NMR Chemical Shifts of Trace Impurities PDF

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Summary

Impurities guide...

Description

1

2

3

Corrections and Comments ........................................................................................................ S2 1

H NMR Data (Table S1) ............................................................................................................ S3

13

C NMR Data (Table S2) ........................................................................................................... S5

Individual Solvent Tables – NMR Data Sorted by Chemical Shift (Tables S3–S26) ............ S7 References .................................................................................................................................. S19

S1

In the preparation of this manuscript, several errors were discovered in the original paper1 and are reported herein. While comparing the 1H NMR spectral data 1 obtained in toluene- 8 to that in C6D6, it was discovered that the H NMR chemical shifts

for acetic acid (C 3), acetonitrile (C 3) and

-butyl alcohol (O ) in C6D6 had each

been misreported at 1.55 ppm in the original paper; the values have now been correctly listed as 1.52, 0.58, and 0.63 ppm, respectively. The original paper's assignments for BHT's

(3,5) and

(4) in C6D6, (CD3)2CO, (CD3)2SO, CD3CN, and CD3OD were

reversed and are now corrected. The resonances for 1,2-dimethoxyethane ( H2) in (CD 3)2CO, silicone grease ( H3) in CDCl3, and 2-propanol (C

3)

in CD3 OD have been

corrected and are reported as 72.47, 1.04, and 1.15 ppm, respectively. No other significant differences were discovered when comparing our data to that which had been previously reported; however, we have additionally provided the O ethanol in C6D6 (0.50 ppm), the C

3

resonance for

resonance for silicone grease in (CD3)2SO (–0.06

ppm), and replaced the “grease” entry (formerly motor oil1 ) with VWR vacuum pump oil #19, which is now reported in each deuterated solvent.

S2

1

Table S1. H NMR Data proton

mult

THF- 8 1.72 3.58

CD2 Cl2 5.32

CDCl 3 7.26

s s s s ddt ddt ddt ddd s s m m m s s s s s s s s s s s s s s t m m ddt ddt ddt ddd s s t, 7 q, 7 m m s s s s s s s s s s s s s s s t, 7 q, 7 s s q, 7 t, 7 s q, 7 t, 7 s s dd dd m br s s s

2.46 1.89 2.05 1.95 5.90 5.27 5.15 4.50 1.98 9.98 7.86–7.88 7.51–7.55 7.60–7.64 7.31 1.15 3.16 6.68 5.64 3.68 1.40 6.92 5.81 2.21 1.40 7.89 3.57 1.44 2.24 1.77–1.82 1.68–1.71 5.92 5.31 5.19 4.58 3.77 5.51 1.12 3.38 3.43 3.53 3.28 3.28 3.43 1.94 2.95 2.82 3.69 3.65 3.35 7.91 2.88 2.76 2.45 3.56 0.85 1.10 3.51 3.30 1.94 4.04 1.19 2.03 2.39 0.96 5.36 3.48 7.48 6.37 0.85–0.91 1.29 2.18 0.07

1.52 2.06 2.12 1.97 5.92 5.31 5.22 4.55 2.05 10.01 7.87–7.89 7.53–7.57 7.63–7.67 7.35 1.24 6.73 4.76 3.73 1.42 6.97 5.00 2.25 1.42 7.32 3.59 1.44 2.29 1.81–1.87 1.69–1.72 5.95 5.35 5.26 4.61 3.76 5.33 1.15 3.43 3.57 3.50 3.33 3.34 3.49 2.02 2.97 2.87 3.75 3.72 3.37 7.96 2.91 2.82 2.55 3.65 0.85 1.19 3.66 1.33 2.00 4.08 1.23 2.09 2.43 1.00 5.40 3.66 7.46 6.41 0.84–0.90 1.27 2.20 0.07

1.56 2.10 2.17 2.10 5.93 5.32 5.24 4.57 2.09 10.03 7.88–7.91 7.51–7.57 7.61–7.65 7.36 1.28 6.76 4.76 3.77 1.44 6.98 5.01 2.27 1.43 7.26 3.67 1.43 2.33 1.84–1.86 1.71–1.73 5.94 5.37 5.27 4.64 3.73 5.30 1.21 3.48 3.65 3.57 3.39 3.40 3.55 2.09 3.02 2.94 3.79 3.75 3.40 8.02 2.96 2.88 2.62 3.71 0.87 1.25 3.72 1.32 2.05 4.12 1.26 2.14 2.46 1.06 5.40 3.76 7.45 6.40 0.84–0.87 1.25 2.24 0.07

solvent residual signals

water acetic acid acetone acetonitrile allyl acetate

OH CH3 CH3 CH3 C CH 2 CHC 2(1) CHC 2(2) CH2 CH3 benzaldehyde HCO CH(2,6) CH(3,5) CH(4) benzene CH -butyl alcohol CH3 OH BHA ArH OH ArOCH 3 ArC(CH3 )3 BHT ArH OH ArCH3 ArC(CH3 )3 chloroform CH CH2 18-crown-6 CH2 cyclohexane cyclohexanone CH2 (2,6) CH2 (3,5) CH2 (4) diallyl carbonate C CH 2 CHC 2(1) CHC 2(2) CH2 CH2 1,2-dichloroethane dichloromethane CH2 diethyl ether CH3 CH2 diglyme CH2 CH2 OCH 3 CH3 1,2-dimethoxyethane CH2 dimethylacetamide CH3 CO NCH 3 NCH 3 dimethyl carbonate CH3 dimethyl malonate CH3 CH2 dimethylformamide CH CH3 CH3 dimethyl sulfoxide CH3 1,4-dioxane CH2 ethane CH3 ethanol CH3 CH2 OH CH3 CO ethyl acetate C 2 CH3 CH2C 3 ethyl methyl ketone CH3 CO C 2 CH3 CH2C 3 ethylene CH2 CH2 ethylene glycol furan CH(2,5) CH(3,4) H grease CH3 CH2 CH3 hexamethylbenzene CH3 hexamethyldisiloxane

S3

toluene- 8 2.08 6.97 7.01 7.09 0.43 1.57 1.57 0.69 5.67 5.05 4.94 4.34 1.63 9.57 7.45–7.47 6.95–6.99 7.03–7.07 7.12 1.03 0.58 6.83 4.45 3.48 1.34 6.99 4.72 2.23 1.36 6.10 3.36 1.40 1.95 1.33–1.39 1.16–1.20 5.63 5.09 4.92 4.34 2.91 4.32 1.10 3.25 3.43 3.31 3.12 3.12 3.31 1.59 2.56 2.11 3.31 3.24 2.92 7.57 2.37 1.96 1.64 3.33 0.81 0.97 3.36 0.83 1.69 3.87 0.94 1.59 1.82 0.84 5.25 3.36 7.10 6.07 0.89–0.96 1.33 2.10 0.10

C6 D6 7.16

C6 D5Cl 6.96 6.99 7.14

0.40 1.52 1.55 0.58 5.68 5.06 4.94 4.38 1.63 9.64 7.49–7.53 6.93–6.99 7.01–7.07 7.15 1.05 0.63 6.93 4.53 3.48 1.41 7.05 4.79 2.24 1.38 6.15 3.39 1.40 1.98 1.28–1.37 1.08–1.16 5.65 5.09 4.92 4.38 2.90 4.27 1.11 3.26 3.46 3.34 3.11 3.12 3.33 1.60 2.57 2.05 3.30 3.23 2.97 7.63 2.36 1.86 1.68 3.35 0.80 0.96 3.34 0.50 1.65 3.89 0.92 1.58 1.81 0.85 5.25 3.41 7.13 6.08 0.90–0.98 1.32 2.13 0.12

1.03 1.76 1.77 1.21 5.77 5.15 5.04 4.44 1.80 9.77 7.59–7.61 7.15–7.19 7.24–7.28 7.20 1.12 1.30 6.83 4.62 3.61 1.37 6.97 5.50 2.20 1.37 6.74 3.41 1.37 2.08 1.48–1.53 1.33–1.37 5.75 5.17 5.03 4.46 3.26 4.77 1.10 3.31 3.49 3.37 3.16 3.17 3.37 1.74 2.65 2.42 3.48 3.41 3.15 7.73 2.51 2.30 2.03 3.45 0.79 1.06 3.51 1.39 1.78 3.96 1.04 1.78 2.06 0.89 5.29 3.58 7.24 6.19 0.86–0.92 1.30 2.10 0.10

(CD3) 2CO (CD 3 ) 2SO 2.05 2.50

2.84 1.96 2.09 2.05 5.92 5.29 5.18 4.53 2.02 10.05 7.92–7.94 7.59–7.63 7.69–7.73 7.36 1.18 6.72 5.65 3.72 1.41 6.96 2.22 1.41 8.02 3.59 1.43 2.27 1.79–1.83 1.70–1.74 5.96 5.35 5.23 4.62 3.87 5.63 1.11 3.41 3.56 3.47 3.28 3.28 3.46 1.97 3.00 2.83 3.72 3.68 3.42 7.96 2.94 2.78 2.52 3.59 0.83 1.12 3.57 3.39 1.97 4.05 1.20 2.07 2.45 0.96 5.38 3.28 7.56 6.43 0.90 1.29 2.17 0.07

3.33 1.91 2.09 2.07 5.91 5.29 5.20 4.52 2.03 10.02 7.91–7.93 7.61–7.67 7.69–7.75 7.37 1.11 4.19 6.62 6.52 3.66 1.36 6.87 6.65 2.18 1.36 8.32 3.51 1.40 2.25 1.74–1.78 1.64–1.66 5.93 5.33 5.25 4.61 3.90 5.76 1.09 3.38 3.51 3.38 3.24 3.24 3.43 1.96 2.94 2.78 3.69 3.65 3.53 7.95 2.89 2.73 2.54 3.57 0.82 1.06 3.44 4.63 1.99 4.03 1.17 2.07 2.43 0.91 5.41 3.34 7.67 6.47 0.82–0.88 1.24 2.14 0.06

CD3CN 1.94

TFE- 3 5.02 3.88

CD3 OD 3.31

D 2O 4.79

2.13 1.96 2.08 1.96 5.93 5.29 5.21 4.53 2.02 10.01 7.89–7.91 7.57–7.61 7.67–7.71 7.37 1.16 2.18 6.73 4.98 3.72 1.40 6.97 5.20 2.22 1.39 7.58 3.51 1.44 2.27 1.79–1.84 1.67–1.72 5.96 5.34 5.25 4.61 3.81 5.44 1.12 3.42 3.53 3.45 3.29 3.28 3.45 1.97 2.96 2.83 3.72 3.68 3.38 7.92 2.89 2.77 2.50 3.60 0.85 1.12 3.54 2.47 1.97 4.06 1.20 2.06 2.43 0.96 5.41 3.51 7.52 6.44 2.19 0.07

3.66 2.06 2.19 1.95 5.93 5.32 5.25 4.58 2.07 9.88 7.90–7.92 7.56–7.59 7.68–7.72 7.36 1.28 2.20 6.87 3.79 1.44 7.06 2.24 1.43 7.33 3.64 1.47 2.38 1.87–1.92 1.75–1.78 5.92 5.35 5.28 4.62 3.71 5.24 1.20 3.58 3.67 3.62 3.41 3.40 3.61 2.09 3.05 2.94 3.77 3.76 3.41 7.86 2.98 2.88 2.63 3.76 0.85 1.22 3.71 2.03 4.14 1.26 2.16 2.49 1.05 5.40 3.72 7.44 6.42 0.88–0.94 1.33 2.24 0.08

4.87 1.99 2.15 2.03 5.94 5.30 5.21 4.56 2.05 10.00 7.90–7.93 7.56–7.60 7.66–7.70 7.33 1.40 6.71 4.85 3.72 1.41 6.92 2.21 1.40 7.90 3.64 1.45 2.34 1.85–1.87 1.74–1.76 5.94 5.34 5.25 4.61 3.78 5.49 1.18 3.49 3.61 3.58 3.35 3.35 3.52 2.07 3.31 2.92 3.74 3.72 3.44 7.97 2.99 2.86 2.65 3.66 0.85 1.19 3.60 2.01 4.09 1.24 2.12 2.50 1.01 5.39 3.59 7.49 6.40 0.86–0.93 1.29 2.19 0.07

2.08 2.22 2.06 5.99 5.37 5.30 4.62 2.13 9.96 7.97–7.99 7.57–7.66 7.76–7.80 1.24 3.80 2.40 1.85–1.90 1.70–1.75 5.99 5.40 5.32 4.69 1.17 3.56 3.67 3.61 3.37 3.37 3.60 2.08 3.06 2.90 3.69 3.78 3.60 7.92 3.01 2.85 2.71 3.75 0.82 1.17 3.65 2.07 4.14 1.24 2.19 3.18 1.26 5.44 3.65 7.57 6.51 0.28

-hexane HMPA hydrogen imidazole methane methanol nitromethane -pentane propane 2-propanol propylene

pump oil pyridine

pyrrole

pyrrolidine silicone grease tetrahydrofuran toluene

triethylamine

CH3 CH2 CH3 H2 CH(2) CH(4,5) CH4 CH3 OH CH3 CH3 CH2 CH3 CH2 CH3 CH CH3 CH 2(1) CH 2(2) CH CH3 CH2 CH(2,6) CH(3,5) CH(4) NH CH (2,5) CH (3,4) CH2 (2,5) CH2 (3,4) CH3 CH2 (2,5) CH2 (3,4) CH3 CH(2,4,6) CH(3,5) CH3 CH2

S4

0.88 0.89 0.85 t, 7 0.89 0.89 0.88 0.88 1.26 1.24 1.19 m 1.29 1.27 1.22 1.28 2.65 2.40 2.47 d, 9.5 2.58 2.60 2.42 2.59 4.62 4.47 4.49 s 4.55 4.59 4.50 4.54 s 7.48 7.63 7.67 7.30 7.33 7.53 7.62 s 6.94 7.07 7.10 6.86 6.90 7.01 7.04 s 0.19 0.21 0.22 0.17 0.16 0.15 0.17 3.27 3.42 3.49 3.03 3.07 3.25 3.31 s 1.09 1.30 3.02 1.09 3.12 s 4.33 2.94 3.59 s 4.31 4.31 3.01 4.43 0.88 0.87 0.84 t, 7 0.89 0.89 0.87 0.88 1.27 1.23 1.23 m 1.31 1.30 1.25 1.27 0.90 0.86 0.84 t, 7.3 0.90 0.90 0.89 0.88 sept, 7.3 1.33 1.32 1.32 1.32 1.26 1.26 1.31 d, 6 1.08 1.17 1.22 0.95 0.95 1.04 1.10 sept, 6 3.82 3.97 4.04 3.65 3.67 3.82 3.90 1.73 1.55 1.68 dt, 6.4, 1.5 1.69 1.71 1.55 1.58 4.94 4.95 4.90 dm, 10 4.89 4.93 4.92 4.91 5.03 5.01 5.00 dm, 17 4.99 5.03 4.98 4.98 5.83 5.72 5.81 m 5.79 5.84 5.70 5.72 m 0.86–0.90 0.84–0.89 0.83–0.89 0.88–0.96 0.91–0.97 0.88–0.91 0.87 br s 1.29 1.27 1.26 1.30 1.37 1.31 1.29 m 8.54 8.59 8.62 8.47 8.53 8.51 8.58 m 7.25 7.28 7.29 6.67 6.66 6.90 7.35 7.25 m 7.65 7.68 7.68 6.99 6.98 7.76 8.61 br t 9.96 8.69 8.40 7.71 7.80 10.02 6.62 m 6.66 6.79 6.83 6.43 6.48 6.77 6.27 m 6.02 6.19 6.26 6.27 6.37 6.07 m 2.75 2.82 2.87 2.54 2.54 2.64 1.43 m 1.59 1.67 1.68 1.36 1.33 0.14 s 0.11 0.09 0.07 0.26 0.29 0.13 3.59 m 3.62 3.69 3.76 3.54 3.57 3.63 1.55 m 1.79 1.82 1.85 1.43 1.40 1.79 s 2.31 2.34 2.36 2.11 2.11 2.16 2.32 m 7.10 7.15 7.17 6.96–7.01 7.02 7.01–7.08 7.10–7.20 m 7.19 7.24 7.25 7.09 7.13 7.10–7.17 7.10–7.20 t, 7 0.97 0.99 1.03 0.95 0.96 0.93 0.96 2.39 q, 7 2.46 2.48 2.53 2.39 2.40 2.45

0.86 1.25 2.53 4.61 7.63 7.01 0.20 3.16 4.01 4.42 0.86 1.27 0.87 1.29 1.04 3.78 1.68 4.94 5.03 5.80 0.74 1.15 8.58 7.39 7.79 10.75 6.73 6.01 2.67 1.55 –0.06 3.60 1.76 2.30 7.18 7.25 0.93 2.43

0.91 0.90 0.89 1.31 1.29 1.28 2.63 2.64 2.57 4.53 4.56 4.57 7.57 7.61 7.67 7.01 7.03 7.05 0.20 0.18 0.20 3.28 3.44 3.34 2.16 4.28 4.34 4.31 0.90 0.90 0.89 1.33 1.29 1.29 0.90 0.91 0.90 1.33 1.33 1.34 1.09 1.20 1.15 3.87 4.05 3.92 1.70 1.70 1.70 4.93 4.91 4.93 5.03 5.01 5.04 5.87 5.82 5.85 0.85 0.99 0.86–0.91 1.27 1.41 1.29 8.57 8.45 8.53 7.33 7.40 7.44 7.82 7.73 7.85 9.27 6.84 6.75 6.72 6.24 6.10 6.08 2.75 3.11 2.80 1.93 1.61 1.72 0.16 0.08 0.10 3.78 3.64 3.71 1.91 1.80 1.87 2.33 2.33 2.32 7.10–7.30 7.10–7.30 7.16 7.10–7.30 7.10–7.30 7.16 0.96 1.31 1.05 3.12 2.45 2.58

2.61 7.78 7.14 0.18 3.34 4.40 0.88 1.30 1.17 4.02 1.70 4.95 5.06 5.90 8.52 7.45 7.87 6.93 6.26 3.07 1.87 3.74 1.88 0.99 2.57

13

1

Table S2. C{ H} NMR Data carbon solvent signals

acetic acid

CO CH3 acetone CO CH3 acetonitrile CN CH3 allyl acetate CO HCH2 CH H2 CH2 CH3 benzaldehyde HCO C(1) CH(2,6) CH(3,5) CH (4) benzene CH (CH3 )3 -butyl alcohol ( H3 )3 C BHA C(1) C(2,6) CH(3,5) C(4) CH3 O ( H3 )3 C (CH3 )3 BHT C(1) C(2,6) CH(3,5) C(4) CH3 Ar ( H3 )3 C (CH3 )3 carbon dioxide CO2 CS2 carbon disulfide carbon tetrachloride CCl4 chloroform CH 18-crown-6 CH2 CH2 cyclohexane cyclohexanone CO CH 2 (2,6) CH 2 (3,5) CH2 (4) diallyl carbonate CO HCH2 CH H2 CH2 CH2 1,2-dichloroethane dichloromethane CH2 diethyl ether CH3 CH2 CH3 diglyme CH2 CH2 CH3 1,2-dimethoxyethane CH2 dimethylacetamide CH3 CO NCH 3 NCH 3 dimethyl carbonate CO CH3 dimethyl malonate CO2 CH3 CH2 dimethylformamide CH CH3 CH3 CH3 dimethyl sulfoxide 1,4-dioxane CH2 ethane CH3 CH3 ethanol CH2

S5

THF- 8 67.21 25.31

171.69 20.13 204.19 30.17 116.79 0.45 170.14 133.90 117.58 65.31 20.45 191.95 137.78 129.98 129.56 134.67 128.84 67.50 30.57 154.07 148.62 110.94 140.07 55.39 30.65 35.51 152.48 137.93 125.71 128.64 21.21 31.55 34.91 125.69 193.37 96.89 79.24 71.34 27.58 208.79 42.17 27.69 25.76 155.36 133.08 117.70 68.58 44.64 54.67 15.49 66.14 58.72 71.17 72.72 58.72 72.58 21.15 169.77 34.60 37.56 156.91 54.58 167.14 52.07 41.15 161.96 35.65 30.70 41.21 67.65 6.79 18.90 57.60

CD2Cl 2 53.84

CDCl3 77.16

175.85 20.91 206.78 31.00 116.92 2.03 170.83 132.94 118.00 65.36 21.06 192.61 136.98 129.98 129.42 134.79 128.68 69.11 31.46 153.05 148.06 110.93 137.77 55.88 30.37 34.91 151.92 136.32 125.84 128.73 21.27 30.54 34.56 125.26 192.95 96.52 77.99 70.47 27.38 211.82 42.31 27.47 25.42 155.15 132.24 118.75 68.76 44.35 54.24 15.44 66.11 58.95 70.70 72.25 59.02 72.24 21.64 171.05 35.23 38.22 156.73 55.09 167.32 52.75 41.48 162.57 36.56 31.39 41.33 67.47 6.91 18.69 58.57

175.99 20.81 207.07 30.92 116.43 1.89 170.81 132.33 118.34 65.28 21.02 192.67 136.58 129.91 129.16 134.64 128.37 69.15 31.25 152.57 147.85 110.69 137.36 55.70 30.32 34.72 151.55 135.87 125.55 128.27 21.20 30.33 34.25 124.99 192.83 96.34 77.36 70.55 26.94 212.57 41.97 27.00 24.97 154.88 131.58 118.96 68.55 43.50 53.52 15.20 65.91 59.01 70.51 71.90 59.08 71.84 21.53 171.07 35.28 38.13 156.45 54.89 167.18 52.57 41.11 162.62 36.50 31.45 40.76 67.14 6.89 18.41 58.28

toluene- 8 137.48 128.87 127.96 125.13 20.43 175.30 20.27 204.00 30.03 115.76 0.03 169.44 132.98 117.49 64.87 20.21 191.09 137.12 129.61 128.68 133.88 128.57 68.12 30.49 153.50 148.06 110.99 137.34 55.04 30.30 34.69 152.06 136.12 125.79 128.44 21.42 31.39 34.39 124.86 192.71 96.57 77.89 70.86 27.31 208.60 41.78 27.05 25.15 155.15 132.30 118.04 68.20 43.40 53.47 15.47 65.94 58.62 70.92 72.39 58.63 72.25 21.05 169.65 34.58 36.98 156.61 54.13 166.49 51.76 40.88 161.93 35.22 30.64 40.41 67.17 6.94 18.78 57.81

C6 D6 128.06

C6D5 Cl 134.19 129.26 128.25 125.96

(CD3 )2 CO 29.84 206.26

(CD3) 2SO 39.52

175.82 20.37 204.43 30.14 116.02 0.20 169.67 132.90 117.64 64.92 20.37 191.43 137.05 129.65 128.95 133.95 128.62 68.19 30.47 153.62 148.13 111.15 137.50 55.27 30.35 34.72 152.05 136.08 125.83 128.52 21.40 31.34 34.35 124.76 192.69 96.44 77.79 70.59 27.23 209.10 41.83 27.00 25.03 155.24 132.18 118.22 68.28 43.59 53.46 15.46 65.94 58.66 70.87 72.35 58.68 72.21 21.16 169.95 34.67 37.03 156.71 54.30 166.66 51.86 41.04 162.13 35.25 30.72 40.03 67.16 6.96 18.72 57.86

175.67 20.40 204.83 30.12 115.93 0.63 169.59 132.69 117.63 64.86 20.40 191.24 136.78 129.49 128.87 134.02 128.38 68.19 31.13 153.19 147.87 110.84 137.29 55.08 30.21 34.56 151.69 135.92 125.58 128.26 21.10 30.19 34.11 126.08 192.49 96.38 77.67 70.55 26.99 209.30 41.79 27.02 25.07 154.87 131.93 118.22 68.19 43.60 53.54 15.35 65.79 58.42 70.56 72.07 58.31 71.81 21.03 169.79 34.59 37.13 156.36 54.23 166.51 51.89 40.93 162.01 35.45 30.71 40.27 66.95 6.91 18.55 57.63

172.31 20.51 205.87 30.60 117.60 1.12 170.61 133.76 117.81 65.28 20.68 192.95 137.66 130.23 129.90 135.14 129.15 68.13 30.72 153.97 148.48 111.00 140.32 55.51 30.64 35.45 152.51 138.19 126.03 129.05 21.31 31.61 35.00 125.81 193.58 96.65 79.19 71.25 27.51 210.36 42.24 27.68 25.59 155.48 133.16 118.53 68.78 45.25 54.95 15.78 66.12 58.77 71.03 72.63 58.45 72.47 21.51 170.61 34.89 37.92 157.04 54.95 167.58 52.47 41.43 162.79 36.15 31.03 41.23 67.60 6.88 18.89 57.72

171.93 20.95 206.31 30.56 117.91 1.03 169.97 132.71 117.64 64.32 20.54 193.08 136.20 129.45 129.10 134.52 128.30 66.88 30.38 152.53 147.44 109.80 141.16 54.89 30.30 34.76 151.47 139.12 124.85 127.97 20.97 31.25 34.33 124.21 192.63 95.44 79.16 69.85 26.33 210.63 41.32 26.46 24.32 154.16 132.18 118.32 67.86 45.02 54.84 15.12 62.05 57.98 69.54 71.25 58.03 71.17 21.29 169.54 34.42 37.38 155.76 54.63 166.91 52.08 40.72 162.29 35.73 30.73 40.45 66.36 6.61 18.51 56.07

CD 3CN 1.32 118.26

TFE- 3 61.50 126.28

CD3 OD 49.00

173.21 20.73 207.43 30.91 118.26 1.79 171.32 133.83 118.06 65.55 21.02 193.64 137.62 130.42 130.07 135.40 129.32 68.74 30.68 154.02 148.39 111.35 140.20 55.94 30.55 35.48 152.42 138.13 126.38 129.61 21.23 31.50 35.05 125.89 193.60 96.68 79.17 71.22 27.63 211.99 42.44 27.80 25.62 155.66 133.20 118.86 69.09 45.54 55.32 15.63 66.32 58.90 70.99 72.63 58.89 72.47 21.76 171.31 35.17 38.26 157.26 55.39 168.07 52.95 41.77 163.31 36.57 31.32 41.31 67.72 6.99 18.80 57.96

177.96 20.91 32.35 214.98 118.95 1.00 175.98 133.33 119.39 67.61 21.10 197.63 137.84 131.78 130.82 137.17 129.84 72.35 31.07 153.74 150.52 112.90 140.23 57.55 30.80 36.07 153.46 138.59 127.11 130.62 21.34 31.01 35.69 126.92 196.26 97.74 78.83 70.80 28.34 221.30 43.16 28.56 26.00 157.39 132.72 120.15 70.69 45.28 54.46 15.33 67.55 59.40 73.05 71.33 59.52 72.87 21.40 175.74 36.28 39.06 159.04 56.17 170.88 54.00 42.13 166.01 37.76 30.96 40.06 68.52 7.01 18.11 59.68

175.11 20.56 209.67 30.67 118.06 0.85 172.41 133.71 118.22 66.14 20.71 194.11 137.96 130.64 130.12 135.60 129.34 69.40 30.91 154.34 149.04 111.30 141.36 55.96 30.82 35.83 152.85 139.09 126.11 129.49 21.38 31.15 35.36 126.31 193.82 97.21 79.44 71.47 27.96 214.69 42.61 28.16 25.86 156.28 133.25 118.74 69.35 45.11 54.78 15.46 66.88 59.06 71.33 72.92 59.06 72.72 21.32 173.32 35.50 38.43 157.91 55.25 168.70 52.83 41.60 164.73 36.89 31.61 40.45 68.11 6.98 18.40 58.26

D2 O -

177.21 21.03 215.94 30.89 119.68 1.47 174.78 132.48 119.03 66.52 21.00 191.67 136.11 130.09 129.48 134.70 70.36 30.29 197.25 96.73 70.14 221.22 42.02 27.50 24.77 157.78 132.76 118.75 68.81 14.77 66.42 58.67 70.05 71.63 58.67 71.49 21.09 174.57 35.03 38.76 163.96 55.81 170.12 53.65 42.13 165.53 37.54 32.03 39.39 67.19 17.47 58.05

ethyl acetate

H3 CO CO CH2 CH3 ethyl methyl ketone H3 CO CO H2 CH 3 CH2 H 3 ethylene CH2 ethylene glycol CH2 furan CH(2,5) CH(3,4) CH2 H grease hexamethylbenzene C CH3 hexamethyldisiloxane CH3 -hexane CH3 CH 2 (2,5) CH 2 (3,4) HMPA CH3 imidazole CH(2) CH(4,5) CH4 methane CH3 methanol nitromethane CH3 -pentane CH3 CH 2 (2,4) CH2 (3) propane CH3 CH2 CH3 2-propanol CH propylene CH3 CH2 CH CH2 pump oil pyridine CH(2,6) CH(3,5) CH(4) pyrrole CH(2,5) CH(3,4) pyrrolidine CH 2 (2,5) CH 2 (3,4) CH3 silicone grease tetrahydrofuran CH 2 (2,5) CH 2 (3,4) toluene CH3 C(1) CH(2,6) CH(3,5) CH(4) triethylamine CH3 CH2

S6

20.45 170.32 60.30 14.37 28.92 207.05 36.59 7.87 123.09 64.35 143.26 109.88 30.45 131.88 16.71 1.83 14.22 23.33 32.34 36.89 135.72 122.20 –4.90 49.64 62.49 14.18 23.00 34.87 16.60 16.82 25.70 66.14 19.27 115.74 134.02 30.63 150.57 124.08 135.99 118.03 107.74 45.82 26.17 1.20 68.03 26.19 21.29 138.24 129.47 128.71 125.84 12.51 47.18

21.15 171.24 60.63 14.37 29.55 209.57 37.01 7.94 123.20 64.08 142.98 109.86 30.14 132.09 16.93 1.96 14.28 23.07 32.01 36.99 135.76 122.16 –4.33 50.45 63.03 14.24 22.77 34.57 16.63 16.63 25.43 64.67 19.47 115.70 134.21 30.13 150.27 124.06 136.16 117.93 108.02 47.02 25.83 1.22 68.16 25.98 21.53 138.36 129.35 128.54 125.62 12.12 46.75

21.04 171.36 60.49 14.19 29.49 209.56 36.89 7.86 123.13 63.79 142.71 109.57 29.71 132.21 16.98 1.97 14.14 22.70 31.64 36.87 135.38 122.00 –4.63 50.41 62.50 14.08 22.38 34.16 16.63 16.37 25.14 64.50 19.50 115.74 133.91 29.84 149.90 123.75 135.96 117.77 107.98 46.93 25.56 1.19 67.97 25.62 21.46 137.89 129.07 128.26 125.33 11.61 46.25

20.46 170.02 60.08 14.23 28.74 206.31 36.32 7.89 122.92 64.29 142.65 109.63 30.31 131.72 16.84 1.99 14.34 23.12 32.06 36.80 135.57 122.13 –4.34 49.90 61.14 14.27 22.79 34.54 16.65 16.63 25.24 64.12 19.32 115.89 133.61 30.33 150.25 123.46 135.17 117.61 108.15 47.12 25.75 1.37 67.75 25.79 21.37 137.84 129.33 128.51 125.66 12.39 46.82

20.56 170.44 60.21 14.19 28.56 206.55 36.36 7.91 122.96 64.34 142.73 109.67 30.22 131.79 16.95 2.05 14.32 23.04 31.96 36.88 135.76 122.16 –4.29 49.97 61.16 14.25 22.72 34.45 16.66 1...