* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
General procedure: Adamantane carboxylic acid 1a–1s or 3, 0.5 g, wasadded in portions under vigorous stirring and cooling to a mixture of 2.5, 3, or 7 equiv of MnO2 and 2.5–14 mL of 93percent H2SO4, maintaining the temperature within 25-30°C. The mixture was kept for 0.5–24 h at that temperature and treated with cold water on coolingwith an ice bath. The precipitate was filtered off andwashed with a small amount of water and butan-1-ol. The products were extracted with butan-1-ol (5 ×2 mL). In the isolation of 2j–2l and 2q–2s, the mixture was adjusted to pH 3–4 with 30percent aqueous sodium hydroxide prior to extraction. The organic phases werecombined, washed with water, a solution of sodiumhydrogen carbonate, and water again, and dried byazeotropic distillation. The solvent was removed under reduced pressure on a rotary evaporator, and the product was purified by recrystallization.
Reference：
[1] Russian Journal of Organic Chemistry, 2016, vol. 52, # 6, p. 785 - 790[2] Zh. Org. Khim., 2016, vol. 52, # 6, p. 800 - 805,6
2
[ 201230-82-2 ]
[ 281-23-2 ]
[ 39269-10-8 ]
Yield
Reaction Conditions
Operation in experiment
80%
Stage #1: With Al2Br7(1-)*CBr3(1+) In 1,2-dibromomethane at 0℃; for 3 h; Stage #2: With water In 1,2-dibromomethaneCooling
At room temperature, CBr4*2AlBr3 was prepared by stirring CBr4 with AlBr3 in a molar ratio of 1-2 in anhydrous CH2Br2. Next, at 0 °C under atmospheric CO pressure, AdH (1) (1.43 mmol) was added to the freshly prepared CBr4*2AlBr3 (2.87 mmol) in CH2Br2 (3 mL). The mixture was stirred for 3 h. Then at atmospheric CO pressure, H2O (15 mL) was added carefully with cooling. The reaction mixture was kept for 1-2 d until the precipitation of 1,3-Ad(COOH)2 was complete. The Ad(COOH)2 was filtered, washed with H2O, dried, and crystallized from AcOH. The yield of analytically pure compound was 80percent with respect to 1. Mp 285-286 °C. Calcd. for C12H16O4, (percent): C, 64.27; H, 7.19. Found (percent): C, 64.21; H, 7.24.
Reference：
[1] Tetrahedron Letters, 2012, vol. 53, # 27, p. 3493 - 3496
[2] Journal of Organic Chemistry, 1998, vol. 63, # 2, p. 222 - 223
[3] Journal of Organic Chemistry, 1978, vol. 43, p. 4978 - 4980
3
[ 64-18-6 ]
[ 5001-18-3 ]
[ 39269-10-8 ]
Yield
Reaction Conditions
Operation in experiment
85%
Stage #1: With sulfuric acid In water at 20℃; for 1 h; Stage #2: at 0 - 20℃; for 4 h;
In 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: 92.8percent
79.5%
at 20℃; for 12 h; Cooling with ice
In 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).
79.5%
at 20℃; for 12 h; Cooling with ice
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]−). 1H-NMR (DMSO-d6, ppm): 1.56-1.88 (m, 12H), 2.06 (s, 2H), 12.12 (s, 2H).
92.9 %Chromat.
Stage #1: at 20℃; Stage #2: at 10 - 35℃; for 3.5 h;
The same reaction apparatus as shown in Example 1 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 Example 1 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).
Stage #1: for 0.25 h; Stage #2: at 0 - 80℃; for 11.5 h;
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.
Stage #1: for 0.25 h; Stage #2: at 0 - 60℃; for 11.5 h;
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.
Stage #1: for 0.25 h; Stage #2: at 0 - 50℃; for 9.5 h;
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.
Stage #1: for 0.25 h; Stage #2: at 0 - 50℃; for 11.5 h;
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.
In a 100 mL two-neck flask was placed 7.168 g (32.0 millimol) of <strong>[39269-10-8]1,3-adamantanedicarboxylic acid</strong> and was gradually added 46.0 mL (638 millimol) of thionyl chloride at room temperature with stirring. At the point of this time, the reaction liquid turned to white slurry. Subsequently, the reaction liquid thus obtained was heated in an oil bath at 50°C to proceed with reaction for approximately 6 hours. At the point of this time, the reaction liquid was flowable non-sticky white solution. Then the reaction liquid thus obtained was heated in an oil bath at 95°C to distill away excessive thionyl chloride. As a result, the reaction liquid turned to transparent solution after approximately 25 mL of the thionyl chloride was distilled away, and finally approximately 35 mL thereof was distilled away. Further the residual thionyl chloride was distilled away at 50°C under 133.3 Pa. Subsequently, the residual reaction liquid was cooled, and thus <strong>[39269-10-8]1,3-adamantanedicarboxylic acid</strong> dichloride in the form of white crystal was obtained as described hereunder. yield amount: 7.757 g (29.7 millimol), yield rate: 93.0percent All procedures of the synthesis of <strong>[39269-10-8]1,3-adamantanedicarboxylic acid</strong> dichloride including raw material charging, post-treatment and storage were carried out in a stream of nitrogen so as not to be influenced by moisture.
With thionyl chloride; In chloroform; at 0 - 25℃;
To a solution of <strong>[39269-10-8]1,3-adamantanedicarboxylic acid</strong> (0.112 g) in chloroform (10 ml) at 0° C. was added thionyl chloride (0.18 g). The solution was allowed to warm to room temperature overnight and reduced to a residue at reduced pressure. The residue was dissolved in dry tetrahydrofuran and concentrated twice more to remove excess thionyl chloride. To a solution of the resulting acid chloride in tetrahydrofuran (20 ml) at 0° C. was added 5-aminoindole (0.13 g) and triethylamine (0.1 g) and the resulting suspension was allowed to warm to room temperature overnight. The precipitated triethylamine hydrochloride was removed by filtration and washed with tetrahydrofuran. The residue left on concentrating the combined filtrate and washings was chromatographed over silica gel with a mixture of ethyl acetate and hexanes to give 0.16 g of the title compound. MS ES (MH+)=453
With thionyl chloride; In N,N-dimethyl-formamide;
Example 1 In a 3-L round bottom flask equipped with a stirrer, cooling tube, thermometer, and acidic gas trap, 500 g (2.230 mol) of <strong>[39269-10-8]1,3-adamantanedicarboxylic acid</strong> and 1326 g (11.148 mol) of thionyl chloride were placed and were stirred, and to this mixture, 8.15 g (0.112 mol) of N,N-dimethylformamide (DMF) was added dropwise at room temperature, followed by gradual heating and stirring at 70° C. for 2 hours. The reaction mixture was cooled to room temperature, and the remained thionyl chloride and DMF were removed under a reduced pressure to thereby yield 599 g (2.294 mol) of 1,3-adamantanedicarboxylic dichloride as a crudely purified product. [Spectral data of 1,3-adamantanedicarboxylic dichloride] 13C-NMR (500 MHz, CDCl3) delta: 27.7, 34.6, 37.8, 39.9, 178.6
With oxalyl dichloride; In dichloromethane; N,N-dimethyl-formamide; at 20℃; for 21h;Inert atmosphere;
To a solution of<strong>[39269-10-8]1,3-adamantanedicarboxylic acid</strong> (0.449 g, 2.00 mmol) and DMF (16 muL, 0.200mmol) in CH2Cl2 (4 mL) was added oxalyl chloride (0.677mL, 8.00 mmol) dropwise over 5 min. Stirring was continued at rt for 21 h. Thereaction mixture was concentrated invacuo, and the crude product used directly in the next step without furtherpurification.
With thionyl chloride; N,N-dimethyl-formamide; In chloroform; at 75℃;
I) according to the reaction scheme shown in fig. 2 of, adamantanedicarboxylic napththalendicarbonyl dichloride synthesized as follows: the flask solanaceae 1L, 1, 3-dicarboxylic amman tank 50g (0. 22mol), in addition to the chloroform 300 ml, stirring with magnetic stirrer. Furthermore, the dropped to 1 ml DMF. Thionyl chloride 34 ml (0. 47mol) is added, at 75 °C back to the heating. After confirming that runs unmelting, under reduced pressure at the evaporator. Soln. fluoronitric xeroderma, white powder is obtained. Connected to the vacuum line, stored overnight under lower pressure.
With thionyl chloride; In dichloromethane; at 20 - 70℃;
Di-, tri- or tetra-carboxylic acids (1 eq.) and CH2CI2(0.114 M concentration) were added to a two-dram vial. SOCl2(15 eq. per carboxylic acid) was then added and the reaction mixture was left to stir for four hours at room temperature (some substrates required heating at 70 °C overnight for full solution and/or conversion). The solvent was removed via N2flow. The residue was dissolved in 3 mL of dry CH2CI2which was then removed under N2flow. This process was performed two additional times in an attempt to remove any free HCl from the sample. The resulting residue was then used without purification in the dimerization reaction.
As a result, the conversion of 1,3-dicarboxyadamantane was 99percent, and 1,3-bis(hydroxymethyl)adamantane (yield 95percent) was formed. White solid Mass spectral data [M]+: 196 IR(cm-1): 3310, 1490, 720
55%
Compound NM-008a (2.24 g, 10 mmol) was dissolved in 100 mL of dry tetrahydrofuran, and cooled with anice bath. Then 3.0 mL of triethylamine and 3.0 mL of ethyl chloroformate were added in order. The ice bath was removed30 minutes later, and the reaction was run at room temperature for 4 hours. The resulting materials were filtered, and the filter cake was washed with tetrahydrofuran. The filtrate was collected, and to which 6 g of sodium borohydride wasadded, and 3 mL of water was slowly added with dropping funnel within 1 hour. After the water being added completely,the reaction was reacted at room temperature for 1 hour and monitored with TLC. When the reaction was completed,50 mL of water was added, and organic phase was removed to dryness under reduced pressure. The aqueous layerswas extracted with ethyl acetate (40 mL34). The organic layers were combined, and were washed with 50 mL of 0.5 Nhydrochloric acid and saturated sodium chloride aqueous solution and water, respectively, and then dried with anhydroussodium sulfate. The solvent was evaporated under reduced pressure, to give a crude product as a white solid, whichwas washed with ethyl acetate to give NM-008b as a white solid (1.08 g, 55percent). ESI-MS: mlz 274.2 ([M+2K]2+). 1H-NMR(DMSO-d6, ppm): 1.14 (s, 2 H), 1.26-1.47 (m, 8 H), 1.54 (s, 2 H), 1.99 (m, 2 H), 2.99 (d, 4 H, J = 5.5 Hz), 4.30 (t, 1 H,J = 5.5 Hz).
55%
Compound NM-008a (2.24 g, 10 mmol) was dissolved in 100 mL of dry tetrahydrofuran, and cooled with an ice bath. Then 3.0 mL of triethylamine and 3.0 mL of ethyl chloroformate were added in order. The ice bath was removed 30 minutes later, and the reaction was run at room temperature for 4 hours. The resulting materials were filtered, and the filter cake was washed with tetrahydrofuran. The filtrate was collected, and to which 6 g of sodium borohydride was added, and 3 mL of water was slowly added with dropping funnel within 1 hour. After the water being added completely, the reaction was reacted at room temperature for 1 hour and monitored with TLC. When the reaction was completed, 50 mL of water was added, and organic phase was removed to dryness under reduced pressure. The aqueous layers was extracted with ethyl acetate (40 mL×4). The organic layers were combined, and were washed with 50 mL of 0.5 N hydrochloric acid and saturated sodium chloride aqueous solution and water, respectively, and then dried with anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, to give a crude product as a white solid, which was washed with ethyl acetate to give NM-008b as a white solid (1.08 g, 55percent). ESI-MS: m/z 274.2 ([M+2K]2+). 1H-NMR (DMSO-d6, ppm): 1.14 (s, 2H), 1.26-1.47 (m, 8H), 1.54 (s, 2H), 1.99 (m, 2H), 2.99 (d, 4H, J=5.5 Hz), 4.30 (t, 1H, J=5.5 Hz).
General procedure: A round-bottom flask (50 mL) equipped with a condenser and N2 inlet was charged with carboxylic acid (1 mmol). Under a stream of N2 the acid was suspended in anhydrous toluene (10 mL). To the suspension, triethylamine (2 mmol, 1 mmol for 5) was added, and the suspension was stirred at rt for 45 min, and then, diphenylphosphoryl azide DPPA (2.1 mmol, 1.1 mmol for 5) was added. The reaction mixture was heated at 40 °C for 1 h, and after that 4 h at reflux. To the mixture, a solution of beta-naphthylamine (2 mmol, 1 mmol for 5) in 1 mL of dry toluene was added, and refluxing was continued for 16 h. The solvent was removed on a rotational evaporator and the residue treated with methanol. Product in the form of precipitate was filtered off, washed with water and methanol, and dried in vacuum (10 mbar) at 40 °C for 1 h.
Adamantane-l,3-dicarboxylic acid (1 0 g, 4 4 mmol) was dissolved in 5 mL thionyl chloride and heated to reflux for 1 5 hours The mixture was cooled to ambient temperatuie and then concentrated under reduced pressure To a solution of the unpurifed acid chloride and the pioduct of Example 46A (0 82 g, 4.4 mmol) in 20 ml of THF at 0 0C was added triethylamine (1.4 ml , 9 7 mmol) The mixture was warmed to 65 0C and stirred for 6 hours The mixture was diluted with ethyl acetate and washed with saturated potassium carbonate, water and brine The aqueous washings were combined and extracted with ethyl acetate The combined organic extracts were dried over magnesium sulfate and concentrated under reduced pressure <n="60"/>Purification by column chromatography (SiO?, 20-40percent ethyl acetate/hexanes gradient) affoided the title compound. 1H NMR (DMSO-d, 300 MHz) delta ppm 1 62 (s,2 H), 1 69- 1 92 (m, 10 H), 2 08 (s, 2 H), 2 15 (s, 3 H), 2 20 (s, 3 H), 3 24 (s, 3 H),3 64 (t, ./=5 4 Hz, 2 H), 4 24 (t, ,/=5.4 Hz, 2 H), 12 01 (br s, 1 H); MS (DCI/NH3) m/z 393 (M+H)+ Anal Calculated foi C20H28N2O4S 0.3H2O: C, 60 37; H, 7 24; N, 7,04Found: C, 60.21 ; H, 7 15; N, 7 1 1
With ammonia; ammonium bicarbonate; In water; at 290 - 305℃;
General procedure: In a 1L reactor was charged with 500g of carboxylic acid raw material (chemically pure) and NH3 mole number of the carboxyl group contained in the carboxylic acid starting material 1.4 times the amount of aqueous ammonium bicarbonate (ammonium bicarbonate concentration 30wtpercent) 1.6 times that of the carboxyl group contained in the carboxylic acid starting material (NH3 content 25wtpercent, industrial product)The reaction kettle was closed and the stirrer was turned on (600r/min). After allowing the reaction to proceed for TC hours at reaction temperature TA,The contents of the reactor sampling, Do nuclear magnetic resonance spectroscopy and elemental analysis,To characterize the amide intermediate.The specific reaction conditions and characterization results are shown in Table A-1, Table A-2, Table A-3, Table A-4 and Table A-5 below.These characterization results indicate that the amide intermediate obtained has an extremely high purity (99percent or more).
With ammonia; at 280℃; for 0.5h;
General procedure: Into a 1 L reaction vessel, 500 g of a carboxylic acid raw material (chemically pure) was charged and charged with 1.3 times the molar amount of ammonia gas (water content: 0.5percent by weight, industrial product) of the carboxyl group contained in the carboxylic acid raw material or ammonium ion The number of moles was 1.4 times that of the carboxyl group contained in the carboxylic acid starting material (pure chemical), the reaction kettle was closed, and stirring was started (600 r / min). After the reaction was allowed to proceed for Tc at the reaction temperature Talpha, the contents of the reactor were sampled and subjected to 1H NMR and elemental analysis to characterize the amide intermediate. The specific reaction conditions and characterization results are shown in Table A-1, Table A-2, Table A-3, Table A-4 and Table A-5 below. These characterization results indicate that the amide intermediate obtained has an extremely high purity (99percent or more).
With ammonia; for 0.5h;Heating;
General procedure: 500 g of carboxylic acid raw material (chemically pure) was added to a 1 L open reaction vessel, and stirring was started (600 r/min).Ammonia gas is continuously introduced into the carboxylic acid raw material from the bottom of the reactor (chemically pure, the water content is 5.1 wtpercent,The flow rate is 100g/min). After the reaction is carried out at the reaction temperature TA for TC hours,Stop introducing ammonia. Sampling the contents of the reactor, performing nuclear magnetic resonance spectroscopy and elemental analysis,To characterize the amide intermediate. The specific reaction conditions and characterization results are shown in Table A-1 below.Table A-2, Table A-3, Table A-4 and Table A-5. These characterization results show thatThe amide intermediate obtained has an extremely high purity (99percent or more).
With sulfuric acid; nitric acid; at 35 - 50℃; for 5.5h;
As a reaction apparatus, a stirrer,thermometer,A dropping funnel,Into a glass flask equipped with a Dimroth condenser,100.0 g of <strong>[39269-10-8]1,3-adamantanedicarboxylic acid</strong> (purity of 99percent referred to as ADCA)900 g of 96 mass percent concentrated sulfuric acid (9 mass times with respect to the raw material) was added.After stirring at 35 ° C. to confirm dissolution of the raw material,Cool the Lasco and keep the liquid temperature at 35 to 50 ° C120 g of 70percent by mass nitric acid was added dropwise over 30 minutes so as to stay within the range.After completion of the dropwise addition,The reaction was carried out at a reaction temperature of 50 ° C. for 5 hours.When the progress of the reaction was confirmed with a gas chromatogram (GC)The conversion of <strong>[39269-10-8]1,3-adamantane dicarboxylic acid</strong> was 100percentWith a GC peak area ratio of 98.0percent5-hydroxy<strong>[39269-10-8]adamantane-1,3-dicarboxylic acid</strong> was formed. A stirrer,To a reaction stopping apparatus equipped with a glass flask equipped with a thermometer and an alkali trap,900 g of ion exchange water (pure water) was added.next,While cooling the flask,In order to keep the liquid temperature within the range of 10 to 40 ° C.,The reaction solution of 5-hydroxy<strong>[39269-10-8]adamantane-1,3-dicarboxylic acid</strong> was added dropwise to terminate the reaction to precipitate crystals of the objective substance.The total amount of the reaction stopped solution after completion of dropping of the reaction solution was 2020 g,It was 20 times the charged mass of <strong>[39269-10-8]1,3-adamantane dicarboxylic acid</strong>.Incidentally,The pH of the reaction stopped solution was <0.The precipitated crystals were separated by filtration,It was washed with water.The obtained crystals were dried under reduced pressure at 40 ° C. for 8 hours,80.7 g (yield 75.5percent) of white crystal of 5-hydroxy<strong>[39269-10-8]adamantane-1,3-dicarboxylic acid</strong> was obtained.
28 g
With nitric acid; at 35 - 50℃; for 5.5h;
The same reaction apparatus as shown in Example 1 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 <strong>[39269-10-8]1,3-adamantane dicarboxylic acid</strong> 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 <strong>[39269-10-8]1,3-adamantane dicarboxylic acid</strong> was found to be 95.0percent and 5-hydroxy <strong>[39269-10-8]adamantane-1,3-dicarboxylic acid</strong> was generated in a reaction yield of 64.5percent The same purification apparatus as shown in Example 1 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-<strong>[39269-10-8]1,3-adamantane dicarboxylic acid</strong> 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 <strong>[39269-10-8]adamantane-1,3-dicarboxylic acid</strong> (28.0 g, yield: 65.4percent).
With diisopropyl-carbodiimide; In DMF (N,N-dimethyl-formamide); for 1h;
Adamantane-1,3-dicarboxylic acid (3.5 g) was taken in DMF (20 ml) DIC (1.36 ml) was added and stirred for 1 hr.; Symmetrical anhydride prepared from adamantane 1,3-dicarboxylic acid using DIC in DMF
In 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: 92.8percent
79.5%
With sulfuric acid; at 20℃; for 12h;Cooling with ice;
In 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).
79.5%
With sulfuric acid; at 20℃; for 12h;Cooling with ice;
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]?). 1H-NMR (DMSO-d6, ppm): 1.56-1.88 (m, 12H), 2.06 (s, 2H), 12.12 (s, 2H).
sulfuric acid; In water; 1,2-dichloro-ethane; at 25℃; for 11h;Product distribution / selectivity;
The synthesis of 2-methacryloyloxy-2-(3-(2-hydroxy-2-propyl)1-1-adamantyl)propane was performed by the following method. First, according to the method described in Japanese Patent Application Laid-open No. 2002-167342, 1000 g of 1,3-dihydroxyadamantane was synthesized from adamantane. Next, a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a Dimroth condenser was charged with 100 g of 1,3-dihydroxyadamantane, 500 mL of 1,2-dichloroethane and 800 g of 96percent sulfuric acid, and further 300 g of formic acid was dropped into the flask for 1 h. Thereafter, the contents of the flask were reacted at 25° C. for 10 h. The resultant reaction solution was filtered to separate precipitated crystals therefrom. The thus separated crystals were washed with water to obtain 140 g of 1,3-adamantanedicarboxylic acid. Then, a four-necked flask equipped with a stirrer, a thermometer and a Dimroth condenser was charged with 140 g of 1,3-adamantanedicarboxylic acid, 12 g of 96percent sulfuric acid, 200 g of methanol and 1000 mL of 1,2-dichloroethane, and the contents of the flask were reacted at 62° C. for 10 h.After completion of the reaction, the resultant reaction solution was separated into an organic phase and a water phase. The organic phase was washed with a saturated sodium hydrogencarbonate aqueous solution, and then concentrated. The thus obtained crystals were separated from the organic phase by filtration, thereby obtaining 150 g of methyl 1,3-adamantanedicarboxylate. Next, a four-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser and a dropping funnel was charged with 100 g of methyl 1,3-adamantanedicarboxylate and 500 mL of tetrahydrofuran, and then 600 mL of a 3M magnesium methyl bromide/diethyl ether solution was dropped into the flask for 1 h. Thereafter, the contents of the flask were stirred at 25° C. for 3 h, and then mixed with water to terminate the reaction. The resultant reaction solution was separated into an organic phase and a water phase. The thus separated organic phase was concentrated to obtain 90 g of 1,3-adamantanediisopropanol.Next, a five-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser and two dropping funnels was charged with 90 g of 1,3-adamantanediisopropanol and 100 mL of 1,2-dichloroethane, and then 63 g of methacryloyl chloride and 81 g of triethylamine were simultaneously dropped into the flask for 1 h. Thereafter, the contents of the flask were stirred at 25° C. for 3 h, and then mixed with water to terminate the reaction. The resultant reaction solution was separated into an organic phase and a water phase. The thus separated organic phase was washed with ion-exchanged water, filtered, concentrated and then purified by silica gel column chromatography to obtain 80 g of 2-methacryloyloxy-2-(3-(2-hydroxy-2-propyl)-1-adamantyl)propane as represented by the following formula (hereinafter referred to as "compound A"). The thus obtained compound A was identified by 1H-NMR and 13C-NMR (refer to FIGS. 1 and 2).; The synthesis of 2-methacryloyloxy-2-(3-(2-methacryloyloxy-2-propyl)-1-adamantyl)propane was performed by the following method. First, according to the method described in Japanese Patent Application Laid-open No. 2002-167342, 100 g of 1,3-dihydroxyadamantane was synthesized from adamantane. Next, a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a Dimroth condenser was charged with 100 g of 1,3-dihydroxyadamantane, 500 mL of 1,2-dichloroethane and 800 g of 96percent sulfuric acid, and further 300 g of formic acid was dropped into the flask for 1 h. Thereafter, the contents of the flask were reacted at 25° C. for 10 h. The resultant reaction solution was filtered to separate precipitated crystals therefrom. The thus separated crystals were washed with water to obtain 140 g of 1,3-adamantanedicarboxylic acid.Then, a four-necked flask equipped with a stirrer, a thermometer and a Dimroth condenser was charged with 140 g of 1,3-adamantanedicarboxylic acid, 12 g of 96percent sulfuric acid, 200 g of methanol and 1000 mL of 1,2-dichloroethane, and the contents of the flask were reacted at 62° C. for 10 h. After completion of the reaction, the resultant reaction solution was separated into an organic phase and a water phase. The thus separated organic phase was washed with a saturated sodium hydrogencarbonate aqueous solution, and then concentrated. The obtained crystals were separated by filtration from the organic phase, thereby obtaining 150 g of methyl 1,3-adamantanedicarboxylate. Next, a four-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser and a dropping funnel was charged with 100 g of methyl 1,3-adamantanedicarboxylate and 500 mL of tetrahydrofuran, and then 600 mL of a 3M magnesium methyl bromide/diethyl ether solution was dropped into the flask for 1 h. Thereafter, the contents of the flask were stirred at 25° C. for 3 h, and then mixed with water ...
92.9%Chromat.
The same reaction apparatus as shown in Example 1 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 Example 1 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).
sulfuric acid; In water; 1,2-dichloro-ethane; at 62℃; for 10h;Product distribution / selectivity;
The synthesis of 2-methacryloyloxy-2-(3-(2-hydroxy-2-propyl)1-1-adamantyl)propane was performed by the following method. First, according to the method described in Japanese Patent Application Laid-open No. 2002-167342, 1000 g of 1,3-dihydroxyadamantane was synthesized from adamantane. Next, a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a Dimroth condenser was charged with 100 g of 1,3-dihydroxyadamantane, 500 mL of 1,2-dichloroethane and 800 g of 96percent sulfuric acid, and further 300 g of formic acid was dropped into the flask for 1 h. Thereafter, the contents of the flask were reacted at 25° C. for 10 h. The resultant reaction solution was filtered to separate precipitated crystals therefrom. The thus separated crystals were washed with water to obtain 140 g of <strong>[39269-10-8]1,3-adamantanedicarboxylic acid</strong>. Then, a four-necked flask equipped with a stirrer, a thermometer and a Dimroth condenser was charged with 140 g of <strong>[39269-10-8]1,3-adamantanedicarboxylic acid</strong>, 12 g of 96percent sulfuric acid, 200 g of methanol and 1000 mL of 1,2-dichloroethane, and the contents of the flask were reacted at 62° C. for 10 h.After completion of the reaction, the resultant reaction solution was separated into an organic phase and a water phase. The organic phase was washed with a saturated sodium hydrogencarbonate aqueous solution, and then concentrated. The thus obtained crystals were separated from the organic phase by filtration, thereby obtaining 150 g of methyl 1,3-adamantanedicarboxylate. Next, a four-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser and a dropping funnel was charged with 100 g of methyl 1,3-adamantanedicarboxylate and 500 mL of tetrahydrofuran, and then 600 mL of a 3M magnesium methyl bromide/diethyl ether solution was dropped into the flask for 1 h. Thereafter, the contents of the flask were stirred at 25° C. for 3 h, and then mixed with water to terminate the reaction. The resultant reaction solution was separated into an organic phase and a water phase. The thus separated organic phase was concentrated to obtain 90 g of 1,3-adamantanediisopropanol.Next, a five-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser and two dropping funnels was charged with 90 g of 1,3-adamantanediisopropanol and 100 mL of 1,2-dichloroethane, and then 63 g of methacryloyl chloride and 81 g of triethylamine were simultaneously dropped into the flask for 1 h. Thereafter, the contents of the flask were stirred at 25° C. for 3 h, and then mixed with water to terminate the reaction. The resultant reaction solution was separated into an organic phase and a water phase. The thus separated organic phase was washed with ion-exchanged water, filtered, concentrated and then purified by silica gel column chromatography to obtain 80 g of 2-methacryloyloxy-2-(3-(2-hydroxy-2-propyl)-1-adamantyl)propane as represented by the following formula (hereinafter referred to as "compound A"). The thus obtained compound A was identified by 1H-NMR and 13C-NMR (refer to FIGS. 1 and 2).; The synthesis of 2-methacryloyloxy-2-(3-(2-methacryloyloxy-2-propyl)-1-adamantyl)propane was performed by the following method. First, according to the method described in Japanese Patent Application Laid-open No. 2002-167342, 100 g of 1,3-dihydroxyadamantane was synthesized from adamantane. Next, a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a Dimroth condenser was charged with 100 g of 1,3-dihydroxyadamantane, 500 mL of 1,2-dichloroethane and 800 g of 96percent sulfuric acid, and further 300 g of formic acid was dropped into the flask for 1 h. Thereafter, the contents of the flask were reacted at 25° C. for 10 h. The resultant reaction solution was filtered to separate precipitated crystals therefrom. The thus separated crystals were washed with water to obtain 140 g of <strong>[39269-10-8]1,3-adamantanedicarboxylic acid</strong>.Then, a four-necked flask equipped with a stirrer, a thermometer and a Dimroth condenser was charged with 140 g of <strong>[39269-10-8]1,3-adamantanedicarboxylic acid</strong>, 12 g of 96percent sulfuric acid, 200 g of methanol and 1000 mL of 1,2-dichloroethane, and the contents of the flask were reacted at 62° C. for 10 h. After completion of the reaction, the resultant reaction solution was separated into an organic phase and a water phase. The thus separated organic phase was washed with a saturated sodium hydrogencarbonate aqueous solution, and then concentrated. The obtained crystals were separated by filtration from the organic phase, thereby obtaining 150 g of methyl 1,3-adamantanedicarboxylate. Next, a four-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser and a dropping funnel was charged with 100 g of methyl 1,3-adamantanedicarboxylate and 500 mL of tetrahydrofuran, and then 600 mL of a 3M magnesium methyl bromide/diethyl ether solution was dropped into the flask for 1 h. Thereafter, the contents of the flask were stirred at 25° C. for 3 h, and then mixed with water ...
(2) Introduction of a Protective Group and Hydroxylation In accordance with a conventional method in which isobutene is used under acidic conditions, 10 mmol of 1,3-dicarboxyadamantane was t-butoxylated to give 1,3-di(t-butoxycarbonyl)adamantane.
Example 72 The operation was effected in the same manner as Example 68 except for using 1,3-dicarboxyadamantane obtained by the method of Example 64 instead of 1-carboxy-3-nitroadmantane. The conversion of 1,3-dicarboxyadamantane was 90percent, and 1-carboxy-3-methoxycarbonyladamantane (yield 80percent) was formed. White solid Mass spectral data [M]+: 238 IR(cm-1): 3030, 1670, 1630
Yield
Reaction Conditions
Operation in experiment
80%
Example 74 The operation was effected in the same manner as Example 69 except for using 1,3-dicarboxyadamantane obtained by the method of Example 64 instead of 1-carboxy-3-nitroadmantane. The conversion of 1,3-dicarboxyadamantane was 90percent, and 1-carboxy-3-(N,N-dimethylcarbamoyl)adamantane (yield 80percent) was formed. Pale yellow solid Mass spectral data [M]+: 251 IR(cm-1): 3010, 1670, 1630
30
[ 828-51-3 ]
[ 39269-10-8 ]
Yield
Reaction Conditions
Operation in experiment
70%
Example 64 The reaction was effected in the same manner as Example 44 except for using 1-carboxyadamantane instead of adamantane. The conversion of 1-carboxyadamantane was 80percent, and 1,3-dicarboxyadamantane (yield 70percent) was formed. White solid Mass spectral data [M]+: 224 IR(cm-1): 3010, 1630, 1140
With thionyl chloride; triethylamine; In methanol; N,N-dimethyl-formamide;
Example 84 In an atmosphere of nitrogen, 10 mmole of 1,3-dicarboxyadamantane obtained by the method of Example 64 was dissolved in 10 ml of DMF. To the mixture, 30 mmole of thionyl chloride was added dropwise over 30 minutes and the mixture was heated to begin to reflux around the conclusion of addition. After refluxing for 2 hours, the mixture was cooled. To the mixture, 40 mmole of triethylamine was added followed by 22 mmole of methanol over 30 minutes while retaining the temperature of the mixture at 10°C or less, and then stirred for more 2 hours. As a result, the conversion of 1,3-dicarboxyadamantane was 99percent, and 1,3-bis(methoxycarbonyl)adamantane (yield 95percent) was formed. White solid Mass spectral data [M]+: 252 IR(cm-1): 1620, 1240, 1030
As a result, The conversion of 1,3-dicarboxyadamantane was 90percent, and 1-carboxy-3-hydroxymethyladamantane (yield 80percent) was formed. White solid Mass spectral data [M]+: 210 IR(cm-1): 3350, 3000, 1650
With thionyl chloride; dimethyl amine; In N,N-dimethyl-formamide;
Example 86 In an atmosphere of nitrogen, 10 mmole of 1,3-dicarboxyadamantane obtained by the method of Example 64 was dissolved in 10 ml of DMF. To the mixture, 30 mmole of thionyl chloride was added dropwise over 30 minutes and the mixture was heated to begin to reflux around the conclusion of addition. After refluxing for 2 hours, the mixture was cooled. To the mixture, 50 mmole of dimethylamine was added dropwise over 30 minutes while retaining the temperature of the mixture at 10°C or less, and then stirred for more 2 hours. As a result, the conversion of 1,3-dicarboxyadamantane was 99percent, and 1,3-bis(N,N-dimethylcarbamoyl)adamantane (yield 95percent) was formed. Pale yellow solid Mass spectral data [M]+: 278 IR(cm-1): 1670, 1420, 1170
1,3-Adamantanedicarboxylic acid (10.0 g) was converted into its diacid chloride by refluxing with 40 ml thionyl chloride. The acid chloride was obtained by evaporating off excess thionyl chloride. The diacid chloride (0.0438 mole, 11.45 g) was added slowly to a solution of AlCl3 (14.03 g, 0.1052 mole) in anhydrous anisole (47.41 g, 0.4384 mole), chilled with an ice bath. The reaction mixture was stirred overnight at room temperature under a nitrogen atmosphere. The mixture was worked up in about 400 ml of 0.2 M HCl, filtered and stirred in methanol to precipitate a crude white solid. The solid was recrystallized from toluene to yield 11.6 grams of the crystals (66percent, melting point 148-150° C.).
2.4 g (10 mmoles) of <strong>[39269-10-8]adamantane-1,3-dicarboxylic acid</strong> and 4 ml of concentrated sulphuric acid in 100 ml of 95percent ethanol were heated under reflux for 9 h. The mixture was allowed to return to ambient temperature. 50 ml of NH4OH was added to the reaction medium then the solvents were evaporated off. The dry residue was taken up in 100 ml of water saturated with NaCl then extracted with 200 ml of CH2Cl2. The organic phase was dried over Na2SO4, filtered and concentrated to produce an oil identified as 12: 2.6 g (Yield=93percent).
With sodium hydroxide; In water; at 180℃; for 72h;Autoclave;
General procedure: Compound 7 was prepared using a procedure similar to the synthesis of 5 with the use of 1,3-adcH2 (0.126 g, 0.5 mmol) in place of 1,3-adaH2. The product was isolated as pale green plate-shaped crystals in 45percent yield (based on Ni). Elemental analysis (percent): C34H36O8N2Ni (387.08): calc. C, 58.96; H, 5.73; N.3.62. Found: C, 58.82; H, 5.98; N 3.55. IR (KBr, cm?1): nu = 3426m, 3101w, 2939s, 2906s, 2858m, 1602s, 1535m, 1487w, 1450w, 1400s, 1339w, 1314w, 1286w, 1219m, 1227w, 1070w, 1042w, 1003w, 953w, 881w, 810m, 774w, 710m, 628w, 507m, 435w.
With sodium hydroxide; In water; at 180℃; for 72h;Autoclave;
General procedure: A mixture of Cu(NO3)2·4H2O (0.242 g, 1.0 mmol), 1,3-adcH2 (0.112 g, 0.5 mmol), NaOH (0.04 g, 1.0 mmol) in de-ionized water (15 mL) was stirred for 15 min in air. The resulting mixture was sealed in a 25-mL Teflon-lined reactor, heated at 180 °C for 3 days and then cooled to room temperature at a rate of 5 °C h?1. The crude product was isolated as green plate-shaped crystals, washed with water and ethanol, and dried under vacuo (yield 35percent based on Cu). Elemental analysis (percent): C12H15O5Cu (302.78): calc. C, 47.60; H, 4.99. Found: C, 47.36; H, 5.08. IR (KBr, cm?1): nu = 3440s, 2930s, 2857m, 1660w, 1587s, 1499w, 1465w, 1394s 1341w, 1313m, 1260w, 1119w, 998w, 880w, 824w, 775w, 748w, 696m, 677w, 617w, 507m, 437m.
[Zn(1,4-bis(2-methylimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene)(1,3-ADC)]·2H2O}n[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
60%
In acetonitrile; at 140℃; for 7h;High pressure;
General procedure: A mixture of Zn(CH3COO)2·2H2O (21.9 mg, 0.1 mmol), bmimx (32.3 mg, 0.1 mmol) and 1,2-H2BDC (16.6 mg, 0.1 mmol) in 8 mL of the component solvent (H2O/CH3CN=3:1) was sealed in a 25 mL Teflon-lined stainless steel vessel and heated to 140 °C for 70h. After the mixture was cooled to room temperature at a rate of 5°C h?1, colorless crystals of 2 were obtained with a yield of 65percent (based on Zn).
A mixture of H2ADC (0.10mmol, 22.4mg) and bib (0.10mmol, 21.8mg) in 5mL CH3OH was layered onto a solution of AgNO3 (0.10mmol, 17.0mg) in 5mL H2O, and then was kept in the dark at room temperature resulting in colorless block crystals formation after one week. Yield: 50percent. Anal. calcd for C18H25Ag2N2O5: C 38.25, H 4.46, N 4.96. Found: C 38.62, H 4.26, N 4.81. IR (KBr, cm?1): 3425 (m), 3143 (w), 2903 (m), 1897 (w), 1686 (w), 1613 (m), 1579 (s), 1501 (m), 1442 (w), 1388 (s), 1224 (w), 1124 (m), 1081 (w), 1032 (m), 878 (w), 830 (m), 768 (m), 684 (w), 640 (w). Crystal data for 1: [Ag2(ADC)(bib)0.5]·H2O}n, T=293(2) K, M=565.14, monoclinic, space group P21/c, a=10.3065(10)A, b=12.5605(12)A, c=15.3345(14)A, alpha=90°, beta=103.463°, gamma=90°. V=1930.57A3, Z=4, R1=0.0285, wR2=0.0888.
2Co(2+)*H2O*C12H14O4(2-)*2C19H15N2O4(1-)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
30.5%
With sodium hydroxide; In water; N,N-dimethyl-formamide; at 140℃; for 72h;Autoclave;
A mixture of CoSO4.7H2O (0.20mmol,0.056g), HL (0.10mmol,0.034g), H2adbc (0.15mmol,0.034g) and NaOH(0.30mmol,0.012g), in H2O (14ml) and DMF (2 drops) was sealed in a 25 ml Teflon-lined stainless steel container, which was heated to 140 1C for 72h and then cooled down to room temperature at a rate of 5 C h. Purple crystals of 2 were collected and washed with distilled water and dried in air to give the product: 30.5%yield(based onHL).Anal.Calc.forC50H44Co2N4O13 (%): C,58.48;H,4.29;N, 5.46.FoundC,58.47;H,4.31;N,5.45.IR(KBrpellet,cm1): 34293056,1710,1619,1581,1467,1373,1166,1062,788,and719.
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