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Supporting Information
In situ generation of formaldehyde and triphenylphosphine from
(hydroxymethyl)triphenylphosphonium and its application in Wittig
olefination
Wenhua Huang* and Jie Xu
Department of Chemistry, Tianjin University, 92 Weijin Road, Tianjin 300072, P. R. China.
Email: [email protected].
Table of Contents Page Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d)…….... S2 NMR data of 3a-e…...…………………………………………………….. S2 NMR data of 3f-l………………………………………………………… S3 NMR data of 3m-p………………………………………………………… S4 Acknowledgement………………………………………………………… S4 References………………………………………………………………… S4 NMR spectra of 1d………………………………………………………… S6-8 NMR spectra of 3a…………………………………………………………. S9-10 NMR spectra of 3b………………………………………………………… S11-12NMR spectra of 3c…………………………………………………………. S13-14NMR spectra of 3d………………………………………………………… S15-16NMR spectra of 3e…………………………………………………………. S17-18NMR spectra of 3f…………………………………………………………. S19-20NMR spectra of 3g…………………………………………………………. S21-22NMR spectra of 3h………………………………………………………. S23-24NMR spectra of 3i…………………………………………………………. S25-26NMR spectra of 3j…………………………………………………………. S27-28NMR spectra of 3k………………………………………………………. S29-30NMR spectra of 3l…………………………………………………………. S31-32NMR spectra of 3m………………………………………………………. S33-34NMR spectra of 3n………………………………………………………. S35-36NMR spectra of 3o…………………………………………………………. S37-38NMR spectra of 3p………………………………………………………. S39-40
1S
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EXPERIMENTAL
Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d)
A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was added dropwise to a mixture of tricyclohexylphosphine (5.609 g, 0.02 mmol), paraformaldehyde (0.601 g, 0.02 mol) and ether (20 mL) in a round-bottom flask (100 mL). After stirred at rt for 16 h, the reaction mixture was evaporated to remove ether, diluted with water (30 mL), and then extracted with CH2Cl2 (30 mL x 2). The combined extracts were dried over anhydrous MgSO4, evaporated to dryness, and then treated with tert-buty methylether. The resulting precipitates were collected by filtration, and dried in vacuo to afford 1d (4.334 g, 54%). A white solid, mp 134-137 C; 1H-NMR (400 MHz, CDCl3) 1.25-1.50 (m, 9 H), 1.55-1.70 (m, 6 H), 1.77-1.83 (m, 3 H), 1.90-2.04 (m, 12 H), 2.40-2.53 (m, 3 H), 4.32 (brs, 1 H), 4.62 (s, 2 H). 13C-NMR (100 MHz, CDCl3) 50.8 (d, JC-P = 59.0 Hz), 28.7 (d, JC-P = 38.5 Hz), 26.6 (d, JC-P = 4.0 Hz). 26.5 (d, JC-P = 11.7 Hz), 25.3. 31P-NMR (162 MHz, CDCl3) 28.78. HRMS-ESI (positive) m/z: calcd for C19H36OP+ (1d-cation), 311.2498; found, 311.2499.
2-Vinylnaphthalene (3a)
A white solid, yield: 66.8 mg, 87%; Rf = 0.53 (PE); mp 62-64 (lit.1 64-66); 1H-NMR (600 MHz, CDCl3) 5.32 (d, J = 10.9 Hz, 1 H), 5.85 (d, J = 17.6 Hz, 1 H), 6.86 (dd, J = 10.9, 17.6 Hz, 1 H), 7.39-7.45 (m, 2 H), 7.62 (d, J = 8.5 Hz, 1 H), 7.72 (s, 1 H), 7.75-7.79 (m, 3 H). 13C-NMR (151 MHz, CDCl3) 137.0, 135.0, 133.6, 133.2, 128.2, 128.1, 127.7, 126.4, 126.3, 125.9, 123.2, 114.2.
1-Methoxy-4-vinylbenzene (3b)2
A colorless oil, yield: 46.8 mg, 73%; Rf = 0.66 (CCl4); 1H-NMR (600 MHz, CDCl3) 3.80 (s, 3 H), 5.12 (d, 1 H, J = 10.9 Hz), 5.61 (d, 1 H, J = 17.5 Hz), 6.66 (dd, 1 H, J = 10.9, 17.5 Hz), 6.86 (d, 2 H, J = 8.0 Hz), 7.34 (d, 2 H, J = 8.0 Hz). 13C-NMR (151 MHz, CDCl3) 159.3, 136.2, 130.4, 127.4, 113.9, 111.6, 55.3.
1-Methyl-4-vinylbenzene (3c)1
A colorless oil, yield: 46.8 mg, 79%; Rf = 0.77 (PE); 1H-NMR (400 MHz, CDCl3) 2.39 (s, 3 H), 5.23 (d, 1 H, J = 10.9 Hz), 5.75 (d, 1 H, J = 17.6 Hz), 6.74 (dd, 1 H, J = 10.9, 17.6 Hz), 7.18 (d, 2 H, J = 7.9 Hz), 7.36 (d, 2 H, J = 8.0 Hz). 13C-NMR (100 MHz, CDCl3) 137.6, 136.7, 134.8, 129.2, 126.1, 112.7, 21.2.
1-(tert-Butyl)-4-vinylbenzene (3d)3
A colorless oil, yield: 63.0 mg, 79%; Rf = 0.55 (PE); 1H-NMR (600 MHz, CDCl3) 1.31 (s, 9 H), 5.19 (d, 1 H, J = 10.9 Hz), 5.70 (d, 1 H, J = 17.6 Hz), 6.69 (dd, 1 H, J = 10.9, 17.6 Hz), 7.35 (s, 4 H). 13C-NMR (151 MHz, CDCl3) 150.9, 136.6, 134.8, 125.9, 125.4, 113.0, 34.6, 31.3.
1,4-Divinylbenzene (3e)3
In this case, 1a (1.0 mmol) and K2CO3 (2.0 mmol) was used. A pale yellow semi-
2S
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solid, yield: 45.1 mg, 69%; Rf = 0.54 (PE); 1H-NMR (600 MHz, CDCl3) 5.23 (d, 2 H, J = 10.9 Hz), 5.74 (d, 2 H, J = 17.6 Hz), 6.70 (dd, 2 H, J = 10.9, 17.6 Hz), 7.37 (s, 4 H). 13C-NMR (151 MHz, CDCl3) 137.1, 136.4, 126.4, 113.7.
(E)-Buta-1,3-dien-1-ylbenzene (3f)1
A pale yellow oil, yield: 53.1 mg, 82%; Rf = 0.58 (PE); 1H-NMR (400 MHz, CDCl3), 5.25 (d, 1 H, J = 10.1 Hz), 5.41 (d, 1 H, J = 16.9 Hz), 6.53-6.68 (m, 2 H), 6.87 (dd, 1 H, J = 10.5, 15.6 Hz), 7.30 (t, 1 H, J = 7.3 Hz), 7.36-7.42 (m, 2 H), 7.48 (d, 2 H, J = 7.4 Hz). 13C-NMR (100 MHz, CDCl3) 137.17, 137.15, 132.8, 129.6, 128.6, 127.6, 126.4, 117.5.
Buta-1,3-dien-2-ylbenzene (3g)4
A pale yellow oil, yield: 40.0 mg, 61%; Rf = 0.61 (PE); 1H-NMR (400 MHz, CDCl3) 5.19-5.27 (m, 3 H), 5.34 (s, 1 H), 6.66 (dd, 1 H, J = 10.9, 17.3 Hz), 7.31-7.41 (m, 5 H). 13C-NMR (100 MHz, CDCl3) 148.2, 139.7, 138.1, 128.2, 128.1, 127.4, 117.1, 116.8.
1-Bromo-4-vinylbenzene (3h)3
A pale yellow oil, yield: 80.2 mg, 88%; Rf = 0.54 (PE); 1H-NMR (600 MHz, CDCl3) 5.26 (d, 1 H, J = 10.9 Hz), 5.73 (d, 1 H, J = 17.6 Hz), 6.64 (dd, 1 H, J = 10.9, 17.6 Hz), 7.25 (d, 2 H, J = 8.4 Hz), 7.43 (d, 2 H, J = 8.4 Hz). 13C-NMR (151 MHz, CDCl3) 136.4, 135.7, 131.6, 127.7, 121.6, 114.6.
1-Chloro-4-vinylbenzene (3i)1
A colorless oil, yield: 55.9 mg, 81%; Rf = 0.70 (PE); 1H-NMR (400 MHz, CDCl3) 5.30 (d, 1 H, J = 10.9 Hz), 5.76 (d, 1 H, J = 17.5 Hz), 6.70 (dd, 1 H, J =10.9, 17.5 Hz), 7.31-7.38 (m, 4 H). 13C-NMR (100 MHz, CDCl3) 136.0, 135.6, 133.4, 128.6, 127.4, 114.4.
Methyl 4-vinylbenzoate (3j)1
A white semi-solid, yield: 69.2 mg, 85%; Rf = 0.30 (PE: EtOAc 25:1); 1H-NMR (400 MHz, CDCl3) 3.91 (s, 3 H), 5.38 (d, 1 H, J = 10.9 Hz), 5.86 (d, 1 Hz, J = 17.6 Hz), 6.75 (dd, 1 H, J = 10.9, 17.6 Hz), 7.46 (d, 2 H, J = 8.3 Hz), 8.00 (d, 2 H, J = 8.3 Hz). 13C-NMR (100 MHz, CDCl3) 166.8, 141.9, 136.0, 129.8, 129.2, 126.1, 116.4, 52.0.
4-Vinylbenzonitrile (3k)1
A colorless oil, yield: 55.0 mg, 85%; Rf = 0.24 (PE: EtOAc 25:1); 1H-NMR (600 MHz, CDCl3) 5.45 (d, 1 H, J = 10.9 Hz), 5.88 (d, 1 H, J = 17.6 Hz), 6.73 (dd, 1 H, J = 10.9, 17.6 Hz), 7.49 (d, 2 H, J = 8.2 Hz), 7.62 (d, 2 H, J = 8.2 Hz). 13C-NMR (151 MHz, CDCl3) 141.9, 135.3, 132.4, 126.7, 118.9, 117.7, 111.1.
2-Vinylbenzonitrile (3l)1
A colorless oil, yield: 55.9 mg, 87%; Rf = 0.48 (PE: EtOAc 25:1); 1H-NMR (600 MHz, CDCl3) 5.53 (d, 1 H, J = 11.0 Hz), 5.95 (d, 1 H, J = 17.4 Hz), 7.07 (dd, 1 H, J
3S
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= 11.0, 17.4 Hz), 7.34 (t, 1 H, J = 7.7 Hz), 7.56 (t, 1 H, J = 7.7Hz), 7.62 (d, 1 H, J = 7.7 Hz), 7.67 (d, 1 H, J = 7.7 Hz). 13C-NMR (151 MHz, CDCl3) 140.6, 132.9, 132.8, 132.7, 127.9, 125.4, 118.9, 117.7, 111.1.
1-Nitro-4-vinylbenzene (3m)1
A yellow oil, yield: 65.3 mg, 88%; Rf = 0.33 (PE: EtOAc 25:1); 1H-NMR (600 MHz, CDCl3) 5.41 (d, 1 H, J = 10.9 Hz), 5.84 (d, 1 H, J = 17.6 Hz), 6.69 (dd, 1 H, J = 10.9, 17.6 Hz), 7.44 (d, 2 H, J = 8.8 Hz), 8.09 (d, 2 H, J = 8.8 Hz). 13C-NMR (151 MHz, CDCl3) 147.1, 143.8, 134.9, 126.8, 123.9, 118.6,
1-Nitro-2-vinylbenzene (3n)5
A yellow oil, yield: 66.1 mg, 89%; Rf = 0.31 (PE: EtOAc 25:1); 1H-NMR (600 MHz, CDCl3) 5.48 (d, 1 H, J = 11.0 Hz), 5.75 (d, 1 H, J = 17.3 Hz), 7.17 (dd, 1 H, J = 11.0, 17.3 Hz), 7.38-7.45 (m, 1 H), 7.56-7.60 (m, 1 H), 7.63 (d, 1 H, J = 7.8 Hz), 7.92 (d, 1H, J = 8.2 Hz). 13C-NMR (151 MHz, CDCl3) 147.8, 133.3, 133.1, 132.4, 128.5, 128.3, 124.4, 118.9.
1-Nitro-3-vinylbenzene (3o)6
A yellow oil, yield: 65.4 mg, 88%; Rf = 0.10 (PE); 1H-NMR (600 MHz, CDCl3) 5.44 (d, 1 H, J = 10.9 Hz), 5.90 (d, 1 H, J = 17.6 Hz), 6.76 (dd, 1 H, J = 10.9, 17.6 Hz), 7.49 (t, 1 H, J = 7.9 Hz),7.71 (d, 1 H, J = 7.9 Hz), 8.10 (d, 1 H, J = 7.9 Hz), 8.24 (s, 1 H). 13C-NMR (151 MHz, CDCl3) 148.5, 139.2, 134.7, 132.1, 129.4, 122.4, 120.8, 117.0.
Phenyl(4-vinylphenyl)methanone (3p)7
A pale yellow oil, yield: 91.0 mg, 87%; Rf = 0.12 (PE: EtOAc 25:1); 1H-NMR (600 MHz, CDCl3) 5.38 (d, 1 H, J = 10.9 Hz), 5.87 (d, 1 H, J = 17.6 Hz), 6.76 (dd, 1 H, J = 10.9, 17.6 Hz), 7.44-7.51 (m, 4 H), 7.54-7.59 (m, 1 H), 7.76-7.80 (m, 4 H). 13C-NMR (151 MHz, CDCl3) 196.1, 141.5, 137.7, 136.6, 136.0, 132.3, 130.5, 129.9, 128.3, 126.0, 116.6.
ACKNOWLEDGEMENT
We thank the National Natural Science Foundation of China for their financial support of our program (Grant No. 21272170)
REFERENCES
(1) Smith, C. R.; RajanBabu, T. V. Tetrahedron 2010, 66, 1102‐1110.
(2) Iwasaki, T.; Miyata, Y.; Akimoto, R.; Fujii, Y.; Kuniyasu, H.; Kambe, N. J Am Chem Soc 2014,
136, 9260‐9263.
(3) Wienhofer, G.; Westerhaus, F. A.; Jagadeesh, R. V.; Junge, K.; Junge, H.; Beller, M. Chem
Commun 2012, 48, 4827‐4827‐4829.
(4) Chou, T. S.; Hung, S. C.; Tso, H. H. The Journal of Organic Chemistry 1987, 52, 3394‐3399.
(5) Joucla, L.; Cusati, G.; Pinel, C.; Djakovitch, L. Tetrahedron Lett 2008, 49, 4738‐4741.
(6) Lee, P. H.; Lee, S. W.; Seomoon, D. Org Lett 2003, 5, 4963‐4966.
4S
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(7) Alacid, E.; Nájera, C. The Journal of Organic Chemistry 2009, 74, 8191‐8150.
5S
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P
OH
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1d
6S
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ppm (t1)-100102030405060708090100110120130140150160170180190200210
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P
OH
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ppm (t1)-200-150-100-50050100
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31P-NMR (162 MHz, CDCl3)
P
OH
F4B-
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8S
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ppm (t1)0.01.02.03.04.05.06.07.08.09.0
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9S
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ppm (t1)-100102030405060708090100110120130140150160170180190200210
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ppm (t1)-100102030405060708090100110120130140150160170180190200210
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3e
17S
![Page 18: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/18.jpg)
ppm (t1)050100150200
137.
113
6.5
126.
4
113.
8
77.3
77.1
76.8
13C-NMR ︵151 MHz, CDCl3 ︶
3e
18S
![Page 19: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/19.jpg)
ppm (t1)-1.00.01.02.03.04.05.06.07.08.09.0
7.49
17.
472
7.40
97.
391
7.37
2
7.32
17.
302
7.28
4
6.90
26.
876
6.86
36.
837
6.66
26.
635
6.62
26.
610
6.59
36.
584
6.56
76.
542
5.43
5
5.39
2
5.26
75.
242
1.001.02
1.98
0.98
1.032.021.95
1H-NMR ︵400 MHz, CDCl3 ︶
3f
19S
![Page 20: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/20.jpg)
ppm (t1)-100102030405060708090100110120130140150160170180190200210
137.
213
7.2
132.
9
129.
6
128.
6
127.
6
126.
4
117.
6
77.3
77.0
76.7
13C-NMR ︵100 MHz, CDCl3 ︶
3f
20S
![Page 21: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/21.jpg)
ppm (t1)-1.00.01.02.03.04.05.06.07.08.09.0
7.40
57.
388
7.38
47.
370
7.36
57.
357
7.34
97.
337
7.32
77.
321
7.28
26.
693
6.66
66.
650
6.62
3
5.33
6
5.26
35.
250
5.23
95.
206
1.00
5.10
1.033.09
1H-NMR ︵400 MHz, CDCl3 ︶
3g
21S
![Page 22: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/22.jpg)
ppm (t1)110.0112.0114.0116.0118.0120.0122.0124.0126.0128.0130.0132.0134.0136.0138.0140.0142.0144.0146.0148.0150.0152.0154.0
148.
3
139.
7
138.
2
128.
312
8.1
127.
5
117.
1
116.
8
13C-NMR ︵100 MHz, CDCl3 ︶
3g
22S
![Page 23: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/23.jpg)
ppm (t1)-1.00.01.02.03.04.05.06.07.08.09.0
7.43
97.
425
7.26
17.
246
6.66
16.
643
6.63
16.
613
5.74
15.
712
5.27
35.
255
1.00
0.97
0.99
2.021.94
1H-NMR (600 MHz, CDCl3)
Br
3h
23S
![Page 24: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/24.jpg)
ppm (t1)050100150200
136.
513
5.8
131.
712
7.8
121.
6
114.
6
77.3
77.1
76.9
13C-NMR (151 MHz, CDCl3)
Br
3h
24S
![Page 25: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/25.jpg)
ppm (t1)-1.00.01.02.03.04.05.06.07.08.09.0
7.37
67.
371
7.35
57.
334
7.31
87.
313
6.73
86.
711
6.69
46.
667
5.78
0
5.73
6
5.31
75.
289
1.00
1.00
0.97
3.91
1H-NMR (400 MHz, CDCl3)
Cl
3i
25S
![Page 26: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/26.jpg)
ppm (t1)-100102030405060708090100110120130140150160170180190200210
136.
113
5.7
133.
5
128.
7
127.
4
114.
5
77.3
77.0
76.7
13C-NMR (100 MHz, CDCl3)
Cl
3i
26S
![Page 27: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/27.jpg)
ppm (t1)-1.00.01.02.03.04.05.06.07.08.09.0
8.01
27.
991
7.46
87.
447
6.78
46.
757
6.74
06.
713
5.88
4
5.84
0
5.39
35.
366
3.91
2
1.00
1.00
3.05
0.97
2.00
1.95
1H-NMR (400 MHz, CDCl3)
MeOOC
3j
27S
![Page 28: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/28.jpg)
ppm (t1)-100102030405060708090100110120130140150160170180190200210
166.
8
141.
9
136.
012
9.9
129.
3
126.
1
116.
4
77.4
77.1
76.8
52.0
13C-NMR (100 MHz, CDCl3)
MeOOC
3j
28S
![Page 29: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/29.jpg)
ppm (t1)-1.00.01.02.03.04.05.06.07.08.09.0
7.62
27.
608
7.49
37.
480
6.75
36.
735
6.72
46.
706
5.89
45.
865
5.46
05.
442
1.00
1.01
0.97
1.922.19
1H-NMR (CDCl3, 600 MHz)
NC
3k
29S
![Page 30: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/30.jpg)
ppm (t1)050100150200
141.
9
135.
4
132.
412
6.8
118.
9
117.
8
111.
1
77.3
77.0
76.8
13C-NMR (151 MHz, CDCl3)
NC
3k
30S
![Page 31: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/31.jpg)
ppm (t1)-1.00.01.02.03.04.05.06.07.08.09.0
7.67
47.
661
7.62
37.
610
7.56
87.
555
7.54
27.
351
7.33
87.
326
7.26
87.
094
7.07
57.
065
7.04
6
5.96
05.
931
5.54
15.
523
1.00
0.98
0.95
0.97
0.951.010.93
1H-NMR (600 MHz, CDCl3)
CN
3l
31S
![Page 32: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/32.jpg)
ppm (t1)-100102030405060708090100110120130140150160170180190200210
140.
6
132.
913
2.9
132.
8
128.
012
5.4
118.
9
117.
8
111.
1
77.3
77.1
76.9
13C-NMR (151 MH, CDCl3)
CN
3l
32S
![Page 33: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/33.jpg)
ppm (t1)-1.00.01.02.03.04.05.06.07.08.09.0
8.09
58.
080
7.44
97.
435
6.71
26.
694
6.68
36.
665
5.85
55.
826
5.41
95.
401
1.00
1.01
1.00
2.00
2.01
1H-NMR (600 MHz, CDCl3)
O2N
3m
33S
![Page 34: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/34.jpg)
ppm (t1)050100150200
147.
2
143.
8
135.
0
126.
8
123.
9
118.
6
77.3
77.1
76.9
13C-NMR (151 MHz, CDCl3)
O2N
3m
34S
![Page 35: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/35.jpg)
ppm (t1)-1.00.01.02.03.04.05.06.07.08.09.0
7.92
77.
914
7.63
37.
620
7.59
37.
580
7.56
7
7.42
37.
421
7.41
07.
398
7.19
37.
174
7.16
47.
146
5.76
15.
732
5.49
25.
473
1.00
1.00
0.97
0.99
0.98
0.980.98
1H-NMR (600 MHz, CDCl3)
NO2
3n
35S
![Page 36: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/36.jpg)
ppm (t1)050100150200
147.
9
133.
313
3.1
132.
512
8.5
128.
412
4.4
119.
0
77.3
77.1
76.9
13C-NMR (600 MHz, CDCl3)
NO2
3n
36S
![Page 37: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/37.jpg)
ppm (t1)-1.00.01.02.03.04.05.06.07.08.09.0
8.24
0
8.10
38.
089
7.71
27.
699
7.50
87.
495
7.48
2
6.78
86.
769
6.75
86.
740
5.91
05.
881
5.45
25.
434
1.00
0.97
0.95
0.95
0.96
0.900.93
1H-NMR (600 MHz, CDCl3)
O2N
3o
37S
![Page 38: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/38.jpg)
(t1)-100102030405060708090100110120130140150160170180190200210
148.
6
139.
2
134.
7
132.
1
129.
5
122.
4
120.
911
7.1
77.3
77.1
76.9
13C-NMR (151 MHz, CDCl3)
O2N
3o
38S
![Page 39: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/39.jpg)
ppm (t1)-1.00.01.02.03.04.05.06.07.08.09.0
7.78
67.
779
7.77
47.
772
7.76
57.
573
7.56
17.
548
7.53
6
7.49
27.
479
7.47
27.
459
7.44
7
7.24
8
6.78
56.
767
6.75
66.
738
5.88
75.
858
5.39
45.
375
1.00
1.02
1.00
1.104.09
4.04
1H-NMR (600 MHz, CDCl3)
O
3p
39S
![Page 40: Huang WittigOlefinatnUsingPh3PCH2OH SIExp...EXPERIMENTAL Tricyclohexyl(hydroxymethyl)phosphonium tetrafluoroborate (1d) A solution of HBF4 in water (40 w%, 11.152 g, 0.05 mol) was](https://reader033.vdocument.in/reader033/viewer/2022041512/5e28f448fcad891015743840/html5/thumbnails/40.jpg)
ppm (t1)-100102030405060708090100110120130140150160170180190200210
196.
1
141.
613
7.8
136.
713
6.0
132.
4
130.
613
0.0
128.
312
6.1
116.
6
77.4
77.1
76.9
13C-NMR (151 MHz, CDCl3)
O
3p
40S