* 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.
200 g of the compound obtained in the above (2) and 1.5 L of toluene were mixed, heated and completely dissolved, and then charged into a 4 L high-pressure reactor. 10 g of the Pd / Pt catalyst was introduced into the high-pressure reactor, and hydrogen was introduced at 10 bar and purged for 5 minutes. After purging, hydrogen was injected at 12 bar and hydrogenated at 160 and 20 bar. The reaction was maintained for 70 minutes and then the catalyst was removed. The catalyst was separated into 5 L of hexane, followed by filtration and drying to obtain 182 g of a white compound (4). The obtained compounds were identified by NMR (1H and 13C) (JEOL, JNM-LA400) and IR (AVATAR, 360 FT-IR). The results are shown in FIGS. 4 and 5, respectively.
182 g
With hydrogen In toluene at 160℃; for 1.16667 h;
200 g of the compound obtained in the above (2) and 1.5 L of toluene were mixed, heated and completely dissolved, and then charged into a 4 L high-pressure reactor.In the high-pressure reactor In the Pd / Pt catalyst 10 g was charged with hydrogen to 10 bar and then purged (purge) 5 minutes.After purging, hydrogen was injected at 12 bar and heated to 160 ° C,The hydrogenation reaction was carried out at 20 bar.The reaction was maintained for 70 minutes and then the catalyst was removed. The catalyst was separated into 5 L of hexane, followed by filtration and drying to obtain 182 g of a white compound (4).
Reference：
[1] Journal of Organic Chemistry, 1982, vol. 47, # 20, p. 3953 - 3959
[2] Organic Preparations and Procedures International, 1999, vol. 31, # 2, p. 220 - 222
[3] Chemical and Pharmaceutical Bulletin, 1991, vol. 39, # 9, p. 2288 - 2300
[4] Chemical and Pharmaceutical Bulletin, 1995, vol. 43, # 12, p. 2139 - 2151
[5] Monatshefte fur Chemie, 2004, vol. 135, # 7, p. 839 - 847
[6] Bioorganic and Medicinal Chemistry, 2004, vol. 12, # 17, p. 4565 - 4573
[7] Journal of the American Chemical Society, 1951, vol. 73, p. 4889,4891
[8] Journal of the American Chemical Society, 2003, vol. 125, # 35, p. 10498 - 10499
[9] Journal of the American Chemical Society, 2005, vol. 127, # 1, p. 247 - 254
[10] Patent: WO2013/121440, 2013, A1, . Location in patent: Page/Page column 29
[11] Patent: KR2018/65404, 2018, A, . Location in patent: Paragraph 0092; 0099; 0100
[12] Patent: KR2018/65407, 2018, A, . Location in patent: Paragraph 0107-0108
2
[ 129-64-6 ]
[ 17812-27-0 ]
[ 14166-28-0 ]
Yield
Reaction Conditions
Operation in experiment
76%
With sodium hydroxide In water at 70℃; for 0.166667 h;
(Example 16) To 10.0 g of norbornane-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (2) type = 50percent) were added 33.8 g of water and 16.0 g of a 30 wtpercent aqueous solution of sodium hydroxide (1.0 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 4.62 g (exo stereoisomeric ratio for the general formula (2) type = 88percent).; (Example 17) With the exception of adding 48.9 g of water, preparation was conducted in the same manner as the example 16. The obtained solid was 2.42 g (exo stereoisomeric ratio for the general formula (2) type = 91 percent).; (Example 18) With the exceptions of using 41.6 g of water and 12.0 g of the 30 wtpercent aqueous solution of sodium hydroxide (0.75 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 1.84 g (exo stereoisomeric ratio for the general formula (2) type = 88percent).; (Example 19) With the exceptions of using 38.8 g of water and 16.0 g of the 30 wtpercent aqueous solution of sodium hydroxide (1.0 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 4.01 g (exo stereoisomeric ratio for the general formula (2) type = 88percent).; (Example 20) With the exceptions of using 33.2 g of water and 24.1 g of the 30 wtpercent aqueous solution of sodium hydroxide (1.5 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 6.91 g (exo stereoisomeric ratio for the general formula (2) type = 83percent). Furthermore, the filtrate exhibited an endo stereoisomeric ratio for the general formula (2) type = 83percent.; (Example 21) With the exceptions of using 27.6 g of water and 32.2 g of the 30 wtpercent aqueous solution of sodium hydroxide (2.0 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 9.24 g (exo stereoisomeric ratio for the general formula (2) type = 76percent). Furthermore, the filtrate exhibited an endo stereoisomeric ratio for the general formula (2) type = 90percent.; (Example 22) With the exceptions of using 21.6 g of water and 12.0 g of the 30 wtpercent aqueous solution of sodium hydroxide (0.75 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 5.39 g (exo stereoisomeric ratio for the general formula (2) type = 85percent). Furthermore, the filtrate exhibited an endo stereoisomeric ratio for the general formula (2) type = 76percent.; (Example 23) With the exceptions of using 18.8 g of water and 16.1 g of the 30 wtpercent aqueous solution of sodium hydroxide (1.0 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 7.61 g (exo stereoisomeric ratio for the general formula (2) type = 81 percent). Furthermore, the filtrate exhibited an endo stereoisomeric ratio for the general formula (2) type = 83percent.
5-norbornene-endo-2,3-dicarboxylic anhydride and 5-norbornene-exo-2,3-dicarboxylic anhydride were mixed together, tetrahydrofuran was added to the resulting mixture, and a hydrogenation was conducted under a hydrogen atmosphere using 5percent palladium-carbon as a catalyst. The hydrogenation rate was 100percent. Following completion of the hydrogenation reaction, the product was filtered and dried. The resulting powdered mixture of norbornane-endo-2,3-dicarboxylic anhydride and norbornane-exo-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (2) type = 50percent) was used as the test material
Hexadecanoic acid (R)-2-{diethylamino-[2-((1S,2R,6S,7R)-3,5-dioxo-4-aza-tricyclo[5.2.1.02,6]dec-4-yl)-ethoxy]-thiophosphoryloxy}-1-hexadecanoyloxymethyl-ethyl ester[ No CAS ]
With hydrogen;5%-palladium/activated carbon; In tetrahydrofuran;Product distribution / selectivity;
5-norbornene-endo-2,3-dicarboxylic anhydride and 5-norbornene-exo-2,3-dicarboxylic anhydride were mixed together, tetrahydrofuran was added to the resulting mixture, and a hydrogenation was conducted under a hydrogen atmosphere using 5% palladium-carbon as a catalyst. The hydrogenation rate was 100%. Following completion of the hydrogenation reaction, the product was filtered and dried. The resulting powdered mixture of norbornane-endo-2,3-dicarboxylic anhydride and norbornane-exo-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (2) type = 50%) was used as the test material
With sodium hydroxide; In water; at 70℃; for 0.166667h;Product distribution / selectivity;
(Example 16) To 10.0 g of norbornane-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (2) type = 50%) were added 33.8 g of water and 16.0 g of a 30 wt% aqueous solution of sodium hydroxide (1.0 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), and the mixture was stirred at 70C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 4.62 g (exo stereoisomeric ratio for the general formula (2) type = 88%).; (Example 17) With the exception of adding 48.9 g of water, preparation was conducted in the same manner as the example 16. The obtained solid was 2.42 g (exo stereoisomeric ratio for the general formula (2) type = 91 %).; (Example 18) With the exceptions of using 41.6 g of water and 12.0 g of the 30 wt% aqueous solution of sodium hydroxide (0.75 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 1.84 g (exo stereoisomeric ratio for the general formula (2) type = 88%).; (Example 19) With the exceptions of using 38.8 g of water and 16.0 g of the 30 wt% aqueous solution of sodium hydroxide (1.0 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 4.01 g (exo stereoisomeric ratio for the general formula (2) type = 88%).; (Example 20) With the exceptions of using 33.2 g of water and 24.1 g of the 30 wt% aqueous solution of sodium hydroxide (1.5 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 6.91 g (exo stereoisomeric ratio for the general formula (2) type = 83%). Furthermore, the filtrate exhibited an endo stereoisomeric ratio for the general formula (2) type = 83%.; (Example 21) With the exceptions of using 27.6 g of water and 32.2 g of the 30 wt% aqueous solution of sodium hydroxide (2.0 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 9.24 g (exo stereoisomeric ratio for the general formula (2) type = 76%). Furthermore, the filtrate exhibited an endo stereoisomeric ratio for the general formula (2) type = 90%.; (Example 22) With the exceptions of using 21.6 g of water and 12.0 g of the 30 wt% aqueous solution of sodium hydroxide (0.75 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 5.39 g (exo stereoisomeric ratio for the general formula (2) type = 85%). Furthermore, the filtrate exhibited an endo stereoisomeric ratio for the general formula (2) type = 76%.; (Example 23) With the exceptions of using 18.8 g of water and 16.1 g of the 30 wt% aqueous solution of sodium hydroxide (1.0 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 7.61 g (exo stereoisomeric ratio for the general formula (2) type = 81 %). Furthermore, the filtrate exhibited an endo stereoisomeric ratio for the general formula (2) type = 83%.
5,5'-exo-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bisbicyclo[2.2.1] heptane-exo-2,3-dicarboxylic anhydride[ No CAS ]
[ 14166-28-0 ]
Yield
Reaction Conditions
Operation in experiment
platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane; In xylene; at 80 - 90℃; for 2h;
Example 1Synthesis of Tetracarboxylic Dianhydride Represented by Chemical Formula (6)In a 1 L four-necked flask equipped with a stirrer, dropping funnel, condenser tube and thermometer there were charged 240 g of toluene and 123.20 g (0.7505 mol) of exo-HAC, and heating and stirring were initiated. When the temperature in the flask reached 80 C., 2.99 g of a platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (xylene solution with 2% platinum concentration) (3.07×10-4 gram atom as platinum metal) by Aldrich Co. was added and 50.17 g (0.3735 mol) of 1,1,3,3-tetramethyldisiloxane (hereunder referred to as ?TMDS?) was slowly added dropwise into the flask through a dropping funnel. Since the reaction temperature increases with dropwise addition of the TMDS, it was added dropwise over a period of one hour while taking care to maintain a temperature of 90 C. in the flask, and then reaction was continued for 1 hour while maintaining a temperature of 90 C. inside the flask. Next, the reaction mixture was cooled, 15 g of active carbon was added and the mixture was stirred at room temperature for 2 hours, after which the active carbon was removed by filtration. A rotary evaporator was used for concentration of the filtrate under reduced pressure, to obtain 166.4 g of a viscous, colorless transparent liquid. As a result of GPC analysis, it was confirmed that none of the toluene used as a solvent was present in the liquid.Next, extraction for purification were performed to remove the compound represented by chemical formula (9a), as a by-product of the reaction. After charging 86.8 g of the viscous, colorless transparent liquid, 169.4 g of hexane and 23.9 g of toluene into the extraction-end flask of a continuous simple extraction apparatus, there were charged into the distillation-end flask 101.3 g of hexane, and then 60.0 g of hexane through a dropping funnel. Operation was conducted for 10 hours with a water bath temperature of 65 C. at the extraction-end and an oil bath temperature of 115 C. at the distillation-end. When the lower layer in the extraction-end flask was recovered and the solvent therein was removed and weighed, it was found to be 62.0 g. Also, the compound represented by chemical formula (9b), as another by-product component, was removed by distillation while blowing in a trace amount of nitrogen under reduced pressure of 70 Pa.The target substance 5,5'-exo-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bisbicyclo[2.2.1] heptan e-exo-2,3-dicarboxylic anhydride represented by chemical formula (6) (hereunder refereed to as ?exo-NB-DiSXDA?) was thus obtained. The purity of the exo-NB-DiSXDA was 98.3 wt %, and it was a colorless transparent, viscous liquid having a viscosity of 2960 Pa·s at 40 C. and 42500 Pa·s at 25 C., with no visible changes in appearance even after 2 months of storage.By NMR measurement, the obtained exo-NB-DiSXDA was confirmed to have the stereostructure of a tetracarboxylic dianhydride represented by chemical formula (6). FIG. 1 shows the 1H-NMR spectrum of the exo-NB-DiSXDA as the tetracarboxylic dianhydride of Example 1. In FIG. 1, the circled numerals indicate the carbon positions, the subscript ?a? being used for protons measured at the low frequency end and the subscript ?b? being used for protons measured at the high frequency end, for the methylene protons. The dashed lines in the stereostructure are the symmetry lines of the molecule. The integrated intensity ratio reflects the structure. FIG. 2 is a 13C-NMR spectrum for exo-NB-DiSXDA, and 11 carbon peaks were measured for the structure
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
110K+ Compounds
Competitive Price
1-2 Day Shipping
