CN102875274B - Polyfluorinated aromatic ether compounds and synthesis method and application thereof - Google Patents

Polyfluorinated aromatic ether compounds and synthesis method and application thereof Download PDF

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CN102875274B
CN102875274B CN201210390666.3A CN201210390666A CN102875274B CN 102875274 B CN102875274 B CN 102875274B CN 201210390666 A CN201210390666 A CN 201210390666A CN 102875274 B CN102875274 B CN 102875274B
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ether compounds
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CN102875274A (en
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翁志强
孙兰宝
荣明光
白正帅
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Fuzhou University
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Abstract

The invention discloses polyfluorinated aromatic ether compounds and a synthesis method and application thereof. In organic solvent, substituted phenol, penta fluoro benzene, inorganic base and oxidant react at the reaction temperature of 120 DEG C under the action of a palladium catalyst to form the polyfluorinated aromatic ether compounds. The polyfluorinated aromatic ether compounds are efficiently and selectively synthesized through catalysis of palladium; the compounds have wide application in the aspect of preparation of thin film transistor-liquid crystal display (TFT-LCD) liquid crystal materials; and the synthesis route has the advantages of high reaction yield and short reaction time.

Description

A kind of polyfluoro aromatic oxide compounds and synthetic method and application
Technical field
The invention belongs to synthetic chemistry field, be specifically related to a kind of polyfluoro aromatic oxide compounds and synthetic method and application.
Background technology
The research work of China's liquid crystal material starts from 1969, but owing to being subject to domestic LCD industry overall technology, the restriction of equipment level and infusion of financial resources, liquid crystal material is never put into national key scientific and technological project, the development of reasearch funds and manpower shortage restriction the sector, until China in 1987 just formally produces liquid crystal material, broken the long-term technical monopoly of Japan and Germany, but except obtaining some breakthroughs perfluor benzyne class liquid crystal material synthetic aspect in organic place, Shanghai, very slow in TFT-LCD liquid crystal material research and development progress especially with abroad there is a big difference aspect the new development and application that obtains liquid crystal material.For TFT-LCD, with liquid crystal material, generally to possess good chemical stability, wider operating temperature range, low-viscosity and high electric charge conservation rate.Wherein fluoro liquid crystals is due to comparatively approaching on fluorine atom and hydrogen atom volume, therefore structurally can not affect because of the steric hindrance of group the ordered arrangement of liquid crystal, fluorine atom has higher electronegativity simultaneously, can guarantee that fluorinated liquid crystal structurally has suitable moment of dipole, and fluorinated liquid crystal viscosity is lower, show that speed of response is fast, resistance conservation rate is high and become the quality matetrial of the high-grade liquid crystal of development TFT-LCD class.Therefore research and develop polyfluoro class liquid crystalline cpd and become the synthetic main flow of current liquid crystal material, in polyfluoro class liquid crystalline cpd synthetic, the effectively synthetic of polyfluoro aromatic compound is committed step, based on the importance of this compounds, invention is a kind of efficient, and the novel method that low cost is prepared polyfluoro aromatic compound is very necessary.
Summary of the invention
The object of the present invention is to provide a kind of polyfluoro aromatic oxide compounds and synthetic method and application, the present invention be a kind of by palladium catalysis efficient selective synthesize polyfluoro aromatic oxide compounds, this compounds is having been widely used aspect preparation TFT-LCD liquid crystal material, it is high that synthetic route of the present invention has reaction yield, the advantage that the reaction times is short.
For achieving the above object, the present invention adopts following technical scheme:
A method for synthetic polyfluoro aromatic oxide compounds, is in organic solvent, makes fortified phenol, penta fluoro benzene, mineral alkali and oxygenant, and under palladium catalyst effect, temperature of reaction is 120 ℃, generates polyfluoro aromatic oxide compounds.Reaction formula is:
Figure 2012103906663100002DEST_PATH_IMAGE001
, wherein said R is H, Cl, NO 2, NH 2, OCH 3, OC 2h 5, Ph, F, CH 3cO, CH 3cONH, CH 3, (CH3) 3c.
The mol ratio of described fortified phenol, penta fluoro benzene, palladium catalyst, mineral alkali and oxygenant is 2:1:0.1:2:2.
Described palladium catalyst is Pd (OAc) 2.
Described oxygenant is AgNO 3.
Described mineral alkali is K 2cO 3.
Described organic solvent is DMF.
The synthetic polyfluoro aromatic oxide compounds of a kind of method as above is for the preparation of liquid crystal material.
Beneficial effect of the present invention: the present invention be a kind of by palladium catalysis efficient selective synthesize polyfluoro aromatic oxide compounds, this compounds is having been widely used aspect preparation TFT-LCD liquid crystal material, it is high that synthetic route of the present invention has reaction yield, the advantage that the reaction times is short.
Embodiment
Figure 433468DEST_PATH_IMAGE002
Using DMF (2ml) as solvent, add phenol (0.20 mmol), K 2cO 3(0.20 mmol) reacts 30min, then adds penta fluoro benzene (0.10 mmol and AgNO 3(0.20 mmol), at Pd (OAc) 2(0.010 mmol) katalysis, heating 120 oc reacts 12h.Except after desolventizing, column chromatography obtains corresponding polyfluoro aromatic oxide.
Figure DEST_PATH_IMAGE003
Figure 225975DEST_PATH_IMAGE004
Productive rate 91%. 1h NMR (400 MHz, CDCl 3) δ7.27 – 7.18 (m, 2H), 7.06 – 6.97 (m, 1H), 6.90 – 6.78 (m, 3H). 13c NMR (101 MHz, CDCl 3) δ156.0 (s), 146.7 – 146.4 (m), 144.2 – 143.9 (m), 141.8 – 141.5 (m), 139.3 – 139.0 (m), 133.2 – 133.0 (m), 128.6 (s), 122.6 (s), 114.3 (s), 100.6 (t j=22.9 Hz). 19f NMR (376 MHz, CDCl 3) δ-138.7 –-138.9 (m, 2F) ,-154.0 –-154.1 (m, 2F) .GC-MS m/z242 (M +). HRMS (EI): calcd. for C 12h 6f 4o 242.0355; Found 242.0357. IR (KBr) n 1641,1591,1521,1485,1202,1067,947,839,811,754,687 cm 1.
Figure 2012103906663100002DEST_PATH_IMAGE005
Productive rate 87%. 1h NMR (400 MHz, CDCl 3) δ7.04 (d, j=7.6 Hz, 2H), 6.94 – 6.82 (m, 1H), 6.79 (d, j=7.6 Hz, 2H), 2.24 (s, 3H). 13c NMR (101 MHz, CDCl 3) δ155.2 (s), 147.8 – 147.5 (m), 145.3 – 145.0 (m), 142.9 – 142.7 (m), 140.4 – 140.2 (m), 133.3 (s), 130.2 (s), 115.4 (s), 101.6 (t j=22.9 Hz), 20.56 (s). 19f NMR (376 MHz, CDCl 3) δ-138.8 –-139.0 (m, 2F) ,-154.3 –-154.2 (m, 2F). GC-MS m/z256 (M +). HRMS (EI): calcd. for C 13h 8f 4o 256.0511; Found 256.0510. IR (KBr) n 3084,2926,1641,1591,1521,1485,1203,1172,1067,947,755 cm 1.
Figure 943395DEST_PATH_IMAGE006
Productive rate 85%. 1h NMR (400 MHz, CDCl 3) δ7.33 (d, j=7.4 Hz, 1H), 7.18 (t, j=7.8 Hz, 1H), 7.11 (t, j=7.3 Hz, 1H), 7.05 – 6.93 (m, 1H), 6.72 (d, j=8.0 Hz, 1H), 2.52 (s, 3H). 13c NMR (101 MHz, CDCl 3) δ155.6 (s), 147.9 – 147.6 (m), 145.4 – 145.2 (m), 142.9 – 142.7 (m), 140.4 – 140.2 (m), 135.1 – 134.7 (m), 131.5 (s), 127.3 (s), 127.0 (s), 123.7 (s), 113.56 (s), 101.48 (t j=23.0 Hz), 15.87 (s). 19f NMR (376 MHz, CDCl 3) δ-138.9 –-139.1 (m, 2F) ,-154.3 –-154.2 (m, 2F). GC-MS m/z256 (M +). HRMS (EI): calcd. for C 13h 8f 4o 256.0511; Found 256.0510. IR (KBr) n 3084,2931,1642,1588,1519,1483,1224,1176,1118,1067,945,750 cm 1.
Figure DEST_PATH_IMAGE007
Productive rate 85%. 1h NMR (400 MHz, CDCl 3) δ7.39 (d, j=7.8 Hz, 2H), 7.05 – 6.95 (m, 1H), 6.93 (d, j=7.8 Hz, 2H), 1.36 (s, 9H). 13c NMR (101 MHz, CDCl 3) δ155.0 (s), 147.8 – 147.6 (m), 146.7 (s), 145.4 – 145.1 (m), 143.0 – 142.8 (m), 140.5 – 140.3 (m), 134.8 – 134.3 (m), 126.6 (s), 115.0 (s), 101.7 (t j=22.9 Hz), 34.29 (s), 31.40 (s). 19f NMR (376 MHz, CDCl 3) δ-138.86 –-139.02 (m, 2F) ,-154.08 (dt, j=17.8,8.6 Hz, 2F). GC-MS m/z298 (M +). HRMS (EI): calcd. for C 16h 14f 4o 298.0981; Found 298.0985. IR (KBr) n 3085,2966,1641,1606,1517,1483,1221,1175,1067,944,831,716,546 cm 1.
Figure 273358DEST_PATH_IMAGE008
Productive rate 82%. 1h NMR (400 MHz, CDCl 3) δ7.47 (d, j=7.5 Hz, 1H), 7.18 – 7.10 (m, 2H), 7.06 – 6.93 (m, 1H), 6.65 (d, j=7.9 Hz, 1H), 1.55 (s, 9H). 13c NMR (101 MHz, CDCl 3) δ156.0 (s), 148.0 – 147.7 (m), 145.5 – 145.2 (m), 142.7 – 142.6 (m), 140.3 – 140.1 (m), 138.3 (s), 134.1 – 133.9 (m), 127.5 (s), 127.1 (s), 123.5 (s), 113.8 (s), 101.4 (t j=23.0 Hz), 34.95 (s), 29.85 (s). 19f NMR (376 MHz, CDCl 3) δ-138.78 –-138.94 (m, 2F) ,-153.96 (dt, j=21.3,8.7 Hz, 2F). GC-MS m/z298 (M +). HRMS (EI): calcd. for C 16h 14f 4o 298.0981; Found 298.0987. IR (KBr) n 3084,2963,2873,1642,1520,1482,1364,1189,945,809,749,482 cm 1.
Figure DEST_PATH_IMAGE009
Productive rate 90%. 1h NMR (400 MHz, CDCl 3) δ7.73 – 7.70 (m, 2H), 7.55 – 7.51 (m, 3H), 7.47 – 7.43 (m, 1H), 7.38 – 7.27 (m, 2H), 7.00 – 6.89 (m, 2H). 13c NMR (101 MHz, CDCl 3) δ154.0 (s), 147.9 – 147.6 (m), 145.4 – 145.1 (m), 142.7 – 142.5 (m), 140.2 – 140.0 (m), 137.4 (s), 134.8 – 134.5 (m), 131.7 (s), 131.5 (s), 129.5 (s), 128.7 (s), 128.3 (s), 127.6 (s), 124.2 (s), 114.6 (s), 101.49 (t j=23.0 Hz). 19f NMR (376 MHz, CDCl 3) δ-138.87 (dt, j=19.8,9.7 Hz, 2F) ,-154.05 –-154.30 (m, 2F). GC-MS m/z318 (M +). HRMS (EI): calcd. for C 18h 10f 4o 318.0668; Found 318.0666. IR (KBr) n 3078,1642,1520,1483,1258,1195,1119,1064,946,722 cm 1.
Figure 963096DEST_PATH_IMAGE010
Productive rate 93%. 1h NMR (400 MHz, CDCl 3) δ7.05 – 6.97 (m, 1H), 6.88 – 6.86 (m, 1H), 6.74 – 6.72 (m, 2H), 2.41 – 2.40 (m, 6H). 13c NMR (101 MHz, CDCl 3) δ157.3 (s), 155.7 (s), 147.9 – 147.6 (m), 145.5 – 145.2 (m), 143.1 – 142.9 (m), 140.6 – 140.4 (m), 139.9 (s), 125.6 (s), 113.2 (s), 101.7 (t j=23.0 Hz), 21.18 (s). 19f NMR (376 MHz, CDCl 3) δ-138.86 –-139.25 (m, 2F) ,-154.14 –-154.43 (m, 2F). GC-MS m/z270 (M +). HRMS (EI): calcd. for C 14h 10f 4o 270.0668; Found 270.0667. IR (KBr) n 3082,2924,1642,1619,1592,1486,1290,1143,1079,946,834,716,682 cm 1.
Figure DEST_PATH_IMAGE011
Productive rate 83%. 1h NMR (400 MHz, CDCl 3) δ7.04 – 6.92 (m, 3H), 6.52 (d, j=8.0 Hz, 1H), 2.37 (s, 6H). 13c NMR (101 MHz, CDCl 3) δ155.5 (s), 147.8 – 147.6 (m), 145.4 – 145.1 (m), 142.8 – 142.6 (m), 140.4 – 140.2 (m), 139.0 (s), 135.2 (s), 125.9 (s), 125.8 (s), 125.2 (d j=1.8 Hz), 111.2 (s), 101.3 (t, j=23.0 Hz), 20.0 (s), 11.8 (s). 19f NMR (376 MHz, CDCl 3) δ-138.99 –-139.21 (m, 2F) ,-154.77 –-154.98 (m, 2F). GC-MS m/z270 (M +). HRMS (EI): calcd. for C 14h 10f 4o 270.0668; Found 270.0664. IR (KBr) n 3092,2919,2851,1643,1581,1189,1126,941,847,765,717 cm 1.
Figure 723242DEST_PATH_IMAGE012
Productive rate 85%. 1h NMR (400 MHz, CDCl 3) δ7.14 (d, j=7.4 Hz, 1H), 7.03 – 6.91 (m, 1H), 6.86 (d, j=7.4 Hz, 1H), 6.44 (s, 1H), 2.39 (s, 3H), 2.26 (s, 3H). 13c NMR (101 MHz, CDCl 3) δ155.4 (s), 147.8 – 147.5 (m), 145.4 – 145.1 (m), 142.8 – 142.6 (m), 140.4 – 140.2 (m), 137.0 (s), 131.2 (s), 124.2 (d j=31.8 Hz), 114.3 (s), 101.4 (t, j=23.0 Hz), 21.04 (s), 15.53 (s). 19f NMR (376 MHz, CDCl 3) δ-138.92 –-139.15 (m, 2F) ,-154.17 –-154.37 (m, 2F). GC-MS m/z270 (M +). HRMS (EI): calcd. for C 14h 10f 4o 270.0668; Found 270.0667. IR (KBr) n 3096,2923,2857,1644,1515,1489,1243,1125,941,842,813,713 cm 1.
Figure DEST_PATH_IMAGE013
Productive rate 92%. 1h NMR (400 MHz, CDCl 3) δ8.32 (dd, j=6.3,2.8 Hz, 1H), 7.80 (dd, j=6.1,2.9 Hz, 1H), 7.51 (dt, j=7.5,7.0 Hz, 3H), 7.24 (t, j=8.0 Hz, 1H), 6.93 (tt, j=9.9,7.0 Hz, 1H), 6.59 (d, j=7.7 Hz, 1H). 13c NMR (101 MHz, CDCl 3) δ153.2 (s), 147.9 – 147.6 (m), 145.4 – 145.2 (m), 143.0 – 142.7 (m), 140.5 – 140.2 (m), 134.8 (s), 134.6 – 134.3 (m), 127.7 (s), 127.0 (s), 126.2 (s), 125.2 (s), 124.8 (s), 123.6 (s), 121.6 (s), 107.6 (s), 102.1 (t j=22.9 Hz). 19f NMR (376 MHz, CDCl 3) δ-138.69 –-138.86 (m, 2F) ,-153.98 –-154.17 (m, 2F). GC-MS m/z292 (M +). HRMS (EI): calcd. for C 16h 8f 4o 292.0511; Found 292.0507. IR (KBr) n 3093,1642,1599,1577,1513,1493,1231,1177,1104,938,788,766 cm 1.
Figure 865641DEST_PATH_IMAGE014
Productive rate 94%. 1h NMR (400 MHz, CDCl 3) δ7.26 (t, j=8.3 Hz, 1H), 7.04 – 6.96 (m, 1H), 6.73 – 6.70 (m, 1H), 6.62 (t, j=2.4 Hz, 1H), 6.59 – 6.56 (m, 1H), 3.83 (s, 3H). 13c NMR (101 MHz, CDCl 3) δ161.0 (s), 158.2 (s), 147.8 – 147.5 (m), 145.3 – 145.0 (m), 142.9 – 142.7 (m), 140.4 – 140.2 (m), 134.3 – 134.0 (m), 130.2 (s), 109.1 (s), 107.5 (s), 102.3 (s), 102.0 (t j=23.2 Hz), 55.3 (s). 19f NMR (376 MHz, CDCl 3) δ-136.64 –-140.96 (m, 2F) ,-154.21 (ddd, j=21.5,9.8,7.1 Hz, 2F). GC-MS m/z292 (M +). HRMS (EI): calcd. for C 13h 8f 4o 2272.0460; Found 272.0452. IR (KBr) n 3075,2976,1601,1529,1259,1147,1063,949,855,771 cm 1.
Figure DEST_PATH_IMAGE015
Productive rate 84%. 1h NMR (400 MHz, CDCl 3) δ6.97 – 6.91 (m, 1H), 6.87 – 6.78 (m, 2H), 6.78 – 6.67 (m, 2H), 3.91 (q, j=7.0 Hz, 2H), 1.18 (t, j=7.0 Hz, 3H). 13c NMR (101 MHz, CDCl 3) δ149.1 (s), 147.6 – 147.4 (m), 146.3 (s), 145.2-144.9 (m), 142.4 – 142.2 (m), 140.0 – 139.8 (m), 136.3 – 136.0 (m), 124.9 (s), 120.8 (s), 117.9 (s), 114.1 (s), 100.4 (t j=23.0 Hz), 64.5 (s), 14.5 (s). 19f NMR (376 MHz, CDCl 3) δ-139.97 –-140.09 (m, 2F) ,-155.22 –-155.36 (m, 2F). GC-MS m/z286 (M +). HRMS (EI): calcd. for C 14h 10f 4o 2286.0617; Found 286.0619. IR (KBr) n 3094,2982,1641,1605,1587,1320,1253,1122,1196,927,835,752 cm 1.
Figure 2224DEST_PATH_IMAGE016
Productive rate 75%. 1h NMR (400 MHz, CDCl 3) δ6.98 (t, j=8.0 Hz, 1H), 6.92 – 6.79 (m, 1H), 6.33 (d, j=7.9 Hz, 1H), 6.22 (s, 2H), 3.53 (s, 2H). 13c NMR (101 MHz, CDCl 3) δ152.7 (s), 150.2,147.8 – 147.5 (m), 145.3 – 145.1 (m), 142.6 – 142.4 (m), 140.1 – 140.0 (m), 139.4 (s), 136.0 (s), 129.8 (s), 126.1 (s), 123.3 (s), 122.2 (s), 112.2 (s), 101.83 (t j=22.9 Hz). 19f NMR (376 MHz, CDCl 3) δ-138.83 –-139.06 (m, 2F) ,-154.15 (dt, j=21.8,8.6 Hz, 2F). GC-MS m/z257 (M +). HRMS (EI): calcd. for C 12h 7f 4nO 257.0464; Found 257.0462. IR (KBr) n 3325,1642,1535,1487,1132,1259,1147,1063,949,855,775 cm 1.
Figure DEST_PATH_IMAGE017
Productive rate 63%. 1h NMR (400 MHz, CDCl 3) δ8.05 (s, 1H), 7.40 – 7.33 (m, 2H), 6.90 – 6.83 (m, 1H), 6.80 (d, j=9.0 Hz, 2H), 2.03 (s, 3H). 13c NMR (101 MHz, CDCl 3) δ168.9 (s), 153.6 (s), 147.8 – 147.5 (m), 145.4 – 145.1 (m), 142.8 – 142.6 (m), 140.3 – 140.1 (m), 134.6 – 134.3 (m), 134.0 (s), 121.8 (s), 116.0 (s), 101.85 (t j=22.9 Hz), 24.15 (s). 19f NMR (376 MHz, CDCl 3) δ-138.61 –-138.84 (m, 2F) ,-154.27 (ddd, j=21.5,9.7,7.1 Hz, 2F). GC-MS m/z299 (M +). HRMS (EI): calcd. for C 14h 9f 4nO 2299.0569; Found 299.0565. IR (KBr) n 3288,1660,1507,1487,1207,1177,1070,943,831,715 cm 1.
Productive rate 64%. 1h NMR (400 MHz, CDCl 3) δ7.95 – 7.85 (m, 2H), 7.02 – 6.89 (m, 3H), 2.51 (s, 3H). 13c NMR (101 MHz, CDCl 3) δ196.4 (s), 160.4 (s), 147.6 – 147.8 (m), 145.4 – 145.1 (m), 142.7 – 142.5 (m), 140.2 – 140.0 (m), 133.1 (s), 130.7 (s), 115.25 (s), 102.62 (t j=22.9 Hz), 26.44 (s). 19f NMR (376 MHz, CDCl 3) δ-137.94 –-138.09 (m, 2F) ,-153.66 (ddd, j=21.5,10.0,7.1 Hz, 2F). GC-MS m/z284 (M +). HRMS (EI): calcd. for C 14h 8f 4o 2284.0460; Found 284.0458. IR (KBr) n 3045,1678,1644,1599,1504,1488,1268,1220,1166,938,847,716,590 cm 1.
Figure 412270DEST_PATH_IMAGE020
Productive rate 85% yield. 1h NMR (400 MHz, CDCl 3) δ8.04 (d, j=8.1 Hz, 1H), 7.81 (s, 1H), 7.57 (t, j=8.0 Hz, 1H), 7.38 (d, j=8.3 Hz, 1H), 7.17 – 7.02 (m, 1H). 13c NMR (101 MHz, CDCl 3) δ157.3 (s), 149.3 (s), 147.9 – 147.7 (m), 145.4 – 145.2 (m), 142.6 – 142.4 (m), 140.1 – 139.9 (m), 133.2 – 133.0 (m), 130.7 (s), 121.9 (s), 118.8 (s), 110.7 (s), 103.1 (t j=22.9 Hz). 19f NMR (376 MHz, CDCl 3) δ-130.78 –-142.50 (m, 2F) ,-154.15 (dt, j=21.8,8.6 Hz, 2F). GC-MS m/z287 (M +). HRMS (EI): calcd. for C 12h 5f 4nO 3287.0206; Found 287.0205. IR (KBr) n 1642,1532,1438,1351,1220,1173,958,755,715 cm 1.
Figure DEST_PATH_IMAGE021
Productive rate 57%. 1h NMR (400 MHz, CDCl 3) δ7.09 – 6.94 (m, 5H). 13c NMR (101 MHz, CDCl 3) δ160.2 (s), 157.8 (s), 153.2 (s), 147.9 – 147.6 (m), 145.4 – 145.1 (m), 142.8 – 142.6 (m), 140.3 – 140.1 (m), 134.7 – 134.4 (m), 117.1 (d j=8.3 Hz), 116.4 (s), 116.2 (s), 101.9 (t, j=22.9 Hz). 19f NMR (376 MHz, CDCl 3) δ-119.53 –-119.72 (m, 1F) ,-138.47 –-138.63 (m, 2F) ,-154.19 –-154.32 (m, 2F). GC-MS m/z260 (M +). HRMS (EI): calcd. for C 12h 5f 5o 260.0261; Found 260.0259. IR (KBr) n 3088,1642,1502,1485,1274,1190,1068,945,832,736,513 cm 1.
Figure 104282DEST_PATH_IMAGE022
Productive rate 80%. 1h NMR (400 MHz, CDCl 3) δ7.38 – 7.23 (m, 2H), 7.09 – 6.85 (m, 3H). 13c NMR (101 MHz, CDCl 3) δ155.68 (s), 147.72 (td, j=12.0,4.3 Hz), 145.24 (td, j=12.0,4.2 Hz), 142.68 (ddd, j=14.7,4.9,2.3 Hz), 140.18 (ddd, j=15.0,4.8,2.3 Hz), 134.04 (tt, j=13.1,3.9 Hz), 129.77 (s), 128.99 (s), 116.96 (s), 102.19 (t, j=22.9 Hz). 19f NMR (376 MHz, CDCl 3) δ-138.38 (qt, j=11.7,1.8 Hz, 2F) ,-154.03 (ddd, j=21.5,9.9,7.0 Hz, 2F). GC-MS m/z275 (M +) .IR (KBr) n 3086,1642,1588,1521,1485,1210,1177,1066,949,827,716,502 cm 1.
Figure DEST_PATH_IMAGE023
Productive rate 78%. 1h NMR (400 MHz, CDCl 3) δ9.02 (s, 1H), 8.23 (d, j=8.3 Hz, 1H), 7.62 (d, j=8.1 Hz, 1H), 7.58 – 7.48 (m, 1H), 7.44 (t, j=7.9 Hz, 1H), 7.09 – 6.92 (m, 2H). 13c NMR (101 MHz, CDCl 3) δ152.7 (s), 150.2 (s), 147.8 – 147.6 (m), 145.4 – 145.1 (m), 142.7 – 142.4 (m), 140.2 – 140.0 (m), 139.4 (s), 136.0 (s), 135.1 – 134.6 (m), 129.8 (s), 126.1 (s), 123.3 (s), 122.2 (s), 112.2 (s), 101.8 (t j=22.9 Hz). 19f NMR (376 MHz, CDCl 3) δ-138.64 –-138.87 (m, 2F) ,-153.84 (dt, j=21.1,8.6 Hz, 2F). GC-MS m/z293 (M +). HRMS (EI): calcd. for C 15h 7f 4nO 293.0464; Found 293.0461. IR (KBr) n 3046,1643,1500,1486,1470,1315,1246,1186,1104,943,822,789,789,719 cm 1.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.

Claims (4)

1. a method for synthetic polyfluoro aromatic oxide compounds, is characterized in that: in organic solvent, make fortified phenol, penta fluoro benzene, mineral alkali and oxygenant, under palladium catalyst effect, temperature of reaction is 120 ℃, generates polyfluoro aromatic oxide compounds;
Reaction formula is:
Figure DEST_PATH_IMAGE002
，
Wherein said R is H, Cl, NO 2, NH 2, OCH 3, OC 2h 5, Ph, F, CH 3cO, CH 3cONH, CH 3, (CH 3) 3c;
Described palladium catalyst is Pd (OAc) 2;
Described oxygenant is AgNO 3.
2. the method for synthetic polyfluoro aromatic oxide compounds according to claim 1, is characterized in that: the mol ratio of described fortified phenol, penta fluoro benzene, palladium catalyst, mineral alkali and oxygenant is 2:1:0.1:2:2.
3. the method for synthetic polyfluoro aromatic oxide compounds according to claim 1, is characterized in that: described mineral alkali is K 2cO 3.
4. the method for synthetic polyfluoro aromatic oxide compounds according to claim 1, is characterized in that: described organic solvent is DMF.
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* Cited by examiner, † Cited by third party
Title
Aromatic Polyfluoro-compounds. Part L1V.l Copper-assisted Nucleophilic;J. Burdon et al.;《J.C.S》;19721231;763-769 *
Highly fluorinated biphenyl ether systems as dopants for fast-response liquid crystal display applications;Matthew R. Cargill et al.;《Liquid Crystals》;20111231;第38卷(第8期);1069-1078 *
J. Burdon et al..Aromatic Polyfluoro-compounds. Part L1V.l Copper-assisted Nucleophilic.《J.C.S》.1972,763-769.
Matthew R. Cargill et al..Highly fluorinated biphenyl ether systems as dopants for fast-response liquid crystal display applications.《Liquid Crystals》.2011,第38卷(第8期),1069-1078.

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