Copper Catalysed Synthesis of Trifluoromethyl(hetero ... · Copper Catalysed Synthesis of...
Transcript of Copper Catalysed Synthesis of Trifluoromethyl(hetero ... · Copper Catalysed Synthesis of...
Supporting information
Copper Catalysed Synthesis of Trifluoromethyl(hetero)arenes from
Di(hetero)aryl- λ3-iodanes
Vinay Kumar Pandey and Pazhamalai Anbarasan*
Department of Chemistry, Indian Institute of Technology Madras, Chennai-600036, India.
Table of contents
1 General Comments 2
2 Analytical Methods 2
3 Copper(I) catalyzed trifluoromethylation of diphenyliodonium salt: Optimization 3
4 Standard procedure for copper(I) catalyzed trifluoromethylation of diaryliodonium salt 4
5 19F NMR and GCMS diagram for synthesized products 4
6 Electronic and steric factor (Effect of substituent) 41
7 Mechanistic and NMR studies 41
8 NMR spectra of isolated compound 45
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2016
2
1. General Comments:
All reactions were carried out under an atmosphere of dry nitrogen using reaction tubes and
round bottom flask. Dry DCM and DMF was prepared by distilling over CaH2 and stored over
molecular sieves 4Å under N2 atmosphere. The other dry solvent was also prepared by
employing standard distillation procedureand stored over molecular sieves 4Å under N2
atmosphere.
(Trifluoromethyl)trimethylsilane, KF, CuI, PPh3, substituted arenes, iodoarenes, arylboronic
acid, trifluoromethanesulfonicacid, m-CPBA and other reagents were obtained from
commercially available sources and they were used as received. All the iododiacetate1 and
diaryliodonium2 derivatives were synthesized from corresponding iodoarenes and arenes
employing literature procedure.
Column chromatography was performed using Rankem Silica gel (100-200 mesh) and ethyl
acetate-hexanes was used as solvent system, unless otherwise specified, with various
percentage of polarity depending on the nature of the substrate.
2. Analytical Methods:
NMR data were recorded on Bruker DPX 400 and AVC 500 MHz spectrometers. 13
C and 1H
NMR spectra were referenced to signals of deutero solvents and residual protiated solvents,
respectively.19
F NMR spectra were recorded on AVC 470 MHZ spectrometers using
hexafluorobenzene as standard. Infrared spectra were recorded on a Thermo Nicolet iS10 FT
spectrometer. HRMS were recorded by electron spry ionization (ESI) method on a Q-TOF
Micro with lock spray source. Melting points are corrected. The GCMS analysis was
performed on Agilent Technologies Inc. 7890A gas chromatography mass spectrometer.
1 Bielawski, M.; Olofsson, B. Chem. Commun.2007, 2521–2523; 2a) Bielawski, M.; Malmgren, J.; Pardo, L. M.; Wikmark, Y.; Olofsson, B. ChemistryOpen2014, 3, 19–22; b) Bielawski, M.;
Aili, D.; Olofsson, B. J. Org. Chem. 2008, 73, 4602–4607
3
3. Copper(I) catalyzed trifluoromethylation of diphenyliodonium salt:
Optimization:
Table S1: Copper (I) mediated trifluoromethylation of 1a:
Entry Cu Cat. (equiv) Ligand
(equiv)
F source
(equiv)
Solvent
(mL)
Temp.
(ºC)
Yield(%)b
1 CuI (0.2) – CsF (1) DMF 65 50
2 CuI (0.2) – KF (1) DMF 65 75
3 CuI (0.2) – tBuOK DMF 65 7
c
4 CuI (0.2) – TBAF DMF 65 15c
5 CuI (0.1) – KF (1) DMF 65 65
6 CuI (0.1) X-Phos (0.1) KF (1) DMF 65 91
7 CuI (0.1) Bipy (0.1) KF (1) CH3CN 65 48
8 CuI (0.1) o-phen (0.1) KF (1) DMF 65 71
9 CuI (0.1) P(tolyl)3 (0.1) KF (1) DMF 65 88
10 CuI (0.1) DPPE (0.1) KF (1) DMF 65 86
11 CuI (0.1) PPh3 (0.1) KF (1) DMF 65 85
12 Cu(OTf)2 (0.1) PPh3 (0.1) KF (1) DMF 65 10
13 Cu(CH3CN)BF4(0.1) PPh3 (0.1) KF (1) DMF 65 6
14 CuI (0.1) PPh3 (0.1) KF (1) CH3CN 65 23
15 CuI (0.1) PPh3 (0.1) KF (1) DCE 65 2
16 CuI (0.1) PPh3 (0.1) KF (1) Dioxane 65 32
17 CuI (0.1) PPh3 (0.1) KF (1) Toluene 65 3
18 CuI (0.1) PPh3 (0.1) KF (1) DMF rt 20
19 CuI (0.1) PPh3 (0.1) KF (1) DMF 90 83
20 CuI (0.1) PPh3 (0.1) – DMF 65 0
21 – – KF (1) DMF 65 0
[a] reaction condition: substrate ( 0.11 mmol), CF3TMS (2.0 equiv) and 1.5 mL solvent were
used, reaction time 12 h.[b] yield was determine by 19
F NMR using hexafluorobenzene as
internal standard.[c] (1.0 equiv) of tBuOK and TBAF were used.
4
4. Standard procedure for copper(I) catalyzed trifluoromethylation of
diaryliodonium salt:
In an oven dried reaction tube KF (6.7 mg, 0.11mmol) was taken, then evacuated with flame
heating and refilled with argon three times. CuI (2.2 mg, 0.01 mmol), PPh3 (3.0 mg,
0.01mmol), and a solution of diaryliodonium salt 1/6 (50 mg, 0.11 mmol) in 1.5 mL DMF
were added under argon atmosphere and the reaction mixture was stirred at room temperature
untila homogeneous solution was obtained. Next, CF3TMS (33.0 mg, 0.23 mmol, 34 µl) was
added, sealed with stopper and kept at 65 ºC on preheated oil bath. The reaction mixture was
stirred for 12 h, then cooled to room temperature. Hexafluorobenzene was added as internal
standard (17.0 mg, 0.09mmol). The crude mixture was analyzed by 19
F NMR.
5. 19
F NMR and GCMS diagram for synthesized product:
Trifluoromethylbenzene 2a:
The product trifluoromethylbenzene was synthesized from diphenyliodoniumtriflate in 85%
yield. Yield was determined by 19
F NMR spectroscopy using hexafluorobenzene (17.0 mg,
0.09mmol) as the internal standard. The product peak was observed at (-65.4 ppm) in 19
F
NMR. The formation of product was further confirmed by GCMS analysis where, product
peak found at 2.07 min
5
19F NMR (470 MHz, CDCl3/C6F6, 24°C)
-200-180-160-140-120-100-80-60-40-200 ppm
-164.902
-160.175
-87.771
-81.456
-65.439
-37.258
1.000
0.541
Current Data ParametersNAME 02-05-15EXPNO 9PROCNO 1
F2 - Acquisition ParametersDate_ 20150502Time 18.45INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 297.0 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6123674 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Mass spectrum of product peak (2.07 min) from GCMS analysis:
8 0 8 5 9 0 9 5 1 0 0 1 0 5 1 1 0 1 1 5 1 2 0 1 2 5 1 3 0 1 3 5 1 4 0 1 4 5 1 5 0
0
1 0 0 0 0 0
2 0 0 0 0 0
3 0 0 0 0 0
4 0 0 0 0 0
5 0 0 0 0 0
6 0 0 0 0 0
7 0 0 0 0 0
8 0 0 0 0 0
9 0 0 0 0 0
1 0 0 0 0 0 0
1 1 0 0 0 0 0
m / z-->
A b u n d a n c e
S c a n 3 7 5 (2 .0 7 2 m in ): V K P -1 1 6 7 w ith so lv e n t d e la y .D \ d a ta .m s
1 4 6 .0
1 2 7 .0
9 6 .0
8 3 .0
1 0 7 .01 0 1 .0 1 1 9 .08 8 .0 1 1 2 .0 1 3 3 .1 1 4 0 .1 1 5 1 .2
6
1,4-dimethyl-2-(trifluoromethyl)benzene 2b:
The reaction was performed on a (50 mg, 0.10 mmol) scale of bis(2,5-
dimethylphenyl)iodoniumtriflate to achieve 1,4-dimethyl-2-(trifluoromethyl)benzene in 85%
yield using standard procedure. The yield was determined by 19
F NMR spectroscopy using
hexafluorobenzene (20 mg, 0.10 mmol) as internal standard .The product peak was observed
at (-64.55 ppm) in 19
F NMR. The formation of product was further confirmed by GCMS
analysis where, product peak found at 4.30 min.
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.903
-160.541
-88.192
-72.430
-64.559
1.000
0.420
Current Data ParametersNAME spa50615EXPNO 38PROCNO 1
F2 - Acquisition ParametersDate_ 20150605Time 14.32INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 300.4 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6124024 MHzWDW EMSSB 0LB 4.30 HzGB 0PC 1.00
7
Mass spectrum of product peak (4.30 min) from GCMS analysis:
9 0 9 5 1 0 0 1 0 5 1 1 0 1 1 5 1 2 0 1 2 5 1 3 0 1 3 5 1 4 0 1 4 5 1 5 0 1 5 5 1 6 0 1 6 5 1 7 0 1 7 5
0
5 0 0
1 0 0 0
1 5 0 0
2 0 0 0
2 5 0 0
3 0 0 0
3 5 0 0
4 0 0 0
4 5 0 0
5 0 0 0
5 5 0 0
6 0 0 0
6 5 0 0
7 0 0 0
7 5 0 0
8 0 0 0
m / z - - >
A b u n d a n c e
S c a n 4 3 1 ( 4 . 3 0 1 m in ) : V K P - 1 1 3 7 N E W M . D \ d a t a . m s
1 7 4 . 01 5 9 . 0
1 0 5 . 1
1 3 3 . 1
1 5 1 . 01 2 7 . 11 2 0 . 0
9 5 . 91 4 5 . 08 9 . 1 1 3 9 . 1
1 1 4 . 01 6 5 . 3
1-(Trifluoromethyl)naphthalene 2c:
The reaction was performed on a (50 mg, 0.09 mmol) scale of di(naphthalen-1-
yl)iodoniumtriflate to achieve 1-(trifluoromethyl)naphthalene in 68% yield using standard
procedure. The yield was determined by 19
F NMR spectroscopy using hexafluorobenzene
(21.3 mg, 0.11 mmol) as the internal standard. The product peak was observed at (-62.15
ppm) in 19
F NMR. The formation of product was further confirmed by GCMS analysis where,
product peak found at 18.60 min.
8
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-180-160-140-120-100-80-60-40-200 ppm-1
64.9
03
-159.6
15
-81.0
70
-62.1
52
-36.7
44
1.0
00
0.2
78
Current Data ParametersNAME spa50514EXPNO 153PROCNO 1
F2 - Acquisition ParametersDate_ 20140522Time 20.00INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 296.9 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6120969 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Mass spectrum of product peak (18.60 min) from GCMS analysis:
9
1-Bromo-4-(trifluoromethyl)benzene 2d:3a
The reaction was performed on a (50 mg, 0.08 mmol) scale of bis(4-
bromophenyl)iodoniumtriflate to achieve 1-bromo-4-(trifluoromethyl)benzene 59% yield,
along with 8% of 1,3,5-trimethyl-2-(trifluoromethyl)benzene as side product using standard
procedure. The yield was determined by 19
F NMR spectroscopy using hexafluorobenzene
(19.4 mg, 0.10 mmol) as internal standard . The product peak was observed at (-65.73 ppm) in
19F NMR. The formation of product was further confirmed by GCMS analysis where, product
peak found at 5.25 min.
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-180-160-140-120-100-80-60-40-20 ppm
-164.903
-160.547
-88.180
-72.433
-65.730
-56.618
1.000
0.259
0.037
Current Data ParametersNAME all product spectraEXPNO 148PROCNO 1
F2 - Acquisition ParametersDate_ 20150529Time 15.27INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 294.5 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6123865 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
3a)
Morimoto, H.; Tsubogo, T.; Litvinas, N. D.; Hartwig, J. F. Angew. Chem. Int. Ed. 2011, 50, 3793; b) Khan, B. A.; Buba,
A. E.; Gooßen, L. J. Chem. Eur. J. 2012, 18, 1577; c) Zheng, J.; Lin, J-H.; Deng, X-Y.; Xiao, J-C. Org. Lett. 2015, 17, 532
10
Mass spectrum of product peak (5.25 min) from GCMS analysis:
80 90 100 110 120 130 140 150 160 170 180 190 200 210 2200
50000
100000
150000
200000
250000
300000
350000
400000
450000
500000
550000
600000
650000
700000
750000
m/ z-->
Abundance
Scan 616 (5.251 min): VKP-1149-Br D .D \ data.ms145.0 223.9
95.0 125.0206.9
173.981.0 107.0 157.0 184.8 195.9
1-Chloro-4-(trifluoromethyl)benzene 2e:
The reaction was performed on a (50 mg, 0.10 mmol) scale of bis(4-
chlorophenyl)iodoniumtriflate to achieve 1-chloro-4-(trifluoromethyl)benzene in 42% yield
using standard procedure. The yield was determined by 19
F NMR spectroscopy using
hexafluorobenzene (15.5 mg, 0.08 mmol) as internal standard .The product peak was
observed at (-65.50 ppm) in 19
F NMR. The formation of product was further confirmed by
GCMS analysis where, product peak found at 3.46 min.
11
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.902
-160.429
-65.502
1.000
0.257
Current Data ParametersNAME all product spectraEXPNO 87PROCNO 1
F2 - Acquisition ParametersDate_ 20150518Time 17.40INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 296.9 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6123102 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Mass spectrum of product peak (3.46 min) from GCMS analysis:
8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 00
5 0 0 0
1 0 0 0 0
1 5 0 0 0
2 0 0 0 0
2 5 0 0 0
3 0 0 0 0
3 5 0 0 0
4 0 0 0 0
4 5 0 0 0
5 0 0 0 0
5 5 0 0 0
6 0 0 0 0
6 5 0 0 0
7 0 0 0 0
7 5 0 0 0
8 0 0 0 0
8 5 0 0 0
m / z -->
A b u n d a n c e
S c a n 2 6 8 (3 . 4 6 3 m in ): V K P -1 1 5 4 -P .D \ d a t a . m s
1 8 0 . 0
1 4 5 . 01 6 1 . 0
1 3 0 . 0
8 3 . 0
9 5 . 01 1 1 . 0
1 1 9 . 9 1 9 0 . 81 7 0 . 9 1 9 9 . 6
12
1-Methoxy-4-(trifluoromethyl)benzene 2f :3a
The reaction was performed on a (50 mg, 0.10 mmol) scale of bis(4-
methoxyphenyl)iodoniumtriflate to achieve 1-methoxy-4-(trifluoromethyl)benzene in 97%
yield using standard procedure. The yield was determined by 19
F NMR spectroscopy using
hexafluorobenzene (17.0 mg, 0.09 mmol) as internal standard. The product peak was
observed at (-64.41 ppm) in 19
F NMR. The formation of product was further confirmed by
GCMS analysis where, product peak found at 4.88 min.
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.902
-160.477
-64.419
1.000
0.542
Current Data ParametersNAME all product spectraEXPNO 73PROCNO 1
F2 - Acquisition ParametersDate_ 20150518Time 14.26INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 295.9 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6123206 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
13
Mass spectrum of product peak (4.88 min) from GCMS analysis:
7 5 8 0 8 5 9 0 9 5 1 0 0 1 0 5 1 1 0 1 1 5 1 2 0 1 2 5 1 3 0 1 3 5 1 4 0 1 4 5 1 5 0 1 5 5 1 6 0 1 6 5 1 7 0 1 7 50
5 0 0 0 0
1 0 0 0 0 0
1 5 0 0 0 0
2 0 0 0 0 0
2 5 0 0 0 0
3 0 0 0 0 0
3 5 0 0 0 0
4 0 0 0 0 0
4 5 0 0 0 0
5 0 0 0 0 0
5 5 0 0 0 0
6 0 0 0 0 0
6 5 0 0 0 0
m / z - ->
A b u n d a n c e
S c a n 5 4 4 (4 . 8 8 1 m in ) : V K P -1 1 4 6 -O m e D . D \ d a t a . m s1 7 6 . 0
1 3 3 . 0 1 4 5 . 0
1 5 7 . 0
1 1 3 . 0
8 3 . 09 6 . 0
1 2 5 . 0
1 0 5 . 0 1 6 4 . 4
1-nitro-4-(trifluoromethyl)benzene 2g:
The reaction was performed on a (50 mg, 0.09 mmol) scale of mesityl(4-
nitrophenyl)iodoniumtriflate to achieve 1-nitro-4-(trifluoromethyl)benzene in 60% yield,
using standard procedure. The yield was determined by 19
F NMR spectroscopy using
hexafluorobenzene (18.9 mg, 0.10 mmol) as internal standard. The product peak was
observed at (-66.03 ppm) in 19
F NMR. The formation of product was further confirmed by
GCMS analysis where, product peak found at 6.09 min.
14
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.902
-160.462
-88.095
-85.262
-72.381
-66.037
1.000
0.288
Current Data ParametersNAME all product spectraEXPNO 69PROCNO 1
F2 - Acquisition ParametersDate_ 20150513Time 20.41INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 297.3 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6122929 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Mass spectrum of product peak (6.09 min) from GCMS analysis:
8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 0
0
2 0 0 0 0
4 0 0 0 0
6 0 0 0 0
8 0 0 0 0
1 0 0 0 0 0
1 2 0 0 0 0
1 4 0 0 0 0
1 6 0 0 0 0
1 8 0 0 0 0
2 0 0 0 0 0
2 2 0 0 0 0
2 4 0 0 0 0
2 6 0 0 0 0
m/ z-->
A b u n d a n c e
S c a n 7 8 1 (6 .0 9 8 min ): V K P -1 1 5 3 -n itro l D .D \ d a ta .ms
1 4 5 .0
1 9 1 .0
1 6 1 .0
9 5 .01 2 5 .0
1 1 1 .0 1 7 2 .0
8 3 .0
1 3 3 .9 1 8 1 .0
15
1-Methyl-4-(trifluoromethyl)benzene 2i:
The reaction was performed on a (50 mg, 0.10 mmol) scale of mesityl(p-
tolyl)iodoniumtriflate to achieve 1-methyl-4-(trifluoromethyl)benzene in 56% yield along
with 22% of 1,3,5-trimethyl-2-(trifluoromethyl)benzene as side product, using standard
procedure. The yield was determined by 19
F NMR spectroscopy using hexafluorobenzene
(21.8 mg, 0.11 mmol) as internal standard. The product peak was observed at (-65.13 ppm) in
19F NMR. The formation of product was further confirmed by GCMS analysis where, product
peak found at 3.07 min.
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.902
-160.289
-81.029
-65.134
-56.413
1.000
0.246
0.120
Current Data ParametersNAME 26-05-15EXPNO 62PROCNO 1
F2 - Acquisition ParametersDate_ 20150512Time 22.01INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6122079 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
16
Mass spectrum of product peak (3.07 min) from GCMS analysis:
9 0 9 5 1 0 0 1 0 5 1 1 0 1 1 5 1 2 0 1 2 5 1 3 0 1 3 5 1 4 0 1 4 5 1 5 0 1 5 5 1 6 0 1 6 5 1 7 0 1 7 50
2 0 0 0
4 0 0 0
6 0 0 0
8 0 0 0
1 0 0 0 0
1 2 0 0 0
1 4 0 0 0
1 6 0 0 0
1 8 0 0 0
2 0 0 0 0
2 2 0 0 0
2 4 0 0 0
2 6 0 0 0
2 8 0 0 0
3 0 0 0 0
m / z -->
A b u n d a n c e
S c a n 1 8 1 (3 .0 1 7 m in ): V K P -1 1 4 3 -m e D .D \ d a ta .m s9 1 .1
1 6 0 .1
1 4 1 .0
1 0 9 .0
1 1 9 .1
1 3 3 .09 9 .01 4 9 .0 1 7 6 .81 2 5 .9 1 6 9 .0
1-(tert-butyl)-4-(trifluoromethyl)benzene 2j:
The reaction was performed on a (50 mg, 0.09 mmol) scale of (4-(tert-
butyl)phenyl)(mesityl)iodoniumtriflate to achieve 1-(tert-butyl)-4-(trifluoromethyl)benzene in
69% yield along with 18% of 1,3,5-trimethyl-2-(trifluoromethyl)benzene as side product,
using standard procedure. The yield was determined by 19
F NMR spectroscopy using
hexafluorobenzene (17.4 mg, 0.09 mmol) as internal standard. The product peak was
observed at (-65.1 ppm) in 19
F NMR. The formation of product was further confirmed by
GCMS analysis where, product peak found at 5.86 min.
17
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-180-160-140-120-100-80-60-40-200 ppm
-164.902
-160.341
-88.000
-72.311
-65.189
-56.457
1.000
0.353
0.095
Current Data ParametersNAME all product spectraEXPNO 63PROCNO 1
F2 - Acquisition ParametersDate_ 20150512Time 22.06INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6122443 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Mass spectrum of product peak (5.86 min) from GCMS analysis:
8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 0 2 0 0
0
5 0 0 0
1 0 0 0 0
1 5 0 0 0
2 0 0 0 0
2 5 0 0 0
3 0 0 0 0
3 5 0 0 0
4 0 0 0 0
4 5 0 0 0
5 0 0 0 0
5 5 0 0 0
6 0 0 0 0
6 5 0 0 0
7 0 0 0 0
7 5 0 0 0
8 0 0 0 0
8 5 0 0 0
9 0 0 0 0
m / z - ->
A b u n d a n c e
S c a n 7 3 5 (5 . 8 6 2 m in ) : V K P -1 1 3 8 -T B U N E W M . D \ d a t a . m s
1 8 7 . 1
1 5 9 . 0
2 0 2 . 1
8 3 . 01 0 9 . 1 1 2 7 . 0 1 7 1 . 01 4 5 . 0
9 5 . 0 1 1 8 . 1 1 3 6 . 2
18
4-(trifluoromethyl)-1,1'-biphenyl 2k:3a
The reaction was performed on a (50 mg, 0.09 mmol) scale of [1,1'-biphenyl]-4-
yl(mesityl)iodoniumtriflate to achieve 4-(trifluoromethyl)-1,1'-biphenyl in 81% yield along
with 17% of 1,3,5-trimethyl-2-(trifluoromethyl)benzene as side product using standard
procedure. Yield was determined by 19
F NMR spectroscopy using hexafluorobenzene (19.0
mg, 0.10 mmol) as the internal standard. The product peak was observed at (-65.4 ppm) in 19
F
NMR. The formation of product was further confirmed by GCMS analysis where, product
peak found at 11.06 min.
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.901
-160.622
-88.253
-65.407
-56.677
1.000
0.365
0.080
Current Data ParametersNAME all product spectraEXPNO 144PROCNO 1
F2 - Acquisition ParametersDate_ 20150529Time 15.11INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 294.3 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6124559 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
19
Mass spectrum of product peak (11.06 min) from GCMS analysis:
80 90 100 110 120 130 140 150 160 170 180 190 200 210 2200
2000
4000
6000
8000
10000
12000
14000
m/z-->
Abundance
Scan 1748 (11.065 min): VKP-1150-Biphenyl D.D\data.ms222.0
152.0
201.085.0
104.9 172.0127.9 183.0117.0 139.9
1-Methyl-2-(trifluoromethyl)benzene 2l:
The reaction was performed on a (50 mg, 0.10 mmol) scale of mesityl(o-
tolyl)iodoniumtriflate to achieve 1-methyl-2-(trifluoromethyl)benzene in 65% yield, along
with 14% of 1,3,5-trimethyl-2-(trifluoromethyl)benzene as side product, using standard
procedure. The yield was determined by 19
F NMR spectroscopy using hexafluorobenzene
(19.6 mg, 0.10 mmol) as internal standard. The product peak was observed at (-64.22 ppm) in
19F NMR. The formation of product was further confirmed by GCMS analysis where, product
peak found at 3.05 min.
20
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.902
-160.587
-88.225
-72.459
-64.696
-56.653
1.000
0.322
0.073
Current Data ParametersNAME all product spectraEXPNO 149PROCNO 1
F2 - Acquisition ParametersDate_ 20150529Time 15.32INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 294.6 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6124316 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Mass spectrum of product peak (3.05 min) from GCMS analysis:
8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 0 2 0 0 2 1 0
0
5 0 0 0
1 0 0 0 0
1 5 0 0 0
2 0 0 0 0
2 5 0 0 0
3 0 0 0 0
3 5 0 0 0
4 0 0 0 0
4 5 0 0 0
5 0 0 0 0
5 5 0 0 0
6 0 0 0 0
6 5 0 0 0
7 0 0 0 0
7 5 0 0 0
8 0 0 0 0
8 5 0 0 0
9 0 0 0 0
m / z - ->
A b u n d a n c e
S c a n 1 8 8 (3 . 0 5 2 m in ) : V K P -1 1 4 8 -P . D \ d a t a . m s
9 1 . 1
1 6 0 . 0
1 4 0 . 1
1 0 9 . 0
1 1 9 . 0
2 0 7 . 08 1 . 0 1 9 0 . 91 7 2 . 91 3 0 . 2 1 4 9 . 9 2 1 6 . 9
21
1-(trifluoromethyl)naphthalene 2m:
The reaction was performed on a (40 mg, 0.07mmol) scale of 2-(
naphthaleny)(mesityl)iodoniumtriflate to achieve 2-(trifluoromethyl)naphthalene in 78%yield,
along with 16% of 1,3,5-trimethyl-2-(trifluoromethyl)benzene as side product using standard
procedure.The yield was determined by 19
F NMR spectroscopy using hexafluorobenzene
(18.8 mg, 0.10 mmol) as internal standard. The product peak was observed at (-65.2 ppm) in
19F NMR. The formation of product was further confirmed by GCMS analysis where, product
peak found at 8.36 min.
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.901
-160.587
-65.278
-56.647
1.000
0.299
0.061
Current Data ParametersNAME all product spectraEXPNO 151PROCNO 1
F2 - Acquisition ParametersDate_ 20150529Time 15.40INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 294.7 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6124195 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
22
Mass spectrum of product peak (8.36 min) from GCMS analysis:
80 90 100 110 120 130 140 150 160 170 180 1900
50000
100000
150000
200000
250000
300000
350000
400000
450000
m/ z-->
Abundance
Scan 1222 (8.363 min): VKP-1170-P.D\ data.ms196.0
146.1177.0
127.198.088.2 157.0112.0 166.9137.0 186.4
1,3-dimethyl-5-(trifluoromethyl)benzene 2n:
The reaction was performed on a (50 mg, 0.10 mmol) scale of 3,5-
dimethylphenyl)(mesityl)iodoniumtriflate to achieve 1,3-dimethyl-5-(trifluoromethyl)benzene
in 84% yield along with 9% of 1,3,5-trimethyl-2-(trifluoromethyl)benzene as side product
using standard procedure. The yield was determined by 19
F NMR spectroscopy using
hexafluorobenzene (17.4 mg, 0.09 mmol) as internal standard. The product peak was
observed at (-65.26 ppm) in 19
F NMR. The formation of product was further confirmed by
GCMS analysis where, product peak found at 4.17 min.
23
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.902
-160.134
-87.752
-81.405
-79.728
-78.203
-72.271
-65.262
-56.371
-37.210
1.000
0.445
0.050
Current Data ParametersNAME 26-05-15EXPNO 57PROCNO 1
F2 - Acquisition ParametersDate_ 20150512Time 21.39INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 298.2 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6123119 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Mass spectrum of product peak (4.17 min) from GCMS analysis:
80 90 100 110 120 130 140 150 160 170 180 1900
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
55000
60000
m/ z-->
Abundanc e
Sc an 407 (4.177 min): VKP-1147-xylene D .D \ data.ms
159.0 174.0
105.1
83.0
133.0
119.0 145.096.0 190.9
24
1-Fluoro-4-(trifluoromethyl)benzene 2o:
The reaction was performed on a (50 mg, 0.10 mmol) scale of 4-
(fluorophenyl)(mesityl)iodoniumtriflate to achieve 1-fluoro-4-(trifluoromethyl)benzene in
72% yield, along with 23% of 1,3,5-trimethyl-2-(trifluoromethyl)benzene as side product
using standard procedure. The yield was determined by 19
F NMR spectroscopy using
hexafluorobenzene (18.0 mg, 0.09 mmol) as internal standard. The product peak was
observed at (-64.98 ppm) in 19
F NMR. The formation of product was further confirmed by
GCMS analysis where, product peak found at 8.94 min.
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.903
-160.580
-117.339
-110.448
-88.214
-72.453
-64.985
-56.637
1.000
0.381
0.123
Current Data ParametersNAME all product spectraEXPNO 105PROCNO 1
F2 - Acquisition ParametersDate_ 20150520Time 14.40INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 297.7 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6124107 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
25
Mass spectrum of product peak (8.94 min) from GCMS analysis:
8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 0
2 0 0 0
4 0 0 0
6 0 0 0
8 0 0 0
1 0 0 0 0
1 2 0 0 0
1 4 0 0 0
1 6 0 0 0
1 8 0 0 0
2 0 0 0 0
2 2 0 0 0
2 4 0 0 0
m / z - - >
A b u n d a n c e
S c a n 1 1 4 1 ( 8 . 9 4 7 m in ) : v k p - f lu o r o - o ld 2 . D \ d a t a . m s
1 2 1 . 1
1 3 6 . 1
1 6 4 . 0
9 1 . 0
1 0 5 . 1
8 1 . 0 1 8 2 . 81 5 2 . 0 1 9 3 . 11 7 3 . 2
1-iodo-4-(trifluoromethyl)benzene 2p:
The reaction was performed on a (50 mg, 0.08 mmol) scale of (4-
iodophenyl)(mesityl)iodoniumtriflate to achieve 1-iodo-4-(trifluoromethyl)benzene in 61%
yield, along with 10% of 1,3,5-trimethyl-2-(trifluoromethyl)benzene as side product using
standard procedure. The yield was determined by 19
F NMR spectroscopy using
hexafluorobenzene (16.10 mg, 0.08 mmol) as internal standard. The product peak was
observed at (-65.69 ppm) in 19
F NMR. The formation of product was further confirmed by
GCMS analysis where, product peak found at 6.03 min.
26
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.902
-160.160
-87.882
-80.996
-65.698
-56.328
-37.053
1.000
0.298
0.050
Current Data ParametersNAME all product spectraEXPNO 77PROCNO 1
F2 - Acquisition ParametersDate_ 20150518Time 14.42INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 295.8 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6121871 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Mass spectrum of product peak (6.03 min) from GCMS analysis:
8 0 1 0 0 1 2 0 1 4 0 1 6 0 1 8 0 2 0 0 2 2 0 2 4 0 2 6 0 2 8 0 3 0 0
0
1 0 0 0 0 0
2 0 0 0 0 0
3 0 0 0 0 0
4 0 0 0 0 0
5 0 0 0 0 0
6 0 0 0 0 0
7 0 0 0 0 0
8 0 0 0 0 0
9 0 0 0 0 0
1 0 0 0 0 0 0
1 1 0 0 0 0 0
1 2 0 0 0 0 0
1 3 0 0 0 0 0
1 4 0 0 0 0 0
m / z - - >
A b u n d a n c e
S c a n 7 6 9 ( 6 . 0 3 7 m in ) : V K P - 1 1 5 9 - P . D \ d a t a . m s
2 7 1 . 9
1 4 5 . 0
9 5 . 01 2 5 . 0
2 5 2 . 9
1 8 8 . 1
1 6 9 . 1 2 2 2 . 02 0 4 . 0 2 9 9 . 6
27
1,4-bis(trifluoromethyl)benzene 2q:
The reaction was performed on a (50 mg, 0.09mmol) scale of mesityl(4-
(trifluoromethyl)phenyl)iodoniumtriflateto achieve 1,4-bis(trifluoromethyl)benzene in 71%
yield along with trace amount of 1,3,5-trimethyl-2-(trifluoromethyl)benzene as side product,
using standard procedure. The yield was determined by 19
F NMR spectroscopy using
hexafluorobenzene (19.1 mg, 0.10mmol) as internal standard. The product peak was observed
at (-65.87 ppm) in 19
F NMR. The formation of product was further confirmed by GCMS
analysis where, product peak found at 15.10 min.
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.902
-160.134
-87.841
-72.171
-65.874
1.000
0.638
0.018
Current Data ParametersNAME all product spectraEXPNO 76PROCNO 1
F2 - Acquisition ParametersDate_ 20150518Time 14.39INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 295.8 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6121298 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
28
Mass spectrum of product peak (15.10 min) from GCMS analysis:
4-(trifluoromethyl)benzonitrile 2r:
The reaction was performed on a (50 mg, 0.10 mmol) scale of 4-
(cyanophenyl)(mesityl)iodoniumtriflate to achieve 4-(trifluoromethyl)benzonitrile in 57%
yield, using standard procedure. The yield was determined by 19
F NMR spectroscopy using
hexafluorobenzene (19.6 mg, 0.10 mmol) as internal standard. The product peak was
observed at (-66.54 ppm) in 19
F NMR. The formation of product was further confirmed by
GCMS analysis where, product peak found at 4.92 min.
29
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.901
-160.638
-88.257
-72.484
-66.542
1.000
0.275
Current Data ParametersNAME all product spectraEXPNO 75PROCNO 1
F2 - Acquisition ParametersDate_ 20150518Time 14.34INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 295.8 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6124403 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Mass spectrum of product peak (4.92 min) from GCMS analysis:
80 90 100 110 120 130 140 150 160 170 180
0
100000
200000
300000
400000
500000
600000
700000
800000
900000
m/ z-->
Abundanc e
Sc an 553 (4 .927 min ): VKP-1156-P .D \ da ta .ms
171 .0
121 .0
152 .0
102 .1
94 .0144 .085 .4 132 .0112 .0 181 .7162 .8
30
Ethyl 4-(trifluoromethyl)benzoate 2s :3a
The reaction was performed on a (50 mg, 0.09 mmol) scale of (4-
ethoxycarbonyl)phenyl)(mesityl)iodoniumtriflate to achieve ethyl 4-(trifluoromethyl)benzoate
in 72% yield, along with 7% of 1,3,5-trimethyl-2-(trifluoromethyl)benzene as side product,
using standard procedure. The yield was determined by 19
F NMR spectroscopy using
hexafluorobenzene (19.7 mg, 0.10mmol) as internal standard. The product peak wasobserved
at (-66.01 ppm) in 19
F NMR. The formation of product was further confirmed by GCMS
analysis where, product peak found at 7.67 min.
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.901
-160.444
-88.077
-77.750
-72.371
-66.011
-56.527
1.000
0.316
0.034
Current Data ParametersNAME all product spectraEXPNO 68PROCNO 1
F2 - Acquisition ParametersDate_ 20150513Time 20.37INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 297.3 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6122825 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
31
Mass spectrum of product peak (7.67 min) from GCMS analysis:
8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 0 2 0 0 2 1 0
0
5 0 0
1 0 0 0
1 5 0 0
2 0 0 0
2 5 0 0
3 0 0 0
3 5 0 0
4 0 0 0
4 5 0 0
5 0 0 0
5 5 0 0
m / z - ->
A b u n d a n c e
S c a n 1 0 8 7 (7 . 6 7 0 m in ) : V K P -1 1 5 1 -E s t e r l D . D \ d a t a . m s
1 7 3 . 0
1 2 3 . 0
1 4 5 . 0
8 2 . 9
1 8 9 . 9
9 5 . 1
2 0 7 . 0 2 1 8 . 0
1 0 5 . 1
1 3 2 . 9
1 6 2 . 1
Phenyl(4-(trifluoromethyl)phenyl)methanone 2t:3b
The reaction was performed on a (50 mg, 0.08 mmol) scale of (4-
benzoylphenyl)(mesityl)iodoniumtriflate to achieve phenyl(4-
(trifluoromethyl)phenyl)methanone in 93% yield along with 6% of 1,3,5-trimethyl-2-
(trifluoromethyl)benzene as side product using standard procedure. The yield was determined
by 19
F NMR spectroscopy using hexafluorobenzene (13.8 mg, 0.07mmol) as internal standard.
The product peak was observed at (-65.78 ppm) in 19
F NMR. The formation of product was
further confirmed by GCMS analysis where, product peak found at 13.48 min.
32
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-180-160-140-120-100-80-60-40-200 ppm-1
64
.90
1
-16
0.6
76
-88
.30
6
-76
.98
8
-65
.78
9
-56
.71
5
1.0
00
0.5
49
0.0
43
Current Data ParametersNAME all product spectraEXPNO 146PROCNO 1
F2 - Acquisition ParametersDate_ 20150529Time 15.19INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 294.4 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6124958 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Mass spectrum of product peak (13.48 min) from GCMS analysis:
8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 0 2 0 0 2 1 0 2 2 0 2 3 0 2 4 00
5 0 0 0 0
1 0 0 0 0 0
1 5 0 0 0 0
2 0 0 0 0 0
2 5 0 0 0 0
3 0 0 0 0 0
3 5 0 0 0 0
4 0 0 0 0 0
4 5 0 0 0 0
5 0 0 0 0 0
5 5 0 0 0 0
m / z - ->
A b u n d a n c e
S c a n 2 0 2 5 (1 3 . 4 8 8 m in ) : v k p -b e n z o p h e n o n e 1 . D \ d a t a . m s
2 5 0 . 0
1 0 5 . 0
1 7 3 . 0
1 4 5 . 0
2 0 1 . 0
2 3 1 . 11 8 5 . 0
1 2 5 . 08 3 . 1
1 5 7 . 0 2 1 9 . 1
33
1-(4-(trifluoromethyl)phenyl)ethanone 2u:
The reaction was performed on a (50 mg, 0.09mmol) scale of (4-
acetylphenyl)(mesityl)iodoniumto achieve 1-(4-(trifluoromethyl)phenyl)ethanone in 94%
yield along with 4% of 1,3,5-trimethyl-2-(trifluoromethyl)benzene as side product using
standard procedure. The yield was determined by 19
F NMR spectroscopy using
hexafluorobenzene (20.0 mg, 0.10mmol) as internal standard. The product peak was observed
at (-65.70 ppm) in 19
F NMR. The formation of product was further confirmed by GCMS
analysis where, product peak found at 6.03 min.
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.901
-88.224
-83.740
-72.462
-65.705
-56.656
1.000
0.429
0.020
Current Data ParametersNAME all product spectraEXPNO 147PROCNO 1
F2 - Acquisition ParametersDate_ 20150529Time 15.23INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 294.5 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6124299 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
34
Mass spectrum of product peak (6.03 min) from GCMS analysis:
80 90 100 110 120 130 140 150 160 170 180 190
0
20000
40000
60000
80000
100000
120000
140000
160000
180000
200000
220000
m/ z-->
Abundance
Scan 768 (6.032 min): VKP-1158-P.D\ data.ms
188.1119.1
173.0
91.1133.1
151.1103.082.0 164.0141.9 199.1
1-nitro-2-(trifluoromethyl)benzene 2v:
The reaction was performed on a (50 mg, 0.09 mmol) scale of mesityl(2-
nitrophenyl)iodoniumtriflate to achieve 1-nitro-2-(trifluoromethyl)benzene in 54% yield,
using standard procedure. The yield was determined by 19
F NMR spectroscopy using
hexafluorobenzene (18.5 mg, 0.09 mmol) as internal standard. The product peak was
observed at (-63.02 ppm) in 19
F NMR. The formation of product was further confirmed by
GCMS analysis where, product peak found at 7.0 min.
35
19F NMR (470 MHz, CDCl3/C6F6, 24°C)
-200-180-160-140-120-100-80-60-40-200 ppm
-164.902
-160.602
-88.239
-72.466
-63.026
1.000
0.263
Current Data ParametersNAME all product spectraEXPNO 85PROCNO 1
F2 - Acquisition ParametersDate_ 20150518Time 17.31INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 296.8 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6124368 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Mass spectrum of product peak (7.0 min) from GCMS analysis:
8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 00
5 0 0 0
1 0 0 0 0
1 5 0 0 0
2 0 0 0 0
2 5 0 0 0
3 0 0 0 0
3 5 0 0 0
4 0 0 0 0
4 5 0 0 0
5 0 0 0 0
5 5 0 0 0
6 0 0 0 0
6 5 0 0 0
7 0 0 0 0
7 5 0 0 0
8 0 0 0 0
8 5 0 0 0
m / z -->
A b u n d a n c e
S c a n 9 5 7 (7 . 0 0 2 m in ): V K P -1 1 6 1 -P . D \ d a ta .m s1 4 5 .0
1 9 1 . 0
9 5 .0
1 6 1 .01 2 5 . 0
1 1 4 . 01 7 5 . 0
8 3 .0
1 3 4 . 01 0 5 .1
36
2-Trifluoromethylthiophene 2w:
The reaction was performed on a (50 mg, 0.10 mmol) scale of mesityl(thiophen-2-
yl)iodoniumtriflate to achieve 2-(trifluoromethyl)thiophene in 49% yield, along with 7% of
1,3,5-trimethyl-2-(trifluoromethyl)benzene as side product using standard procedure. The
yield was determined by 19
F NMR spectroscopy using hexafluorobenzene (19.60 mg, 0.10
mmol) as internal standard. The product peak was observed at (-57.92 ppm) in 19
F NMR. The
formation of product was further confirmed by GCMS analysis where, product peak found at
15.34 min.
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.902
-160.506
-57.927
-56.575
1.000
0.245
0.039
Current Data ParametersNAME all product spectraEXPNO 66PROCNO 1
F2 - Acquisition ParametersDate_ 20150513Time 20.28INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 297.2 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6123310 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
37
Mass spectrum of product peak (15.34 min) from GCMS analysis:
75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 1500
200
400
600
800
1000
1200
1400
1600
1800
2000
m/z-->
Abundance
Scan 2582 (15.349 min): VKP-1155-thiophene D.D\data.ms
152.0
83.1 135.0
105.1
91.1115.1
128.0
121.097.1
145.0
2-Chloro-5-(trifluoromethyl)pyridine 2x:
The reaction was performed on a (50 mg, 0.09 mmol) scale of 6-chloropyridin-3-
yl)(mesityl)iodoniumtriflate to achieve 2-chloro-5-(trifluoromethyl)pyridine in 72% yield,
along with 7% of 1,3,5-trimethyl-2-(trifluoromethyl)benzene as side product using standard
procedure. The yield was determined by 19
F NMR spectroscopy using hexafluorobenzene
(17.30 mg, 0.09mmol) as internal standard. The product peak was observed at (-65.11 ppm) in
19F NMR. The formation of product was further confirmed by GCMS analysis where, product
peak found at 3.76 min.
38
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.902
-160.230
-81.482
-65.112
-56.461
-37.326
1.000
0.383
0.040
Current Data ParametersNAME all product spectraEXPNO 70PROCNO 1
F2 - Acquisition ParametersDate_ 20150518Time 14.12INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 296.2 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6123900 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Mass spectrum of product peak (16.76 min) from GCMS analysis:
8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0
0
1 0 0 0 0 0
2 0 0 0 0 0
3 0 0 0 0 0
4 0 0 0 0 0
5 0 0 0 0 0
6 0 0 0 0 0
7 0 0 0 0 0
8 0 0 0 0 0
9 0 0 0 0 0
1 0 0 0 0 0 0
1 1 0 0 0 0 0
1 2 0 0 0 0 0
1 3 0 0 0 0 0
m / z - - >
A b u n d a n c e
S c a n 3 2 7 ( 3 . 7 6 6 m in ) : V K P - 1 1 6 2 - P . D \ d a t a . m s
1 8 1 . 01 4 6 . 0
1 2 6 . 0
1 6 2 . 0
9 9 . 08 5 . 0
1 1 2 . 0 1 3 5 . 0 1 5 4 . 0 1 7 0 . 9 1 8 9 . 1
39
6-Trifluoromethylquinoline 2y:3c
The reaction was performed on a (50 mg, 0.09 mmol) scale of mesityl(quinolin-6-
yl)iodoniumtriflate to achieve 6-(trifluoromethyl)quinoline in 88% yield along with 2% of
1,3,5-trimethyl-2-(trifluoromethyl)benzene as side product using standard procedure. The
yield was determined by 19
F NMR spectroscopy using hexafluorobenzene (19.7 mg,
0.10mmol) as internal standard. The product peak was observed at (-65.22 ppm) in 19
F NMR.
The formation of product was further confirmed by GCMS analysis where, product peak
found at 8.73 min.
19F NMR (470 MHz, CDCl3/C6F6, 24°C):
-200-180-160-140-120-100-80-60-40-200 ppm
-164.900
-160.370
-88.014
-72.330
-65.222
-56.479
1.000
0.401
0.018
Current Data ParametersNAME all product spectraEXPNO 61PROCNO 1
F2 - Acquisition ParametersDate_ 20150512Time 21.57INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6122651 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
40
Mass spectrum of product peak (8.73 min) from GCMS analysis:
8 0 9 0 1 0 0 1 1 0 1 2 0 1 3 0 1 4 0 1 5 0 1 6 0 1 7 0 1 8 0 1 9 0
0
1 0 0 0 0 0
2 0 0 0 0 0
3 0 0 0 0 0
4 0 0 0 0 0
5 0 0 0 0 0
6 0 0 0 0 0
7 0 0 0 0 0
8 0 0 0 0 0
9 0 0 0 0 0
1 0 0 0 0 0 0
1 1 0 0 0 0 0
1 2 0 0 0 0 0
1 3 0 0 0 0 0
1 4 0 0 0 0 0
1 5 0 0 0 0 0
m / z - ->
A b u n d a n c e
S c a n 1 2 9 5 (8 . 7 3 8 m in ) : V K P -1 1 4 1 . D \ d a t a . m s
1 9 7 . 0
1 4 7 . 0
1 7 8 . 0
1 6 9 . 01 2 8 . 0
9 8 . 8
1 5 8 . 08 8 . 7 1 1 9 . 0 1 3 8 . 01 0 8 . 0 1 8 8 . 1
41
6. Electronic and steric factor (Effect of substituent):
In order to understand the effect of substituent like, electron withdrawing electron releasing
and neutral substrate has been subjected under standard reaction condition. The result is given
in the scheme.
7. Mechanistic study:
7a. Radical scavenger experiment:
Copper(I) catalyzed trifluoromethylation of diphenyliodonium salt 1a with 2 equiv of
TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) was performed, employing standard
conditions, which the formation of trifluoromethylbenzene in 89% yield.
42
Without diaryliodonium salt under the standard reaction condition with (1 equiv.) of TEMPO,
we did not observe TEMPO-CF3 substituted product.
7b. Radical clock probe experiment:
Radical clock probe experiment was performed with (2-
(allyloxy)phenyl)(mesityl)iodoniumtrifluoromethanesulfonate, which was synthesized
according to literature procedure. (2-allyloxy)phenyl)(mesityl)iodonium
trifluomethanesulfonate was subjected under standard conditions and we observed 1-
(allyloxy)-2-(trifluoromethyl)benzene in 36% yield, along with 50% of 1,3,5-trimethyl-2-
(trifluoromethyl)benzene as side product. There is no formation any cyclized product. The
yield was determined by 19
F NMR using hexafluorobenzene as internal standard.
Theformation of product was further confirmed by GCMS.
The above experiment suggests that, formation of trifluoromethyl radical or aryl radical is less
likely.
43
7c. 31
P and 19
F NMR studies:
To identify the possible intermediate species formation, 31
P and 19
F NMR studies were
performed at various temperatures (‒50 ºC to +50 ºC).
Equimolar mixture of CuI and PPh3 31
P NMR (202 MHz, DMF, 24°C):
Equimolar mixture of CuI, PPh3, CF3TMS and KF at variable temperature
31P NMR (202 MHz, DMF, 24°C):
–50 °C
–30 °C
0 °C
+30 °C
+50 °C
–8.70 ppm –21.21 ppm
44
19F NMR (470 MHz, DMF, 24°C):
Equimolar mixture of CuI, PPh3, CF3TMS, KF and mesityl(4-
methylphenyl)iodonium triflate at variable temperature
31P NMR (202 MHz, DMF, 24°C):
19
F NMR (470 MHz, DMF, 24°C):
–50 °C
–30 °C
0 °C
+30 °C
+50 °C
–34.19 ppm
–50 °C
–30 °C
0 °C
+30 °C
+50 °C
–50 °C
–30 °C
0 °C
+30 °C
+50 °C
–26.69 ppm –21.21 ppm
–34.14 ppm –37.60 ppm
45
8. NMR spectra of isolated compound
1-Bromo-4-(trifluoromethyl)benzene 2d: 1H NMR (500 MHz, CDCl3, 24°C):
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm
7.2
11
7.2
16
7.2
20
7.2
30
7.2
34
7.2
39
7.2
60
7.5
26
7.5
31
7.5
35
7.5
45
7.5
48
7.5
54
2.0
00
2.0
25
Current Data ParametersNAME spa51015EXPNO 71PROCNO 1
F2 - Acquisition ParametersDate_ 20151011Time 16.16INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 32768SOLVENT CDCl3NS 32DS 2SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6384000 secRG 124.08DW 50.000 usecDE 6.50 usecTE 295.2 KD1 0.50000000 secTD0 1
======== CHANNEL f1 ========SFO1 500.1525008 MHzNUC1 1HP1 11.75 usecPLW1 15.30000019 W
F2 - Processing parametersSI 65536SF 500.1500221 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
19F NMR (470 MHz, CDCl3, 24°C):
-180-160-140-120-100-80-60-40-200 ppm
-62.6
50
Current Data ParametersNAME spa51015EXPNO 67PROCNO 1
F2 - Acquisition ParametersDate_ 20151011Time 16.19INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 295.3 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6111960 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
46
1-Methoxy-4-(trifluoromethyl)benzene 2f: 1H NMR (400 MHz, CDCl3, 24°C):
123456789 ppm
3.7
76
6.6
71
6.6
76
6.6
88
6.6
93
7.2
60
7.5
43
7.5
49
7.5
60
7.5
66
3.0
18
2.0
00
2.0
07
Current Data ParametersNAME spa41015EXPNO 190PROCNO 1
F2 - Acquisition ParametersDate_ 20151009Time 17.07INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 79.8DW 62.400 usecDE 6.50 usecTE 293.1 KD1 0.50000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 15.70 usecPLW1 7.75000000 WSFO1 400.1320007 MHz
F2 - Processing parametersSI 65536SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
19F NMR (470 MHz, CDCl3, 24°C):
-180-160-140-120-100-80-60-40-200 ppm
-61.3
73 Current Data Parameters
NAME spa51015EXPNO 72PROCNO 1
F2 - Acquisition ParametersDate_ 20151011Time 16.55INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 295.9 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6111960 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
47
4-(trifluoromethyl)-1,1'-biphenyl 2k: 1H NMR (500 MHz, CDCl3, 24°C):
12345678910 ppm
7.2
60
7.3
24
7.3
41
7.4
10
7.4
26
7.4
39
7.4
42
7.4
57
7.4
64
7.4
76
7.4
79
7.4
94
7.5
42
7.5
44
7.5
58
7.5
94
7.5
96
7.6
06
7.6
10
7.6
13
7.6
97
7.7
58
7.7
75
1.0
06
3.0
24
1.0
16
1.0
85
2.0
62
1.0
00
Current Data ParametersNAME spa51015EXPNO 70PROCNO 1
F2 - Acquisition ParametersDate_ 20151011Time 16.50INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 32768SOLVENT CDCl3NS 32DS 2SWH 10000.000 HzFIDRES 0.305176 HzAQ 1.6384000 secRG 180.86DW 50.000 usecDE 6.50 usecTE 295.9 KD1 0.50000000 secTD0 1
======== CHANNEL f1 ========SFO1 500.1525008 MHzNUC1 1HP1 11.75 usecPLW1 15.30000019 W
F2 - Processing parametersSI 65536SF 500.1500221 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
19F NMR (470 MHz, CDCl3, 24°C):
-180-160-140-120-100-80-60-40-20 ppm
-62.3
68
Current Data ParametersNAME spa51015EXPNO 33PROCNO 1
F2 - Acquisition ParametersDate_ 20151005Time 11.14INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 297.3 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6111960 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
48
Ethyl 4-(trifluoromethyl)benzoate 2s: 1H NMR (400 MHz, CDCl3, 24°C):
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
1.3
66
1.3
84
1.4
02
4.3
37
4.3
55
4.3
72
4.3
90
7.2
60
7.7
32
7.7
36
7.7
48
7.7
53
7.7
78
7.7
82
7.7
87
7.8
04
3.0
32
2.0
16
2.0
19
2.0
00
Current Data ParametersNAME isolated nmrEXPNO 172PROCNO 1
F2 - Acquisition ParametersDate_ 20151009Time 4.04INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 169.77DW 62.400 usecDE 6.50 usecTE 293.0 KD1 0.50000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 15.70 usecPLW1 7.75000000 WSFO1 400.1320007 MHz
F2 - Processing parametersSI 65536SF 400.1300093 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
19F NMR (470 MHz, CDCl3, 24°C):
-180-160-140-120-100-80-60-40-200 ppm
-63.0
44
Current Data ParametersNAME isolated nmrEXPNO 52PROCNO 1
F2 - Acquisition ParametersDate_ 20151009Time 13.18INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 295.4 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6111960 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
49
Phenyl(4-(trifluoromethyl)phenyl)methanone 2t: 1H NMR (400 MHz, CDCl3, 24°C):
9 8 7 6 5 4 3 2 1 ppm
7.2
60
7.4
69
7.4
88
7.4
90
7.4
92
7.5
07
7.5
12
7.5
29
7.5
30
7.5
32
7.5
33
7.5
85
7.5
88
7.5
99
7.6
04
7.6
09
7.6
12
7.6
15
7.6
19
7.6
22
7.6
29
7.6
34
7.6
39
7.6
49
7.6
52
7.7
47
7.7
60
7.7
64
7.7
65
7.7
67
7.7
68
3.0
00
1.0
59
5.0
15
Current Data ParametersNAME isolated nmrEXPNO 168PROCNO 1
F2 - Acquisition ParametersDate_ 20151009Time 3.40INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 200.34DW 62.400 usecDE 6.50 usecTE 293.0 KD1 0.50000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 15.70 usecPLW1 7.75000000 WSFO1 400.1320007 MHz
F2 - Processing parametersSI 65536SF 400.1300095 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
19F NMR (470 MHz, CDCl3, 24°C):
-180-160-140-120-100-80-60-40-200 ppm
-62.9
69
Current Data ParametersNAME isolated nmrEXPNO 53PROCNO 1
F2 - Acquisition ParametersDate_ 20151009Time 13.22INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 295.4 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6111960 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
50
6-Trifluoromethylquinoline 2y: 1H NMR (400 MHz, CDCl3, 24°C):
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
7.2
60
7.3
98
7.4
08
7.4
19
7.4
29
7.8
22
7.8
45
7.9
34
7.9
38
7.9
56
7.9
60
8.0
34
8.0
37
8.0
55
8.0
58
8.2
16
8.2
20
8.9
10
8.9
14
8.9
21
8.9
24
1.0
14
1.0
17
1.0
00
1.0
58
1.0
26
1.0
00
Current Data ParametersNAME isolated nmrEXPNO 170PROCNO 1
F2 - Acquisition ParametersDate_ 20151009Time 3.52INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 200.34DW 62.400 usecDE 6.50 usecTE 293.0 KD1 0.50000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 15.70 usecPLW1 7.75000000 WSFO1 400.1320007 MHz
F2 - Processing parametersSI 65536SF 400.1300094 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
19F NMR (470 MHz, CDCl3, 24°C):
-180-160-140-120-100-80-60-40-200 ppm
-62.3
16
Current Data ParametersNAME isolated nmrEXPNO 51PROCNO 1
F2 - Acquisition ParametersDate_ 20151009Time 13.12INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgfhigqn.2TD 131072SOLVENT CDCl3NS 16DS 4SWH 113636.367 HzFIDRES 0.866977 HzAQ 0.5767168 secRG 202.34DW 4.400 usecDE 6.50 usecTE 295.4 KD1 1.00000000 secD11 0.03000000 secD12 0.00002000 secTD0 1
======== CHANNEL f1 ========SFO1 470.5641349 MHzNUC1 19FP1 15.00 usecPLW1 46.00000000 W
======== CHANNEL f2 ========SFO2 500.1520006 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 80.00 usecPLW2 15.30000019 WPLW12 0.33006001 W
F2 - Processing parametersSI 65536SF 470.6111960 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00