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Copyright of Journal of Laboratory Medicine / Laboratoriums Medizin is the property of De Gruyter and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

This synthetic and structural work describes a series of half-sandwich cyclopentadienylruthenium(II) complexes containing the diphosphazane ligands [(CH)P]N R ( R=H:H dppa, 1a; R=CH: dppma, 1b; R=CH: dppea, 1c; R=Li:Li dppa, 1d). Treatment of 1a, d with CpRuCl(PPh) (Cp=η-CH, Ph=CH, 2) in a molar ratio of 1:1 in boiling aromatic hydrocarbons affords the neutral complexes CpRuCl(H dppa) ( 3) and CpRu( dppa)PPh ( 6). The ionic complexes [CpRu(PhP-N R-(PPh)PPh)Cl ( R=CH: 4a; R=CH: 4b) are formed by the reaction of 1b, c with 2. One pot reactions of 1a-c with 2 in the presence of NHPF in boiling CHOH give only the ionic compounds [CpRu(PhP-NR-PPh)(PPh)]PF ( R=H, CH, CH; 5a-c). The sulfur dioxide and hydride complexes [CpRu(H dppa)η-SO]Cl ( 7) and CpRu(H)H dppa ( 8) are obtained by the interaction of 3 with SO or NaOCH. All compounds are characterized as far as possible by IR, Raman,P{H} NMR,H NMR,C{H} NMR, FD mass spectra, and their conductivity in CHCl solution. The X-ray crystal structures of 3 and 5a reveal that the P(1)-N(1)-P(2) angle of the coordinated ligand 1a in both complexes is reduced to about 100° in comparison to free uncoordinated 1a (119°). This small angle leads to a short P(1)-P(2) bond distance of 259.4 pm in 3 and 254.3 pm in 5a. The molecules of 3 are connected by intermolecular (NH...Cl) hydrogen bridging bonds forming chains along the z axis of the unit cell. The crystals of 5a contain two independent pairs of ions in the unit cell ( Z=8). In 5a no hydrogen bonds exist between the NH-groups and the PF anions. [ABSTRACT FROM AUTHOR]

The title compounds were prepared as follows: tert.-butyl-indane ( 10) was formylated to give a 72:28 mixture of the aldehydes 23a and 23b which were submitted to a Knoevenagel-Doebner condensation to afford the cinnamonic acids 24. From the mixture, the pure stereoisomer 24a was obtained by one crystallization in 57% yield. Its methylester 27a could be quantitatively dealkylated to the methylester 8 by treatment with AlCl in toluene. Cyclization to the indanone 9 was then performed via the propionic acid 7 with polyphosphoric acid in 95% yield. From 9 the carboxymethyl derivative 30 was obtained by treatment with dimethylcarbonate and NaH. The second synthone 4-chlormethyl-indane ( 19) was prepared from the corresponding alcohol 18 (in 82% yield) which in turn could be obtained from methylester 17 by reduction with LiAlH. The latter was accessible in 75% yield by dealkylation of ester 13. [ABSTRACT FROM AUTHOR]

The isomeric dimethyl methylbenzoates 5, obtained from the bromides via Grignard reactions with dimethylcarbonate, were reduced with LiAlH to the hydroxymethyl derivatives 6. The latter were then transformed both to the benzylchlorides 7 (with SOCl) and to the aldehydes 8 (with pyridinium chlorochromate). Knoevenagel-Doebner reaction of 8 afforded the acrylic acids 9 which (after hydrogenation to 11) were cyclized to the desired indanones 12 with polyphosphoric acid. On the other hand, 12c and 12e were prepared from dimethyl 3-chloropropiophenone ( 14) by warming with sulfuric acid. After NaH-catalyzed reaction with dimethylcarbonate, the indanones 12 gave the ketoesters 15 which then could be hydrogenated to the indanes 16. All reactions proceeded with satisfactory to excellent yields (60-90%). [ABSTRACT FROM AUTHOR]

The isomeric methyl phthalaldehydic acids 11 were obtained from phthalides 4 by bromation ( NBS) to the 3-bromo derivatives 7 and subsequent hydrolysis with water. 4 in turn were accessible from dimethyl methyl benzoates 1 by dibromination with NBS and subsequent thermical cyclization to the bromo derivatives 3 which, on catalytic dehalogenation, afforded the phthalides 4. Reaction of 11 with methanol or ethanol gave the pseudo-esters 13 and 14, resp. Short treatment of 11 with diazomethane on the other hand yielded the methyl formyl benzoates 15b to 15e. Prolonged reaction (several hours) gave the oxiranyl compounds 17; in addition, the acetonyl derivatives 18 were also found, obviously formed by a double methylene insertion into 15. All reactions proceeded with good to excellent yields. [ABSTRACT FROM AUTHOR]

The spiroketones 19, 21, 24, 27, and 31 were prepared by cyclisation of the dicarboxylic acids and their acid chlorides, resp., ( 18, 20, 22, 23, 25, 26, 28, and 30) with polyphosphoric acid ( PPA) or SnCl. The latter compounds were synthesized by alkylation of the appropriate β-keto esters 10, 11, 12, and 13 with the 'benzyl chlorides' 14, 15, 16, and subsequent retro-Claisen-reaction. The spiro compounds 21a and 39 were obtained by PPA-cyclisation of the keto acids 35 and 38, which in turn were prepared by aldol-reaction of the ketones s-hydrindacen-1-on and 9a with phthalaldehydic acid to the olefinic keto acids 33 and 36 followed by catalytic hydrogenation. [ABSTRACT FROM AUTHOR]

The spiroketones 9, 16, and 28 were prepared by cyclisation of the carboxylic acids 7c, 13b, and 25c and their acid chlorides, resp. ( 7d, 13c, and 25d) with polyphosphoric acid ( PPA) or SnCl. The precursors of the latter compounds were synthesized by alkylation of the appropriate β-ketoester 1 or 2 with the 'benzylchlorides' 3 or 4 with NaH in DMF. Subsequent hydrogenation with Pd/C led to the desired alkylated indane-esters. The chiral compounds 11, 17, and 31 were obtained by Friedel-Crafts acetylation. The chiral disubstituted 2,2′-Spirobiindanes 22 and 36 were prepared from the ketones 20 and 32/33 by catalytic reduction followed by Friedel-Crafts acetylation. [ABSTRACT FROM AUTHOR]

The title compound 6 a was prepared by cyclisation of the diacid 4 b. The diester 4 a of 4 b was synthesized by alkylation of 2 with 3 and following Retro- Claisen-reaction. After catalytic reduction of 6 a to 8 a two identical substituents were introduced by Friedel-Crafts-reaction ( 28). By transformation of the acetylgroups several other derivates ( 29-36) could be obtained. The unsymmetrical compounds (e.g. 21) were prepared from 20, whose precurser was the spiroketon 10 a. [ABSTRACT FROM AUTHOR]

Copyright of Archives of Toxicology is the property of Springer Nature and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Copyright of Archives of Toxicology is the property of Springer Nature and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)