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第 7 期 王春琴，等: 2-(4-芳氧苯氧基)丙酸衍生物的合成及除草活性 ·1203·

10 min，滴入三乙胺 1.0 g（10 mmol），继续搅拌 3 h， CH), 6.45 (br, s, 1H, NH), 6.86 (d, J=8.8 Hz, 2H,
PhH), 7.08~7.10 (m, 4H, PhH), 7.18~7.29 (m, 3H,
倒入 100 mL 冰水中，CH 2 Cl 2 萃取，Na 2 SO 4 干燥，
PhH), 7.51 (dd, J=8.8Hz, 2.4 Hz, 1H, Py-H), 7.85 (d,
减压脱溶，柱层析得到 2-(4-芳氧苯氧基)丙酸衍生物 13
J=2.4 Hz, 1H, Py-H); CNMR (CDCl 3 , 100 MHz)，δ:
Ⅳa~v。 18.93, 35.67, 40.06, 75.57, 116.24, 122.55, 124.90,
吡啶-3-基-(R)-2-[4-(3-氟-5-氯吡啶-2-氧基)苯氧 125.09, 126.53, 128.64, 128.76, 138.46, 140.09,
基]丙酸酯（Ⅳa）：0.58 g，产率 45%，黄色油状液 140.15, 147.23, 150.14, 154.26, 171.92。 Anal. Calcd.
1
体， HNMR (CDCl 3 , 400 MHz)，δ: 1.81 (d, J=6.8 Hz, for C 22 H 20 ClFN 2 O 3 ，%: C 63.69, H 4.86, N 6.75,
3H, CH 3 ), 5.00 (q, J=6.8 Hz, 1H, CH), 7.02 (d, found：C 63.55, H 4.87, N 6.56。
J=9.2 Hz, 2H, PhH), 7.11 (d, J=9.2 Hz, 2H, PhH), (R)-四氢异喹啉-2-基-2-[4-(3-氟-5-氯吡啶-2-氧
7.35 (dd, J= 8.4 Hz,4.4 Hz, 1H, Py-H), 7.44~7.47 (m,
1H, Py-H), 7.50 (dd, J= 9.2 Hz, 2.0 Hz, 1H, Py-H), 基)苯氧基]丙酮（Ⅳe）：0.78 g，产率 55%，黄色油
1
7.88 (d, J=2.0 Hz, 1H, Py-H), 8.39 (d, J=2.8 Hz, 1H, 状液体，HNMR (CDCl 3 , 400 MHz)，δ: 1.67 (d, J=6.8
Py-H), 8.50 (dd, J= 4.4 Hz, 1.6 Hz, 1H, Py-H); Hz, 3H, CH 3 ), 2.73~2.94 (m, 2H, CH 2 ), 3.64~3.99 (m,
13 CNMR (CDCl 3 , 100 MHz)，δ: 18.57, 73.19, 116.28, 2H, CH 2 ), 4.66~4.96 (m, 2H, CH 2 ), 5.01 (q, J=6.8 Hz,
122.47, 124.02, 124.90, 125.08, 129.06, 140.17, 1H, CH), 6.91~7.20 (m, 8H, PhH), 7.48 (dd, J=8.8
142.94, 145.63, 147.00, 147.24, 147.40, 148.28, Hz, 2.0 Hz, 1H, Py-H), 7.85 (d, J=2.0 Hz, 1H, Py-H);
13 CNMR (CDCl 3 , 100 MHz)，δ: 17.87, 29.52, 44.98,
154.67, 170.22。Anal. Calcd. for C 19 H 14 ClFN 2 O 4 ，%:
46.82, 74.91, 115.77, 122.39, 124.82, 125.00, 126.51,
C 58.70, H 3.63, N 7.21, found：C 58.91, H 3.55, N
128.38, 128.96, 132.72, 133.73, 140.13, 145.63,
7.10。
146.93, 148.27, 151.19, 154.61, 170.03。 Anal. Calcd.
(R)-2-[4-(3-氟-5-氯吡啶-2-氧基)苯氧基]丙酸苯
for C 23 H 20 ClFN 2 O 3 ，%: C 64.72, H 4.72, N 6.56,
乙基酯（Ⅳb）：0.71 g，产率 51%，无色油状液体， found：C 64.52, H 4.49, N 6.69。
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HNMR (CDCl 3 , 400 MHz)，δ: 1.56 (d, J=6.8 Hz, 3H, 吡啶-3-基-(R)-2-[4-(3-氯-5-三氟甲基吡啶-2-氧
CH 3 ), 2.95 (t, J =6.8 Hz, 2H, CH 2 ), 4.40 (t, J=6.8 Hz,
2H, CH 2 ), 4.68 (q, J=6.8 Hz, 1H, CH), 6.84 (d, J=9.2 基)苯氧基]丙酸酯（Ⅳf）：0.76 g，产率 52%，淡黄
1
Hz, 2H, PhH), 7.03 (d, J=9.2 Hz, 2H, PhH), 7.17~7.31 色透明液体， HNMR (CDCl 3 , 400 MHz)，δ: 1.83 (d,
(m, 5H, PhH), 7.49(dd, J =9.2Hz, 2.4 Hz, 1H, Py-H), J=6.8 Hz, 3H, CH 3 ), 5.02 (q, J=6.8 Hz, 1H, CH), 7.05
13
7.85 (d, J=2.4 Hz, 1H, Py-H); CNMR (CDCl 3 , 100 (d, J=8.8 Hz, 2H, Ph-H), 7.12 (d, J=8.8 Hz, 2H, Ph-H),
MHz)，δ: 18.58, 34.94, 65.56, 73.06, 116.01, 122.25, 7.35 (dd, J=8.4 Hz, 4.8 Hz, 1H, Py-H), 7.44~7.48 (m,
124.82, 125.00, 126.65, 128.52, 128.87, 137.30, 1H, Py-H), 7.97 (d, J=2.4 Hz, 1H, Py-H), 8.27~8.28
140.09, 145.64, 146.95, 148.28, 154.91, 172.02。Anal. (m,1H, Py-H), 8.39 (d, J=2.4 Hz, 1H, Py-H), 8.50 (d,
13
J=4.0 Hz, 1H, Py-H); CNMR (CDCl 3 , 100 MHz)，δ:
Calcd. for C 22 H 19 ClFNO 4 ，%: C 63.54, H 4.61, N 3.37,
18.56, 73.20, 116.10, 116.30, 119.18, 122.61, 122.86,
found：C 63.40, H 4.49, N 3.30。
124.00, 129.03, 136.30, 142.61, 142.95, 147.19,
(R)-2-[4-(3-氟-5-氯吡啶-2-氧基)苯氧基]丙酸萘 147.27, 155.03, 161.29, 170.18, 172.27。Anal. Calcd.
酯（Ⅳc）：0.86 g，产率 59%，淡黄色固体，熔点 for C 20 H 14 ClF 3 N 2 O 4 ，%: C 54.75, H 3.22, N 6.38,
1
125.7~126.5 ℃； HNMR (CDCl 3 , 400 MHz)，δ: 1.84 found：C 54.61, H 3.01, N 6.23。
(d, J=6.8 Hz, 3H, CH 3 ), 5.02 (q, J=6.8 Hz, 1H, CH), (R)-2-[4-(3-氯-5-三氟甲基吡啶-2-氧基)苯氧基]
7.06 (d, J=9.2 Hz, 2H, PhH), 7.13~7.18 (m, 3H, PhH
+ Naphthol-H), 7.47~7.53 (m, 4H, Naphthol-H), 7.80 丙酸苯乙基酯（Ⅳg）：0.73 g，产率 47%，透明黏稠
1
(dd, J=7.2Hz, 2.0 Hz, 1H, Py-H), 7.83~7.86 (m, 2H, 状液体，HNMR (CDCl 3 , 400 MHz)，δ: 1.57 (d, J=6.8
13
Naphthol-H), 7.88 (d, J=2.4 Hz, 1H, Py-H); CNMR Hz, 3H, CH 3 ), 2.95 (t, J=6.8 Hz, 2H, CH 2 ), 4.41 (t,
(CDCl 3 , 100 MHz)，δ: 18.67, 73.37, 116.30, 118.33, J=6.8 Hz, 2H, CH 2 ), 4.698 (q, J=6.8 Hz, 1H, CH),
120.54, 122.42, 124.88, 125.06, 125.91, 126.70, 6.87 (d, J=9.2 Hz, 2H, Ph-H), 7.03 (d, J=9.2 Hz, 2H,
127.65, 127.78, 129.56, 131.56, 133.62, 140.13, Ph-H), 7.17~7.31 (m, 5H, Ph-H), 7.96 (d, J=2.4 Hz,
13
140.19, 145.68, 147.29, 147.81, 154.89, 170.86。Anal. 1H, Py-H), 8.24 (s, 1H, Py-H); CNMR (CDCl 3 , 100
Calcd. for C 24 H 17 ClFNO 4 ，%: C 65.84, H 3.91, N 3.20, MHz)，δ: 18.57, 34.93, 65.58, 73.03, 116.00, 119.13,
121.48, 122.07, 122.58, 126.65, 128.52, 128.86, 136.22,
found：C 65.73, H 3.89, N 3.11。
137.28, 142.56, 146.70, 155.22, 161.35, 171.95。Anal.
N-苯乙基-(R)-2-[4-(3-氟-5-氯吡啶-2-氧基)苯氧
Calcd. for C 23 H 19 ClF 3 NO 4 ，%: C 59.30, H 4.11, N 3.01,
基]丙酰胺（Ⅳd）：0.84 g，产率 61%，白色固体，
1
熔点 108.0~109.1 ℃； HNMR (CDCl 3 , 400 MHz)， found：C 59.12, H 4.00, N 3.19。
δ:1.54 (d, J=6.8 Hz, 3H, CH 3 ), 2.71~2.85 (m, 2H, (R)-2-[4-(3-氯-5-三氟甲基吡啶-2-氧基)苯氧基]
CH 2 ), 3.47~3.66 (m, 2H, CH 2 ), 4.61 (q, J=6.8 Hz, 1H, 丙酸萘酯（Ⅳh）：0.73 g，产率 45%，白色固体，