Efficient Bromination of Olefins, Alkynes, and Ketones ... · Typical procedure for dibromination...
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S1 Electronic Supplementary Information: Efficient Bromination of Olefins, Alkynes, and Ketones with Dimethyl Sulfoxide and Hydrobromic Acid Song Song, Xinwei Li, Xiang Sun, Yizhi Yuan and Ning Jiao* Tables of Contents: (A) General Remarks.................................................................................................S2 (B) Experimental Procedure and Analytical Data of Products..........................S2 (C) References.…………………………………………………………...………...S10 (D) 1 H NMR and 13 C NMR Spectra of Products………………………………...S11 Electronic Supplementary Material (ESI) for Green Chemistry. This journal is © The Royal Society of Chemistry 2015
Transcript of Efficient Bromination of Olefins, Alkynes, and Ketones ... · Typical procedure for dibromination...
S1
Electronic Supplementary Information:
Efficient Bromination of Olefins, Alkynes, and Ketones with
Dimethyl Sulfoxide and Hydrobromic Acid
Song Song, Xinwei Li, Xiang Sun, Yizhi Yuan and Ning Jiao*
Tables of Contents:
(A) General Remarks.................................................................................................S2
(B) Experimental Procedure and Analytical Data of Products..........................S2
(C) References.…………………………………………………………...………...S10
(D) 1H NMR and 13C NMR Spectra of Products………………………………...S11
Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2015
S2
(A) General Remarks
All commercially available compounds were purchased from Sigma-Aldrich, Alfa-
Aesar, Acros, Beijing Ouhe and Beijing Chemical Works, Ltd. Unless otherwise
noted, materials obtained from commercial suppliers were used without further
purification. Analysis of crude reaction mixture was done on an Agilent 7890 GC
System with an Agilent 5975 Mass Selective Detector. Products were purified by
flash chromatography on silica gel. 1H-NMR spectra were recorded on Bruker
AVANCE III-400 spectrometers. Chemical shifts (in ppm) were referenced TMS in
CDCl3 (0 ppm). 13C-NMR spectra were obtained by using the same NMR
spectrometers and were calibrated with CDCl3 (δ = 77.00 ppm). Mass spectra were
recorded using a PE SCLEX QSTAR spectrometer. High resolution mass spectra
were obtained with a Bruker APEX IV Fourier transform ion cyclotron resonance
mass spectrometer.
(B) Experimental Procedure and Characterization Data of Products
Typical procedure for dibromination of olefins and alkynes: Olefin 1 or alkyne 6 (0.5 mmol) and DMSO (43 μL, 0.6 mmol) were dissolved in EA (2 mL). Aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) was added to the solution at 60 oC and the mixture were stirred for 0.5 h under air at that temperature. After cooling down to room temperature and concentrating in vacuum, the residue was purified by chromatography on silica gel (petroleum ether/ethyl acetate) to afford the dibrominated product 3 or 7.
2-(1,2-Dibromoethyl)naphthalene (3a)[1]
The reaction of 2-vinylnaphthalene 1a (77.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 125.4 mg (80%) of 3a as a white solid. 1H NMR (400 MHz, CDCl3) δ 7.89–7.83 (m, 4H), 7.53–7.50 (m, 3H), 5.33 (dd,
J = 8.8, 7.2 Hz, 1H), 4.16–4.13 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 135.7, 133.5, 132.9, 129.1, 128.2, 127.8, 127.4, 126.9, 126.7, 124.4, 51.3, 34.8.
(1,2-Dibromoethyl)benzene (3b)[2]
The reaction of styrene 1b (52.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in
Br
Br
3a
Br
Br
3b
S3
EA (2 mL) at 60 oC for 0.5 h, affords 93.6 mg (71%) of 3b as a white solid. 1H NMR (400 MHz, CDCl3) δ 7.38–7.31 (m, 5H), 5.13 (dd, J = 10.4, 5.6 Hz, 1H), 4.08–3.98 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 138.6, 129.1, 128.8, 127.6, 50.9, 35.0.
1-Bromo-4-(1,2-dibromoethyl)benzene (3c)[3]
The reaction of 1-bromo-4-vinylbenzene 1c (91.5 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 130.1 mg (76%) of 3c as a white solid. 1H NMR (CDCl3, 400 MHz): δ 7.52 (d, J = 8.8 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 5.09
(dd, J = 11.2, 5.2 Hz, 1H), 4.06 (dd, J = 10.2, 5.0 Hz, 1H), 3.99–3.94 (m, 1H). 13C NMR (CDCl3, 100 MHz): δ 137.7, 132.1, 129.3, 123.2, 49.5, 34.6.
1-Chloro-4-(1,2-dibromoethyl)benzene (3d)[4]
The reaction of 1-chloro-4-vinylbenzene 1d (69.3 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 110.5 mg (74%) of 3d as a white solid. 1H NMR (CDCl3, 400 MHz): δ 7.38–7.33 (m, 4H), 5.10 (dd, J = 11.0, 5.0 Hz, 1H),
4.06 (dd, J = 10.4, 5.2 Hz, 1H), 3.99–3.94 (m, 1H). 13C NMR (CDCl3, 100 MHz): δ 137.1, 135.0, 129.1, 129.0, 49.5, 34.6.
1-(1,2-Dibromoethyl)-4-methylbenzene (3e)[4] The reaction of 1-methyl-4-vinylbenzene 1e (59.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 109.7 mg (79%) of 3e as a white solid. 1H NMR (CDCl3, 400 MHz): δ 7.29 (d, J = 8.0 Hz, 2H), 7.19 (d, J = 8.0 Hz, 2H),
5.14 (dd, J = 10.6, 5.2 Hz, 1H), 4.07 (dd, J = 10.4, 5.6 Hz, 1H), 4.05–3.99 (m, 1H), 2.36 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 139.2, 135.6, 129.6, 127.5, 51.0, 35.0, 21.3.
4-(1,2-Dibromoethyl)-1,1'-biphenyl (3f)[5]
The reaction of 4-vinyl-1,1'-biphenyl 1f (90.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 137.7 mg (81%) of 3f as a white solid. 1H NMR (400 MHz, CDCl3) δ 7.65–7.63 (m, 4H), 7.52–7.41 (m, 5H), 5.25 (dd, J =
8.7, 5.9 Hz, 1H), 4.16–4.07 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 142.0, 140.1, 137.4, 128.8, 128.0, 127.6, 127.5, 127.1, 50.7, 34.8.
1-(1,2-Dibromoethyl)-3-nitrobenzene (3g)[6]
Br
Br
3cBr
Br
Br
3dCl
Br
Br
3eMe
Br
Br
3fPh
S4
The reaction of 1-nitro-3-vinylbenzene 1g (74.6 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 117.4 mg (76%) of 3g as a yellow solid. 1H NMR (CDCl3, 400 MHz): δ 8.29 (t, J = 1.8 Hz, 1H), 8.23–8.21 (m,
1H), 7.75 (d, J = 7.6 Hz, 1H), 7.59 (t, J = 8.0 Hz, 1H), 5.19 (dd, J = 11.2, 4.8 Hz, 1H), 4.11 (dd, J = 10.6, 5.0 Hz, 1H), 4.04–3.98 (m, 1H). 13C NMR (CDCl3, 100 MHz): δ 148.4, 140.8, 133.7, 129.9, 124.0, 122.8, 48.0, 34.1.
1-(1,2-Dibromoethyl)-3-methylbenzene (3h)[7]
The reaction of 1-methyl-3-vinylbenzene 1h (59.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 104.0 mg (75%) of 3h as a white solid. 1H NMR (CDCl3, 400 MHz): δ 7.29–7.25 (m, 1H), 7.20–7.19 (m, 2H), 7.15 (d, J =
7.2 Hz, 1H), 5.11 (dd, J = 10.4, 5.6 Hz, 1H), 4.08–3.99 (m, 2H), 2.37 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 138.6, 138.5, 130.0, 128.7, 128.3, 124.7, 51.1, 35.0, 21.4.
1-Chloro-2-(1,2-dibromoethyl)benzene (3i) The reaction of 1-chloro-2-vinylbenzene 1i (69.3 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 110.3 mg (74%) of 3i as a white solid. 1H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 7.6 Hz, 1H), 7.39 (d, J = 7.8 Hz, 1H), 7.33 (t, J = 7.4 Hz, 1H), 7.27
(t, J = 8.2 Hz, 1H), 5.70 (t, J = 7.7 Hz, 1H), 4.12–4.07 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 136.0, 133.9, 130.1, 130.0, 128.3, 127.5, 45.5, 33.6.
(1,2-Dibromopropan-2-yl)benzene (3j)[8] The reaction of -methylstryene 1j (59.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 101.0 mg (73%) of 3j as colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.56–7.54 (m, 2H), 7.38–7.30 (m, 3H), 4.35 (d, J = 10.2 Hz, 1H), 4.13 (d, J = 10.2 Hz, 1H), 2.31 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 141.9, 128.5, 128.4, 126.5, 63.7,
43.5, 29.9.
(1,2-Dibromopropyl)benzene (3k)[8]
The reaction of (E)--methylstryene 1k (59.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 108.4 mg (78%) of 3k as a white solid. 1H NMR (400 MHz, CDCl3) δ 7.41–7.32 (m, 5H), 5.05 (d, J = 10.4 Hz, 1H), 4.63–4.59 (m, 1H), 2.05(d, J = 6.4 Hz, 3H).
13C NMR (100 MHz, CDCl3) δ 140.6, 128.8, 126.6, 127.7, 59.1, 51.1, 25.8.
1,2-Dibromo-2,3-dihydro-1H-indene (3l)[9]
Br
Br
3j
Br
Br
3k
Br
Br
3h
Me
Br
Br
3i
Cl
Br
Br
3g
O2N
S5
The reaction of indene 1l (58.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 101.2 mg (73%) of 3l as colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.46–7.44 (m, 1H), 7.34–7.27 (m, 3H), 5.62 (s, 1H), 4.86 (dt, J = 5.2, 1.2 Hz, 1H), 3.79 (dd, J
= 17.5, 5.2 Hz, 1H), 3.25 (d, J = 17.5 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 140.5, 140.5, 129.7, 127.9, 125.7, 125.4, 57.7, 54.4, 41.4.
1,2-Dibromo-1,2,3,4-tetrahydronaphthalene (3m)[10]
The reaction of 1,2-dihydronaphthalene 1m (65.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 112.4 mg (78%) of 3m as colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.29 (dd, J = 7.5, 1.4 Hz, 1H), 7.25–7.16 (m, 2H), 7.11 (d, J = 7.5 Hz, 1H),
5.64–5.63 (m, 1H), 4.93–4.90 (m, 1H), 3.25 (ddd, J = 17.7, 11.9, 6.2 Hz, 1H), 2.91 (dd, J = 17.4, 6.0 Hz, 1H), 2.84–2.76 (m, 1H), 2.20–2.13 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 134.4, 132.8, 131.2, 129.2, 128.9, 126.6, 51.52, 51.49, 25.1, 24.4.
5,6-Dibromo-6,7,8,9-tetrahydro-5H-benzo[7]annulene (3n)[11]
The reaction of 6,7-dihydro-5H-benzo[7]annulene 1n (72.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 129.2 mg (85%) of 3n as colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.25–7.12 (m, 4H), 5.49 (d, J = 5.3 Hz, 1H), 4.88–4.85 (m, 1H), 3.31–3.23 (m, 1H), 3.00–2.92 (m, 1H), 2.80–2.74 (m, 1H), 2.27–2.21
(m, 1H), 1.98–1.91 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 142.9, 136.3, 131.3, 130.9, 129.3, 126.1, 58.4, 54.7, 35.3, 34.6, 22.8.
1,2-Dibromodecane (3o)[8]
The reaction of 1-decene 1o (70.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 141.0 mg (94%) of 3o as colorless oil.
1H NMR (400 MHz, CDCl3) δ 4.20–4.13 (m, 1H), 3.85 (dd, J = 10.2, 4.4 Hz, 1H), 3.63 (t, J = 10.0 Hz, 1H), 2.18–2.09 (m, 1H), 1.83–1.73 (m, 1H), 1.60–1.53 (m, 1H), 1.45–1.28 (m, 11H), 0.89 (t, J = 6.5 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 53.1, 36.3, 36.0, 31.8, 29.3, 29.1, 28.8, 26.7, 22.6, 14.1.
(2,3-Dibromopropoxy)benzene (3p)[12]
The reaction of (allyloxy)benzene 1p (67.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 119.1 mg (81%) of 3p as colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.32–7.28 (m, 2H), 7.00 (t, J = 7.4 Hz, 1H),
Br
Br
3o
O
Br
Br
3p
Br
Br
3l
Br
Br
3m
BrBr
3n
S6
6.95–6.92 (m, 2H), 4.44–4.33 (m, 3H), 3.95–3.86 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 157.9, 129.6, 121.6, 114.8, 69.0, 47.7, 32.7.
(3,4-Dibromobutyl)benzene (3q)[13]
The reaction of (allyloxy)benzene 1q (66.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 131.5 mg (90%) of 3q as colorless oil. 1H NMR (CDCl3, 400 MHz): δ 7.29–7.21 (m, 5H) ,4.09 (m, 1H), 3.83–3.81 (m,
1H), 3.64–3.59 (m, 1H), 2.92–2.90 (m, 1H), 2.75–2.73 (m, 1H), 2.46–2.45 (m, 1H), 2.07–2.06 (m, 1H). 13C NMR (CDCl3, 100 MHz): δ 140.2, 128.51, 128.47, 126.2, 52.0, 37.6, 36.2, 32.9.
(2,3-Dibromo-2-methylpropyl)benzene (3r)[14]
The reaction of (2-methylallyl)benzene 1r (66.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 121.7 mg (83%) of 3r as colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.40–
7.31 (m, 5H), 3.81 (d, J = 10.2 Hz, 1H), 3.74 (d, J = 10.2 Hz, 1H), 3.33–3.21 (m, 2H), 1.91 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 136.0, 130.9, 128.0, 127.3, 66.6, 47.1, 42.2, 30.7.
1,2-Dibromocyclohexane (3s)[15]
The reaction of cyclohexene 1s (41.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 100.5 mg (83%) of 3s as colorless oil. 1H NMR (CDCl3, 400 MHz): δ 4.46 (s, 2H), 2.49–2.43 (m, 2H), 1.91–1.79
(m, 4H), 1.55–1.50 (m, 2H). 13C NMR (CDCl3, 100 MHz): δ 55.2, 31.9, 22.4.
6,7-Dibromodecahydro-1,4-methanonaphthalene (3t)[16]
The reaction of octahydro-1,4-methanonaphthalene 1t (74.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 135.5 mg (88%) of 3t as a white solid. 1H NMR (400 MHz, CDCl3) δ 4.70 (dt, J = 6.3, 3.1 Hz, 1H), 4.34–4.27 (m, 1H), 2.02
(dt, J = 12.9, 5.0 Hz, 1H), 1.96–1.87 (m, 5H), 1.72–1.66 (m, 1H), 1.60–1.50 (m, 4H), 1.29–1.19 (m, 2H), 1.12 (d, J = 10.4 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 56.8, 54.8, 42.8, 41.9, 41.3, 36.4, 36.1, 33.5, 33.2, 29.3, 29.2.
1,2-Dibromocyclooctane (3u)[17]
The reaction of (Z)-cyclooctene 1u (55.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 109.3 mg (81%) of 3u as colorless oil. 1H NMR (CDCl3, 400 MHz): δ 4.61–4.56 (m, 2H), 2.45–2.38 (m, 2H),
Br
Br3r
Br
Br3s
Br
Br
3t
Br
Br
3q
Br Br
3u
S7
2.14–2.05 (m, 2H) ,1.89–1.82 (m, 2H), 1.71–1.55 (m, 4H), 1.52–1.45 (m, 2H). 13C NMR (CDCl3, 100 MHz): δ 61.5, 33.2, 25.9, 25.4.
1,2-Dibromo-1-methylcyclohexane (3v)[18]
The reaction of 1-methylcyclohexene 1v (48.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 0.5 h, affords 107.7 mg (84%) of 3v as colorless oil. 1H NMR (400 MHz, CDCl3) δ 4.65 (s, 1H), 2.58–2.50 (m, 1H), 2.12–2.05 (m, 1H), 2.02–1.93 (m, 5H), 1.86–1.75 (m, 2H), 1.68–1.53 (m, 2H).
13C NMR (100 MHz, CDCl3) δ 70.7, 61.9, 37.6, 34.0, 32.5, 22.7, 20.7.
3-(Bromomethyl)-3-methylisobenzofuran-1(3H)-one (5a) The reaction of 2-(prop-1-en-2-yl)benzoic acid 4a (81.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 1 h, affords 105.4 mg (87%) of 5a as a white solid. 1H NMR (400 MHz, CDCl3) δ 7.82 (d, J = 7.6 Hz, 1H), 7.64 (t, J = 7.3 Hz, 1H), 7.50 (t, J = 7.4 Hz,
1H), 7.45 (d, J = 7.6 Hz, 1H), 3.68 (d, J = 11.1 Hz, 1H), 3.65 (d, J = 11.1 Hz, 1H), 1.75 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 168.9, 151.1, 134.3, 129.8, 126.2, 125.8, 121.4, 84.5, 37.8, 24.2. HRMS (ESI) Calcd for [C10H10BrO2, M + H]+: 240.9859, Found: 240.9863.
3-(Bromomethyl)-3-phenylisobenzofuran-1(3H)-one (5b) The reaction of 2-(1-phenylvinyl)benzoic acid 4b (112.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 1 h, affords 148.2 mg (98%) of 5b as a white solid. 1H NMR (400 MHz, CDCl3) δ 7.93 (d, J = 7.6 Hz, 1H), 7.76–7.72 (m, 1H), 7.67 (d, J = 7.7 Hz, 1H), 7.61–7.56 (m, 3H), 7.42–7.36 (m, 3H), 4.15 (d, J =
11.4 Hz, 1H), 4.09 (d, J = 11.4 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 168.8, 149.8, 137.5, 134.3, 129.9, 129.1, 129.0, 126.5, 126.0, 125.4, 122.5, 87.2, 37.9. HRMS (ESI) Calcd for [C15H12BrO2, M + H]+: 303.0015, Found: 303.0018.
(E)-(1,2-Dibromoprop-1-en-1-yl)benzene (7a)[14]
The reaction of 1-phenyl-1-propyne 6a (58.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 8 h, affords 118.7 mg (86%) of 7a as colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.38–7.32 (m, 5H), 2.62 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 140.8, 129.1, 128.6, 128.2, 117.2, 116.8, 29.3.
(E)-(1,2-Dibromohex-1-en-1-yl)benzene (7b)[19]
The reaction of hex-1-yn-1-ylbenzene 6b (79.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 8 h, affords 108.3 mg (68%) of 7b as colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.38–7.23 (m, 5H), 2.85 (t, J
BrMe
Br3v
Ph
MeBr
Br
7a
S8
= 7.6 Hz, 2H), 1.72–1.64 (m, 2H), 1.50–1.42 (m, 2H), 0.99 (t, J = 7.6 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 141.0, 129.1, 128.5, 128.2, 123.7, 116.2, 40.8, 29.6, 21.8, 14.0.
(E)-5,6-Dibromodec-5-ene (7c)[20] The reaction of dec-5-yne 6c (69.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 8 h, affords 123.2 mg (83%) of 7c as colorless oil. 1H NMR (400 MHz, CDCl3) δ 2.67 (t, J = 7.4 Hz, 4H), 1.59–1.52 (m, 4H), 1.40–1.31 (m, 4H), 0.94 (t, J = 7.4 Hz, 6H). 13C NMR (100
MHz, CDCl3) δ 121.6, 40.5, 29.6, 21.7, 13.9.
(E)-1-(1,2-Dibromovinyl)-4-methoxybenzene (7d)[20]
The reaction of 1-ethynyl-4-methoxybenzene 6d (66.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 5 h, affords 118.2 mg (81%) of 7d as colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.48 (d, J = 8.4 Hz, 2H), 6.90 (d, J = 8.4 Hz, 2H),
6.73 (s, 1H), 3.83 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 160.2, 130.8, 129.1, 121.5, 113.5, 101.9, 55.3.
(E)-1,2-dibromooct-1-ene (7e)[21]
The reaction of 1-phenyl-1-propyne 6e (55.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 202 mg, 1.2 mmol) in EA (2 mL) at 60 oC for 8 h, affords 86.6 mg (64%) of 7e as colorless oil. 1H NMR (400 MHz, CDCl3) δ 6.40 (s, 1H), 2.59 (t, J = 7.4 Hz, 2H), 1.59–1.55 (m. 2H), 1.36–1.31 (m. 6H), 0.90 (t, J = 6.8 Hz,
3H). 13C NMR (100 MHz, CDCl3) δ 127.0, 102.1, 36.9, 31.5, 28.0, 27.0, 22.5, 14.0.
Typical procedure for bromination of ketones: Ketone 8 (0.5 mmol) and DMSO (43 μL, 0.6 mmol) in EA (2 mL) were added hydrobromic acid (48%, 0.6 mmol) at 60 oC under air. The mixture were stirred at that temperature. After cooling down to room temperature and concentrating in vacuum, the residue was purified by chromatography on silica gel (petroleum ether/ethyl acetate) to afford the brominated product 9.
2-Bromoacetophenone (9a)[22]
The reaction of acetophenone 8a (60.1 mg, 0.5 mmol), DMSO (43 μL, 0.55 mmol), and aqueous hydrobromic acid (48%, 101 mg, 0.6 mmol) in EA (2 mL) at 60 oC for 2 h, affords 72.3 mg (73%) of 9a as a pale yellow solid. 1H NMR (400 MHz, CDCl3) δ 7.99–7.97 (m, 2H), 7.62–7.59 (m, 1H), 7.50–7.47 (m, 2H), 4.45 (s, 2H). 13C NMR (100 MHz,
CDCl3) δ 191.2, 133.9, 133.9, 128.9, 128.8, 30.9.
2-Bromo-1-phenylbutan-1-one (9b)[23]
O
Br
9a
S9
The reaction of butyrophenone 8b (74.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 101 mg, 0.6 mmol) in EA (2 mL) at 60 oC for 6 h, affords 108.0 mg (94%) of 9b as pale yellow oil. 1H NMR (400 MHz, CDCl3) δ 8.02–8.01 (m, 2H), 7.61 (t, J = 7.6 Hz, 1H), 7.50 (t, J = 7.8 Hz, 1H), 5.08 (dd, J =
7.6, 6.4 Hz, 1H), 2.28–2.10 (m, 2H), 1.08 (t, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 193.2, 134.5, 133.6, 128.8, 128.7, 49.0, 26.9, 12.1.
2-Bromo-1-phenylbutan-1-one (9c)[24]
The reaction of isobutyrophenone 8c (74.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 101 mg, 0.6 mmol) in EA (2 mL) at 60 oC for 6 h, affords 102.6 mg (90%) of 9c as colorless oil. 1H NMR (400 MHz, CDCl3) δ 8.15–8.12 (m, 2H), 7.54–7.50 (m, 1H), 7.45–7.42 (m, 1H), 2.04 (s, 6H). 13C NMR (100
MHz, CDCl3) δ 196.9, 134.9, 132.3, 130.0, 128.1, 60.3, 31.5.
(1-Bromocyclohexyl)(phenyl)methanone (9d)[25]
The reaction of cyclohexyl(phenyl)methanone 8d (94.1 mg, 0.5 mmol), DMSO (43 μL, 0.6 mmol), and aqueous hydrobromic acid (48%, 101 mg, 0.6 mmol) in EA (2 mL) at 60 oC for 6 h, affords 122.9 mg (92%) of 9d as colorless oil. 1H NMR (400 MHz, CDCl3) δ 8.09–8.07 (m, 2H), 7.53 (t, J = 7.6 Hz, 1H), 7.43 (t, J = 7.6 Hz,
2H), 2.38–2.32 (m, 2H), 2.22–2.17 (m, 2H), 1.83–1.77 (m, 2H), 1.59–1.52 (m, 3H), 1.41–1.38 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 197.4, 135.8, 132.0, 129.7, 128.1, 67.9, 38.2, 24.9, 23.5.
O
Br
9b
O
Br
9c
OBr
9d
S10
(F) References
[1] Nair, V.; Panicker, S. B.; Augustine, A.; George, T. G.; Thomas, S.; Vairamani, M. Tetrahedron 2001, 57, 7417.
[2] Yu, T.-Y.; Wang, Y.; Hu, X.-Q.; Xu, P.-F. Chem. Commun. 2014, 50, 7817. [3] Das, B.; Srinivas, Y.; Sudhakar, C.; Ravikanth, B. J. Chem. Res. 2008 , 4, 188. [4] MacHarla, A. K.; Chozhiyath N. R.; Nama, N. Tetrahedron Lett. 2012, 53, 1401. [5] Piou, T.; Rovis, T. J. Am. Chem. Soc. 2014, 136, 11292. [6] Wang, Y.-F.; Ton, K. K.; Chiba, S.; Narasaka, K. Org. Lett. 2008, 10, 5019. [7] Qaseer Polish J. Chemistry, 2007, 81, 31. [8] Kikushima, K.; Moriuchi, T.; Hirao, T. Chem. Asian J. 2009, 4, 1213. [9] Austin, R. A.; Lillya, C. P. J. Org. Chem. 1969, 34, 1327. [10] Cagle, Mike D.; Firsan, Sharbil J.; Eisenbraun, E. J. Org. Prep. Proced. Int. 1994,
26, 370. [11] Yildiz, Y. K.; Ozturk, T.; Balci, M. Tetrahedron 1999, 55, 9317. [12] Braddock, D. C.; Cansell, G.; Hermitage, S. A. Synlett 2004, 3, 461. [13] Hernandez-Torres, G.; Tan, B.; Barbas, C. F. Org. Lett. 2012, 14, 1858. [11] Braddock, D. C.; Cansell, G.; Hermitage, S. A. Synlett 2004, 3, 461. [14] Stodulski, M.; Gotzinger, A.; Kohlhepp, S. V.; Gulder, T. Chem. Commun. 2014,
50, 3435. [15] Van Zee, N. J.; Dragojlovic, V. Org. Lett. 2009, 11, 3190. [16] Rye, A. R.; Wege, D. Australia J. Chem. 1974, 27, 1943. [17] Wu, L.; Yin, Z. Eur. J. Inorg. Chem. 2013, 6156. [18] Altona, C.; Buys, H. R.; Hageman, H. J.; Havinga, E. Tetrahedron 1967, 23,
2265. [19] Bianchini, R.; Chiappe, C.; Moro, G. L.; Lenoir, D.; Lemmen, P.; Goldberg, N.
Chem.– Eur. J. 1999, 5, 1570. [20] Xiang, J.; Yuan, R.; Wang, R.; Yi, N.; Lu, L.; Zou, H.; He, W. J. Org. Chem.
2014, 79, 11378 [21] Yonehara, K.; Kamata, K.; Yamaguchi, K.; Mizuno, N. Chem. Commun. 2011,
47, 1692. [19] Zhang, J.; Wang, J.; Qiu, Z.; Wang, Y. Tetrahedron 2011, 67, 6859. [20] Lundin, P. M.; Esquivias, J.; Fu, G. C. Angew. Chem. Int. Ed. 2009, 48, 154. [21] Tada, N.; Ban, K.; Hirashima, S.; Miura, T.; Itoh, A. Org. Biomol. Chem. 2010, 8,
4701. [22] Meneguzzo, E.; Norcini, G.; Li, B. G. Patent: US2011/65962 A1,2011. [23] Patel, A.; Bӧhmdorfer, S.; Hofinger, A.; Netscher, T.; Rosenau, T. Eur. J. Org.
Chem. 2009, 4873.
S11
(G) 1H NMR and 13C NMR Spectra of Products
7
.89
1
7.8
70
7
.85
3
7.8
34
7
.52
7
7.5
18
7
.51
6
7.5
08
7
.50
3
5
.34
7
5.3
30
5
.32
6
5.3
07
4
.15
8
4.1
41
4
.13
6
4.1
34
-0
.00
0
1.0
0
2.0
4
4.1
2
3.0
5
10 8 6 4 2 0 PPM
S12
13
5.7
08
13
3.5
13
13
2.9
13
12
9.0
82
12
8.1
97
12
7.7
71
12
7.4
21
12
6.9
06
12
6.6
77
12
4.3
57
77
.31
6 7
7.0
00
76
.67
6
51
.33
9
34
.78
0
200 150 100 50 0 PPM
S13
7
.38
0
7.3
62
7
.34
1
7.3
22
7
.30
8
5
.14
9
5.1
35
5
.12
3
5.1
09
4
.07
9
4.0
63
4
.05
3
4.0
38
4
.03
5
4.0
30
4
.00
4
3.9
78
-0
.00
0
1.0
0
2.0
8
5.0
4
10 8 6 4 2 0 PPM
Br
Br
3b
S14
13
8.5
68
12
9.1
22
12
8.8
03
12
7.6
10
77
.31
9 7
7.0
00
76
.67
5
50
.85
5
34
.98
8
200 180 160 140 120 100 80 60 40 20 PPM
Br
Br
3b
S15
7
.52
8
7.5
06
7
.29
0
7.2
70
7
.25
8
5
.10
9
5.0
96
5
.08
1
5.0
68
4
.07
7
4.0
64
4
.05
1
4.0
39
3
.99
0
3.9
63
3
.93
6
2.0
0
2.0
1
1.0
1 1.0
4 1
.04
10 8 6 4 2 0 PPM
Br
Br
Br
3c
S16
13
7.6
66
13
2.0
73
12
9.3
13
12
3.1
75
77
.32
5 7
7.0
00
76
.68
6
49
.54
2
34
.57
0
200 150 100 50 0 PPM
Br
Br
Br
3c
S17
7
.37
6
7.3
69
7
.35
4
7.3
49
7
.33
3
7.3
27
7
.25
8
5
.12
4
5.1
11
5
.09
6
5.0
84
4
.08
3
4.0
70
4
.05
7
4.0
44
3
.99
4
3.9
67
3
.94
0
-0
.00
0
1.0
0 1.0
2
4.0
0
1.0
3
10 8 6 4 2 0 PPM
Cl
Br
Br
3d
S18
13
7.1
47
13
4.9
84
12
9.1
06
12
9.0
35
77
.32
5 7
7.0
05
76
.68
6
49
.50
5
34
.63
7
200 150 100 50 0 PPM
Cl
Br
Br
3d
S19
7
.30
3
7.2
83
7
.24
7
7.1
96
7
.17
6
5
.15
6
5.1
43
5
.13
0
5.1
16
4
.09
1
4.0
77
4
.06
5
4.0
51
4
.04
6
4.0
19
3
.99
4
2
.35
5
-0
.00
0
2.0
0 2
.01
0.9
8
1.0
2 1
.05
3.0
5
10 8 6 4 2 0 PPM
Br
Br
3e
S20
13
9.2
31
13
5.6
38
12
9.5
62
12
7.4
91
77
.31
9 7
7.0
00
76
.67
7
51
.01
6
35
.02
6
21
.25
0
200 150 100 50 0 PPM
Br
Br
3e
S21
7
.65
0
7.6
31
7
.51
7
7.4
93
7
.47
0
7.4
26
7
.40
8
5
.26
4
5.2
50
5
.24
3
5.2
28
4
.16
3
4.1
37
4
.12
5
4.0
99
4
.07
3
1.0
0
2.0
4
4.1
0
5.0
7
10 8 6 4 2 0 PPM
Br
Br
3fPh
S22
14
1.9
74
14
0.1
28
13
7.4
45
12
8.7
86
12
8.0
34
12
7.6
29
12
7.4
98
12
7.0
63
77
.32
0 7
7.0
00
76
.68
1
50
.67
8
34
.82
7
200 150 100 50 PPM
Br
Br
3fPh
S23
8
.29
0
8.2
86
8
.28
1
8.2
34
8
.23
2
8.2
29
8
.21
3
8.2
11
8
.20
8
7.7
55
7
.73
6
7.6
09
7
.58
9
7.5
69
7
.26
5
5
.21
3
5.2
01
5
.18
5
5.1
73
4
.13
3
4.1
20
4
.10
6
4.0
94
4
.03
6
4.0
09
3
.98
2
-0
.00
0
1.0
0 1.0
6 1
.03
1.0
1 1
.01
1.0
4 1
.04
10 8 6 4 2 0 PPM
Br
Br
3g
O2N
S24
14
8.4
22
14
0.7
75
13
3.7
37
12
9.9
11
12
3.9
65
12
2.8
11
77
.31
2 7
7.0
00
76
.68
1
47
.97
4
34
.10
4
200 150 100 50 0 PPM
Br
Br
3g
O2N
S25
7
.28
6
7.2
66
7
.24
6
7.2
03
7
.18
6
7.1
59
7
.14
1
5
.12
9
5.1
15
5
.10
3
5.0
89
4
.08
4
4.0
69
4
.05
8
4.0
43
4
.01
7
3.9
91
2
.36
7
0
.00
0
3.0
0
1.0
1
2.0
7
0.9
8 2
.04
1.1
7
10 8 6 4 2 0 PPM
Br
Br
3h
S26
13
8.6
02
13
8.4
69
13
0.0
14
12
8.7
11
12
8.2
67
12
4.6
50
77
.31
8 7
7.0
00
76
.67
6
51
.08
7
34
.99
1
21
.37
8
200 150 100 50 0 PPM
Br
Br
3h
S27
7
.53
1
7.5
12
7
.40
2
7.3
83
7
.34
8
7.3
29
7
.31
1
7.2
89
7
.27
0
7.2
48
5
.72
4
5.7
06
5
.68
6
4
.11
7
4.0
90
4
.06
9
0
.00
0
1.0
0
2.1
5
1.0
3 1
.01
1.0
5 1
.08
10 8 6 4 2 0 PPM
Br
Br
3i
Cl
S28
13
5.9
74
13
3.8
59
13
0.0
95
13
0.0
16
12
8.2
56
12
7.5
21
77
.32
9 7
7.0
00
76
.68
5
45
.52
9
33
.55
1
200 150 100 50 0 PPM
Br
Br
3i
Cl
S29
7
.56
1
7.5
57
7
.55
2
7.5
43
7
.53
9
7.5
37
7
.37
8
7.3
75
7
.37
0
7.3
58
7
.35
3
7.3
42
7
.33
8
7.3
22
7
.31
8
7.3
15
7
.30
6
7.3
00
4
.36
1
4.3
36
4
.14
0
4.1
14
2
.31
2
0
.00
0
3.0
0
1.0
0
1.1
1
2.0
0
3.0
4
10 8 6 4 2 0 PPM
Br
Br
3j
S30
14
1.8
62
12
8.4
69
12
8.4
14
12
6.5
24
77
.32
2 7
7.0
00
76
.68
7
63
.70
5
43
.47
8
29
.87
5
150 100 50 0PPM
Br
Br
3j
S31
7
.41
0
7.4
05
7
.38
9
7.3
87
7
.36
9
7.3
67
7
.35
2
7.3
48
7
.34
5
7.3
40
7
.33
4
7.3
24
7
.26
0
5
.06
2
5.0
36
4
.63
0
4.6
20
4
.61
3
4.6
04
4
.59
7
4.5
88
2
.05
9
2.0
43
1.0
0
1.0
2
3.1
2
5.0
6
10 8 6 4 2 0 PPM
S32
14
0.5
58
12
8.7
75
12
8.6
23
12
7.7
00
77
.31
2 7
7.0
00
76
.68
4
59
.13
8
51
.12
6
25
.78
9
200 150 100 50 0 PPM
S33
7
.46
3
7.4
59
7
.45
2
7.4
45
7
.44
0
7.3
38
7
.33
4
7.3
21
7
.31
6
7.3
09
7
.30
5
7.3
00
7
.29
1
7.2
80
7
.26
6
5.6
19
4
.87
0
4.8
67
4
.86
4
4.8
57
4
.85
4
4.8
51
3
.81
6
3.8
03
3
.77
2
3.7
59
3
.26
9
3.2
25
-0
.00
0
1.0
1
1.0
5
1.0
6
1.0
0
1.0
1
3.0
5
10 8 6 4 2 0 PPM
S34
14
0.5
33
14
0.5
21
12
9.6
60
12
7.9
16
12
5.6
87
12
5.3
64
77
.31
2 7
7.0
00
76
.68
2
57
.70
5
54
.39
9
41
.40
3
200 150 100 50 0 PPM
S35
7
.30
5
7.3
02
7
.28
6
7.2
82
7
.24
5
7.2
42
7
.22
7
7.2
23
7
.21
5
7.2
09
7
.20
5
7.1
92
7
.17
5
7.1
57
7
.11
7
7.0
98
5
.64
0
5.6
35
5
.63
1
4
.92
6
4.9
19
4
.91
5
4.9
10
4
.90
4
3
.29
6
3.2
80
3
.26
6
3.2
51
3
.23
7
3.2
22
3
.20
7
2.9
41
2
.92
7
2.8
98
2
.88
2
2.8
43
2
.83
7
2.8
28
2
.82
2
2.8
13
2
.80
7
2.8
01
2
.79
2
2.7
86
2
.77
7
2.7
71
2
.76
2
2.7
56
2
.19
9
2.1
95
2
.19
0
2.1
85
2
.18
0
2.1
74
2
.17
0
2.1
65
2
.16
2
2.1
59
2
.15
3
2.1
48
2
.14
3
2.1
38
2
.13
3
0.0
00
1.0
0
1.0
1
1.0
6
1.0
6 1
.06
1.0
6
1.0
1 2
.11
0.9
8
1.0
0
8 7 6 5 4 3 2 1 0 PPM
S36
13
4.3
95
13
2.7
90
13
1.1
83
12
9.1
52
12
8.8
58
12
6.6
15
77
.31
3 7
7.0
00
76
.68
7
51
.52
2 5
1.4
92
25
.09
8 2
4.4
27
200 150 100 50 PPM
S37
7
.22
9
7.2
24
7
.21
7
7.2
11
7
.20
6
7.1
83
7
.16
8
7.1
64
7
.15
8
7.1
40
7
.12
2
5
.49
5
5.4
82
4
.88
3
4.8
75
4
.87
1
4.8
66
4
.86
3
4.8
52
3
.30
5
3.2
97
3
.27
6
3.2
69
3
.25
9
3.2
46
3
.24
1
3.2
32
3
.00
1
2.9
94
2
.98
9
2.9
83
2
.97
9
2.9
72
2
.96
2
2.9
55
2
.94
4
2.9
39
2
.93
4
2.9
23
2
.91
6
2.7
97
2
.79
4
2.7
88
2
.78
4
2.7
78
2
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4
2.7
56
2
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1
2.2
74
2
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4
2.2
60
2
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7
2.2
47
2
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6
2.2
29
2
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2.2
22
2
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9
2.2
16
2
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2
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1
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6
1.9
70
19
64
1.0
0
0.9
9
1.0
2
1.0
3
1.0
4
1.0
3
2.0
5
4.1
4
8 7 6 5 4 3 2 1 PPM
S38
14
2.9
10
13
6.3
45
13
1.3
14
13
0.8
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12
9.3
02
12
6.0
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77
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2 7
7.0
00
76
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0
58
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3
54
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8
35
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8 3
4.5
99
22
.76
7
200 150 100 50 PPM
S39
4
.19
8
4.1
90
4
.17
7
4.1
66
4
.15
7
4.1
43
4
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4
3.8
64
3
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3
3.8
38
3
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7
3.6
51
3
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6
3.6
01
2
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5
2.1
65
2
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3
2.1
39
2
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9
2.1
16
2
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5
2.0
93
1
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9
1.8
17
1
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5
1.7
93
1
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1
1.7
69
1
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7
1.7
45
1
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4
1.6
04
1
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2
1.5
61
1
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1
1.5
34
1
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0
1.4
51
1
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8
1.4
27
1
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3
1.3
95
1
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3
1.2
83
0
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2
0.8
87
0
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0
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00
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0
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2
1.0
0
1.0
0
1.0
3
1.0
8
11
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3.1
7
8 7 6 5 4 3 2 1 0 PPM
S40
77
.31
8 7
7.0
00
76
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5
53
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6
36
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7 3
6.0
14
31
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2 2
9.3
17
29
.16
1 2
8.7
94
26
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7 2
2.6
22
14
.06
3
140 120 100 80 60 40 20 0 PPM
S41
7
.32
2
7.3
17
7
.30
4
7.3
00
7
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5
7.2
87
7
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2
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36
7
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4
6.9
96
6
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8
6.9
46
6
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3
6.9
24
4
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0
4.4
28
4
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0
4.4
16
4
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8
4.4
02
4
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8
4.3
77
4
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6
4.3
53
4
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9
4.3
27
3
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1
3.9
31
3
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5
3.9
04
3
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1
3.8
89
3
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5
3.8
62
0
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0
2.0
0
2.9
8
1.9
4
0.9
7 1
.93
10 8 6 4 2 0 PPM
S42
15
7.9
41
12
9.5
90
12
1.6
46
11
4.8
39
77
.31
6 7
7.0
00
76
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1
69
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5
47
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3
32
.73
6
200 150 100 50 0 PPM
S43
7
.28
5
7.2
13
4
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6
3.8
33
3
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1
3.8
07
3
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9
3.6
15
3
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1
2
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4
2.7
45
2
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0
2.4
62
2
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9
2.4
47
2
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4
2.0
56
1.0
0
1.0
1
1.0
2
1.0
2
1.0
1
1.0
2
1.0
2
1.9
8 2
.96
10 8 6 4 2 0 PPM
3q
Br
Br
S44
14
0.1
76
12
8.5
10
12
8.4
74
12
6.2
46
77
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1 7
6.9
94
76
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7
52
.01
7
37
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1 3
6.1
81
32
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8
200 150 100 50 0 PPM
3q
Br
Br
S45
7
.40
4
7.3
88
7
.33
0
7.3
13
3
.82
6
3.8
00
3
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2
3.7
26
3
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0
3.2
86
3
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0
3.2
42
3
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6
1
.90
6
-0
.00
0
1.0
0 0
.98
1.9
9
2.9
9
5.1
4
10 8 6 4 2 0 PPM
S46
13
5.9
76
13
0.8
59
12
8.0
40
12
7.2
53
77
.31
2 7
7.0
00
76
.68
2
66
.55
0
47
.14
3
42
.18
4
30
.69
6
200 150 100 50 0 PPM
S47
7
.26
5
4
.45
6
2.4
90
2
.48
5
2.4
80
2
.47
2
2.4
65
2
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5
2.4
48
2
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1
2.4
36
2
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9
1.9
14
1
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9
1.9
04
1
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9
1.8
95
1
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0
1.8
80
1
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2
1.8
60
1
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4
1.8
35
1
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0
1.8
23
1
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4
1.8
06
1
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7
1.7
89
1
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0
1.5
32
1
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6
1.5
18
1
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9
1.5
00
-0
.00
0
2.0
0
2.0
7
4.0
6
2.0
6
10 8 6 4 2 0 PPM
3s
Br
Br
S48
77
.31
9 7
6.9
94
76
.68
1
55
.17
6
31
.94
9
22
.35
4
200 150 100 50 0 PPM
3s
Br
Br
S49
4
.71
4
4.7
08
4
.70
5
4.6
99
4
.69
0
4.3
39
4
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0
4.3
26
4
.31
6
4.3
07
4
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6
4.2
86
2
.04
7
2.0
35
2
.02
2
2.0
15
2
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3
1.9
90
1
.96
3
1.9
51
1
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4
1.9
28
1
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3
1.9
20
1
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1
1.9
03
1
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1
1.8
79
1
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9
1.7
24
1
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0
1.7
08
1
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2
1.6
78
1
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2
1.6
29
1
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7
1.5
79
1
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5
1.5
58
1
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0
1.5
47
1
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7
1.5
15
1
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0
1.4
98
1
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8
1.2
93
1
.26
9
1.2
67
12
60
1.0
0
1.0
0
1.1
0
5.1
5
1.0
6
4.0
3
2.1
6 1
.06
7 6 5 4 3 2 1 PPM
Br
Br
3t
S50
77
.31
3 7
7.0
00
76
.68
3
56
.82
4 5
4.7
69
42
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5 4
1.9
30
41
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2 3
6.4
34
36
.13
7 3
3.5
37
33
.16
9 2
9.2
56
29
.18
9
140 120 100 80 60 40 20 0 PPM
Br
Br
3t
S51
4
.61
2
4.6
08
4
.59
5
4.5
88
4
.58
4
4.5
79
4
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7
4.5
64
4
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0
2
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1
2.4
48
2
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2
2.4
40
2
.42
8
2.4
26
2
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0
2.4
17
2
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2
2.4
09
2
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3
2.4
01
2
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7
2.3
81
2
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9
2.1
31
2
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6
2.1
20
2
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1
2.1
06
2
.10
0
2.0
92
2
.08
6
2.0
80
2
.07
2
2.0
67
2
.06
1
2.0
53
1
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2
1.8
84
1
.87
8
1.8
69
1
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6
1.8
43
1
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1
1.8
20
1
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8
1.7
11
1
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5
1.6
99
1
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2
1.6
85
1
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8
1.6
75
1
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0
1.6
62
1
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5
1.6
47
1
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9
1.6
33
1
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8
1.6
23
1.6
19
2.0
3
2.0
4
2.0
3
2.0
0 4
.03
1.9
310 8 6 4 2 0 PPM
3u
Br Br
S52
77
.32
0 7
7.0
00
76
.68
2
61
.46
7
33
.21
0
25
.88
7 2
5.3
83
200 150 100 50 0 PPM
3u
Br Br
S53
4
.64
6
2
.58
3
2.5
73
2
.56
5
2.5
55
2
.54
6
2.5
36
2
.52
7
2.5
18
2
.50
9
2.5
00
2
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2
2.1
15
2
.09
9
2.0
89
2
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7
2.0
63
2
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3
2.0
22
2
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2
2.0
03
2
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2
1.9
93
1
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2
1.9
43
1
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3
1.8
58
1
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0
1.8
21
1
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7
1.8
03
1
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5
1.7
87
1
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9
1.7
59
1
.75
1
1.6
84
1
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2
1.6
58
1
.64
8
1.6
37
1
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4
1.5
89
1
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6
1.5
64
1
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3
0.9
5
1.0
0
1.1
3
5.1
1
1.9
7
2.1
5
7 6 5 4 3 2 1 0 PPM
S54
77
.31
5 7
7.0
00
76
.68
5
70
.69
4
61
.93
2
37
.61
1
34
.04
0 3
2.5
00
22
.69
6 2
0.6
75
140 120 100 80 60 40 20 0 PPM
S55
7
.83
4
7.8
15
7
.65
7
7.6
39
7
.62
0
7.5
18
7
.49
9
7.4
81
7
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9
7.4
39
3
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7
3.6
69
3
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0
3.6
32
1
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3
0
.00
0
3.0
0
1.0
0 0
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0.9
3 0.9
8 0
.95
0.9
7
10 8 6 4 2 0 PPM
S56
16
8.8
61
15
1.0
88
13
4.2
79
12
9.7
79
12
6.2
10
12
5.8
05
12
1.4
05
84
.48
1
77
.32
6 7
7.0
00
76
.68
7
37
.83
4
24
.19
9
200 150 100 50 0 PPM
S57
7
.94
1
7.9
22
7
.75
9
7.7
56
7
.74
0
7.7
21
7
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9
7.6
80
7
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0
7.6
05
7
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2
7.5
84
7
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2
7.5
77
7
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2
7.5
65
7
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0
7.5
57
7
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3
7.4
17
7
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3
7.4
01
7
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8
7.3
86
7
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2
7.3
76
7
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2
7.3
66
7
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9
7.2
59
4
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1
4.1
33
4
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6
4.0
78
0
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0
1.0
0
1.0
1 1
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2.9
9
3.0
2
1.0
6 1
.06
10 8 6 4 2 0 PPM
S58
16
8.8
48
14
9.7
60
13
7.4
82
13
4.3
37
12
9.9
27
12
9.1
07
12
8.9
60
12
6.5
14
12
5.9
55
12
5.4
24
12
2.5
42
87
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4
77
.31
4 7
7.0
00
76
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1
37
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5
200 150 100 50 0PPM
S59
7
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3
7.3
73
7
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8
7.3
54
7
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8
7.3
38
7
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7
7.3
20
7
.26
0
2
.62
2 3
.00
5.0
6
10 8 6 4 2 0 PPM
S60
14
0.7
72
12
9.0
86
12
8.5
84
12
8.2
16
11
7.2
17
11
6.7
96
77
.31
7 7
7.0
00
76
.68
1
29
.30
0
200 150 100 50 0 PPM
S61
7
.37
8
7.3
54
7
.34
4
7.3
24
7
.31
7
7.3
13
7
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3
7.2
89
7
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4
2
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5
2.8
46
2
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7
1
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9
1.7
01
1
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2
1.6
63
1
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4
1.4
97
1
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8
1.4
59
1
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1
1.4
22
1
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7
0.9
89
0
.97
0
0.0
00
2.0
0
1.9
9
2.0
9
2.9
7
4.9
4
10 8 6 4 2 0 PPM
S62
14
0.9
58
12
9.0
90
12
8.5
11
12
8.2
16
12
3.6
75
11
6.1
58
77
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9 7
7.0
06
76
.68
6
40
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8
29
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4
21
.76
6
13
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0
200 150 100 50 0 PPM
S63
2
.68
5
2.6
67
2
.64
8
1
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2
1.5
74
1
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4
1.5
48
1
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7
1.5
16
1
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7
1.3
79
1
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0
1.3
41
1
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3
1.3
05
0
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5
0.9
36
0
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8
0.0
00
4.0
0
4.1
4
4.1
2
6.0
9
10 8 6 4 2 0 PPM
S64
12
1.6
42
77
.31
8 7
7.0
00
76
.67
9
40
.53
9
29
.57
4
21
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4
13
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2
200 150 100 50 0 PPM
S65
7.4
91
7.4
70
6.9
09
6.8
88
6.7
32
3.8
28
0.0
00
2.0
2
2.0
5
0.9
3
3.0
0
10 8 6 4 2 0 PPM
S66
16
0.1
55
13
0.7
69
12
9.1
19
12
1.4
60
11
3.5
24
10
1.9
20
77
.31
5 7
7.0
00
76
.68
1
55
.29
5
200 150 100 50 0 PPM
S67
7
.26
1
6
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1
2
.61
2
2.5
94
2
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5
1
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4
1.5
77
1
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9
1.5
49
1
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5
1.3
22
1
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3
0.9
14
0
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7
0.8
81
0
.00
0
0.9
3
2.0
0
2.1
9
6.1
7
3.0
3
10 8 6 4 2 0 PPM
S68
12
7.0
47
10
2.0
87
77
.31
9 7
7.0
00
76
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1
36
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5
31
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6 2
8.0
23
26
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4
22
.50
4
14
.02
9
200 150 100 50 0 PPM
S69
7
.98
7
7.9
69
7
.62
2
7.6
03
7
.58
5
7.5
05
7
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6
7.4
67
7
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0
4
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2
2.0
0
0.9
9 2
.01
2.0
310 8 6 4 2 0 PPM
S70
19
1.2
10
13
3.9
33
13
3.8
88
12
8.8
57
12
8.8
13
77
.32
0 7
7.0
00
76
.68
1
30
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9
200 150 100 50 0 PPM
S71
8
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3
8.0
05
8
.00
1
7.6
02
7
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4
7.5
65
7
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6
7.4
76
7
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7
5
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6
5.0
80
5
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7
5.0
61
2
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0
2.2
62
2
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4
2.2
27
2
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9
2.1
75
2
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7
2.1
38
2
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0
2.1
01
1
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0
1.0
81
1
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3 3
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2.0
4
0.9
8
1.9
1
0.9
5 1
.96
10 8 6 4 2 0PPM
S72
19
3.1
76
13
4.5
13
13
3.5
71
12
8.7
64
12
8.6
97
77
.31
9 7
7.0
00
76
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6
49
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6
26
.86
2
12
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2
200 150 100 50 0 PPM
S73
8
.14
7
8.1
45
8
.13
2
8.1
27
8
.12
4
7.5
48
7
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5
7.5
30
7
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5
7.5
14
7
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2
7.5
08
7
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3
7.4
33
7
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9
7.4
15
7
.26
0
2
.03
7 6
.00
1.9
4
0.9
9 1
.96
10 8 6 4 2 0 PPM
S74
19
6.9
07
13
4.8
77
13
2.3
27
13
0.0
36
12
8.1
22
77
.31
5 7
7.0
00
76
.68
1
60
.32
3
31
.49
3
200 150 100 50 0 PPM
S75
8
.09
4
8.0
77
8
.07
3
7
.54
9
7.5
46
7
.53
0
7.5
12
7
.45
1
7.4
31
7
.41
2
2
.37
6
2.3
67
2
.35
8
2.3
41
2
.33
2
2.3
24
2
.22
0
2.1
99
2
.16
8
1.8
25
1
.81
7
1.8
03
1
.79
3
1.7
70
1
.59
4
1.5
74
1
.55
9
1.5
34
1
.52
4
1.5
16
1
.41
0
1.4
03
1
.39
0
1.3
81
2.0
0
1.0
4 2
.02
2.0
8 1
.93
2.1
1 3.0
5 1
.05
10 8 6 4 2 0 PPM
OBr
9d
S76
19
7.4
10
13
5.7
90
13
1.9
69
12
9.7
17
12
8.0
64
77
.32
8 7
7.0
12
76
.69
4 6
7.9
04
38
.19
5
24
.89
9 2
3.4
86
200 150 100 50 0 PPM
OBr
9d
