Supporting Information� Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2014

Gold-Catalyzed 6-Exo-Dig Cycloisomerization: A Versatile Approach toFunctionalized Phenanthrenes

Chao Shu, Long Li, Cheng-Bin Chen, Hong-Cheng Shen, and Long-Wu Ye*[a]

asia_201400034_sm_miscellaneous_information.pdf

State Key Laboratory for Physical Chemistry of Solid Surfaces, The Key Laboratory for

Chemical Biology of Fujian Province and Department of Chemistry, College of

Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, P. R.

China

Content    Page number 

General 2

Preparation of Starting Materials 2

General Procedure: Gold Catalysis 11 1H and 13C NMR spectra 24

General Information. Ethyl acetate (ACS grade), hexanes (ACS grade) and

anhydrous 1, 2-dichloroethane (ACS grade) were obtained commercially and used

without further purification. Methylene chloride, tetrahydrofuran and diethyl ether were

purified according to standard methods unless otherwise noted. Commercially available

reagents were used without further purification. Reactions were monitored by thin layer

chromatography (TLC) using silicycle pre-coated silica gel plates. Flash column

chromatography was performed over silica gel (300-400 mesh). Infrared spectra were

recorded on a Nicolet AVATER FTIR330 spectrometer as thin film and are reported in

reciprocal centimeter (cm-1). Mass spectra were recorded with Micromass QTOF2

Quadrupole/Time-of-Flight Tandem mass spectrometer using electron spray ionization. 1H NMR spectra were recorded on a Bruker AV-400 spectrometer and a Bruker AV-

500 spectrometer in chloroform-d3. Chemical shifts are reported in ppm with the internal

TMS signal at 0.0 ppm as a standard. The data is being reported as (s = singlet, d =

doublet, t = triplet, m = multiplet or unresolved, brs = broad singlet, coupling constant(s)

in Hz, integration). 13C NMR spectra were recorded on on a Bruker AV-400 spectrometer and a Bruker

AV-500 spectrometer in chloroform-d3. Chemical shifts are reported in ppm with the

internal chloroform signal at 77.0 ppm as a standard.

Representative synthetic procedures for the preparation of starting materials: 1

Procedure for the preparation of 1-benzyl-2-ethynylbenzene (1a)

85% yield

CHO phenylboronic acidPd(OAc)2 (5 mol %)

Na2CO3 (1.1 equiv)DMF/H2O, rt

Br

Ph

CHO

MeOH, 0 °C to rt

Ph

OH

MeCN, rt

Ph

Br

K2CO3 (1.1 equiv), MeCN, 75 C

TMS Ph

TMS

Ph

NaBH4 (1.5 equiv)

PPh3 (1.5 equiv)CBr4 (1.5 equiv) CuI (1.0 equiv), TBAI (1.0 equiv)

(1.5 equiv)

MeOH, rt

K2CO3

80% yield (2 steps) 83% yield

75% yield

2-(prop-2-yn-1-yl)-1,1'-biphenyl (1a)

1a 1H NMR (400 MHz, CDCl3) 7.55 (dd, 1H, J = 1.2 Hz, J = 8.0 Hz), 7.49 – 7.31 (m, 7H),

7.26 – 7.24 (m, 1H), 3.57 (d, 2H, J = 2.8 Hz), 2.42 (t, 1H, J = 2.8 Hz); 13C NMR (100

MHz, CDCl3) 141.4, 140.9, 133.7, 130.0, 129.1, 128.9, 128.3, 127.7, 127.2, 126.8, 82.6,

70.3, 23.0; IR (neat): 3294, 3059, 3024, 2919, 2118, 1597, 1478, 1450, 1261, 1009, 750,

702; MS (ES+) Calculated for [C15H12Na]+: 215.1; Found: 215.1.

3',5'-dimethoxy-2-(prop-2-yn-1-yl)-1,1'-biphenyl (1b)

1b

This compound is known and the spectroscopic data match those reported.1 1H NMR (400

MHz, CDCl3) δ 7.60 (d, 1H, J = 8.4 Hz), 7.36 (dt, 1H, J = 1.6 Hz, J = 7.4 Hz), 7.31 –

7.23 (m, 2H), 6.51 – 6.49 (m, 2H), 6.48 – 6.46 (m, 1H), 3.80 (s, 6H), 3.50 (d, 2H, J = 2.4

Hz), 2.15 (t, 1H, J = 2.8 Hz); 13C NMR (100 MHz, CDCl3) 160.5, 142.8, 141.3, 133.6,

129.6, 128.9, 127.8, 126.8, 107.2, 99.4, 82.9, 70.3, 55.4, 23.0.

5-(2-(prop-2-yn-1-yl)phenyl)benzo[d][1,3]dioxole (1c)

1c 1H NMR (400 MHz, CDCl3) δ 7.59 (d, 1H, J = 7.6 Hz), 7.33 – 7.17 (m, 3H), 6.84 – 6.80

(m, 2H), 6.76 – 6.74 (m, 1H), 5.94 (s, 2H), 3.48 (d, 2H, J = 2.4 Hz), 2.13 (t, 1H, J = 2.4

Hz); 13C NMR (100 MHz, CDCl3) 147.4, 146.7, 140.9, 134.6, 133.8, 129.9, 128.8,

127.6, 126.7, 122.4, 109.6, 108.1, 101.0, 82.6, 70.4, 23.0; IR (neat): 3294, 3060, 3021,

2890, 2774, 2118, 1606, 1503, 1478, 1451, 1245, 1039, 937, 762, 640; MS (ES+)

Calculated for [C16H12NaO2]+: 259.1; Found: 259.1.

4'-methoxy-2-(prop-2-yn-1-yl)-1,1'-biphenyl (1d)

1d

This compound is known and the spectroscopic data match those reported.2 1H NMR

(400 MHz, CDCl3) δ 7.65 – 7.59 (m, 1H), 7.36 – 7.21 (m, 5H), 6.97 – 6.94 (m, 2H), 3.85

(s, 3H), 3.49 (d, 2H, J = 2.8 Hz), 2.13 (t, 1H, J = 2.8 Hz); 13C NMR (100 MHz, CDCl3)

158.8, 141.0, 133.9, 133.3, 130.2, 130.1, 128.9, 127.5, 126.8, 113.7, 82.8, 70.3, 55.3, 23.1;

IR (neat): 3291, 2955, 2933, 2835, 2118, 1611, 1515, 1481, 1295, 1244, 1177, 1037, 934,

762, 638;; MS (ES+) Calculated for [C16H14NaO]+: 245.1; Found: 245.1.

4'-fluoro-2-(prop-2-yn-1-yl)-1,1'-biphenyl (1e)

1e 1H NMR (400 MHz, CDCl3) δ 7.61 (d, 1H, J = 8.0 Hz), 7.36 (dt, 1H, J = 1.2 Hz, J = 7.2

Hz), 7.32 – 7.27 (m, 3H), 7.22 – 7.19 (m, 1H), 7.13 – 7.07 (m, 2H), 3.44 (d, 2H, J = 2.8

Hz), 2.13 (t, 1H, J = 2.8 Hz); 13C NMR (100 MHz, CDCl3) 162.1 (d, J = 244.8 Hz),

140.4, 136.8 (d, J = 3.3 Hz), 133.8, 130.7 (d, J = 7.9 Hz), 130.0, 129.0, 127.9, 126.9,

115.2 (d, J = 21.2 Hz), 82.5, 70.5, 23.1; IR (neat): 3302, 3066, 2923, 2121, 1608, 1513,

1481, 1223, 1158, 1008, 839, 762, 640, 561; MS (ES+) Calculated for [C15H11FNa]+:

233.1; Found: 233.0.

4'-chloro-2-(prop-2-yn-1-yl)-1,1'-biphenyl (1f)

1f 1H NMR (500 MHz, CDCl3) δ 7.60 (d, 1H, J = 8.0 Hz), 7.38 – 7.33 (m, 3H), 7.30 – 7.23

(m, 3H), 7.19 – 7.17 (m, 1H), 3.44 (d, 2H, J = 3.0 Hz), 2.12 (t, 1H, J = 2.5 Hz); 13C NMR

(125 MHz, CDCl3) 140.1, 139.3, 133.7, 133.3, 130.4, 129.8, 129.1, 128.4, 128.1, 126.9,

82.4, 70.6, 23.0; IR (neat): 3299, 3061, 3026, 2119, 1594, 1475, 1426, 1089, 1019, 1006,

833, 761, 640, 553; MS (ES+) Calculated for [C15H11ClNa]+: 249.0; Found: 249.0.

4'-bromo-2-(prop-2-yn-1-yl)-1,1'-biphenyl (1g)

1g 1H NMR (500 MHz, CDCl3) δ 7.62 – 7.58 (m, 1H), 7.39 – 7.33 (m, 3H), 7.30 – 7.24 (m,

3H), 7.20 – 7.17 (m, 1H), 3.44 (d, 2H, J = 2.5 Hz), 2.12 (t, 1H, J = 2.5 Hz); 13C NMR

(125 MHz, CDCl3) 140.1, 139.3, 133.7, 133.3, 130.4, 129.9, 129.1, 128.5, 128.1, 127.0,

82.4, 70.5, 23.0; IR (neat): 3299, 3061, 3026, 2118, 1594, 1498, 1475, 1426, 1089, 1019,

833, 761, 639, 533; MS (ES+) Calculated for [C15H11BrNa]+: 293.0; Found: 293.0.

2'-(prop-2-yn-1-yl)-[1,1'-biphenyl]-4-carbonitrile (1h)

1h 1H NMR (400 MHz, CDCl3) δ 7.72 (d, 2H, J = 8.0 Hz), 7.62 (d, 1H, J = 7.6 Hz), 7.48 (d,

2H, J = 8.4 Hz), 7.42 (dt, 1H, J = 1.2 Hz, J = 7.6 Hz), 7.37 – 7.32 (m, 1H), 7.21 (dd, 1H,

J = 1.2 Hz, J = 7.6 Hz), 3.43 (d, 2H, J = 2.8 Hz), 2.15 (t, 1H, J = 2.8 Hz); 13C NMR (100

MHz, CDCl3) 145.7, 139.5, 133.5, 132.1, 129.9, 129.6, 129.4, 128.8, 127.2, 118.7,

111.2, 82.0, 70.8, 23.1; IR (neat): 3258, 3069, 2926, 2231, 1608, 1481, 1398, 1109, 848,

768, 747, 687; MS (ES+) Calculated for [C16H11NNa]+: 240.1; Found: 240.1.

3'-fluoro-2-(prop-2-yn-1-yl)-1,1'-biphenyl (1i)

1i 1H NMR (400 MHz, CDCl3) δ 7.62 (dd, 1H, J = 0.4 Hz, J = 7.6 Hz), 7.40 – 7.34 (m, 2H),

7.30 (dt, 1H, J = 1.2 Hz, J = 7.6 Hz), 7.22 (dd, 1H, J = 1.6 Hz, J = 7.6 Hz), 7.13 – 7.09

(m, 1H), 7.08 – 7.03 (m, 2H), 3.47 (d, 2H, J = 2.8 Hz), 2.14 (t, 1H, J = 2.8 Hz); 13C NMR

(100 MHz, CDCl3) 162.6 (d, J = 245.0 Hz), 143.0 (d, J = 7.6 Hz), 140.1, 133.6, 129.7

(d, J = 6.8 Hz), 129.0, 128.2, 126.9, 124.9 (d, J = 2.9 Hz), 116.1 (d, J = 21.3 Hz), 116.1,

114.1 (d, J = 20.8 Hz), 82.3, 70.6, 23.0; IR (neat): 3301, 3063, 2920, 2118, 1614, 1585,

1427, 1190, 1774, 879, 789, 759, 640; MS (ES+) Calculated for [C15H11FNa]+: 233.1;

Found: 233.1.

2-(2-(prop-2-yn-1-yl)phenyl)naphthalene (1j)

1j

This compound is known and the spectroscopic data match those reported.2 1H NMR

(400 MHz, CDCl3) 7.85 – 7.79 (m, 3H), 7.70 (d, 1H, J = 0.4 Hz), 7.76 (d, 1H, J = 7.6

Hz), 7.48 – 7.42 (m, 3H), 7.39 – 7.33 (m, 1H), 7.31 – 7.29 (m, 2H), 3.51 (d, 2H, J = 2.8

Hz), 2.12 (t, 1H, J = 2.8 Hz); 13C NMR (100 MHz, CDCl3) 141.3, 138.3, 133.9, 133.2,

132.4, 130.1, 128.9, 128.0, 127.9, 127.8(2), 127.7(9), 127.6, 127.4, 126.9, 126.3, 126.0,

82.6, 70.5, 23.1; IR (neat): 3294, 3054, 2920, 2118, 1597, 1489, 1465, 1270, 859, 758,

640; MS (ES+) Calculated for [C19H14Na]+: 265.1; Found: 265.1.

1-(2-(prop-2-yn-1-yl)phenyl)naphthalene (1k)

1k 1H NMR (400 MHz, CDCl3) 7.90 (t, 2H, J = 8.8 Hz), 7.76 (d, 1H, J = 8.0 Hz), 7.55 –

7.43 (m, 3H), 7.41 – 7.34 (m, 4H), 7.28 – 7.25 (m, 1H), 3.25 (t, 2H, J = 2.0 Hz), 2.08 (t,

1H, J = 2.8 Hz); 13C NMR (100 MHz, CDCl3) 139.4, 138.4, 134.8, 133.5, 131.9, 130.5,

128.2(6), 128.2(3), 128.1, 127.8, 126.9, 126.7, 126.2, 125.9, 125.8, 125.4, 82.1, 70.5,

22.8; IR (neat): 3289(bs), 3054, 3021, 2919, 2104, 1632, 1599, 1508, 1482, 1446, 958,

813, 757, 654, 621; IR (neat): 3055, 2921, 2174, 1591, 1505, 1393, 1206, 1158, 803, 778,

758, 621; MS (ES+) Calculated for [C19H14Na]+: 265.1; Found: 265.1.

4-methoxy-2-(prop-2-yn-1-yl)-1,1'-biphenyl (1l)

1l 1H NMR (500 MHz, CDCl3) 7.39 – 7.34 (m, 2H), 7.32 – 7.26 (m, 3H), 7.19 (d, 1H, J =

2.5 Hz), 7.14 (d, 1H, J = 8.0 Hz), 6.82 (dd, 1H, J = 3.0 Hz, J = 8.5 Hz), 3.81 (m, 3H),

3.46 (d, 2H, J = 3.0 Hz), 2.12 (t, 1H, J = 3.0 Hz); 13C NMR (125 MHz, CDCl3) 159.1,

140.6, 134.9, 133.9, 130.9, 129.3, 128.2, 126.8, 114.3, 112.2, 82.4, 70.5, 55.2, 23.2; IR

(neat): 3290, 3027, 2934, 2830, 2118, 1609, 1508, 1483, 1287, 1232, 1159, 1052, 768,

704, 643; MS (ES+) Calculated for [C16H14NaO]+: 245.1; Found: 245.1.

4-methyl-2-(prop-2-yn-1-yl)-1,1'-biphenyl (1m)

1m

1H NMR (400 MHz, CDCl3) δ 7.51 (d, 1H, J = 8.0 Hz), 7.43 – 7.39 (m, 2H), 7.37 – 7.31

(m, 3H), 7.17 (dd, 1H, J = 1.2 Hz, J = 8.0 Hz), 7.07 (s, 1H), 3.44 (d, 2H, J = 2.8 Hz), 2.39

(s, 3H), 2.12 (t, 1H, J = 2.8 Hz); 13C NMR (100 MHz, CDCl3) 141.2, 141.0, 136.4,

130.7(0), 130.6(7), 129.1, 128.8, 128.4, 128.2, 127.1, 83.0, 70.1, 22.6, 21.0; IR (neat):

3295, 3024, 2920, 2850, 2118, 1602, 1487, 1443, 913, 747, 701, 630, 585; MS (ES+)

Calculated for [C16H14Na]+: 229.1; Found: 229.1.

4-fluoro-2-(prop-2-yn-1-yl)-1,1'-biphenyl (1n)

1n

1H NMR (500 MHz, CDCl3) δ 7.41 – 7.32 (m, 4H), 7.29 – 7.24 (m, 2H), 7.17 (dd, 1H, J

= 6.0 Hz, J = 8.5 Hz), 6.98 (dt, 1H, J = 6.0 Hz, J = 8.5 Hz), 3.45 (d, 2H, J = 2.5 Hz), 2.16

(t, 1H, J = 2.5 Hz); 13C NMR (125 MHz, CDCl3) 162.3 (d, J = 244.6 Hz), 139.9, 137.2

(d, J = 3.2 Hz), 136.0 (d, J = 7.6 Hz), 131.3 (d, J = 8.0 Hz), 129.2, 128.4, 127.3, 115.5 (d,

J = 22.4 Hz), 113.6 (d, J = 21.0 Hz), 81.7, 71.0, 23.2; IR (neat): 3302, 3066, 2920, 2019,

1614, 1590, 1448, 1396, 1260, 1006, 727, 640; MS (ES+) Calculated for [C15H11FNa]+:

233.1; Found: 233.1.

5-fluoro-2-(prop-2-yn-1-yl)-1,1'-biphenyl (1o)

1o 1H NMR (400 MHz, CDCl3) δ 7.61 (dd, 1H, J = 6.0 Hz, J = 8.8 Hz), 7.48 – 7.38 (m, 3H),

7.37 – 7.32 (m, 2H), 7.08 (dt, 1H, J = 2.8 Hz, J = 7.6 Hz), 6.99 (dd, 1H, J = 2.8 Hz, J =

9.2 Hz), 3.46 (d, 2H, J = 2.8 Hz), 2.17 (t, 1H, J = 2.8 Hz); 13C NMR (125 MHz, CDCl3)

161.5 (d, J = 244.2 Hz), 143.2 (d, J = 7.9 Hz), 139.9, 130.5 (d, J = 8.1 Hz), 129.5 (d, J =

3.0 Hz), 128.9, 128.4, 127.6, 116.6 (d, J = 21.5 Hz), 114.4 (d, J = 20.9 Hz), 82.5, 70.5,

22.4; IR (neat): 3302, 2920, 2118, 1614, 1596, 1485, 1296, 1257, 1186, 890, 702, 640;

MS (ES+) Calculated for [C15H11FNa]+: 233.1; Found: 233.1.

4-chloro-2-(prop-2-yn-1-yl)-1,1'-biphenyl (1p)

1p 1H NMR (400 MHz, CDCl3) δ 7.70 (d, 1H, J = 2.0 Hz), 7.50 – 7.40 (m, 4H), 7.35 – 7.31

(m, 2H), 7.22 (d, 1H, J = 8.0 Hz), 3.51 (d, 2H, J = 2.8 Hz), 2.24 (t, 1H, J = 2.8 Hz); 13C

NMR (100 MHz, CDCl3) 139.8, 139.7, 135.5, 133.5, 131.1, 129.0, 128.8, 128.4, 127.5,

127.0, 81.6, 71.1, 23.0; IR (neat): 3299, 3059, 3025, 2124, 1593, 1472, 1444, 1179, 1115,

1095, 1009, 865, 825, 702, 642; MS (ES+) Calculated for [C15H11ClNa]+: 249.0; Found:

249.0.

1-phenyl-2-(prop-2-yn-1-yl)naphthalene (1q)

1q 1H NMR (400 MHz, CDCl3) δ 7.87 (t, 2H, J = 8.8 Hz), 7.76 (d, 1H, J = 8.4 Hz), 7.53 –

7.28 (m, 8H), 3.45 (d, 2H, J = 2.8 Hz), 2.12 (t, 1H, J = 2.8 Hz); 13C NMR (100 MHz,

CDCl3) 138.5, 138.0, 132.8, 132.5, 131.4, 130.1, 128.5, 127.9, 127.8, 127.5, 126.5,

126.4, 126.0, 125.4, 82.7, 70.1, 23.5; IR (neat): 3296, 3055, 2922, 2115, 1602, 1508,

1441, 1261, 1072, 1027, 814, 762, 704, 638; MS (ES+) Calculated for [C19H14Na]+: 265.1;

Found: 265.1.

2-(hept-2-yn-1-yl)-1,1'-biphenyl (1r)

1r 1H NMR (400 MHz, CDCl3) δ 7.63 (d, 1H, J = 8.4 Hz), 7.43 – 7.21 (m, 8H), 3.45 (t, 2H,

J = 2.4 Hz), 2.21 – 2.16 (m, 2H), 1.52 – 1.36 (m, 4H), 0.90 (t, 3H, J = 7.2 Hz); 13C NMR

(125 MHz, CDCl3) 141.3, 141.2, 135.2, 129.8, 129.2, 128.9, 128.1, 127.6, 127.0, 126.5,

82.6, 78.2, 31.1, 23.5, 21.9, 18.5, 13.6; IR (neat): 2956, 2929, 2858, 2177, 1695, 1597,

1478, 1466, 1452, 1011, 913, 747, 701; MS (ES+) Calculated for [C19H20Na]+: 271.1;

Found: 271.2.

ethyl 4-([1,1'-biphenyl]-2-yl)but-2-ynoate (1s)

1s

This compound is known and the spectroscopic data match those reported.1 1H NMR (400

MHz, CDCl3) δ 7.56 (d, 1H, J = 9.6 Hz), 7.45 – 7.28 (m, 7H), 7.27 – 7.24 (m, 1H), 4.21

(q, 2H, J = 6.8 Hz), 3.63 (s, 2H), 1.30 (t, 3H, J = 7.2 Hz); 13C NMR (125 MHz, CDCl3)

153.7, 141.7, 140.6, 131.8, 130.1, 129.1, 129.1, 128.4, 127.9, 127.4, 127.3, 86.9, 74.7,

61.8, 23.2, 14.0; IR (neat): 2982, 2918, 2234, 1710(s), 1478, 1365, 1250, 1066, 913, 747;

MS (ES+) Calculated for [C18H16NaO2]+: 287.1; Found: 287.1.

2-(3-phenylprop-2-yn-1-yl)-1,1'-biphenyl (1t)

1t

This compound is known and the spectroscopic data match those reported.1 1H NMR (400

MHz, CDCl3) δ 7.69 (dd, 1H, J = 0.8 Hz, J = 7.6 Hz), 7.44 – 7.24 (m, 13H), 3.71 (s, 2H); 13C NMR (100 MHz, CDCl3) 141.4, 141.0, 134.3, 131.6, 129.9, 129.3, 129.2, 129.0,

128.2(4), 128.1(6), 127.7, 127.1, 126.7, 123.8, 88.2, 82.5, 24.1

General procedure:

HNTf2 (3.0 mL, 0.05 M in DCE), and [(C6F5)3PAuNTf2] (15.1 mg, 0.015 mmol) were

added to a solution of the o-propargylbiaryls 1 (0.30 mmol) in DCE (3.0 mL) at room

temperature. The reaction mixture was stirred at room temperature and the progress of the

reaction was monitored by TLC. The reaction typically took 5 h. Upon completion, the

reaction diluted with DCM (30 mL) and washed with saturated aqueous NaHCO3 (2 × 15

mL). The resulting solution was extracted again with DCM (30 mL) and the combined

organic layers were dried with MgSO4. The mixture was then concentrated and the

residue was purified by chromatography on silica gel (eluent: hexanes/ethyl acetate) to

afford the desired products 2.

9-methylphenanthrene (2a)

2a

Compound 2a was prepared in 94% yield according to the general procedure. This

compound is known and the spectroscopic data match those reported.2 1H NMR (400

MHz, CDCl3) 8.69 (d, 1H, J = 9.6 Hz), 8.62 (d, 1H, J = 8.8 Hz), 8.05 – 8.01 (m, 1H),

7.78 (d, 1H, J = 9.2 Hz), 7.66 – 7.59 (m, 2H), 7.58 – 7.51 (m, 3H), 2.70 (s, 3H); 13C

NMR (100 MHz, CDCl3) 132.5, 132.1, 132.0, 130.4, 129.7, 127.8, 126.7, 126.6, 126.5,

126.2, 125.8, 124.6, 123.0, 122.4, 20.0.

1,3-dimethoxy-10-methylphenanthrene (2b)

2b

Compound 2b was prepared in 91% yield according to the general procedure. This

compound is known and the spectroscopic data match those reported.1 1H NMR (400

MHz, CDCl3) 8.51 – 8.43 (m, 1H), 7.74 – 7.70 (m, 1H), 7.64 (d, 1H, J = 1.2 Hz), 7.52 –

7.46 (m, 2H), 7.30 (s, 1H), 6.62 (d, 1H, J = 2.4 Hz), 3.96 (s, 3H), 3.87 (s, 3H), 2.86 (d,

3H, J = 0.8 Hz); 159.7, 158.3, 133.8, 133.2, 132.5, 128.6, 127.4, 126.6, 125.8, 125.1,

122.9, 118.7, 98.6, 96.1, 55.3, 55.2, 25.8.

4-methylphenanthro[1,2-d][1,3]dioxole (2c)

2c

Compound 2c was prepared in 96% yield according to the general procedure. 1H NMR

(400 MHz, CDCl3) 8.35 (d, 1H, J = 8.0 Hz), 7.98 (s, 1H), 7.73 –7.70 (m, 1H), 7.51 –

7.40 (m, 3H), 7.32 (s, 1H), 6.02 (s, 2H), 2.59 (d, 3H, J = 0.8 Hz); 13C NMR (100 MHz,

CDCl3) 147.5(5),147.5(0), 131.8, 131.4, 129.4, 128.4, 127.8, 126.5, 125.6, 125.4, 125.3,

122.1, 102.3, 101.3, 101.1, 20.4; IR (neat): 2928, 2853, 1600, 1484, 1437, 1330, 1242,

1201, 1144, 1099, 913, 745; MS (ES+) Calculated for [C16H12NaO2]+: 259.1; Found:

259.1.

2-methoxy-10-methylphenanthrene (2d)

2d

Compound 2d was prepared in 85% yield according to the general procedure. 1H NMR

(400 MHz, CDCl3) 8.61 (d, 1H, J = 8.8 Hz), 8.53 (d, 1H, J = 8.0 Hz), 7.77 (d, 1H, J =

8.0 Hz), 7.57 – 7.46 (m, 3H), 7.39 – 7.28 (m, 1H), 7.31 – 7.23 (m, 1H), 3.97 (s, 3H), 2.68

(s, 3H); 13C NMR (100 MHz, CDCl3) 158.3, 133.5, 131.8, 131.0, 129.8, 127.8, 127.3,

125.9, 125.6, 124.7, 124.6, 121.9, 115.9, 105.8, 55.4, 20.1; IR (neat): 3049, 2920, 1635,

1530, 1454, 1268, 1201, 1143, 970, 883, 804, 738; IR (neat): 2999, 2933, 2838, 1617,

1532, 1488, 1467, 1435, 1274, 1260, 1222, 1042, 912, 772, 747; MS (ES+) Calculated for

[C16H14NaO]+: 245.1; Found: 245.1.

2-fluoro-10-methylphenanthrene (2e)

2e

Compound 2e was prepared in 80% yield according to the general procedure except at 80 oC.1H NMR (400 MHz, CDCl3) 8.69 (dd, 1H, J = 2.0 Hz, J = 8.8 Hz), 8.56 (d, 1H, J =

8.4 Hz), 7.82 – 7.79 (m, 1H), 7.66 (dd, 1H, J = 2.4 Hz, J = 10.4 Hz), 7.64 – 7.53 (m, 3H),

7.42 – 7.37 (m, 1H), 2.68 (d, 3H, J = 0.4 Hz); 13C NMR (100 MHz, CDCl3) 161.4 (d, J

= 244.3 Hz), 133.7 (d, J = 8.1 Hz), 131.8 (d, J = 3.7 Hz), 131.5, 129.4, 128.0, 127.9,

127.0, 126.4, 126.2, 125.3 (d, J = 8.7 Hz), 122.2, 114.9 (d, J = 23.2 Hz), 109.3 (d, J =

21.2 Hz), 19.9; IR (neat): 2920, 2850, 1616, 1442, 1256, 1213, 1177, 923, 890, 772, 749;

MS (ES+) Calculated for [C15H11FNa]+: 233.1; Found: 233.1.

2-chloro-10-methylphenanthrene (2f)

2f

Compound 2f was prepared in 83% yield according to the general procedure except at 80 oC. 1H NMR (500 MHz, CDCl3) 8.57 (d, 1H, J = 8.5 Hz), 8.53 (d, 1H, J = 8.0 Hz), 7.98

(d, 1H, J = 2.5 Hz), 7.79 – 7.75 (m, 1H), 7.59 – 7.53 (m, 4H), 2.66 (d, 3H, J = 1.0 Hz); 13C NMR (125 MHz, CDCl3) 133.3, 132.6, 131.9, 131.5, 129.2, 128.8, 127.9(4),

127.(0), 126.9, 126.6, 126.2, 124.6, 124.1, 122.3, 19.8; IR (neat): 2996, 2933, 1626, 1464,

1434, 1283, 1218, 1178, 1162, 1022, 886, 744; IR (neat): 2924, 2852, 1598, 1484, 1438,

1378, 1099, 885, 770, 746, 619; MS (ES+) Calculated for [C15H11ClNa]+: 249.0; Found:

249.0.

2-bromo-10-methylphenanthrene (2g)

2g

Compound 2g was prepared in 93% yield according to the general procedure except at 80 oC. 1H NMR (500 MHz, CDCl3) 8.58 (d, 1H, J = 9.0 Hz), 8.54 (d, 1H, J = 8.0 Hz), 7.98

(d, 1H, J = 2.0 Hz), 7.77 (d, 1H, J = 9.0 Hz), 7.59 – 7.53 (m, 4H), 2.67 (s, 3H); 13C NMR

(125 MHz, CDCl3) 133.3, 132.6, 131.9, 131.5, 129.2, 128.8, 128.0, 127.9, 126.9, 126.6,

126.2, 124.6, 124.1, 122. 4, 19.8; IR (neat): 2923, 2851, 1598, 1484, 1437, 1378, 1113,

1099, 885, 842, 745; MS (ES+) Calculated for [C15H11BrNa]+: 293.1; Found: 293.1.

10-methylphenanthrene-2-carbonitrile (2h)

2h

Compound 2h was prepared in 80% yield according to the general procedure except at 80 oC. 1H NMR (400 MHz, CDCl3) 8.68 (d, 1H, J = 8.4 Hz), 8.59 – 8.53 (m, 1H), 8.31 (d,

1H, J = 1.6 Hz), 7.82 – 7.74 (m, 2H), 7.65 – 7.59 (m, 3H), 2.68 (d, 3H, J = 0.8 Hz); 13C

NMR (100 MHz, CDCl3) 133.0, 132.9, 131.6(4), 131.6(2), 129.9, 128.6, 128.5, 128.2,

128.1, 127.5, 126.6, 124.0, 122.9, 119.4, 109.7, 19.6; IR (neat): 2957, 2922, 2851, 2227,

1720, 1645, 1442, 1223, 1126, 1091, 608; MS (ES+) Calculated for [C16H11NNa]+: 240.1;

Found: 240.1.

3-fluoro-10-methylphenanthrene (2i)

2i

Compound 2i was prepared in 95% yield according to the general procedure except at 80 oC. 1H NMR (500 MHz, CDCl3) δ 8.47 – 7.43 (m, 1H), 8.26 (dd, 1H, J = 2.5 Hz, J = 11.0

Hz), 7.97 (d, 1H, J = 6.0 Hz, J = 9.0 Hz), 7.78 – 7.74 (m, 1H), 7.56 – 7.53 (m, 2H), 7.48

(s, 1H), 7.36 – 7.32 (m, 1H), 2.67 (s, 3H); 13C NMR (125 MHz, CDCl3) 161.4 (d, J =

243.6 Hz), 132.5, 132.2 (d, J = 8.1 Hz), 132.1, 129.1 (d, J = 4.4 Hz), 128.8, 127.9, 127.2,

126.8 (d, J = 8.8 Hz), 126.0 (d, J = 2.3 Hz), 125.8, 122.6, 115.2 (d, J = 23.2 Hz), 108.0 (d,

J = 21.9 Hz), 20.0; IR (neat): 2923, 2847, 1617, 1604, 1533, 1500, 1438, 1273, 1186,

1142, 907, 879, 745; MS (ES+) Calculated for [C15H11FNa]+: 233.1; Found: 233.1.

5-methylchrysene (2j)

2j

Compound 2j was prepared in 95% yield according to the general procedure. This

compound is known and the spectroscopic data match those reported.3 1H NMR (500

MHz, CDCl3) 8.95 (d, 1H, J = 9.0 Hz), 8.70 (t, 2H, J = 9.0 Hz), 7.99 – 7.93 (m, 2H),

7.86 (d, 1H, J = 8.0 Hz), 7.81 (s, 1H), 7.63 – 7.57 (m, 4H), 3.20 (s, 3H); 13C NMR (125

MHz, CDCl3) 133.4, 133.2, 131.6(9), 131.6(8), 130.6, 129.9, 129.6, 129.4, 128.6, 127.6,

127.5, 127.4, 126.4, 125.9, 125.7, 125.3, 123.1, 121.7, 27.7.

6-methylbenzo[c]phenanthrene (2k)

2k

Compound 2k was prepared in 90% yield according to the general procedure. This

compound is known and the spectroscopic data match those reported.4 1H NMR (400

MHz, CDCl3) δ 9.10 (d, 1H, J = 8.0 Hz), 9.06 – 9.03 (m, 1H), 8.06 – 8.01 (m, 2H), 7.91 –

7.53 (m, 2H), 7.74 (s, 1H), 7.68 – 7.56 (m, 4H), 2.82 (d, 3H, J = 0.8 Hz); 13C NMR (100

MHz, CDCl3) 133.3, 133.0, 132.3, 130.7, 130.3, 129.4, 128.4, 128.2, 128.1, 127.8,

127.6, 127.4, 127.2, 125.9, 125.9, 125.8, 125.2, 122.6, 20.4.

2-methoxy-9-methylphenanthrene (2l)

2l

Compound 2l was prepared in 83% yield according to the general procedure. This

compound is known and the spectroscopic data match those reported.5 1H NMR (500

MHz, CDCl3) 8.60 (d, 1H, J = 10.0 Hz), 8.53 (d, 1H, J = 11.5 Hz), 8.01 (d, 1H, J = 10.0

Hz), 7.64 – 7.54 (m, 2H), 7.50 (s, 1H), 7.23 – 7.16 (m, 2H), 3.94 (s, 3H) , 2.71 (s, 3H); 13C NMR (125 MHz, CDCl3) 158.3, 133.4, 133.2, 131.0, 130.5, 126.4, 126.3, 125.5,

124.6, 124.1, 124.0, 122.5, 116.2, 108.0, 55.3, 20.0.

2,9-dimethylphenanthrene (2m)

2m

Compound 2m was prepared in 94% yield according to the general procedure. 1H NMR

(400 MHz, CDCl3) 8.72 – 8.68 (m, 1H), 8.43 (s, 1H), 8.05 – 8.00 (m, 1H), 7.69 (d, 1H,

J = 8.0 Hz), 7.65 – 7.59 (m, 2H), 7.53 (s, 1H), 7.38 (d, 1H, J = 9.2 Hz), 2.70 (s, 3H), 2.59

(s, 3H); 13C NMR (100 MHz, CDCl3) 135.4, 132.2, 131.4, 130.1, 130.0, 129.7, 128.3,

127.7, 126.5, 126.3, 126.0, 124.6, 123.0, 122.2, 22.1, 19.9; IR (neat): 3018, 2965, 2921,

1607, 1505, 1443, 1090, 1040, 876, 804, 754, 722; MS (ES+) Calculated for [C16H14Na]+:

229.1; Found: 229.1.

2-fluoro-9-methylphenanthrene (2n)

2n

Compound 2n was prepared in 91% yield according to the general procedure except at 80 oC. 1H NMR (400 MHz, CDCl3) 8.55 – 8.49 (m, 2H), 7.98 (d, 1H, J = 7.6 Hz), 7.66 –

7.56 (m, 2H), 7.41 (s, 1H), 7.36 (d, 1H, J = 9.2 Hz), 7.26 (t, 1H, J = 8.8 Hz), 2.75 (s, 3H); 13C NMR (100 MHz, CDCl3) 161.4 (d, J = 244.3 Hz), 134.0, 133.4 (d, J = 8.7 Hz),

131.5, 130.1, 126.5, 126.3, 125.9, 124.8, 124.7, 122.7, 114.5 (d, J = 23.5 Hz), 114.4,

111.7 (d, J = 20.3 Hz), 20.0; IR (neat): 3071, 2942, 1623, 1491, 1466, 1244, 1155, 951,

893, 824, 761, 717; MS (ES+) Calculated for [C15H11FNa]+: 233.1; Found: 233.1.

3-fluoro-9-methylphenanthrene (2o)

2o

Compound 2o was prepared in 92% yield according to the general procedure except at 80 oC. 1H NMR (400 MHz, CDCl3) 8.56 – 8.51 (m, 1H), 8.22 (d, 1H, J = 2.4 Hz, J = 11.2

Hz), 8.06 – 8.00 (m, 1H), 7.74 (dd, 1H, J = 6.0 Hz, J = 8.8 Hz), 7.65 – 7.62 (m, 2H), 7.51

(s, 1H), 7.29 (dt, 1H, J = 2.4 Hz, J = 8.4 Hz), 2.69 (s, 3H); 13C NMR (100 MHz, CDCl3)

161.2 (d, J = 242.6 Hz), 132.3, 131.6 (d, J = 8.3 Hz), 131.1 (d, J = 8.6 Hz), 131.0,

129.7, 128.7, 127.1, 126.2, 126.0, 124.7, 123.2, 115.5 (d, J = 23.7 Hz), 107.5 (d, J = 22.2

Hz), 19.8; IR (neat): 3080, 2922, 2856, 1605, 1502, 1449, 1433, 1221, 1175, 904, 879,

810, 755; MS (ES+) Calculated for [C15H11FNa]+: 233.1; Found: 233.1.

2-chloro-9-methylphenanthrene (2p)

2p

Compound 2p was prepared in 95% yield according to the general procedure except at 80 oC.1H NMR (400 MHz, CDCl3) 8.59 – 8.54 (m, 1H), 8.47 (d, 1H, J = 8.8 Hz), 8.02 –

7.97 (m, 1H), 7.70 (d, 1H, J = 1.0 Hz), 7.65 – 7.58 (m, 2H), 7.46 (dd, 1H, J = 2.0 Hz, J =

8.8 Hz), 7.39 (s, 1H), 2.66 (d, 3H, J = 1.2 Hz); 13C NMR (100 MHz, CDCl3) 133.6,

133.0, 132.2, 131.9, 129.9, 127.9, 126.7, 126.7, 126.6, 126.1, 125.6, 124.7, 124.1, 122.9,

20.0; IR (neat): 3083, 2920, 2853, 1518, 1484, 1446, 1404, 1089, 980, 894, 822, 759, 718;

MS (ES+) Calculated for [C15H11ClNa]+: 249.0; Found: 249.0.

5-methylbenzo[c]phenanthrene (2q)

2q

Compound 2q was prepared in 83% yield according to the general procedure. This

compound is known and the spectroscopic data match those reported.6 1H NMR (400

MHz, CDCl3) 9.16 – 9.12 (m, 1H), 9.07 (d, 1H, J = 8.4 Hz), 8.21 – 8.17 (m, 1H), 8.00

(d, 1H, J = 7.6 Hz), 7.88 (d, 1H, J = 8.8 Hz), 7.70 (d, 1H, J = 8.8 Hz), 7.72 – 7.65 (m,

4H), 7.59 (d, 1H, J = 7.6 Hz), 2.82 (s, 3H); 13C NMR (100 MHz, CDCl3) 133.2, 133.1,

133.1, 130.8, 130.4, 130.2, 128.5, 128.4, 127.8, 127.5, 127.1, 126.4, 126.3, 126.1, 125.8,

125.6, 125.4, 124.4, 19.7.

9-pentylphenanthrene (2r)

( )4

2r

Compound 2r was prepared in 63% yield according to the general procedure except at 80 oC. 1H NMR (400 MHz, CDCl3) 8.75 – 8.71 (m, 1H), 8.66 – 8.64 (m, 1H), 8.13 – 8.09

(m, 1H), 7.82 (d, 1H, J = 9.2 Hz), 7.67 – 7.54 (m, 5H), 3.10 (t, 2H, J = 7.6 Hz), 1.86 –

1.78 (m, 2H), 1.51 – 1.36 (m, 4H), 0.92 (t, 3H, J = 7.2 Hz); 13C NMR (125 MHz, CDCl3)

137.0, 132.0, 131.4, 130.7, 129.6, 128.0, 126.5, 126.4, 126.0, 125.9, 125.8, 124.5, 123.2,

122.4, 33.4, 32.1, 30.0, 22.6, 14.1; IR (neat): 2955, 2927, 2856, 1516, 1482, 1260, 1090,

1019, 981, 912, 745, 724; MS (ES+) Calculated for [C19H20Na]+: 271.1; Found: 271.1.

ethyl 2-(phenanthren-9-yl)acetate (2s)

2s

Compound 2s was prepared in 95% yield according to the general procedure. 1H NMR

(400 MHz, CDCl3) 8.73 (dd, 1H, J = 2.0 Hz, J = 7.2 Hz), 8.66 (d, 1H, J = 8.4 Hz), 8.04

(dd, 1H, J = 2.4 Hz, J = 7.6 Hz), 7.84 (dd, 1H, J = 0.8 Hz, J = 7.6 Hz), 7.68 – 7.55 (m,

5H), 4.19 – 4.14 (m, 2H), 4.10 (s, 2H), 1.22 (t, 3H, J = 7.2 Hz); 13C NMR (100 MHz,

CDCl3) 171.6, 131.6, 131.1, 130.7, 130.2, 129.2, 128.8, 128.4, 126.8, 126.7, 126.6,

126.4, 124.5, 123.2, 122.5, 61.0, 39.8, 14.1; IR (neat): 2979, 2922, 2236, 1731(s), 1452,

1366, 1251, 1162, 1026, 716; MS (ES+) Calculated for [C18H16NaO2]+: 287.1; Found:

287.1

7-phenyl-5H-dibenzo[a,c][7]annulene (2t)

2t

Compound 2t was prepared in 70% yield according to the general procedure. 1H NMR

(500 MHz, CDCl3) δ 7.68 (dd, 1H, J = 0.8 Hz, J = 8.0 Hz), 7.62 (dd, 1H, J = 3.0 Hz, J =

7.5 Hz), 7.39 – 7.19 (m, 11H), 6.37 (dd, 1H, J = 6.5 Hz, J = 8.5 Hz), 3.23 (dd, 1H, J = 8.0

Hz, J = 12.5 Hz), 2.91 (dd, 1H, J = 6.5 Hz, J = 12.5 Hz); 13C NMR (125 MHz, CDCl3)

143.2, 143.8, 140.8, 140.5, 138.7, 137.9, 130.2, 129.7, 129.5, 129.2, 128.6, 128.0, 127.5,

127.0, 126.8, 126.3, 126.2, 33.4; IR (neat): 3056, 3022, 1600, 1490, 1484, 1444, 1434,

1353, 1266, 765, 750, 733, 699; MS (ES+) Calculated for [C21H16Na]+: 291.1; Found:

291.1.

10-methyl-2-phenylphenanthrene (4)

To a THF solution (10 mL) of a mixture of 2g (109 mg, 0.40 mmol) and phenylboronic

acid (98 mg, 0.80 mmol) were successively added Pd(PPh3)4 (24 mg, 0.020 mmol) and an

aqueous solution of K2CO3 (2.0 M, 0.5 mL), and the mixture was thoroughly degassed by

freezing-pump-thaw cycles and refluxed under argon overnight. The mixture was then

concentrated and the residue was purified by chromatography on silica gel (eluent:

hexanes/ethyl acetate) to afford the desired product 4 (94 mg, 0.35 mmol) in 87% yield.7 1H NMR (400 MHz, CDCl3) δ 8.55 (d, 1H, J = 8.8 Hz), 8.51 (d, 1H, J = 8.4 Hz), 7.96 (d,

1H, J = 2.0 Hz), 7.78 – 7.32 (m, 1H), 7.61 – 7.52 (m, 6H), 7.42 (t, 2H, J = 7.6 Hz), 7.34 –

7.31 (m, 1H), 2.64 (s, 3H); 13C NMR (100 MHz, CDCl3) 141.2, 133.2, 132.5, 131.8,

131.5, 129.2, 128.7, 127.9, 127.87, 127.2, 127.1, 126.8, 126.5, 126.2, 124.6, 124.0, 122.3,

19.8; IR (neat): 3060, 2924, 2853, 1598, 1496, 1439, 1207, 1113, 1207, 1099, 858, 842,

820, 771, 738; MS (ES+) Calculated for [C21H16Na]+: 291.1; Found: 291.1.

10-methyl-2-(naphthalen-2-yl)phenanthrene (5)

A solution of K2CO3 (78 mg, 0.56 mmol) in 5 mL of water was added to a solution of 2g

(109 mg, 0.40 mmol), 2-naphthylboronic acid (83 mg, 0.48 mmol) and Pd(OAc)2 (5.0 mg,

0.020 mmol) in 5 mL of DMF. The resultant mixture was heated at 90 oC for 15 h under

stirring. The final solution was allowed to cool to room temperature, and extracted with

ethyl acetate. The organic layer was washed with water and aqueous 0.1 M NaOH, dried

over anhydrous sodium sulfate and evaporated, yielding the desired product 5 (108 mg,

0.34 mmol) in 85% yield.8 1H NMR (500 MHz, CDCl3) δ 8.82 (d, 1H, J = 8.5 Hz), 8.69

(d, 1H, J = 8.5 Hz), 8.37 (d, 1H, J = 2.0 Hz), 8.22 (s, 1H), 8.05 (dd, 1H, J = 2.0 Hz, J =

8.5 Hz), 8.00 – 7.89 (m, 4H), 7.83 (dd, 1H, J = 1.0 Hz, J = 7.5 Hz), 7.64 (s, 1H), 7.62 –

7.50 (m, 4H), 2.83 (s, 3H); 13C NMR (100 MHz, CDCl3) 139.1, 138.6, 133.7, 132.7,

132.6, 132.5, 132.0, 129.54, 129.53, 128.6, 128.2, 127.9, 127.7, 127.2, 126.6, 126.4,

126.2, 126.0, 125.9, 125.8, 125.7, 123.7, 123.2, 122.5, 20.2; IR (neat): 2960, 2921, 2851,

1435, 1259, 1090, 1016, 887, 857, 815, 799, 741; MS (ES+) Calculated for [C25H18Na]+:

341.1; Found: 341.1.

1-([1,1'-biphenyl]-2-yl)propan-2-one (3a)

3a 1H NMR (400 MHz, CDCl3) δ 7.44 – 7.32 (m, 5H), 7.28 – 7.19 (m, 4H), 3.68 (s, 2H),

1.98 (s, 3H); 13C NMR (100 MHz, CDCl3) 206.4, 142.4, 141.3, 132.2, 130.6, 130.2,

129.0, 128.3, 127.6, 127.2, 127.1, 48.4, 29.6; IR (neat): 2924, 2852, 1716, 1692, 1597,

1489, 1351, 1196, 1139, 748; MS (ES+) Calculated for [C15H14NaO]+: 233.1; Found:

233.1.

Reference:

1. Kwon, Y.; Cho, H.; Kim, S. Org. Lett. 2013, 15, 920.

2. Sugimoto, A.; Yamano, J.; Yasueda, M.; Yoneda, S. J. Chem. Soc. Perkin. Trans.1

1988, 2579.

3. Fut, P. P.; Harvey, R. G. J. Org. Chem. 1983, 48, 1534.

4. Brulé, C.; Laali, K. K.; Okazaki, T.; Lakshman, M. K. J. Org. Chem. 2007, 72, 3232.

5. Stern, A. J.; Swenton, J. S. J. Org. Chem. 1988, 53, 2465.

6. Paul, S.; Jana, R.; Ray, J. K. Synlett. 2010, 10, 1463.

7. Jin, W.; Yamamoto, Y.; Fukushima, T.; Ishii, N.; Kim, J.; Kato, K.; Takata, M.; Aida

T. J. Am. Chem. Soc. 2008, 130, 9434.

8. Lima, C. F.R.A.C.; Rodriguez-Borges, J. E.; Santos, L. M.N.B.F. Tetrahedron 2011,

67, 689.

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