Please do not adjust margins
Green Chemistry
Page 6 of 10
DOI: 10.1039/C8GC02628A
ARTICLE
Journal Name
equipped with an ultraviolet cut-off filter or LED lamp was used as
light source to irradiate the reaction mixture for 6-8 h and the
reaction was monitored by GC. Upon completion, the reaction
solution was filtered to reclaim the photocatalyst, and the solution
separated. The inorganic/aqueous phase was collected for future
use and the organic phase was dried (MgSO4) and the solid product
obtained by evaporation. GC-MS showed the conversion of
adamantane was 76%, the ratio of 1-chloroadamantane and 2-
chloroadamantane was approximately 4:3, and the yield of two
chlorination products was 92%. The ratio of 1-bromoadamantane
and 2-bromoadamantane was approximately 95:5, obtained in a
yield of 88%.
use in further reactions and the organic phase was dried (MgSO4)
and the halogenation product obtained by distillation.
Chlorination of cyclopentane
Product (CAS registry No: 930-28-9) was obtained according to
the general procedure in 71% conversion and 94% yield. 1H NMR
(CDCl3, 500 MHz) δ 4.32-4.39 (m, 1H), 1.92-2.01 (m, 2H), 1.82-1.89
(m, 4H), 1.67-1.62 (m, 2H); 13C NMR (CDCl3, 125 MHz) δ 62.1, 37.1
(2C), 23.0 (2C); GC-MS (m/z) 105.1 [M+H]+ (cald for C5H9Cl , 104.04).
Bromination of cyclopentane
Product (CAS registry No: 137-43-9) was obtained according to
the general procedure in 62% conversion and 92% yield. 1H NMR
(CDCl3, 500 MHz) δ 4.35-4.38 (q, J= 4.5 Hz, 1H), 1.99-2.01 (m, 4H),
1.81-1.85 (m, 2H), 1.56-1.60 (m, 2H); 13C NMR (CDCl3, 125 MHz) δ
53.4, 37.9 (2C), 25.8 (2C); GC-MS (m/z) 148.1 [M]+ (cald for C5H9Br,
148.0).
Chlorination of adamantane
1-Cl-adamantane (CAS registry No: 935-56-8), 53%, mp. 164.5-
166oC.1H NMR (CDCl3, 500 MHz) δ 2.14 (s, 9H), 1.68 (s, 6H); 13CNMR
(CDCl3, 125 MHz) δ 69.1, 47.9 (3C), 35.7 (3C), 31.9 (3C); GC-MS
(m/z) 170.10 [M]+ (cald for C10H15Cl, 170.09), 135 (M + - Cl).
2-Cl-adamantane (CAS registry No: 7346-41-0), 39%, mp. 192~195
oC.1H NMR (CDCl3, 500 MHz) δ 4.39 (s, 1H), 2.28~ 2.26 (d, J = 12.5Hz,
2H), 2.14 (s, 2H), 1.96~1.95 (d, J = 2.5Hz, 2H), 1.78~1.76 (d, J = 10.0
Hz, 4H), 1.58~1.56 (d, J = 10.0Hz, 4H); 13CNMR (CDCl3, 125 MHz) δ
68.4, 38.3 (2C), 37.8, 35.9 (2C), 31.1 (2C), 27.5, 27.0; GC-MS (m/z)
170.10 [M]+ (cald for C10H15Cl , 170.09), 134.1 (M + - Cl).
Chlorination of cyclohexane
Product (CAS registry No: 542-18-7) was obtained according to
the general procedure in 78% conversion and 95% yield. 1H NMR
(CDCl3, 500 MHz) δ 3.96-4.01 (m, 1H), 2.03-2.07 (m, 2H), 1.69-1.82
(m, 2H), 1.61-1.68 (m, 2H), 1.50-1.54 (m, 1H), 1.32-1.40 (m, 3H); 13
C
NMR (CDCl3, 125 MHz) δ 60.0, 36.7 (2C), 25.2 (2C), 24.8; GC-MS
(m/z) 118.10 [M]+ (cald for C6H11Cl, 118.05).
Bromination of cyclohexane
Bromination of adamantine
Product (CAS registry No: 108-85-0) was obtained according to
the general procedure in 72% total conversion and 93% yield. 1H
NMR (CDCl3, 500 MHz) δ 4.16-4.20 (m, 1H), 2.13-2.16 (m, 2H), 1.76-
1.86 (m, 5H), 1.56-1.58 (m, 2H), 1.33-1.37 (m, 1H); 13C NMR (CDCl3,
125 MHz) δ 53.1, 37.6 (2C), 25.9, 25.2 (2C); GC-MS (m/z) 162.10
[M]+ (cald for C6H11Br, 162.00).
1-Br-adamantane (CAS registry No: 768-90-1), 84%, mp. 164.5-
166 °C. 1H NMR (CDCl3, 500 MHz) δ 2.35-2.34 (d, J = 3.0 Hz, 6H),
2.09 (s, 3H), 1.75-1.71 (m, 6H); 13C NMR (CDCl3, 125 MHz) δ 66.8,
49.4 (3C), 35.6 (3C), 32.7 (3C); GC-MS (m/z) 215.00 [M+1]+ (cald for
C10H15Br, 214.04), 135.2 ([M+1]+ - HBr).
The photocatalytic chlorination of alkanes
Chlorination of cycloheptane
TBAC (1.5 mmol) and Ag@AgCl photocatalyst (0.9 g) was
suspended and dissolved in the hydrocarbon (0.5 mol) and the
solution was transferred into a photocatalytic reaction vessel (PLS-
SXE300CUV). The mixture solution (50 ml), containing saturated
potassium chloride (45 ml) and hydrochloric acid (5 ml) was added
to the above solution. Blue light produced by an LED lamp was used
as light source to irradiate the reaction mixture for 5-8 h and the
reaction was monitored by GC. The reaction solution was filtered to
reclaim the photocatalyst and the remaining solution separated.
The inorganic/aqueous phase was collected for future use and the
organic phase was dried (MgSO4) and the halogenation products
obtained by distillation.
Product (CAS registry No: 2453-46-5) was obtained according to
the general procedure in 58% conversion and 90% yield. 1H NMR
(CDCl3, 500 MHz) δ 4.11-4.14 (m, 1H), 2.08-2.14 (m, 2H), 1.82-1.90
(m, 2H), 1.67-1.71 (m, 2H), 1.45-1.53 (m, 4H), 1.37-1.44 (m, 2H); 13
C
NMR(CDCl3, 125 MHz) δ 62.8, 31.0 (2C), 27.7 (2C), 24.8 (2C); GC-MS
(m/z) 132.00 [M]+ (cald for C7H13Cl , 132.07).
Chlorination of cyclooctane
Product (CAS registry No: 2453-46-5) was obtained according to
the general procedures at 44% conversion and 72% yield. 1H NMR
(CDCl3, 500 MHz) δ 4.10-4.16 (m, 1H), 1.99-1.93 (m, 2H), 1.77-1.72
(m, 2H), 1.63-1.58 (m, 4H), 1.48-1.51 (m, 6H); 13C NMR (CDCl3, 125
MHz) δ 63.3, 35.2 (2C), 27.5 (2C), 25.0, 23.6 (2C); GC-MS (m/z):
146.10 [M]+ (cald for C8H15Cl, 146.09), 82.1 ([M]+-C2H5Cl).
Chlorination of n-pentane
The chlorination products were mixture contained 1-Cl-pentane,
2-Cl-pentane, and 3-Cl-pentane. The yield was 86%, the ratio was
approximately 3:4:2 successively.
Bromination of cyclooctane
Product (CAS registry No: 1556-09-8) was obtained according to
the general procedure in 50% conversion and 89% yield. 1H NMR
(CDCl3, 500 MHz) δ 4.42-4.37 (m, 1H), 2.41-2.19 (m, 2H), 2.16-2.07
(m, 3H), 1.78-1.71 (m, 3H), 1.59-1.52 (m, 6H); 13C NMR (CDCl3, 125
MHz) δ 57.4, 36.0, 35.2, 27.5, 26.8, 25.1, 24.8, 23.7; GC-MS (m/z)
111.2 ([M+1]+-HBr) (cald for C8H15Br, 190.04).
1-Cl-pentane (CAS registry No: 543-59-9), 1H NMR (CDCl3, 500
MHz) δ 3.49-3.54 (t, J = 7.0 Hz, 2H), 1.81-1.77 (m, 2H), 1.29-1.36 (m,
4H), 0.85-0.86 (m, 3H); 13C NMR (CDCl3, 125 MHz) δ 58.5, 42.6, 25.4,
20.0, 13.6; GC-MS (m/z) 106.0 [M]+ (cald for C5H11Cl, 106.05), 70.2
(M + - Cl).
2-Cl-pentane (CAS registry No: 625-29-6), 1H NMR (CDCl3, 500
MHz) δ 4.04-3.97 (m, 1H), 1.51-1.50 (d, J = 2 Hz, 3H), 151-1.59 (m,
2H), 1.39-1.30 (m, 2H), 0.91-0.86 (m, 3H); 13C NMR (CDCl3, 125 MHz)
δ 45.1, 32.5, 29.2, 22.1, 14.0; GC-MS (m/z) 106.0 [M]+ (cald for
C5H11Cl, 106.05), 70.2 (M + - Cl).
The photocatalytic halogenation of adamantane
The phase transfer catalyst TBAC (1.5 mmol) and Ag@AgX
photocatalyst (0.8 g) were suspended and dissolved in the solution
of fluorobenzene and adamantane (0.3 mol), and the solution was
transferred into a photocatalytic reaction vessel (PLS-SXE300CUV).
Saturated potassium chloride or bromide solution (60 ml)
containing hydrochloric acid (6 ml) or 48% hydrobromic acid (5 ml)
was added. The visible light produced by a 300 W xenon lamp
3-Cl-pentane (CAS registry No: 616-20-6), 1H NMR (CDCl3, 500
MHz): δ 3.78-3.73 (m, 1H), 1.74-1.59 (m, 4H), 1.07-1.03 (t, J = 3.0 Hz,
6H); 13C NMR (CDCl3, 125 MHz) δ 67.4, 31.2(2C), 11.00 (2C); GC-MS
(m/z) 106.0 [M]+ (cald for C5H11Cl, 106.05), 70.2(M+ - Cl).
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins