1,3-Cyclopentanedicarboxylic acid

A 22-L, 3-neck, round bottom flask was equipped with a mechanical stirrer, a J-KEM temperature controller, and anitrogen inlet. The flask was charged with norbornene (200 g, 2.123 mol), ethyl acetate(1.95 L), and acetonitrile (1.95 L). The reaction mixture was cooled to 5 °C using anacetone/dry ice bath. Ruthenium trichloride (9.69 g, 46.72 mmol) was added in oneportion followed by the slow addition of a suspension of sodium periodate (1.816 kg, 8.707 mol) in water (2.925 L) over 30 min. The reaction slowly began to exotherm and was monitored to keep the temperature between 10 °C and 15 °C. After 90 min thereaction mixture suddenly thickened to the point where stirring was difficult andexothermed rapidly up to 39 °C (a large amount of dry ice was added to the cooling bath to control the exotherm). The reaction mixture was allowed to cool to 20 °C, the dryice/acetone bath was removed, and the mixture was stirred at room temperature overnight.The solids were removed by filtration through a pad of celite and the filtrate wasconcentrated to a solid which was triturated with hexane (2 L), filtered, and rinsed with hexane (2 x 500 mL) to yield 195 g (58percent) of cyclopentane-l, 3-dicarboxylic acid.1H NMR (500 Hz, DMSO-<3/4) δ ppm 12.07 (s, 2H), 2.66-2.73 (m, 2H), 2.06-2.12 (m, 1H), 1.85-1.89 (m, 1H), 1.72-1.85 (m, 4H).A mixture of commercially available norbonene (15 g) and RuClA 22-L, 3-neck, round bottom flask was equipped with a mechanical stirrer, a J-KEM temperature controller, and anitrogen inlet. The flask was charged with norbornene (200 g, 2.123 mol), ethyl acetate(1.95 L), and acetonitrile (1.95 L). The reaction mixture was cooled to 5 C using anacetone/dry ice bath. Ruthenium trichloride (9.69 g, 46.72 mmol) was added in oneportion followed by the slow addition of a suspension of sodium periodate (1.816 kg, 8.707 mol) in water (2.925 L) over 30 min. The reaction slowly began to exotherm and was monitored to keep the temperature between 10 C and 15 C. After 90 min thereaction mixture suddenly thickened to the point where stirring was difficult andexothermed rapidly up to 39 C (a large amount of dry ice was added to the cooling bath to control the exotherm). The reaction mixture was allowed to cool to 20 C, the dryice/acetone bath was removed, and the mixture was stirred at room temperature overnight.The solids were removed by filtration through a pad of celite and the filtrate wasconcentrated to a solid which was triturated with hexane (2 L), filtered, and rinsed with hexane (2 x 500 mL) to yield 195 g (58%) of cyclopentane-l, 3-dicarboxylic acid.1H NMR (500 Hz, DMSO-A mixture of commercially available norbonene (15 g) and RuCl3 (0.3 g) in CHCl3 (100 mL) was stirred at room temperature for 5 min. Then a solution OfNaIO4 (163 g) in H2O (1200 mL) was added and the mixture was stirred at room temperature for 2 d. The mixture was filtered through a pad of celite and the organic phase was separated. The aqueous phase was saturated with NaCl and extracted with EtOAc (3 x 500 mL). The combined organic phases were treated with MgSO4 and charcoal, filtered and concentrated to afford the crude title compound as thick slightly purple liquid (13.5 g, 53%). [MH]+ = 159.The monobenzyl esters of the following dicarboxylic acids are obtained similarly by the above procedures. 1, 2-cyclopropanedicarboxylic acid 1, 3-cyclobutanedicarboxylic acid trans-1, 2-cyclobutanedicarboxylic acid 1, 3-cyclopentanedicarboxylic acid trans-1, 3-cyclohexanedicarboxylic acid 1, 4-cycloheptanedicarboxylic acid 1, 3-cycloheptanedicarboxylic acid 1, 4-naphthalenedicarboxylic acid 2, 6-pyridinedicarboxylic acid ...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 30wt%) 1.6 times that of the carboxyl group contained in the carboxylic acid starting material (NH3 content 25wt%, 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 (99% or more).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: 0.5% 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 (99% or more).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 wt%, 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 (99% or more).

Molecular Weight:158.15
XLogP3:0.1
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:4
Rotatable Bond Count:2
Exact Mass:158.05790880
Monoisotopic Mass:158.05790880
Topological Polar Surface Area:74.6
Heavy Atom Count:11
Complexity:167
Undefined Atom Stereocenter Count:2
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes