7,11-methanocycloocta [B] quinoline derivative as highly functionalizable acetylcholinesterase inhibitors
A compound, C1-C4 technology, applied in biochemical equipment and methods, medical preparations containing active ingredients, enzymes, etc., can solve problems such as hepatotoxicity, reduction of therapeutic effective dose, limited functionalization of compounds, etc.
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no. 1 approach
[0085] In a first embodiment, the method of the present invention comprises the following steps:
[0086] a) contacting a diketone of formula 1 with an α-haloester,
[0087]
[0088] to obtain the compound of formula 2
[0089]
[0090] where R' is C 1 -C 4 Alkyl;
[0091] b) converting the alcohol group on the compound of formula 2 into a leaving group to give the compound of formula 3
[0092]
[0093] wherein R" is a leaving group;
[0094] b') converting the compound of formula 3 into a compound of formula 4;
[0095]
[0096] c) contacting the compound of formula 4 with the compound of formula 5
[0097]
[0098] where R a , R b , R c and R d is as defined in formula I, and R e is CN or COOH to give compounds of formula HUP.
[0099]
[0100] where R' is C 1 -C 4 Alkyl and R 10 is NH 2 or Cl.
[0101] In a second embodiment, the method of the present invention comprises the following steps:
[0102] a) contacting a diketone of formula 1 w...
Embodiment 1
[0141] Example 1: Ethyl (12-amino-3-chloro-6,7,10,11-tetrahydro-7,11-methylenecyclooctano[b]quinolin-9-yl)acetate (HUP 1)
[0142] Preparation of tetramethyl 3,7-dihydroxybicyclo[3.3.1]nona-2,6-diene-2,4,6,8-tetracarboxylate
[0143] A mixture of 1,1,3,3-tetramethoxypropane (32.8 g, 0.20 mol) and 2M hydrochloric acid (100 mL) was stirred at room temperature for 1.5 hours. To this mixture cooled to 0° C. was added sequentially and carefully 5M aqueous NaOH (pH=8) (within 30 min) and methanol (100 mL). At 0°C, dimethyl-3-oxoglutaric acid (69.6 g, 0.40 mol) was added followed by methanol (70 mL). The reaction mixture was warmed to room temperature and stirred for 3 days. The reaction mixture was acidified to pH=3 with 10M HCl. Fractions were filtered, washed with water, and dried in a desiccator to afford the desired tetraester as a white solid (39.2 g, 51%).
[0144] Preparation of bicyclo[3.3.1]nonane-3,7-dione (1)
[0145] Tetramethyl 3,7-dihydroxybicyclo[3.3.1]nona-...
Embodiment 2
[0169] Example 2: 2-(12-Amino-3-chloro-6,7,10,11-tetrahydro-7,11-methylenecyclooctano[b]quinolin-9-yl)ethanol (HUP 2)
[0170]
[0171] To cold (0°C) anhydrous LiAlH 4 (400 mg, 10 mmol) in anhydrous THF (50 mL) was added dropwise to a solution of ester (HUP 1 ) (1.78 g, 5.0 mmol) in anhydrous THF (15 mL). The solution was stirred for 1 h (0° C. to room temperature) and then carefully quenched at 0° C. by the addition of water (1.75 mL), followed by 5M NaOH solution (1.75 mL) followed by water (5 mL). The reaction mixture was stirred at room temperature for 10 min, then washed with Na 2 SO 4 dry. Filtration and concentration gave the desired huperzine alpha complex (HUP 2) (1.60 g, quantitative) as a very pale yellow solid. Recrystallization from acetone gave a white solid.
[0172] Rf (AcOEt / MeOH 8 / 2, v / v) = 0.15.
[0173] m.p.=174℃(decomposition).
[0174] IR(KBr): ν=3352, 3252, 2894, 1645, 1609, 1573, 1490, 1424, 1373, 1309, 1285, 1046, 928, 818, 770cm -1 .
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