rb and P) and successive difference-Fourier for oxygen and hydrogen atoms. In the early stages of the structure determination, it appears clearly that this salt was in fact an hemihydrate, Rb2H2P2O7.1/2 H2O and that in one of the two independent H2P2O7 groups, the bonding oxygen atom, O (L 2), is disordered and occupies in fact two different positions in the mirror plane with occupancy rates refined to the values of 0.215 and 0.285. The final refinements of this arrangement show clearly that the proper space group is the centrosymmetric Pnma. Hydrogen atoms of the anionic entities were easily located but those of the water molecule could not be localized with a sufficient degree of certainty. The final refinements (on F) were performed using 2,220 reflections corresponding to I > 4 o (I) with a unitary weighting scheme. All non-hydrogen atoms were anisotropically refined, the hydrogen ones, isotropically. The final R value is 0.037 (Rw = 0.039 and S = 2.438). SDP system was used for all calculations. Final atomic coordinates are given in table I. DESCRIPTION OF THE STRUCTURE. — Due to the organization of the strong hydrogen-bond network connecting the H2P2O7 groups, this atomic arrangement must be described as a layer structure. Thick layers built by the (H2P2O7)n macroanion spread perpendicular to the a direction approximately centred by planes x = 1/4 and 3/4, while all the other atoms building the arrangement are located in the mirror planes situated in z = 1/4 and 3/4. Figure 1 gives a projection of this structure along the b direction. The two independent H2P2O7 groups have rather different behaviors. Both have a mirror internal symmetry, their bonding oxygen atoms being located in the mirror planes. One of these two phosphoric groups built by the P (1) O4 tetrahedra has a quite usual configuration with inside the PO4 tetrahedron, as can be expected, three types of P-O bonds, a long corresponding to the P-O-P bridge (1.613 Å), an intermediate one (1.560
STRUCTURE. — Due to the organization of the strong hydrogen-bond network connecting the H2P2O7 groups, this atomic arrangement must be described as a layer structure. Thick layers built by the (H2P2O7)n macroanion spread perpendicular to the a direction approximately centred by planes x = 1/4 and 3/4, while all the other atoms building the arrangement are located in the mirror planes situated in z = 1/4 and 3/4. Figure 1 gives a projection of this structure along the b direction. The two independent H2P2O7 groups have rather different behaviors. Both have a mirror internal symmetry, their bonding oxygen atoms being located in the mirror planes. One of these two phosphoric groups built by the P (1) O4 tetrahedra has a quite usual configuration with inside the PO4 tetrahedron, as can be expected, three types of P-O bonds, a long corresponding to the P-O-P bridge (1.613 Å), an intermediate one (1.560 Å) for the P-OH bond and two short ones (1.490 and 1.501 Å) for the normal P-O bonds. The average values for the P-O distances and the O-P-O angles are respectively 1.541 Å and 109.2°. In the second H2P2O7 group built by the P(2)O4 tetrahedra, the situation is different; the central oxygen atom is disordered and must be described as two fragments, O(L2) and O(L2') both located on the mirror plane with the occupancy rates reported in the previous section. This type of disorder is commonly observed in diphosphate groups having a linear P-O-P bond, but rarely for other types of internal symmetries. The hydrogen bonds interconnecting these H2P2O7 entities correspond to O-O distances (2.519 and 2.508 Å) shorter than the O-O distance average inside the PO4 tetrahedra. Figure 2 reports schematically the two-dimensional macroanion as observed in this arrangement. The four independent rubidium atoms, all located in the mirror planes, have various oxygen coordinations; two of them, Rb(2) and Rb(4) have eight neighbors, Rb(3) has ten and Rb(1) twelve. As said above, the hydrogen atoms of the water molecule could not be located with certainty, but the examination of the neighbors of this molecule shows clearly that the hydrogen
central oxygen atom is disordered and must be described as two fragments, O(L2) and O(L2') both located on the mirror plane with the occupancy rates reported in the previous section. This type of disorder is commonly observed in diphosphate groups having a linear P-O-P bond, but rarely for other types of internal symmetries. The hydrogen bonds interconnecting these H2P2O7 entities correspond to O-O distances (2.519 and 2.508 Å) shorter than the O-O distance average inside the PO4 tetrahedra. Figure 2 reports schematically the two-dimensional macroanion as observed in this arrangement. The four independent rubidium atoms, all located in the mirror planes, have various oxygen coordinations; two of them, Rb(2) and Rb(4) have eight neighbors, Rb(3) has ten and Rb(1) twelve. As said above, the hydrogen atoms of the water molecule could not be located with certainty, but the examination of the neighbors of this molecule shows clearly that the hydrogen bridge must be established with the oxygen O(E21) its only oxygen neighbor within a range of 3.2 Å. The main interatomic distances and bond angles in this arrangement are given in table II. Drawings were performed using the STRUPLO system [7]. INTRODUCTION. — Antérieurement à ce travail, la préparation chimique et quelques données cristallographiques sur un dihydrogéno-phosphate de rubidium ont été décrites par Larbot, Norbert et Cot [1]. Ce sel était donné comme anhydre, avec les paramètres de réseau suivants : a= 19,55(4), b= 10,534(3), c=7,784(3) Å. Le groupe spatial suggéré par les auteurs était Pna21. Il faut aussi signaler que durant l'étude à 298 K du système NH3-K2O-H4P2O7H3PO4-H2O effectuée par Frazier Dillard, Thrasher et Waerstad [2], trois diphosphates acides furent caractérisés: (NH4)1.6 K2.4 (H2P2O7)2. H2O, (NH4)3 (H2P2O7)2 et (NH4)3K3 (HP2O7)2. Les caractéristiques cristallines de ces trois diphosphates déterminées plus tard par Waerstad et Frazier [3] montrent que le premier d'entre eux possède la maille suivante : a= 19,22(2), b = 10,39 (1), c = 7,64 (1) Å, et que deux groupes spatiaux sont possibles : Pna21 ou Pnam. L'ensemble de ces données très proches de celles rapportées pour le sel de rubidium [1] suggère une isotypie mais laissent planer
et quelques données cristallographiques sur un dihydrogéno-phosphate de rubidium ont été décrites par Larbot, Norbert et Cot [1]. Ce sel était donné comme anhydre, avec les paramètres de réseau suivants : a= 19,55(4), b= 10,534(3), c=7,784(3) Å. Le groupe spatial suggéré par les auteurs était Pna21. Il faut aussi signaler que durant l'étude à 298 K du système NH3-K2O-H4P2O7H3PO4-H2O effectuée par Frazier Dillard, Thrasher et Waerstad [2], trois diphosphates acides furent caractérisés: (NH4)1.6 K2.4 (H2P2O7)2. H2O, (NH4)3 (H2P2O7)2 et (NH4)3K3 (HP2O7)2. Les caractéristiques cristallines de ces trois diphosphates déterminées plus tard par Waerstad et Frazier [3] montrent que le premier d'entre eux possède la maille suivante : a= 19,22(2), b = 10,39 (1), c = 7,64 (1) Å, et que deux groupes spatiaux sont possibles : Pna21 ou Pnam. L'ensemble de ces données très proches de celles rapportées pour le sel de rubidium [1] suggère une isotypie mais laissent planer un doute sur l'état d'hydratation. La principale motivation du présent travail était la détermination de la géométrie du réseau formé par les entités anioniques [H2P2O7]2-. Dans tous les arrangements atomiques renfermant des groupements diphosphoriques acides, [H3P2O7]-1, [H2P2O7]2 ou [HP2O7]3-, ces derniers sont toujours reliés par des liaisons hydrogène fortes correspondant à des distances O-O dans bien des cas plus courtes que celles observées à l'intérieur des groupements PO4 constituant l'anion. Ces enchaînements infinis peuvent adopter diverses géométries telles que chaîne, ruban, plan ou même réseau tridimensional. Il nous semblait intéressant de déterminer quel type d'association anionique existe dans le présent sel de rubidium. Le présent travail va montrer que dans ce cas les entités anioniques s'assemblent de façon à former des couches infinies. Ce travail a aussi le mérite de lever l'ambiguité sur l'état d'hydratation en montrant que le sel décrit est bien un hémihydrate, Rb2H2P2O7 1/2 H2O. PRÉPARATION. — Récemment, nous avons décrit la préparation chimique et la structure cristalline de Ag2H2P2O7 [4]. Ce dernier sel, maintenant bien caractérisé, a été utilisé comme matière première dans la présente étude pour la préparation de Rb2H2P2O7.1/2 H2O selon le schéma réactionnel suivant : 2 RbCl + Ag2H2P2O7 → Rb2H2P2O7 + 2
à des distances O-O dans bien des cas plus courtes que celles observées à l'intérieur des groupements PO4 constituant l'anion. Ces enchaînements infinis peuvent adopter diverses géométries telles que chaîne, ruban, plan ou même réseau tridimensional. Il nous semblait intéressant de déterminer quel type d'association anionique existe dans le présent sel de rubidium. Le présent travail va montrer que dans ce cas les entités anioniques s'assemblent de façon à former des couches infinies. Ce travail a aussi le mérite de lever l'ambiguité sur l'état d'hydratation en montrant que le sel décrit est bien un hémihydrate, Rb2H2P2O7 1/2 H2O. PRÉPARATION. — Récemment, nous avons décrit la préparation chimique et la structure cristalline de Ag2H2P2O7 [4]. Ce dernier sel, maintenant bien caractérisé, a été utilisé comme matière première dans la présente étude pour la préparation de Rb2H2P2O7.1/2 H2O selon le schéma réactionnel suivant : 2 RbCl + Ag2H2P2O7 → Rb2H2P2O7 + 2 AgCl TABLEAU II Principales distances interatomiques (Å) et angles de liaison (°). Les déviations standard sont données entre parenthèses. Main interatomic distances (Å) and bond angles (°) with their Esd in parentheses. Les groupements P2O7. The P2O7 groups. Le tétraèdre P(1)O4. The P(1) O4 tetrahedron. Le tétrahédre P(2)O4. The P(2)O4 tetrahedron. P(2) O(E21) O (E 22) O(E23) O(L2) O(L2') O(E21) 1,494(3) 2,513(5) 2,558(5) 2,571(8) 2,507(10) O (E 22) 111,6(2) 1,545(4) 2,460(5) 2,624(9) 2,192(8) O (E 23) 118,2(2) 108,5(3) 1,487(4) 2,262(6) 2,672(9) O(L2) 111,5(3) 112,2(4) 93,6(4) 1,615(3) 0,836(15) O(L2') 107,5(5) 87,9(5) 119,1(5) 30,0(5) 1,613(4) P(2)-P(2) 3,009(2) P(2)-O (E 22)-H(2) 110(5) P(2)-O(L2')-P(2) 137,7(8) P(2)-O(L2)-P(2) 137,3(6) Les liaisons hydrogène. The hydrogen-bonds. O-H. O O-H H. O O-0 O-H .O O(E 11)-H(1).O(E23) 0,94(7) 1,65(8) 2,508(5) 149(7) O (E 22)-H(2). O (E 13) 1,12(9) 1,41(9) 2,519(5) 169(8) Une suspension de Ag2H2P2O7 dans l'eau, maintenue en agitation mécanique constante, est additionnée lentement d'une solution de chlorure de rubidium dans les proportions requises par la réaction ci-dessus. Après élimination par filtration du chlorure d'argent formé, la solution obtenue est évaporée lentement à température ambiante jusqu'à l'apparition de prismes orthorhombiques de Rb2H2P2O7.1/2 H2O. DÉTERMINATION DE LA STRUCTURE. — Un diffractomètre Nonius CAD 4 fonctionnant à la longueur d'onde