Síntesis y reactividad de nuevos derivados de quinona

(1)

A NEXO

NMR spectra and X-ray structures

(2)

-

2.5 3.0

3.5 4.0

4.5 5.0

5.5 6.0

6.5 7.0

7.5 ppm

2.20

2.30

3.59

3.77

6.52 3.003.00

3.16

3.27

1.00

20 30 40 50 60 70 80 90 100 110 120 130 140 150

160 ppm

16.59

56.51

60.32

111.39111.86

130.11132.63

151.07152.20

(3)

2.5 3.0

3.5 4.0

4.5 5.0

5.5 6.0

6.5 7.0

7.5 ppm

2.30

2.46

3.64

3.82

5.73

6.57 2.96

2.88

3.06

3.01

1.82

1.00

200 180 160 140 120 100 80 60 40 20 0 ppm

15.1715.97

133.84

146.71

157.46

187.66

195.10

(4)

2.0 2.5

3.0 3.5 4.0

4.5 5.0 5.5

6.0 6.5 7.0

7.5

8.0 ppm

2.11

2.45

6.646.65

6.91 3.45

3.09

1.00

1.99

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

15.4815.90

134.26

146.45

157.60

188.28

194.59

(5)

5.0 5.2 5.4 5.6 5.8 6.0 6.2 6.4 6.6 6.8 7.0 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 8.1

2.00

2.09

1.06

1.19

12.16

3.06 5.545.59

7.097.107.137.147.17

7.327.337.35

7.487.507.607.627.637.687.757.767.777.777.797.80

(6)

1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0

3.00

1.91

1.93

1.90

14.53 3.68

5.215.26

6.606.62

6.986.99

7.617.657.707.72

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1.4 1.8 2.2 2.6 3.0 3.4 3.8 4.2 4.6 5.0 5.4 5.8 6.2 6.6 7.0 7.2 7.4 7.6 7.8

3.12

1.97

1.091.96

1.11

5.02

1.00 3.57

3.78

6.466.506.686.726.746.77

7.097.197.227.227.247.27

7.527.527.547.55

(12)

29.88

55.35

98.39

109.03

114.23114.96

119.79120.24121.48

127.70128.06130.01130.64

138.05138.83

159.52

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NH O

O

Ph E-104a

(17)

(18)

N Ph

O O

105a

(19)

106a

N O

Ph O

(20)

N -oBrPh

O O

105b

(21)

N -pMeOPh

O O

105c

(22)

106c

N O

p-MeOPh O

(23)

N

O O

105e

(24)

(25)

(26)

(27)

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10 9 8 7 6 5 4 3 2 1 0 ppm

2.022.022.052.142.562.592.682.70

6.536.53 6.003.31

2.032.12

1.00

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

12.1515.87

20.96

29.73

41.90

133.16

141.53143.11145.58

187.23187.91

206.92

(29)

2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0

8.5 ppm

2.022.032.062.412.432.462.762.782.81

4.074.104.124.15

6.546.54 6.09

1.91

2.00

1.85

0.93

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

12.1914.1815.87

22.10

32.83

60.62

133.20

141.74142.58145.51

172.32

186.98187.97

(30)

O O

CO₂Et

173

(31)

2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0

8.5 ppm

2.032.032.092.412.442.462.762.792.812.943.00

6.546.54 2.953.08

2.09

2.073.063.15

1.00

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

12.1815.90

22.60

32.1335.4837.24

133.17

141.72143.34145.58

171.53

187.45188.04

(32)

1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0

8.5 ppm

2.072.082.18

3.113.143.173.20

4.074.09

6.596.60

7.387.387.477.50 3.413.24

1.06

1.22

1.02

1.00

2.481.082.28

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

12.7816.05

35.12

40.13

126.72128.79129.26132.21133.02

140.29144.59146.57

174.62175.92

186.08186.85

(33)

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(43)

OMe

OMe OH

196j

(44)

2.993.06

1.01

3.04

2.03

2.00 3.753.76

6.06

6.786.796.826.826.85

7.557.57

8.148.17 55.7255.87

71.55

111.97113.33114.14

123.39

127.09

131.75

147.05

150.60150.67

153.89

(45)

2.96

2.92

0.99

1.00

1.101.13

1.08

1.18

2.11 3.70

3.83

6.37

6.586.596.806.816.846.867.167.167.317.347.347.527.537.547.547.557.557.567.57 55.6156.01

70.63

111.56112.76114.44

123.22

127.44128.76128.93131.62132.62

141.29

151.31

153.59

OMe

OH Br

200f

(46)

(47)

(48)

(49)

(50)

O

OH Br

195f

(51)

3.013.14

1.02

1.05

1.061.00

1.40 2.072.072.14

4.594.62

5.965.99

6.556.566.886.886.936.94

7.257.257.267.27

(52)

(53)

N HN

S Ph

O O

239k

(54)

(55)

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(68)

OMe N NN

N pMeOPh 241mb

(69)

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(88)

O OMe

O

N N

pMeOPh

pMeOPh 246cb

(89)

O OMe

O N

N pMeOPh

pMeOPh 246cb'

(90)

O

N N

pTol

Ph 222ka

(91)

O

N N

pTol

Ph N

N

Ph p^-Tol

221ka

(92)

O

N N

pMeOPh

Ph 222kb

(93)

O

N N

pMeOPh

Ph N

N

Ph -pMeOPh

221kb

(94)

O

N N

pMeOPh

pMeOPh 222cb

(95)

O

N N

pMeOPh

pCNPh 222lb

(96)

O

N N

pMeOPh

mMeOPh 222nb

(97)

O

N N

pMeOPh

Ph 222ob

(98)

O

N N

pMeOPh N

N -pMeOPh

Ph Ph 221ob

(99)

O

N N

pMeOPh

N 222hb

(100)

O

N N

pMeOPh

S 222ib

(101)

O

N N

pMeOPh

222pb N

(102)

X-ray Structures

Summary of Data CCDC 952314 Formula: C20H21NO2 (105e)

Unit cell parameters: a 10.4429(3) b 11.4676(3) c 14.1151(4), α 90 β 107.3140(10) γ 90, space group P 21/c.

Summary of Data CCDC 952315 Formula: C25H22BrNO4 (124b)

Unit cell parameters: a 8.0904(2) b 27.0158(7) c 9.5814(2), α 90 β 100.7800(10) γ 90, space group P 21/n.

(103)

Formula: C26.75H21.5Cl1.5N2O5 (246cb)

Unit cell parameters: a 8.4865(4) b 11.2145(5) c 13.6340(7), α 74.360(2) β 75.284(2) γ 87.240(2), space group P-1.

Formula: C36H28Cl4N4O4 (221kb)

Unit cell parameters: a 9.3027(4) b 13.1946(6) c 15.2858(6), α 65.986(3) β 78.854(3) γ 74.755(3), space group P-1.

N N O

O

pMeOPh

Ph N

N Ph

-pMeOPh

221kb

X-ray (221kb)