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Tandospirone citrate, SM-3997, Sediel

枸橼酸坦度螺酮 坦度螺酮 Chemical Name: 3aalpha,4alpha,5,6,7alpha,7aalpha-Hexahydro-2-[4- [4-(2-pyrimidinyl)-1-piperazinyl]butyl]-4,7-methano-1H-isoindole-1,3(2H)-dione dihydrogen citrate; (1R*,2S*,3R*,4S*)-N-[4-[4-(2-Pyrimidinyl)-1-piperazinyl]butyl]-2,3-norbornanedicarboximide citrate
CAS No. 112457-95-1, 87760-53-0 (free base)
项目整合开发状态: Launched-1996
项目研究机构: Sumitomo Pharmaceuticals (Originator), Pfizer (Licensee)
合成路线:The cyclization of methyl 3-[4-(4-methoxybenzoylamino)-3-nitrobenzoyl]butyrate (I) with hydrazine hydrate in refluxing acetic acid gives 4,5-dihydro-6-[4-(4-methoxybenzoylamino)-3-nitrobenzoyl]-5-methylpyridazin-3(2H)-one (II),which is reduced with H2 over Pd/C in ethanol yielding the corresponding amino derivative (III).Finally,this compound is cyclized in refluxing acetic acid.

合成路线:By condensation of norbornane-2,3-di-endo-carboxylic anhydride (I) with 1-(4-aminobutyl)-4-(2 pyrimidinyl)piperazine (II) in refluxing pyridine.
📌 参考资料/链接:
参考文献标题:Succimide derivatives,compositions and method of use
文献作者:Ishizumi,K.; Antoku,F.; Asami,Y.(Sumitomo Chemical Co.,Ltd.)
参考来源:CA 1184915; EP 0082402

📄 详细内容


合成路线:By condensation of norbornane-2,3-di-endo-carboxylic anhydride (I) with 1-(4-aminobutyl)-4-(2 pyrimidinyl)piperazine (II) in refluxing pyridine.

参考文献标题:SM-3997
文献作者:Castar,J.; Prous,J.
参考来源:Drugs Fut 1986,11(11),949


合成路线:New syntheses of tandospirone have been described:1) The hydrogenation of bicyclo[2.2.1]hept-5-ene-2,3-di-exo-carboxylic acid anhydride (I) with H2 over Pd/C in THF-water gives bicyclo[2.2.1]heptane-2,3-di-exo-carboxylic acid anhydride (II),which by reaction with ammonia in THF-water is converted into the imide (III).The reaction of (III) with 1,4-dibromobutane by means of K2CO3 in refluxing acetone yields N-(4-bromobutyl)bicyclo[2.2.1]heptane-2,3-di-exo-carboximide (IV),which is finally condensed with 1-(2-pyrimidinyl)piperazine (V) by means of K2CO3 and KI in hot DMF.2) Imide (III) is condensed with propargyl bromide (VI) by means of K2CO3 in refluxing acetone affording N-propargylbicyclo[2.2.1]heptane-2,3-di-exo-carboximide (VII),which is allowed to react with piperazine (V) and formaldehyde by means of CuSO4 in dioxane to give N-[4-[4-(2-pyrimidinyl)piperazin-1-yl]-2-butynyl]bicyclo[2.2.1]heptane-2,3-di-exo-carboximide (VIII).Finally,this compound is reduced with H2 over Pd/C.3) The condensation of piperazine (V) with 4-chlorobutyronitrile (IX) by means of NaOH in acetone gives 4-[4-(2-pyrimidinyl)piperazin-1-yl]butyronitrile (X),which is reduced with LiAlH4 in ether yielding 1-(4-aminobutyl)-4-(2-pyrimidinyl)piperazine (XI).Finally,this compound is condensed with anhydride (II) in refluxing pyridine.

参考文献标题:Synthesis and anxiolytic activity of N-substituted cyclic imides (1R*,2S*,3R*,4S*)-N-[4-[4-(2-pyrimidinyl)-1-piperazinyl]butyl]-2,3-bicyclo[2.2.1]heptanedicarboximide (tandospirone) and related compounds
文献作者:Ishizumi,K.; Kojima,A.; Antoku,F.
参考来源:Chem Pharm Bull 1991,39(9),2288


合成路线:The synthesis of SM-3997 labeled in the carbonyl groups or the pyrimidine ring has been reported:The Diels-Alder condensation of cyclopentadiene (II) with [14C]-labeled maleic anhydride (I) gives bicyclo[2.2.1]hept-5-ene-2,3-endo-di[14C]-carboxylic anhydride (III),which by treatment with ammonia in THF is converted to the corresponding imide (IV endo).Heating of (IV endo) at 190 C in diphenylether affords the corresponding exo isomer (IV exo),which is hydrogenated with H2 over Pd/C in ethanol - THF to give the saturated exo-imide (V).The condensation of (V) with 1,4-dibromobutane (VI) by means of K2CO3 in refluxing acetone yields the N-(4-bromobutyl)imide (VII),which is finally condensed with 1-(2-pyrimidinyl)piperazine (VIII) by means of K2CO3 and KI in hot DMF to afford SM-399 [14C]-labeled at the carbonyl groups.

合成路线:The condensation of piperazine (I) with [14C]-labeled 2-chloropyrimidine (II) in refluxing ethanol gives the labeled 1-(2-pyrimidinyl)piperazine (III),which is then condensed with the N-(4-bromobutyl)imide (IV) by means of K2CO3 and KI as before,affording SM-3997 labeled at the pyrimidine ring.
参考文献标题:14C-labeling of a novel anxiolytic agent tandospirone
文献作者:Kanamaru,H.; Nishioka,K.
参考来源:J Label Compd Radiopharm 1992,31(6),427


产品链接: CAS No. 112457-95-1››

产品链接: CAS No.87760-53-0››