JP5363010B2 - α―アミノジフルオロメチレン誘導体の製造方法 - Google Patents
α―アミノジフルオロメチレン誘導体の製造方法 Download PDFInfo
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- 0 **(*)C(*)(C(N)(N)N)O* Chemical compound **(*)C(*)(C(N)(N)N)O* 0.000 description 5
- PICVMEWLYHWHNC-WOJBJXKFSA-N CCCC[C@]1(C([C@@H](c2ccccn2)O)(F)F)Oc(cccc2)c2N1CC=C Chemical compound CCCC[C@]1(C([C@@H](c2ccccn2)O)(F)F)Oc(cccc2)c2N1CC=C PICVMEWLYHWHNC-WOJBJXKFSA-N 0.000 description 1
- IDNYANAXRJLAAE-VGAJERRHSA-N CCCC[C@]1(CC(c2ncccc2)O)Oc(cccc2)c2N1CC=C Chemical compound CCCC[C@]1(CC(c2ncccc2)O)Oc(cccc2)c2N1CC=C IDNYANAXRJLAAE-VGAJERRHSA-N 0.000 description 1
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
J. Molecular Biology, 255, 321 (1996) J. Molecular Biology, 315, 21 (2002) Chemical Reviews, 96, 1642 (1996) Tetrahedron Lett., 37, 1061 (1996) J. Org. Chem., 63, 8049 (1998) J. Chem. Soc., Perkin Trans. 1, 2525 (1999) J. Org. Chem., 69, 1634 (2004) J. Org. Chem., 67, 8276 (2002) J. Fluor. Chem., 125, 767 (2004) J. Org. Chem., 71, 2159 (2006) J. Org. Chem., 59, 607 (1994)
1.下記一般式(1)
で表されるトリフルオロアセトアルデヒド−N,O−アセタール化合物と下記一般式(2)
R4Li (2)
(式中、R4は、置換基を有してもよい炭素数1〜20のアルキル基もしくはアルケニル基、または置換基を有してもよい炭素数6〜30のアリール基もしくはヘテロ芳香族基を表す。)
で表される有機リチウム化合物を反応させた後、アルデヒド化合物、ケトン化合物、イミニウム化合物、求電子性ハロゲン化剤及びブレンステッド酸からなる群から選ばれる1種以上の求電子性化合物を反応させることを特徴とする、一般式(3)
で表されるα―アミノジフルオロメチレン誘導体の製造方法。
で表されるアルデヒド化合物またはケトン化合物であり、α―アミノジフルオロメチレン誘導体が下記一般式(5)
で表される化合物であることを特徴とする1項に記載のα―アミノジフルオロメチレン誘導体の製造方法。
で表されるイミニウム化合物であり、α―アミノジフルオロメチレン誘導体が下記一般式(7)
で表される化合物であることを特徴とする1項に記載のα―アミノジフルオロメチレン誘導体の製造方法。
Y−Z (8)
(式中、Yは塩素原子、臭素原子またはヨウ素原子を表し、Zは塩素原子、臭素原子、ヨウ素原子、アミノ基、アミド基またはイミド基を表す。)
で表される求電子性ハロゲン化剤であり、α―アミノジフルオロメチレン誘導体が下記一般式(9)
で表される化合物であることを特徴とする1項に記載のα―アミノジフルオロメチレン誘導体の製造方法。
で示されるα―アミノジフルオロメチレン誘導体。
で示されるα―アミノジフルオロメチレン誘導体。
で示されるα―アミノジフルオロメチレン誘導体。
で示されるα―アミノジフルオロメチレン誘導体。
以下に実施例を用いて本発明を詳細に説明するが、本発明はこの実施例によって限定されるものではない。
IR (neat) 3064, 2983, 1487, 1291, 1156, 739 cm-1;
1H NMR (400 MHz, CDCl3) d3.77 (1H, dd, J = 15.8, 6.9 Hz), 3.91 (1H, dd, J = 15.8, 5.2 Hz), 5.28 (1H, dd, J = 8.7, 1.4 Hz), 5.32 (1H, dd, J = 15.6, 1.4 Hz), 5.66 (1H, q, JH-F = 4.0 Hz), 5.78-5.89 (1H, m), 6.73 (1H, d, J = 7.7 Hz), 6.78-6.83 (2H, m), 6.84-6.91 (1H, m);
13C NMR (100 MHz, CDCl3) d54.2, 92.8 (q, JC-F = 35.8 Hz), 108.3, 110.4, 119.3, 121.3, 121.8 (q, JC-F= 284.5 Hz), 122.2, 136.1, 138.0, 150.2;
19F NMR (282 Hz, CDCl3) d-21.3 (3F, d, JH-F = 4.0 Hz);
MS (ESI-TOF) m/z230 [M+H]+;
HRMS calcd for C11H11F3NO [M+H]+, 230.0793; found, 230.0804.
IR (neat) 3065, 2888, 1601, 1488, 1292, 1254, 1153, 739, 697 cm-1;
1H NMR (400 MHz, CDCl3) d4.35 (1H, d, J = 15.4 Hz), 4.54 (1H, d, J = 15.4 Hz), 5.68 (1H, q, JH-F = 4.0 Hz), 6.67 (1H, brd, J = 6.9 Hz), 6.78-6.88 (3H, m), 7.28-7.40 (5H, m);
13C NMR (100 MHz, CDCl3) d55.2, 93.0 (q, JC-F = 35.8 Hz), 108.3, 110.0, 121.1, 121.8 (q, JC-F= 284.3 Hz), 122.2, 127.8, 128.0, 128.8, 136.2, 138.4, 149.9;
19F NMR (282 Hz, CDCl3) d-20.9 (3F, d, JH-F = 4.0 Hz);
MS (ESI-TOF) m/z280 [M+H]+;
HRMS calcd for C15H13F3NO [M+H]+, 280.0949; found, 280.0968.
油状物質;
IR (neat) 3543, 3064, 2959, 2872, 1599, 1495, 1401, 1317, 1239, 1031, 731, 731, 699 cm-1;
1H NMR (400 MHz, CDCl3) d 0.88 (3H, t, J = 7.3 Hz), 1.12-1.26 (1H, m), 1.26-1.52 (3H, m), 2.00-2.13 (1H, m), 2.22-2.35 (1H, m), 2.77 (1H, br, OH), 3.70-3.82 (2H, m), 5.19-5.26 (2H, m), 5.33 (1H, d, J = 17.2 Hz), 5.77-5.90 (1H, m), 6.40 (1H, d, 7.6 Hz), 6.62 (1H, t, J = 7.6 Hz), 6.70 (1H, d, J = 7.6 Hz), 6.79 (1H, t, J = 7.6 Hz), 7.29-7.40 (5H, m);
13C NMR (100 MHz, CDCl3) d 13.9, 22.6, 23.5, 30.5, 47.7 (d, JC-F= 2.7 Hz), 72.3 (dd, JC-F= 30.5, 22.4 Hz), 104.3 (t, JC-F= 29.3 Hz), 105.5, 106.8, 117.1, 118.1, 119.1 (dd, JC-F = 265.5, 254.0 Hz), 122.0, 128.05, 128.09, 128.6, 133.9, 136.5, 139.3, 148.6;
19F NMR (282 Hz, CDCl3) d-60.4 (1F, dd, JF-F = 269.6 Hz, JH-F = 17.8 Hz), -52.0 (1F, dd, JF-F = 269.6 Hz, JH-F = 4.0 Hz);
MS (ESI-TOF) m/z 396 [M+Na]+;
HRMS calcd for C22H25F2NNaO2[M+Na]+, 396.1751; found, 396.1777.
Anal. Calcd for C22H25F2NO2: C, 70.76; H, 6.75; N, 3.75. Found: C, 70.58; H, 6.98; N, 3.58.
油状物質;
IR (neat) 3540, 3064, 2959, 2872, 1599, 1465, 1316, 1239, 1086, 1062, 929, 732, 699 cm-1;
1H NMR (400 MHz, CDCl3) d 0.88 (3H, t, J= 7.2 Hz), 1.16-1.52 (4H, m), 2.00-2.18 (2H, m), 3.85 (1H, dd, J = 16.2, 6.5 Hz), 3.96-4.04 (1H, m), 5.13-5.22 (1H, m), 5.29 (1H, dd, J = 10.2, 1.3 Hz), 5.40 (1H, dd, J = 17.2, 1.3 Hz), 5.94-6.07 (1H, m), 6.51 (1H, d, J = 7.5 Hz), 6.60-6.67 (2H, m), 6.74-6.83 (1H, m), 7.30-7.38 (3H, m), 7.39-7.45 (2H, m);
13C NMR (100 MHz, CDCl3) d 13.9, 22.6, 23.6, 30.4, 48.1, 72.7 (dd, JC-F= 28.7, 23.8 Hz), 103.7 (t, JC-F= 29.6 Hz), 105.9, 106.9, 117.6, 118.5, 118.7 (dd, JC-F = 260.9, 257.8 Hz), 121.8, 128.0, 128.2, 128.5, 133.9, 136.2, 139.1, 148.8;
19F NMR (282 Hz, CDCl3) d -63.6 (1F, dd, JF-F= 269.3 Hz, JH-F = 17.8 Hz), -51.0 (1F, d, JF-F = 269.3 Hz);
MS (ESI-TOF) m/z 396 [M+H]+;
HRMS calcd for C22H25F2NNaO2[M+Na]+, 396.1751; found, 396.1726.
Anal. Calcd for C22H25F2NO2: C, 70.76; H, 6.75; N, 3.75. Found: C, 70.75; H, 6.77; N, 3.66.
油状物質;
IR (neat) 3469, 3064, 2958, 2871, 1613, 1599, 1514, 1496, 1249, 1069, 734 cm-1;
1H NMR (400 MHz, CDCl3) d 0.88 (3H, d, J= 7.3 Hz), 1.12-1.26 (1H, m), 1.26-1.51 (3H, m), 2.00-2.11 (1H, m), 2.22-2.34 (1H, m), 2.69 (1H, br, OH), 3.74 (1H, dd, J= 16.4, 6.1 Hz), 3.76-3.84 (1H, m), 3.80 (3H, s), 5.19 (1H, dd, JH-F = 17.8, 4.2 Hz), 5.24 (1H, d, J = 10.3 Hz), 5.33 (1H, d, J = 17.2 Hz), 5.78-5.90 (1H, m), 6.39 (1H, m), 6.58-6.64 (1H, m), 6.69 (1H, d, J = 7.6 Hz), 6.75-6.80 (1H, m), 6.86 (2H, d, J = 8.6 Hz), 7.28 (2H, d, J = 8.6 Hz);
13C NMR (100 MHz, CDCl3) d 13.9, 22.6, 23.5, 30.5, 47.6 (d, JC-F = 2.5 Hz), 55.2, 71.9 (dd, JC-F = 30.6, 22.7 Hz), 104.2 (t, JC-F = 29.5 Hz), 105.4, 106.8, 113.5, 117.1, 118.0, 119.2 (dd, JC-F = 265.6, 253.5 Hz), 122.0, 128.7, 129.3, 133.9, 139.3, 148.6, 159.8;
19F NMR (282 Hz, CDCl3) d -60.7 (1F, dd, JF-F= 269.3 Hz, JH-F = 17.8 Hz), -51.3 (1F, dd, JF-F = 269.5 Hz, JH-F = 4.2 Hz);
MS (ESI-TOF) m/z 426 [M+Na]+;
HRMS calcd for C23H27F2NNaO3[M+Na]+, 426.1857; found, 426.1863.
油状物質;
IR (neat) 3485, 3064, 2959, 2872, 1613, 1599, 1514, 1496, 1248, 1176, 1070, 1034, 734 cm-1;
1H NMR (400 MHz, CDCl3) d 0.87 (3H, d, J = 7.2 Hz), 1.14-1.50 (4H, m), 1.99-2.16 (2H, m), 3.21 (1H, br, OH), 3.80 (3H, s), 3.83 (1H, dd, J = 16.3, 6.2 Hz), 3.96-4.03 (1H, m), 5.09-5.16 (1H, m), 5.27 (1H, dd, J = 10.2, 1.4 Hz), 5.39 (1H, dd, J = 17.2, 1.4 Hz), 5.92-6.05 (1H, m), 6.47 (1H, d, J = 7.5 Hz), 6.59-6.64 (2H, m), 6.73-6.80 (1H, m), 6.86 (2H, d, J = 8.6 Hz), 7.32 (2H, d, J = 8.6 Hz);
13C NMR (100 MHz, CDCl3) d13.9, 22.6, 23.6, 30.4, 48.1, 55.2, 72.3 (dd, JC-F = 29.3, 23.2 Hz), 103.7 (t, JC-F = 28.6 Hz), 105.9, 106.9, 113.5, 117.6, 118.5, 118.8 (dd, JC-F = 260.6, 257.5 Hz), 121.8, 128.3 (d, JC-F= 1.2 Hz), 129.4, 133.9, 139.1, 148.8, 159.8;
19F NMR (282 Hz, CDCl3) d-63.7 (1F, dd, JF-F = 267.3 Hz, JH-F = 17.8 Hz), -51.3 (1F, d, JF-F = 267.3 Hz);
MS (ESI-TOF) m/z 426 [M+Na]+;
HRMS calcd for C23H27F2NNaO3[M+Na]+, 426.1857; found, 426.1836.
油状物質;
IR (neat) 3485, 3067, 2961, 2874, 1599, 1496, 1326, 1239, 1167, 1127, 1068, 1018, 930, 782, 735 cm-1;
1H NMR (400 MHz, CDCl3) d 0.88 (3H, t, J = 7.2 Hz), 1.12-1.25 (1H, m), 1.26-1.50 (3H, m), 2.01-2.14 (1H, m), 2.19-2.31 (1H, m), 2.95 (1H, br, OH), 3.70-3.86 (2H, m), 5.21-5.34 (2H, m), 5.34 (1H, d, J = 16.3 Hz), 5.74-5.90 (1H, m), 6.42 (1H, d, J = 7.5 Hz), 6.60-6.69 (1H, m), 6.42 (1H, d, J = 7.5 Hz), 6.60-6.69 (1H, m), 6.70 (1H, d, J = 7.5 Hz), 6.77-6.84 (1H, m), 7.47 (2H, d, J = 8.2 Hz), 7.59 (2H, d, J= 8.2 Hz);
13C NMR (100 MHz, CDCl3) d 13.9, 22.6, 23.4, 30.4, 47.9 (d, JC-F = 3.0 Hz), 71.9 (dd, JC-F = 29.5, 23.3 Hz), 104.4 (t, JC-F = 29.4 Hz), 105.8, 107.0, 117.3, 118.5, 118.8 (dd, JC-F = 266.2, 254.3 Hz), 122.3, 124.1 (q, JC-F = 272.0 Hz), 124.9 (q, JC-F= 3.7 Hz), 128.5, 130.7 (q, JC-F= 32.5 Hz), 133.7, 139.2, 140.2, 148.4;
19F NMR (282 Hz, CDCl3) d-59.7 (1F, dd, JF-F = 269.6, JH-F = 18.0 Hz), -52.3 (1F, d, JF-F = 269.6 Hz), 0.05 (3F, s);
MS (ESI-TOF) m/z 464 [M+Na]+;
HRMS calcd for C23H24F5NNaO2[M+Na]+, 464.1625; found, 464.1628.
油状物質;
IR (neat) 3500, 3067, 2961, 2874, 1599, 1494, 1326, 1239, 1166, 1127, 1067, 1019, 735 cm-1;
1H NMR (400 MHz, CDCl3) d 0.89 (3H, t, J = 7.2 Hz), 1.21-1.52 (4H, m), 2.04-2.20 (2H, m), 3.54 (1H, br, OH), 3.84 (1H, dd, J = 16.1, 6.6 Hz), 3.96-4.04 (1H, m), 5.19-5.28 (1H, m), 5.30 (1H, dd, J = 10.2, 1.4 Hz), 5.42 (1H, dd, J = 17.2, 1.4 Hz), 5.94-6.07 (1H, m), 6.53 (1H, d, J = 7.6 Hz), 6.57-6.68 (2H, m), 6.76-6.84 (1H, m), 7.52 (2H, d, J= 8.3 Hz), 7.58 (2H, d, J = 8.3 Hz);
13C NMR (100 MHz, CDCl3) d 13.8, 22.6, 23.5, 30.3, 48.4, 72.3 (dd, JC-F = 28.9, 23.7 Hz), 103.7 (t, JC-F = 28.7 Hz), 106.3, 107.1, 117.9, 118.3 (t, JC-F= 260.3 Hz), 119.0, 122.0, 124.1 (q, JC-F= 272.2 Hz), 124.8, (q, JC-F= 3.6 Hz), 128.6, 130.5 (q, JC-F= 32.4 Hz), 133.7, 139.0, 140.0, 148.6;
19F NMR (282 Hz, CDCl3) d-63.4 (1F, dd, JF-F = 269.7, 17.9 Hz), -50.8 (1F, d, JF-F= 269.7 Hz), 0.05 (3F, s);
MS (ESI-TOF) m/z 442 [M+H]+;
HRMS calcd for C23H25F5NO2[M+H]+, 442.1805; found, 442.1800.
油状物質;
IR (neat) 3442, 3065, 2959, 2872, 1599, 1496, 1239, 1110, 1080, 924, 733 cm-1;
1H NMR (400 MHz, CDCl3) d 0.88 (3H, d, J = 7.2 Hz), 1.14-1.52 (4H, m), 2.00-2.12 (1H, m), 2.20-2.31 (1H, m), 2.68 (1H, br, OH), 3.78 (1H, dd, J = 16.3, 6.3 Hz), 3.81-3.89 (1H, m), 5.19-5.30 (2H, m), 5.33 (1H, d, J = 17.2 Hz), 5.79-5.83 (1H, m), 6.28-6.36 (2H, m), 6.38 (1H, d, J = 7.6 Hz), 6.75 (1H, td, J = 7.6, 1.0 Hz), 6.65 (1H, d, J = 7.6, 1.0 Hz), 6.71-6.79 (1H, m), 7.39-7.42 (1H, m);
13C NMR (100 MHz, CDCl3) d 13.9, 22.6, 23.5, 30.4, 47.6, 66.9 (dd, JC-F = 30.6, 24.4 Hz), 103.6 (t, JC-F = 28.4 Hz), 105.3, 106.7, 109.3, 110.4, 117.1, 118.0, 119.0 (dd, JC-F = 264.6, 256.0 Hz), 121.8, 134.0, 139.2, 142.7, 147.7, 149.7;
19F NMR (282 Hz, CDCl3) d -59.2 (1F, dd, JF-F= 267.3 Hz, JH-F = 17.8 Hz), -51.3 (1F, dd, JF-F = 267.3 Hz, JH-F = 5.9 Hz);
MS (ESI-TOF) m/z 386 [M+Na]+;
HRMS calcd for C20H23F2NNaO3[M+Na]+, 386.1544; found, 386.1543.
油状物質;
IR (neat) 3521, 3064, 2959, 2872, 1599, 1496, 1240, 1110, 1083, 1060, 1013, 923, 791, 734 cm-1;
1H NMR (400 MHz, CDCl3) d 0.86 (3H, t, J = 7.2 Hz), 1.13-1.25 (1H, m), 1.25-1.49 (3H, m), 1.93-2.03 (1H, m), 2.04-2.15 (1H, m), 2.98 (1H, br, OH), 3.83 (1H, dd, J = 16.3, 6.3 Hz), 3.95-4.05 (1H, m), 5.17-5.30 (1H, m), 5.26 (1H, dd, J = 10.3, 1.5 Hz), 5.38 (1H, dd, J = 17.2, 1.5 Hz), 5.91-6.04 (1H, m), 6.32 (2H, d, J = 1.3 Hz), 6.46 (1H, d, J = 7.2 Hz), 6.55-6.63 (2H, m), 6.71-6.79 (1H, m), 7.40 (1H, t, J = 1.3 Hz);
13C NMR (100 MHz, CDCl3) d 13.9, 22.5, 23.5, 30.1, 48.0, 66.9 (dd, JC-F = 29.0, 24.9 Hz), 103.3 (t, JC-F = 28.0 Hz), 105.8, 106.9, 109.6, 110.4, 117.5, 118.4, 118.7 (t, JC-F = 260.0 Hz), 121.7, 133.9, 139.1, 142.7, 148.8, 149.4 (d, JC-F = 3.0 Hz);
19F NMR (282 Hz, CDCl3) d -60.7 (1F, dd, JF-F= 267.6 Hz, JH-F = 15.8 Hz), -51.3 (1F, dd, JF-F = 267.6 Hz, JH-F = 7.9 Hz);
MS (ESI-TOF) m/z 386 [M+Na]+;
HRMS calcd for C20H23F2NNaO3[M+Na]+, 386.1544; found, 386.1542.
油状物質;
IR (neat) 3365, 3063, 2958, 2871, 1597, 1496, 1402, 1315, 1239, 1206, 1110, 1085, 935, 754, 732 cm-1;
1H NMR (400 MHz, CDCl3) d 0.91 (3H, t, J = 7.2 Hz), 1.20-1.60 (4H, m), 2.06-2.18 (1H, m), 2.53-2.66 (1H, m), 3.86 (1H, dd, J = 16.5, 6.0 Hz), 3.94 (1H, dd, J = 16.5, 5.6 Hz), 5.06-5.60 (1H, br, OH), 5.20 (1H, dd, J = 10.4, 1.2 Hz), 5.25 (1H, JH-F = 21.7 Hz), 5.34 (1H, dd, J = 17.2, 1.2 Hz), 5.84-5.97 (1H, m), 6.49 (1H, d, J = 7.5 Hz), 6.57 (1H, t, J = 7.5 Hz), 6.65 (1H, d, J = 7.5 Hz), 6.75 (1H, t, J = 7.5 Hz), 7.24-7.28 (1H, m), 7.34 (1H, dd, J = 7.8, 2.7 Hz), 7.61-7.69 (1H, m), 8.54 (1H, d, J = 4.9 Hz);
13C NMR (100 MHz, CDCl3) d 14.0, 22.6, 23.8, 31.2, 47.2, 70.7 (dd, JC-F = 32.4, 24.3 Hz), 103.7 (dd, JC-F = 29.3, 24.5 Hz), 104.5, 106.4, 116.8, 117.2, 120.1 (dd, JC-F= 264.8, 255.4 Hz), 121.4, 123.47, 123.50 (t, JC-F = 5.4 Hz), 134.1, 136.4, 139.4, 147.7, 149.2, 153.8; 19F NMR (282 Hz, CDCl3) d -61.8 (1F, dd, JF-F= 263.4 Hz, JH-F = 21.7 Hz), -51.0 (1F, d, JF-F = 263.4 Hz);
MS (ESI-TOF) m/z 397 [M+Na]+;
HRMS calcd for C21H24F2N2NaO2 [M+Na]+, 397.1704; found, 397.1714.
Anal. Calcd for C21H24F2N2O2: C, 67.36; H, 6.46; N, 7.48. Found: C, 67.35; H, 6.53; N, 7.42.
油状物質;
IR (neat) 3361, 2958, 2871, 1597, 1495, 1401, 1313, 1241, 1207, 1109, 1085, 733 cm-1;
1H NMR (400 MHz, CDCl3) d 0.88 (3H, t, J = 7.1 Hz), 1.15-1.51 (4H, m), 2.13-2.31 (2H, m), 3.87 (1H, dd, J= 16.7, 5.7 Hz), 4.03-4.12 (1H, m), 5.10 (1H, dd, JH-F = 17.8, 4.6 Hz), 5.24 (1H, dd, J = 10.3, 1.5 Hz), 5.39 (1H, dd, J = 17.2, 1.5 Hz), 5.91-6.02 (1H, m), 6.41 (1H, d, J = 7.5 Hz), 6.47 (1H, d, J = 7.6 Hz), 6.51-6.57 (1H, m), 6.70-6.77 (1H, m), 7.26-7.31 (1H, m), 7.34 (1H, d, J = 8.0 Hz), 7.63-7.70 (1H, m), 8.58 (1H, d, J = 4.7 Hz);
13C NMR (100 MHz, CDCl3) d 14.0, 22.6, 23.7, 31.0, 47.6, 70.9 (dd, JC-F = 29.8, 26.2 Hz), 103.6 (t, JC-F = 26.5 Hz), 105.3, 106.3, 116.8, 117.7, 119.5 (dd, JC-F= 263.0, 257.9 Hz), 121.4, 123.3 (br), 123.5, 134.2, 136.6, 139.6, 147.7, 149.1, 153.9; 19F NMR (282 Hz, CDCl3) d -60.6 (1F, dd, JF-F= 265.6 Hz, JH-F = 17.8 Hz), -51.6 (1F, dd, JF-F = 265.6 Hz, JH-F = 4.6 Hz);
MS (ESI-TOF) m/z 397 [M+Na]+;
HRMS calcd for C21H24F2N2NaO2 [M+Na]+, 397.1704; found, 397.1678.
Anal. Calcd for C21H24F2N2O2: C, 67.36; H, 6.46; N, 7.48. Found: C, 67.41; H, 6.66; N, 7.43.
油状物質;
IR (neat) 3417, 3061, 2959, 2871, 1599, 1496, 1238, 1070, 732 cm-1;
1H NMR (400 MHz, CDCl3) d 0.91 (3H, t, J = 7.2 Hz), 1.17-1.55 (4H, m), 2.05-2.17 (1H, m), 2.22-2.34 (1H, m), 2.52 (1H, br, OH), 3.82 (1H, dd, J = 16.3, 6.3 Hz), 3.94 (1H, dd, J = 16.3, 5.1 Hz), 4.80 (1H, ddd, JH-F = 13.8, 9.9 Hz, JH-H = 6.9 Hz), 5.22 (1H, d, J = 10.2 Hz), 5.34 (1H, d, J = 17.2 Hz), 5.86-5.99 (1H, m), 6.28 (1H, dd, J = 15.9, 6.9 Hz), 6.37 (1H, d, J = 7.5 Hz), 6.52 (1H, d, J = 15.9 Hz), 6.60 (1H, t, J = 7.5 Hz), 6.68 (1H, d, J = 7.5 Hz), 6.74 (1H, t, J = 7.5 Hz), 7.22-7.37 (5H, m);
13C NMR (100 MHz, CDCl3) d 13.9, 22.5, 23.4, 30.4, 47.8, 71.6 (t, JC-F = 26.4 Hz), 103.5 (t, JC-F = 29.0 Hz), 105.4, 106.7, 117.2, 118.0, 119.8 (dd, JC-F = 261.8, 257.1 Hz), 122.4, 123.5 (t, JC-F = 3.2 Hz), 126.7, 127.9, 128.4, 133.7, 133.9, 136.1, 139.2, 148.7;
19F NMR (282 Hz, CDCl3) d-57.6 (1F, dd, JF-F = 267.6 Hz, JH-F = 13.8 Hz), -56.4 (1F, dd, JF-F = 267.6 Hz, JH-F = 9.9 Hz);
MS (ESI-TOF) m/z 422 [M+Na]+;
HRMS calcd for C24H27F2NNaO2[M+Na]+, 422.1908; found, 422.1899.
Anal. Calcd for C24H27F2NO2: C, 72.16; H, 6.81; N, 3.51. Found: C, 71.91; H, 6.83; N, 3.49.
油状物質;
IR (neat) 3426, 3061, 2959, 2872, 1599, 1495, 1239, 1069, 733 cm-1;
1H NMR (400 MHz, CDCl3) d 0.87 (3H, t, J = 7.2 Hz), 1.12-1.51 (4H, m), 2.05-2.21 (2H, m), 2.69 (1H, br, OH), 3.82 (1H, dd, J = 16.2, 6.4 Hz), 3.98 (1H, dd, J = 16.2, 4.9 Hz), 4.75 (1H, ddd, JH-F = 23.8, 9.2 Hz, JH-H = 7.0 Hz), 5.25 (1H, d, J = 10.2 Hz), 5.36 (1H, d, J = 17.1 Hz), 5.90-6.03 (1H, m), 6.26 (1H, dd, J = 16.0, 7.0 Hz), 6.45 (1H, d, J = 7.6 Hz), 6.50-6.58 (3H, m), 6.69-6.78 (1H, m), 7.20-7.33 (5H, m);
13C NMR (100 MHz, CDCl3) d 13.9, 22.6, 23.4, 30.2, 48.1, 71.8 (dd, JC-F = 27.9, 24.5 Hz), 103.4 (t, JC-F = 28.6 Hz), 105.6, 107.3, 117.5, 118.4, 119.4 (t, JC-F = 259.1 Hz), 121.7, 123.4 (t, JC-F = 3.3 Hz), 126.7, 127.9, 128.4, 133.9, 134.1, 136.2, 139.1, 148.7; 19F NMR (282 Hz, CDCl3) d -60.8 (1F, dd, JF-F= 266.4 Hz, JH-F = 12.8 Hz), -54.9 (1F, dd, JF-F = 266.4 Hz, JH-F = 9.2 Hz);
MS (ESI-TOF) m/z 422 [M+Na]+;
HRMS calcd for C24H27F2NNaO2[M+Na]+, 422.1908; found, 422.1883.
Anal. Calcd for C24H27F2NO2: C, 72.16; H, 6.81; N, 3.51. Found: C, 71.91; H, 6.91; N, 3.32.
油状物質;
IR (neat) 3547, 3063, 3027, 2959, 2871, 1599, 1495, 1240, 1085, 734, 700 cm-1;
1H NMR (400 MHz, CDCl3) d 0.95 (3H, t, J = 7.2 Hz), 1.19-1.33 (1H, m), 1.34-1.59 (3H, m), 1.93-2.06 (1H, m), 2.06-2.20 (3H, m), 2.67-2.78 (2H, m), 2.89-3.00 (1H, m), 3.85 (1H, dd, J = 16.3, 6.3 Hz), 3.96-4.04 (1H, m), 4.08-4.21 (1H, m), 5.28 (1H, d, J = 10.2 Hz), 5.37 (1H, d, J = 17.2 Hz), 5.89-6.01 (1H, m), 6.51 (1H, d, J = 7.5 Hz), 6.67-6.76 (2H, m), 6.81-6.87 (1H, m), 7.18-7.28 (3H, m), 7.29-7.36 (2H, m);
13C NMR (100 MHz, CDCl3) d 13.9, 22.6, 23.6, 30.3, 31.4, 48.1, 69.4 (dd, JC-F = 29.0, 23.7 Hz), 103.6 (t, JC-F = 28.9 Hz), 105.9, 106.8, 117.4, 118.5, 119.5 (t, JC-F = 258.6 Hz), 121.8, 125.8, 128.3, 128.4, 133.8, 139.0, 141.4, 148.8;
19F NMR (282 Hz, CDCl3) d -64.0 (1F, dd, JF-F= 267.3 Hz, JH-F = 17.8 Hz), -54.6 (1F, d, JF-F = 267.3 Hz);
MS (ESI-TOF) m/z 424 [M+Na]+;
HRMS calcd for C24H29F2NNaO2[M+Na]+, 424.2064; found, 424.2044.
無色結晶;
IR (neat) 3564, 2929, 2854, 1599, 1496, 1240, 1089, 924, 732 cm-1;
1H NMR (400 MHz, CDCl3) d 0.90 (3H, t, J = 7.2), 1.08-1.52 (9H, m), 1.53-1.61 (1H, m), 1.62-1.70 (1H, m), 1.70-1.94 (4H, m), 2.11 (2H, t, J = 7.4 Hz), 2.51 (1H, br, OH), 3.81 (1H, dd, J = 16.3, 6.3 Hz), 3.86-4.06 (2H, m), 5.27 (1H, dd, J = 10.3, 1.4 Hz), 5.38 (1H, dd, J = 17.1, 1.4 Hz), 5.91-6.04 (1H, m), 6.47 (1H, d, J = 7.5 Hz), 6.59-6.70 (2H, m), 6.73-6.80 (1H, td, J = 7.5, 1.3 Hz);
13C NMR (100 MHz, CDCl3) d 13.9, 22.6, 23.7, 26.1, 26.2 (2C), 26.7, 30.2, 30.4, 38.4 (d, JC-F = 2.5 Hz), 48.2, 73.1 (dd, JC-F = 28.2, 22.2 Hz), 103.8 (t, JC-F = 28.9 Hz), 105.8, 106.7, 117.4, 118.4, 120.2 (t, JC-F= 260.4 Hz), 121.7, 134.0, 139.3, 149.0;
19F NMR (282 Hz, CDCl3) d for major isomer -60.6 (1F, dd, JF-F= 269.6 Hz, JH-F = 21.7 Hz), -52.6 (1F, d, JF-F = 269.6 Hz), for minor isomer -58.3 (1F, dd, JF-F= 265.6 Hz, JH-F = 21.7 Hz), -55.5 (1F, d, JF-F = 265.6 Hz);
MS (ESI-TOF) m/z 402 [M+Na]+;
HRMS calcd for C22H31F2NNaO2[M+Na]+, 402.2221; found, 402.2206.
IR (neat) 3548, 3064, 2936, 2864, 1599, 1496, 1239, 1086, 989, 731 cm-1;
1H NMR (400 MHz, CDCl3) d 0.87 (3H, t, J = 7.3 Hz), 1.08-1.22 (2H, m), 1.24-1.48 (3H, m), 1.51-1.79 (8H, m), 1.91-2.00 (1H, m), 2.02-2.13 (1H, m), 2.23-2.34 (1H, m), 2.26 (1H, brs, OH), 3.81 (1H, dd, J = 16.2, 6.5 Hz), 3.94-4.03 (1H, m), 5.25 (1H, dd, J = 10.2, 1.4 Hz), 5.37 (1H, dd, J = 17.2, 1.4 Hz), 5.91-6.03 (1H, m), 6.45 (1H, d, J = 7.5 Hz), 6.57-6.67 (2H, m), 6.75 (1H, td, J = 7.5, 1.4 Hz);
13C NMR (100 MHz, CDCl3) d 14.0, 20.8, 20.9, 22.6, 23.8, 25.3, 30.6 (m), 31.5 (t, JC-F = 3.3 Hz), 32.2, 48.3, 75.4 (t, JC-F = 25.2 Hz), 105.2 (t, JC-F = 28.8 Hz), 105.6, 106.6, 117.3, 118.1, 120.7 (t, JC-F= 260.9 Hz), 121.6, 134.1, 139.3, 148.9;
19F NMR (282 Hz, CDCl3) d -57.4 (1F, d, JF-F = 271.6 Hz), -55.8 (1F, d, JF-F = 271.6 Hz);
MS (ESI-TOF) m/z 388 [M+Na]+; HRMS calcd for C21H29F2NNaO2[M+Na]+, 388.2064; found, 388.2071.
Anal. Calcd for C21H29F2NO2: C, 69.02; H, 8.00; N, 3.83. Found: C, 68.98; H, 7.91; N, 3.73.
IR (neat) 3464, 3064, 2959, 2873, 1599, 1496, 1239, 1071, 732 cm-1;
1H NMR (400 MHz, CDCl3) d 0.88 (3H, t, J = 7.3 Hz), 1.11-1.25 (1H, m), 1.26-1.50 (3H, m), 1.36 (3H, s), 1.40 (3H, s), 2.03-2.16 (1H, m), 2.22-2.36 (1H, m), 2.59 (1H, brs, OH), 3.82 (1H, dd, J = 16.1, 6.5 Hz), 3.99 (1H, dd, J = 16.1, 4.9 Hz), 5.26 (1H, d, J = 10.3 Hz), 5.38 (1H, d, J = 17.2 Hz), 5.91-6.06 (1H, m), 6.47 (1H, d, J = 7.4 Hz), 6.58-6.67 (2H, m), 6.73-6.80 (1H, m);
13C NMR (100 MHz, CDCl3) d 13.9, 22.6, 23.7, 14.7 (t, JC-F= 3.2 Hz), 25.6 (t, J = 3.3 Hz), 31.9, 48.4, 74.2 (t, JC-F = 26.4 Hz), 104.8 (dd, JC-F = 30.4, 29.6 Hz), 105.7, 106.7, 117.4, 118.3, 120.7 (t, JC-F = 260.9 Hz), 121.7, 134.0, 139.1, 148.8;
19F NMR (282 Hz, CDCl3) d-55.9 (1F, d, J = 271.4 Hz), -53.6 (1F, d, J = 271.4 Hz);
MS (ESI-TOF) m/z 326 [M+H]+;
HRMS calcd for C18H26F2NO2[M+H]+, 326.1964; found, 326.1964.
油状物質;
IR (neat) 3542, 3062, 2959, 2872, 1599, 1496, 1239, 1093, 1067, 925, 732, 700 cm-1;
1H NMR (400 MHz, CDCl3) d 0.82 (3H, t, J = 7.2 Hz), 1.04-1.17 (1H, m), 1.18-1.38 (3H, m), 1.76 (3H, s), 1.79-1.89 (1H, m), 1.89-2.00 (1H, m), 3.82 (1H, dd, J = 16.0, 6.8 Hz), 3.92-4.01 (1H, m), 4.06 (1H, br, OH), 5.34 (1H, dd, J = 10.2, 1.4 Hz), 5.44 (1H, dd, J = 17.2, 1.4 Hz), 5.99-6.01 (1H, m), 6.33 (1H, dd, J = 7.7, 0.9 Hz), 6.52 (1H, dd, J = 7.5, 1.1 Hz), 6.55-6.60 (1H, m), 6.75-6.81 (1H, m), 7.24-7.33 (3H, m), 7.46-7.52 (2H, m);
13C NMR (100 MHz, CDCl3) d 13.7, 22.4, 23.4, 25.5 (t, JC-F= 3.7 Hz), 31.5, 48.5, 76.7-77.3 (m), 105.0 (t, JC-F = 29.9 Hz), 106.0, 106.9, 117.8, 118.7, 119.9 (t, JC-F = 264.0 Hz), 121.6, 125.4 (d, JC-F = 2.4 Hz), 127.2, 127.6, 133.9, 138.8, 142.1 (d, JC-F= 3.4 Hz), 148.3;
19F NMR (282 Hz, CDCl3) d -53.8 (1F, d, JF-F= 271.3 Hz), -48.9 (1F, d, JF-F= 271.3 Hz);
MS (ESI-TOF) m/z 410 [M+Na]+;
HRMS calcd for C23H27F2NNaO2[M+Na]+, 410.1908; found, 410.1872.
Anal. Calcd for C23H27F2NO2: C, 71.30; H, 7.02; N, 3.61. Found: C, 71.32; H, 7.04; N, 3.48.
油状物質;
IR (neat) 3548, 3062, 2959, 2872, 1599, 1496, 1239, 1090, 1074, 921, 732, 701 cm-1;
1H NMR (400 MHz, CDCl3) d 0.86 (3H, t, J = 7.2 Hz), 1.08-1.20 (1H, m), 1.22-1.41 (3H, m), 1.74 (3H, s), 1.93-2.04 (1H, m), 2.15-2.25 (1H, m), 3.23 (1H, br, OH), 3.62 (1H, dd, J= 16.2, 5.4 Hz), 3.69 (1H, dd, J = 16.2, 6.6 Hz), 5.21 (1H, dd, J = 10.2, 1.4 Hz), 5.30 (1H, dd, J = 17.2, 1.4 Hz), 5.81-5.94 (1H, m), 6.26 (1H, dd, J = 7.5, 1.0 Hz), 6.47 (1H, dd, J = 7.6, 1.0 Hz), 6.54-6.61 (1H, m), 6.68-6.74 (1H, m), 7.23-7.34 (3H, m), 7.42-7.49 (2H, m);
13C NMR (100 MHz, CDCl3) d 13.9, 22.5, 23.5, 26.4 (t, JC-F= 3.5 Hz), 31.7, 47.7, 76.5-77.1 (m), 104.8 (t, JC-F = 29.8 Hz), 105.7, 106.7, 117.4, 118.0, 120.2 (t, JC-F = 263.8 Hz), 121.5, 126.1, 127.2, 127.5, 133.9, 138.6, 141.4 (d, JC-F = 2.8 Hz), 148.6;
19F NMR (282 Hz, CDCl3) d -52.4 (1F, d, JF-F= 271.3 Hz), -50.2 (1F, d, JF-F= 271.3 Hz);
MS (ESI-TOF) m/z 410 [M+Na]+;
HRMS calcd for C23H27F2NNaO2[M+H]+, 410.1908; found, 410.1889.
油状物質;
IR (neat) 3063, 2958, 2871, 2826, 2775, 1599, 1496, 1228, 1073, 923, 731 cm-1;
1H NMR (400 MHz, CDCl3) d 0.88 (3H, t, J = 7.2 Hz), 1.10-1.22 (1H, m), 1.25-1.49 (3H, m), 2.06 (2H, t, J = 7.9 Hz), 2.35 (6H, s), 2.85 (1H, td, J= 14.8, 9.1 Hz), 2.94 (1H, td, J = 14.8, 8.5 Hz), 3.79 (1H, dd, J = 16.3, 5.6 Hz), 3.88-3.97 (1H, m), 5.22 (1H, dd, J = 10.2, 1.4 Hz), 5.34 (1H, dd, J = 17.2, 1.4 Hz), 5.84-5.96 (1H, m), 6.39 (1H, d, J = 7.5 Hz), 6.54-6.60 (1H, m), 6.64 (1H, d, J = 7.6 Hz), 6.70-6.76 (1H, m);
13C NMR (100 MHz, CDCl3) d 13.9, 22.6, 23.5, 29.5, 47.2, 47.6, 57.8 (t, JC-F= 21.9 Hz), 103.0 (t, JC-F= 28.7 Hz), 104.9, 106.5, 117.0, 117.8, 121.5, 122.2 (dd, JC-F = 257.1, 252.6 Hz), 133.9, 139.4, 149.1; 19F NMR (282 Hz, CDCl3) d -54.8 ~ -53.6 (1F, m), -51.4 ~ -50.3 (1F, m);
MS (ESI-TOF) m/z325 [M+H]+;
HRMS calcd for C23H28F2NO2[M+H]+, 325.2091; found, 325.2002.
Anal. Calcd for C18H26F2N2O: C, 66.64; H, 8.08; N, 8.64. Found: C, 66.71; H, 7.99; N, 8.63.
IR (neat) 3065, 2961, 2873, 1601, 1495, 1241, 1123, 1046, 911, 732 cm-1;
1H NMR (400 MHz, CDCl3) d0.92 (3H, t, J = 7.2 Hz), 1.19-1.58 (4H, m), 2.07-2.25 (2H, m), 3.87 (1H, dd, J= 16.7, 6.0 Hz), 3.95-4.03 (1H, m), 5.28 (1H, dd, J = 10.3, 1.2 Hz), 2.39 (1H, dd, J = 17.3, 1.2 Hz), 5.86-5.98 (1H, m), 6.47 (1H, d, J = 7.5 Hz), 6.65 (1H, td, J = 7.5, 1.1 Hz), 6.74 (1H, d, J = 7.5 Hz), 6.79 (1H, td, J = 7.5/, 1.1 Hz);
13C NMR (100 MHz, CDCl3) d13.9, 22.5, 23.8, 29.7, 47.5, 103.4 (t, JC-F= 26.6 Hz), 105.5, 106.8, 117.2, 118.3, 121.7, 128.9 (dd, JC-F = 307.6, 305.5 Hz), 133.4, 138.8, 148.9; 19F NMR (282 Hz, CDCl3) d -5.81 (1F, d, JF-F = 167.5 Hz), -4.71 (1F, d, JF-F = 167.5 Hz);
MS (ESI-TOF) m/z302 [M+H]+;
HRMS calcd for C15H19ClF2NO [M+H]+, 302.1123; found, 302.1131.
IR (neat) 3065, 2959, 2872, 1600, 1494, 1237, 1095, 1031, 771, 732 cm-1;
1H NMR (400 MHz, CDCl3) d0.90 (3H, t, J = 7.2 Hz), 1.18-1.57 (4H, m), 2.04-2.14 (1H, m), 2.14-2.25 (1H, m), 3.84 (1H, dd, J = 16.5, 6.3 Hz), 3.92-4.01 (1H, m), 5.28 (brd, J = 10.2 Hz), 5.41 (1H, brd, J = 17.2 Hz), 5.89-6.01 (1H, m), 6.49 (1H, d, J = 7.6 Hz), 6.61-6.68 (1H, m), 6.74 (1H, d, J = 7.6 Hz), 6.76-6.82 (1H, m);
13C NMR (100 MHz, CDCl3) d13.9, 22.6, 24.1, 28.9, 47.6, 104.5 (t, JC-F= 23.2 Hz), 105.5, 107.0, 108.7 (dd, JC-F= 332.1, 326.6 Hz), 117.5, 118.4, 121.8, 133.6, 139.0, 148.8;
19F NMR (282 Hz, CDCl3) d6.15 (1F, d, JF-F = 188.3 Hz), 10.6 (1F, d, JF-F = 188.3 Hz);
MS (ESI-TOF) m/z394 [M+H]+;
HRMS calcd for C15H19F2INO [M+H]+, 394.0479; found, 394.0495.
IR (neat) 3064, 2959, 2873, 1599, 1456, 1398, 1311, 1235, 1201, 1116, 1073, 732 cm-1;
1H NMR (400 MHz, CDCl3) d 0.90 (3H, t, J = 7.2 Hz), 1.25-1.59 (4H, m), 1.97 (2H, t, J = 7.9 Hz), 3.76-3.95 (2H, m), 5.21 (1H, dd, J= 10.3, 1.5 Hz), 5.33 (1H, dd, J = 17.2, 1.5 Hz), 5.68 (1H, t, JH-F= 55.4 Hz), 5.83-5.94 (1H, m), 6.39 (1H, dd, J = 7.5, 1.0 Hz), 6.54-6.62 (1H, m), 6.65 (1H, dd, J = 7.6, 1.0 Hz), 6.70-6.77 (1H, m);
13C NMR (100 MHz, CDCl3) d 13.9, 22.6, 23.4, 28.8, 46.9, 100.9 (t, JC-F = 23.6 Hz), 105.2, 106.8, 114.0 (dd, JC-F = 254.8, 251.0 Hz), 116.8, 117.9, 121.6, 133.9, 139.0, 148.9;
19F NMR (282 Hz, CDCl3) d -71.3 (1F, dd, JF-F= 285.4 Hz, JH-F = 55.4 Hz), -66.7 (1F, dd, JF-F = 285.4 Hz, JH-F = 55.4 Hz);
MS (ESI-TOF) m/z 268 [M+H]+;
HRMS calcd for C15H20F2NO [M+H]+, 268.1513; found, 268.1500.
IR (neat) 3064, 2986, 1599, 1494, 1394, 1302, 1227, 1096, 1074, 735 cm-1;
1H NMR (400 MHz, CDCl3) d 1.64 (3H, brs), 3.79 (1H, dd, J= 16.8, 5.6 Hz), 3.90-3.98 (1H, m), 5.21 (1H, dd, J = 10.3, 1.5 Hz), 5.31 (1H, dd, J = 17.1, 1.5 Hz), 5.67 (1H, t, JH-F= 55.3 Hz), 5.83-8.94 (1H, m), 6.46 (1H, d, J= 7.5 Hz), 6.61-6.70 (2H, m), 6.74-6.81 (1H, m);
13C NMR (100 MHz, CDCl3) d 15.7, 47.5, 99.4 (t, JC-F= 25.0 Hz), 106.8, 107.5, 113.7 (dd, J= 254.9, 249.6 Hz), 116.9, 118.7, 121.7, 134.2, 138.4, 148.4;
19F NMR (282 Hz, CDCl3) d -70.9 (1F, dd, JF-F= 287.3 Hz, JH-F = 55.3 Hz), -66.8 (1F, dd, JF-F = 287.3 Hz, JH-F = 55.3 Hz);
MS (EI) m/z 225 (M+, 100).
IR (neat) 3064, 3015, 2980, 1599, 1494, 1230, 1074, 734 cm-1;
1H NMR (400 MHz, CDCl3) d 0.48-0.55 (2H, m), 0.65-0.72 (1H, m), 0.86-0.92 (1H, m), 1.38-1.46 (1H, m), 3.91 (1H, dd, J = 16.7, 5.4 Hz), 4.14 (1H, dd, J = 16.7, 5.2 Hz), 5.23 (1H, d, J = 10.3 Hz), 5.36 (1H, J = 17.2 Hz), 5.72 (1H, t, JH-F = 55.5 Hz), 5.91-6.03 (1H, m), 6.47 (1H, d, J = 7.6 Hz), 6.58-6.66 (1H, m), 6.76 (1H, t, J = 7.2 Hz);
13C NMR (100 MHz, CDCl3) d -0.6, 1.8, 9.9, 48.0, 99.2 (t, JC-F= 23.7 Hz), 106.26 107.0, 114.1 (dd, JC-F= 252.9, 250.9 Hz), 116.6, 118.3, 121.6, 134.6, 139.3, 148.8; 19F NMR (282 Hz, CDCl3) d -71.8 (1F, dd, JF-F= 285.2 Hz, JH-F = 55.5 Hz), -67.4 (1F, dd, JF-F = 285.2 Hz, JH-F = 55.5 Hz);
MS (ESI-TOF) m/z 252 [M+H]+;
HRMS calcd for C14H16F2NO [M+H]+, 252.1200; found, 252.1179.
Mp. 62.5-63.0 °C; IR (KBr) 3063, 2959, 2872, 1645, 1600, 1494, 1235, 1074, 732, 703 cm-1;
1H NMR (400 MHz, CDCl3) d 0.93 (3H, t, J = 7.1 Hz), 1.29-1.44 (3H, m), 1.52-1.61 (1H, m), 2.01-2.07 (2H, m), 4.43 (1H, d, J = 16.1 Hz), 4.54 (1H, d, J = 16.1 Hz), 5.78 (1H, t, JH-F = 55.3 Hz), 6.12 (1H, d, J = 7.3 Hz), 6.59-6.73 (3H, m), 7.27-7.43 (5H, m);
13C NMR (100 MHz, CDCl3) d 13.9, 22.7, 23.6, 295, 48.7, 101.2 (t, JC-F = 23.3 Hz), 106.0, 106.9, 114.3 (dd, JC-F = 254.5, 251.5 Hz), 118.4, 121.6, 126.8, 127.3, 128.7, 137.7, 139.4, 149.0; 19F NMR (282 Hz, CDCl3) d -71.0 (1F, dd, JF-F= 285.4 Hz, JH-F = 55.3 Hz), -66.4 (1F, dd, JF-F = 285.4 Hz, JH-F = 55.3 Hz);
MS (EI) m/z 317 (M+, 39), 266 (M+-CHF2, 100).
Claims (8)
- 下記一般式(1)
で表されるトリフルオロアセトアルデヒド−N,O−アセタール化合物と下記一般式(2)
R4Li (2)
(式中、R4は、置換基を有してもよい炭素数1〜20のアルキル基もしくはアルケニル基、または置換基を有してもよい炭素数6〜30のアリール基もしくはヘテロ芳香族基を表す。)
で表される有機リチウム化合物を反応させた後、アルデヒド化合物、ケトン化合物、イミニウム化合物、求電子性ハロゲン化剤及びブレンステッド酸からなる群から選ばれる1種以上の求電子性化合物を反応させることを特徴とする、一般式(3)
で表されるα―アミノジフルオロメチレン誘導体の製造方法。 - アルデヒド化合物またはケトン化合物が下記一般式(4)
で表されるアルデヒド化合物またはケトン化合物であり、α―アミノジフルオロメチレン誘導体が下記一般式(5)
で表される化合物であることを特徴とする請求項1に記載のα―アミノジフルオロメチレン誘導体の製造方法。 - イミニウム化合物が下記一般式(6)
で表されるイミニウム化合物であり、α―アミノジフルオロメチレン誘導体が下記一般式(7)
で表される化合物であることを特徴とする請求項1に記載のα―アミノジフルオロメチレン誘導体の製造方法。
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