核磁各基团出峰位置

Supporting Information

NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the

Organometallic Chemist

Gregory R. Fulmer,*,1 Alexander J. M. Miller,2 Nathaniel H. Sherden,2 Hugo E. Gottlieb,3 Abraham Nudelman,3 Brian M. Stoltz,2 John E. Bercaw,2 and Karen I.

Goldberg1

1 Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195-1700;

2 Arnold and Mabel Beckman Laboratories of Chemical Synthesis, and Caltech Center for Catalysis and Chemical Synthesis, Division of Chemistry and Chemical Engineering California Institute of Technology,

Pasadena, California 91125;

3 Department of Chemistry, Bar Ilan University, Ramat Gan 52900, Israel.

Corrections and Comments........................................................................................................S2 1H NMR Data (Table S1)............................................................................................................S3 13C NMR Data (Table S2)...........................................................................................................S5 Individual Solvent Tables – NMR Data Sorted by Chemical Shift (Tables S3–S26)............S7 References..................................................................................................................................S19

Corrections and Comments

In the preparation of this manuscript, several errors were discovered in the original paper1and are reported herein. While comparing the 1H NMR spectral data obtained in toluene-d8 to that in C6D6, it was discovered that the 1H NMR chemical shifts for acetic acid (C H3), acetonitrile (C H3) and tert-butyl alcohol (O H) in C6D6had 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 C(3,5) and C(4) in C6D6, (CD3)2CO, (CD3)2SO, CD3CN, and CD3OD were reversed and are now corrected. The resonances for 1,2-dimethoxyethane (C H2) in (CD3)2CO, silicone grease (C H3) in CDCl3, and 2-propanol (C H3) in CD3OD 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 H resonance for ethanol in C6D6 (0.50 ppm), the C H3 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.

Table S1.1H NMR Data2

proton mult THF-d8CD2Cl2CDCl3toluene-d8C6D6C6D5Cl(CD3)2CO(CD3)2SO CD3CN TFE-d3CD3OD D2O solvent residual signals 1.72 5.327.26 2.087.16 6.96 2.05 2.50 1.94 5.02 3.31 4.79

3.58 6.97 6.99 3.88

7.017.14

7.09

water OH s 2.46 1.52 1.560.430.40 1.03 2.843 3.333 2.13 3.66 4.87-acetic acid CH3s 1.89 2.06 2.10 1.57 1.52 1.76 1.96 1.91 1.96 2.06 1.99 2.08 acetone CH3s 2.05 2.12 2.17 1.57 1.55 1.77 2.09 2.09 2.08 2.19 2.15 2.22 acetonitrile CH3s 1.95 1.97 2.100.690.58 1.21 2.05 2.07 1.96 1.95 2.03 2.06 allyl acetate C H CH2ddt 5.90 5.92 5.93 5.674 5.684 5.77 5.92 5.91 5.93 5.93 5.94 5.99 CHC H2(1)ddt 5.27 5.31 5.32 5.05 5.06 5.15 5.29 5.29 5.29 5.32 5.30 5.37

CHC H2(2)ddt 5.15 5.22 5.24 4.94 4.94 5.04 5.18 5.20 5.21 5.25 5.21 5.30 CH2ddd 4.50 4.55 4.57 4.34 4.38 4.44 4.53 4.52 4.53 4.58 4.56 4.62

CH3s 1.98 2.05 2.09 1.63 1.63 1.80 2.02 2.03 2.02 2.07 2.05 2.13 benzaldehyde HCO s9.9810.0110.039.579.649.7710.0510.0210.019.8810.009.96 CH(2,6)m7.86–7.887.87–7.897.88–7.917.45–7.477.49–7.537.59–7.617.92–7.947.91–7.937.89–7.917.90–7.927.90–7.937.97–7.99

CH(3,5)m7.51–7.557.53–7.577.51–7.57 6.95–6.99 6.93–6.997.15–7.197.59–7.637.61–7.677.57–7.617.56–7.597.56–7.607.57–7.66

CH(4)m7.60–7.647.63–7.677.61–7.657.03–7.077.01–7.077.24–7.287.69–7.737.69–7.757.67–7.717.68–7.727.66–7.707.76–7.80 benzene CH s7.317.357.367.127.157.207.367.377.377.367.33-tert-butyl alcohol CH3s 1.15 1.24 1.28 1.03 1.05 1.12 1.18 1.11 1.16 1.28 1.40 1.24 OH s5 3.16--0.580.63 1.30- 4.19 2.18 2.20--BHA ArH s 6.68 6.73 6.76 6.83 6.93 6.83 6.72 6.62 6.73 6.87 6.71-OH s5 5.64 4.76 4.76 4.45 4.53 4.62 5.65 6.52 4.98- 4.85-

ArOCH3s 3.68 3.73 3.77 3.48 3.48 3.61 3.72 3.66 3.72 3.79 3.72-

ArC(CH3)3s 1.40 1.42 1.44 1.34 1.41 1.37 1.41 1.36 1.40 1.44 1.41-BHT ArH s 6.92 6.97 6.98 6.997.05 6.97 6.96 6.87 6.977.06 6.92-OH s5 5.81 5.00 5.01 4.72 4.79 5.50- 6.65 5.20---

ArCH3s 2.21 2.25 2.27 2.23 2.24 2.20 2.22 2.18 2.22 2.24 2.21-

ArC(CH3)3s 1.40 1.42 1.43 1.36 1.38 1.37 1.41 1.36 1.39 1.43 1.40-chloroform CH s7.897.327.26 6.10 6.15 6.748.028.327.587.337.90-

18-crown-6CH2s 3.57 3.59 3.67 3.36 3.39 3.41 3.59 3.51 3.51 3.64 3.64 3.80 cyclohexane CH2s 1.44 1.44 1.43 1.40 1.40 1.37 1.43 1.40 1.44 1.47 1.45-cyclohexanone CH2(2,6)t 2.24 2.29 2.33 1.95 1.98 2.08 2.27 2.25 2.27 2.38 2.34 2.40 CH2(3,5)m 1.77–1.82 1.81–1.87 1.84–1.86 1.33–1.39 1.28–1.37 1.48–1.53 1.79–1.83 1.74–1.78 1.79–1.84 1.87–1.92 1.85–1.87 1.85–1.90

CH2(4)m 1.68–1.71 1.69–1.72 1.71–1.73 1.16–1.20 1.08–1.16 1.33–1.37 1.70–1.74 1.64–1.66 1.67–1.72 1.75–1.78 1.74–1.76 1.70–1.75 diallyl carbonate C H CH2ddt 5.92 5.95 5.94 5.63 5.65 5.75 5.96 5.93 5.96 5.92 5.94 5.99 CHC H2(1)ddt 5.31 5.35 5.37 5.09 5.09 5.17 5.35 5.33 5.34 5.35 5.34 5.40

CHC H2(2)ddt 5.19 5.26 5.27 4.92 4.92 5.03 5.23 5.25 5.25 5.28 5.25 5.32 CH2ddd 4.58 4.61 4.64 4.34 4.38 4.46 4.62 4.61 4.61 4.62 4.61 4.69 1,2-dichloroethane CH2s 3.77 3.76 3.73 2.91 2.90 3.26 3.87 3.90 3.81 3.71 3.78-dichloromethane CH2s 5.51 5.33 5.30 4.32 4.27 4.77 5.63 5.76 5.44 5.24 5.49-diethyl ether CH3t, 7 1.12 1.15 1.21 1.10 1.11 1.10 1.11 1.09 1.12 1.20 1.18 1.17 CH2q, 7 3.38 3.43 3.48 3.25 3.26 3.31 3.41 3.38 3.42 3.58 3.49 3.56 diglyme CH2m 3.43 3.57 3.65 3.43 3.46 3.49 3.56 3.51 3.53 3.67 3.61 3.67 CH2m 3.53 3.50 3.57 3.31 3.34 3.37 3.47 3.38 3.45 3.62 3.58 3.61

OCH3s 3.28 3.33 3.39 3.12 3.11 3.16 3.28 3.24 3.29 3.41 3.35 3.37 1,2-dimethoxyethane CH3s 3.28 3.34 3.40 3.12 3.12 3.17 3.28 3.24 3.28 3.40 3.35 3.37 CH2s 3.43 3.49 3.55 3.31 3.33 3.37 3.46 3.43 3.45 3.61 3.52 3.60 dimethylacetamide CH3CO s 1.94 2.02 2.09 1.59 1.60 1.74 1.97 1.96 1.97 2.09 2.07 2.08 NCH3s 2.95 2.97 3.02 2.56 2.57 2.65 3.00 2.94 2.96 3.05 3.31 3.06

NCH3s 2.82 2.87 2.94 2.11 2.05 2.42 2.83 2.78 2.83 2.94 2.92 2.90 dimethyl carbonate CH3s 3.69 3.75 3.79 3.31 3.30 3.48 3.72 3.69 3.72 3.77 3.74 3.69 dimethyl malonate CH3s 3.65 3.72 3.75 3.24 3.23 3.41 3.68 3.65 3.68 3.76 3.72 3.78 CH2s 3.35 3.37 3.40 2.92 2.97 3.15 3.42 3.53 3.38 3.41 3.44 3.60 dimethylformamide CH s7.917.968.027.577.637.737.967.957.927.867.977.92 CH3s 2.88 2.91 2.96 2.37 2.36 2.51 2.94 2.89 2.89 2.98 2.99 3.01

CH3s 2.76 2.82 2.88 1.96 1.86 2.30 2.78 2.73 2.77 2.88 2.86 2.85 dimethyl sulfoxide CH3s 2.45 2.55 2.62 1.64 1.68 2.03 2.52 2.54 2.50 2.63 2.65 2.71 1,4-dioxane CH2s 3.56 3.65 3.71 3.33 3.35 3.45 3.59 3.57 3.60 3.76 3.66 3.75 ethane CH3s0.850.850.870.810.800.790.830.820.850.850.850.82 ethanol CH3t, 7 1.10 1.19 1.250.970.96 1.06 1.12 1.06 1.12 1.22 1.19 1.17 CH2q, 76 3.51 3.66 3.72 3.36 3.34 3.51 3.57 3.44 3.54 3.71 3.60 3.65

OH s5,6 3.30 1.33 1.320.830.50 1.39 3.39 4.63 2.47---ethyl acetate CH3CO s 1.94 2.00 2.05 1.69 1.65 1.78 1.97 1.99 1.97 2.03 2.01 2.07

C H2CH3q, 7 4.04 4.08 4.12 3.87 3.89 3.96 4.05 4.03 4.06 4.14 4.09 4.14

CH2C H3t, 7 1.19 1.23 1.260.940.92 1.04 1.20 1.17 1.20 1.26 1.24 1.24 ethyl methyl ketone CH3CO s 2.03 2.09 2.14 1.59 1.58 1.78 2.07 2.07 2.06 2.16 2.12 2.19

C H2CH3q, 7 2.39 2.43 2.46 1.82 1.81 2.06 2.45 2.43 2.43 2.49 2.50 3.18

CH2C H3t, 70.96 1.00 1.060.840.850.890.960.910.96 1.05 1.01 1.26 ethylene CH2s 5.36 5.40 5.40 5.25 5.25 5.29 5.38 5.41 5.41 5.40 5.39 5.44 ethylene glycol CH2s7 3.48 3.66 3.76 3.36 3.41 3.58 3.28 3.34 3.51 3.72 3.59 3.65 furan CH(2,5)dd7.487.467.457.107.137.247.567.677.527.447.497.57 CH(3,4)dd 6.37 6.41 6.40 6.07 6.08 6.19 6.43 6.47 6.44 6.42 6.40 6.51

H grease8CH3m0.85–0.910.84–0.900.84–0.870.89–0.960.90–0.980.86–0.920.900.82–0.88-0.88–0.940.86–0.93-

CH2br s 1.29 1.27 1.25 1.33 1.32 1.30 1.29 1.24- 1.33 1.29-hexamethylbenzene CH3s 2.18 2.20 2.24 2.10 2.13 2.10 2.17 2.14 2.19 2.24 2.19-hexamethyldisiloxane CH3s0.070.070.070.100.120.100.070.060.070.080.070.28

n-hexane CH3t, 70.890.890.880.880.890.850.880.860.890.910.90-CH2m 1.29 1.27 1.26 1.22 1.24 1.19 1.28 1.25 1.28 1.31 1.29-HMPA CH3d, 9.5 2.58 2.60 2.65 2.42 2.40 2.47 2.59 2.53 2.57 2.63 2.64 2.61 hydrogen H2s 4.55 4.59 4.62 4.50 4.47 4.49 4.54 4.61 4.57 4.53 4.56-imidazole CH(2)s7.487.637.677.307.337.537.627.637.577.617.677.78 CH(4,5)s 6.947.077.10 6.86 6.907.017.047.017.017.037.057.14 methane CH4s0.190.210.220.170.160.150.170.200.200.180.200.18 methanol CH3s9 3.27 3.42 3.49 3.03 3.07 3.25 3.31 3.16 3.28 3.44 3.34 3.34 OH s5,9 3.02 1.09 1.09-- 1.30 3.12 4.01 2.16---nitromethane CH3s 4.31 4.31 4.33 3.01 2.94 3.59 4.43 4.42 4.31 4.28 4.34 4.40 n-pentane CH3t, 70.890.890.880.870.870.840.880.860.890.900.90-CH2m 1.31 1.30 1.27 1.25 1.23 1.23 1.27 1.27 1.29 1.33 1.29-propane CH3t, 7.30.900.900.900.890.860.840.880.870.900.900.910.88 CH2sept, 7.3 1.33 1.32 1.32 1.32 1.26 1.26 1.31 1.29 1.33 1.33 1.34 1.30 2-propanol CH3d, 6 1.08 1.17 1.220.950.95 1.04 1.10 1.04 1.09 1.20 1.15 1.17 CH sept, 6 3.82 3.97 4.04 3.65 3.67 3.82 3.90 3.78 3.87 4.05 3.92 4.02 propylene CH3dt, 6.4, 1.5 1.69 1.71 1.73 1.55 1.55 1.58 1.68 1.68 1.70 1.70 1.70 1.70 CH2(1)dm, 10 4.89 4.93 4.94 4.92 4.95 4.91 4.90 4.94 4.93 4.93 4.91 4.95

CH2(2)dm, 17 4.99 5.03 5.03 4.98 5.01 4.98 5.00 5.03 5.04 5.03 5.01 5.06

CH m 5.79 5.84 5.83 5.70 5.72 5.72 5.81 5.80 5.85 5.87 5.82 5.90 pump oil CH3m0.86–0.900.84–0.890.83–0.890.88–0.960.91–0.970.88–0.910.870.740.850.990.86–0.91-CH2br s 1.29 1.27 1.26 1.30 1.37 1.31 1.29 1.15 1.27 1.41 1.29-pyridine CH(2,6)m8.548.598.628.478.538.518.588.588.578.458.538.52 CH(3,5)m7.257.287.29 6.67 6.66 6.907.357.397.337.407.447.45

CH(4)m7.657.687.68 6.99 6.987.257.767.797.737.827.857.87 pyrrole NH br t9.968.698.407.717.808.6110.0210.759.27---CH(2,5)m 6.66 6.79 6.83 6.43 6.48 6.62 6.77 6.73 6.75 6.84 6.72 6.93

CH(3,4)m 6.02 6.19 6.26 6.27 6.37 6.27 6.07 6.01 6.10 6.24 6.08 6.26 pyrrolidine10CH2(2,5)m 2.75 2.82 2.87 2.54 2.54 2.64- 2.67 2.75 3.11 2.80 3.07 CH2(3,4)m 1.59 1.67 1.68 1.36 1.33 1.43- 1.55 1.61 1.93 1.72 1.87 silicone grease CH3s0.110.090.070.260.290.140.13–0.060.080.160.10-tetrahydrofuran CH2(2,5)m 3.62 3.69 3.76 3.54 3.57 3.59 3.63 3.60 3.64 3.78 3.71 3.74 CH2(3,4)m 1.79 1.82 1.85 1.43 1.40 1.55 1.79 1.76 1.80 1.91 1.87 1.88 toluene CH3s 2.31 2.34 2.36 2.11 2.11 2.16 2.32 2.30 2.33 2.33 2.32-CH(2,4,6)m7.107.157.17 6.96–7.017.027.01–7.087.10–7.20 7.187.10–7.30 7.10–7.307.16-

CH(3,5)m7.197.247.257.097.137.10–7.177.10–7.20 7.257.10–7.30 7.10–7.307.16-triethylamine CH3t, 70.970.99 1.030.950.960.930.960.930.96 1.31 1.050.99 CH2q, 7 2.46 2.48 2.53 2.39 2.40 2.39 2.45 2.43 2.45 3.12 2.58 2.57

Table S2.13C{1H} NMR Data2

carbon THF-d8CD2Cl2CDCl3toluene-d8C6D6C6D5Cl(CD3)2CO(CD3)2SO CD3CN TFE-d3CD3OD D2O solvent signals67.2153.8477.16137.48128.06134.1929.8439.52 1.3261.5049.00-

25.31128.87129.26206.26118.26126.28

127.96128.25

125.13125.96

20.43

acetic acid CO171.69175.85175.99175.30175.82175.67172.31171.93173.21177.96175.11177.21 CH320.1320.9120.8120.2720.3720.4020.5120.9520.7320.9120.5621.03 acetone CO204.19206.78207.07204.00204.43204.83205.87206.31207.4332.35209.67215.94 CH330.1731.0030.9230.0330.1430.1230.6030.5630.91214.9830.6730.89 acetonitrile CN116.79116.92116.43115.76116.02115.93117.60117.91118.26118.95118.06119.68 CH30.45 2.03 1.890.030.200.63 1.12 1.03 1.79 1.000.85 1.47 allyl acetate CO170.14170.83170.81169.44169.67169.59170.61169.97171.32175.98172.41174.78

C HCH2133.90132.94132.33132.98132.90132.69133.76132.71133.83133.33133.71132.48

CH C H2117.58118.00118.34117.49117.64117.63117.81117.64118.06119.39118.22119.03

CH265.3165.3665.2864.8764.9264.8665.2864.3265.5567.6166.1466.52

CH320.4521.0621.0220.2120.3720.4020.6820.5421.0221.1020.7121.00 benzaldehyde HCO191.95192.61192.67191.09191.43191.24192.95193.08193.64197.63194.11191.67 C(1)137.78136.98136.58137.12137.05136.78137.66136.20137.62137.84137.96136.11

CH(2,6)129.98129.98129.91129.61129.65129.49130.23129.45130.42131.78130.64130.09

CH(3,5)129.56129.42129.16128.68128.95128.87129.90129.10130.07130.82130.12129.48

CH (4)134.67134.79134.64133.88133.95134.02135.14134.52135.40137.17135.60134.70 benzene CH128.84128.68128.37128.57128.62128.38129.15128.30129.32129.84129.34-tert-butyl alcohol(CH3)3C67.5069.1169.1568.1268.1968.1968.1366.8868.7472.3569.4070.36

(C H3)3C30.5731.4631.2530.4930.4731.1330.7230.3830.6831.0730.9130.29 BHA C(1) 154.07153.05152.57153.50153.62153.19153.97152.53154.02153.74154.34-C(2,6) 148.62148.06147.85148.06148.13147.87148.48147.44148.39150.52149.04-

CH(3,5) 110.94110.93110.69110.99111.15110.84111.00109.80111.35112.90111.30-

C(4) 140.07137.77137.36137.34137.50137.29140.32141.16140.20140.23141.36-

CH3O55.3955.8855.7055.0455.2755.0855.5154.8955.9457.5555.96-

(C H3)3C30.6530.3730.3230.3030.3530.2130.6430.3030.5530.8030.82-

(CH3)3C35.5134.9134.7234.6934.7234.5635.4534.7635.4836.0735.83-BHT C(1) 152.48151.92151.55152.06152.05151.69152.51151.47152.42153.46152.85-C(2,6) 137.93136.32135.87136.12136.08135.92138.19139.12138.13138.59139.09-

CH(3,5) 125.71125.84125.55125.79125.83125.58126.03124.85126.38127.11126.11-

C(4) 128.64128.73128.27128.44128.52128.26129.05127.97129.61130.62129.49-

CH3Ar21.2121.2721.2021.4221.4021.1021.3120.9721.2321.3421.38-

(C H3)3C31.5530.5430.3331.3931.3430.1931.6131.2531.5031.0131.15-

(CH3)3C34.9134.5634.2534.3934.3534.1135.0034.3335.0535.6935.36-carbon dioxide CO2125.69125.26124.99124.86124.76126.08125.81124.21125.89126.92126.31-carbon disulfide CS2193.37192.95192.83192.71192.69192.49193.58192.63193.60196.26193.82197.25 carbon tetrachloride CCl496.8996.5296.3496.5796.4496.3896.6595.4496.6897.7497.2196.73 chloroform CH79.2477.9977.3677.8977.7977.6779.1979.1679.1778.8379.44-18-crown-6CH271.3470.4770.5570.8670.5970.5571.2569.8571.2270.8071.4770.14 cyclohexane CH227.5827.3826.9427.3127.2326.9927.5126.3327.6328.3427.96-cyclohexanone CO208.79211.82212.57208.60209.10209.30210.36210.63211.99221.30214.69221.22 CH2(2,6)42.1742.3141.9741.7841.8341.7942.2441.3242.4443.1642.6142.02

CH2(3,5)27.6927.4727.0027.0527.0027.0227.6826.4627.8028.5628.1627.50

CH2(4)25.7625.4224.9725.1525.0325.0725.5924.3225.6226.0025.8624.77 diallyl carbonate CO155.36155.15154.88155.15155.24154.87155.48154.16155.66157.39156.28157.78

C HCH2133.08132.24131.58132.30132.18131.93133.16132.18133.20132.72133.25132.76

CH C H2117.70118.75118.96118.04118.22118.22118.53118.32118.86120.15118.74118.75

CH268.5868.7668.5568.2068.2868.1968.7867.8669.0970.6969.3568.81 1,2-dichloroethane CH244.6444.3543.5043.4043.5943.6045.2545.0245.5445.2845.11-dichloromethane CH254.6754.2453.5253.4753.4653.5454.9554.8455.3254.4654.78-diethyl ether CH315.4915.4415.2015.4715.4615.3515.7815.1215.6315.3315.4614.77 CH266.1466.1165.9165.9465.9465.7966.1262.0566.3267.5566.8866.42 diglyme CH358.7258.9559.0158.6258.6658.4258.7757.9858.9059.4059.0658.67 CH271.1770.7070.5170.9270.8770.5671.0369.5470.9973.0571.3370.05

CH272.7272.2571.9072.3972.3572.0772.6371.2572.6371.3372.9271.63 1,2-dimethoxyethane CH358.7259.0259.0858.6358.6858.3158.4558.0358.8959.5259.0658.67 CH272.5872.2471.8472.2572.2171.8172.4771.1772.4772.8772.7271.49 dimethylacetamide CH321.1521.6421.5321.0521.1621.0321.5121.2921.7621.4021.3221.09 CO169.77171.05171.07169.65169.95169.79170.61169.54171.31175.74173.32174.57

NCH334.6035.2335.2834.5834.6734.5934.8934.4235.1736.2835.5035.03

NCH337.5638.2238.1336.9837.0337.1337.9237.3838.2639.0638.4338.76 dimethyl carbonate CO156.91156.73156.45156.61156.71156.36157.04155.76157.26159.04157.91163.96 CH354.5855.0954.8954.1354.3054.2354.9554.6355.3956.1755.2555.81 dimethyl malonate CO2167.14167.32167.18166.49166.66166.51167.58166.91168.07170.88168.70170.12 CH352.0752.7552.5751.7651.8651.8952.4752.0852.9554.0052.8353.65

CH241.1541.4841.1140.8841.0440.9341.4340.7241.7742.1341.6042.13 dimethylformamide CH161.96162.57162.62161.93162.13162.01162.79162.29163.31166.01164.73165.53 CH335.6536.5636.5035.2235.2535.4536.1535.7336.5737.7636.8937.54

CH330.7031.3931.4530.6430.7230.7131.0330.7331.3230.9631.6132.03 dimethyl sulfoxide CH341.2141.3340.7640.4140.0340.2741.2340.4541.3140.0640.4539.39 1,4-dioxane CH267.6567.4767.1467.1767.1666.9567.6066.3667.7268.5268.1167.19 ethane CH3 6.79 6.91 6.89 6.94 6.96 6.91 6.88 6.61 6.997.01 6.98-ethanol CH318.9018.6918.4118.7818.7218.5518.8918.5118.8018.1118.4017.47 CH257.6058.5758.2857.8157.8657.6357.7256.0757.9659.6858.2658.05

ethyl acetate C H3CO20.4521.1521.0420.4620.5620.5020.8320.6821.1621.1820.8821.15 CO170.32171.24171.36170.02170.44170.20170.96170.31171.68175.55172.89175.26

CH260.3060.6360.4960.0860.2160.0660.5659.7460.9862.7061.5062.32

CH314.3714.3714.1914.2314.1914.0714.5014.4014.5414.3614.4913.92 ethyl methyl ketone C H3CO28.9229.5529.4928.7428.5628.8229.3029.2629.6029.6429.3929.49 CO207.05209.57209.56206.31206.55206.87208.30208.72209.88218.31212.16218.43

C H2CH336.5937.0136.8936.3236.3636.3936.7535.8337.0938.2337.3437.27

CH2C H37.877.947.867.897.917.798.037.618.148.298.097.87 ethylene CH2123.09123.20123.13122.92122.96122.95123.47123.52123.69124.08123.46-ethylene glycol CH264.3564.0863.7964.2964.3464.0364.2662.7664.2264.8764.3063.17 furan CH(2,5)143.26142.98142.71142.65142.73142.49143.49142.82143.74144.22143.68143.57 CH(3,4)109.88109.86109.57109.63109.67109.64110.24109.62110.49111.06110.33110.23 H grease8CH230.4530.1429.7130.3130.2230.11------hexamethylbenzene C131.88132.09132.21131.72131.79131.54132.22131.10132.61134.04132.53-CH316.7116.9316.9816.8416.9516.6816.8616.6016.9417.0416.90-hexamethyldisiloxane CH3 1.83 1.96 1.97 1.99 2.05 1.92 2.01 1.96 2.07 2.09 1.99 2.31 n-hexane CH314.2214.2814.1414.3414.3214.1814.3413.8814.4314.6314.45-CH2(2,5)23.3323.0722.7023.1223.0422.8623.2822.0523.4024.0623.68-

CH2(3,4)32.3432.0131.6432.0631.9631.7732.3030.9532.3633.1732.73-HMPA11CH336.8936.9936.8736.8036.8836.6437.0436.4237.1037.2137.0036.46 imidazole CH(2)135.72135.76135.38135.57135.76135.50135.89135.15136.33136.58136.31136.65 CH(4,5)122.20122.16122.00122.13122.16121.96122.31121.55122.78122.93122.60122.43 methane CH4–4.90–4.33–4.63–4.34–4.29–4.33–5.33–4.01–4.61–5.88–4.90-methanol CH349.6450.4550.4149.9049.9749.6649.7748.5949.9050.6749.8649.5012 nitromethane CH362.4963.0362.5061.1461.1661.6863.2163.2863.6663.1763.0863.22 n-pentane CH314.1814.2414.0814.2714.2514.1014.2913.2814.3714.5414.39-CH2(2,4)23.0022.7722.3822.7922.7222.5422.9821.7023.0823.7523.38-

CH2(3)34.8734.5734.1634.5434.4534.2634.8333.4834.8935.7635.30-propane CH316.6016.6316.6316.6516.6616.5616.6816.3416.7316.9316.80-CH216.8216.6316.3716.6316.6016.4816.7815.6716.9117.4617.19-

2-propanol CH325.7025.4325.1425.2425.1825.1425.6725.4325.5525.2125.2724.38 CH66.1464.6764.5064.1264.2364.1863.8564.9264.3066.6964.7164.88 propylene CH319.2719.4719.5019.3219.3819.3219.4219.2019.4819.6319.50-CH2115.74115.70115.74115.89115.92115.86116.03116.07116.12116.38116.04-

CH134.02134.21133.91133.61133.69133.57134.34133.55134.78136.00134.61-pump oil CH230.6330.1329.8430.3330.2430.1130.3629.3330.8631.8531.35-pyridine CH(2,6)150.57150.27149.90150.25150.27149.93150.67149.58150.76149.76150.07149.18 CH(3,5)124.08124.06123.75123.46123.58123.49124.57123.84127.76126.27125.53125.12

CH(4)135.99136.16135.96135.17135.28135.32136.56136.05136.89139.62138.35138.27 pyrrole CH(2,5)118.03117.93117.77117.61117.78117.65117.98117.32118.47119.61118.28119.06 CH(3,4)107.74108.02107.98108.15108.21108.03108.04107.07108.31108.85108.11107.83 pyrrolidine10CH2(2,5)45.8247.0246.9347.1246.8646.75-46.5147.5747.4347.2346.83 CH2(3,4)26.1725.8325.5625.7525.6525.59-25.2626.3425.7326.2925.86 silicone grease CH3 1.20 1.22 1.19 1.37 1.38 1.09 1.40-- 2.87 2.10-tetrahydrofuran CH2(2,5)68.0368.1667.9767.7567.8067.6468.0767.0368.3369.5368.8368.68 CH2(3,4)26.1925.9825.6225.7925.7225.6826.1525.1426.2726.6926.4825.67 toluene CH321.2921.5321.4621.3721.1021.2321.4620.9921.5021.6221.50-C(1)138.24138.36137.89137.84137.91137.65138.48137.35138.90139.92138.85-

CH(2,6)129.47129.35129.07129.33129.33129.12129.76128.88129.94130.58129.91-

CH(3,5)128.71128.54128.26128.51128.56128.31129.03128.18129.23129.79129.20-

CH(4)125.84125.62125.33125.66125.68125.43126.12125.29126.28126.82126.29-triethylamine CH312.5112.1211.6112.3912.3511.8712.4911.7412.389.5111.099.07 CH247.1846.7546.2546.8246.7746.3647.0745.7447.1048.4546.9647.19

shift mult proton impurity shift mult proton impurity shift mult proton impurity

0.07 s CH3hexamethyldisiloxane 2.21 s ArCH3BHT 4.50 ddd CH2allyl acetate

0.11 s CH3silicone grease 2.24 t CH2(2,6) cyclohexanone 4.55 s H2hydrogen

0.19 s CH4methane 2.31 s CH3toluene 4.58 ddd CH2diallyl carbonate

0.85 s CH3ethane 2.39 q, 7 C H2CH3ethyl methyl ketone 4.89 dm, 10 CH2(1) propylene

0.85–0.91 m CH3H grease8 2.45 s CH3dimethyl sulfoxide 4.99 dm, 17 CH2(2) propylene

0.86–0.90 m CH3pump oil 2.46 s OH water 5.15 ddt CHC H2(2) allyl acetate

0.89 t, 7 CH3n-hexane 2.46 q, 7 CH2triethylamine 5.19 ddt CHC H2(2) diallyl carbonate

0.89 t, 7 CH3n-pentane 2.58 d, 9.5 CH3HMPA 5.27 ddt CHC H2(1) allyl acetate

0.90 t, 7.3 CH3propane 2.75 m CH2(2,5) pyrrolidine 5.31 ddt CHC H2(1) diallyl carbonate

0.96 t, 7 CH2C H3ethyl methyl ketone 2.76 s CH3dimethylformamide 5.36 s CH2ethylene

0.97 t, 7 CH3triethylamine 2.82 s NCH3dimethylacetamide 5.51 s CH2dichloromethane

1.08 d, 6 CH32-propanol

2.88 s CH3dimethylformamide 5.64 s OH BHA

1.10 t, 7 CH3ethanol

2.95 s NCH3dimethylacetamide 5.79 m CH propylene

1.12 t, 7 CH3diethyl ether 3.02 s9OH methanol 5.81 s OH BHT

1.15 s CH3tert-butyl alcohol 3.16 s OH tert-butyl alcohol 5.90 ddt C H CH2allyl acetate

1.19 t, 7 CH2C H3ethyl acetate 3.27 s9CH3methanol 5.92 ddt C H CH2diallyl carbonate

1.29 br s CH2H grease8 3.28 s OCH3diglyme 6.02 m CH(3,4) pyrrole

1.29 m CH2n-hexane 3.28 s CH31,2-dimethoxyethane 6.37 dd CH(3,4) furan

1.29 br s CH2pump oil 3.30 s6OH ethanol 6.66 m CH(2,5) pyrrole

1.31 m CH2n-pentane 3.35 s CH2dimethyl malonate 6.68 s ArH BHA

1.33 sept, 7.3 CH2propane 3.38 q, 7 CH2diethyl ether 6.92 s ArH BHT

1.40 s ArC(CH3)3BHA 3.43 m CH2diglyme 6.94 s CH(4,5) imidazole

1.40 s ArC(CH3)3BHT 3.43 s CH21,2-dimethoxyethane 7.10 m CH(2,4,6) toluene

1.44 s CH2cyclohexane 3.48 s CH2ethylene glycol 7.19 m CH(3,5) toluene

1.59 m CH2(3,4) pyrrolidine 3.51 q, 76CH2ethanol 7.25 m CH(3,5) pyridine

1.68–1.71 m CH2(4) cyclohexanone 3.53 m CH2diglyme 7.31 s CH benzene

1.69 dt, 6.4, 1.5 CH3propylene 3.56 s CH21,4-dioxane 7.48 dd CH(2,5) furan

1.72 m CHD(3,4) THF-d8 residual 3.57 s CH218-crown-6 7.48 s CH(2) imidazole

1.77–1.82 m CH2(3,5) cyclohexanone 3.58 m CHD(2,5) THF-d8 residual 7.51–7.55 m CH(3,5) benzaldehyde

1.79 m CH2(3,4) tetrahydrofuran 3.62 m CH2(2,5) tetrahydrofuran 7.60–7.64 m CH(4) benzaldehyde

1.89 s CH3acetic acid 3.65 s CH3dimethyl malonate 7.65 m CH(4) pyridine

1.94 s CH3CO dimethylacetamide 3.68 s ArOCH3BHA 7.86–7.88 m CH(2,6) benzaldehyde

1.94 s CH3CO ethyl acetate 3.69 s CH3dimethyl carbonate 7.89 s CH chloroform

1.95 s CH3acetonitrile 3.77 s CH21,2-dichloroethane 7.91 s CH dimethylformamide

1.98 s CH3allyl acetate 3.82 sept, 6 CH 2-propanol 8.54 m CH(2,6) pyridine

2.03 s CH3CO ethyl methyl ketone 4.04 q, 7 C H2CH3ethyl acetate 9.96 br t NH pyrrole

2.05 s CH3acetone 4.31 s CH3nitromethane 9.98 s HCO benzaldehyde

2.18 s CH3hexamethylbenzene

Table S4. THF-d8 (13C{1H} NMR data by chemical shift in ppm)

shift carbon impurity shift carbon impurity shift carbon impurity shift carbon impurity

–4.90 CH4methane 30.17 CH3acetone 64.35 CH2ethylene glycol 129.47 CH(2,6) toluene

0.45 CH3acetonitrile 30.45 CH2H grease865.31 CH2allyl acetate 129.56 CH(3,5) benzaldehyde

1.20 CH3silicone grease 30.57 (C H3)3C tert-butyl alcohol66.14 CH2diethyl ether 129.98 CH(2,6) benzaldehyde 1.83 CH3hexamethyldisiloxane 30.63 CH2pump oil 66.14 CH 2-propanol 131.88 C hexamethylbenzene

6.79 CH3ethane 30.65 (C H3)3C BHA 6

7.21 (p) CD2(2,5) THF-d8 signal 133.08 C HCH2diallyl carbonate

7.87 CH2C H3ethyl methyl ketone 30.70 CH3dimethylformamide 67.50 (CH3)3C tert-butyl alcohol133.90 C HCH2allyl acetate 12.51 CH3triethylamine 31.55 (C H3)3C BHT 67.65 CH21,4-dioxane 134.02 CH propylene 14.18 CH3n-pentane32.34 CH2(3,4) n-hexane68.03 CH2(2,5) tetrahydrofuran 134.67 CH (4) benzaldehyde 14.22 CH3n-hexane34.60 NCH3dimethylacetamide 68.58 CH2diallyl carbonate 135.72 CH(2) imidazole

14.37 CH3ethyl acetate 34.87 CH2(3) n-pentane71.17 CH2diglyme 135.99 CH(4) pyridine

15.49 CH3diethyl ether 34.91 (CH3)3C BHT 71.34 CH218-crown-6 137.78 C(1) benzaldehyde

16.60 CH3propane 35.51 (CH3)3C BHA 72.58 CH21,2-dimethoxyethane 137.93 C(2,6) BHT

16.71 CH3hexamethylbenzene 35.65 CH3dimethylformamide 72.72 CH2diglyme 138.24 C(1) toluene 16.82 CH2propane 36.59 C H2CH3ethyl methyl ketone 79.24 CH chloroform 140.07 C(4) BHA

18.90 CH3ethanol 36.89 (d) CH3HMPA1196.89 CCl4carbon tetrachloride 143.26 CH(2,5) furan

19.27 CH3propylene 37.56 NCH3dimethylacetamide 107.74 CH(3,4) pyrrole 148.62 C(2,6) BHA

20.13 CH3acetic acid 41.15 CH2dimethyl malonate 109.88 CH(3,4) furan 150.57 CH(2,6) pyridine 20.45 CH3allyl acetate 41.21 CH3dimethyl sulfoxide 110.94 CH(3,5) BHA 152.48 C(1) BHT

20.45 C H3CO ethyl acetate 42.17 CH2(2,6) cyclohexanone 115.74 CH2propylene 154.07 C(1) BHA

21.15 CH3dimethylacetamide 44.64 CH21,2-dichloroethane 116.79 CN acetonitrile 155.36 CO diallyl carbonate 21.21 CH3Ar BHT 45.82 CH2(2,5) pyrrolidine 117.58 CH C H2allyl acetate 156.91 CO dimethyl carbonate 21.29 CH3toluene 47.18 CH2triethylamine 117.70 CH C H2diallyl carbonate 161.96 CH dimethylformamide 23.00 CH2(2,4) n-pentane49.64 CH3methanol 118.03 CH(2,5) pyrrole 167.14 CO2dimethyl malonate 23.33 CH2(2,5) n-hexane52.07 CH3dimethyl malonate 122.20 CH(4,5) imidazole 169.77 CO dimethylacetamide 25.31 (p) CD2(3,4) THF-d8 signal 54.58 CH3dimethyl carbonate 123.09 CH2ethylene 170.14 CO allyl acetate 25.70 CH32-propanol 54.67 CH2dichloromethane 124.08 CH(3,5) pyridine 170.32 CO ethyl acetate

25.76 CH2(4) cyclohexanone 55.39 CH3O BHA 125.69 CO2carbon dioxide 171.69 CO acetic acid

26.17 CH2(3,4) pyrrolidine 57.60 CH2ethanol 125.71 CH(3,5) BHT 191.95 HCO benzaldehyde

26.19 CH2(3,4) tetrahydrofuran 58.72 CH3diglyme 125.84 CH(4) toluene 193.37 CS2carbon disulfide

27.58 CH2cyclohexane 58.72 CH31,2-dimethoxyethane 128.64 C(4) BHT 204.19 CO acetone

27.69 CH2(3,5) cyclohexanone 60.30 CH2ethyl acetate 128.71 CH(3,5) toluene 207.05 CO ethyl methyl ketone

28.92 C H3CO ethyl methyl ketone 62.49 CH3nitromethane 128.84 CH benzene 208.79 CO cyclohexanone

shift mult proton impurity shift mult proton impurity shift mult proton impurity

0.07 s CH3hexamethyldisiloxane 2.09 s CH3CO ethyl methyl ketone 4.61 ddd CH2diallyl carbonate

0.09 s CH3silicone grease 2.12 s CH3acetone 4.76 s OH BHA

0.21 s CH4methane 2.20 s CH3hexamethylbenzene 4.93 dm, 10 CH2(1) propylene

0.84–0.89 m CH3pump oil 2.25 s ArCH3BHT 5.00 s OH BHT

0.84–0.90 m CH3H grease8 2.29 t CH2(2,6) cyclohexanone 5.03 dm, 17 CH2(2) propylene

0.85 s CH3ethane 2.34 s CH3toluene 5.22 ddt CHC H2(2) allyl acetate

0.89 t, 7 CH3n-hexane 2.43 q, 7 C H2CH3ethyl methyl ketone 5.26 ddt CHC H2(2) diallyl carbonate

0.89 t, 7 CH3n-pentane 2.48 q, 7 CH2triethylamine 5.31 ddt CHC H2(1) allyl acetate

0.90 t, 7.3 CH3propane 2.55 s CH3dimethyl sulfoxide 5.32 t CDHCl2CD2Cl2 residual

0.99 t, 7 CH3triethylamine 2.60 d, 9.5 CH3HMPA 5.33 s CH2dichloromethane

1.00 t, 7 CH2C H3ethyl methyl ketone

2.82 s CH3dimethylformamide 5.35 ddt CHC H2(1) diallyl carbonate

1.09 s9OH methanol

2.82 m CH2(2,5) pyrrolidine 5.40 s CH2ethylene

1.15 t, 7 CH3diethyl ether

2.87 s NCH3dimethylacetamide 5.84 m CH propylene

1.17 d, 6 CH32-propanol

2.91 s CH3dimethylformamide 5.92 ddt C H CH2allyl acetate

1.19 t, 7 CH3ethanol

2.97 s NCH3dimethylacetamide 5.95 ddt C H CH2diallyl carbonate

1.23 t, 7 CH2C H3ethyl acetate 3.33 s OCH3diglyme 6.19 m CH(3,4) pyrrole

1.24 s CH3tert-butyl alcohol 3.34 s CH31,2-dimethoxyethane 6.41 dd CH(3,4) furan

1.27 br s CH2H grease8 3.37 s CH2dimethyl malonate 6.73 s ArH BHA

1.27 m CH2n-hexane 3.42 s9CH3methanol 6.79 m CH(2,5) pyrrole

1.27 br s CH2pump oil 3.43 q, 7 CH2diethyl ether 6.97 s ArH BHT

1.30 m CH2n-pentane 3.49 s CH21,2-dimethoxyethane 7.07 s CH(4,5) imidazole

1.32 sept, 7.3 CH2propane 3.50 m CH2diglyme 7.15 m CH(2,4,6) toluene

1.33 s6OH ethanol 3.57 m CH2diglyme 7.24 m CH(3,5) toluene

1.42 s ArC(CH3)3BHA 3.59 s CH218-crown-6 7.28 m CH(3,5) pyridine

1.42 s ArC(CH3)3BHT 3.65 s CH21,4-dioxane 7.32 s CH chloroform

1.44 s CH2cyclohexane 3.66 q, 76CH2ethanol 7.35 s CH benzene

1.52 s OH water 3.66 s CH2ethylene glycol 7.46 dd CH(2,5) furan

1.69–1.72 m CH2(4) cyclohexanone 3.69 m CH2(2,5) tetrahydrofuran 7.53–7.57 m CH(3,5) benzaldehyde

1.67 m CH2(3,4) pyrrolidine 3.72 s CH3dimethyl malonate 7.63 s CH(2) imidazole

1.71 dt, 6.4, 1.5 CH3propylene 3.73 s ArOCH3BHA 7.63–7.67 m CH(4) benzaldehyde

1.81–1.87 m CH2(3,5) cyclohexanone 3.75 s CH3dimethyl carbonate 7.68 m CH(4) pyridine

1.82 m CH2(3,4) tetrahydrofuran 3.76 s CH21,2-dichloroethane 7.87–7.89 m CH(2,6) benzaldehyde

1.97 s CH3acetonitrile 3.97 sept, 6 CH 2-propanol 7.96 s CH dimethylformamide

2.00 s CH3CO ethyl acetate 4.08 q, 7 C H2CH3ethyl acetate 8.59 m CH(2,6) pyridine

2.02 s CH3CO dimethylacetamide 4.31 s CH3nitromethane 8.69 br t NH pyrrole

2.05 s CH3allyl acetate 4.55 ddd CH2allyl acetate 10.01 s HCO benzaldehyde

2.06 s CH3acetic acid 4.59 s H2hydrogen

Table S6. CD2Cl2 (13C{1H} NMR data by chemical shift in ppm)

shift carbon impurity shift carbon impurity shift carbon impurity shift carbon impurity

–4.33 CH4methane 30.14 CH2H grease864.08 CH2ethylene glycol 129.42 CH(3,5) benzaldehyde 1.22 CH3silicone grease 30.37 (C H3)3C BHA 64.67 CH 2-propanol 129.98 CH(2,6) benzaldehyde

1.96 CH3hexamethyldisiloxane 30.54 (C H3)3C BHT 65.36 CH2allyl acetate 13

2.09 C hexamethylbenzene

2.03 CH3acetonitrile 31.00 CH3acetone 66.11 CH2diethyl ether 132.24 CHCH2diallyl carbonate

6.91 CH3ethane 31.39 CH3dimethylformamide 6

7.47 CH21,4-dioxane 132.94 CHCH2allyl acetate

7.94 CH2C H3ethyl methyl ketone 31.46 (C H3)3C tert-butyl alcohol 68.16 CH2(2,5) tetrahydrofuran 134.21 CH propylene 12.12 CH3triethylamine 32.01 CH2(3,4) n-hexane 68.76 CH2diallyl carbonate 134.79 CH (4) benzaldehyde 14.24 CH3n-pentane 34.56 (CH3)3C BHT 69.11 (CH3)3C tert-butyl alcohol 135.76 CH(2) imidazole 14.28 CH3n-hexane 34.57 CH2(3) n-pentane 70.47 CH218-crown-6 136.16 CH(4) pyridine

14.37 CH3ethyl acetate 34.91 (CH3)3C BHA 70.70 CH2diglyme 136.32 C(2,6) BHT

15.44 CH3diethyl ether 35.23 NCH3dimethylacetamide 72.24 CH21,2-dimethoxyethane 136.98 C(1) benzaldehyde

16.63 CH3propane 36.56 CH3dimethylformamide 72.25 CH2diglyme 137.77 C(4) BHA

16.63 CH2propane 36.99 (d) CH3HMPA i77.99 CH chloroform 138.36 C(1) toluene 16.93 CH3hexamethylbenzene 37.01 CH2CH3ethyl methyl ketone 96.52 CCl4carbon tetrachloride 142.98 CH(2,5) furan

18.69 CH3ethanol 38.22 NCH3dimethylacetamide 108.02 CH(3,4) pyrrole 148.06 C(2,6) BHA

19.47 CH3propylene 41.33 CH3dimethyl sulfoxide 109.86 CH(3,4) furan 150.27 CH(2,6) pyridine

20.91 CH3acetic acid 41.48 CH2dimethyl malonate 110.93 CH(3,5) BHA 151.92 C(1) BHT

21.06 CH3allyl acetate 42.31 CH2(2,6) cyclohexanone 115.7 CH2propylene 153.05 C(1) BHA

21.15 CH3CO ethyl acetate 44.35 CH21,2-dichloroethane 116.92 CN acetonitrile 155.15 CO diallyl carbonate 21.27 CH3Ar BHT 46.75 CH2triethylamine 117.93 CH(2,5) pyrrole 156.73 CO dimethyl carbonate 21.53 CH3toluene 47.02 CH2(2,5) pyrrolidine 118.00 CH C H2allyl acetate 162.57 CH dimethylformamide

21.64 CH3dimethylacetamide 50.45 CH3methanol 118.75 CH C H2diallyl carbonate 167.32 CO2dimethyl malonate

22.77 CH2(2,4) n-pentane 52.75 CH3dimethyl malonate 122.16 CH(4,5) imidazole 170.83 CO allyl acetate

23.07 CH2(2,5) n-hexane 53.84 (p) CD2Cl2CD2Cl2 signal 123.20 CH2ethylene 171.05 CO dimethylacetamide 25.42 CH2(4) cyclohexanone 54.24 CH2dichloromethane 124.06 CH(3,5) pyridine 171.24 CO ethyl acetate 25.43 CH32-propanol 55.09 CH3dimethyl carbonate 125.26 CO2carbon dioxide 175.85 CO acetic acid 25.83 CH2(3,4) pyrrolidine 55.88 CH3O BHA 125.62 CH(4) toluene 192.61 HCO benzaldehyde 25.98 CH2(3,4) tetrahydrofuran 58.57 CH2ethanol 125.84 CH(3,5) BHT 192.95 CS2carbon disulfide 27.38 CH2cyclohexane 58.95 CH3diglyme 128.54 CH(3,5) toluene 206.78 CO acetone 27.47 CH2(3,5) cyclohexanone 59.02 CH31,2-dimethoxyethane 128.68 CH benzene 209.57 CO ethyl methyl ketone

29.55 CH3CO ethyl methyl ketone 60.63 CH2ethyl acetate 128.73 C(4) BHT 211.82 CO cyclohexanone

30.13 CH2pump oil 63.03 CH3nitromethane 129.35 CH(2,6) toluene

shift mult proton impurity shift mult proton impurity shift mult proton impurity

0.07 s CH3hexamethyldisiloxane 2.14 s CH3CO ethyl methyl ketone 4.64 ddd CH2diallyl carbonate

0.07 s CH3silicone grease 2.17 s CH3acetone 4.76 s OH d BHA

0.22 s CH4methane 2.24 s CH3hexamethylbenzene 4.94 dm, 10 CH2(1) propylene

0.83–0.89 m CH3pump oil 2.27 s ArCH3BHT 5.01 s OH d BHT

0.84–0.87 m CH3H grease8 2.33 t CH2(2,6) cyclohexanone 5.03 dm, 17 CH2(2) propylene

0.87 s CH3ethane 2.36 s CH3toluene 5.24 ddt CHC H2(2) allyl acetate

0.88 t, 7 CH3n-hexane 2.46 q, 7 C H2CH3ethyl methyl ketone 5.27 ddt CHC H2(2) diallyl carbonate

0.88 t, 7 CH3n-pentane 2.53 q, 7 CH2triethylamine 5.30 s CH2dichloromethane

0.90 t, 7.3 CH3propane 2.62 s CH3dimethyl sulfoxide 5.32 ddt CHC H2(1) allyl acetate

1.03 t, 7 CH3triethylamine

2.65 d, 9.5 CH3HMPA 5.37 ddt CHC H2(1) diallyl carbonate

1.06 t, 7 CH2C H3ethyl methyl ketone

2.87 m CH2(2,5) pyrrolidine 5.40 s CH2ethylene

1.09 s9OH methanol

2.88 s CH3dimethylformamide 5.83 m CH propylene

1.21 t, 7 CH3diethyl ether

2.94 s NCH3dimethylacetamide 5.93 ddt C H CH2allyl acetate

1.22 d, 6 CH32-propanol

2.96 s CH3dimethylformamide 5.94 ddt C H CH2diallyl carbonate

1.25 t, 7 CH3ethanol 3.02 s NCH3dimethylacetamide 6.26 m CH(3,4) pyrrole

1.25 br s CH2H grease8 3.39 s OCH3diglyme 6.40 dd CH(3,4) furan

1.26 t, 7 CH2C H3ethyl acetate 3.40 s CH31,2-dimethoxyethane 6.76 s ArH BHA

1.26 m CH2n-hexane 3.40 s CH2dimethyl malonate 6.83 m CH(2,5) pyrrole

1.26 br s CH2pump oil 3.48 q, 7 CH2diethyl ether 6.98 s ArH BHT

1.27 m CH2n-pentane 3.49 s9CH3methanol 7.10 s CH(4,5) imidazole

1.28 s CH3tert-butyl alcohol 3.55 s CH21,2-dimethoxyethane 7.17 m CH(2,4,6) toluene

1.32 s6OH ethanol 3.57 m CH2diglyme 7.25 m CH(3,5) toluene

1.32 sept, 7.3 CH2propane 3.65 m CH2diglyme 7.26 s CH CDCl3 residual

1.43 s ArC(CH3)3BHT 3.67 s CH218-crown-6 7.26 s CH chloroform

1.43 s CH2cyclohexane 3.71 s CH21,4-dioxane 7.29 m CH(3,5) pyridine

1.44 s ArC(CH3)3BHA 3.72 q, 79CH2ethanol 7.36 s CH benzene

1.56 s OH water 3.73 s CH21,2-dichloroethane 7.45 dd CH(2,5) furan

1.68 m CH2(3,4) pyrrolidine 3.75 s CH3dimethyl malonate 7.51–7.57 m CH(3,5) benzaldehyde

1.71–1.73 m CH2(4) cyclohexanone 3.76 s CH2ethylene glycol 7.61–7.65 m CH(4) benzaldehyde

1.73 dt, 6.4, 1.5 CH3propylene 3.76 m CH2(2,5) tetrahydrofuran 7.67 s CH(2) imidazole

1.84–1.86 m CH2(3,5) cyclohexanone 3.77 s ArOCH3BHA 7.68 m CH(4) pyridine

1.85 m CH2(3,4) tetrahydrofuran 3.79 s CH3dimethyl carbonate 7.88–7.91 m CH(2,6) benzaldehyde

2.05 s CH3CO ethyl acetate 4.04 sept, 6 CH 2-propanol 8.02 s CH dimethylformamide

2.09 s CH3allyl acetate 4.12 q, 7 C H2CH3ethyl acetate 8.40 br t NH pyrrole

2.09 s CH3CO dimethylacetamide 4.33 s CH3nitromethane 8.62 m CH(2,6) pyridine

2.10 s CH3acetic acid 4.57 ddd CH2allyl acetate 10.03 s HCO benzaldehyde

2.10 s CH3acetonitrile 4.62 s H2hydrogen

Table S8. CDCl3 (13C{1H} NMR data by chemical shift in ppm)

shift carbon impurity shift carbon impurity shift carbon impurity shift carbon impurity

–4.63 CH4methane 29.84 CH2pump oil 64.50 CH 2-propanol 129.16 CH(3,5) benzaldehyde 1.19 CH3silicone grease 30.32 (C H3)3C BHA 65.28 CH2allyl acetate 129.91 CH(2,6) benzaldehyde 1.89 CH3acetonitrile 30.33 (C H3)3C BHT 65.91 CH2diethyl ether 131.58 C HCH2diallyl carbonate 1.97 CH3hexamethyldisiloxane 30.92 CH3acetone 67.14 CH21,4-dioxane 132.21 C hexamethylbenzene

6.89 CH3ethane 31.25 (C H3)3C tert-butyl alcohol6

7.97 CH2(2,5) tetrahydrofuran 132.33 C HCH2allyl acetate

7.86 CH2C H3ethyl methyl ketone 31.45 CH3dimethyl malonate 68.55 CH2diallyl carbonate 133.91 CH propylene 11.61 CH3triethylamine 31.64 CH2(3,4) n-hexane69.15 (CH3)3C tert-butyl alcohol134.64 CH (4) benzaldehyde 14.08 CH3n-pentane34.16 CH2(3) n-pentane70.51 CH2diglyme 135.38 CH(2) imidazole 14.14 CH3n-hexane34.25 (CH3)3C BHT 70.55 CH218-crown-6 135.87 C(2,6) BHT

14.19 CH3ethyl acetate 34.72 (CH3)3C BHA 71.84 CH21,2-dimethoxyethane 135.96 CH(4) pyridine

15.20 CH3diethyl ether 35.28 NCH3dimethylacetamide 71.90 CH2diglyme 136.58 C(1) benzaldehyde

16.37 CH2propane 36.50 CH3dimethyl malonate 77.16 (t) CDCl3CDCl3 signal 137.36 C(4) BHA

16.63 CH3propane 36.87 (d) CH3HMPA i77.36 CH chloroform 137.89 C(1) toluene 16.98 CH3hexamethylbenzene 36.89 C H2CH3ethyl methyl ketone 96.34 CCl4carbon tetrachloride 142.71 CH(2,5) furan

18.41 CH3ethanol 38.13 NCH3dimethylacetamide 107.98 CH(3,4) pyrrole 147.85 C(2,6) BHA

19.50 CH3propylene 40.76 CH3dimethyl sulfoxide 109.57 CH(3,4) furan 149.90 CH(2,6) pyridine

20.81 CH3acetic acid 41.11 CH2dimethyl malonate 110.69 CH(3,5) BHA 151.55 C(1) BHT

21.02 CH3allyl acetate 41.97 CH2(2,6) cyclohexanone 115.74 CH2propylene 152.57 C(1) BHA

21.04 C H3CO ethyl acetate 43.50 CH21,2-dichloroethane 116.43 CN acetonitrile 154.88 CO diallyl carbonate 21.20 CH3Ar BHT 46.25 CH2triethylamine 117.77 CH(2,5) pyrrole 156.45 CO dimethyl carbonate 21.46 CH3toluene 46.93 CH2(2,5) pyrrolidine 118.34 CH C H2allyl acetate 162.62 CH dimethylformamide

21.53 CH3dimethylacetamide 50.41 CH3methanol 118.96 CH C H2diallyl carbonate 167.18 CO2dimethyl malonate

22.38 CH2(2,4) n-pentane52.57 CH3dimethyl malonate 122.00 CH(4,5) imidazole 170.81 CO allyl acetate 22.70 CH2(2,5) n-hexane53.52 CH2dichloromethane 123.13 CH2ethylene 171.07 CO dimethylacetamide

24.97 CH2(4) cyclohexanone 54.89 CH3dimethyl carbonate 123.75 CH(3,5) pyridine 171.36 CO ethyl acetate

25.14 CH32-propanol 55.70 CH3O BHA 124.99 CO2carbon dioxide 175.99 CO acetic acid 25.56 CH2(3,4) pyrrolidine 58.28 CH2ethanol 125.33 CH(4) toluene 192.67 HCO benzaldehyde

25.62 CH2(3,4) tetrahydrofuran 59.01 CH3diglyme 125.55 CH(3,5) BHT 192.83 CS2carbon disulfide

26.94 CH2cyclohexane 59.08 CH31,2-dimethoxyethane 128.26 CH(3,5) toluene 207.07 CO acetone

27.00 CH2(3,5) cyclohexanone 60.49 CH2ethyl acetate 128.27 C(4) BHT 209.56 CO ethyl methyl ketone 29.49 C H3CO ethyl methyl ketone 62.50 CH3nitromethane 128.37 CH benzene 212.57 CO cyclohexanone 29.71 CH2H grease863.79 CH2ethylene glycol 129.07 CH(2,6) toluene

Table S9. Toluene-d8 (1H NMR data by chemical shift in ppm) shift mult proton impurity shift mult proton impurity shift mult proton impurity

0.10 s CH3hexamethyldisiloxane 1.64 s CH3dimethyl sulfoxide 4.45 s OH5BHA

0.17 s CH4methane 1.69 s CH3CO ethyl acetate 4.50 s H2hydrogen

0.26 s CH3silicone grease 1.82 q, 7 C H2CH3ethyl methyl ketone 4.72 s OH5BHT

0.43 s OH water 1.95 t CH2(2,6) cyclohexanone 4.92 ddt CHC H2(2) diallyl carbonate

0.58 s OH tert-butyl alcohol 1.96 s CH3dimethylformamide 4.92 dm, 10 CH2(1) propylene

0.69 s CH3acetonitrile 2.08 p CH3Toluene-d8 residual 4.94 ddt CHC H2(2) allyl acetate

0.81 s CH3ethane 2.10 s CH3hexamethylbenzene 4.98 dm, 17 CH2(2) propylene

0.83 s6OH ethanol 2.11 s NCH3dimethylacetamide 5.05 ddt CHC H2(1) allyl acetate

0.84 t, 7 CH2C H3ethyl methyl ketone 2.11 s CH3toluene 5.09 ddt CHC H2(1) diallyl carbonate

0.87 t, 7 CH3n-pentane 2.23 s ArCH3BHT 5.25 s CH2ethylene

0.88 t, 7 CH3n-hexane 2.37 s CH3dimethylformamide 5.63 ddt C H CH2diallyl carbonate

0.88–0.96 m CH3pump oil 2.39 q, 7 CH2triethylamine 5.674t(nfo ABX) C H CH2allyl acetate

0.89 t, 7.3 CH3propane 2.42 d, 9.5 CH3HMPA 5.70 m CH propylene

0.89–0.96 m CH3H grease8 2.54 m CH2(2,5) pyrrolidine 6.07 dd CH(3,4) furan

0.94 t, 7 CH2C H3ethyl acetate 2.56 s NCH3dimethylacetamide 6.10 s CH chloroform

0.95 d, 6 CH32-propanol 2.91 s CH21,2-dichloroethane 6.27 m CH(3,4) pyrrole

0.95 t, 7 CH3triethylamine 2.92 s CH2dimethyl malonate 6.43 m CH(2,5) pyrrole

0.97 t, 7 CH3ethanol 3.01 s CH3nitromethane 6.67 m CH(3,5) pyridine

1.03 s CH3tert-butyl alcohol 3.03 s9CH3methanol 6.83 s ArH BHA

1.10 t, 7 CH3diethyl ether 3.12 s OCH3diglyme 6.86 s CH(4,5) imidazole

1.16–1.20 m CH2(4) cyclohexanone 3.12 s CH31,2-dimethoxyethane 6.95–6.99 m CH(3,5) benzaldehyde

1.22 m CH2n-hexane 3.24 s CH3dimethyl malonate 6.96–7.01 m CH(2,4,6) toluene

1.25 m CH2n-pentane 3.25 q, 7 CH2diethyl ether 6.97 p CH(4) Toluene-d8 residual

1.30 br s CH2pump oil 3.31 m CH2diglyme 6.99 s ArH BHT

1.32 sept, 7.3 CH2propane 3.31 s CH21,2-dimethoxyethane 6.99 m CH(4) pyridine

1.33 br s CH2H grease8 3.31 s CH3dimethyl carbonate 7.01 s CH(2,6) Toluene-d8 residual

1.33–1.39 m CH2(3,5) cyclohexanone 3.33 s CH21,4-dioxane 7.03–7.07 m CH(4) benzaldehyde

1.34 s ArC(CH3)3BHA 3.36 s CH218-crown-6 7.09 m CH(3,5) Toluene-d8 residual

1.36 s ArC(CH3)3BHT 3.36 q, 76CH2ethanol 7.09 m CH(3,5) toluene

1.36 m CH2(3,4) pyrrolidine 3.36 s CH2ethylene glycol 7.10 dd CH(2,5) furan

1.40 s CH2cyclohexane 3.43 m CH2diglyme 7.12 s CH benzene

1.43 m CH2(3,4) tetrahydrofuran 3.48 s ArOCH3BHA 7.30 s CH(2) imidazole

1.55 dt, 6.4, 1.5 CH3propylene 3.54 m CH2(2,5) tetrahydrofuran 7.45–7.47 m CH(2,6) benzaldehyde

1.57 s CH3acetic acid 3.65 sept, 6 CH 2-propanol 7.57 s CH dimethylformamide

1.57 s CH3acetone 3.87 q, 7 C H2CH3ethyl acetate 7.71 br t NH pyrrole

1.59 s CH3CO dimethylacetamide 4.32 s CH2dichloromethane 8.47 m CH(2,6) pyridine

1.59 s CH3CO ethyl methyl ketone 4.34 ddd CH2allyl acetate 9.57 s HCO benzaldehyde

1.63 s CH3allyl acetate 4.34 ddd CH2diallyl carbonate

Table S10. Toluene-d8 (13C{1H} NMR data by chemical shift in ppm)

shift carbon impurity shift carbon impurity shift carbon impurity shift carbon impurity –4.34 CH4methane 30.30 (C H3)3C BHA 64.87 CH2allyl acetate 129.33 CH(2,6) toluene

0.03 CH3acetonitrile 30.31 CH2H grease865.94 CH2diethyl ether 129.61 CH(2,6) benzaldehyde

1.37 CH3silicone grease 30.33 CH2pump oil 67.17 CH21,4-dioxane 131.72 C hexamethylbenzene

1.99 CH3hexamethyldisiloxane 30.49 (C H3)3C tert-butyl alcohol67.75 CH2(2,5) tetrahydrofuran 13

2.30 C HCH2diallyl carbonate

6.94 CH3ethane 30.64 CH3dimethylformamide 68.12 (CH3)3C tert-butyl alcohol132.98 C HCH2allyl acetate

7.89 CH2C H3ethyl methyl ketone 31.39 (C H3)3C BHT 68.20 CH2diallyl carbonate 133.61 CH propylene

12.39 CH3triethylamine 32.06 CH2(3,4) n-hexane70.86 CH218-crown-6 133.88 CH (4) benzaldehyde

14.23 CH3ethyl acetate 34.39 (CH3)3C BHT 70.92 CH2diglyme 135.17 CH(4) pyridine

14.27 CH3n-pentane34.54 CH2(3) n-pentane72.25 CH21,2-dimethoxyethane 135.57 CH(2) imidazole

14.34 CH3n-hexane34.58 NCH3dimethylacetamide 72.39 CH2diglyme 136.12 C(2,6) BHT

15.47 CH3diethyl ether 34.69 (CH3)3C BHA 77.89 CH chloroform 137.12 C(1) benzaldehyde

16.63 CH2propane 35.22 CH3dimethylformamide 96.57 CCl4carbon tetrachloride 137.34 C(4) BHA

16.65 CH3propane 36.32 C H2CH3ethyl methyl ketone 108.15 CH(3,4) pyrrole 137.48 C toluene-d8 signal

16.84 CH3hexamethylbenzene 36.8 (d) CH3HMPA11109.63 CH(3,4) furan 137.84 C(1) toluene

18.78 CH3ethanol 36.98 NCH3dimethylacetamide 110.99 CH(3,5) BHA 142.65 CH(2,5) furan

19.32 CH3propylene 40.41 CH3dimethyl sulfoxide 115.76 CN acetonitrile 148.06 C(2,6) BHA

20.21 CH3allyl acetate 40.88 CH2dimethyl malonate 115.89 CH2propylene 150.25 CH(2,6) pyridine

20.27 CH3acetic acid 41.78 CH2(2,6) cyclohexanone 117.49 CH C H2allyl acetate 152.06 C(1) BHT

20.43 (sept) CD3toluene-d8 signal 43.40 CH21,2-dichloroethane 117.61 CH(2,5) pyrrole 153.50 C(1) BHA

20.46 C H3CO ethyl acetate 46.82 CH2triethylamine 118.04 CH C H2diallyl carbonate 155.15 CO diallyl carbonate

21.05 CH3dimethylacetamide 47.12 CH2(2,5) pyrrolidine 122.13 CH(4,5) imidazole 156.61 CO dimethyl carbonate

21.37 CH3toluene 49.90 CH3methanol 122.92 CH2ethylene 161.93 CH dimethylformamide

21.42 CH3Ar BHT 51.76 CH3dimethyl malonate 123.46 CH(3,5) pyridine 166.49 CO2dimethyl malonate

22.79 CH2(2,4) n-pentane53.47 CH2dichloromethane 124.86 CO2carbon dioxide 169.44 CO allyl acetate

23.12 CH2(2,5) n-hexane54.13 CH3dimethyl carbonate 125.13 (t) CD(4) toluene-d8 signal 169.65 CO dimethylacetamide

25.15 CH2(4) cyclohexanone 55.04 CH3O BHA 125.66 CH(4) toluene 170.02 CO ethyl acetate

25.24 CH32-propanol 57.81 CH2ethanol 125.79 CH(3,5) BHT 175.30 CO acetic acid

25.75 CH2(3,4) pyrrolidine 58.62 CH3diglyme 127.96 (t) CD(3,5) toluene-d8 signal 191.09 HCO benzaldehyde

25.79 CH2(3,4) tetrahydrofuran 58.63 CH31,2-dimethoxyethane 128.44 C(4) BHT 192.71 CS2carbon disulfide

27.05 CH2(3,5) cyclohexanone 60.08 CH2ethyl acetate 128.51 CH(3,5) toluene 204.00 CO acetone

27.31 CH2cyclohexane 61.14 CH3nitromethane 128.57 CH benzene 206.31 CO ethyl methyl ketone

28.74 C H3CO ethyl methyl ketone 64.12 CH 2-propanol 128.68 CH(3,5) benzaldehyde 208.60 CO cyclohexanone

30.03 CH3acetone 64.29 CH2ethylene glycol 128.87 (t) CD(2,6) toluene-d8 signal

shift mult proton impurity shift mult proton impurity shift mult proton impurity

0.12 s CH3hexamethyldisiloxane 1.63 s CH3allyl acetate 4.38 ddd CH2diallyl carbonate

0.16 s CH4methane 1.65 s CH3CO ethyl acetate 4.47 s H2hydrogen

0.29 s CH3silicone grease 1.68 s CH3dimethyl sulfoxide 4.53 s OH5BHA

0.40 s OH water 1.81 q, 7 C H2CH3ethyl methyl ketone 4.79 s OH5BHT

0.50 s6OH ethanol 1.86 s CH3dimethylformamide 4.92 ddt CHC H2(2) diallyl carbonate

0.58 s CH3acetonitrile 1.98 t CH2(2,6) cyclohexanone 4.94 ddt CHC H2(2) allyl acetate

0.63 s OH tert-butyl alcohol 2.05 s NCH3dimethylacetamide 4.95 dm, 10 CH2(1) propylene

0.80 s CH3ethane 2.11 s CH3toluene 5.01 dm, 17 CH2(2) propylene

0.85 t, 7 CH2C H3ethyl methyl ketone 2.13 s CH3hexamethylbenzene 5.06 ddt CHC H2(1) allyl acetate

0.86 t, 7.3 CH3propane 2.24 s ArCH3BHT 5.09 ddt CHC H2(1) diallyl carbonate

0.87 t, 7 CH3n-pentane 2.36 s CH3dimethylformamide 5.25 s CH2ethylene

0.89 t, 7 CH3n-hexane 2.40 d, 9.5 CH3HMPA 5.65 ddt C H CH2diallyl carbonate

0.90–0.98 m CH3H grease8 2.40 q, 7 CH2triethylamine 5.684t(nfo ABX) C H CH2allyl acetate

0.91–0.97 m CH3pump oil 2.54 m CH2(2,5) pyrrolidine 5.72 m CH propylene

0.92 t, 7 CH2C H3ethyl acetate 2.57 s NCH3dimethylacetamide 6.08 dd CH(3,4) furan

0.95 d, 6 CH32-propanol 2.90 s CH21,2-dichloroethane 6.15 s CH chloroform

0.96 t, 7 CH3ethanol 2.94 s CH3nitromethane 6.37 m CH(3,4) pyrrole

0.96 t, 7 CH3triethylamine 2.97 s CH2dimethyl malonate 6.48 m CH(2,5) pyrrole

1.05 s CH3tert-butyl alcohol 3.07 s9CH3methanol 6.66 m CH(3,5) pyridine

1.08–1.16 m CH2(4) cyclohexanone 3.11 s OCH3diglyme 6.90 s CH(4,5) imidazole

1.11 t, 7 CH3diethyl ether 3.12 s CH31,2-dimethoxyethane 6.93 s ArH BHA

1.23 m CH2n-pentane 3.23 s CH3dimethyl malonate 6.93–6.99 m CH(3,5) benzaldehyde

1.24 m CH2n-hexane 3.26 q, 7 CH2diethyl ether 6.98 m CH(4) pyridine

1.26 sept, 7.3 CH2propane 3.30 s CH3dimethyl carbonate 7.01–7.07 m CH(4) benzaldehyde

1.28–1.37 m CH2(3,5) cyclohexanone 3.33 s CH21,2-dimethoxyethane 7.02 m CH(2,4,6) toluene

1.32 br s CH2H grease8 3.34 m CH2diglyme 7.05 s ArH BHT

1.33 m CH2(3,4) pyrrolidine 3.34 q, 76CH2ethanol 7.13 dd CH(2,5) furan

1.37 br s CH2pump oil 3.35 s CH21,4-dioxane 7.13 m CH(3,5) toluene

1.38 s ArC(CH3)3BHT 3.39 s CH218-crown-6 7.15 s CH benzene

1.40 s CH2cyclohexane 3.41 s CH2ethylene glycol 7.16 s CH C6D6 residual

1.40 m CH2(3,4) tetrahydrofuran 3.46 m CH2diglyme 7.33 s CH(2) imidazole

1.41 s ArC(CH3)3BHA 3.48 s ArOCH3BHA 7.49–7.53 m CH(2,6) benzaldehyde

1.52 s CH3acetic acid 3.57 m CH2(2,5) tetrahydrofuran 7.63 s CH dimethylformamide

1.55 s CH3acetone 3.67 sept, 6 CH 2-propanol 7.80 br t NH pyrrole

1.55 dt, 6.4, 1.5 CH3propylene 3.89 q, 7 C H2CH3ethyl acetate 8.53 m CH(2,6) pyridine

1.58 s CH3CO ethyl methyl ketone 4.27 s CH2dichloromethane 9.64 s HCO benzaldehyde

1.60 s CH3CO dimethylacetamide 4.38 ddd CH2allyl acetate

Table S12. C6D6 (13C{1H} NMR data by chemical shift in ppm)

shift carbon impurity shift carbon impurity shift carbon impurity shift carbon impurity

–4.29 CH4methane 30.22 CH2H grease864.34 CH2ethylene glycol 129.33 CH(2,6) toluene

0.20 CH3acetonitrile 30.24 CH2pump oil 64.92 CH2allyl acetate 129.65 CH(2,6) benzaldehyde

1.38 CH3silicone grease 30.35 (C H3)3C BHA 65.94 CH2diethyl ether 131.79 C hexamethylbenzene

2.05 CH3hexamethyldisiloxane 30.47 (C H3)3C tert-butyl alcohol67.16 CH21,4-dioxane 132.18 C HCH2diallyl carbonate

6.96 CH3ethane 30.72 CH3dimethylformamide 6

7.80 CH2(2,5) tetrahydrofuran 132.90 C HCH2allyl acetate

7.91 CH2C H3ethyl methyl ketone 31.34 (C H3)3C BHT 68.19 (CH3)3C tert-butyl alcohol133.69 CH propylene 12.35 CH3triethylamine 31.96 CH2(3,4) n-hexane68.28 CH2diallyl carbonate 133.95 CH (4) benzaldehyde 14.19 CH3ethyl acetate 34.35 (CH3)3C BHT 70.59 CH218-crown-6 135.28 CH(4) pyridine 14.25 CH3n-pentane34.45 CH2(3) n-pentane70.87 CH2diglyme 135.76 CH(2) imidazole

14.32 CH3n-hexane34.67 NCH3dimethylacetamide 72.21 CH21,2-dimethoxyethane 136.08 C(2,6) BHT

15.46 CH3diethyl ether 34.72 (CH3)3C BHA 72.35 CH2diglyme 137.05 C(1) benzaldehyde

16.60 CH2propane 35.25 CH3dimethylformamide 77.79 CH chloroform 137.50 C(4) BHA

16.66 CH3propane 36.36 C H2CH3ethyl methyl ketone 96.44 CCl4carbon tetrachloride 137.91 C(1) toluene 16.95 CH3hexamethylbenzene 36.88 (d) CH3HMPA11108.21 CH(3,4) pyrrole 142.73 CH(2,5) furan

18.72 CH3ethanol 37.03 NCH3dimethylacetamide 109.67 CH(3,4) furan 148.13 C(2,6) BHA

19.38 CH3propylene 40.03 CH3dimethyl sulfoxide 111.15 CH(3,5) BHA 150.27 CH(2,6) pyridine

20.37 CH3acetic acid 41.04 CH2dimethyl malonate 115.92 CH2propylene 152.05 C(1) BHT

20.37 CH3allyl acetate 41.83 CH2(2,6) cyclohexanone 116.02 CN acetonitrile 153.62 C(1) BHA

20.56 C H3CO ethyl acetate 43.59 CH21,2-dichloroethane 117.64 CH C H2allyl acetate 155.24 CO diallyl carbonate

21.10 CH3toluene 46.77 CH2triethylamine 117.78 CH(2,5) pyrrole 156.71 CO dimethyl carbonate 21.16 CH3dimethylacetamide 46.86 CH2(2,5) pyrrolidine 118.22 CH C H2diallyl carbonate 162.13 CH dimethylformamide

21.40 CH3Ar BHT 49.97 CH3methanol 122.16 CH(4,5) imidazole 166.66 CO2dimethyl malonate

22.72 CH2(2,4) n-pentane51.86 CH3dimethyl malonate 122.96 CH2ethylene 169.67 CO allyl acetate

23.04 CH2(2,5) n-hexane53.46 CH2dichloromethane 123.58 CH(3,5) pyridine 169.95 CO dimethylacetamide 25.03 CH2(4) cyclohexanone 54.30 CH3dimethyl carbonate 124.76 CO2carbon dioxide 170.44 CO ethyl acetate 25.18 CH32-propanol 55.27 CH3O BHA 125.68 CH(4) toluene 175.82 CO acetic acid 25.65 CH2(3,4) pyrrolidine 57.86 CH2ethanol 125.83 CH(3,5) BHT 191.43 HCO benzaldehyde 25.72 CH2(3,4) tetrahydrofuran 58.66 CH3diglyme 128.06 (t) CD C6D6 signal 192.69 CS2carbon disulfide 27.00 CH2(3,5) cyclohexanone 58.68 CH31,2-dimethoxyethane 128.52 C(4) BHT 204.43 CO acetone

27.23 CH2cyclohexane 60.21 CH2ethyl acetate 128.56 CH(3,5) toluene 206.55 CO ethyl methyl ketone

28.56 C H3CO ethyl methyl ketone 61.16 CH3nitromethane 128.62 CH benzene 209.10 CO cyclohexanone 30.14 CH3acetone 64.23 CH 2-propanol 128.95 CH(3,5) benzaldehyde

shift mult proton impurity shift mult proton impurity shift mult proton impurity

0.10 s CH3hexamethyldisiloxane 1.78 s CH3CO ethyl methyl ketone 4.62 s OH5BHA

0.14 s CH3silicone grease 1.80 s CH3allyl acetate 4.77 s CH2dichloromethane

0.15 s CH4methane 2.03 s CH3dimethyl sulfoxide 4.91 dm, 10 CH2(1) propylene

0.79 s CH3ethane 2.06 q, 7 C H2CH3ethyl methyl ketone 4.98 dm, 17 CH2(2) propylene

0.84 t, 7 CH3n-pentane 2.08 t CH2(2,6) cyclohexanone 5.03 ddt CHC H2(2) diallyl carbonate

0.84 t, 7.3 CH3propane 2.10 s CH3hexamethylbenzene 5.04 ddt CHC H2(2) allyl acetate

0.85 t, 7 CH3n-hexane 2.16 s CH3toluene 5.15 ddt CHC H2(1) allyl acetate

0.86–0.92 m CH3H grease8 2.20 s ArCH3BHT 5.17 ddt CHC H2(1) diallyl carbonate

0.88–0.91 m CH3pump oil 2.30 s CH3dimethylformamide 5.29 s CH2ethylene

0.89 t, 7 CH2C H3ethyl methyl ketone 2.39 q, 7 CH2triethylamine 5.50 s OH5BHT

0.93 t, 7 CH3triethylamine 2.42 s NCH3dimethylacetamide 5.72 m CH propylene

1.03 s OH water

2.47 d, 9.5 CH3HMPA 5.75 ddt C H CH2diallyl carbonate

1.04 t, 7 CH2C H3ethyl acetate

2.51 s CH3dimethylformamide 5.77 ddt C H CH2allyl acetate

1.04 d, 6 CH32-propanol

2.64 m CH2(2,5) pyrrolidine 6.19 dd CH(3,4) furan

1.06 t, 7 CH3ethanol

2.65 s NCH3dimethylacetamide 6.27 m CH(3,4) pyrrole

1.10 t, 7 CH3diethyl ether 3.15 s CH2dimethyl malonate 6.62 m CH(2,5) pyrrole

1.12 s CH3tert-butyl alcohol 3.16 s OCH3diglyme 6.74 s CH chloroform

1.19 m CH2n-hexane 3.17 s CH31,2-dimethoxyethane 6.83 s ArH BHA

1.21 s CH3acetonitrile 3.25 s9CH3methanol 6.90 m CH(3,5) pyridine

1.23 m CH2n-pentane 3.26 s CH21,2-dichloroethane 6.96 br. s CH(4) C6D5Cl residual

1.26 sept, 7.3 CH2propane 3.31 q, 7 CH2diethyl ether 6.97 s ArH BHT

1.30 s OH tert-butyl alcohol 3.37 m CH2diglyme 6.99 br. s CH(3,5) C6D5Cl residual

1.30 br s CH2H grease8 3.37 s CH21,2-dimethoxyethane 7.01 s CH(4,5) imidazole

1.30 s9OH methanol 3.41 s CH218-crown-6 7.01–7.08 m CH(2,4,6) toluene

1.31 br s CH2pump oil 3.41 s CH3dimethyl malonate 7.10–7.17 m CH(3,5) toluene

1.33–1.37 m CH2(4) cyclohexanone 3.45 s CH21,4-dioxane 7.14 br. s CH(2,6) C6D5Cl residual

1.37 s ArC(CH3)3BHA 3.48 s CH3dimethyl carbonate 7.15–7.19 m CH(3,5) benzaldehyde

1.37 s ArC(CH3)3BHT 3.49 m CH2diglyme 7.20 s CH benzene

1.37 s CH2cyclohexane 3.51 q, 76CH2ethanol 7.24 dd CH(2,5) furan

1.39 s6OH ethanol 3.58 s CH2ethylene glycol 7.24–7.28 m CH(4) benzaldehyde

1.43 m CH2(3,4) pyrrolidine 3.59 s CH3nitromethane 7.25 m CH(4) pyridine

1.48–1.53 m CH2(3,5) cyclohexanone 3.59 m CH2(2,5) tetrahydrofuran 7.53 s CH(2) imidazole

1.55 m CH2(3,4) tetrahydrofuran 3.61 s ArOCH3BHA 7.59–7.61 m CH(2,6) benzaldehyde

1.58 dt, 6.4, 1.5 CH3propylene 3.82 sept, 6 CH 2-propanol 7.73 s CH dimethylformamide

1.74 s CH3CO dimethylacetamide 3.96 q, 7 C H2CH3ethyl acetate 8.51 m CH(2,6) pyridine

1.76 s CH3acetic acid 4.44 ddd CH2allyl acetate 8.61 br t NH pyrrole

1.77 s CH3acetone 4.46 ddd CH2diallyl carbonate 9.77 s HCO benzaldehyde

1.78 s CH3CO ethyl acetate 4.49 s H2hydrogen

Table S14. C6D5Cl (13C{1H} NMR data by chemical shift in ppm)

shift carbon impurity shift carbon impurity shift carbon impurity shift carbon impurity

–4.33 CH4methane 30.12 CH3acetone 65.79 CH2diethyl ether 129.26 (t) CD(2,6) C6D5Cl signal

0.63 CH3acetonitrile 30.19 (C H3)3C BHT 66.95 CH21,4-dioxane 129.49 CH(2,6) benzaldehyde

1.09 CH3silicone grease 30.21 (C H3)3C BHA 67.64 CH2(2,5) tetrahydrofuran 131.54 C hexamethylbenzene 1.92 CH3hexamethyldisiloxane 30.71 CH3dimethylformamide 68.19 (CH3)3C tert-butyl alcohol131.93 C HCH2diallyl carbonate

6.91 CH3ethane 31.13 (C H3)3C tert-butyl alcohol68.19 CH2diallyl carbonate 132.69 C HCH2allyl acetate

7.79 CH2C H3ethyl methyl ketone 31.77 CH2(3,4) n-hexane70.55 CH218-crown-6 133.57 CH propylene 11.87 CH3triethylamine 34.11 (CH3)3C BHT 70.56 CH2diglyme 134.02 CH (4) benzaldehyde 14.07 CH3ethyl acetate 34.26 CH2(3) n-pentane71.81 CH21,2-dimethoxyethane 134.19 CCl C6D5Cl signal 14.10 CH3n-pentane34.56 (CH3)3C BHA 72.07 CH2diglyme 135.32 CH(4) pyridine

14.18 CH3n-hexane34.59 NCH3dimethylacetamide 77.67 CH chloroform 135.50 CH(2) imidazole

15.35 CH3diethyl ether 35.45 CH3dimethylformamide 96.38 CCl4carbon tetrachloride 135.92 C(2,6) BHT

16.48 CH2propane 36.39 C H2CH3ethyl methyl ketone 108.03 CH(3,4) pyrrole 136.78 C(1) benzaldehyde 16.56 CH3propane 36.64 (d) CH3HMPA11109.64 CH(3,4) furan 137.29 C(4) BHA

16.68 CH3hexamethylbenzene 37.13 NCH3dimethylacetamide 110.84 CH(3,5) BHA 137.65 C(1) toluene

18.55 CH3ethanol 40.27 CH3dimethyl sulfoxide 115.86 CH2propylene 142.49 CH(2,5) furan

19.32 CH3propylene 40.93 CH2dimethyl malonate 115.93 CN acetonitrile 147.87 C(2,6) BHA

20.40 CH3acetic acid 41.79 CH2(2,6) cyclohexanone 117.63 CH C H2allyl acetate 149.93 CH(2,6) pyridine 20.40 CH3allyl acetate 43.60 CH21,2-dichloroethane 117.65 CH(2,5) pyrrole 151.69 C(1) BHT

20.50 C H3CO ethyl acetate 46.36 CH2triethylamine 118.22 CH C H2diallyl carbonate 153.19 C(1) BHA

21.03 CH3dimethylacetamide 46.75 CH2(2,5) pyrrolidine 121.96 CH(4,5) imidazole 154.87 CO diallyl carbonate 21.10 CH3Ar BHT 49.66 CH3methanol 122.95 CH2ethylene 156.36 CO dimethyl carbonate

21.23 CH3toluene 51.89 CH3dimethyl malonate 123.49 CH(3,5) pyridine 162.01 CH dimethylformamide

22.54 CH2(2,4) n-pentane53.54 CH2dichloromethane 125.43 CH(4) toluene 166.51 CO2dimethyl malonate 22.86 CH2(2,5) n-hexane54.23 CH3dimethyl carbonate 125.58 CH(3,5) BHT 169.59 CO allyl acetate 25.07 CH2(4) cyclohexanone 55.08 CH3O BHA 125.96 (t) CD(4) C6D5Cl signal 169.79 CO dimethylacetamide 25.14 CH32-propanol 57.63 CH2ethanol 126.08 CO2carbon dioxide 170.20 CO ethyl acetate 25.59 CH2(3,4) pyrrolidine 58.31 CH31,2-dimethoxyethane 128.25 (t) CD(3,5) C6D5Cl signal 175.67 CO acetic acid

25.68 CH2(3,4) tetrahydrofuran 58.42 CH3diglyme 128.26 C(4) BHT 191.24 HCO benzaldehyde

26.99 CH2cyclohexane 60.06 CH2ethyl acetate 128.31 CH(3,5) toluene 192.49 CS2carbon disulfide

27.02 CH2(3,5) cyclohexanone 61.68 CH3nitromethane 128.38 CH benzene 204.83 CO acetone

28.82 C H3CO ethyl methyl ketone 64.03 CH2ethylene glycol 128.87 CH(3,5) benzaldehyde 206.87 CO ethyl methyl ketone 30.11 CH2H grease864.18 CH 2-propanol 129.12 CH(2,6) toluene 209.30 CO cyclohexanone 30.11 CH2pump oil 64.86 CH2allyl acetate

shift mult proton impurity shift mult proton impurity shift mult proton impurity

0.07 s CH3hexamethyldisiloxane 2.17 s CH3hexamethylbenzene 4.54 s H2hydrogen

0.13 s CH3silicone grease 2.22 s ArCH3BHT 4.62 ddd CH2diallyl carbonate

0.17 s CH4methane 2.27 t CH2(2,6) cyclohexanone 4.90 dm, 10 CH2(1) propylene

0.83 s CH3ethane 2.32 s CH3toluene 5.00 dm, 17 CH2(2) propylene

0.87 m CH3pump oil 2.45 q, 7 C H2CH3ethyl methyl ketone 5.18 ddt CHC H2(2) allyl acetate

0.88 t, 7 CH3n-hexane 2.45 q, 7 CH2triethylamine 5.23 ddt CHC H2(2) diallyl carbonate

0.88 t, 7 CH3n-pentane 2.52 s CH3dimethyl sulfoxide 5.29 ddt CHC H2(1) allyl acetate

0.88 t, 7.3 CH3propane 2.59 d, 9.5 CH3HMPA 5.35 ddt CHC H2(1) diallyl carbonate

0.90 m CH3H grease8 2.78 s CH3dimethylformamide 5.38 s CH2ethylene

0.96 t, 7 CH2C H3ethyl methyl ketone 2.83 s NCH3dimethylacetamide 5.63 s CH2dichloromethane

0.96 t, 7 CH3triethylamine 2.843s OH water 5.65 s OH5BHA

1.10 d, 6 CH32-propanol

2.94 s CH3dimethylformamide 5.81 m CH propylene

1.11 t, 7 CH3diethyl ether 3.00 s NCH3dimethylacetamide 5.92 ddt C H CH2allyl acetate

1.12 t, 7 CH3ethanol 3.12 s9OH methanol 5.96 ddt C H CH2diallyl carbonate

1.18 s CH3tert-butyl alcohol 3.28 s OCH3diglyme 6.07 m CH(3,4) pyrrole

1.20 t, 7 CH2C H3ethyl acetate 3.28 s CH31,2-dimethoxyethane 6.43 dd CH(3,4) furan

1.27 m CH2n-pentane 3.28 s CH2ethylene glycol 6.72 s ArH BHA

1.28 m CH2n-hexane 3.31 s9CH3methanol 6.77 m CH(2,5) pyrrole

1.29 br s CH2H grease8 3.39 s6OH ethanol 6.96 s ArH BHT

1.29 br s CH2pump oil 3.41 q, 7 CH2diethyl ether 7.04 s CH(4,5) imidazole

1.31 sept, 7.3 CH2propane 3.42 s CH2dimethyl malonate 7.10–7.20 m CH(2,4,6) toluene

1.41 s ArC(CH3)3BHA 3.46 s CH21,2-dimethoxyethane 7.10–7.20 m CH(3,5) toluene

1.41 s ArC(CH3)3BHT 3.47 m CH2diglyme 7.35 m CH(3,5) pyridine

1.43 s CH2cyclohexane 3.56 m CH2diglyme 7.36 s CH benzene

1.68 dt, 6.4, 1.5 CH3propylene 3.57 q, 76CH2ethanol 7.56 dd CH(2,5) furan

1.70–1.74 m CH2(4) cyclohexanone 3.59 s CH218-crown-6 7.59–7.63 m CH(3,5) benzaldehyde

1.79 m CH2(3,4) tetrahydrofuran 3.59 s CH21,4-dioxane 7.62 s CH(2) imidazole

1.79–1.83 m CH2(3,5) cyclohexanone 3.63 m CH2(2,5) tetrahydrofuran 7.69–7.73 m CH(4) benzaldehyde

1.96 s CH3acetic acid 3.68 s CH3dimethyl malonate 7.76 m CH(4) pyridine

1.97 s CH3CO dimethylacetamide 3.72 s ArOCH3BHA 7.92–7.94 m CH(2,6) benzaldehyde

1.97 s CH3CO ethyl acetate 3.72 s CH3dimethyl carbonate 7.96 s CH dimethylformamide

2.02 s CH3allyl acetate

3.87 s CH21,2-dichloroethane 8.02 s CH chloroform

2.05 s CH3acetonitrile

3.90 sept, 6 CH 2-propanol 8.58 m CH(2,6) pyridine

2.05 p CHD2(CD3)2CO residual 4.05 q, 7 C H2CH3ethyl acetate 10.02 br t NH pyrrole

2.07 s CH3CO ethyl methyl ketone 4.43 s CH3nitromethane 10.05 s HCO benzaldehyde

2.09 s CH3acetone 4.53 ddd CH2allyl acetate

Table S16. (CD3)2CO (13C{1H} NMR data by chemical shift in ppm)

shift carbon impurity shift carbon impurity shift carbon impurity shift carbon impurity –5.33 CH4methane 30.60 CH3acetone 65.28 CH2allyl acetate 130.23 CH(2,6) benzaldehyde

1.12 CH3acetonitrile 30.64 (C H3)3C BHA 66.12 CH2diethyl ether 13

2.22 C hexamethylbenzene

1.40 CH3silicone grease 30.72 (C H3)3C tert-butyl alcohol67.60 CH21,4-dioxane 133.16 C HCH2diallyl carbonate

2.01 CH3hexamethyldisiloxane 31.03 CH3dimethylformamide 68.07 CH2(2,5) tetrahydrofuran 13

3.76 C HCH2allyl acetate

6.88 CH3ethane 31.61 (C H3)3C BHT 68.13 (CH3)3C tert-butyl alcohol134.34 CH propylene

8.03 CH2C H3ethyl methyl ketone 32.30 CH2(3,4) n-hexane68.78 CH2diallyl carbonate 135.14 CH (4) benzaldehyde

12.49 CH3triethylamine 34.83 CH2(3) n-pentane71.03 CH2diglyme 135.89 CH(2) imidazole

14.29 CH3n-pentane34.89 NCH3dimethylacetamide 71.25 CH218-crown-6 136.56 CH(4) pyridine

14.34 CH3n-hexane35.00 (CH3)3C BHT 72.47 CH21,2-dimethoxyethane 137.66 C(1) benzaldehyde

14.50 CH3ethyl acetate 35.45 (CH3)3C BHA 72.63 CH2diglyme 138.19 C(2,6) BHT

15.78 CH3diethyl ether 36.15 CH3dimethylformamide 79.19 CH chloroform 138.48 C(1) toluene

16.68 CH3propane 36.75 C H2CH3ethyl methyl ketone 96.65 CCl4carbon tetrachloride 140.32 C(4) BHA

16.78 CH2propane 37.04 (d) CH3HMPA11108.04 CH(3,4) pyrrole 143.49 CH(2,5) furan

16.86 CH3hexamethylbenzene 37.92 NCH3dimethylacetamide 110.24 CH(3,4) furan 148.48 C(2,6) BHA

18.89 CH3ethanol 41.23 CH3dimethyl sulfoxide 111.00 CH(3,5) BHA 150.67 CH(2,6) pyridine

19.42 CH3propylene 41.43 CH2dimethyl malonate 116.03 CH2propylene 152.51 C(1) BHT

20.51 CH3acetic acid 42.24 CH2(2,6) cyclohexanone 117.60 CN acetonitrile 153.97 C(1) BHA

20.68 CH3allyl acetate 45.25 CH21,2-dichloroethane 117.81 CH C H2allyl acetate 155.48 CO diallyl carbonate

20.83 C H3CO ethyl acetate 47.07 CH2triethylamine 117.98 CH(2,5) pyrrole 157.04 CO dimethyl carbonate

21.31 CH3Ar BHT 49.77 CH3methanol 118.53 CH C H2diallyl carbonate 162.79 CH dimethylformamide

21.46 CH3toluene 52.47 CH3dimethyl malonate 122.31 CH(4,5) imidazole 167.58 CO2dimethyl malonate

21.51 CH3dimethylacetamide 54.95 CH2dichloromethane 123.47 CH2ethylene 170.61 CO allyl acetate

22.98 CH2(2,4) n-pentane54.95 CH3dimethyl carbonate 124.57 CH(3,5) pyridine 170.61 CO dimethylacetamide

23.28 CH2(2,5) n-hexane55.51 CH3O BHA 125.81 CO2carbon dioxide 170.96 CO ethyl acetate

25.59 CH2(4) cyclohexanone 57.72 CH2ethanol 126.03 CH(3,5) BHT 172.31 CO acetic acid

25.67 CH32-propanol 58.45 CH31,2-dimethoxyethane 126.12 CH(4) toluene 192.95 HCO benzaldehyde

26.15 CH2(3,4) tetrahydrofuran 58.77 CH3diglyme 129.03 CH(3,5) toluene 193.58 CS2carbon disulfide

27.51 CH2cyclohexane 60.56 CH2ethyl acetate 129.05 C(4) BHT 205.87 CO acetone

27.68 CH2(3,5) cyclohexanone 63.21 CH3nitromethane 129.15 CH benzene 206.26 CO (CD3)2CO signal

29.30 C H3CO ethyl methyl ketone 63.85 CH 2-propanol 129.76 CH(2,6) toluene 208.30 CO ethyl methyl ketone

29.84 (sept) CD3(CD3)2CO signal 64.26 CH2ethylene glycol 129.90 CH(3,5) benzaldehyde 210.36 CO cyclohexanone

30.36 CH2pump oil

shift mult proton impurity shift mult proton impurity shift mult proton impurity –0.06 s CH3 silicone grease 2.18 s ArCH3 BHT 4.61 ddd CH2 diallyl carbonate

0.06 s CH3 hexamethyldisiloxane 2.25 t CH2(2,6) cyclohexanone 4.61 s H2 hydrogen

0.20 s CH4 methane 2.30 s CH3 toluene 4.63 s6 OH ethanol

0.74 m CH3 pump oil 2.43 q, 7 C H2CH3 ethyl methyl ketone 4.94 dm, 10 CH2(1) propylene

0.82 s CH3 ethane 2.43 q, 7 CH2 triethylamine 5.03 dm, 17 CH2(2) propylene

0.82–0.88 m CH3 H grease8 2.50 p CHD2 (CD3)2SO residual 5.20 ddt CHC H2(2) allyl acetate

0.86 t, 7 CH3 n-hexane 2.53 d, 9.5 CH3 HMPA 5.25 ddt CHC H2(2) diallyl carbonate

0.86 t, 7 CH3 n-pentane 2.54 s CH3 dimethyl sulfoxide 5.29 ddt CHC H2(1) allyl acetate

0.87 t, 7.3 CH3 propane 2.67 m CH2(2,5) pyrrolidine 5.33 ddt CHC H2(1) diallyl carbonate

0.91 t, 7 CH2C H3 ethyl methyl ketone 2.73 s CH3 dimethylformamide 5.41 s CH2 ethylene

0.93 t, 7 CH3 triethylamine 2.78 s NCH3 dimethylacetamide 5.76 s CH2 dichloromethane

1.04 d, 6 CH3 2-propanol

2.89 s CH3 dimethylformamide 5.80 m CH propylene

1.06 t, 7 CH3 ethanol

2.94 s NCH3 dimethylacetamide 5.91 ddt C H CH2 allyl acetate

1.09 t, 7 CH3 diethyl ether 3.16 s9 CH3 methanol 5.93 ddt C H CH2 diallyl carbonate

1.11 s CH3 tert-butyl alcohol 3.24 s OCH3 diglyme 6.01 m CH(3,4) pyrrole

1.15 br s CH2 pump oil 3.24 s CH3 1,2-dimethoxyethane 6.47 dd CH(3,4) furan

1.17 t, 7 CH2C H3 ethyl acetate 3.333 s OH water 6.52 s OH5 BHA

1.24 br s CH2 H grease8 3.34 s CH2 ethylene glycol 6.62 s ArH BHA

1.25 m CH2 n-hexane 3.38 q, 7 CH2 diethyl ether 6.65 s OH5 BHT

1.27 m CH2 n-pentane 3.38 m CH2 diglyme 6.73 m CH(2,5) pyrrole

1.29 sept, 7.3 CH2 propane 3.43 s CH2 1,2-dimethoxyethane 6.87 s ArH BHT

1.36 s ArC(CH3)3 BHA 3.44 q, 76 CH2 ethanol 7.01 s CH(4,5) imidazole

1.36 s ArC(CH3)3 BHT 3.51 s CH2 18-crown-6 7.18 m CH(2,4,6) toluene

1.40 s CH2 cyclohexane 3.51 m CH2 diglyme 7.25 m CH(3,5) toluene

1.55 m CH2(3,4) pyrrolidine 3.53 s CH2 dimethyl malonate 7.37 s CH benzene

1.64–1.66 m CH2(4) cyclohexanone 3.57 s CH2 1,4-dioxane 7.39 m CH(3,5) pyridine

1.68 dt, 6.4, 1.5 CH3 propylene 3.60 m CH2(2,5) tetrahydrofuran 7.61–7.67 m CH(3,5) benzaldehyde

1.74–1.78 m CH2(3,5) cyclohexanone 3.65 s CH3 dimethyl malonate 7.63 s CH(2) imidazole

1.76 m CH2(3,4) tetrahydrofuran 3.66 s ArOCH3 BHA 7.67 dd CH(2,5) furan

1.91 s CH3 acetic acid 3.69 s CH3 dimethyl carbonate 7.69–7.75 m CH(4) benzaldehyde

1.96 s CH3CO dimethylacetamide 3.78 sept, 6 CH 2-propanol 7.79 m CH(4) pyridine

1.99 s CH3CO ethyl acetate 3.90 s CH2 1,2-dichloroethane 7.91–7.93 m CH(2,6) benzaldehyde

2.03 s CH3 allyl acetate 4.01 s9 OH methanol 8.32 s CH chloroform

2.07 s CH3 acetonitrile 4.03 q, 7 C H2CH3 ethyl acetate 8.58 m CH(2,6) pyridine

2.07 s CH3CO ethyl methyl ketone 4.19 s OH tert-butyl alcohol 10.02 s HCO benzaldehyde

2.09 s CH3 acetone 4.42 s CH3 nitromethane 10.75 br t NH pyrrole

2.14 s CH3 hexamethylbenzene 4.52 ddd CH2 allyl acetate

Table S18. (CD3)2SO (13C{1H} NMR data by chemical shift in ppm)

shift carbon impurity shift carbon impurity shift carbon impurity shift carbon impurity

–4.01 CH4 methane 30.38 (C H3)3C tert-butyl alcohol 63.28 CH3 nitromethane 129.10 CH(3,5) benzaldehyde 1.03 CH3 acetonitrile 30.56 CH3 acetone 64.32 CH2 allyl acetate 129.45 CH(2,6) benzaldehyde 1.96 CH3 hexamethyldisiloxane 30.73 CH3 dimethylformamide 64.92 CH 2-propanol 131.10 C hexamethylbenzene

6.61 CH3 ethane 30.95 CH2(3,4) n-hexane 66.36 CH2 1,4-dioxane 132.18 C HCH2 diallyl carbonate

7.61 CH2C H3 ethyl methyl ketone 31.25 (C H3)3C BHT 66.88 (CH3)3C tert-butyl alcohol 132.71 C HCH2 allyl acetate 11.74 CH3 triethylamine 33.48 CH2(3) n-pentane 67.03 CH2(2,5) tetrahydrofuran 133.55 CH propylene 13.28 CH3 n-pentane 34.33 (CH3)3C BHT 67.86 CH2 diallyl carbonate 134.52 CH (4) benzaldehyde

13.88 CH3 n-hexane 34.42 NCH3 dimethylacetamide 69.54 CH2 diglyme 135.15 CH(2) imidazole

14.40 CH3 ethyl acetate 34.76 (CH3)3C BHA 69.85 CH2 18-crown-6 136.05 CH(4) pyridine

15.12 CH3 diethyl ether 35.73 CH3 dimethylformamide 71.17 CH2 1,2-dimethoxyethane 136.20 C(1) benzaldehyde

15.67 CH2 propane 35.83 C H2CH3 ethyl methyl ketone 71.25 CH2 diglyme 137.35 C(1) toluene

16.34 CH3 propane 36.42 (d) CH3 HMPA11 79.16 CH chloroform 139.12 C(2,6) BHT

16.60 CH3 hexamethylbenzene 37.38 NCH3 dimethylacetamide 95.44 CCl4 carbon tetrachloride 141.16 C(4) BHA

18.51 CH3 ethanol 39.52 (sept) CD3 (CD3)2SO signal 107.07 CH(3,4) pyrrole 142.82 CH(2,5) furan

19.20 CH3 propylene 40.45 CH3 dimethyl sulfoxide 109.62 CH(3,4) furan 147.44 C(2,6) BHA

20.54 CH3 allyl acetate 40.72 CH2 dimethyl malonate 109.80 CH(3,5) BHA 149.58 CH(2,6) pyridine 20.68 C H3CO ethyl acetate 41.32 CH2(2,6) cyclohexanone 116.07 CH2 propylene 151.47 C(1) BHT

20.95 CH3 acetic acid 45.02 CH2 1,2-dichloroethane 117.32 CH(2,5) pyrrole 152.53 C(1) BHA

20.97 CH3Ar BHT 45.74 CH2 triethylamine 117.64 CH C H2 allyl acetate 154.16 CO diallyl carbonate

20.99 CH3 toluene 46.51 CH2(2,5) pyrrolidine 117.91 CN acetonitrile 155.76 CO dimethyl carbonate

21.29 CH3 dimethylacetamide 48.59 CH3 methanol 118.32 CH C H2 diallyl carbonate 162.29 CH dimethylformamide

21.70 CH2(2,4) n-pentane 52.08 CH3 dimethyl malonate 121.55 CH(4,5) imidazole 166.91 CO2 dimethyl malonate

22.05 CH2(2,5) n-hexane 54.63 CH3 dimethyl carbonate 123.52 CH2 ethylene 169.54 CO dimethylacetamide

24.32 CH2(4) cyclohexanone 54.84 CH2 dichloromethane 123.84 CH(3,5) pyridine 169.97 CO allyl acetate

25.14 CH2(3,4) tetrahydrofuran 54.89 CH3O BHA 124.21 CO2 carbon dioxide 170.31 CO ethyl acetate 25.26 CH2(3,4) pyrrolidine 56.07 CH2 ethanol 124.85 CH(3,5) BHT 171.93 CO acetic acid

25.43 CH3 2-propanol 57.98 CH3 diglyme 125.29 CH(4) toluene 192.63 CS2 carbon disulfide

26.33 CH2 cyclohexane 58.03 CH3 1,2-dimethoxyethane 127.97 C(4) BHT 193.08 HCO benzaldehyde 26.46 CH2(3,5) cyclohexanone 59.74 CH2 ethyl acetate 128.18 CH(3,5) toluene 206.31 CO acetone 29.26 C H3CO ethyl methyl ketone 62.05 CH2 diethyl ether 128.30 CH benzene 208.72 CO ethyl methyl ketone

29.33 CH2 pump oil 62.76 CH2 ethylene glycol 128.88 CH(2,6) toluene 210.63 CO cyclohexanone

30.30 (C H3)3C BHA

shift mult proton impurity shift mult proton impurity shift mult proton impurity

0.07 s CH3 hexamethyldisiloxane 2.18 s OH tert-butyl alcohol 4.57 s H2 hydrogen

0.08 s CH3 silicone grease 2.19 s CH3 hexamethylbenzene 4.61 ddd CH2 diallyl carbonate

0.20 s CH4 methane 2.22 s ArCH3 BHT 4.93 dm, 10 CH2(1) propylene

0.85 s CH3 ethane 2.27 t CH2(2,6) cyclohexanone 4.98 s OH5 BHA

0.85 m CH3 pump oil 2.33 s CH3 toluene 5.04 dm, 17 CH2(2) propylene

0.89 t, 7 CH3 n-hexane 2.43 q, 7 C H2CH3 ethyl methyl ketone 5.20 s OH5 BHT

0.89 t, 7 CH3 n-pentane 2.45 q, 7 CH2 triethylamine 5.21 ddt CHC H2(2) allyl acetate

0.90 t, 7.3 CH3 propane 2.47 s6 OH ethanol 5.25 ddt CHC H2(2) diallyl carbonate

0.96 t, 7 CH2C H3 ethyl methyl ketone 2.50 s CH3 dimethyl sulfoxide 5.29 ddt CHC H2(1) allyl acetate

0.96 t, 7 CH3 triethylamine 2.57 d, 9.5 CH3 HMPA 5.34 ddt CHC H2(1) diallyl carbonate

1.09 d, 6 CH3 2-propanol

2.697 m7 OH7 ethylene glycol7 5.41 s CH2 ethylene

1.12 t, 7 CH3 diethyl ether

2.75 m CH2(2,5) pyrrolidine 5.44 s CH2 dichloromethane

1.12 t, 7 CH3 ethanol

2.77 s CH3 dimethylformamide 5.85 m CH propylene

1.16 s CH3 tert-butyl alcohol

2.83 s NCH3 dimethylacetamide 5.93 ddt C H CH2 allyl acetate

1.20 t, 7 CH2C H3 ethyl acetate

2.89 s CH3 dimethylformamide 5.96 ddt C H CH2 diallyl carbonate

1.27 br s CH2 pump oil

2.96 s NCH3 dimethylacetamide 6.10 m CH(3,4) pyrrole

1.28 m CH2 n-hexane 3.28 s CH3 1,2-dimethoxyethane 6.44 dd CH(3,4) furan

1.29 m CH2 n-pentane 3.28 s9 CH3 methanol 6.73 s ArH BHA

1.33 sept, 7.3 CH2 propane 3.29 s OCH3 diglyme 6.75 m CH(2,5) pyrrole

1.39 s ArC(CH3)3 BHT 3.38 s CH2 dimethyl malonate 6.97 s ArH BHT

1.40 s ArC(CH3)3 BHA 3.42 q, 7 CH2 diethyl ether 7.01 s CH(4,5) imidazole

1.44 s CH2 cyclohexane 3.45 m CH2 diglyme 7.10–7.30 m CH(2,4,6) toluene

1.61 m CH2(3,4) pyrrolidine 3.45 s CH2 1,2-dimethoxyethane 7.10–7.30 m CH(3,5) toluene

1.67–1.72 m CH2(4) cyclohexanone 3.51 s CH2 18-crown-6 7.33 m CH(3,5) pyridine

1.70 dt, 6.4, 1.5 CH3 propylene 3.51 m7 CH2 ethylene glycol 7.37 s CH benzene

1.79–1.84 m CH2(3,5) cyclohexanone 3.53 m CH2 diglyme 7.52 dd CH(2,5) furan

1.80 m CH2(3,4) tetrahydrofuran 3.54 q, 76 CH2 ethanol 7.57 s CH(2) imidazole

1.94 p CHD2 CD3CN residual 3.60 s CH2 1,4-dioxane 7.57–7.61 m CH(3,5) benzaldehyde

1.96 s CH3 acetic acid 3.64 m CH2(2,5) tetrahydrofuran 7.58 s CH chloroform

1.96 s CH3 acetonitrile 3.68 s CH3 dimethyl malonate 7.67–7.71 m CH(4) benzaldehyde

1.97 s CH3CO dimethylacetamide 3.72 s ArOCH3 BHA 7.73 m CH(4) pyridine

1.97 s CH3CO ethyl acetate 3.72 s CH3 dimethyl carbonate 7.89–7.91 m CH(2,6) benzaldehyde

2.02 s CH3 allyl acetate

3.81 s CH2 1,2-dichloroethane 7.92 s CH dimethylformamide

2.06 s CH3CO ethyl methyl ketone

3.87 sept, 6 CH 2-propanol 8.57 m CH(2,6) pyridine

2.08 s CH3 acetone 4.06 q, 7 C H2CH3 ethyl acetate 9.27 br t NH pyrrole

2.13 s OH water 4.31 s CH3 nitromethane 10.01 s HCO benzaldehyde

2.16 s9 OH methanol 4.53 ddd CH2 allyl acetate

Table S20. CD3CN (13C{1H} NMR data by chemical shift in ppm)

shift carbon impurity shift carbon impurity shift carbon impurity shift carbon impurity

–4.61 CH4 methane 30.68 (C H3)3C tert-butyl alcohol 65.55 CH2 allyl acetate 130.07 CH(3,5) benzaldehyde 1.32 (sept) CD3 CD3CN signal 30.86 CH2 pump oil 66.32 CH2 diethyl ether 130.42 CH(2,6) benzaldehyde

1.79 CH3 acetonitrile 30.91 CH3 acetone 67.72 CH2 1,4-dioxane 13

2.61 C hexamethylbenzene

2.07 CH3 hexamethyldisiloxane 31.32 CH3 dimethylformamide 68.33 CH2(2,5) tetrahydrofuran 13

3.20 C HCH2 diallyl carbonate

6.99 CH3 ethane 31.50 (C H3)3C BHT 68.74 (CH3)3C tert-butyl alcohol 133.83 C HCH2 allyl acetate

8.14 CH2C H3 ethyl methyl ketone 32.36 CH2(3,4) n-hexane 69.09 CH2 diallyl carbonate 134.78 CH propylene 12.38 CH3 triethylamine 34.89 CH2(3) n-pentane 70.99 CH2 diglyme 135.40 CH (4) benzaldehyde 14.37 CH3 n-pentane 35.05 (CH3)3C BHT 71.22 CH2 18-crown-6 136.33 CH(2) imidazole 14.43 CH3 n-hexane 35.17 NCH3 dimethylacetamide 72.47 CH2 1,2-dimethoxyethane 136.89 CH(4) pyridine

14.54 CH3 ethyl acetate 35.48 (CH3)3C BHA 72.63 CH2 diglyme 137.62 C(1) benzaldehyde

15.63 CH3 diethyl ether 36.57 CH3 dimethylformamide 79.17 CH chloroform 138.13 C(2,6) BHT

16.73 CH3 propane 37.09 C H2CH3 ethyl methyl ketone 96.68 CCl4 carbon tetrachloride 138.90 C(1) toluene 16.91 CH2 propane 37.10 (d) CH3 HMPA11 108.31 CH(3,4) pyrrole 140.20 C(4) BHA

16.94 CH3 hexamethylbenzene 38.26 NCH3 dimethylacetamide 110.49 CH(3,4) furan 143.74 CH(2,5) furan

18.80 CH3 ethanol 41.31 CH3 dimethyl sulfoxide 111.35 CH(3,5) BHA 148.39 C(2,6) BHA

19.48 CH3 propylene 41.77 CH2 dimethyl malonate 116.12 CH2 propylene 150.76 CH(2,6) pyridine

20.73 CH3 acetic acid 42.44 CH2(2,6) cyclohexanone 118.06 CH C H2 allyl acetate 152.42 C(1) BHT

21.02 CH3 allyl acetate 45.54 CH2 1,2-dichloroethane 118.26 CN CD3CN signal 154.02 C(1) BHA

21.16 C H3CO ethyl acetate 47.10 CH2 triethylamine 118.26 CN acetonitrile 155.66 CO diallyl carbonate 21.23 CH3Ar BHT 47.57 CH2(2,5) pyrrolidine 118.47 CH(2,5) pyrrole 157.26 CO dimethyl carbonate 21.50 CH3 toluene 49.90 CH3 methanol 118.86 CH C H2 diallyl carbonate 163.31 CH dimethylformamide 21.76 CH3 dimethylacetamide 52.95 CH3 dimethyl malonate 122.78 CH(4,5) imidazole 168.07 CO2 dimethyl malonate 23.08 CH2(2,4) n-pentane 55.32 CH2 dichloromethane 123.69 CH2 ethylene 171.31 CO dimethylacetamide 23.40 CH2(2,5) n-hexane 55.39 CH3 dimethyl carbonate 125.89 CO2 carbon dioxide 171.32 CO allyl acetate 25.55 CH3 2-propanol 55.94 CH3O BHA 126.28 CH(4) toluene 171.68 CO ethyl acetate

25.62 CH2(4) cyclohexanone 57.96 CH2 ethanol 126.38 CH(3,5) BHT 173.21 CO acetic acid

26.27 CH2(3,4) tetrahydrofuran 58.89 CH3 1,2-dimethoxyethane 127.76 CH(3,5) pyridine 193.60 CS2 carbon disulfide

26.34 CH2(3,4) pyrrolidine 58.90 CH3 diglyme 129.23 CH(3,5) toluene 193.64 HCO benzaldehyde

27.63 CH2 cyclohexane 60.98 CH2 ethyl acetate 129.32 CH benzene 207.43 CO acetone 27.80 CH2(3,5) cyclohexanone 63.66 CH3 nitromethane 129.61 C(4) BHT 209.88 CO ethyl methyl ketone

29.60 C H3CO ethyl methyl ketone 64.22 CH2 ethylene glycol 129.94 CH(2,6) toluene 211.99 CO cyclohexanone

30.55 (C H3)3C BHA 64.30 CH 2-propanol

shift mult proton impurity shift mult proton impurity shift mult proton impurity

0.08 s CH3 hexamethyldisiloxane 2.20 s OH tert-butyl alcohol 4.53 s H2 hydrogen

0.16 s CH3 silicone grease 2.24 s ArCH3 BHT 4.58 ddd CH2 allyl acetate

0.18 s CH4 methane 2.24 s CH3 hexamethylbenzene 4.62 ddd CH2 diallyl carbonate

0.85 s CH3 ethane 2.33 s CH3 toluene 4.93 dm, 10 CH2(1) propylene

0.88–0.94 m CH3 H grease8 2.38 t CH2(2,6) cyclohexanone 5.02 s OH TFE-d3 residual

0.90 t, 7 CH3 n-pentane 2.49 q, 7 C H2CH3 ethyl methyl ketone 5.03 dm, 17 CH2(2) propylene

0.90 t, 7.3 CH3 propane 2.63 s CH3 dimethyl sulfoxide 5.24 s CH2 dichloromethane

0.91 t, 7 CH3 n-hexane 2.63 d, 9.5 CH3 HMPA 5.25 ddt CHC H2(2) allyl acetate

0.99 m CH3 pump oil 2.88 s CH3 dimethylformamide 5.28 ddt CHC H2(2) diallyl carbonate

1.05 t, 7 CH2C H3 ethyl methyl ketone

2.94 s NCH3 dimethylacetamide 5.32 ddt CHC H2(1) allyl acetate

1.20 t, 7 CH3 diethyl ether

2.98 s CH3 dimethylformamide 5.35 ddt CHC H2(1) diallyl carbonate

1.20 d, 6 CH3 2-propanol 3.05 s NCH3 dimethylacetamide 5.40 s CH2 ethylene

1.22 t, 7 CH3 ethanol 3.11 m CH2(2,5) pyrrolidine 5.87 m CH propylene

1.26 t, 7 CH2C H3 ethyl acetate 3.12 q, 7 CH2 triethylamine 5.92 ddt C H CH2 diallyl carbonate

1.28 s CH3 tert-butyl alcohol 3.40 s CH3 1,2-dimethoxyethane 5.93 ddt C H CH2 allyl acetate

1.31 m CH2 n-hexane 3.41 s OCH3 diglyme 6.24 m CH(3,4) pyrrole

1.31 t, 7 CH3 triethylamine 3.41 s CH2 dimethyl malonate 6.42 dd CH(3,4) furan

1.33 br s CH2 H grease8 3.44 s CH3 methanol 6.84 m CH(2,5) pyrrole

1.33 m CH2 n-pentane 3.58 q, 7 CH2 diethyl ether 6.87 s ArH BHA

1.33 sept, 7.3 CH2 propane 3.61 s CH2 1,2-dimethoxyethane 7.03 s CH(4,5) imidazole

1.41 br s CH2 pump oil 3.62 m CH2 diglyme 7.06 s ArH BHT

1.43 s ArC(CH3)3 BHT 3.64 s CH2 18-crown-6 7.10–7.30 m CH(2,4,6) toluene

1.44 s ArC(CH3)3 BHA 3.66 s OH water 7.10–7.30 m CH(3,5) toluene

1.47 s CH2 cyclohexane 3.67 m CH2 diglyme 7.33 s CH chloroform

1.70 dt, 6.4, 1.5 CH3 propylene 3.71 s CH2 1,2-dichloroethane 7.36 s CH benzene

1.75–1.78 m CH2(4) cyclohexanone 3.71 q, 7 CH2 ethanol 7.40 m CH(3,5) pyridine

1.87–1.92 m CH2(3,5) cyclohexanone 3.72 s CH2 ethylene glycol 7.44 dd CH(2,5) furan

1.91 m CH2(3,4) tetrahydrofuran 3.76 s CH3 dimethyl malonate 7.56–7.59 m CH(3,5) benzaldehyde

1.93 m CH2(3,4) pyrrolidine 3.76 s CH2 1,4-dioxane 7.61 s CH(2) imidazole

1.95 s CH3 acetonitrile 3.77 s CH3 dimethyl carbonate 7.68–7.72 m CH(4) benzaldehyde

2.03 s CH3CO ethyl acetate

3.78 m CH2(2,5) tetrahydrofuran 7.82 m CH(4) pyridine

2.06 s CH3 acetic acid

3.79 s ArOCH3 BHA 7.86 s CH dimethylformamide

2.07 s CH3 allyl acetate

3.88 tq CDH TFE-d3 residual 7.90–7.92 m CH(2,6) benzaldehyde

2.09 s CH3CO dimethylacetamide 4.05 sept, 6 CH 2-propanol 8.45 m CH(2,6) pyridine

2.16 s CH3CO ethyl methyl ketone 4.14 q, 7 C H2CH3 ethyl acetate 9.88 s HCO benzaldehyde

2.19 s CH3 acetone 4.28 s CH3 nitromethane

Table S22. TFE-d3 (13C{1H} NMR data by chemical shift in ppm)

shift carbon impurity shift carbon impurity shift carbon impurity shift carbon impurity

–5.88 CH4 methane 30.96 CH3 dimethylformamide 66.69 CH 2-propanol 130.82 CH(3,5) benzaldehyde

1.00 CH3 acetonitrile 31.01 (C H3)3C BHT 67.55 CH2 diethyl ether 131.78 CH(2,6) benzaldehyde

2.09 CH3 hexamethyldisiloxane 31.07 (C H3)3C tert-butyl alcohol 67.61 CH2 allyl acetate 132.72 C HCH2 diallyl carbonate 2.87 CH3 silicone grease 31.85 CH2 pump oil 68.52 CH2 1,4-dioxane 13

3.33 C HCH2 allyl acetate

7.01 CH3 ethane 32.35 CO acetone 69.53 CH2(2,5) tetrahydrofuran 134.04 C hexamethylbenzene

8.29 CH2C H3 ethyl methyl ketone 33.17 CH2(3,4) n-hexane 70.69 CH2 diallyl carbonate 136.00 CH propylene

9.51 CH3 triethylamine 35.69 (CH3)3C BHT 70.80 CH2 18-crown-6 136.58 CH(2) imidazole 14.36 CH3 ethyl acetate 35.76 CH2(3) n-pentane 71.33 CH2 diglyme 137.17 CH (4) benzaldehyde 14.54 CH3 n-pentane 36.07 (CH3)3C BHA 72.35 (CH3)3C tert-butyl alcohol 137.84 C(1) benzaldehyde

14.63 CH3 n-hexane 36.28 NCH3 dimethylacetamide 72.87 CH2 1,2-dimethoxyethane 138.59 C(2,6) BHT

15.33 CH3 diethyl ether 37.21 (d) CH3 HMPA i 73.05 CH2 diglyme 139.62 CH(4) pyridine

16.93 CH3 propane 37.76 CH3 dimethylformamide 78.83 CH chloroform 139.92 C(1) toluene

17.04 CH3 hexamethylbenzene 38.23 C H2CH3 ethyl methyl ketone 97.74 CCl4 carbon tetrachloride 140.23 C(4) BHA

17.46 CH2 propane 39.06 NCH3 dimethylacetamide 108.85 CH(3,4) pyrrole 144.22 CH(2,5) furan

18.11 CH3 ethanol 40.06 CH3 dimethyl sulfoxide 111.06 CH(3,4) furan 149.76 CH(2,6) pyridine

19.63 CH3 propylene 42.13 CH2 dimethyl malonate 112.90 CH(3,5) BHA 150.52 C(2,6) BHA

20.91 CH3 acetic acid 43.16 CH2(2,6) cyclohexanone 116.38 CH2 propylene 153.46 C(1) BHT

21.10 CH3 allyl acetate 45.28 CH2 1,2-dichloroethane 118.95 CN acetonitrile 153.74 C(1) BHA

21.18 C H3CO ethyl acetate 47.43 CH2(2,5) pyrrolidine 119.39 CH C H2 allyl acetate 157.39 CO diallyl carbonate 21.34 CH3Ar BHT 48.45 CH2 triethylamine 119.61 CH(2,5) pyrrole 159.04 CO dimethyl carbonate 21.40 CH3 dimethylacetamide 50.67 CH3 methanol 120.15 CH C H2 diallyl carbonate 166.01 CH dimethylformamide 21.62 CH3 toluene 54.00 CH3 dimethyl malonate 122.93 CH(4,5) imidazole 170.88 CO2 dimethyl malonate

23.75 CH2(2,4) n-pentane 54.46 CH2 dichloromethane 124.08 CH2 ethylene 175.55 CO ethyl acetate

24.06 CH2(2,5) n-hexane 56.17 CH3 dimethyl carbonate 126.27 CH(3,5) pyridine 175.74 CO dimethylacetamide

25.21 CH3 2-propanol 57.55 CH3O BHA 126.28 (q) CF3 TFE-d3 signal 175.98 CO allyl acetate

25.73 CH2(3,4) pyrrolidine 59.40 CH3 diglyme 126.82 CH(4) toluene 177.96 CO acetic acid

26.00 CH2(4) cyclohexanone 59.52 CH3 1,2-dimethoxyethane 126.92 CO2 carbon dioxide 196.26 CS2 carbon disulfide 26.69 CH2(3,4) tetrahydrofuran 59.68 CH2 ethanol 127.11 CH(3,5) BHT 197.63 HCO benzaldehyde 28.34 CH2 cyclohexane 61.5 (qp) CD2 TFE-d3 signal 129.79 CH(3,5) toluene 214.98 CH3 acetone

28.56 CH2(3,5) cyclohexanone 62.70 CH2 ethyl acetate 129.84 CH benzene 218.31 CO ethyl methyl ketone

29.64 C H3CO ethyl methyl ketone 63.17 CH3 nitromethane 130.58 CH(2,6) toluene 221.30 CO cyclohexanone

30.80 (C H3)3C BHA 64.87 CH2 ethylene glycol 130.62 C(4) BHT

shift mult proton impurity shift mult proton impurity shift mult proton impurity

0.07 s CH3 hexamethyldisiloxane 2.19 s CH3 hexamethylbenzene 4.56 s H2 hydrogen

0.10 s CH3 silicone grease 2.21 s ArCH3 BHT 4.61 ddd CH2 diallyl carbonate

0.20 s CH4 methane 2.32 s CH3 toluene 4.85 s OH d BHA

0.85 s CH3 ethane 2.34 t CH2(2,6) cyclohexanone 4.87 s OH water

0.86–0.91 m CH3 pump oil 2.50 q, 7 C H2CH3 ethyl methyl ketone 4.91 dm, 10 CH2(1) propylene

0.86–0.93 m CH3 H grease8 2.58 q, 7 CH2 triethylamine 5.01 dm, 17 CH2(2) propylene

0.90 t, 7 CH3 n-hexane 2.64 d, 9.5 CH3 HMPA 5.21 ddt CHC H2(2) allyl acetate

0.90 t, 7 CH3 n-pentane 2.65 s CH3 dimethyl sulfoxide 5.25 ddt CHC H2(2) diallyl carbonate

0.91 t, 7.3 CH3 propane 2.80 m CH2(2,5) pyrrolidine 5.30 ddt CHC H2(1) allyl acetate

1.01 t, 7 CH2C H3 ethyl methyl ketone

2.86 s CH3 dimethylformamide 5.34 ddt CHC H2(1) diallyl carbonate

1.05 t, 7 CH3 triethylamine

2.92 s NCH3 dimethylacetamide 5.39 s CH2 ethylene

1.15 d, 6 CH3 2-propanol

2.99 s CH3 dimethylformamide 5.49 s CH2 dichloromethane

1.18 t, 7 CH3 diethyl ether 3.31 p CD2H CD3OD residual 5.82 m CH propylene

1.19 t, 7 CH3 ethanol 3.31 s NCH3 dimethylacetamide 5.94 ddt C H CH2 allyl acetate

1.24 t, 7 CH2C H3 ethyl acetate 3.34 s CH3 methanol 5.94 ddt C H CH2 diallyl carbonate

1.29 br s CH2 H grease8 3.35 s OCH3 diglyme 6.08 m CH(3,4) pyrrole

1.29 m CH2 n-hexane 3.35 s CH3 1,2-dimethoxyethane 6.40 dd CH(3,4) furan

1.29 m CH2 n-pentane 3.44 s CH2 dimethyl malonate 6.71 s ArH BHA

1.29 br s CH2 pump oil 3.49 q, 7 CH2 diethyl ether 6.72 m CH(2,5) pyrrole

1.34 sept, 7.3 CH2 propane 3.52 s CH2 1,2-dimethoxyethane 6.92 s ArH BHT

1.40 s CH3 tert-butyl alcohol 3.58 m CH2 diglyme 7.05 s CH(4,5) imidazole

1.40 s ArC(CH3)3 BHT 3.59 s CH2 ethylene glycol 7.16 m CH(2,4,6) toluene

1.41 s ArC(CH3)3 BHA 3.60 q, 7 CH2 ethanol 7.16 m CH(3,5) toluene

1.45 s CH2 cyclohexane 3.61 m CH2 diglyme 7.33 s CH benzene

1.70 dt, 6.4, 1.5 CH3 propylene 3.64 s CH2 18-crown-6 7.44 m CH(3,5) pyridine

1.72 m CH2(3,4) pyrrolidine 3.66 s CH2 1,4-dioxane 7.49 dd CH(2,5) furan

1.74–1.76 m CH2(4) cyclohexanone 3.71 m CH2(2,5) tetrahydrofuran 7.56–7.60 m CH(3,5) benzaldehyde

1.85–1.87 m CH2(3,5) cyclohexanone 3.72 s ArOCH3 BHA 7.66–7.70 m CH(4) benzaldehyde

1.87 m CH2(3,4) tetrahydrofuran 3.72 s CH3 dimethyl malonate 7.67 s CH(2) imidazole

1.99 s CH3 acetic acid 3.74 s CH3 dimethyl carbonate 7.85 m CH(4) pyridine

2.01 s CH3CO ethyl acetate

3.78 s CH2 1,2-dichloroethane 7.90 s CH chloroform

2.03 s CH3 acetonitrile

3.92 sept, 6 CH 2-propanol 7.90–7.93 m CH(2,6) benzaldehyde

2.05 s CH3 allyl acetate 4.09 q, 7 C H2CH3 ethyl acetate 7.97 s CH dimethylformamide

2.07 s CH3CO dimethylacetamide 4.34 s CH3 nitromethane 8.53 m CH(2,6) pyridine

2.12 s CH3CO ethyl methyl ketone 4.56 ddd CH2 allyl acetate 10.00 s HCO benzaldehyde

2.15 s CH3 acetone

Table S24. CD3OD (13C{1H} NMR data by chemical shift in ppm)

shift carbon impurity shift carbon impurity shift carbon impurity shift carbon impurity

–4.90 CH4 methane 30.82 (C H3)3C BHA 64.71 CH 2-propanol 130.12 CH(3,5) benzaldehyde

0.85 CH3 acetonitrile 30.91 (C H3)3C tert-butyl alcohol 66.14 CH2 allyl acetate 130.64 CH(2,6) benzaldehyde

1.99 CH3 hexamethyldisiloxane 31.15 (C H3)3C BHT 66.88 CH2 diethyl ether 13

2.53 C hexamethylbenzene

2.10 CH3 silicone grease 31.35 CH2 pump oil 68.11 CH2 1,4-dioxane 13

3.25 C HCH2 diallyl carbonate 6.98 CH3 ethane 31.61 CH3 dimethylformamide 68.83 CH2(2,5) tetrahydrofuran 133.71 C HCH2 allyl acetate 8.09 CH2C H3 ethyl methyl ketone 32.73 CH2(3,4) n-hexane 69.35 CH2 diallyl carbonate 13

4.61 CH propylene 11.09 CH3 triethylamine 3

5.30 CH2(3) n-pentane 69.40 (CH3)3C tert-butyl alcohol 135.60 CH (4) benzaldehyde 14.39 CH3 n-pentane 35.36 (CH3)3C BHT 71.33 CH2 diglyme 13

6.31 CH(2) imidazole 14.45 CH3 n-hexane 35.50 NCH3 dimethylacetamide 71.47 CH2 18-crown-6 13

7.96 C(1) benzaldehyde

14.49 CH3 ethyl acetate 35.83 (CH3)3C BHA 72.72 CH2 1,2-dimethoxyethane 138.35 CH(4) pyridine

15.46 CH3 diethyl ether 36.89 CH3 dimethylformamide 72.92 CH2 diglyme 138.85 C(1) toluene

16.80 CH3 propane 37.00 (d) CH3 HMPA i 79.44 CH chloroform 139.09 C(2,6) BHT

16.90 CH3 hexamethylbenzene 37.34 C H2CH3 ethyl methyl ketone 97.21 CCl4 carbon tetrachloride 141.36 C(4) BHA

17.19 CH2 propane 38.43 NCH3 dimethylacetamide 108.11 CH(3,4) pyrrole 143.68 CH(2,5) furan

18.40 CH3 ethanol 40.45 CH3 dimethyl sulfoxide 110.33 CH(3,4) furan 149.04 C(2,6) BHA

19.50 CH3 propylene 41.60 CH2 dimethyl malonate 111.30 CH(3,5) BHA 150.07 CH(2,6) pyridine

20.56 CH3 acetic acid 42.61 CH2(2,6) cyclohexanone 116.04 CH2 propylene 152.85 C(1) BHT

20.71 CH3 allyl acetate 45.11 CH2 1,2-dichloroethane 118.06 CN acetonitrile 154.34 C(1) BHA

20.88 C H3CO ethyl acetate 46.96 CH2 triethylamine 118.22 CH C H2 allyl acetate 156.28 CO diallyl carbonate

21.32 CH3 dimethylacetamide 47.23 CH2(2,5) pyrrolidine 118.28 CH(2,5) pyrrole 157.91 CO dimethyl carbonate 21.38 CH3Ar BHT 49.00 (sept) CD3 CD3OD signal 118.74 CH C H2 diallyl carbonate 164.73 CH dimethylformamide 21.50 CH3 toluene 49.86 CH3 methanol 122.60 CH(4,5) imidazole 168.70 CO2 dimethyl malonate 23.38 CH2(2,4) n-pentane 52.83 CH3 dimethyl malonate 123.46 CH2 ethylene 172.41 CO allyl acetate 23.68 CH2(2,5) n-hexane 54.78 CH2 dichloromethane 125.53 CH(3,5) pyridine 172.89 CO ethyl acetate 25.27 CH3 2-propanol 55.25 CH3 dimethyl carbonate 126.11 CH(3,5) BHT 173.32 CO dimethylacetamide

25.86 CH2(4) cyclohexanone 55.96 CH3O BHA 126.29 CH(4) toluene 175.11 CO acetic acid

26.29 CH2(3,4) pyrrolidine 58.26 CH2 ethanol 126.31 CO2 carbon dioxide 193.82 CS2 carbon disulfide

26.48 CH2(3,4) tetrahydrofuran 59.06 CH3 diglyme 129.20 CH(3,5) toluene 194.11 HCO benzaldehyde

27.96 CH2 cyclohexane 59.06 CH3 1,2-dimethoxyethane 129.34 CH benzene 209.67 CO acetone

28.16 CH2(3,5) cyclohexanone 61.50 CH2 ethyl acetate 129.49 C(4) BHT 212.16 CO ethyl methyl ketone

29.39 C H3CO ethyl methyl ketone 63.08 CH3 nitromethane 129.91 CH(2,6) toluene 214.69 CO cyclohexanone

30.67 CH3 acetone 64.30 CH2 ethylene glycol

Table S25. D2O (1H NMR data by chemical shift in ppm) shift mult proton impurity shift mult proton impurity shift mult proton impurity

0.18 s CH4 methane 2.71 s CH3 dimethyl sulfoxide 4.69 ddd CH2 diallyl carbonate

0.28 s CH3 hexamethyldisiloxane 2.85 s CH3 dimethylformamide 4.79 s HOD D2O residual

0.82 s CH3 ethane 2.90 s NCH3 dimethylacetamide 4.95 dm, 10 CH2(1) propylene

0.88 t, 7.3 CH3 propane 3.01 s CH3 dimethylformamide 5.06 dm, 17 CH2(2) propylene

0.99 t, 7 CH3 triethylamine 3.06 s NCH3 dimethylacetamide 5.30 ddt CHC H2(2) allyl acetate

1.17 t, 7 CH3 diethyl ether 3.07 m CH2(2,5) pyrrolidine 5.32 ddt CHC H2(2) diallyl carbonate

1.17 t, 7 CH3 ethanol 3.18 q, 7 C H2CH3 ethyl methyl ketone 5.37 ddt CHC H2(1) allyl acetate

1.17 d, 6 CH3 2-propanol 3.34 s CH3 methanol 5.40 ddt CHC H2(1) diallyl carbonate

1.24 s CH3 tert-butyl alcohol 3.37 s OCH3 diglyme 5.44 s CH2 ethylene

1.24 t, 7 CH2C H3 ethyl acetate 3.37 s CH3 1,2-dimethoxyethane 5.90 m CH propylene

1.26 t, 7 CH2C H3 ethyl methyl ketone 3.56 q, 7 CH2 diethyl ether 5.99 ddt C H CH2 allyl acetate

1.30 sept, 7.3 CH2 propane 3.60 s CH2 1,2-dimethoxyethane 5.99 ddt C H CH2 diallyl carbonate

1.70 dt, 6.4, 1.5 CH3 propylene 3.60 s CH2 dimethyl malonate 6.26 m CH(3,4) pyrrole

1.70–1.75 m CH2(4) cyclohexanone 3.61 m CH2 diglyme 6.51 dd CH(3,4) furan

1.85–1.90 m CH2(3,5) cyclohexanone 3.65 q, 7 CH2 ethanol 6.93 m CH(2,5) pyrrole

1.87 m CH2(3,4) pyrrolidine 3.65 s CH2 ethylene glycol 7.14 s CH(4,5) imidazole

1.88 m CH2(3,4) tetrahydrofuran 3.67 m CH2 diglyme 7.45 m CH(3,5) pyridine

2.06 s CH3 acetonitrile

3.69 s CH3 dimethyl carbonate 7.57 dd CH(2,5) furan

2.07 s CH3CO ethyl acetate

3.74 m CH2(2,5) tetrahydrofuran 7.57–7.66 m CH(3,5) benzaldehyde

2.08 s CH3 acetic acid

3.75 s CH2 1,4-dioxane 7.76–7.80 m CH(4) benzaldehyde

2.08 s CH3CO dimethylacetamide

3.78 s CH3 dimethyl malonate 7.78 s CH(2) imidazole

2.13 s CH3 allyl acetate

3.80 s CH2 18-crown-6 7.87 m CH(4) pyridine

2.19 s CH3CO ethyl methyl ketone 4.02 sept, 6 CH 2-propanol 7.92 s CH dimethylformamide

2.22 s CH3 acetone 4.14 q, 7 C H2CH3 ethyl acetate 7.97–7.99 m CH(2,6) benzaldehyde

2.40 t CH2(2,6) cyclohexanone 4.40 s CH3 nitromethane 8.52 m CH(2,6) pyridine

2.57 q, 7 CH2 triethylamine 4.62 ddd CH2 allyl acetate 9.96 s HCO benzaldehyde

2.61 d, 9.5 CH3 HMPA

Table S26. D2O (13C{1H} NMR data by chemical shift in ppm)

shift carbon impurity shift carbon impurity shift carbon impurity shift carbon impurity

1.47 CH3 acetonitrile 36.46 (d) CH3 HMPA i 67.19 CH2 1,4-dioxane 13

2.76 C HCH2 diallyl carbonate

2.31 CH3 hexamethyldisiloxane 37.27 C H2CH3 ethyl methyl ketone 68.68 CH2(2,5) tetrahydrofuran 134.70 CH (4) benzaldehyde 7.87 CH2C H3 ethyl methyl ketone 37.54 CH3 dimethylformamide 68.81 CH2 diallyl carbonate 136.11 C(1) benzaldehyde 9.07 CH3 triethylamine 38.76 NCH3 dimethylacetamide 70.05 CH2 diglyme 136.65 CH(2) imidazole

13.92 CH3 ethyl acetate 39.39 CH3 dimethyl sulfoxide 70.14 CH2 18-crown-6 138.27 CH(4) pyridine

14.77 CH3 diethyl ether 42.02 CH2(2,6) cyclohexanone 70.36 (CH3)3C tert-butyl alcohol 143.57 CH(2,5) furan

17.47 CH3 ethanol 42.13 CH2 dimethyl malonate 71.49 CH2 1,2-dimethoxyethane 149.18 CH(2,6) pyridine 21.00 CH3 allyl acetate 46.83 CH2(2,5) pyrrolidine 71.63 CH2 diglyme 157.78 CO diallyl carbonate 21.03 CH3 acetic acid 47.19 CH2 triethylamine 96.73 CCl4 carbon tetrachloride 163.96 CO dimethyl carbonate 21.09 CH3 dimethylacetamide 49.5012 CH3 methanol 107.83 CH(3,4) pyrrole 165.53 CH dimethylformamide 21.15 C H3CO ethyl acetate 53.65 CH3 dimethyl malonate 110.23 CH(3,4) furan 170.12 CO2 dimethyl malonate 24.38 CH3 2-propanol 55.81 CH3 dimethyl carbonate 118.75 CH C H2 diallyl carbonate 174.57 CO dimethylacetamide

24.77 CH2(4) cyclohexanone 58.05 CH2 ethanol 119.03 CH C H2 allyl acetate 174.78 CO allyl acetate

25.67 CH2(3,4) tetrahydrofuran 58.67 CH3 diglyme 119.06 CH(2,5) pyrrole 175.26 CO ethyl acetate 25.86 CH2(3,4) pyrrolidine 58.67 CH3 1,2-dimethoxyethane 119.68 CN acetonitrile 177.21 CO acetic acid 27.50 CH2(3,5) cyclohexanone 62.32 CH2 ethyl acetate 122.43 CH(4,5) imidazole 191.67 HCO benzaldehyde

29.49 C H3CO ethyl methyl ketone 63.17 CH2 ethylene glycol 125.12 CH(3,5) pyridine 197.25 CS2 carbon disulfide

30.29 (C H3)3C tert-butyl alcohol 63.22 CH3 nitromethane 129.48 CH(3,5) benzaldehyde 215.94 CO acetone 30.89 CH3 acetone 64.88 CH 2-propanol 130.09 CH(2,6) benzaldehyde 218.43 CO ethyl methyl ketone 32.03 CH3 dimethylformamide 66.42 CH2 diethyl ether 132.48 C HCH2 allyl acetate 221.22 CO cyclohexanone 35.03 NCH3 dimethylacetamide 66.52 CH2 allyl acetate

References

(1) Gottlieb, H. E.; Kotlyar, V.; Nudelman, A. J. Org. Chem.1997, 62, 7512.

(2) Except for the compounds in solutions 8–10, as well as the gas samples,

hexamethylbenzene, and the corrected values (vide supra), all data for the solvents CDCl3, C6D6, (CD3)2CO, (CD3)2SO, CD3CN, CD3OD, and D2O were previously reported in ref 1.

(3) A signal for HDO is also observed in (CD3)2SO (3.30 ppm) and (CD3)2CO (2.81

ppm), often seen as a 1:1:1 triplet (2J H,D = 1 Hz).

(4) Splitting pattern observed as a triplet of a non-first-order ABX pattern.

(5) Not all OH signals were observable.

(6) In some solvents, the coupling interaction between the CH2 and the OH protons may

be observed (J = 5 Hz).

(7) In CD3CN, the OH proton was seen as a multiplet at 2.69 ppm, as well as extra

coupling to the CH2 peak.

(8) Apiezon-brand H grease.

(9) In some solvents, the coupling interaction between the CH3 and the OH protons may

be observed (J = 5.5 Hz).

(10) Pyrrolidine was observed to react with the solvent (CD3)2CO.

(11) Phosphorus coupling was observed (2J PC = 3 Hz).

(12) Internal reference; see Experimental Section in text.

(完整版)红外各基团特征峰对照表

红外各基团特征峰对照表 一、红外吸收光谱中的重要区段： 1) O-H、N-H伸缩振动区(3750~3000 cm-1) 2) 不饱和碳上的C-H伸缩振动区(3300~3000 cm-1) 不饱和碳(三键和双键、苯环)上的C-H的伸缩振动在3300~3000 cm-1区域中出现不同的吸收峰。 3) C-H伸缩振动区(3000~2700 cm-1) 饱和碳上的C-H伸缩振动(包括醛基上的C-H) 4) 叁键和累积双键区(2400~2100 cm-1) 波数在2400~2100 cm-1区域内的谱带较少。 5) 羰基的伸缩振动区(1900~1650 cm-1) 羰基的吸收最常见出现的区域为1755~1670 cm-1。由于羰基的电偶极矩较大，一般吸收都很强烈，常成为IR光谱中的第一强峰。 6) 双键伸缩振动区(1690~1500 cm-1) 该区主要包括C=C，C=N，N=N，N=O等的伸缩振动以及苯环的骨架振动(σC=C)。 7) X-H面内弯曲振动及X-Y伸缩振动区(1475~1000 cm-1) 这个区域主要包括C-H面内弯曲振动, C-O、C-X(卤素)等伸缩振动, 以及C-C单键骨架振动等。该区域是指纹区的一部分。 8) C-H面外弯曲振动区（1000~650 cm-1） 烯烃、芳烃的C-H面外弯曲振动（σC-H）在1000~650 cm-1区。苯环邻二取代：770~735cm-1；苯环间二取代：710~690、810~750cm-1；苯环对二取代：830~810cm-1 具体对照表如下所示： （其中：VS：很强；W：弱；S：强；VW：很弱；m：中等；w：宽） 1、O-H、

红外出峰位置

因为官能团特征吸收是解析谱图的基础。 对一张已经拿到手的红外谱图： （1）首先依据谱图推出化合物碳架类型：根据分子式计算不饱和度，公式： 不饱和度＝F+1+(T-O)/2 其中： F：化合价为4价的原子个数（主要是C原子）， T：化合价为3价的原子个数（主要是N原子）， O：化合价为1价的原子个数（主要是H原子）， 我以前本科上谱学导论时老师给过公式，但字母都被我改了:F、T、O 分别是英文4,3，1的首字母，这样我记起来就不会忘了：）。 举个例子：比如苯：C6H6，不饱和度＝6+1+（0-6）/2＝4，3个双键加一个环，正好 为4个不饱和度； （2）分析3300~2800cm^-1区域C-H伸缩振动吸收；以3000 cm^-1为界:高于3000cm^-1为不 饱和碳C-H伸缩振动吸收，有可能为烯, 炔, 芳香化合物,而低于3000cm^-1一般为饱 和C-H伸缩振动吸收； （3）若在稍高于3000cm^-1有吸收,则应在 2250~1450cm^-1频区，分析不饱和碳碳键的伸 缩振动吸收特征峰，其中： 炔 2200~2100 cm^-1

烯 1680~1640 cm^-1 芳环 1600,1580,1500,1450 cm^-1 若已确定为烯或芳香化合物，则应进一步解析指纹区，即 1000~650cm^-1的频区 ,以 确定取代基个数和位置（顺反，邻、间、对）； （4）碳骨架类型确定后,再依据其他官能团,如 C=O, O-H, C-N 等特征吸收来判定化合物 的官能团； （5）解析时应注意把描述各官能团的相关峰联系起来，以准确判定官能团的存在,如2820 ，2720和1750~1700cm^-1的三个峰，说明醛基的存在。 解析的过程基本就是这样吧，至于制样以及红外谱图软件的使用，一般的有机实验书上都 有比较详细的介绍的，这里就不唠叨了。 这是一个令人头疼的问题，有事没事就记一两个吧： 1.烷烃：C-H伸缩振动（3000-2850cm^-1） C-H弯曲振动（1465-1340cm^-1） 一般饱和烃C-H伸缩均在3000cm^-1以下，接近3000cm^-1的频率吸收。 2.烯烃：烯烃C-H伸缩（3100~3010cm^-1） C=C伸缩(1675~1640 cm^-1) 烯烃C-H面外弯曲振动（1000~675cm^1）。

主要基团的红外特征吸收峰

主要基团的红外特征 吸收峰

主要基团的红外特征吸收峰 基团振动类型波数（cm-1）波长 （μm）强 度 备注 一、烷烃类CH伸 CH伸（反 称） CH伸（对 称） CH弯（面内） C-C伸3000～2843 2972～2880 2882～2843 1490～1350 1250～1140 3.33～ 3.52 3.37～ 3.47 3.49～ 3.52 6.71～ 7.41 8.00～ 8.77 中、 强 中、 强 中、 强 分为反称与对 称 二、烯烃类CH伸 C＝C伸 CH弯（面内） CH弯（面外） 单取代 双取代 顺式 反式3100～3000 1695～1630 1430～1290 1010～650 995～985 910～905 730～650 980～965 3.23～ 3.33 5.90～ 6.13 7.00～ 7.75 9.90～ 15.4 10.05～10.15 10.99～11.05 13.70～15.38 10.20～10.36 中、 弱 中 强 强 强 强 强 C＝C＝C为 2000～1925 cm-1 三、炔烃类CH伸 C≡C 伸 CH弯（面内） CH弯（面外） ～3300 2270～2100 1260～1245 645～615 ～3.03 4.41～ 4.76 7.94～ 8.03 15.50～16.25 中 中 强 四、取代苯类CH伸 泛频峰 骨架振动 （C C= ν） CH弯（面内） CH弯（面外）3100～3000 2000～1667 1600±20 1500±25 1580±10 1450±20 1250～1000 910～665 3.23～ 3.33 5.00～ 6.00 6.25±0.08 6.67±0.10 6.33±0.04 6.90±0.10 8.00～ 10.00 10.99～15.03 变 弱 强 三、四个峰， 特征 确定取代位置

红外--各类有机物的红外吸收峰

各类有机化合物红外吸收光谱 σ伸缩振动，δ面内弯曲振动，γ面外弯曲振动 一、烷烃 饱和烷烃IR光谱主要由C-H键的骨架振动所引起，而其中以C-H键的伸缩振动最为有用。在确定分子结构时，也常借助于C-H键的变形振动和C-C 键骨架振动吸收。烷烃有下列四种振动吸收。 1、σC-H在2975—2845 cm-1范围，包括甲基、亚甲基和次甲基的对称与不对称伸缩振动 2、δC-H在1460 cm-1和1380 cm-1处有特征吸收，前者归因于甲基及亚甲基C-H的σas，后者归因于甲基C-H的σs。1380 cm-1峰对结构敏感，对于识别甲基很有用。共存基团的电负性对1380 cm-1峰位置有影响，相邻基团电负性愈强，愈移向高波数区，例如，在CH3F中此峰移至1475 cm-1。 异丙基1380 cm-1裂分为两个强度几乎相等的两个峰1385 cm-1、1375 cm-1叔丁基1380 cm-1裂分1395 cm-1、1370cm-1两个峰，后者强度差不多是前者的两倍，在1250 cm-1、1200 cm-1附近出现两个中等强度的骨架振动。 3、σC-C在1250—800 cm-1范围内，因特征性不强，用处不大。 4、γC-H分子中具有—（CH2）n—链节，n大于或等于4时，在722 cm-1有一个弱吸收峰，随着CH2个数的减少，吸收峰向高波数方向位移，由此可推断分子链的长短。 二、烯烃 烯烃中的特征峰由C=C-H键的伸缩振动以及C=C-H键的变形振动所引起。烯烃分子主要有三种特征吸收。 1、σC=C-H 烯烃双键上的C-H键伸缩振动波数在3000 cm-1以上，末端双键氢 C=CH2 在3075—3090 cm-1有强峰最易识别。 2、σC=C 吸收峰的位置在1670—1620 cm-1。随着取代基的不同，σC=C吸收峰的位置有所不同，强度也发生变化。 3、δC=C-H烯烃双键上的C-H键面内弯曲振动在1500—1000 cm-1，对结构不敏感，用途较少；而面外摇摆振动吸收最有用，在1000—700 cm-1范围内，该振动对结构敏感，其吸收峰特征性明显，强度也较大，易于识别，可借以判

红外光谱特征吸收峰

物质的红外光谱是其分子结构的反映，谱图中的吸收峰与分子中各基团的振动形式相对应。多原子分子的红外光谱与其结构的关系，一般是通过实验手段得到。这就是通过比较大量已知化合物的红外光谱，从中总结出各种基团的吸收规律。实验表明，组成分子的各种基团，如O-H、N-H、C-H、C=C、C=OH和C C 等，都有自己的特定的红外吸收区域，分子的其它部分对其吸收位置影响较小。通常把这种能代表及存在、并有较高强度的吸收谱带称为基团频率，其所在的位置一般又称为特征吸收峰。 一、基团频率区和指纹区 （一）基团频率区 中红外光谱区可分成4000 cm-1 ~1300 cm-1和1800cm-1 （1300 cm-1 ）~ 600 cm-1两个区域。最有分析价值的基团频率在4000 cm-1 ~ 1300 cm-1 之 间，这一区域称为基团频率区、官能团区或特征区。区内的峰是由伸缩振动产生的吸收带，比较稀疏，容易辨认，常用于鉴定官能团。在1800 cm-1 （1300 cm-1 ）~600 cm-1 区域内，除单键的伸缩振动外，还有因变形振动产生的谱带。这种振动与整个分子的结构有关。当分子结构稍有不同时，该区的吸收就有细微的差异，并显示出分子特征。这种情况就像人的指纹一样，因此称为指纹区。指纹区对于指认结构类似的化合物很有帮助，而且可以作为化合物存在某种基团的旁证。基团频率区可分为三个区域： （1）4000 ~2500 cm-1 X-H伸缩振动区，X可以是O、H、C或S等原子。 O-H基的伸缩振动出现在3650 ~3200 cm-1 范围内，它可以作为判断有无醇类、酚类和有机酸类的重要依据。当醇和酚溶于非极性溶剂（如CCl4），浓度于0.01mol. dm-3时，在3650 ~3580 cm-1处出现游离O-H基的伸缩振动吸收，峰形尖锐，且没有其它吸收峰干扰，易于识别。当试样浓度增加时，羟基化合物产生缔合现象，O-H基的伸缩振动吸收峰向低波数方向位移，在3400 ~3200 cm-1 出现一个宽而强的吸收峰。胺和酰胺的N-H伸缩振动也出现在3500~3100 cm-1 因此，可能会对O-H伸缩振动有干扰C-H的伸缩振动可分为饱和和不饱和的两种。饱和的C-H伸缩振动出现在3000 cm-1以下，约3000~2800 cm-1 ，取代基对它们影响很小。如-CH3 基的伸缩吸收出现在2960 cm-1和2876 cm-1附近；-

主要基团的红外特征吸收峰

主要基团的红外特征吸收峰 基团振动类型波数（cm-1）波长（μm）强 度 备注 一、烷烃类CH伸 CH伸（反称） CH伸（对称） CH弯（面内） C-C伸3000～2843 2972～2880 2882～2843 1490～1350 1250～1140 ～ ～ ～ ～ ～ 中、 强 中、 强 中、 强 分为反称与对 称 二、烯烃类CH伸 C＝C伸 CH弯（面内） CH弯（面外） 单取代 双取代 顺式 反式3100～3000 1695～1630 1430～1290 1010～650 995～985 910～905 730～650 980～965 ～ ～ ～ ～ ～ ～ ～ ～ 中、 弱 中 强 强 强 强 强 C＝C＝C为 2000～1925 cm-1 三、炔烃类CH伸 C≡C 伸 CH弯（面内） CH弯（面外） ～3300 2270～2100 1260～1245 645～615 ～ ～ ～ ～ 中 中 强 四、取代苯类CH伸 泛频峰 骨架振动（ C C= ν） CH弯（面内） CH弯（面外）3100～3000 2000～1667 1600±20 1500±25 1580±10 1450±20 1250～1000 910～665 ～ ～ ± ± ± ± ～ ～ 变 弱 强 三、四个峰，特 征 确定取代位置

单取代 邻双取代 间双取代 对双取代 1,2,3,三取代 1,3,5,三取代1,2,4,三取代 ﹡1,2,3,4四取代 ﹡1,2,4,5四取代 ﹡1,2,3,5四取代 ﹡五取代CH弯（面外） CH弯（面外） CH弯（面外） CH弯（面外） CH弯（面外） CH弯（面外） CH弯（面外） CH弯（面外） CH弯（面外） CH弯（面外） CH弯（面外） 770～730 770～730 810～750 900～860 860～800 810～750 874～835 885～860 860～800 860～800 860～800 865～810 ～860 ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ 极强 极强 极强 中 极强 强 强 中 强 强 强 强 强 五个相邻氢 四个相邻氢 三个相邻氢 一个氢（次要） 二个相邻氢 三个相邻氢与 间双易混 一个氢 一个氢 二个相邻氢 二个相邻氢 一个氢 一个氢 一个氢 五、醇类、酚类OH伸 OH弯（面内） C—O伸 O—H弯（面外）3700～3200 1410～1260 1260～1000 750～650 ～ ～ ～ ～ 变 弱 强 强液态有此峰 OH伸缩频率 游离OH 分子间氢键 分子内氢键 OH弯或C—O 伸 伯醇（饱和） 仲醇（饱和） 叔醇（饱和） 酚类（ФOH）OH伸 OH伸 OH伸（单桥） OH弯（面内） C—O伸 OH弯（面内） C—O伸 OH弯（面内） C—O伸 OH弯（面内） Ф—O伸 3650～3590 3500～3300 3570～3450 ～1400 1250～1000 ～1400 1125～1000 ～1400 1210～1100 1390～1330 1260～1180 ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ 强 强 强 强 强 强 强 强 强 中 强 锐峰 钝峰（稀释向低 频移动*） 钝峰（稀释无影 响） 六、醚类C—O—C伸1270～1010～强或标C—O伸

最新总结-红外光谱频率与官能团特征吸收峰分析

红外波谱 分子被激发后，分子中各个原子或基团（化学键）都会产生特征的振动，从而在特点的位置会出现吸收。相同类型的化学键的振动都是非常接近的，总是在某一范围内出现。 整个红外谱图可以分为两个区，4000~1350区是由伸缩振动所产生的吸收带，光谱比较简单但具有强烈的特征性，1350~650处指纹区。

通常，4000~2500 处高波数端，有与折合质量小的氢原子相结合的官能团O-H, N-H, C-H, S-H 键的伸缩振动吸收带，在2500-1900 波数范围内常常出现力常数大的三件、累积双键如：- y, - gN, -C=C=C-,-C=C=O,-N=C=O等的伸缩振动吸收带。在1900以下的波数端有 -C=C-, -C=O, -C=N-, -C=O 等的伸缩振动以及芳环的骨架振动。 1350~650指纹区处，有C-O, C-X的伸缩振动以及C-C的骨架振动，还有力常数较小的弯曲振动产生的吸收峰, 因此光谱非常复杂。该区域各峰的吸收位置受整体分子结构的影响较大, 分子结构稍有不同, 吸收也会有细微的差别, 所以指纹区对于用已知物来鉴别未知物十分重要。

有机化学有机化合物红外吸收光谱 C伸缩振动，S面内弯曲振动，丫面外弯曲振动 一、烷烃 饱和烷烃IR光谱主要由C-H键的骨架振动所引起，而其中以C-H键的伸缩振动最为有用。在确定分子结构时，也常借助于C-H键的变形振动和C-C键骨架振动吸收。烷烃有下列四种振动吸收。 1、（T C-H在2975—2845 cm-1范围，包括甲基、亚甲基和次甲基的对称与不对称 伸缩振动 2、S C-H在1460 cm-1和1380 cm-1处有特征吸收，前者归因于甲基及亚甲基C-H 的（T as,后者归因于甲基C-H的（T s。1380 cm-1峰对结构敏感，对于识别甲基很有用。共存基团的电负性对1380 cm-1峰位置有影响，相邻基团电负性愈强，愈移向高波数区，例如，在CH3F中此峰移至1475 cm-1。 异丙基1380 cm-1裂分为两个强度几乎相等的两个峰1385 cm-1、1375 cm-1 1 1 1 叔丁基1380 cm 裂分1395 cm 、1370cm两个峰，后者强度差不多是前者 的两倍，在1250 cm-1、1200 cm-1附近出现两个中等强度的骨架振动。 3、（T C-C在1250—800 cm-1范围内，因特征性不强，用处不大。 4、丫C-H分子中具有一（CH2）n—链节，n大于或等于4时，在722 cm-1有一个弱吸收峰，随着CH2个数的减少，吸收峰向高波数方向位移，由此可推断分子链的长短。 二、烯烃 烯烃中的特征峰由C=C-H键的伸缩振动以及C=C-H键的变形振动所引起。烯烃分子主要有三种特征吸收。 1、（T C=C-H烯烃双键上的C-H键伸缩振动波数在3000 cm-1以上，末端双键氢 \ 1 zC=CH 2 在3075—3090 cm 有强峰最易识别。 2、（T C=C吸收峰的位置在1670—1620 cm-1。随着取代基的不同，c C=C吸收峰的位置有所不同，强度也发生变化。 3、S C=C-H烯烃双键上的C-H键面内弯曲振动在1500—1000 cm-1,对结构不敏感，用途较少；而面外摇摆振动吸收最有用，在1000- 700 cm-1范围内，该振动对结构敏感，其吸收

红外吸收光谱特征峰特别整理版

表15.1 典型有机化合物的重要基团频率（/cm-1） asCH asCH sCH sCH asCH CH sCH CH CH CH C=C CH CH CH C=C CH CH C≡C CH CH C=C CH OH OH

CO OH OH C=C OH CO CO C=O CH C=O OH C=O OH CO CO C=O C=O 泛频C=O C=O COC NH2NH CN CN NH NH CN CN asNH C=O CN

sNH NH NH2 NH CN+NH C=O NH+CN C=O C=O C≡N NO2NO2 CN NO2NO2 CN 吡啶类 CH C=C及C=N CH CH 嘧啶类 CH C=C及C=N CH CH *表中vs,s,m,w,vw用于定性地表示吸收强度很强，强，中，弱，很弱。

中红外光谱区一般划分为官能团区和指纹区两个区域，而每个区域又可以分为若干个波段。 官能团区 官能团区（或称基团频率区）波数范围为4000～1300cm -1 ， 又可以分为四个波段。 ★ 4000～2500cm -1 为含氢基团x —H （x 为O 、N 、C ）的伸缩振动区，因为折合质量小，所以波数高，主要有以下五种基团吸收 ● 醇、酚中O —H ：3700～3200cm -1 ， 无缔合的O —H 在高 一侧，峰形尖锐， 强度为ｓ 缔合的O —H 在低 一侧， 峰形宽钝， 强度为ｓ ● 羧基中O —H ： 3600～2500 cm -1 ， 无缔合的O —H 在高 一侧，峰形尖锐， 强度为ｓ 缔合可延伸至2500 cm -1 ，峰非常宽钝， 强度为ｓ ● N —H ： 3500～3300 cm -1 ， 伯胺有两个H ，有对称和非对称两个峰， 强度为ｓ—ｍ 叔胺无H ，故无吸收峰 ● C —H ： ＜3000 cm -1 为饱和C ： ～2960 cm -1 ( ),～2870 cm -1 ( ) 强度为ｍ-ｓ ～2925 cm -1 ( ),～2850 cm -1 ( ) 强度为ｍ-ｓ ～2890 cm -1 强度为ｗ ＞3000 cm -1 为不饱和 C ： (及苯环上C-H)3090～3030 cm -1 强度为ｍ ～3300 cm -1 强度为ｍ ● 醛基中C —H ：～2820及～2720两个峰 强度为ｍ－ｓ

各类物质的红外吸收峰

第四节各类有机化合物红外吸收光谱 σ伸缩振动，δ面内弯曲振动，γ面外弯曲振动 一、烷烃 饱和烷烃IR光谱主要由C-H键的骨架振动所引起，而其中以C-H键的伸缩振动最为有用。在确定分子结构时，也常借助于C-H键的变形振动和C-C 键骨架振动吸收。烷烃有下列四种振动吸收。 1、σC-H在2975—2845cm-1范围，包括甲基、亚甲基和次甲基的对称与不对称伸缩振动 2、δC-H在1460cm-1和1380cm-1处有特征吸收，前者归因于甲基及亚甲基C-H的σas，后者归因于甲基C-H的σs。1380cm-1峰对结构敏感，对于识别甲基很有用。共存基团的电负性对1380cm-1峰位置有影响，相邻基团电负性愈强，愈移向高波数区，例如，在CH3F中此峰移至1475cm-1。 异丙基1380cm-1裂分为两个强度几乎相等的两个峰1385cm-1、1375cm-1叔丁基1380cm-1裂分1395cm-1、1370cm-1两个峰，后者强度差不多是前者的两倍，在1250cm-1、1200cm-1附近出现两个中等强度的骨架振动。 3、σC-C在1250—800cm-1范围内，因特征性不强，用处不大。 4、γC-H分子中具有—（CH2）n—链节，n大于或等于4时，在722cm-1有一个弱吸收峰，随着CH2个数的减少，吸收峰向高波数方向位移，由此可推断分子链的长短。 二、烯烃 烯烃中的特征峰由C=C-H键的伸缩振动以及C=C-H键的变形振动所引起。烯烃分子主要有三种特征吸收。 1、σC=C-H烯烃双键上的C-H键伸缩振动波数在3000cm-1以上，末端双键氢 C=CH2 在3075—3090cm-1有强峰最易识别。 2、σC=C吸收峰的位置在1670—1620cm-1。随着取代基的不同，σC=C吸收峰的位置有所不同，强度也发生变化。 3、δC=C-H烯烃双键上的C-H键面内弯曲振动在1500—1000cm-1，对结构不敏感，用途较少；而面外摇摆振动吸收最有用，在1000—700cm-1范围内，该振动对结构敏感，其吸收峰特征性明显，强度也较大，易于识别，可借以判

红外吸收光谱特征峰,史上最全

表典型有机化合物的重要基团频率（/cm-1）

* 表中vs,s,m,w,vw用于定性地表示吸收强度很强，强，中，弱，很弱。 中红外光谱区一般划分为官能团区和指纹区两个区域，而每个区域又可以分为若干个波段。

官能团区 官能团区（或称基团频率区）波数范围为4000～1300cm-1，又可以分为四个波段。 ★4000～2500cm-1为含氢基团x—H（x为O、N、C）的伸缩振动区，因为折合质量小，所以波数高，主要有以下五种基团吸收 ●醇、酚中O—H：3700～ 无缔合的O—H在高一侧，峰形尖锐，强度为ｓ3200cm-1， 缔合的O—H在低一侧，峰形宽钝，强度为ｓ ●羧基中O—H：3600～2500 无缔合的O—H在高一侧，峰形尖锐，强度为ｓcm-1， 缔合可延伸至2500 cm-1，峰非常宽钝，强度为ｓ ●N—H： 3500～3300 伯胺有两个H，有对称和非对称两个峰，强度为ｓ—ｍcm-1， 叔胺无H，故无吸收峰 ●C—H：＜3000 cm-1为饱和C：～2960 cm-1 (),～2870 cm-1 ()强度为ｍ-ｓ ～2925 cm-1 (),～2850 cm-1 () 强度为ｍ-ｓ ～2890 cm-1强度为ｗ ＞3000 cm-1为不饱和 (及苯环上C-H)3090～3030 cm-1强度为ｍC： ～3300 cm-1强度为ｍ 强度为ｍ－ｓ ●醛基中C—H：～2820及～2720 两个峰 ★2500～2000 cm-1为叁键和累积双键伸缩振动吸收峰，主要包括－C≡C-、-C≡N叁键的伸缩振动及、等累积双键的非对称伸缩振动，呈现中等强度的吸收。在此波段区中，还有S—H、Si—H、P—H、B—H的伸缩振动。 ★2000～1500 cm-1为双键的伸缩振动吸收区，这个波段也是比较重要的区域，主要包括以下几种吸收峰带。