JPWO2012008228A1 - アルコール類の酸化方法 - Google Patents
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Abstract
Description
(a)9-ベンジル-9-アザビシクロ[3.3.1]ノナン-3-オンの合成
1H-NMR (CDCl3, 400MHz): δ 7.41-7.24 (m, 5H), 3.91 (s, 2H), 3.31 (brs, 2H), 2.73 (dd, 2H, J=16.7, 6.5Hz), 2.25 (d, 2H, J=16.7Hz), 1.98-1.90 (m, 2H), 1.56-1.46 (m, 4H).
13C-NMR (CDCl3, 100MHz): δ 211.5, 139.2, 128.4, 128.3, 127.1, 57.1, 53.5, 42.9, 29.3, 16.5.
IR (CHCl3, cm-1): 1704.
EI-MS m/z: 229 (M+).
HRMS (EI): calcd. for C15H19O1N1 229.1467 (M+), Found: 229.1460.
1H-NMR (CDCl3, 400MHz): δ 7.85 (d, 2H, J=8.2Hz), 7.36-7.22 (m, 7H), 3.49 (d, 1H, J=5.1), 3.10-3.06 (m, 2H), 2.66 (dd, 1H, J=6.5, 16.2Hz), 2.43 (s, 3H), 2.33 (brs, 1H), 2.31 (d, 2H, J=16.2Hz), 1.90-1.89 (m, 2H), 1.48-1.34 (m, 4H).
13C-NMR (CDCl3, 100MHz): δ 161.8, 143.9, 139.2, 135.7, 129.5, 128.3, 128.3, 128.0, 127.0, 56.8, 52.0, 51.4, 34.9, 29.5, 28.7, 28.2, 21.6, 16.8.
IR (CHCl3, cm-1): 3217, 1598.
EI-MS m/z: 397 (M+).
HRMS (EI): calcd. for C22H27O2N3S 397.1824 (M+), Found: 397.1815.
1H-NMR (CDCl3, 400MHz): δ 7.36-7.19 (m, 5H), 3.71 (s, 2H), 3.15 (brs, 2H), 2.55 (m, 2H), 1.84 (d, 2H, J=10.1Hz), 1.47 (m,4H).
13C-NMR (CDCl3, 100MHz): δ 140.4, 128.7, 128.1, 126.5, 60.7, 58.0, 40.1, 36.2.
IR (CHCl3, cm-1): 1493, 1453, 1357, 1317.
EI-MS m/z: 213 (M+).
HRMS (EI): calcd. for C15H19N1 223.1517 (M+), Found: 223.1512.
IR(CHCl3, cm-1): 1454.1, 1336.4, 1277.6.
EI-MS m/z: 138 (M+).
HRMS (EI): calcd. for C8H12ON 138.0919 (M+), Found: 138.0915.
Anal: Calcd. for C8H12ON: C, 69.53; H, 8.75; N, 10.14, Found: C, 69.34; H, 8.62; N, 10.06.
次亜塩素酸ナトリウムをバルク酸化剤としてアルコールの酸化反応を行った。Nor-AZADO、並びに比較のためにTEMPO、1-Me-AZADO、AZADO、及びABNOを用いて触媒活性を比較した。結果を表1に示す。
バルク酸化剤として空気を用いてアルコール酸化を行う場合の触媒活性を比較した。結果を表2に示す。
種々のアルコールに対するNor-AZADOの酸化触媒としての機能を調べた。結果を表3に示す。種々の第一級及び第二級アルコールに対して反応は高収率で進行し、目的のアルデヒド又はケトンを与えた。立体的に嵩高く、かつ複雑な構造のアルコールにおいても高収率で目的物が得られており、Nor-AZADOが優れた酸化触媒であることが明らかである。
(a)L-メントールの酸化
1H-NMR (400MHz, CDCl3): δ 2.35 (ddd, J=12.8, 3.7, 2.3 Hz, 1H), 2.18-1.81 (m, 6H), 1.43-1.29 (m, 2H), 1.01 (d, J=6.3 Hz, 3H), 0.91 (d, J=6.8 Hz, 3H), 0.85 (d, J=6.8 Hz, 3H).
13C-NMR (100MHz, CDCl3): δ 212.3, 55.8, 50.8, 35.4, 33.9, 27.8, 25.8, 22.2, 21.2, 18.6.
IR (neat, cm-1): 1711.
EI-MS m/z: 154 (M+).
HRMS (EI): Calcd. for C10H18O: 154.1358, Found: 154.1343.
1H-NMR (400MHz, CDCl3): δ 7.30-7.16 (m, 5H), 2.92-2.98 (m, 2H), 2.78-2.74 (m, 2H), 2.14 (s, 3H).
13C-NMR (100MHz, CDCl3): δ 207.8, 140.9, 128.4, 128.2, 126.0, 45.1, 30.0, 29.6.
IR (neat, cm-1): 1717.
EI-MS m/z: 148 (M+).
HRMS (EI): Calcd. for C10H12O: 148.0888, Found: 148.0873.
1H-NMR (400MHz, CDCl3): δ 9.74 (d, J=1.5Hz, 1H), 7.30-7.15 (m, 5H), 2.65 (t, J=7.7Hz, 2H), 2.43 (dt, J=7.2, 1.5Hz, 2H), 1.95 (tt, J=7.7, 7.2Hz).
13C-NMR (100MHz, CDCl3): δ 202.2, 141.2, 128.4, 128.3, 126.0, 43.1, 34.9, 23.6.
IR (neat, cm-1): 1724.
EI-MS m/z: 148 (M+).
HRMS (EI): Calcd. for C10H12O: 148.0888, Found: 148.0873.
(a)4-フェニルブタン-2-オールの酸化
1H-NMR (400MHz, CDCl3): δ 2.14 (brs, 1H), 1.81-1.68 (m, 3H), 1.60-1.52 (m, 2H), 1.42-1.35 (m, 1H), 1.15 (d, J=1.7 Hz, 3H), 1.04 (s, 3H), 1.04 (s, 3H).
13C-NMR (100MHz, CDCl3): δ 223.4, 54.1, 47.3, 45.3, 41.6, 31.8, 24.9, 23.3, 21.7, 14.6.
IR (neat, cm-1): 1740.
EI-MS m/z: 152 (M+).
HRMS (EI): Calcd. for C10H16O: 152.1201, Found: 152.1205.
1H-NMR (400MHz, CDCl3): δ 7.68 (d, J=7.3 Hz, 2H), 7.48-7.38 (m, 3H), 1.35 (s, 9H).
13C-NMR (100MHz, CDCl3): δ 209.2, 138.6, 130.7, 128.0, 127.8, 44.1, 28.0.
IR (neat, cm-1): 1676.
EI-MS m/z: 162 (M+).
HRMS (EI): Calcd. for C11H14O: 162.1045, Found: 162.1050.
1H-NMR (400MHz, CDCl3): δ 2.46 (t, J=7.2 Hz, 2H), 1.59-1.51 (m, 2H), 1.34-1.24 (m, 4H), 1.24 (s, 9H), 0.89 (t, J=7.2 Hz, 3H).
13C-NMR (100MHz, CDCl3): δ 216.1, 44.1, 36.4, 31.5, 26.4, 23.6, 22.6, 13.9.
IR (neat, cm-1): 1733.
EI-MS m/z: 156 (M+).
HRMS (EI): Calcd. for C10H20O: 156.1514, Found: 156.1500.
1H-NMR (400MHz, CDCl3): δ 7.35-7.13 (m, 5H), 3.61 (dd, J=12.1, 5.3 Hz, 1H), 2.53-2.45 (m, 2H), 2.30-2.25 (m, 1H), 2.17-2.15 (m, 1H), 2.06-1.99 (m, 2H), 1.86-1.80 (m, 2H).
13C-NMR (100MHz, CDCl3): δ 210.2, 138.7, 128.5, 128.3, 126.8, 57.3, 42.1, 35.0, 27.8, 25.3.
IR (CHCl3, cm-1): 1700.
EI-MS m/z: 174 (M+)
HRMS (EI): Calcd. for C12H14O: 174.1045, Found: 174.1058.
1H-NMR (400MHz, CDCl3): δ 4.73 (d, J=5.6 Hz, 1H), 4.61 (d, J=9.4 Hz, 1H), 4.53(m, 1H), 4.39 (dd, J=13.5, 2.2 Hz, 1H), 4.12 (d, J=13.5 Hz, 1H), 4.00 (d, J=9.4 Hz, 1H), 1.55 (s, 3H), 1.47 (s, 3H), 1.40 (s, 6H).
13C-NMR (100MHz, CDCl3): δ 196.9, 113.8, 110.6, 104.1, 77.9, 75.9, 70.0, 60.1, 27.1, 26.5, 26.0, 26.0
IR (neat, cm-1): 1749.
EI-MS m/z: 259 (M++H).
HRMS (EI): Calcd. for C12H19O6: 259.1182, Found: 259.1164.
1H-NMR (400MHz, CDCl3): δ 8.69 (brd, J=4.1Hz, 1H), 8.05 (d, J=8.0Hz, 1H), 7.84 (td, J=7.7, 1.7 Hz, 1H), 7.49-7.30 (m, 1H), 2.73 (s, 3H).
13C-NMR (100MHz, CDCl3): δ 200.0, 153.6, 148.9, 136.8, 127.0, 121.6, 25.7.
IR (neat, cm-1): 1700.
EI-MS m/z: 121 (M+).
HRMS (EI): Calcd. for C7H7NO: 121.0528, Found: 121.0529.
1H-NMR (400MHz, CDCl3):δ 9.89 (s, 1H), 7.84 (d, J=8.7 Hz, 2H), 7.01 (d, J=8.4 Hz, 2H), 3.89 (s, 3H).
13C-NMR (100MHz, CDCl3): δ 190.7, 164.6, 131.9, 129.9, 114.3, 55.5.
IR (neat, cm-1): 1684.
EI-MS m/z: 136 (M+).
HRMS (EI): Calcd. for C8H8O2: 136.0524, Found: 136.0526.
1H-NMR (400MHz, CDCl3): δ 7.99-7.96 (m, 4H), 7.68-7.63 (m, 2H), 7.53-7.49 (t, J=7.7 Hz, 4H).
13C-NMR (100MHz, CDCl3):δ 194.5, 134.9, 133.0, 129.9, 129.0.
IR (CHCl3, cm-1): 1660.
EI-MS m/z: 210 (M+).
HRMS (EI): Calcd. for C14H10O2: 210.0681, Found: 210.0679.
1H-NMR (400MHz, CDCl3): δ 2.55 (s,2H), 2.10-1.94 (m, 12H).
13C-NMR (100MHz, CDCl3): δ 218.4, 47.0, 39.2, 36.1, 27.4.
IR (neat, cm-1): 1719.
EI-MS m/z: 150 (M+).
HRMS (EI): Calcd. for C10H14O: 150.1045, Found: 150.1049.
1H-NMR (400MHz, CDCl3): δ 7.37-7.31 (m, 5H), 5.12 (s, 2H), 4.75 (br s, 1H), 3.99 (br s, 1H), 2.45-2.40 (m, 4H), 2.28-2.24 (m, 2H), 1.75-1.59 (m, 2H).
13C-NMR (100MHz, CDCl3): δ 209.5, 155.6, 136.3, 128.5, 128.2, 128.1, 66.8, 47.9, 38.8, 32.1.
IR (neat, cm-1): 1704, 1530.
EI-MS m/z: 247(M+).
HRMS (EI): Calcd. for C14H17NO3: 247.1208, Found: 247.1206.
1H-NMR (400MHz, CDCl3): δ 8.36 (s, 1H), 8.14 (s, 1H), 6.13 (d, J=8.2 Hz, 1H), 5.85 (br s, 2H), 4.94 (d, J=8.2 Hz, 2H), 4.29 (br s, 1H), 3.97 (m, 2H) 0.92 (s, 9H), 0.72 (s, 9H), 0.10 (s, 3H), 0.07 (s, 3H), -0.02 (s, 3H), -0.20 (s, 3H).
13C-NMR (100MHz, CDCl3): δ 208.6, 155.5, 153.4, 150.4, 138.5, 119.8, 85.0, 82.4, 77.8, 62.4, 25.8, 25.3, 18.2, 18.0, -4.8, -5.5, -5.6, -5.7.
IR (neat, cm-1): 1788, 1647, 1595, 1577.
EI-MS m/z: 436 (M+−tBu).
HRMS (EI): Calcd. for C22H39N5O4Si2: 493.2541, Found: 493.2511.
(a)4-フェニルブタン-2-オールの酸化
1H-NMR (400 MHz, CDCl3): δ 10.16 (s, 1H), 8.40 (dd, J = 8.8, 1.8 Hz, 2H), 8.08 (dd, J = 8.8, 1.8 Hz, 2H).
13C-NMR (100 MHz, DMSO-d6): δ 192.3, 150.6, 140.1, 130.6, 124.2.
IR (neat, cm-1): 1709, 1537.
EI-MS m/z: 131 (M+).
HRMS (EI): Calcd. for C7H5NO3: 151.0269, Found: 151.0253.
(a)4-フェニルブタン-2-オールの酸化
1H-NMR (400 MHz, CDCl3): δ 10.30 (s, 1H), 7.82 (d, J = 8.7 Hz, 1H), 6.55 (dd, J = 8.4, 2.9 Hz, 1H), 6.45 (d, J = 2.9 Hz, 1H), 3.91 (s, 3H), 3.88 (s, 3H).
13C-NMR (100 MHz, CDCl3):δ 188.3, 166.2, 163.6, 130.7, 119.1, 105.7, 97.9, 55.6, 55.6.
IR (neat, cm-1): 1670, 1266; MS m/z: 166 (M+).
HRMS (EI): Calcd. for C9H10O3: 166.0630, Found: 166.0625.
1H-NMR (400 MHz, CDCl3): δ 10.57 (s, 1H), 6.90 (s, 2H), 2.60 (s, 6H), 2.32 (s, 3H).
13C-NMR (100 MHz, CDCl3): δ 192.9, 143.8, 141.4, 130.5, 130.0, 21.4, 20.5.
IR (neat, cm-1): 1686; MS m/z: 148 (M+).
HRMS (EI): Calcd. for C10H12O: 148.0888, Found: 148.0878.
1H-NMR (400 MHz, CDCl3): δ 9.98 (s, 1H), 7.75 (d, J = 8.7 Hz, 1H), 7.69 (d, J = 8.2 Hz, 1H).
13C-NMR (100 MHz, CDCl3): δ 191.0, 135.1, 132.4, 132.4, 130.9, 129.8.
IR (neat, cm-1): 1688, 1066; MS m/z: 184 (M+), 183(M+-H).
HRMS (EI): Calcd. for C7H5BrO: 183.9524, Found: 183.9523.
1H-NMR (400 MHz, CDCl3): δ 9.92 (s, 1H), 7.77 (d, J = 8.7 Hz, 1H), 7.33 (d, J = 8.2 Hz, 1H), 2.54 (s, 3H).
13C-NMR (100 MHz, CDCl3): δ 191.2, 147.9, 133.0, 130.0, 125.2, 14.7.
IR (neat, cm-1): 1695; MS m/z: 152 (M+).
HRMS (EI): Calcd. for C8H8OS: 152.0296, Found: 152.0290.
1H-NMR (400MHz, CDCl3): δ 3.30 (s, 2H), 3.07-2.89 (m, 4H), 2.46 (quin, J = 3.0 Hz, 1H), 2.03-1.98 (m, 4H).
13C-NMR (100MHz, CDCl3): δ 219.6, 62.8, 46.9, 39.6, 25.6.
IR (neat, cm-1): 1725. MS m/z 125 (M+).
HRMS (EI) Calcd. for C7H11O: 125.0841, found: 125.0834.
1H-NMR (400 MHz, CDCl3): δ 9.96 (d, J = 1.0 Hz, 1H), 7.80-7.77 (m, 2H), 7.22 (dd, J = 4.8, 3.9 Hz, 1H), 7.33 (d, J = 8.2 Hz, 1H), 2.54 (s, 3H).
13C-NMR (100 MHz, CDCl3): δ 182.9, 144.1, 136.2, 135.1, 128.3.
IR (neat, cm-1): 1672, 1419, 729; MS m/z: 112 (M+).
HRMS (EI): Calcd. for C5H4OS: 111.9983, Found: 111.9935.
1H-NMR (400MHz, CDCl3): δ 9.72 (d, J = 7.8 Hz, 1H), 7.59-7.56 (m, 2H), 7.49-7.42 (m, 4H), 6.74 (dd, J = 15.9, 7.7 Hz, 2H).
13C-NMR (100MHz, CDCl3): δ 193.7, 152.7, 134.0, 131.2, 129.1, 128.6, 128.5.
IR (CHCl3, cm-1): 1681; MS m/z: 132 (M+).
HRMS (EI): Calcd. for C9H8O: 132.0575, found: 132.0558.
1H-NMR (400 MHz, CDCl3): δ 9.51 (d, J = 7.7 Hz, 1H), 6.85 (dt, J = 15.5, 6.8 Hz, 1H), 6.12 (ddt, J = 15.5, 7.7, 1.4 Hz, 1H), 2.36-2.31 (m, 2H), 1.55-1.28 (m, 2H), 1.37-1.30 (m, 4H), 0.92-0.89 (m, 3H).
13C-NMR (100 MHz, CDCl3): δ 194.1, 158.9, 133.0, 32.7, 31.3, 27.5, 22.4, 13.9.
IR (neat, cm-1): 1693, 1637; MS m/z: 116 (M+).
HRMS (EI): Calcd. for C8H14O: 126.1045, Found: 126.1050.
1H-NMR (400 MHz, CDCl3): δ 9.77 (d, J = 1.9 Hz, 1H), 5.86-5.75 (m, 1H), 5.02-4.92 (m, 2H), 2.42 (dt, J = 7.2, 1.9 Hz, 2H), 2.04 (tt, J = 7.7, 7.2 Hz, 2H), 1.65-1.61 (m, 2H), 1.40-1.32 (m, 8H).
13C-NMR (100 MHz, CDCl3): δ 202.8, 139.0, 114.2, 43.9, 33.7, 29.2, 29.1, 28.8, 28.8, 22.0.
IR (neat, cm-1): 1727, 1640; MS m/z: 154 (M+).
HRMS (EI): Calcd. for C10H18O: 154.1358, Found: 154.1369.
1H-NMR (400 MHz, CDCl3): δ 9.99 (d, J = 7.7 Hz, 1H), 5.88 (d, J = 8.2 Hz, 1H), 5.07 (m, 1H), 2.25-2.19 (m, 4H), 2.17 (s, 3H), 1.69 (s, 3H), 1.61 (s, 3H).
13C-NMR (100 MHz, CDCl3): δ 191.2, 163.7, 132.9, 127.4, 122.5, 40.6, 25.7, 25.6, 17.7, 17.5.
IR (neat, cm-1): 1675, 1632, 1611.
MS m/z: 152 (M+).
HRMS (EI): Calcd. for C10H16O: 152.1201, Found: 152.1199.
1H-NMR (400 MHz, CDCl3): δ 9.70 (d, J = 0.97 Hz, 1H), 5.74-5.68 (m, 2H), 2.55-2.48 (m, 1H), 2.25-2.23 (m, 2H), 2.13-2.08 (m, 2H), 2.03-1.96 (m, 1H), 1.72-1.62 (m, 1H).
13C-NMR (100 MHz, CDCl3): δ 204.4, 127.2, 124.7, 46.0, 24.3, 23.7, 22.1.
IR (neat, cm-1): 1729, 1652.
MS m/z: 110 (M+).
HRMS (EI): Calcd. for C7H10O: 110.0732, Found: 110.0725.
1H-NMR (400 MHz, CDCl3): δ 9.43 (s, 1H), 7.62-7.59 (m, 2H), 7.51-7.47 (m, 1H), 7.43-7.39 (m, 2H).
13C-NMR (100 MHz, CDCl3): δ 176.7, 133.3, 131.3, 128.7, 119.5, 95.1, 88.4.
IR (neat, cm-1): 2188, 1660, 759.
MS m/z: 130 (M+).
HRMS (EI): Calcd. for C9H6O: 130.0419, Found: 130.0405.
1H-NMR (400 MHz, CDCl3): δ 7.93-5.54 (m, 2H), 7.52-7.40 (m, 1H), 7.38-7.23 (m, 7H), 5.95 (d, J = 6.3 Hz, 1H), 4.55 (d, J = 6.3 Hz, 1H).
13C-NMR (100 MHz, CDCl3): δ 198.9, 139.0, 133.8, 133.5, 129.1, 129.1, 128.6, 128.5, 127.7, 76.2.
IR (neat, cm-1): 3414, 1679.
MS m/z: 212 (M+).
HRMS (EI): Calcd. for C14H12O2: 212.0837, Found: 212.0829.
1H-NMR (400 MHz, CDCl3): δ 9.62 (s, 1H), 3.55 (dd, J = 5.1, 4.1 Hz, 1H), 2.07 (brd, J = 5.4 Hz, 1H), 1.92-1.84 (m, 1H), 1.12 (d, J = 4.4 Hz, 6H), 0.97 (d, J = 6.8 Hz, 3H), 0.90 (d, J = 6.8 Hz, 3H).
13C-NMR (100 MHz, CDCl3): δ 206.7, 80.3, 50.5, 29.9, 21.7, 19.8, 18.6, 17.2.
IR (neat, cm-1): 3479, 1714.
MS m/z: 145 (M++H).
HRMS (EI): Calcd. for C8H17O2: 145.1229, Found: 145.1204.
Claims (4)
- アルコール類の酸化方法であって、下記の式(I):
- アルコール類が二級アルコールである請求項1に記載の方法。
- バルク酸化剤が過酸素酸、過酸化水素、次亜ハロゲン酸若しくはその塩、過ハロゲン酸若しくはその塩、過硫酸塩、ハロゲン化物、N-ブロモコハク酸イミド等のハロゲン化剤、トリハロゲン化イソシアヌル酸類、ジアセトキシヨードアレン類、ジアルキルアゾジカルボキシレート、酸素、空気、又はこれらの混合物である請求項1又は2に記載の方法。
- バルク酸化剤が空気である請求項1又は2に記載の方法。
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SG11201400781TA (en) | 2011-09-30 | 2014-04-28 | Hyperion Therapeutics Inc | Methods of therapeutic monitoring of nitrogen scavenging drugs |
US9114390B2 (en) | 2012-02-24 | 2015-08-25 | Tohoku University | 9-azanoradamantane N—oxyl compound and method for producing same, and organic oxidation catalyst and method for oxidizing alcohols using 9-azanoradamantane N—oxyl compound |
US9029605B2 (en) | 2012-09-10 | 2015-05-12 | Basf Se | Method for preparing menthone from isopulegol |
EP2706054A1 (de) | 2012-09-10 | 2014-03-12 | Basf Se | Verfahren zur Herstellung von Menthon aus Isopulegol |
TWI596086B (zh) * | 2013-09-02 | 2017-08-21 | Nippon Light Metal Co | Alcohol oxidation method |
US9914692B2 (en) | 2016-05-25 | 2018-03-13 | Horizon Therapeutics, Llc | Procedure for the preparation of 4-phenyl butyrate and uses thereof |
CN106366082B (zh) * | 2016-08-22 | 2018-03-20 | 深圳市宏辉浩医药科技有限公司 | 2‑氮杂非金刚烷‑n‑氧自由基的制备方法 |
US10668040B2 (en) | 2017-09-11 | 2020-06-02 | Horizon Therapeutics, Llc | Treatment of urea cycle disorders in neonates and infants |
EP3730475B1 (en) | 2019-04-24 | 2023-07-26 | Basf Se | Method for preparing l-menthone |
JP2020200287A (ja) * | 2019-06-12 | 2020-12-17 | 株式会社トクヤマ | カルボニル化合物の製造方法 |
CN118103413A (zh) | 2021-10-22 | 2024-05-28 | 国立大学法人福井大学 | 聚合物及其制造方法 |
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