US 9,703,193 B2  170  169  stirred for aging at room temperature for 6 days. The  reaction solution was quenched with 20 g of water, com› bined with 0.79 g of pyridine, and stirred at room tempera› ture for 30 minutes. An organic layer was taken out, washed  twice with 15 g of water, combined with 2.79 g ofbenzyl- trimethylammonium chloride and 30 g of water, and stirred  for 1 hour. The organic layer was taken out and washed 3  times with 15 g of water, followed by vacuum concentration  to remove dichloromethane. Steps of adding 30 g of diiso- propyl ether to the concentrate, stirring for 5 minutes, and  removing a supernatant were repeated 3 times. Subsequent  vacuum concentration left 2.65 g of the desired Intermediate  $^{19}$F-NMR (500 MHz, DMSO-d$_{4}$ ): o=-78.8 (3F, s) ppm  MALDI-TOF-MS:  Positive M+ 263 (corresponding to C$_{18}$H$_{15}$S+)  Negative M- 364 (corresponding to C$_{8}$H$_{9}$O 2 -OSO$_{1}$N› SO2CF3)  Synthesis Example 3  Synthesis of PAG-3  PAG-3 was synthesized according to the following  scheme.  Intermediate 3  PAG-3  2 as oily product (yield 51%). Analytic results by $^{1}$H- and  $^{19}$F-NMR spectroscopy are shown below.  $^{1}$H-NMR (500 MHz, DMSO-d$_{6}$ ):  o=l.55 (2H, m), 1.83 (lH, m), 1.98 (lH, m), 2.49 (le, m),  2.55 (lH, m), 3.00 (9H, s), 3.18 (lH, m), 4.20 (lH, s), 4.50  (2H, s), 4.67 (lH, d), 7.51-7.54 (5H, m) ppm  $^{19}$F-NMR (500 MHz, DMSO-d$_{6}$ ): o=78.9 (3F, s) ppm  Synthesis Example 2-2  Synthesis of PAG-2  Synthesis Example 3-1  Synthesis of Intermediate 3  Under ice cooling, a solution of 1.64 g of trifluorometh- anesulfonamide and 2.61 g of pyridine in 5 g of acetonitrile  was added dropwise to a solution of 1 .48 g of sulfuryl  chloride in 5 g of acetonitrile. The solution was stirred still  under ice cooling for 10 minutes and then at room tempera› ture for 5.5 hours. Under ice cooling, a solution of 1.52 g of  2-adamantanol and 0.06 g ofN,N-dimethylaminopyridine in  5 g of acetonitrile and 5 g of dichloromethane was added  dropwise to the reaction solution. The solution was stirred at  50°  C. for 76 hours for aging. The reaction solution was  quenched with 0.5 g of methanol and stirred at 50°  C. for a  further 15 hours. Then 5 g of water and 0.5 g of pyridine  were added to the solution, which was stirred for 1 hour.  Further, 40 g of MIBK and 20 g of water were added to the  solution, from which an organic layer was taken out. The  organic layer was washed with 20 g of water, combined with  2.04 g of benzyltrimethylammonium chloride and 20 g of  water, and stirred for 1 hour. The organic layer was taken out  and washed twice with 20 g of water, twice with a mixture  of 20 g water and 5 g methanol, and twice with 20 g of water,  followed by vacuum concentration to remove the solvent.  Steps of adding 30 g of diisopropyl ether to the concentrate,  In a mixture of 20 g of dichloromethane and 10 g of water,  2.64 g of Intermediate 2 and 1.92 g of triphenylsulfonium  methylsulfate were dissolved, followed by stirring at room  temperature for 30 minutes. An organic layer was taken out  and washed 3 times with 10 g of water and 3 times with a  mixture of 10 g water and 1 g methanol. The organic layer  was concentrated in vacuum, combined with 30 g of diiso› propyl ether, and stirred for 30 minutes for crystallization.  Crystals were collected by filtration, washed twice with 20  g of diisopropyl ether, and dried in vacuum, obtaining 2.53  g of the desired PAG-2 as white solid product (yield 79%).  Analytic results by $^{1}$H-NMR, $^{19}$F-NMR and MALDI-TOF› MS are shown below.  $^{1}$H-NMR (500 MHz, DMSO-d$_{6}$ ):  o=l .55 (2H, m), 1.82 (lH, m), 2.00 (lH, m), 2.49 (lH, m), 65  2.55 (lH, d), 3.19 (lH, m), 4.20 (lH, s), 4.67 (lH, d),  7.76-7.88 (15H, m) ppm 