synthesis of substituted nitroolefins: a copper catalyzed … · 2013. 8. 16. · balaji v. rokade...

Electronic Supplimentary Information

Synthesis of Substituted Nitroolefins: A Copper Catalyzed

Nitrodecarboxylation of Unsaturated Carboxylic Acids

Balaji V. Rokade and Kandikere Ramaiah Prabhu*

Department of Organic Chemistry, Indian Institute of Science, Bangalore 560 012, Karnataka,

India.

[email protected]

Telephone: +91-80-22932887; Fax: +91-80-23600529

Contents: Page no.

1. General experimental E SI - 2

2. Preparation of starting materials ESI - 2

3. Typical experimental procedure and spectral data ESI 3-10

4. 1H and

13C NMR spectra ESI 11 – 58

5. Mass Spectra (EI-MS) of selected compounds ESI 59 - 67

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2013

mailto:[email protected]

Balaji and Prabhu/ Organic Chemistry/IISc

ESI - 2

1. General experimental :

NMR spectra were recorded in CDCl3 using Tetramethylsilane (TMS; δ = 0.00 ppm) as internal

standards for 1H NMR and corresponding residual non-deuterated solvent signal (CDCl3: δ =

77.00 ppm) was used as internal standards for 13

C NMR. Mass spectra were measured with

Micromass Q-Tof (ESI-HRMS) and Shimadzu gas chromatograph mass spectrometer model QP-

2010 Ultra EI. Column chromatography were carried out on silica gel 230-400 mesh or 100-200

mesh (Merck). Chemicals obtained from commercial suppliers were used without further

purification.

2. Preparation of starting materials:

The starting materials, substituted cinnamic acid derivatives were prepared from the

corresponding aldehydes using general procedure shown in the following scheme and spectral

data are in agreement with the literature.

a) NaH (60% mineral oil, 2 equiv.), Triethylphosphonoacetate ( 1.5 equiv.) in THF at 0 °C to 60

°C. b) NaOH ( 5 equiv., EtOH:H2O in 8:2 ratio at 60 °C).

All compounds were analyzed by NMR, IR and MS spectroscopy and also compared with

known compounds.



ESI - 3

Typical experimental procedure

α,β-Unsaturated acid (0.5 mmol), CuCl (0.05 mmol) and tertiary butyl nitrite (1.0 mmol) and

CH3CN (2 mL) were added in to an oven dried round bottom flask, the reaction mixture stirred at

80 °C for 12 -18 h and the completion of the reaction was monitored by thin layer

chromatography. After completion of reaction, the reaction mixture was cooled to room

temperature, and solvent was removed under reduced pressure to obtain the crude product, which

was purified on silica gel column to get pure product.

2-nitroethene-1,1-diyl)dibenzene (2a). Prepared as shown in general experimental procedure.

Yellow solid: Yield 96% (108 mg); mp 84-86 °C (lit.1 86-87 °C Rf (); 15% EtOAc/Hexane) 0.80;

IR (KBr, cm-1

) 1517, 1340; 1H NMR (400 MHz, CDCl3) 7.35-7.44 (m, 7H), 7.27 (d, J = 7.2

Hz, 2H), 7.20-7.26(m, 2H); 13

C NMR (100 MHz, CDCl3) 150.4, 138.0, 135.5, 132.3, 130.9,

129.3, 128.9, 128.8, 128.7, 128.4; MS (M/Z) 225 (M+).

(E)-(1-nitroprop-1-en-2-yl)benzene (2b). Prepared as shown in general experimental

procedure. Yellow liquid: Yield 71% (58 mg); Rf (15% EtOAc/Hexane) 0.75; IR (Neat, cm-1

)

1555, 1517, 1340, 1147; 1H NMR (400 MHz, CDCl3) 7.45(m, 5H), 7.31(s, 1H), 2.65(s, 3H);

13C NMR (100 MHz, CDCl3) 149.5, 138.2, 136.3, 130.3, 129.0, 126.8; MS (M/Z) 163 (M+).

(E)-1-methyl-4-(1-nitroprop-1-en-2-yl)benzene (2c). Prepared as shown in general

experimental procedure. Yellow liquid: Yield 70% (62 mg); Rf (10% EtOAc/Hexane) 0.70; IR

(Neat, cm-1

) 2924, 1607, 1336, 1018; 1H NMR (400 MHz, CDCl3) 7.36 (d, J = 8 Hz, 2H), 7.32

(s, 1H), 7.24 (d, J = 8 Hz, 2H), 2.63 (s, 3H), 2.39 (s, 3H); 13

C NMR (100 MHz, CDCl3) 150.0,

140.9, 135.7, 135.3, 129.7, 126.7, 21.2, 18.4; HRESI-MS (M/Z) Calculated for C1oH11NO2

(M+Na) 200.0687, found (M+Na) 200.0685.



ESI - 4

(E)-1-methoxy-4-(1-nitroprop-1-en-2-yl)benzene (2d). Prepared as shown in general


(Neat, cm-1

) 2932, 1600, 1513, 1333, 1249, 1019; 1H NMR (400 MHz, CDCl3) 7.44 (d, J = 8

Hz, 2H), 7.34 (s, 1H), 6.95(d, J = 8 Hz, 2H), 3.86 (s, 3H), 2.64 (s, 3H); 13

C NMR (100 MHz,

CDCl3) 161.6, 149.7, 135.1, 130.2, 128.4, 114.4, 55.4, 18.3; HRESI-MS (M/Z) Calculated for

C10H11NO3 (M+Na) 216.0637, found (M+Na) 216.0637.

(E)-1-bromo-4-(1-nitroprop-1-en-2-yl)benzene (2e). Prepared as shown in general


(Neat, cm-1

) 1516, 1339; 1H NMR (400 MHz, CDCl3) 7.58 (d, J = 8 Hz, 2H), 7.32 (d. J = 8 Hz,

2H), 7.28 (s, 1H), 2.62 (s, 3H); 13

C NMR (100 MHz, CDCl3) 148.5, 137.1, 136.4, 136.3, 128.3,

124.9, 18.4; HRESI-MS (M/Z) Calculated for C9H8BrNO2 (M+) 240.9738, found (M+)

240.9740.

(E)-2-(1-nitroprop-1-en-2-yl)naphthalene (2f). Prepared as shown in general experimental


)

2926, 1616, 1333, 1018; 1H NMR (400 MHz, CDCl3) 7.95 (s, 1H), 7.90 - 7.87 (m, 3H), 7.57 -

7.50 (m, 3H), 7.45 (s, 1H), 2.75 (s, 3H); 13

C NMR (100 MHz, CDCl3) 149.9, 136.6, 135.4,

134.0, 133.2, 128.9, 128.6, 127.8, 127.7, 127.5, 127.0, 123.7, 18.6; HRESI-MS (M/Z) Calculated

for C13H11NO2 (M+Na) 236.0687, found (M+Na) 236.0691.

(E)-2-(1-nitroprop-1-en-2-yl)thiophene (2g). Prepared as shown in general experimental


)

2926, 2103, 1638, 1248, 1018; 1H NMR (400 MHz, CDCl3) 7.57 (d, J = 4 Hz, 1H), 7.47-7.50

(m, 2H), 7.13-7.15 (m, 1H), 2.71 (s, 3H); 13

C NMR (100 MHz, CDCl3) 142.9, 140.5, 133.7,



ESI - 5

129.6, 129.2, 128.6, 17.8; HRESI-MS (M/Z) Calculated for C7H7NO2S (M+Na) 192.0095, found

(M+Na) 192.0099.

2-(3-nitroprop-1-en-2-yl)pyridine (2ha) and (E)-2-(1-nitroprop-1-en-2-yl)pyridine (2hb).

Prepared as shown in general experimental procedure. Yellow liquid: Yield 52% (66 mg); Rf

(15% EtOAc/Hexane) 0.50; IR (Neat, cm-1

) 2923, 1554, 1344, 1018; 1H NMR (400 MHz,

CDCl3) 2ja 8.53 (d, 1H), 7.73-7.65 (m, 2H), 7.23-7.20 (m, 1H), 6.17 (s, 1H), 5.72 (s, 1H), 5.55

(s, 2H); 2jb 8.68 (d, 1H), 7.81 (s, 1H), 7.79-7.77 (m, 1H), 7.57 (d. J = 8 Hz, 1H), 7.38-7.34 (m,

1H), 2.66 (s, 3H); 13

C NMR (100 MHz, CDCl3) 2ja and 2jb 154.6, 154.5, 149.8, 149.0, 146.2,

138.6, 138.2, 137.1, 136.6, 124.7, 123.0, 122.5, 121.8, 119.7, 77.4, 15.8; HRESI-MS (M/Z)

Calculated for C8H8N2O2 (M+H) 165.0664, found (M+H) 165.0659.

(E)-1-methoxy-4-(2-nitrovinyl)benzene (3a). Prepared as shown in general experimental

procedure. Yellow solid: Yield 92% (82 mg); mp 85-86 °C (lit.2 84-86 °C); Rf (10%

EtOAc/Hexane) 0.70; IR (KBr, cm-1

) 2931, 1603, 1338, 1255, 1173, 1025; 1H NMR (400 MHz,

CDCl3) 7.97 (d, J = 12 Hz, 1H), 7.53 (d, J = 12 Hz, 1H), 7.51 (d, J = 8Hz, 2H), 6.96 (d, J = 8

Hz, 2H), 3.87(s, 3H); 13

C NMR (100 MHz, CDCl3) 162.9, 139.0, 135.0, 131.1, 122.5, 114.9,

55.5; HRESI-MS (M/Z) Calculated for C9H9NO3Na (M+Na) 202.0480, found (M+Na) 202.0481.

(E)-(2-nitrovinyl)benzene (3b). Prepared as shown in general experimental procedure. Yellow

solid: Yield 82% (61 mg); mp 55-58 °C (lit.2 56-60 °C); Rf (15% EtOAc/Hexane) 0.8; IR (KBr,

cm-1

) 2829, 1632, 1513, 1347; 1H NMR (400 MHz, CDCl3) 7.99 (d, J = 13.6 Hz, 1H), 7.43-

7.60 (m, 6H); 13

C NMR (100 MHz, CDCl3) 139.0, 137.0, 132.1, 130.0, 129.3, 129.1; MS

(M/Z): 149 (M+).



ESI - 6

(E)-1-methyl-4-(2-nitrovinyl)benzene (3c). Prepared as shown in general experimental

procedure. Yellow solid: Yield 52% (42 mg); mp 101-103 °C (lit.3 103 °C); Rf (15%


) 1632, 1497, 1341; 1H NMR (400 MHz, CDCl3) 7.98 (d, J

= 13.6 Hz, 1H), 7.56 (d, J = 13.6 Hz, 1H), 7.42 (d, J = 8 Hz, 2H), 7.25 (d, J = 10 Hz, 2H), 2.48

(s, 3H); 13

C NMR (100 MHz, CDCl3) 143.0, 139.1, 136.3, 130.1, 129.2, 127.3; HRESI-MS

(M/Z) Calculated for C9H9NO2 (M+Na): 186.0531, found (M+Na): 186.0533.

(E)-1-(2-nitrovinyl)naphthalene (3d). Yellow solid: Yield 91% (91 mg); mp 84-86 °C (lit.3 84

°C); Rf (15% EtOAc/Hexane) 0.8; Prepared as shown in general experimental procedure. IR

(KBr, cm-1

): 1515, 1505, 1342, 1018; 1H NMR (400 MHz, CDCl3) 8.82 (d, J = 13.2 Hz, 1H),

8.13 (d, J = 8.4Hz, 1H), 8.0 (d, J = 8.4 Hz, 1H), 7.92 (d, J = 8 Hz, 1H), 7.74 (d, J = 6.8 Hz,

1H), 7.57-7.66 (m, 3H), 7.50-7.54 (t, J = 7.6 Hz, J = 15.2 Hz, 1H); 13

C NMR (100 MHz, CDCl3)

138.4, 136.1, 133.8, 132.5, 131.5, 129.0, 127.7,127.0, 126.8,126.3, 125.4, 123.0; MS (M/Z)

199 (M+).

(E)-1,2-dimethoxy-4-(2-nitrovinyl)benzene (3e). Prepared as shown in general experimental

procedure. Yellow solid: Yield 69% (72 mg); mp 134-136 °C (lit.4 137 - 140 °C); Rf (15%


) 1599, 1490, 1343, 1272; 1H NMR (400 MHz, CDCl3) 7.96

(d, J = 13.6 Hz, 1H), 7.54(d, J = 13.6 Hz, 1H), 7.17(d, J = 8 Hz, 1H), 7.01(d, J = 1.2 Hz, 1H),

6.92 (d, J = 8 Hz, 1H), 3.94(s, 3H), 3.93(s, 3H); 13

C NMR (100 MHz, CDCl3) 152.8, 149.5,

139.3, 135.1, 124.6, 122.7, 111.3, 110.2, 56.0, 55.9; HRESI-MS (M/Z) Calculated for

C10H11NO4 (M+Na) 232.0586, found (M+Na) 232.0585.

(E)-1-(benzyloxy)-4-(2-nitrovinyl)benzene (3f). Prepared as shown in general experimental




ESI - 7


) 1601, 1491, 1344, 1248; 1H NMR (400 MHz, CDCl3) 7.96

(d, J = 16 Hz, 1H), 7.48-7.52 (m, 3H), 7.35-7.42 (m, 5H), 7.02 (d, J = 8Hz, 2H), 5.12 (s, 2H);

13C NMR (100 MHz, CDCl3) 162.0, 138.9, 135.6, 135.1, 131.1, 128.7, 128.3, 127.4, 122.7,

70.2; HRESI-MS (M/Z) Calculated for C15H13NO3 (M+Na) 278.0793, found (M+Na) 278.0792.

(E)-1-(2-nitrovinyl)-3-phenoxybenzene (3g). Prepared as shown in general experimental

procedure. Yellow solid: Yield 84% (101 mg) and 45% (54 mg); mp 58-59 °C (lit.6 57-59 °C); Rf

(15% EtOAc/Hexane) 0.8; IR (KBr, cm-1

) 1579, 1519, 1487, 1344, 1230; 1H NMR (400 MHz,

CDCl3) 7.95 (d, J = 14 Hz, 1H), 7.53 (d, J = 14Hz, 1H), 7.38-7.44 (m, 3H), 7.28 (d, J = 7.2Hz,

1H), 7.18-7.21 (t, J = 7.2 Hz, J = 14.8 Hz, 1H), 7.06-7.15 (m, 2H), 7.05 (d, J = 7.6 Hz, 2H); 13

C

NMR (100 MHz, CDCl3) 158.3, 156.1, 138.4, 137.6, 131.7, 130.7, 130.0, 124.2, 123.8, 122.0,

119.4, 118.2; HRESI-MS (M/Z) Calculated for C14H11NO3 (M+H) 242.0817, found (M+H)

242.0819.

(E)-1-(2-nitrovinyl)-4-(trifluoromethyl)benzene (3h). Prepared as shown in general

experimental procedure. Yellow solid: Yield 46% (50 mg) and 38% (41 mg); mp 93-94 °C (lit.2

92-95 °C); Rf (15% EtOAc/Hexane) 0.8; IR (KBr, cm-1

) 2926, 2102, 1636, 1324, 1263, 1019; 1H

NMR (400 MHz, CDCl3) 8.03 (d, J = 12 Hz, 1H), 7.73 (d, J = 8 Hz, 2H), 7.68 (d, J = 8 Hz,

2H), 7.62 (d, J = 12 Hz, 1H); 13

C NMR (100 MHz, CDCl3) 138.9, 137.1, 133.5, 133.4 (q, J =

32.7 Hz), 129.2, 126.4, 123.5 (q, J = 271 Hz); MS (M/Z) 217 (M+).

(E)-4-(2-nitrovinyl)benzonitrile (3i). Prepared as shown in general experimental procedure.

Yellow solid: Yield 36% (31 mg) and 32% (28 mg); mp 183-185 °C (lit.7 180-186 °C) Rf (15%


) 2227, 2102, 1638, 1348; 1H NMR (400 MHz, CDCl3) 7.99

(d, J = 12 Hz, 1H), 7.76(d, J = 8 Hz, 2H), 7.63-7.68 (t, J = 8 Hz, J = 20 Hz, 2H) , 7.60 (s, 1H);



ESI - 8

13C NMR (100 MHz, CDCl3) 139.4, 136.5, 134.3, 133.0, 129.3, 117.8, 115.2; MS (M/Z) 174

(M+).

(E)-1-bromo-2-(2-nitrovinyl)benzene (3j). Prepared as shown in general experimental



) 1635, 1522, 1340, 1018; 1H NMR (400 MHz, CDCl3) 8.39

(d, J = 16 Hz, 1H), 7.69 (d, J = 4Hz, 1H), 7.55-7.68 (m, 1H), 7.52 (s, 1H), 7.32-7.41 (m, 2H);

13C NMR (100 MHz, CDCl3) 138.8, 137.6, 134.0, 133.0, 130.3, 128.4, 128.0, 126.3; MS (M/Z)

229 (M+).

(E)-1-fluoro-2-(2-nitrovinyl)benzene (3k). Prepared as shown in general experimental

procedure. Yellow solid: Yield 68% (57 mg); mp 44-46 °C; Rf (15% EtOAc/Hexane) 0.8; IR

(KBr, cm-1

) 1635, 1509, 1357, 1216; 1H NMR (400 MHz, CDCl3) 8.05 (d, J = 13.6 Hz, 1H),

7.73 (d, J = 14Hz, 1H), 7.46-7.54 (m, 2H), 7.16-7.26 (m, 2H); 13

C NMR (100 MHz, CDCl3)

163.1, 160.6, 139.4, 139.2, 133.7, 133.6, 132.4, 131.4, 131.3, 125.0, 124.9, 118.5, 118.3, 116.7,

116.5; HRESI-MS (M/Z) Calculated for C8H6FNO2 (M+Na) 190.0280, found (M+Na) 190.0305.

(E)-1-chloro-4-(2-nitrovinyl)benzene (3l). Prepared as shown in general experimental

procedure. Light yellow solid: Yield 50% (46 mg); mp 110-111 °C (lit.9 110-111 °C); Rf (15%


) 1635, 1491, 1340; 1H NMR (400 MHz, CDCl3) 7.97 (d, J

= 12 Hz, 1H), 7.57 (d, J = 12 Hz, 1H), 7.50 (d, J = 8 Hz, 2H), 7.44 (d, J = 8 Hz, 2H); 13

C NMR

(100 MHz, CDCl3) 138.3, 137.7, 137.4, 130.2, 129.7, 128.5; MS (M/Z) 183 (M+).

(E)-2-(2-nitrovinyl)thiophene (3m). Prepared as shown in general experimental procedure.

Yellow solid: Yield 72% (56 mg); mp 81-83 °C (lit.2 80-82 °C); Rf (15% EtOAc/Hexane) 0.8; IR

(KBr, cm-1

): 2102, 1635, 1325, 1265; 1H NMR (400 MHz, CDCl3) 8.15 (d, J = 12 Hz, 1H),



ESI - 9

7.57 (d, J = 8 Hz, 1H), 7.46-7.50 (m, 2H), 7.14-7.16 (t, J = 4 Hz, J = 8 Hz, 1H); 13

C NMR (100

MHz, CDCl3) 135.3, 134.6, 133.7, 132.1, 131.6, 128.8; HRESI-MS (M/Z) Calculated for

C6H5NO2S (M+Na) 177.9939, found (M+Na) 177.9938.

(E)-2-(2-nitrovinyl)furan (3n). Prepared as shown in general experimental procedure. Yellow

solid: Yield 41% (28.5 mg); mp 67-69 °C (lit.10

68-70 °C); Rf (15% EtOAc/Hexane) 0.8; IR

(KBr, cm-1

): 1631, 1499, 1325, 1018; 1H NMR (400 MHz, CDCl3) 7.78 (d, J = 13.2 Hz, 1H),

7.59 (d, J = 0.4 Hz, 1H), 7.52 (d, J = 13.6 Hz, 1H), 6.89 (d, J = 3.2 Hz, 1H), 6.57-6.58 (m, 1H);

13C NMR (100 MHz, CDCl3) 146.8, 146.6, 135.0, 125.4, 120.0, 113.3; MS (M/Z) 139 (M+).

(E)-(2-(2-nitrovinyl)-1H-indol-1-yl)(phenyl)methanone (3o). Prepared as shown in general

experimental procedure. Yellow solid: Yield 75% (109 mg); mp 42-45 °C; Rf (15%


) 1607, 1438, 1261, 1019; 1

H NMR (400 MHz, CDCl3) 8.05

(d, J = 12 Hz, 1H), 7.77-7.75 (m, 2H), 7.72-7.64 (m, 2H), 7.56-7.50 (m, 3H), 7.28-7.21 (m, 3H),

7.14 (d, J = 8 Hz, 1H)13

C NMR (100 MHz, CDCl3) 168.9, 138.9, 136.5, 134.2, 134.0, 131.2,

130.1, 129.5, 129.1, 128.3, 126.6, 123.9, 122.0, 114.7, 113.8; HRESI-MS (M/Z) Calculated for

C17H12N2O3 (M+Na) 315.0746, found (M+Na) 315.0746.

((1E,3E)-4-nitrobuta-1,3-dien-1-yl)benzene (3p). Prepared as shown in general experimental

procedure. Yellow solid: Yield 34% (30 mg); mp 45-47 °C (lit.11

45-47 C); Rf (15%


) 2922, 1622, 1433, 1018; 1H NMR (400 MHz, CDCl3)

7.73-7.79 (t, J = 12 Hz, J = 24.4 Hz, 1H), 7.49-7.51 (t, J = 2.8 Hz, J = 7.6 Hz, 2H), 7.38-7.40 (m,

3H), 7.22 (d, J = 13.2 Hz, 1H), 7.13 (d, J = 15.6 Hz, 1H), 6.82-6.88 (dd, J = 11.6 Hz, J = 15.2

Hz, 1H); 13

C NMR (100 MHz, CDCl3) 146.0, 139.1, 138.6, 135.0, 130.3, 129.0, 127.7, 120.5;

MS (M/Z) 175 (M+).



ESI - 10

Refereneces

1 T. H. H. Hsieh and V. M. Dong, Tetrahedron 2009, 65, 3062.

2 J. M. Rodriguez and M. D. Pujol, Tetrahedron Lett. 2012, 52, 2629.

3 A. Alizadeh, M. M. Khodaei and A. Eshghi, J. Org. Chem. 2010, 75, 8295.

4 L. Shen, Y. Hu, X. Yang, B. Yang and Q. He, Eur. J. Med. Chem. 2010, 45, 11.

5 W. E. Parham, C. Jr. Serres and P. R. O'Connor, J. Am. Chem. Soc. 1958, 80, 588.

6 Y.-G. Li, Y.-S. Liu, F.-M. Miao, X.-L. Liu and J.-H. Cao, Phosphorus, Sulfur Silicon Relat.

Elem. 1990, 47, 229.

7 M. A. Brook and D. Seebach, Can. J. Chem. 1987, 65, 836.

8 P. Jakubec, D. J. Dixon, D. M. Cockfield, P. S. Hynes and E. Cleator, Tetrahedron:

Asymmetry 2011, 22, 1147.

9 R. Menicagli and S. Samaritani, Tetrahedron 1996, 52, 1425.

10 D. H. O'Donovan and I. Rozas, Tetrahedron Lett. 2012, 53, 4532.

11 M. Tsakos and C. G. Kokotos, Eur. J. Org. Chem. 2012, 576.


http://pubs.acs.org/action/doSearch?action=search&author=Parham%2C+William+E.&qsSearchArea=author

http://pubs.acs.org/action/doSearch?action=search&author=Serres%2C+Carl&qsSearchArea=author

http://pubs.acs.org/action/doSearch?action=search&author=O%27Connor%2C+Paul+R.&qsSearchArea=author


ESI - 11

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

-0.0

0

7.2

0

7.2

1

7.2

2

7.2

3

7.2

6

7.2

7

7.2

8

7.3

5

7.3

7

7.3

7

7.3

9

7.4

1

7.4

2

7.4

2

7.4

3

7.4

3

7.4

5

2.0

0

2.1

0

7.1

5



ESI - 12

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

76.6

82

77.0

00

77.3

18

128

.440

128

.739

128

.826

128

.854

129

.256

130

.851

134

.339

135

.478

137

.019

150

.417



ESI - 13



ESI - 14



ESI - 15

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

0.0

0

2.4

0

2.6

3

7.2

3

7.2

5

7.3

2

7.3

5

7.3

7

3.0

9

3.0

2

2.1

1

1.0

0

2.1

0



ESI - 16



ESI - 17

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

-0.0

0

2.6

4

2.6

4

3.8

6

6.9

4

6.9

6

7.2

6

7.3

4

7.3

4

7.4

3

7.4

5

3.0

2

3.0

1

2.0

2

1.0

0

2.0

2



ESI - 18

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

18.3

06

55.4

41

76.6

82

77.0

00

77.3

17

114

.431

128

.426

130

.184

135

.099

149

.732

161

.585



ESI - 19



ESI - 20

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

18.3

85

76.6

83

77.0

01

77.3

18

124

.863

128

.337

132

.267

136

.382

137

.099

148

.542



ESI - 21



ESI - 22



ESI - 23

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

0.0

0

2.7

1

7.1

2

7.1

3

7.1

5

7.2

6

7.4

7

7.4

8

7.4

8

7.5

0

7.5

7

3.0

2

1.0

3

2.0

0

1.0

1



ESI - 24

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

17.8

52

76.6

81

76.9

99

77.3

17

128

.617

129

.206

129

.557

133

.740

140

.529

142

.889



ESI - 25

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

-0.0

0

2.6

6

2.6

6

5.5

5

5.5

5

5.7

2

6.1

7

7.2

0

7.2

0

7.2

1

7.2

1

7.2

2

7.2

2

7.2

3

7.2

3

7.2

6

7.3

4

7.3

5

7.3

6

7.3

6

7.3

6

7.3

7

7.3

8

7.3

8

7.5

6

7.5

8

7.6

5

7.6

5

7.6

6

7.6

7

7.6

7

7.6

8

7.6

9

7.6

9

7.7

1

7.7

1

7.7

3

7.7

3

7.7

7

7.7

7

7.7

9

7.7

9

7.8

1

1.6

9

2.1

1

1.0

6

1.0

5

1.0

2

0.5

6

0.5

6

1.0

1

1.0

9

0.6

1

0.5

7

1.0

0

0.6

0



ESI - 26

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

15.8

46

76.6

82

76.9

99

77.3

17

77.4

05

119

.718

121

.834

122

.459

123

.039

124

.729

136

.600

137

.084

138

.220

138

.582

146

.216

148

.964

149

.813

154

.490

154

.609



ESI - 27

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

-0.0

0

3.8

7

6.9

5

6.9

7

7.2

7

7.5

0

7.5

1

7.5

2

7.5

4

7.9

6

7.9

9

3.0

4

2.1

3

3.0

6

1.0

0



ESI - 28

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

55.4

98

76.6

84

77.0

02

77.3

20

114

.885

122

.498

131

.143

134

.978

139

.014

162

.909



ESI - 29

10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

-0.0

00

0.0

84

0.0

86

7.2

61

7.4

31

7.4

48

7.4

67

7.4

84

7.4

87

7.5

01

7.5

33

7.5

37

7.5

54

7.5

69

7.6

03

7.9

81

8.0

15

6.2

95

1.0

00



ESI - 30

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

76.6

83

77.0

01

77.3

19

129

.081

129

.324

129

.977

132

.087

137

.029

139

.015



ESI - 31

10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

0.0

00

0.0

76

2.4

08

7.2

45

7.2

60

7.2

65

7.4

32

7.4

52

7.5

47

7.5

81

7.9

64

7.9

98

3.0

55

2.1

45

2.1

21

1.0

44

1.0

00



ESI - 32

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

21.6

40

76.6

81

76.9

98

77.3

16

127

.251

129

.167

130

.120

136

.263

139

.149

143

.084



ESI - 33

10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

0.0

20

7.2

67

7.5

02

7.5

21

7.5

40

7.5

78

7.5

96

7.6

13

7.6

16

7.6

28

7.6

49

7.6

51

7.6

62

7.7

36

7.7

53

7.9

15

7.9

35

7.9

97

8.0

18

8.1

15

8.1

36

8.8

07

8.8

40

1.1

19

3.2

10

1.0

51

1.1

25

1.0

78

1.0

65

1.0

00



ESI - 34

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

76.6

83

77.0

01

77.3

18

122

.918

125

.356

126

.340

126

.753

126

.917

127

.696

129

.018

131

.516

132

.517

133

.716

136

.051

138

.432



ESI - 35

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

-0.0

00

3.9

32

3.9

47

6.9

12

6.9

32

7.0

16

7.0

19

7.1

69

7.1

89

7.2

78

7.5

23

7.5

57

7.9

49

7.9

83

3.1

28

2.9

99

1.0

90

1.1

45

1.0

56

1.0

39

1.0

00



ESI - 36

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

55.9

56

56.0

37

76.6

81

76.9

99

77.3

17

110

.175

111

.279

122

.743

124

.596

135

.110

139

.286

149

.494

152

.751



ESI - 37



ESI - 38



ESI - 39

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.0

22

0.1

00

7.0

46

7.0

65

7.0

67

7.1

41

7.1

57

7.1

58

7.1

81

7.2

00

7.2

18

7.2

74

7.2

77

7.2

92

7.3

86

7.4

04

7.4

25

7.4

44

7.5

14

7.5

48

7.9

38

7.9

73

2.1

50

2.1

11

1.2

13

1.1

92

3.1

19

1.1

15

1.0

00



ESI - 40

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

76.6

81

76.9

99

77.3

17

118

.176

119

.415

121

.996

123

.776

124

.205

130

.036

130

.699

131

.684

137

.575

138

.393

156

.092

158

.346



ESI - 41

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

-0.0

0

7.2

6

7.6

1

7.6

4

7.6

7

7.6

9

7.7

2

7.7

4

8.0

1

8.0

4

1.0

8

2.1

4

2.0

6

1.0

0



ESI - 42

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

76.6

82

77.0

00

77.3

17

119

.401

122

.109

124

.819

126

.293

126

.331

126

.368

126

.404

127

.528

129

.231

132

.964

133

.293

133

.489

133

.621

133

.948

137

.060

138

.874



ESI - 43

9 8 7 6 5 4 3 2 1 0 ppm

0.0

0

7.2

7

7.6

0

7.6

3

7.6

6

7.6

8

7.7

5

7.7

7

7.9

8

8.0

1

1.1

0

2.0

0

2.0

1

1.0

1



ESI - 44

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

76.6

83

77.0

01

77.3

18

115

.202

117

.761

129

.363

133

.006

134

.321

136

.525

139

.438



ESI - 45

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

-0.0

0

7.2

6

7.3

2

7.3

2

7.3

4

7.3

4

7.3

5

7.3

6

7.3

6

7.3

7

7.3

8

7.3

9

7.4

0

7.4

1

7.5

2

7.5

5

7.5

6

7.5

7

7.5

8

7.5

8

7.6

7

7.6

8

7.6

9

7.7

0

8.3

7

8.4

1

2.2

6

1.0

1

1.1

5

1.0

6

1.0

0



ESI - 46

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

76.6

83

77.0

01

77.3

18

126

.302

128

.049

128

.438

130

.303

132

.901

133

.972

137

.554

138

.796



ESI - 47

10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

0.0

00

7.1

65

7.1

87

7.1

90

7.2

13

7.2

31

7.2

50

7.2

69

7.4

66

7.4

70

7.4

84

7.4

89

7.5

04

7.5

23

7.5

41

7.7

15

7.7

50

8.0

37

8.0

71

2.1

77

2.1

58

1.0

33

1.0

00



ESI - 48

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

76.6

81

76.9

99

77.3

17

116

.487

116

.701

118

.336

118

.456

124

.991

125

.027

131

.338

131

.361

132

.473

133

.630

133

.720

139

.267

139

.385

160

.555

163

.104



ESI - 49

9 8 7 6 5 4 3 2 1 0 ppm

0.0

0

7.2

7

7.4

3

7.4

3

7.4

4

7.4

5

7.4

9

7.4

9

7.5

1

7.5

5

7.5

8

7.9

5

7.9

8

2.0

9

2.1

0

1.1

8

1.0

0



ESI - 50

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

76.6

84

77.0

02

77.3

20

128

.501

129

.746

130

.239

137

.397

137

.664

138

.315



ESI - 51

10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

0.0

00

6.5

75

6.5

80

6.5

84

6.5

88

6.8

94

6.9

02

7.2

67

7.5

11

7.5

45

7.5

96

7.5

97

7.7

64

7.7

97

1.0

60

1.0

00

1.0

63

1.0

26

1.0

22



ESI - 52

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

76.6

83

77.0

00

77.3

18

113

.315

119

.950

125

.403

134

.901

146

.626

146

.800



ESI - 53

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

0.0

0

7.1

4

7.1

5

7.1

6

7.2

7

7.4

6

7.4

7

7.5

0

7.5

6

7.5

8

8.1

4

8.1

7

1.0

6

2.0

3

1.0

6

1.0

0



ESI - 54

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

76.6

84

77.0

01

77.3

19

128

.848

131

.588

132

.054

133

.732

134

.596

135

.323



ESI - 55



ESI - 56



ESI - 57

10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

-0.0

01

0.0

01

6.8

20

6.8

49

6.8

58

6.8

87

7.1

16

7.1

55

7.2

10

7.2

43

7.3

85

7.3

89

7.3

97

7.4

02

7.4

99

7.5

11

7.5

18

7.7

30

7.7

61

7.7

91

1.0

52

1.0

00

1.0

74

3.1

41

2.1

84

1.0

27



ESI - 58

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

76.6

84

77.0

01

77.3

19

120

.529

127

.682

128

.984

130

.273

135

.089

138

.561

139

.118

145

.983



ESI - 59

2a (Mass Spectrum EI)



ESI - 60

2b (Mass Spectrum EI)



ESI - 61

3d (Mass Spectrum EI)



ESI - 62

3h (Mass Spectrum EI)



ESI - 63

3i (Mass Spectrum EI)



ESI - 64

3j (Mass Spectrum EI)



ESI - 65

3l (Mass Spectrum EI)



ESI - 66

3n (Mass Spectrum EI)



ESI - 67

3p (Mass Spectrum EI)


synthesis of substituted nitroolefins: a copper catalyzed … · 2013. 8. 16. · balaji v. rokade...

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