1,3-Adamantanedicarboxylic acid

At room temperature, CBrIn a one liter three-neck flask equipped with a dropping funnel were placed 21.515 g (127.9 millimol) of 1, 3-adamantanediol and 200 milliliter (mL) of 95percent by mass of sulfuric acid, so that a uniform solution was obtained over a period of one hour at room temperature. Subsequently, the above-mentioned flask was placed in a ice bath, while 10 mL of 95percent by mass of formic acid was added dropwise under gradual stirring from the dropping funnel in the flask over a period of 2 hours. After the dropwise adding, the flask was taken out from the ice bath, the resultant mixture therein was further reacted for approximately 2 hours at room temperature. Thereafter mixed reaction liquid thus formed was transferred in one liter of crushed ice, and the resultant white crystal was filtered with a glass filter. In addition, the white crystal was dissolved in 50 mL of 30percent by mass of aqueous solution of sodium hydroxide, and was filtered with a glass filter. To the resultant filtrate was added 100 mL of 95percent by mass of sulfuric acid, so that white crystal was precipitated. The precipitated white crystal was filtered, washed with water and further washed with methanol and thus 1, 3-adamantanedicarboxylic acid was obtained as described hereunder. yield amount: 24.365 g (108.65 millimol), yield rate: 85.0percent, purity: 92.8percentIn a two-necked round-bottom flask with a condenser was added 1, 3-adamantanediol (8.4 g, 50 mmol), whichcooled with an ice bath. Then 56 mL of concentrated sulfuric acid was added with stirring, and 5 mL of anhydrous acidwas slowly added dropwise. After the addition, the mixture was maintained with an ice bath for 2 hours. The reactionwas run at room temperature for 10 hours. The pale yellow viscous transparent reaction solution was slowly poured into200 g of ice water, and then a large amount of white solid was precipitated. The resulting materials were filtered, andthe filter cake was washed with water, and then dried to give compound NM-008a (8.9 g, 79.5percent). ESI-MS: m/z 223.2([M-H]-). 1H-NMR (DMSO-d6, ppm): 1.56-1.88 (m, 12 H), 2.06 (s, 2 H), 12.12 (s, 2 H).In a two-necked round-bottom flask with a condenser was added 1, 3-adamantanediol (8.4 g, 50 mmol), which cooled with an ice bath. Then 56 mL of concentrated sulfuric acid was added with stirring, and 5 mL of anhydrous acid was slowly added dropwise. After the addition, the mixture was maintained with an ice bath for 2 hours. The reaction was run at room temperature for 10 hours. The pale yellow viscous transparent reaction solution was slowly poured into 200 g of ice water, and then a large amount of white solid was precipitated. The resulting materials were filtered, and the filter cake was washed with water, and then dried to give compound NM-008a (8.9 g, 79.5percent). ESI-MS: m/z 223.2 ([M−H]The same reaction apparatus as shown in was charged with 1, 3-adamantanediol (purity: 99percent, 30.0 g), followed by addition of 96percent by mass concentrated sulfuric acid (360.1 g). After the mixture was stirred at room temperature and the starting material was confirmed to be dissolved, the flask was cooled to maintain the solution temperature within the range of 10° C. to 20° C. and formic acid (16.8 g) was added dropwise thereto over 30 minutes. After completion of the dropwise addition, the mixture was reacted at a reaction temperature of 35° C. for 3 hours. When the progress of the reaction was confirmed by GC, the conversion of 1, 3-adamantanediol was found to be 100percent and 1, 3-adamantane dicarboxylic acid was generated in a reaction yield of 92.9percent. Subsequently, while maintaining the solution temperature within the range of 35° C. to 50° C., 70percent nitric acid (48.2 g) was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was reacted at a reaction temperature of 50° C. for 5 hours. When the progress of the reaction was confirmed by GC, the conversion of 1, 3-adamantane dicarboxylic acid was found to be 95.0percent and 5-hydroxy adamantane-1, 3-dicarboxylic acid was generated in a reaction yield of 64.5percent The same purification apparatus as shown in was charged with sodium hydroxide (154.2 g), sodium sulfite (74.2 g) and ion exchanged water (873.8 g) to prepare a mixed solution of sodium hydroxide and sodium sulfite, followed by cooling the flask. To the above mixed solution, the reaction mixture containing 5-hydroxy-1, 3-adamantane dicarboxylic acid was added while maintaining the solution temperature within the range of 10° C. to 40° C., and the precipitated crystals were collected by filtration and washed with water. The crystals were dried under reduced pressure at 40° C. for 8 hours to obtain white crystals of 5-hydroxy adamantane-1, 3-dicarboxylic acid (28.0 g, yield: 65.4percent).Equipped with a mechanical stirrer, reflux condenser, constant pressure dropping funnel, Thermometer 250mL four-necked flask was added concentrated sulfuric acid 100mL, with stirring, 15 g (84.1 mmol) of 1-adamantane methyl ketone (R = CH3)After the addition was maintained for 15 minutes, ice water bath control 0 , and then within 30 minutes with a constant pressure dropping funnel slowly dropping mixed acid solution (fuming nitric acid 16ml (0.34mol) + concentrated sulfuric acid 16ml)Insulation 1h, naturally heated to 80 reaction 10h, the reaction was completed, The reaction solution was slowly poured into 200mL ice water, stirring while pouring, white solid precipitation, filtration was precipitated, A small amount of washing cake, Dried in vacuo to give a white powdery solid 14.9g, content 98percent, yield 79.2percent.Equipped with a mechanical stirrer, reflux condenser, constant pressure dropping funnel, Thermometer 250mL four-necked flask was added concentrated sulfuric acid 100mL, with stirring, 15 g (72.0 mmol) of 2- (1-adamantane) -2-oxoacetic acid (R═COOH) After the addition was maintained for 15 minutes, ice water bath control 0 , and then within 30 minutes with a constant pressure dropping funnel slowly dropping mixed acid solution (fuming nitric acid 16ml (0.34mol) + concentrated sulfuric acid 16ml)Insulation 1h, naturally heated to 60 reaction 10h, The reaction was completed, the reaction solution was slowly poured into 200mL ice water, stirring while pouring, white solid precipitation, The precipitate was filtered with suction, washed with a small amount of water cake, vacuum dried to give a white powdery solid 13.2g, content 98percent, yield 81.8percent.A 250 mL four-necked flask equipped with a mechanical stirrer, a reflux condenser, a constant pressure dropping funnel and a thermometer was charged withConcentrated sulfuric acid 100mL, with stirring, slowly add inward 15g (77.3mmol) of 2- (1-adamantane) -2-oxoethanol (R = CH2OH), after the addition was maintained for 15 minutes, ice water bath control 0 , Then within 30 minutes with a constant pressure dropping funnel slowly mixed acid solution (fuming nitric acid 16ml (0.34mol) + concentrated sulfuric acid 16ml), after the addition, Insulation 1h, naturally warmed to 50 reaction 8h, The reaction was completed, the reaction solution was slowly poured into 200mL ice water, stirring while pouring, white solid precipitation, Filtered to give a precipitate, A small amount of water washed cake, dried in vacuo to give a white powdery solid 13.1g, content 98percent, yield 75.4percent.A 250 mL four-necked flask equipped with a mechanical stirrer, a reflux condenser, a constant pressure dropping funnel and a thermometer was charged withConcentrated sulfuric acid 100mL, with stirring, 15 g (78.1 mmol) of 2- (1-adamantane) -2-oxoacetaldehyde (R = CHO)15 minutes after adding plus, ice bath control 0 , Then within 30 minutes with a constant pressure dropping funnel slowly mixed acid solution (fuming nitric acid 16ml (0.34mol) + concentrated sulfuric acid 16ml), after the addition, Insulation 1h, naturally heated to 50 reaction 10h, The reaction was completed, the reaction solution was slowly poured into 200mL ice water, stirring while pouring, white solid precipitation, Filtered to give a precipitate, A small amount of water washed cake, dried in vacuo to give a white powdery solid 14.1g, content 98percent, yield 80.3percent.A mixture of Zn(Ac)2·2H2O (0.2mmol), dbim (0.1mmol), m-H2adica (0.2mmol), and NaOH (0.2mmol) in H2O (10mL) was kept in a 25mL Teflon-lined stainless steel vessel at 140°C for four days. After the mixture was cooled to room temperature at a rate of 5°C/h, colorless crystals suitable for X-ray diffraction were obtained with a yield of 51percent (based on Zn). Anal. calcd for C51H57N6O6Zn (percent): C, 66.91; H, 6.27; N, 9.18. Found: C, 66.89; H, 6.28; N, 9.15. IR (KBr, cm'1): 3432.67(m), 2931.27(s), 2857.99(m), 1562.06(s), 1519.63(m), 1417.42(s), 1334.50(m), 1311.36(s), 1261.22(w), 1124.30(m), 1006.66(w), 809.96(s), 705.82(s), 676.89(w), 549.61(w).General procedure: Cd(NO3)24H2O (86 mg, 0.28 mmol), 4-bpmp (74 mg, 0.28 mmol), and General procedure: Cd(NO3)24H2O (86 mg, 0.28 mmol), 4-bpmp (74 mg, 0.28 mmol), and

1,3-adamantane dicarboxylic acid is used to synthesize pharmaceutical intermediates and electronic chemicals

Molecular Weight:224.25
XLogP3:1.1
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:4
Rotatable Bond Count:2
Exact Mass:224.10485899
Monoisotopic Mass:224.10485899
Topological Polar Surface Area:74.6
Heavy Atom Count:16
Complexity:327
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes