Substituted tartranilic acids. A new series of resolving acids

Montzka, Thomas A.; Pindell, Terry L.; Matiskella, John D.

doi:10.1021/jo01274a084

Cited by 20 publications

(10 citation statements)

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“…1). The (+)- and (−)-BTA were prepared using the procedure of Montzka et al 11 via tartaric acids with known absolute configuration. An X-ray crystallographic structure determination of the (−)-MDPV•(+)-BTA salt 5 provided the necessary proof that the configuration at C8 in (−)-MDPV was S (Fig.…”

Section: Resultsmentioning

confidence: 99%

Chiral Resolution and Absolute Configuration of the Enantiomers of the Psychoactive “Designer Drug” 3,4‐Methylenedioxypyrovalerone

et al. 2015

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Illicit rac-MDPV (3,4-methylenedioxypyrovalerone), manufactured in clandestine labs, has become widely abused for its cocaine-like stimulant properties. It has recently been found as one of the toxic materials in the so-called “bath salts”, producing, among other effects, psychosis and tachycardia in humans when introduced by any of the several routes of administration (e.g., intravenous, oral, etc). The considerable toxicity of this “designer drug” probably resides in one of the enantiomers of the racemate. In order to obtain a sufficient amount of the enantiomers of rac-MDPV to determine their activity, we have improved the known synthesis of rac-MDPV and have found chemical resolving agents, (+)- and (−)-2′-bromotetranilic acid, that gave the MDPV enantiomers in >9896% ee as determined by 1H NMR and chiral HPLC. The absolute stereochemistry of these enantiomers was determined by single-crystal X-ray diffraction studies.

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Section: Resultsmentioning

confidence: 99%

Chiral Resolution and Absolute Configuration of the Enantiomers of the Psychoactive “Designer Drug” 3,4‐Methylenedioxypyrovalerone

et al. 2015

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“…1 The absolute configuration of the latter is known from a recently performed X-ray diffraction analysis. 6 An equimolar amount of (−)-(2S,3S)-o-nitrotartranilic acid 9 and (R)-4 were dissolved with heating in 80% ethanol. The crystallized (2S,3S)-o-nitrotartranilate was analyzed for (R)-4 and (S)-4 by capillary electrophoresis using a solution of the precipitate in running buffer and ␥-cyclodextrin as chiral selector according to the method described below (for conditions see Table 1).…”

Section: Materials and Methods Analytesmentioning

confidence: 99%

“…Recrystallization from 80% EtOH (50 ml solvent for 1 g of the salt) gave (−)-(R)-4 и (−)-2S,3S)-o-nitrotartranilic acid in high purity corresponding to >99% ee referred to the con- The combined brines, enriched with (S)-4, were concentrated in vacuo, basified with NaOH, and extracted with dichloromethane. The organic layer was evaporated, the remaining oil was dissolved in EtOH, and subsequently added to a hot solution of an equimolar amount of (+)-(2R,3R)-o-nitrotartranilic acid 9 in 80% EtOH. After cooling to room temperature the solution was stored at -18°C for 2 weeks to allow crystallization of (+)-(S)-4 и (+)-(2R,3R)-o-nitrotartranilic acid.…”

Section: Materials and Methods Analytesmentioning

confidence: 99%

Chiral separation of pheniramine‐like 3‐phenyl‐3‐heteroarylpropylamines by CE and HPLC methods

et al. 2001

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Analytical CE and HPLC methods were developed for the chiral separation of halogen-substituted 3-phenyl-3-(2-pyridyl)propylamines 1-4 (1: 3-(4-fluorophenyl) approximately, 2: 3-(3,4-difluorophenyl) approximately, 3: 3-(4-chlorophenyl) approximately, 4: 3-(3,4-dichlorophenyl) approximately ), 3-(4-fluorophenyl)-3-(2-thiazolyl)propylamine (5), and 3-(4-fluorophenyl)-3-(1-benzylimidazol-2-yl)propylamine (6), which are building blocks for the preparation of very potent arpromidine-type histamine H(2) receptor agonists. All amines were enantioseparated by CE with resolutions of at least 1.8 using alpha-, beta-, or gamma-cyclodextrin (CD) as chiral selectors. With heparin as buffer additive for CE the optical antipodes of 1-4 and 6 were separated with resolutions > or = 1.8. On RP-18 columns the separation of the (+)-(S)-acetylmandelic acid amides of racemic 2 (R = 0.9, alpha = 1.07) and the thioureas prepared by addition of 6 to 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl isothiocyanate (R = 2.0, alpha = 1.20) was successful, whereas the diastereomeric ureas prepared from 3 and (+)-(S)-1-(1-naphthyl)ethyl isocyanate could not be resolved. Separation of the diastereomeric isoindoles prepared from 1-5, o-phthaldialdehyde and 2,3,4,6-tetra-O-acetyl-1-thio-beta-D-glucopyranoside was achieved on a RP-18 phase (R > or = 0.4, a > or = 1.02). Direct separation of the enantiomers of 3 and 4 was achieved on a Cyclobond I column (R > or = 0.9, alpha > or = 1.07). alpha- and beta-CD were also useful as mobile phase additives for HPLC (3 and 4: RP-18 column, beta-CD, R > or = 0.4, alpha > or = 1.03; 3: RP-18 column, alpha-CD: R = 0.5, alpha = 1.04).

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“…of (&)-lo (4.1 g, 8.5 mmol) in MeOH (125 ml) was added a warm soh. of (-)-2'-bromotartranilic acid hydrate [24] ( = (-)-2'-BTA.H20; 2.7 g, 8.5 mmol) in MeOH (25 ml). The soh.…”

Section: Experimental Partmentioning

confidence: 99%

“…was added a warm soh. of (+)-2'-bromotartranilic acid hydrate [24] ( = (+)-2'-BTA,H,O; 1.67 g, 5.2 mmol) in MeOH (15 ml). The crystals were filtered after standing at r.t. for 1 h. The filter cake was washed with MeOH (2 x 6 ml, 3 ml, r.t.) and Et20 (2 x 6 ml) to give colorless crystals which were recrystallized once from MeOH: colorless silky crystals of pure 10b.(+)-2'-BTA.H20.…”

Section: Experimental Partmentioning

confidence: 99%

ChemInform Abstract: Mammalian Alkaloids: Synthesis and O‐Methylation of (S)‐ and (R)‐3′‐ Hydroxycoclaurine and Their N‐Methylated Analogues with S‐Adenosyl‐L‐( methyl‐14C)methionine in Presence of Mammalian Catechol O‐ Methyltransferase.

He¹,

Tadić²,

Brzostowska³

et al. 1992

ChemInform

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0 -Methylation of the optically active 3'-hydroxycoclaurines 3a and 3b and of the N-methylated analogs 5a,b with S-adenosyl-~-[methyl-'~C]methionine in presence of mammalian COMT was investigated in uitro. The N-unsubstituted (1s)-and (lR)-isomers 3a and 3b, respectively, afforded almost equal amounts of the corresponding N-norreticuline 4 and N-nororientaline 19, besides two unknown by-products (see Fig. and Table I ) . The N-methylated (IS)-isoquinoline 5a, on the other hand, afforded largely (S)-orientaline ((S)-19), while an almost equal mixture of (R)-reticuline (6b) and (R)-orientaline ((R)-19) was obtained from the (1R)-enantiomer 5b. The isoquinolines 3a,b and 5a,b were prepared by a Bischler-Napieralski cyclization yielding 0 -benzyl-protected isoquinoline 10 (Scheme I). The optical resolution of 10 was accomplished with 2'-bromotartranilic acid. The N-methylated isoquinolines were prepared by N-formylation of lOa,b and reduction of the formamides 13a,b with diborane (+ 14a,b). Deblocking of the benzyl-ether moieties of 10a,b and 14a,b was accomplished by catalytic hydrogenation in presence of HCI, affording directly 3a,b.HC1 and 5a,b.HC1, respectively.Introduction. -The biosynthesis of morphine in the opium poppy (Pupuver somniferum) proceeds from (S)-reticuline via dehydroreticulinium salt to (R)-reticuline and then to morphine alkaloids, and this part is rather well elaborated [l] [2]. Details on the biosynthesis of (S)-reticuline (6a) itself, however, were only recently clarified: Zenk and coworkers [3] showed that the first isoquinoline formed in plants which produce benzyltetrahydroisoquinolines is (S)-norcoclaurine (la), converted by an enzymatic O-methylation into (S)-coclaurine (2a), followed by two bioconversions into (S)-N-methylcoclaurine (not shown) and (S)-3'-hydroxy-N-methylcoclaurine (5a) as the ultimate precursor of (S)-reticuline (6a)'). In an earlier biosynthetic scheme, Zenk and coworkers [4] had proposed that 6a was derived from l a via (S)-3'-hydroxycoclaurine (3a) and (S)-N-norreticuline (4a), followed by its N-methylation to 6a as the last step.The correctness of the now proposed scheme (see [3]) for the biosyntheses of 6a from l a in benzylisoquinoline-producing plants is further supported by the complete absence of N-demethyl compounds in these plants [3].

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Substituted tartranilic acids. A new series of resolving acids

Cited by 20 publications

References 4 publications

Chiral Resolution and Absolute Configuration of the Enantiomers of the Psychoactive “Designer Drug” 3,4‐Methylenedioxypyrovalerone

Chiral Resolution and Absolute Configuration of the Enantiomers of the Psychoactive “Designer Drug” 3,4‐Methylenedioxypyrovalerone

Chiral separation of pheniramine‐like 3‐phenyl‐3‐heteroarylpropylamines by CE and HPLC methods

ChemInform Abstract: Mammalian Alkaloids: Synthesis and O‐Methylation of (S)‐ and (R)‐3′‐ Hydroxycoclaurine and Their N‐Methylated Analogues with S‐Adenosyl‐L‐( methyl‐14C)methionine in Presence of Mammalian Catechol O‐ Methyltransferase.

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