Supporting Information for Driving Forces for the Mutual Conversions ...
Supporting Information for Driving Forces for the Mutual Conversions between Phenothiazines and Their Various Reaction Intermediates in Acetonitrile Xiao-Qing Zhu,* Zhi Dai, Ao Yu, Shuai Wu, Jin-Pei Cheng Department of Chemistry, the State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China
CONTENTS
S1
SI-1
General Methods
S2
SI-2
Synthetic routes of XH and X+
S2
SI-3
Representative 1H NMR spectra of XH and X+
S16
SI-4
Representative Esi-Ms spectrum of X+
S41
SI-5
Representative UV spectra of X+
S42
SI-6
Representative CV graphs of XH and X+
S46
S1
SI–1. General Methods 1
Solvents and reagents were obtained from commercial sources and used as received.
H NMR
spectra were recorded in CDCl3, CD3CN and DMSO-d6 on 300MHz NMR spectrometer. The chemical shifts ( ) were described in parts per million (ppm) downfield from tetramethylsilane (TMS, 0.00 ppm) as an internal standard. All reagents of commercial quality were from freshly opened containers or were purified according to the standard methods before use.
Reagent grade acetonitrile was refluxed over
KMnO4 and K2CO3 for several hours and was distilled over P2O5 under argon twice before use. The commercial tetrabutylammonium hexafluorophosphate (Bu4NPF6, Aldrich) was recrystallized from o
CH2Cl2/Et2O and dried in vacuo at 110 C overnight before preparation of a supporting electrolyte solution. Acetonitrile containing 0.1 M tetra-n-butylammonium hexafluorophosphate (TBAPF6) was used as solvent in electrochemical measurements. Ferrocene/ferrocenium redox couple (Fc+/0) was used as an internal reference for all measurements. All electrochemical measurements were performed under dry nitrogen atmosphere using 0.1 V/s scan rate, unless otherwise specified, the concentration of samples was 10-3 M.
SI-2. Synthetic Routes of XH and X+ Synthetic Route of 3H (G = Br)S1 H N S
H N
BrN
Br2
NaBH4 Br
S
Br
Br
S
Br
Phenothiazine (10 mmol) was dissolved in oxygen-free glacial acetic acid (120mL), and a solution of bromine also in acetic acid (100mL, 10% v/v, 195mmol) was added to it all at once with vigorous stirring for about one minute. The water (400 mL) was added to the mixture, the red precipitate was filtered, washed with ether absolute, dried under vacuum, then 3,7-dibromophenothiazinium bromide was obtained. 3,7-Dibromophenothiazinium bromide (8 mmol) was dissolved in methanol S2
(30 mL), and sodium borohydride (15mmol) was added with stirring for about 20 minute. The methanol was eliminated by distillation under vacuum. Column chromatography of the residue solid (eluant: ethyl acetate/petroleum ether) afforded 3,7-dibromophenothiazine. The yield is over 80%.
H N Br 1
S
(3,7-dibromophenothiazine) Br
H NMR (300 MHz, (CD3)2SO), 8.41 (s, 1H), 6.60 (m, 2H), 7.13 (m, 4H). UV-vis:
max =
258nm,
322nm. Anal. Calcd for C12H7NSBr2 (357): C, 40.34; H, 1.96; N, 3.92. Found: C, 40.31; H, 1.94; N, 3.90.
Synthetic Route of 3H (G = Cl )S2 H N
H N
PCl 5 S
Cl
S
Cl
Phenothiazine (10 mmol), PCl5 (30 mmol) in 80 mL of chloroform were heated together and refluxed for 3 hour. The chloroform was eliminated by distillation under vacuum. Then the solid residue was poured into water (200 mL) and stirred for 20 min. The precipitate formed was collected by filtration, washed with 70% ethanol (50mL), then crude 3,7-dichlorophenothiazine was obtained. Column chromatography of the crude product (eluant: ethyl acetate/petroleum ether) afforded 3,7-dichlorophenothiazine. The yield is over 85%. H N Cl 1
S
(3,7-dichlorophenothiazine) Cl
H NMR (300 MHz, (CD3)2SO),
8.3 (s, 1H), 7.1 (m, 5H), 7.32 (m, 1H). UV-vis:
max =
258nm,
325nm. Anal. Calcd for C12H7NSCl2 (268): C, 53.73; H, 2.61; N, 5.22. Found: C, 53.75; H, 2.59; N, 5.24.
Synthetic Route of 1H (G = Br, Cl)S3
S3
NH 2
NO 2
NH 2 SH
G
KOH
S
Ac 2O
+ G
O 2N
NHAc S O 2N
G
H N
KOH
S
G
G
(G = Cl, Br)
To a solution of 19.2 g (0.1 moles) of 2,5-dichloronitrobenzene and 12.5 g (0.1 moles) of 2-aminobenzenethiol in 300 mL of 2-propanol was added dropwise, with stirring, a solution of 6.6 g. (0.1 moles) of 2.8g potassium hydroxide in 15 ml. of 95% ethanol. Subsequently, the mixture was stirred and refluxed for three hours, and then concentrated to dryness. The residual solid was stirred with 40 mL of water, filtered and air-dried.
11 g of the crude product of 2-aminophenyl
4-chloro-2-nitrophenyl sulfide was obtained. The crude sulfide, 100 mL of acetic anhydride, 5 ml of pyridine were mixed and heated for two hours and filtered hot. The filtrate was concentrated to about 15 ml and cooled. The separated solid was filtered and air-dried to give 17g of crude 2-acetamidophenyl 4-chloro-2-nitrophenyl sulfide.
2-Acetamidophenyl 4-chloro-2-nitrophenyl
sulfide was dissolved in 400 ml of acetone and a solution of 3 g of 85% potassium hydroxide in 25 ml of 95% ethanol was added. The mixture was stirred and diffused with nitrogen for about 15 minutes, 7 g of the crude acetamido derivative was added and the mixture distilled from the steambath as rapidly as possible under nitrogen. The residue was stirred with 40 mL of water, the solid was filtered and dried to give 4 g of crude 3-chlorophenothiazine.
The crude product
recrystallized from xylene gave pure product 3.5g. H N S 1
(3-chlorophenothiazine) Cl
H NMR (300 MHz, (CD3)2SO), : 8.71 (s, 1H), 7.01-6.64 (m, 7H). UV-vis:
max =
255nm, 315nm.
Anal. Calcd for C12H8NSCl (233.5): C, 61.67; H, 3.43; N, 6.00. Found: C, 61.64; H, 3.41; N, 6.02. H N S 1
(3-bromoxyphenothiazine) Br
H NMR (300 MHz, (CD3)2SO),
8.70 (s, 1H), 7.10-6.62 (m, 7H). UV-vis:
max =
252nm, 311nm.
Anal. Calcd for C12H7NSBr2 (278): C, 51.80; H, 2.88; N, 5.04. Found: C, 51.83; H, 2.86; N, 5.02. Synthetic Routes of 1H, 3H (G=CH3, CH3O).S4 S4
NH 2
Br
K 2CO 3
G
H N
CuI
+
G
H N
S
G
I2
G
S
G
G
(G = CH 3 CH 3O)
NH 2
I CuI
+
H N
K 2CO 3
H N
S G
I2
S
G
H N
G
G (G = CH 3 CH 3 O NMe 2)
I
NH 2 +
CuI
H N
G
I2
K 2CO 3
G
S
S
(G = CH 3 CH 3 O)
A mixture of aryl halide (30 mmol), aniline (20 mmol), K2CO3 (40 mmol), CuI (2 mmol), and L-proline (4 mmol) in 30 mL of DMSO was heated at 90 °C for 24-30 h under inert atmosphere. The cooled mixture was partitioned between water and ethyl acetate. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo. The residual oil was loaded on a silica gel column and eluted with ethyl acetate/petroleum ether to afford the corresponding diphenylamine. Substituted diphenylamine (10 mmol), I2 (2 mmol) in 20 mL of o-dichlorobenzene were heated together and refluxed for 15-30 min under inert atmosphere. The o-dichlorobenzene was eliminated by distillation under reduced pressure. Column chromatography of the solid residue (eluant: ethyl acetate/petroleum ether) afforded Substituted-phenothiazine. The yield is over 30%.
H N S 1
(3-dimethylaminophenothiazine) N(CH3)2
H NMR (300 MHz, (CD3)2SO), 8.23 (s, 1H), 6.88-6.96 (m, 3H), 6.64-6.73 (m, 3H), 6.36-6.38 (m, S5
1H), 2.83 (s, 3H), 2.76 (s, 3H). UV-vis:
max =
254nm, 317nm. Anal. Calcd for C14H14N2S (242):
C, 69.42; H, 5.79; N, 11.57. Found: C, 69.40; H, 5,77; N, 11.59.
H N H3CO 1
(3,7-dimethoxyphenothiazine)
S
OCH3
H NMR (300 MHz, (CD3)2SO),
8.13 (s, 1H), 6.62-6.57 (m, 6H), 3.65 (s, 6H). UV-vis:
max =
252nm, 316nm. Anal. Calcd for C14H13NSO2 (259): C, 64.86; H, 5.02; N, 5.41. Found: C, 64.89; H, 5.04; N, 5.39.
H N H3C 1
(3,7-dimethylphenothiazine)
S
CH3
H NMR (300 MHz, (CD3)2SO),
8.31 (s, 1H), 6.73-6.57 (m, 6H), 2.12 (s, 6H). UV-vis:
max=
256nm, 314nm. Anal. Calcd for C14H13NS (227): C, 74.01; H, 5.73; N, 6.17. Found: C, 73.98; H, 5.74; N, 6.20.
H N S 1
(3-methoxyphenothiazine) OCH3
H NMR (300 MHz, (CD3)2SO),
8.36 (s, 1H), 6.98-6.63 (m, 7H), 3.65 (s, 3H). UV-vis:
max=
254nm, 315nm; Anal. Calcd for C13H11NSO (229): C, 68.12; H, 4.80; N, 6.11. Found: C, 68.15; H, 4.82; N, 6.14. H N
OCH3
(2-methoxyphenothiazine)
S 1
H NMR (300 MHz, (CD3)2SO), 8.59 (s, 1H), 6.83-6.90 (m, 2H), 6.66-6.75 (m, 3H), 6.32-6.39 (m,
2H), 3.68 (s, 3H). UV-vis:
max=
250 nm, 317 nm. Anal. Calcd for C13H11NSO (229): C, 68.12; H,
4.80; N, 6.11. Found: C, 68.09; H, 4.81; N, 6.13.
S6
H N S 1
(3-methylphenothiazine) CH3
H NMR (300 MHz, (CD3)2SO),
8.45 (s, 1H), 6.97-6.59 (m, 7H), 2.12 (s, 3H). UV-vis:
max =
255nm, 307nm; Anal. Calcd for C13H11NS (213): C, 73.24; H, 5.16; N, 6.57. Found: C, 73.21; H, 5.18; N, 6.59. H N
CH3
(2-methylphenothiazine)
S 1
H NMR (300 MHz, (CD3)2SO), 8.50 (s, 1H), 6.51-6.89 (m, 7H), 2.15 (s, 3H). UV-vis:
max =
249
nm, 316nm. Anal. Calcd for C13H11NS (213): C, 73.24; H, 5.16; N, 6.57. Found: C, 73.27; H, 5.15; N, 6.56.
H N (H3C) 2N 1
(3,7-di-dimethylaminophenothiazine)
S
N(CH3)2
H NMR (300 MHz, CD3CN), 7.10-7.14 (m, 4H), 6.61-6.64 (m, 2H), 3.10 (s, 12H). H N
(phenoxazine)
O 1
H NMR (300 MHz, (CD3CN),
6.50-6.77 (m, 8H). UV-vis:
max =
240 nm, 314nm. Anal. Calcd
for C13H11NS (213): C, 78.69; H, 4.92; N, 7.65. Found: C, 78.66; H, 4.90; N, 7.63.
Synthetic Routes of X+ (1+-4+) Method AS5 H N G
S
H N
H2 O2 G
G
N
HClO4
S O
G
G
S
ClO4G
Substituted phenothiazine (5 mmol) dissolved in 50 mL of heated ethanol, 30% hydrogen peroxide S7
(8 mmol) was added to it and refluxed for 1-2 hour. The ethanol was eliminated by distillation under vacuum. The residue solid washed with water and ethyl acetate/petroleum ether (1/1). The crude product recrystallized from 90% ethanol gave substituted phenothiazine-5-oxide. Substituted phenothiazine-5-oxide (2 mmol) dissolved in 5-10 mL of oxygen-free glacial acetic acid, 70% perchloric acid (2 mL) was added to it at 0 °C and stirred for about 20 minute. Then 150 mL of ether absolute was added to it, the red precipitate formed was collected by filtration, washed with 150 mL of ether absolute, dried under vacuum, and substituted phenothiazinium perchlorate was obtained. The yield is over 50%.
Method B H N G
N
NO+ClO4-
S
G
H N
dry CH3CN
NO+ClO4 dry CH3CN
O
G
S
ClO4G
N ClO4O
Phenoxazine (0.5 mmol) in 20 mL of dry acetonitrile and NO+ClO4- (0.5 mmol) in 20 mL of dry acetonitrile were mix and stirred for about 10 minute. Then 150 mL of ether absolute was added to it, the red precipitate formed was collected by filtration, washed with 150 mL of ether absolute, dried under vacuum, and phenoxazinium perchlorate was obtained. The yield is over 70%.
N
ClO4-
S 1
(3-dimethylaminophenothiazinium perchlorate)
N(CH3 )2
H NMR (300 MHz, CD3CN),
8.23 (m, 1H), 8.10-8.14 (m, 2H), 7.90-7.92 (m, 2H), 7.78-7.81 (m,
2H), 3.67 (s, 3H), 3.63 (s, 3H). UV-vis:
max
= 577nm; ESI-MS/M+ = 241. Anal. Calcd for
C14H13N2SClO4 (340.5): C, 49.34; H, 3.82; N, 8.22. Found: C, 49.37; H, 3.84; N, 8.22.
N H3 CO 1
S
ClO 4-
(3, 7-dimethoxyphenothiazinium perchlorate)
OCH3
H NMR (300 MHz, CD3CN), 8.64 (m, 2H), 8.13 (m, 2H), 7.90 (m, 2H), 4.25 (s, 6H). UV-vis: S8
max
= 285.5nm, 499nm. ESI-MS/M+ = 258. Anal. Calcd for C14H12NSClO6 (357.5): C, 46.99; H, 3.36; N, 3.92. Found: C, 46.96; H, 3.38; N, 3.90.
N H3C 1
ClO4-
S
(3, 7-dimethylphenothiazinium perchlorate)
CH3
H NMR (300 MHz, CD3CN), max =
8.79 (m, 2H), 8.68 (m, 2H), 8.34 (m, 2H), 2.88 (s, 6H). UV-vis:
286nm, 448nm. ESI-MS/M+ = 226. Anal. Calcd for C14H12NSClO4 (325.5): C, 51.61; H,
3.69; N, 4.30. Found: C, 51.65; H, 3.67; N, 4.32.
N
ClO4-
S 1
(3-methoxyphenothiazinium perchlorate)
OCH3
H NMR (300 MHz, CD3CN),
UV-vis:
max
8.81-8.72 (m, 4H), 8.37 (m, 2H), 8.04 (m, 1H), 4.34 (s, 3H).
= 283nm, 443nm. ESI-MS/M+ = 228. Anal. Calcd for C13H10NSClO5 (327.5): C,
47.63; H, 3.05; N, 4.27. Found: C, 47.64; H, 3.06 N, 4.25.
N
OCH3 ClO4-
(2-methoxyphenothiazinium perchlorate)
S 1
H NMR (300 MHz, CD3CN),
3H). UV-vis:
max =
8.92-8.96 (m, 3H), 8.65-8.69 (m, 2H), 8.23-8.26 (m, 2H), 4.15 (s,
284nm, 428nm. ESI-MS/M+ = 228. Anal. Calcd for C13H10NSClO5 (327.5):
C, 47.63; H, 3.05; N, 4.27. Found: C, 47.59; H, 3.04; N, 4.29.
N S 1
ClO4-
(3-methylphenothiazinium perchlorate)
CH3
H NMR (300 MHz, CD3CN), 8.97-8.75 (m, 4H), 8.52 (m, 2H), 8.37 (m, 1H), 2.91 (s, 3H). UV-vis: max =
283.5nm, 433nm. ESI-MS/M+ = 212. Anal. Calcd for C13H10NSClO4 (311.5): C, 50.08; H,
3.21; N, 4.49. Found: C, 50.05; H, 3.23; N, 4.51.
S9
N
CH3
(2-methylphenothiazinium perchlorate)
ClO4S 1
H NMR (300 MHz, CD3CN), UV-vis:
8.73-8.81 (m, 4H), 8.41-8.43 (m, 2H), 8.35 (m, 1H), 2.77 (s, 3H).
282nm, 422nm. ESI-MS/M+ = 212. Anal. Calcd for C13H10NSClO4 (311.5): C,
max =
50.08; H, 3.21; N, 4.49. Found: C, 50.12; H, 3.19; N, 4.47.
N ClO4-
(phenothiazinium perchlorate)
S 1
H NMR (300 MHz, CD3CN),
9.0-8.92 (m, 4H), 8.60-8.49 (m, 4H). UV-vis:
max
= 282nm,
420nm. Anal. Calcd for C12H8NSClO4 (297.5): C, 48.40; H, 2.69; N, 4.71. Found: C, 48.44; H, 2.71; N, 4.73.
N ClO4-
(phenoxazinium perchlorate)
O 1
H NMR (300 MHz, CD3CN), 8.77-8.67 (m, 4H), 8.47-8.43 (m, 2H), 8.36-8.32 (m, 2H). UV-vis: max =
260.5nm, 422nm. Anal. Calcd for C12H8NClO5 (281.5): C, 51.15; H, 2.84; N, 4.97. Found:
C, 51.19; H, 2.86; N, 4.99.
N ClO4S 1
(3-chlorophenothiazinium perchlorate)
Cl
H NMR (300 MHz, CD3CN),
8.98-8.79 (m, 4H), 8.65-8.41 (m, 3H). UV-vis:
max
= 287nm,
439nm. Anal. Calcd for C12H7NSCl2O4 (332): C, 43.37; H, 2.11; N, 4.22. Found: C, 43.35; H, 2.12; N, 4.23.
N
Cl ClO4-
(2-chlorophenothiazinium perchlorate)
S 1
H NMR (300 MHz, CD3CN),
8.95-8.77 (m, 4H), 8.61-8.44 (m, 3H). UV-vis: S10
max
= 285nm,
422nm. Anal. Calcd for C12H7NSCl2O4 (332): C, 43.37; H, 2.11; N, 4.22. Found: C, 43.40; H, 2.10; N, 4.24.
N ClO4S 1
(3-bromoxyphenothiazinium perchlorate)
Br
H NMR (300 MHz, CD3CN),
9.01-8.85 (m, 4H), 8.65-8.43 (m, 3H). UV-vis:
max
= 288nm,
442nm. Anal. Calcd for C12H7NSBrClO4 (376.5): C, 38.25; H, 1.86; N, 3.72. Found: C, 38.21; H, 1.87; N, 3.73.
N Cl 1
ClO 4-
S
(3,7-dichlorophenothiazinium perchlorate)
Cl
H NMR (300 MHz, CD3CN), 9.10-8.98 (m, 4H), 8.6-8.4 (m, 2H). UV-vis:
max =
297nm, 465nm.
Anal. Calcd for C12H6NSCl3O4 (366.5): C, 39.29; H, 1.64; N, 3.82. Found: C, 39.26; H, 1.65; N, 3.84.
N Br 1
ClO4-
S
(3,7-dibromophenothiazinium perchlorate)
Br
H NMR (300 MHz, CD3CN), 9.19-9.15 (m, 2H), 8.81-8.78 (m, 2H), 8.62-8.59 (m, 2H). UV-vis: max
= 294nm, 465nm. Anal. Calcd for C12H6NSBr2ClO4 (455.5): C, 31.61; H, 1.32; N, 3.07.
Found: C, 31.64; H, 1.33; N, 3.09.
N (H3C) 2N 1
S
ClO4 -
(3,7-di-dimethylaminophenothiazinium perchlorate)
N(CH3)2
H NMR (300 MHz, CD3CN), 7.81 (m, 2H), 7.20-7.21 (m, 2H), 7.11 (m, 2H), 3.3 (s, 12H). UV-vis: max=
655nm.
Synthetic Route of X+ (6+, 7+)
S11
O
H
OH
H
HClO 4
NaBH 4 CH 3 OH
X
(CH 3CO)2 O
X
ClO 4X
(X = S, O)
Xanthen-9-one or thioxanthen-9-one (8 mmol) was dissolved in methanol (30 mL), and sodium borohydride (15mmol) was added with stirring for about 20 minute. The methanol was eliminated by distillation under vacuum. acetate/petroleum
ether)
Column chromatography of the residue solid (eluant: ethyl
afforded
Xanthen-9-ol
or
thioxanthen-9-ol.
Xanthen-9-ol
or
thioxanthen-9-ol (2 mmol) dissolved in 5 mL of oxygen-free acetic anhydride, 70% perchloric acid (2 mL) was added to it at 0 °C and stirred for about 10 minute. Then 150 mL of ether absolute was added to it, the precipitate formed was collected by filtration, washed with 150 mL of ether absolute, dried under vacuum, and xanthylium perchlorate or thioxanthylium perchlorate was obtained. The yield is over 70%. H C ClO4-
(xanthylium perchlorate)
O 1
H NMR (300 MHz, CD3CN),
2H).
UV-vis:
max=253nm,
10.40 (s, 1H), 8.66-8.68 (m, 4H), 8.40-8.42 (m, 2H), 8.12-8.13 (m, 371nm.
Anal. Calcd for C13H9ClO5 (280.5): C, 55.61; H, 3.21.
Found: C, 55.64; H, 3.24. H C ClO4-
(thioxanthylium perchlorate)
S 1
H NMR (300 MHz, CD3CN),
2H). UV-vis:
max=275nm,
10.31 (s, 1H), 8.82-8.91 (m, 4H), 8.44-8.47 (m, 2H), 8.23-8.25 (m,
379nm. Anal. Calcd for C13H9SClO4 (296.5): C, 52.61; H, 3.04.
Found: C, 52.65; H, 3.07.
Synthetic Route of XH (6H, 7H)
S12
H
H
H
NaBH 4
ClO 4-
dry CH 3CN
X
X
(X = S, O)
Xanthylium perchlorate or thioxanthylium perchlorate (2 mmol) dissolved in 30 mL of dry acetonitrile, sodium borohydride (4mmol) was added to it with stirring for about 10 minute. The acetonitrile was eliminated by distillation under vacuum. Column chromatography of the residue solid (eluant: ethyl acetate/petroleum ether) afforded Xanthene or thioxanthene.
H
H
(9H-xanthene) O 1
H NMR (300 MHz, Cl3CD), max=210nm,
7.15-7.19 (m, 4H), 6.99-7.02 (m, 4H), 4.05 (s, 2H). UV-vis:
243nm. Anal. Calcd for C13H10O (182): C, 85.71; H, 5.49. Found: C, 85.68; H,
5.47.
H
H
(9H-thioxanthene) S 1
H NMR (300 MHz, Cl3CD),
7.43 (m, 2H), 7.30 (m, 2H), 7.19-7.21 (m, 4H), 3.85 (s, 2H).
max =
213nm, 264nm. Anal. Calcd for C13H10S (198): C, 78.79; H, 5.05. Found: C, 78.76; H, 5.03.
Synthetic Route of 5+S6 O N N
Na 2S 2 O 4
H N
Ac 2 O
N H
O
CH 3
ClO 4
CH 3
N
KH
N
N H
CH 3 I
N CH 3
HClO 4 NaNO 2
N N CH 3
To a boiling solution of phenazine (11 mmol) in ethanol (50 ml) was added a solution of sodium dithionite (110 mmol) in water (200 ml).
The resulting solid immediately precipitated was
collected by filtration and dried over phosphorous pentoxide under reduced pressure to give 5,10-dihydrophenazine. 5,10-Dihydrophenazine (2.5 mmol) in 5 mL of acetic anhydride were heated boiled for 2 min, cooled. The solid which separated was filtered, washed with ether, dried S13
under vacuum, and recrystallized from 90% ethanol gave 10-acetyl-5,10-dihydrophenazine. To 60 ml DMSO solvent containing (10 mmol) 10-acetyl-5,10-dihydrophenazine., 1.20g (> 50%) sodium hydride-mineral oil suspension was added under inert atmosphere. Abundant of gas was released and the solution turned to dark-red. Methyliodide (15 mmol) was added dropwise and the mixture was stirred under nitrogen for 0.5 h, after which the solution was poured into ice-water. The crude product was isolated and extracted with chloroform, dried over the MgSO4 and the solvent removed in vacuo to give the crude material. Further purification was taken on by the column chromatography using ethyl acetate/petroleum ether as the eluant to give 10-acetyl-5- methyl -dihydrophenazine. 10-Acetyl-5- methyl-dihydrophenazine (2 mmol) dissolved in 10 mL of ethanol, and a solution of 70% perchloric acid (6 mL), water (20 mL) and sodium nitrite (0.6 g) was added stirred for about 15 minute. Then 100 mL of ether was added to it, the yellow precipitate formed was collected by filtration, washed with 50 mL of ether absolute, dried under vacuum, and 5-methyl-phenazinium perchlorate was obtained. The yield is over 60%.
N ClO 4
(5-methyl-phenazinium perchlorate)
N CH 3
1
H NMR (300 MHz, (CD3)2CO), 8.91 (d, 2H), 8.63 (d, 2H), 8.53 (t, 2H), 8.30 (t, 2H), 5.18 (s, 3H).
UV-vis:
max=384.5nm.
ESI-MS/M+ = 195. Anal. Calcd for C13H11N2ClO4 (294.5): C, 52.97; H,
3.74; N, 9.51. Found: C, 52.94; H, 3.77; N, 9.53.
Synthetic Route of 5HS7 N ClO 4 N
Na 2S 2 O 4 H 2O
CH 3
H N N CH 3
5- Substituted benzyl-phenazinium perchlorate (2 mmol) dissolved in 5 mL of ethanol, a solution of sodium dithionite (850 mg) in water (40 ml) was added dropwise and the mixture was stirred 5 min. The precipitate formed was collected by filtration, washed with water, dried under vacuum, and S14
5-substituted benzyl-5,10-dihydrophenazine was obtained. The yield is over 85%.
H N
(N-methyldihydrophenazine) N CH 3
1
H NMR (300 MHz, (CD3)2SO), 6.56 (m, 4H), 6.38 (d, 2H), 6.30 (d, 2H), 2.86 (s, 3H).
References (S1) Leventis, N.; Chen, M.; Sotirious-Leventis, C. Tetrahedron, 1997, 53, 10083. (S2) Strell, M.; Rupprecht, M. German Patent No. 938669, 1956; Chem. Abstr. 1959, 57, 8173a. (S3) Yale, H.L. J. Am. Chem. Soc. 1955, 77, 2270. (S4) (a) Zhang, H.; Cai, Q. and Ma, D. J. Org. Chem. 2005, 70, 5164. (b) Craig, J. C.; Rogers, W. P. and Warwick, G. P. Aust. J. Chem. 1955, 8, 252-257. (S5) Kehrmann, F. and Diserens L. Berichte der deutschen chemischen Gesellschaft 1915, 48, 318. (S6) Grande, H.J.; Schagen, C.G.; Jarbandhan, T. and Muller, F. Helv. Chim. Acta 1977, 60, 348. (S7) Sugimoto, A.; Kotani, T.; Tsujimoto, J. and Yoneda, S. J. Het. Chem. 1955, 77, 2270.
S15
0
500
O
5.0
H N
0.0
( in CD3 CN )
1000
SI-3. Representative 1H NMR Spectra of XH and X+
6.495 8.00
10.0 ppm (t1)
6.767 6.642
S16
8.0
6.685 6.672 6.667 6.659 6.642 6.0
5.0
4.0
3.0
2.0
S
7.00
S17
6.770 7.0
H N
9.0 ppm (t1)
Cl
8.714
1.13
7.007
1.0
( in DMSO-d6 )
0.0
0
500
1000
9.0 ppm (t1)
8.0
6.886 6.774
2.36
8.496
1.02
S18
7.0
6.511 6.0
5.0
4.0
3.0
2.154 2.0
H N S
3.18
6.693 6.667 6.663 2.33 3.24
2.502
1.0
0.0
( in DMSO-d6 )
0
100
200
300
400
500
600
700
8.0
6.689 6.662 1.82
6.751 6.747
3.00 2.05
S19
6.832 6.804
7.0
6.397 6.388 6.360 6.326 6.317 6.0
5.0
4.0
3.0
2.0
H N
9.0 ppm (t1)
1.0
H3CO
S
3.678 3.15
8.589
1.12
6.900
0.0
( in DMSO-d6 )
-100
0
100
200
300
400
500
600
700
7.426
ppm (t1)
7.302 7.207 7.196
7.0
6.0
5.0
3.854
2.01
S20
4.0
3.0
2.0
H
H S
4.11 2.03 2.00
1.0
0.0
in CCl3CD
0
500
1000
1500
8.0 ppm (t1)
6.0
5.0
4.050
7.055 7.029 7.019
4.44
S21
4.0
2.00
7.0
H
H O
7.154
4.28
7.190
3.0
in CCl3CD
0
500
1000
1500
2000
2500
3000
5.0
H N
ppm (f1)
Cl
S
6.929 6.902 6.790
2.07 2.14 1.94 1.12
8.764
1.00
S22
6.721
7.016
0.0
( in DMSO-d6 )
0
500
1000
1500
2000
2500
8.0
7.104 1.18 1.09 1.20 1.08 1.08 2.00
8.711
1.03
S23
7.000 7.0
6.0
5.0
4.0
H N
9.0 ppm (f1)
3.0
Br
S
6.622
6.766 6.687
6.899
( in DMSO-d6 )
2.0
-100
0
100
200
300
400
500
600
700
800
5.0
H N
10.0 ppm (f1)
Cl
S
Cl
7.322 7.314 5.12 1.22
8.299
1.00
S24
7.099
0.0
( in DMSO-d6 )
0
100
200
300
400
500
600
5.0
H N
ppm (f1)
Br
S
Br
6.603
2.09
7.128
4.12
8.841
1.00
S25
( in DMSO-d6 )
0.0
0
500
1000
8.0
6.737
6.967 1.67 2.54 2.30
S26
7.0
6.0
H N
9.0 ppm (f1)
5.0
4.0
( in DMSO-d6 )
3.0
2.123 2.0
3.00
S
8.447
1.01
3.332
6.591
1.0
0.0
0
100
200
300
400
ppm (t1)
5.0
H N
S
2.117 6.06
6.566
6.725
2.00 4.14
8.311
0.96
S27
0.0
( in DMSO-d6 )
0
100
200
300
400
500
600
5.0
H N
10.0 ppm (t1)
OCH3
S
3.652 3.19
6.977 1.18 3.02 1.29 1.01 1.32
8.364
0.75
S28
6.625
6.897
0.0
( in DMSO-d6 )
-100
0
100
200
300
400
500
600
700
5.0
H N
ppm (t1)
OCH3
S
OCH3
3.648 6.00
6.608 6.572 6.02
8.128 8.120
1.15
S29
2.502
0.0
( in DMSO-d6 )
0
100
200
300
400
500
600
ppm (f1)
10.0
8.755
9.0
8.432 8.359 8.335 8.332 8.0
7.0
6.0
N O ClO4
8.708 8.679 8.462 2.00 2.09
4.21
S30
5.0
( in CD3CN )
4.0
0
100
200
300
400
500
5.0
N
10.0 ppm (f1)
OCH3
S ClO4
OCH3
4.252 6.38
8.134 7.905 7.898 7.874 7.866
2.00 1.99
8.645 8.614
2.09
S31
( in CD3CN )
0.0
0
100
200
300
400
500
600
10.0
5.0
N
15.0 ppm (t1)
0.0
OCH3
S ClO4
S32
4.341
8.044 8.036 8.012 8.004
8.367
8.755 8.723
( in CD3CN )
0
100
200
300
400
500
600
11.0 ppm (f1)
10.0
9.0
8.127 8.123 2.07
8.421 2.00 8.0
7.0
6.0
5.0
4.0
H C O
ClO4
8.668 4.19
10.403
1.02
S33
3.0
2.0
( in CD3CN )
0
100
200
300
400
ppm (f1)
11.0
10.0
8.255 2.03
8.790 8.472 2.00
8.910 8.882 8.819 4.09
S34
9.0
8.0
7.0
H C S
ClO4
10.307
1.11
6.0
( in CD3CN )
0
100
200
300
400
8.407 8.402 8.377 8.372
8.0
7.0
6.0
ClO4
5.0
S
8.879 8.848 8.751 8.519 8.506 8.493
1.04 2.11 1.02
S35
9.0
N
8.972 8.939
ppm (f1)
4.0
( in CD3CN )
2.911 3.0
3.00
CH3
1.18 2.04
2.0
1.0
-100
0
100
200
300
400
500
600
700
800
8.313
8.0
7.0
6.0
5.0
4.0
2.881 6.14
8.342
2.04
8.793 8.684
4.00
S36
3.0
2.0
N
9.0 ppm (f1)
1.0
CH3
S ClO4
CH3
0.0
( in CD3CN )
-50
0
50
100
150
200
250
300
350
10.0 ppm (f1)
ClO4
5.0
N S
8.568
4.13
8.992 8.952
4.00
S37
( in CD3CN )
0.0
-100
0
100
200
300
400
500
600
700
5.0
N
8.813 8.782
2.13 2.30
9.191 9.184
2.00
ppm (t1)
Br
S ClO4
Br
S38
8.627 8.620 8.597 8.590
( in CD3CN )
0.0
0
100
200
300
400
500
600
7.171
7.277 7.268
7.0
6.0
ClO4
5.0
N
7.840
1.07 1.19
S39
8.0 ppm (f1)
4.0
( in CD3CN )
3.250 12.00
N(CH3)2
S
N(CH3) 2
7.808 7.309 7.300
2.11 1.08 1.10
3.0
2.0
1.0
0
100
200
300
400
500
600
S40
ppm (t1)
8.913 8.638 8.635 8.607
2.29 2.28 2.34 2.23
8.534 8.529 8.301 8.298
3.00
5.181
5.0 ClO4
N
N
( in CD3CN )
0.0 0
500
SI-4. Representative Esi-Ms Spectrum of X+
06-12-14-2 #2 RT: 0.02 AV: 1 NL: 1.90E7 T: + c ESI Full ms [ 50.00-600.00] 228.3
100 95 90
N
85
ClO4-
80
S
75
OCH3
70
Relative Abundance
65 60 55 50 45 40 35 30 25 197.4 20
229.3
101.2
15
185.3
10 204.3 213.2
179.1
5 92.3 99.3 102.2
70.9
0 60
80
100
120.1 120
135.2 141.2 140
153.1
195.3
167.3 160 m/z
S41
180
230.2 242.2
200
220
240
259.1 260
274.8
SI-5. Representative UV Spectra of X+
=281 nm
max
1.4
N ClO4-
1.0
S 0.8 0.6
=420 nm
max
0.4 0.2 0.0 250
300
350
400
450
500
Wavelength (nm)
=260.5 nm
max
=422 nm
max
0.8
Absorbance
Absorbance
1.2
N 0.6
ClO4O
0.4
0.2
0.0 250
300
350
400
450
Wavelength (nm)
S42
500
550
600
1.6
N
=297 nm
max
Absorbance
1.4
Cl
ClO 4-
S
Cl
1.2 1.0
=465 nm
0.8
max
0.6 0.4 0.2 0.0
250
300
350
400
450
500
550
Wavelength (nm)
2.5
=288 nm
max
N ClO4-
Absorbance
2.0 S
Br
1.5
=442 nm
max
1.0
0.5
0.0 250
300
350
400
450
Wavelength (nm)
S43
500
550
=284 nm
1.2
N
max
H3 CO
Absorbance
1.0
ClO4-
S
OCH3
=499 nm
max
0.8 0.6 0.4 0.2 0.0 300
400
500
600
700
Wavelength (nm)
1.2
=282 nm
max
N
Absorbance
1.0
ClO4-
S
0.8
CH3
0.6
=465 nm
max
0.4 0.2 0.0 250
300
350
400
Wavelength (nm)
S44
450
500
550
1.0
=384.5 nm
N
max
0.8
ClO4
Absorbance
N
0.6 0.4 0.2 0.0 -0.2 300
350
400
450
Wavelength (nm)
S45
500
550
-
SI-6. Representative CV and/or OSWV Graphs of XH, X+ and X
10 µ
H N S
1000
800
600
400 200 +/0 Potential vs Fc mv
0
10 µ
N ClO4S 250
200
150
100 50 0 -50 +/0 mv Potential vs Fc
S46
-100
-150
10 µ
-
N S
+/0 -800 -1000 mv -1200 Potential vs Fc
-600
-1400
10 µ H N O
600
500
400
300
200
Potential vs Fc
S47
+/0
100
mv
0
-100
-200
10 µ
N ClO4O
400
300
200
100 +/0
Potential vs Fc
mv
0
-100
-200
-1100
-1200
-1300
10 µ
-
N O
-600
-700
-800
-900
-1000
Potential vs Fc
S48
+/0
mv
-308 mv
10 µ H N N
-217 mv 0
-100
-200
-300
Potential vs Fc
-400
+/0
-500
mv
10 µ
N ClO4 N
0
-100
-200
-300
-400
-500
Potential vs Fc
S49
+/0
mv
-600
-700
10 µ
-
N N
-1000
-1100
-1200
-1300
Potential vs Fc
-1400
+/0
mv
-1500
10 µ
H
H
O
1400
1200 1000 +/0 Potential vs Fc mv
S50
800
10 µ H C ClO4O
0
H
H
-200 -400 +/0 Potential vs Fc mv
-600
10 µ
S
1400
1300
1200 1100 1000 900 +/0 Potential vs Fc mv
S51
800
700
600
10 µ H C ClO4S
0
-200 +/0 Potential vs Fc mv
THE END
S52
-400
CONTENTS
S1
SI-1
General Methods
S2
SI-2
Synthetic routes of XH and X+
S2
SI-3
Representative 1H NMR spectra of XH and X+
S16
SI-4
Representative Esi-Ms spectrum of X+
S41
SI-5
Representative UV spectra of X+
S42
SI-6
Representative CV graphs of XH and X+
S46
S1
SI–1. General Methods 1
Solvents and reagents were obtained from commercial sources and used as received.
H NMR
spectra were recorded in CDCl3, CD3CN and DMSO-d6 on 300MHz NMR spectrometer. The chemical shifts ( ) were described in parts per million (ppm) downfield from tetramethylsilane (TMS, 0.00 ppm) as an internal standard. All reagents of commercial quality were from freshly opened containers or were purified according to the standard methods before use.
Reagent grade acetonitrile was refluxed over
KMnO4 and K2CO3 for several hours and was distilled over P2O5 under argon twice before use. The commercial tetrabutylammonium hexafluorophosphate (Bu4NPF6, Aldrich) was recrystallized from o
CH2Cl2/Et2O and dried in vacuo at 110 C overnight before preparation of a supporting electrolyte solution. Acetonitrile containing 0.1 M tetra-n-butylammonium hexafluorophosphate (TBAPF6) was used as solvent in electrochemical measurements. Ferrocene/ferrocenium redox couple (Fc+/0) was used as an internal reference for all measurements. All electrochemical measurements were performed under dry nitrogen atmosphere using 0.1 V/s scan rate, unless otherwise specified, the concentration of samples was 10-3 M.
SI-2. Synthetic Routes of XH and X+ Synthetic Route of 3H (G = Br)S1 H N S
H N
BrN
Br2
NaBH4 Br
S
Br
Br
S
Br
Phenothiazine (10 mmol) was dissolved in oxygen-free glacial acetic acid (120mL), and a solution of bromine also in acetic acid (100mL, 10% v/v, 195mmol) was added to it all at once with vigorous stirring for about one minute. The water (400 mL) was added to the mixture, the red precipitate was filtered, washed with ether absolute, dried under vacuum, then 3,7-dibromophenothiazinium bromide was obtained. 3,7-Dibromophenothiazinium bromide (8 mmol) was dissolved in methanol S2
(30 mL), and sodium borohydride (15mmol) was added with stirring for about 20 minute. The methanol was eliminated by distillation under vacuum. Column chromatography of the residue solid (eluant: ethyl acetate/petroleum ether) afforded 3,7-dibromophenothiazine. The yield is over 80%.
H N Br 1
S
(3,7-dibromophenothiazine) Br
H NMR (300 MHz, (CD3)2SO), 8.41 (s, 1H), 6.60 (m, 2H), 7.13 (m, 4H). UV-vis:
max =
258nm,
322nm. Anal. Calcd for C12H7NSBr2 (357): C, 40.34; H, 1.96; N, 3.92. Found: C, 40.31; H, 1.94; N, 3.90.
Synthetic Route of 3H (G = Cl )S2 H N
H N
PCl 5 S
Cl
S
Cl
Phenothiazine (10 mmol), PCl5 (30 mmol) in 80 mL of chloroform were heated together and refluxed for 3 hour. The chloroform was eliminated by distillation under vacuum. Then the solid residue was poured into water (200 mL) and stirred for 20 min. The precipitate formed was collected by filtration, washed with 70% ethanol (50mL), then crude 3,7-dichlorophenothiazine was obtained. Column chromatography of the crude product (eluant: ethyl acetate/petroleum ether) afforded 3,7-dichlorophenothiazine. The yield is over 85%. H N Cl 1
S
(3,7-dichlorophenothiazine) Cl
H NMR (300 MHz, (CD3)2SO),
8.3 (s, 1H), 7.1 (m, 5H), 7.32 (m, 1H). UV-vis:
max =
258nm,
325nm. Anal. Calcd for C12H7NSCl2 (268): C, 53.73; H, 2.61; N, 5.22. Found: C, 53.75; H, 2.59; N, 5.24.
Synthetic Route of 1H (G = Br, Cl)S3
S3
NH 2
NO 2
NH 2 SH
G
KOH
S
Ac 2O
+ G
O 2N
NHAc S O 2N
G
H N
KOH
S
G
G
(G = Cl, Br)
To a solution of 19.2 g (0.1 moles) of 2,5-dichloronitrobenzene and 12.5 g (0.1 moles) of 2-aminobenzenethiol in 300 mL of 2-propanol was added dropwise, with stirring, a solution of 6.6 g. (0.1 moles) of 2.8g potassium hydroxide in 15 ml. of 95% ethanol. Subsequently, the mixture was stirred and refluxed for three hours, and then concentrated to dryness. The residual solid was stirred with 40 mL of water, filtered and air-dried.
11 g of the crude product of 2-aminophenyl
4-chloro-2-nitrophenyl sulfide was obtained. The crude sulfide, 100 mL of acetic anhydride, 5 ml of pyridine were mixed and heated for two hours and filtered hot. The filtrate was concentrated to about 15 ml and cooled. The separated solid was filtered and air-dried to give 17g of crude 2-acetamidophenyl 4-chloro-2-nitrophenyl sulfide.
2-Acetamidophenyl 4-chloro-2-nitrophenyl
sulfide was dissolved in 400 ml of acetone and a solution of 3 g of 85% potassium hydroxide in 25 ml of 95% ethanol was added. The mixture was stirred and diffused with nitrogen for about 15 minutes, 7 g of the crude acetamido derivative was added and the mixture distilled from the steambath as rapidly as possible under nitrogen. The residue was stirred with 40 mL of water, the solid was filtered and dried to give 4 g of crude 3-chlorophenothiazine.
The crude product
recrystallized from xylene gave pure product 3.5g. H N S 1
(3-chlorophenothiazine) Cl
H NMR (300 MHz, (CD3)2SO), : 8.71 (s, 1H), 7.01-6.64 (m, 7H). UV-vis:
max =
255nm, 315nm.
Anal. Calcd for C12H8NSCl (233.5): C, 61.67; H, 3.43; N, 6.00. Found: C, 61.64; H, 3.41; N, 6.02. H N S 1
(3-bromoxyphenothiazine) Br
H NMR (300 MHz, (CD3)2SO),
8.70 (s, 1H), 7.10-6.62 (m, 7H). UV-vis:
max =
252nm, 311nm.
Anal. Calcd for C12H7NSBr2 (278): C, 51.80; H, 2.88; N, 5.04. Found: C, 51.83; H, 2.86; N, 5.02. Synthetic Routes of 1H, 3H (G=CH3, CH3O).S4 S4
NH 2
Br
K 2CO 3
G
H N
CuI
+
G
H N
S
G
I2
G
S
G
G
(G = CH 3 CH 3O)
NH 2
I CuI
+
H N
K 2CO 3
H N
S G
I2
S
G
H N
G
G (G = CH 3 CH 3 O NMe 2)
I
NH 2 +
CuI
H N
G
I2
K 2CO 3
G
S
S
(G = CH 3 CH 3 O)
A mixture of aryl halide (30 mmol), aniline (20 mmol), K2CO3 (40 mmol), CuI (2 mmol), and L-proline (4 mmol) in 30 mL of DMSO was heated at 90 °C for 24-30 h under inert atmosphere. The cooled mixture was partitioned between water and ethyl acetate. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo. The residual oil was loaded on a silica gel column and eluted with ethyl acetate/petroleum ether to afford the corresponding diphenylamine. Substituted diphenylamine (10 mmol), I2 (2 mmol) in 20 mL of o-dichlorobenzene were heated together and refluxed for 15-30 min under inert atmosphere. The o-dichlorobenzene was eliminated by distillation under reduced pressure. Column chromatography of the solid residue (eluant: ethyl acetate/petroleum ether) afforded Substituted-phenothiazine. The yield is over 30%.
H N S 1
(3-dimethylaminophenothiazine) N(CH3)2
H NMR (300 MHz, (CD3)2SO), 8.23 (s, 1H), 6.88-6.96 (m, 3H), 6.64-6.73 (m, 3H), 6.36-6.38 (m, S5
1H), 2.83 (s, 3H), 2.76 (s, 3H). UV-vis:
max =
254nm, 317nm. Anal. Calcd for C14H14N2S (242):
C, 69.42; H, 5.79; N, 11.57. Found: C, 69.40; H, 5,77; N, 11.59.
H N H3CO 1
(3,7-dimethoxyphenothiazine)
S
OCH3
H NMR (300 MHz, (CD3)2SO),
8.13 (s, 1H), 6.62-6.57 (m, 6H), 3.65 (s, 6H). UV-vis:
max =
252nm, 316nm. Anal. Calcd for C14H13NSO2 (259): C, 64.86; H, 5.02; N, 5.41. Found: C, 64.89; H, 5.04; N, 5.39.
H N H3C 1
(3,7-dimethylphenothiazine)
S
CH3
H NMR (300 MHz, (CD3)2SO),
8.31 (s, 1H), 6.73-6.57 (m, 6H), 2.12 (s, 6H). UV-vis:
max=
256nm, 314nm. Anal. Calcd for C14H13NS (227): C, 74.01; H, 5.73; N, 6.17. Found: C, 73.98; H, 5.74; N, 6.20.
H N S 1
(3-methoxyphenothiazine) OCH3
H NMR (300 MHz, (CD3)2SO),
8.36 (s, 1H), 6.98-6.63 (m, 7H), 3.65 (s, 3H). UV-vis:
max=
254nm, 315nm; Anal. Calcd for C13H11NSO (229): C, 68.12; H, 4.80; N, 6.11. Found: C, 68.15; H, 4.82; N, 6.14. H N
OCH3
(2-methoxyphenothiazine)
S 1
H NMR (300 MHz, (CD3)2SO), 8.59 (s, 1H), 6.83-6.90 (m, 2H), 6.66-6.75 (m, 3H), 6.32-6.39 (m,
2H), 3.68 (s, 3H). UV-vis:
max=
250 nm, 317 nm. Anal. Calcd for C13H11NSO (229): C, 68.12; H,
4.80; N, 6.11. Found: C, 68.09; H, 4.81; N, 6.13.
S6
H N S 1
(3-methylphenothiazine) CH3
H NMR (300 MHz, (CD3)2SO),
8.45 (s, 1H), 6.97-6.59 (m, 7H), 2.12 (s, 3H). UV-vis:
max =
255nm, 307nm; Anal. Calcd for C13H11NS (213): C, 73.24; H, 5.16; N, 6.57. Found: C, 73.21; H, 5.18; N, 6.59. H N
CH3
(2-methylphenothiazine)
S 1
H NMR (300 MHz, (CD3)2SO), 8.50 (s, 1H), 6.51-6.89 (m, 7H), 2.15 (s, 3H). UV-vis:
max =
249
nm, 316nm. Anal. Calcd for C13H11NS (213): C, 73.24; H, 5.16; N, 6.57. Found: C, 73.27; H, 5.15; N, 6.56.
H N (H3C) 2N 1
(3,7-di-dimethylaminophenothiazine)
S
N(CH3)2
H NMR (300 MHz, CD3CN), 7.10-7.14 (m, 4H), 6.61-6.64 (m, 2H), 3.10 (s, 12H). H N
(phenoxazine)
O 1
H NMR (300 MHz, (CD3CN),
6.50-6.77 (m, 8H). UV-vis:
max =
240 nm, 314nm. Anal. Calcd
for C13H11NS (213): C, 78.69; H, 4.92; N, 7.65. Found: C, 78.66; H, 4.90; N, 7.63.
Synthetic Routes of X+ (1+-4+) Method AS5 H N G
S
H N
H2 O2 G
G
N
HClO4
S O
G
G
S
ClO4G
Substituted phenothiazine (5 mmol) dissolved in 50 mL of heated ethanol, 30% hydrogen peroxide S7
(8 mmol) was added to it and refluxed for 1-2 hour. The ethanol was eliminated by distillation under vacuum. The residue solid washed with water and ethyl acetate/petroleum ether (1/1). The crude product recrystallized from 90% ethanol gave substituted phenothiazine-5-oxide. Substituted phenothiazine-5-oxide (2 mmol) dissolved in 5-10 mL of oxygen-free glacial acetic acid, 70% perchloric acid (2 mL) was added to it at 0 °C and stirred for about 20 minute. Then 150 mL of ether absolute was added to it, the red precipitate formed was collected by filtration, washed with 150 mL of ether absolute, dried under vacuum, and substituted phenothiazinium perchlorate was obtained. The yield is over 50%.
Method B H N G
N
NO+ClO4-
S
G
H N
dry CH3CN
NO+ClO4 dry CH3CN
O
G
S
ClO4G
N ClO4O
Phenoxazine (0.5 mmol) in 20 mL of dry acetonitrile and NO+ClO4- (0.5 mmol) in 20 mL of dry acetonitrile were mix and stirred for about 10 minute. Then 150 mL of ether absolute was added to it, the red precipitate formed was collected by filtration, washed with 150 mL of ether absolute, dried under vacuum, and phenoxazinium perchlorate was obtained. The yield is over 70%.
N
ClO4-
S 1
(3-dimethylaminophenothiazinium perchlorate)
N(CH3 )2
H NMR (300 MHz, CD3CN),
8.23 (m, 1H), 8.10-8.14 (m, 2H), 7.90-7.92 (m, 2H), 7.78-7.81 (m,
2H), 3.67 (s, 3H), 3.63 (s, 3H). UV-vis:
max
= 577nm; ESI-MS/M+ = 241. Anal. Calcd for
C14H13N2SClO4 (340.5): C, 49.34; H, 3.82; N, 8.22. Found: C, 49.37; H, 3.84; N, 8.22.
N H3 CO 1
S
ClO 4-
(3, 7-dimethoxyphenothiazinium perchlorate)
OCH3
H NMR (300 MHz, CD3CN), 8.64 (m, 2H), 8.13 (m, 2H), 7.90 (m, 2H), 4.25 (s, 6H). UV-vis: S8
max
= 285.5nm, 499nm. ESI-MS/M+ = 258. Anal. Calcd for C14H12NSClO6 (357.5): C, 46.99; H, 3.36; N, 3.92. Found: C, 46.96; H, 3.38; N, 3.90.
N H3C 1
ClO4-
S
(3, 7-dimethylphenothiazinium perchlorate)
CH3
H NMR (300 MHz, CD3CN), max =
8.79 (m, 2H), 8.68 (m, 2H), 8.34 (m, 2H), 2.88 (s, 6H). UV-vis:
286nm, 448nm. ESI-MS/M+ = 226. Anal. Calcd for C14H12NSClO4 (325.5): C, 51.61; H,
3.69; N, 4.30. Found: C, 51.65; H, 3.67; N, 4.32.
N
ClO4-
S 1
(3-methoxyphenothiazinium perchlorate)
OCH3
H NMR (300 MHz, CD3CN),
UV-vis:
max
8.81-8.72 (m, 4H), 8.37 (m, 2H), 8.04 (m, 1H), 4.34 (s, 3H).
= 283nm, 443nm. ESI-MS/M+ = 228. Anal. Calcd for C13H10NSClO5 (327.5): C,
47.63; H, 3.05; N, 4.27. Found: C, 47.64; H, 3.06 N, 4.25.
N
OCH3 ClO4-
(2-methoxyphenothiazinium perchlorate)
S 1
H NMR (300 MHz, CD3CN),
3H). UV-vis:
max =
8.92-8.96 (m, 3H), 8.65-8.69 (m, 2H), 8.23-8.26 (m, 2H), 4.15 (s,
284nm, 428nm. ESI-MS/M+ = 228. Anal. Calcd for C13H10NSClO5 (327.5):
C, 47.63; H, 3.05; N, 4.27. Found: C, 47.59; H, 3.04; N, 4.29.
N S 1
ClO4-
(3-methylphenothiazinium perchlorate)
CH3
H NMR (300 MHz, CD3CN), 8.97-8.75 (m, 4H), 8.52 (m, 2H), 8.37 (m, 1H), 2.91 (s, 3H). UV-vis: max =
283.5nm, 433nm. ESI-MS/M+ = 212. Anal. Calcd for C13H10NSClO4 (311.5): C, 50.08; H,
3.21; N, 4.49. Found: C, 50.05; H, 3.23; N, 4.51.
S9
N
CH3
(2-methylphenothiazinium perchlorate)
ClO4S 1
H NMR (300 MHz, CD3CN), UV-vis:
8.73-8.81 (m, 4H), 8.41-8.43 (m, 2H), 8.35 (m, 1H), 2.77 (s, 3H).
282nm, 422nm. ESI-MS/M+ = 212. Anal. Calcd for C13H10NSClO4 (311.5): C,
max =
50.08; H, 3.21; N, 4.49. Found: C, 50.12; H, 3.19; N, 4.47.
N ClO4-
(phenothiazinium perchlorate)
S 1
H NMR (300 MHz, CD3CN),
9.0-8.92 (m, 4H), 8.60-8.49 (m, 4H). UV-vis:
max
= 282nm,
420nm. Anal. Calcd for C12H8NSClO4 (297.5): C, 48.40; H, 2.69; N, 4.71. Found: C, 48.44; H, 2.71; N, 4.73.
N ClO4-
(phenoxazinium perchlorate)
O 1
H NMR (300 MHz, CD3CN), 8.77-8.67 (m, 4H), 8.47-8.43 (m, 2H), 8.36-8.32 (m, 2H). UV-vis: max =
260.5nm, 422nm. Anal. Calcd for C12H8NClO5 (281.5): C, 51.15; H, 2.84; N, 4.97. Found:
C, 51.19; H, 2.86; N, 4.99.
N ClO4S 1
(3-chlorophenothiazinium perchlorate)
Cl
H NMR (300 MHz, CD3CN),
8.98-8.79 (m, 4H), 8.65-8.41 (m, 3H). UV-vis:
max
= 287nm,
439nm. Anal. Calcd for C12H7NSCl2O4 (332): C, 43.37; H, 2.11; N, 4.22. Found: C, 43.35; H, 2.12; N, 4.23.
N
Cl ClO4-
(2-chlorophenothiazinium perchlorate)
S 1
H NMR (300 MHz, CD3CN),
8.95-8.77 (m, 4H), 8.61-8.44 (m, 3H). UV-vis: S10
max
= 285nm,
422nm. Anal. Calcd for C12H7NSCl2O4 (332): C, 43.37; H, 2.11; N, 4.22. Found: C, 43.40; H, 2.10; N, 4.24.
N ClO4S 1
(3-bromoxyphenothiazinium perchlorate)
Br
H NMR (300 MHz, CD3CN),
9.01-8.85 (m, 4H), 8.65-8.43 (m, 3H). UV-vis:
max
= 288nm,
442nm. Anal. Calcd for C12H7NSBrClO4 (376.5): C, 38.25; H, 1.86; N, 3.72. Found: C, 38.21; H, 1.87; N, 3.73.
N Cl 1
ClO 4-
S
(3,7-dichlorophenothiazinium perchlorate)
Cl
H NMR (300 MHz, CD3CN), 9.10-8.98 (m, 4H), 8.6-8.4 (m, 2H). UV-vis:
max =
297nm, 465nm.
Anal. Calcd for C12H6NSCl3O4 (366.5): C, 39.29; H, 1.64; N, 3.82. Found: C, 39.26; H, 1.65; N, 3.84.
N Br 1
ClO4-
S
(3,7-dibromophenothiazinium perchlorate)
Br
H NMR (300 MHz, CD3CN), 9.19-9.15 (m, 2H), 8.81-8.78 (m, 2H), 8.62-8.59 (m, 2H). UV-vis: max
= 294nm, 465nm. Anal. Calcd for C12H6NSBr2ClO4 (455.5): C, 31.61; H, 1.32; N, 3.07.
Found: C, 31.64; H, 1.33; N, 3.09.
N (H3C) 2N 1
S
ClO4 -
(3,7-di-dimethylaminophenothiazinium perchlorate)
N(CH3)2
H NMR (300 MHz, CD3CN), 7.81 (m, 2H), 7.20-7.21 (m, 2H), 7.11 (m, 2H), 3.3 (s, 12H). UV-vis: max=
655nm.
Synthetic Route of X+ (6+, 7+)
S11
O
H
OH
H
HClO 4
NaBH 4 CH 3 OH
X
(CH 3CO)2 O
X
ClO 4X
(X = S, O)
Xanthen-9-one or thioxanthen-9-one (8 mmol) was dissolved in methanol (30 mL), and sodium borohydride (15mmol) was added with stirring for about 20 minute. The methanol was eliminated by distillation under vacuum. acetate/petroleum
ether)
Column chromatography of the residue solid (eluant: ethyl
afforded
Xanthen-9-ol
or
thioxanthen-9-ol.
Xanthen-9-ol
or
thioxanthen-9-ol (2 mmol) dissolved in 5 mL of oxygen-free acetic anhydride, 70% perchloric acid (2 mL) was added to it at 0 °C and stirred for about 10 minute. Then 150 mL of ether absolute was added to it, the precipitate formed was collected by filtration, washed with 150 mL of ether absolute, dried under vacuum, and xanthylium perchlorate or thioxanthylium perchlorate was obtained. The yield is over 70%. H C ClO4-
(xanthylium perchlorate)
O 1
H NMR (300 MHz, CD3CN),
2H).
UV-vis:
max=253nm,
10.40 (s, 1H), 8.66-8.68 (m, 4H), 8.40-8.42 (m, 2H), 8.12-8.13 (m, 371nm.
Anal. Calcd for C13H9ClO5 (280.5): C, 55.61; H, 3.21.
Found: C, 55.64; H, 3.24. H C ClO4-
(thioxanthylium perchlorate)
S 1
H NMR (300 MHz, CD3CN),
2H). UV-vis:
max=275nm,
10.31 (s, 1H), 8.82-8.91 (m, 4H), 8.44-8.47 (m, 2H), 8.23-8.25 (m,
379nm. Anal. Calcd for C13H9SClO4 (296.5): C, 52.61; H, 3.04.
Found: C, 52.65; H, 3.07.
Synthetic Route of XH (6H, 7H)
S12
H
H
H
NaBH 4
ClO 4-
dry CH 3CN
X
X
(X = S, O)
Xanthylium perchlorate or thioxanthylium perchlorate (2 mmol) dissolved in 30 mL of dry acetonitrile, sodium borohydride (4mmol) was added to it with stirring for about 10 minute. The acetonitrile was eliminated by distillation under vacuum. Column chromatography of the residue solid (eluant: ethyl acetate/petroleum ether) afforded Xanthene or thioxanthene.
H
H
(9H-xanthene) O 1
H NMR (300 MHz, Cl3CD), max=210nm,
7.15-7.19 (m, 4H), 6.99-7.02 (m, 4H), 4.05 (s, 2H). UV-vis:
243nm. Anal. Calcd for C13H10O (182): C, 85.71; H, 5.49. Found: C, 85.68; H,
5.47.
H
H
(9H-thioxanthene) S 1
H NMR (300 MHz, Cl3CD),
7.43 (m, 2H), 7.30 (m, 2H), 7.19-7.21 (m, 4H), 3.85 (s, 2H).
max =
213nm, 264nm. Anal. Calcd for C13H10S (198): C, 78.79; H, 5.05. Found: C, 78.76; H, 5.03.
Synthetic Route of 5+S6 O N N
Na 2S 2 O 4
H N
Ac 2 O
N H
O
CH 3
ClO 4
CH 3
N
KH
N
N H
CH 3 I
N CH 3
HClO 4 NaNO 2
N N CH 3
To a boiling solution of phenazine (11 mmol) in ethanol (50 ml) was added a solution of sodium dithionite (110 mmol) in water (200 ml).
The resulting solid immediately precipitated was
collected by filtration and dried over phosphorous pentoxide under reduced pressure to give 5,10-dihydrophenazine. 5,10-Dihydrophenazine (2.5 mmol) in 5 mL of acetic anhydride were heated boiled for 2 min, cooled. The solid which separated was filtered, washed with ether, dried S13
under vacuum, and recrystallized from 90% ethanol gave 10-acetyl-5,10-dihydrophenazine. To 60 ml DMSO solvent containing (10 mmol) 10-acetyl-5,10-dihydrophenazine., 1.20g (> 50%) sodium hydride-mineral oil suspension was added under inert atmosphere. Abundant of gas was released and the solution turned to dark-red. Methyliodide (15 mmol) was added dropwise and the mixture was stirred under nitrogen for 0.5 h, after which the solution was poured into ice-water. The crude product was isolated and extracted with chloroform, dried over the MgSO4 and the solvent removed in vacuo to give the crude material. Further purification was taken on by the column chromatography using ethyl acetate/petroleum ether as the eluant to give 10-acetyl-5- methyl -dihydrophenazine. 10-Acetyl-5- methyl-dihydrophenazine (2 mmol) dissolved in 10 mL of ethanol, and a solution of 70% perchloric acid (6 mL), water (20 mL) and sodium nitrite (0.6 g) was added stirred for about 15 minute. Then 100 mL of ether was added to it, the yellow precipitate formed was collected by filtration, washed with 50 mL of ether absolute, dried under vacuum, and 5-methyl-phenazinium perchlorate was obtained. The yield is over 60%.
N ClO 4
(5-methyl-phenazinium perchlorate)
N CH 3
1
H NMR (300 MHz, (CD3)2CO), 8.91 (d, 2H), 8.63 (d, 2H), 8.53 (t, 2H), 8.30 (t, 2H), 5.18 (s, 3H).
UV-vis:
max=384.5nm.
ESI-MS/M+ = 195. Anal. Calcd for C13H11N2ClO4 (294.5): C, 52.97; H,
3.74; N, 9.51. Found: C, 52.94; H, 3.77; N, 9.53.
Synthetic Route of 5HS7 N ClO 4 N
Na 2S 2 O 4 H 2O
CH 3
H N N CH 3
5- Substituted benzyl-phenazinium perchlorate (2 mmol) dissolved in 5 mL of ethanol, a solution of sodium dithionite (850 mg) in water (40 ml) was added dropwise and the mixture was stirred 5 min. The precipitate formed was collected by filtration, washed with water, dried under vacuum, and S14
5-substituted benzyl-5,10-dihydrophenazine was obtained. The yield is over 85%.
H N
(N-methyldihydrophenazine) N CH 3
1
H NMR (300 MHz, (CD3)2SO), 6.56 (m, 4H), 6.38 (d, 2H), 6.30 (d, 2H), 2.86 (s, 3H).
References (S1) Leventis, N.; Chen, M.; Sotirious-Leventis, C. Tetrahedron, 1997, 53, 10083. (S2) Strell, M.; Rupprecht, M. German Patent No. 938669, 1956; Chem. Abstr. 1959, 57, 8173a. (S3) Yale, H.L. J. Am. Chem. Soc. 1955, 77, 2270. (S4) (a) Zhang, H.; Cai, Q. and Ma, D. J. Org. Chem. 2005, 70, 5164. (b) Craig, J. C.; Rogers, W. P. and Warwick, G. P. Aust. J. Chem. 1955, 8, 252-257. (S5) Kehrmann, F. and Diserens L. Berichte der deutschen chemischen Gesellschaft 1915, 48, 318. (S6) Grande, H.J.; Schagen, C.G.; Jarbandhan, T. and Muller, F. Helv. Chim. Acta 1977, 60, 348. (S7) Sugimoto, A.; Kotani, T.; Tsujimoto, J. and Yoneda, S. J. Het. Chem. 1955, 77, 2270.
S15
0
500
O
5.0
H N
0.0
( in CD3 CN )
1000
SI-3. Representative 1H NMR Spectra of XH and X+
6.495 8.00
10.0 ppm (t1)
6.767 6.642
S16
8.0
6.685 6.672 6.667 6.659 6.642 6.0
5.0
4.0
3.0
2.0
S
7.00
S17
6.770 7.0
H N
9.0 ppm (t1)
Cl
8.714
1.13
7.007
1.0
( in DMSO-d6 )
0.0
0
500
1000
9.0 ppm (t1)
8.0
6.886 6.774
2.36
8.496
1.02
S18
7.0
6.511 6.0
5.0
4.0
3.0
2.154 2.0
H N S
3.18
6.693 6.667 6.663 2.33 3.24
2.502
1.0
0.0
( in DMSO-d6 )
0
100
200
300
400
500
600
700
8.0
6.689 6.662 1.82
6.751 6.747
3.00 2.05
S19
6.832 6.804
7.0
6.397 6.388 6.360 6.326 6.317 6.0
5.0
4.0
3.0
2.0
H N
9.0 ppm (t1)
1.0
H3CO
S
3.678 3.15
8.589
1.12
6.900
0.0
( in DMSO-d6 )
-100
0
100
200
300
400
500
600
700
7.426
ppm (t1)
7.302 7.207 7.196
7.0
6.0
5.0
3.854
2.01
S20
4.0
3.0
2.0
H
H S
4.11 2.03 2.00
1.0
0.0
in CCl3CD
0
500
1000
1500
8.0 ppm (t1)
6.0
5.0
4.050
7.055 7.029 7.019
4.44
S21
4.0
2.00
7.0
H
H O
7.154
4.28
7.190
3.0
in CCl3CD
0
500
1000
1500
2000
2500
3000
5.0
H N
ppm (f1)
Cl
S
6.929 6.902 6.790
2.07 2.14 1.94 1.12
8.764
1.00
S22
6.721
7.016
0.0
( in DMSO-d6 )
0
500
1000
1500
2000
2500
8.0
7.104 1.18 1.09 1.20 1.08 1.08 2.00
8.711
1.03
S23
7.000 7.0
6.0
5.0
4.0
H N
9.0 ppm (f1)
3.0
Br
S
6.622
6.766 6.687
6.899
( in DMSO-d6 )
2.0
-100
0
100
200
300
400
500
600
700
800
5.0
H N
10.0 ppm (f1)
Cl
S
Cl
7.322 7.314 5.12 1.22
8.299
1.00
S24
7.099
0.0
( in DMSO-d6 )
0
100
200
300
400
500
600
5.0
H N
ppm (f1)
Br
S
Br
6.603
2.09
7.128
4.12
8.841
1.00
S25
( in DMSO-d6 )
0.0
0
500
1000
8.0
6.737
6.967 1.67 2.54 2.30
S26
7.0
6.0
H N
9.0 ppm (f1)
5.0
4.0
( in DMSO-d6 )
3.0
2.123 2.0
3.00
S
8.447
1.01
3.332
6.591
1.0
0.0
0
100
200
300
400
ppm (t1)
5.0
H N
S
2.117 6.06
6.566
6.725
2.00 4.14
8.311
0.96
S27
0.0
( in DMSO-d6 )
0
100
200
300
400
500
600
5.0
H N
10.0 ppm (t1)
OCH3
S
3.652 3.19
6.977 1.18 3.02 1.29 1.01 1.32
8.364
0.75
S28
6.625
6.897
0.0
( in DMSO-d6 )
-100
0
100
200
300
400
500
600
700
5.0
H N
ppm (t1)
OCH3
S
OCH3
3.648 6.00
6.608 6.572 6.02
8.128 8.120
1.15
S29
2.502
0.0
( in DMSO-d6 )
0
100
200
300
400
500
600
ppm (f1)
10.0
8.755
9.0
8.432 8.359 8.335 8.332 8.0
7.0
6.0
N O ClO4
8.708 8.679 8.462 2.00 2.09
4.21
S30
5.0
( in CD3CN )
4.0
0
100
200
300
400
500
5.0
N
10.0 ppm (f1)
OCH3
S ClO4
OCH3
4.252 6.38
8.134 7.905 7.898 7.874 7.866
2.00 1.99
8.645 8.614
2.09
S31
( in CD3CN )
0.0
0
100
200
300
400
500
600
10.0
5.0
N
15.0 ppm (t1)
0.0
OCH3
S ClO4
S32
4.341
8.044 8.036 8.012 8.004
8.367
8.755 8.723
( in CD3CN )
0
100
200
300
400
500
600
11.0 ppm (f1)
10.0
9.0
8.127 8.123 2.07
8.421 2.00 8.0
7.0
6.0
5.0
4.0
H C O
ClO4
8.668 4.19
10.403
1.02
S33
3.0
2.0
( in CD3CN )
0
100
200
300
400
ppm (f1)
11.0
10.0
8.255 2.03
8.790 8.472 2.00
8.910 8.882 8.819 4.09
S34
9.0
8.0
7.0
H C S
ClO4
10.307
1.11
6.0
( in CD3CN )
0
100
200
300
400
8.407 8.402 8.377 8.372
8.0
7.0
6.0
ClO4
5.0
S
8.879 8.848 8.751 8.519 8.506 8.493
1.04 2.11 1.02
S35
9.0
N
8.972 8.939
ppm (f1)
4.0
( in CD3CN )
2.911 3.0
3.00
CH3
1.18 2.04
2.0
1.0
-100
0
100
200
300
400
500
600
700
800
8.313
8.0
7.0
6.0
5.0
4.0
2.881 6.14
8.342
2.04
8.793 8.684
4.00
S36
3.0
2.0
N
9.0 ppm (f1)
1.0
CH3
S ClO4
CH3
0.0
( in CD3CN )
-50
0
50
100
150
200
250
300
350
10.0 ppm (f1)
ClO4
5.0
N S
8.568
4.13
8.992 8.952
4.00
S37
( in CD3CN )
0.0
-100
0
100
200
300
400
500
600
700
5.0
N
8.813 8.782
2.13 2.30
9.191 9.184
2.00
ppm (t1)
Br
S ClO4
Br
S38
8.627 8.620 8.597 8.590
( in CD3CN )
0.0
0
100
200
300
400
500
600
7.171
7.277 7.268
7.0
6.0
ClO4
5.0
N
7.840
1.07 1.19
S39
8.0 ppm (f1)
4.0
( in CD3CN )
3.250 12.00
N(CH3)2
S
N(CH3) 2
7.808 7.309 7.300
2.11 1.08 1.10
3.0
2.0
1.0
0
100
200
300
400
500
600
S40
ppm (t1)
8.913 8.638 8.635 8.607
2.29 2.28 2.34 2.23
8.534 8.529 8.301 8.298
3.00
5.181
5.0 ClO4
N
N
( in CD3CN )
0.0 0
500
SI-4. Representative Esi-Ms Spectrum of X+
06-12-14-2 #2 RT: 0.02 AV: 1 NL: 1.90E7 T: + c ESI Full ms [ 50.00-600.00] 228.3
100 95 90
N
85
ClO4-
80
S
75
OCH3
70
Relative Abundance
65 60 55 50 45 40 35 30 25 197.4 20
229.3
101.2
15
185.3
10 204.3 213.2
179.1
5 92.3 99.3 102.2
70.9
0 60
80
100
120.1 120
135.2 141.2 140
153.1
195.3
167.3 160 m/z
S41
180
230.2 242.2
200
220
240
259.1 260
274.8
SI-5. Representative UV Spectra of X+
=281 nm
max
1.4
N ClO4-
1.0
S 0.8 0.6
=420 nm
max
0.4 0.2 0.0 250
300
350
400
450
500
Wavelength (nm)
=260.5 nm
max
=422 nm
max
0.8
Absorbance
Absorbance
1.2
N 0.6
ClO4O
0.4
0.2
0.0 250
300
350
400
450
Wavelength (nm)
S42
500
550
600
1.6
N
=297 nm
max
Absorbance
1.4
Cl
ClO 4-
S
Cl
1.2 1.0
=465 nm
0.8
max
0.6 0.4 0.2 0.0
250
300
350
400
450
500
550
Wavelength (nm)
2.5
=288 nm
max
N ClO4-
Absorbance
2.0 S
Br
1.5
=442 nm
max
1.0
0.5
0.0 250
300
350
400
450
Wavelength (nm)
S43
500
550
=284 nm
1.2
N
max
H3 CO
Absorbance
1.0
ClO4-
S
OCH3
=499 nm
max
0.8 0.6 0.4 0.2 0.0 300
400
500
600
700
Wavelength (nm)
1.2
=282 nm
max
N
Absorbance
1.0
ClO4-
S
0.8
CH3
0.6
=465 nm
max
0.4 0.2 0.0 250
300
350
400
Wavelength (nm)
S44
450
500
550
1.0
=384.5 nm
N
max
0.8
ClO4
Absorbance
N
0.6 0.4 0.2 0.0 -0.2 300
350
400
450
Wavelength (nm)
S45
500
550
-
SI-6. Representative CV and/or OSWV Graphs of XH, X+ and X
10 µ
H N S
1000
800
600
400 200 +/0 Potential vs Fc mv
0
10 µ
N ClO4S 250
200
150
100 50 0 -50 +/0 mv Potential vs Fc
S46
-100
-150
10 µ
-
N S
+/0 -800 -1000 mv -1200 Potential vs Fc
-600
-1400
10 µ H N O
600
500
400
300
200
Potential vs Fc
S47
+/0
100
mv
0
-100
-200
10 µ
N ClO4O
400
300
200
100 +/0
Potential vs Fc
mv
0
-100
-200
-1100
-1200
-1300
10 µ
-
N O
-600
-700
-800
-900
-1000
Potential vs Fc
S48
+/0
mv
-308 mv
10 µ H N N
-217 mv 0
-100
-200
-300
Potential vs Fc
-400
+/0
-500
mv
10 µ
N ClO4 N
0
-100
-200
-300
-400
-500
Potential vs Fc
S49
+/0
mv
-600
-700
10 µ
-
N N
-1000
-1100
-1200
-1300
Potential vs Fc
-1400
+/0
mv
-1500
10 µ
H
H
O
1400
1200 1000 +/0 Potential vs Fc mv
S50
800
10 µ H C ClO4O
0
H
H
-200 -400 +/0 Potential vs Fc mv
-600
10 µ
S
1400
1300
1200 1100 1000 900 +/0 Potential vs Fc mv
S51
800
700
600
10 µ H C ClO4S
0
-200 +/0 Potential vs Fc mv
THE END
S52
-400
