172  US 9,703,193 B2  171  stirring for 5 minutes, and removing a supernatant were  repeated 5 times. Subsequent vacuum concentration left 3 .80  g of the desired Intermediate 3 as oily product (yield 68% ).  Analytic results by IR, $^{1}$H-NMR, $^{19}$F-NMR and MALDI› TOF-MS are shown below.  v=3039,2911,2857, 1491, 1479, 1455, 1331, 1219, 1189,  1163, 1139, 1066, 970, 929, 903, 863, 816, 779, 726, 703,  672, 604, 573 cm- 1  $^{1}$H-NMR (500 MHz, DMSO-d$_{6}$ ):  o=l.48 (2H, m), 1.67 (4H, m), 1.74-1.82 (4H, m), 1.94  (2H, d), 2.09 (2H, d), 3.01 (9H, s), 4.50 (2H, s), 4.52 (lH,  t), 7.51-7.55 (5H, m) ppm  $^{19}$F-NMR (500 MHz, DMSO-d$_{6}$ ): o=-78.8 (3F, s) ppm  IR (D-ATR):  MALDI-TOF-MS:  Positive M+ 150 (corresponding to C$_{10}$H$_{16}$N+)  Negative M- 362 (corresponding to C$_{10}$H$_{15}$OSO 2 N- SO$_{2}$CF$_{3}$ )  Synthesis Example 3-2  Synthesis of PAG-3  In a mixture of 20 g of MIBK and 10 g of water, 1.80 g  oflntermediate 3 and 1.44 g oftriphenylsulfonium methyl› sulfate were dissolved, followed by stirring at room tem› perature for 15 minutes. An organic layer was taken out and  washed twice with 10 g of water, twice with a mixture of 10  g water and 2 g methanol, and twice with 10 g of water. The  organic layer was concentrated in vacuum, dissolved in 2 g  of dichloroethane, added to 25 g of diisopropyl ether, and  stirred for 30 minutes for crystallization. White crystals were  collected by filtration, washed twice with 20 g of diisopropyl  ether, and dried in vacuum, obtaining 1.83 g of the desired  PAG-3 as white solid product (yield 89%). Analytic results  by IR, $^{1}$H-NMR, $^{19}$F-NMR and MALDI-TOF-MS are  shown below.  IR (D-ATR):  v=3059,2905,2857, 1475, 1449, 1330, 1314, 1224, 1191,  1172, 1136, 1063, 1041, 996,971,931,903,865,852,816,  776, 753, 685, 672, 637, 604, 573 cm- 1  $^{1}$H-NMR (500 MHz, DMSO-d$_{6}$ ):  o=l.47 (2H, m), 1.66 (4H, m), 1.73-1.82 (4H, m), 1.94  (2H, d), 2.08 (2H, d), 4.52 (lH, t), 7.75-7.88 (15H, m) ppm  $^{19}$F-NMR (500 MHz, DMSO-d$_{6}$ ):  o=-78.8 (3F, s) ppm  MALDI-TOF-MS:  Positive M+ 263 (corresponding to C$_{18}$H$_{15}$S+)  Negative M- 362 (corresponding to C$_{10}$H$_{15}$OSO 2 N› SO2CF3)  Synthesis Example 4  Synthesis of PAG-4  PAG-4  scheme.  was  synthesized according to the following  In a mixture of 20 g of MIBK and 10 g of water, 1.90 g  of Intermediate 3 and 7 .16 g of 1-[ 4-(2-methoxyethoxy )-1- naphthalenyl]tetrahydrothiophenium methylsulfate aqueous  solution (concentration 2011 g/mol) were dissolved, fol› lowed by stirring at room temperature for 15 minutes. An  organic layer was taken out and washed once with 10 g of  water, twice with a mixture of 10 g water and 2 g methanol,  and twice with 10 g of water. The organic layer was  concentrated in vacuum. Steps of dissolving the concentrate  in 2 g of dichloroethane, adding 25 g of diisopropyl ether,  stirring at room temperature for 5 minutes, and removing a  supernatant were repeated twice. The residue was concen- trated in vacuum, obtaining 2.04 g of the desired PAG-4 as  oily product (yield 89%). Analytic results by IR, $^{1}$H-NMR,  and $^{19}$F-NMR are shown below.  IR (D-ATR):  v=2909,2856, 1588, 1571, 1509, 1452, 1429, 1370, 1330,  1272, 1253, 1189, 1162, 1137, 1087, 1067, 1040, 970, 930,  902, 861, 816, 764, 740, 672, 638, 606, 569 cm- 1  $^{1}$H-NMR (500 MHz, DMSO-d$_{6}$ ):  o=l.48 (2H, m), 1.66 (4H, m), 1.73-1.82 (4H, m), 1.94  (2H, d), 2.08 (2H, d), 2.32 (2H, m), 2.43 (2H, m), 3.38 (3H,  s), 3.77 (2H, m), 3.84 (2H, m), 4.05 (2H, m), 4.43 (2H, m),  4.52 (lH, t), 7.23 (lH, d), 7.75 (lH, m), 7.87 (lH, m), 8.11  (lH, m), 8.34 (2H, m) ppm  $^{19}$F-NMR (500 MHz, DMSO-d$_{6}$ ): o=-78.8 (3F, s) ppm  0  0  ~  lCTO-~-N--~-CF~  II  II  -W- O  O  I  Intermediate 3  o/’-....../o’-..  ~  vy  PAG-4 