Radical and Nitrenoid Reactivity of 3-Halo-3 … SUPPORTING INFORMATION Radical and Nitrenoid...

S1

SUPPORTING INFORMATION

Radical and Nitrenoid Reactivity of 3-Halo-3-phenyldiazirines

Rafael Navrátil, Ján Tarábek, Igor Linhart and Tomáš Martinů*

TABLE OF CONTENTS

Reactions of diazirines 1a and 3 with organolithiums ****... S2–S6

1H / 13C NMR spectra of compounds 4, 5, 12–14, 16 and 18 *.. S7–S15

IR spectra of compounds 4, 5, 12–14, 16 and 18 ******.. S16–S19

EPR experiment ********************. S20–S22

References ********************..** S23

S2

Preparation of 3-bromo-3-phenyl-3H-diazirine (1a)

Diazirine 1a, a pale yellow liquid, was prepared according to a literature procedure.S1 1H NMR (300 MHz, CDCl3): δ = 7.41-7.35 (m, 3 H), 7.17-7.12 (m, 2 H) ppm. 13C NMR

(75 MHz, CDCl3): δ = 136.7, 129.4, 128.5, 126.6, 38.0 ppm.

Preparation of 3-phenyl-3H-diazirine (3)

Diazirine 3, a colorless liquid, was prepared according to literature procedures.S2 1H NMR (300 MHz, CDCl3): δ = 7.35-7.30 (m, 3 H), 6.95-6.90 (m, 2 H), 2.05 (s, 1 H) ppm.

13C NMR (75 MHz, CDCl3): δ = 136.3, 128.3, 128.0, 125.1, 23.4 ppm.

Reaction of 3-phenyl-3H-diazirine (3) with t-BuLi (standard procedure)

To a solution of t-BuLi (1.7 M in pentane, 2.5 mL, 4.25 mmol) in THF (10 mL) and Et2O

(2.5 mL), cooled to –115 °C (dry ice + ethanol + liquid N2) under argon, was added dropwise

over 20 min a solution of diazirine 3 (100 mg, 0.85 mmol) in THF (1.5 mL). The reaction

mixture was stirred for another 20 min and then it was quenched by the addition of MeOH-d4

(0.3 mL) in THF (0.5 mL) dropwise over 5 min. After warming to room temperature, the

reaction mixture was diluted with H2O (20 mL), extracted with CH2Cl2 (3 × 20 mL), combined

organic layers were washed with H2O (60 mL), dried over Na2SO4 and concentrated under

reduced pressure at 0 °C to afford a yellow liquid, 1-t-butyl-3-phenyldiaziridine (4), essentially

pure by NMR (148 mg, quant. yield). 1H NMR (300 MHz, CDCl3): δ = 7.42-7.31 (m, 5 H), 3.59

(s, 1 H), 1.68 (br s, 1 H), 1.10 (s, 9 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 138.7, 128.6,

128.4, 126.4, 55.7, 52.9, 25.8 ppm. IR (ATR) ν = 3425, 2962, 2926, 2855, 1459, 1361, 1212,

1101, 715 cm-1. HRMS (ESI+) m/z calcd for C11H17N2 [M + H]+ 177.1392, found 177.1385.

Reaction of 3-phenyl-3H-diazirine (3) with LDA/iPr2ND

To a solution of iPr2NH (429 mg, 4.24 mmol) in THF (7.0 mL), cooled to –78 °C under

argon, was added n-BuLi (2.5 M in hexane, 1.7 mL, 4.24 mmol) followed after 30 min of

stirring by MeOH-d4 (70 mg, 2.12 mmol). To the resulting mixture was added dropwise over

6 min a solution of diazirine 3S1 (86 mg, 0.73 mmol) in THF (3.0 mL). The reaction mixture

was stirred for another 60 min and then quenched by the addition of MeOH-d4 (0.2 mL) in

THF (0.5 mL) dropwise over 3 min. After warming to room temperature, the reaction mixture

was diluted with H2O (40 mL), extracted with CH2Cl2 (3 × 20 mL), combined organic layers

were washed with H2O (60 mL), dried over Na2SO4 and concentrated under reduced

S3

pressure at 0 °C to afford a pale yellow liquid (82 mg), a 1:2 mixture of unreacted 3 and

3-phenyldiaziridine (5) (64% yield) by NMR. A sample of pure 5 was obtained by chromato-

graphy on silicagel using hexane-EtOAc (3:2). 1H NMR (300 MHz, CDCl3): δ = 7.39-7.34 (m,

5 H), 4.04 (br s, 1 H), 2.04 (br s, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 137.8, 128.84,

128.78, 125.9, 51.4 ppm. IR (ATR) ν = 3215, 3034, 1457, 1234, 1158, 1061, 851, 761,

697 cm-1. HRMS (ESI+) m/z calcd for C7H9N2 [M + H]+ 121.0766, found 121.0762.

Reaction of 3-bromo-3-phenyl-3H-diazirine (1a) with t-BuLi

The standard procedure with t-BuLi (1.7 M in pentane, 1.8 mL, 3.06 mmol), THF

(8.0 mL), Et2O (2.0 mL), diazirine 1a (200 mg, 1.02 mmol) in THF (1.5 mL) and MeOH

(0.3 mL) in THF (0.5 mL) afforded a pale yellow liquid, tert-butyl(phenyl)ketimine (6)

essentially pure by NMR (153 mg, 93% yield), identical to an authentic sample of 6 prepared

by the the reaction of t-BuLi (2 eq) with PhCN (1 eq) in THF at –78 °C. 1H NMR (300 MHz,

CDCl3): δ = 9.24 (br s, 1 H), 7.36-7.31 (m, 3 H), 7.22-7.17 (m, 2 H), 1.24 (s, 9 H) ppm.

13C NMR (75 MHz, CDCl3): δ = 184.2, 139.5, 127.9, 127.8, 126.3, 40.1, 28.3 ppm. HRMS

(ESI+) m/z calcd for C11H16N [M + H]+ 162.1283, found 162.1276.

Reactions of 3-bromo-3-phenyl-3H-diazirine (1a) with MeLi

A) The standard procedure with MeLi (1.64 M in Et2O, 3.8 mL, 6.23 mmol), THF

(9.0 mL), Et2O (2.5 mL), pentane (2.5 mL), diazirine 1a (400 mg, 2.03 mmol) in THF

(1.0 mL) and MeOH (0.50 mL) in THF (0.5 mL) afforded a yellow-brown liquid (256 mg), a

2.9:1 mixture of unreacted 1a (54% rsm) and benzonitrile (9) (19% yield) by NMR. Nitrile 9

was identical to an authentic sample. 1H NMR (300 MHz, CDCl3): δ = 7.66 (d, J = 7.8 Hz,

2 H), 7.61 (m, 1 H), 7.48 (t, J = 7.5 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 132.8,

132.1, 129.2, 118.9, 112.4 ppm.

B) The above reaction A performed at –78 °C (instead of –115 °C) afforded an orange

liquid (196 mg), a 1.9:1 mixture of nitrile 9 and methyl(phenyl)ketimine (10), with traces of

acetophenone (total combined yield ca 90%). A similar mixture is produced by the direct

reaction of MeLi (2 eq) with PhCN (1 eq). Ketimine 10: 1H NMR (300 MHz, CDCl3): δ = 8.94

(br s, 1 H), 7.74-7.76 (m, 2 H), 7.42-7.40 (m, 3 H), 2.45 (s, 3 H) ppm. 13C NMR (75 MHz,

CDCl3): δ = 175.1, 138.6, 130.4, 128.4, 126.3, 25.8 ppm. HRMS (ESI+) m/z calcd for C8H10N

[M + H]+ 120.0813, found 120.0809.

C) Optimized conditions for the reduction of 1a to 3: The standard procedure with MeLi

(1.64 M in Et2O, 18.3 mL, 30.0 mmol), THF (26 mL) and pentane (11.5 mL), whereby the

S4

addition of diazirine 1a (65 mg, 0.33 mmol) in THF (3.0 mL) was carried out over the course

of 60 min (syringe pump), followed after another 15 min by quenching with MeOH (2.0 mL) in

THF (2.0 mL), afforded an orange liquid (54 mg), a 1.25:1:2.75 mixture of unreacted 1a

(16.3 mg, 25% rsm), diazirine 3 (7.8 mg, 20% yield) and nitrile 9 (18.7 mg, 55% yield) by 1H

NMR using CH2Br2 as an internal standard. NMR spectra of 1a, 3 and 9 are given above.

Reactions of 3-bromo-3-phenyl-3H-diazirine (1a) with alkylmetals in Et2O afford-

ing N,Nʹ-dialkylbenzamidines 12–14, 16 and 18

NOTE: Due to the hindered rotations of alkyl substituents, their 1H and 13C signals as well as 13C signals of N–C=N and phenyl C1 atoms in NMR spectra of amidines 12, 14, 16 and 18

exhibit broadening, in some cases large enough for the signals to disappear in the base line.

This broadening was partially decreased by taking the NMR spectra at elevated tem-

peratures (323 or 373 K), however, some signals still remained undiscernible. Structure

assignments were also aided by infrared spectroscopy (similarity of bands in the 3400, 1600,

1500 and 700 cm-1 regions for all compounds) as well as by an independent syntheses of

some of the reported compounds.

N,Nʹ-Di-n-butylbenzamidine (12)

The standard procedure with n-BuLi (2.5 M in hexane, 1.3 mL, 3.25 mmol) and Et2O

(6.0 mL) at 0 °C, diazirine 1a (309 mg, 1.57 mmol) in Et2O (3.0 mL) and MeOH (0.30 mL) in

Et2O (0.5 mL) afforded an orange syrup, amidine 12, essentially pure by NMR (285 mg, 78%

yield). The 1H NMR spectrum of 12 corresponds to literature.S3 1H NMR (500 MHz, CDCl3,

323 K): δ = 7.43-7.42 (m, 3 H), 7.29-7.27 (m, 2 H), 3.13 (m(t), 4 H), 1.52 (quint, J = 7.2 Hz,

4 H), 1.33 (sext, J = 7.2 Hz, 4 H), 0.87 (t, J = 7.2 Hz, 6 H) ppm. 1H NMR (500 MHz, DMSO-

d6, 373 K): δ = 7.41-7.36 (m, 3 H), 7.22 (d, J = 6.9 Hz, 2 H), 3.08 (m(t), 4 H), 1.45 (quint, J =

6.7 Hz, 4 H), 1.30 (sext, J = 7.3 Hz, 4 H), 0.85 (t, J = 7.3 Hz, 6 H) ppm. 13C NMR (125 MHz,

CDCl3, 323 K): δ = 129.3, 128.6, 127.5, 33.0, 29.7, 20.2, 13.8 ppm (see the Note above).

13C NMR (125 MHz, DMSO-d6, 373 K): δ = 157.8, 135.3, 127.8, 127.5, 126.9, 32.1, 19.1,

13.0 ppm. IR (ATR) ν = 3262, 2955, 2926, 2858, 1629, 1600, 1497, 1464, 1376, 1299, 1152,

1072, 772, 701 cm-1. HRMS (ESI+) m/z calcd for C15H25N2 [M + H]+ 233.2018, found

233.2010.

S5

N,Nʹ-Dimethylbenzamidine (13)

The standard procedure with MeLi (1.64 M in Et2O, 12.2 mL, 20.0 mmol) and Et2O

(24 mL) at –110 °C, whereby the addition of diazirine 1a (197 mg, 1.00 mmol) in Et2O

(4.0 mL) was carried out over the course of 60 min (syringe pump), followed after another

15 min by quenching with and MeOH (2.0 mL) in Et2O (2.0 mL), afforded a yellow syrup

(132 mg), with amidine 13 as its major constituent (79 mg, 53% yield) by 1H NMR using

CH2Br2 as an internal standard. A sample of pure 13 was obtained by crystallization from

Et2O as a white solid (m.p. = 79-80 °C). 1H NMR (300 MHz, CDCl3): δ = 7.41-7.39 (m, 3 H),

7.29-7.25 (m, 2 H), 3.16 (br s, 1 H), 2.89 (s, 6 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 161.1,

135.4, 128.9, 128.5, 127.5, 26.3 ppm. IR (ATR) ν = 3228, 3057, 2938, 2867, 1628, 1600,

1529, 1404, 1331, 1032, 773, 702 cm-1. HRMS (ESI+) m/z calcd for C9H13N2 [M + H]+

149.1079, found 149.1072.

N,Nʹ-Di-tert-butyl- (14) and N-tert-butylbenzamidine (15)

The standard procedure with t-BuLi (1.7 M in pentane, 2.8 mL, 4.76 mmol) and Et2O

(33 mL) at –110 °C, whereby the addition of diazirine 1a (190 mg, 0.96 mmol) in Et2O


15 min by quenching with MeOH (1.0 mL) in Et2O (1.0 mL), afforded a dark yellow syrup

(118 mg). Separation by preparative TLC on silicagel using hexane-EtOAc (1:1) with 1% of

Et3N afforded purified 14 (Rf ~ 0.07) and 15 (Rf ~ 0.01) as colorless films. The structures

were confirmed by comparison to authentic samples obtained by an independent

synthesis.S4,S5 Subsequent 1H NMR analysis using CH2Br2 as an internal standard indicated

the abundance of 14 (45 mg, 20% yield) and 15 (25 mg, 15% yield) in the crude product.

14: 1H NMR (500 MHz, CDCl3, 323 K): δ = 7.59-7.26 (m, 5H), 1.17 (br s, 18 H) ppm.

13C NMR (125 MHz, CDCl3, 323 K): δ = 128.0 (br), 31.0 (br) ppm (see the Note on page S4).

IR (ATR) ν = 3436, 3232, 2970, 1615, 1476, 1447, 1404, 1371, 1193, 1101, 792, 713 cm-1.

HRMS (ESI+) m/z calcd for C15H25N2 [M + H]+ 233.2018, found 233.2012.

15: 1H NMR (300 MHz, CDCl3): δ = 7.50-7.47 (m, 2 H), 7.39-7.35 (m, 3 H), 6.29 (br s,

1 H), 4.52 (br s, 1 H), 1.48 (s, 9H) ppm. 13C NMR (75 MHz, CDCl3): δ = 164.3, 140.2, 129.5,

128.6, 125.8, 51.3, 28.8 ppm. HRMS (ESI+) m/z calcd for C11H17N2 [M + H]+ 177.1392, found

177.1385.

S6

N,Nʹ-Di-isopropylbenzamidine (16)

The standard procedure with iPrMgCl.LiCl (1.23 M in THF, 6.2 mL, 7.66 mmol) and

THF (5.0 mL) at –78 °C, whereby the addition of diazirine 1a (503 mg, 2.55 mmol) in THF


80 min by quenching with MeOH (2.0 mL) in THF (2.0 mL), afforded a yellow syrup, amidine

16, essentially pure by NMR (341 mg, 65% yield). A sample of analytically pure 16, a white

semisolid, was obtained by room temperature vacuum transfer (5 × 10-2 Torr) into a –196 °C

U-trap followed by preparative TLC on silicagel using hexane-EtOAc (1:1) with 1% of Et3N

(Rf ~ 0.10). 1H NMR (500 MHz, DMSO-d6, 373 K): δ = 7.47 (br s, 3 H), 7.31 (br s, 2 H), 3.60

(br s, 2 H), 1.09 (d, J = 5.2 Hz, 12 H) ppm. 13C NMR (125 MHz, DMSO-d6, 373 K): δ = 157.5,

133.3, 128.8, 127.9, 126.8, 45.1 (br), 22.6 ppm. IR (ATR) ν = 3432, 3210, 2964, 2929, 2871,

2739, 1632, 1600, 1485, 1467, 1446, 1402, 1371, 1333, 1130, 1099, 782, 771, 704 cm-1.

HRMS (ESI+) m/z calcd for C13H21N2 [M + H]+ 205.1705, found 205.1700.

N-Methyl-Nʹ-(2-oxolanyl)benzamidine (18)

To a solution of anhydrous ZnBr2 (3.24 g, 14.4 mmol) in THF (26 mL), cooled to –10 °C

under argon, was added MeLi (1.64 M in Et2O, 26.3 mL, 43.1 mmol). The mixture was stirred

for 30 min and then it was cooled to –78 °C. To this solution of Me3ZnLiS6 was added

dropwise over 80 min (syringe pump) a solution of diazirine 1a (772 mg, 3.92 mmol) in THF

(12 mL). The reaction mixture was stirred for another 40 min and then it was quenched by

the addition of MeOH (4.0 mL) in THF (4.0 mL). After warming to room temperature, the

reaction mixture was diluted with H2O (100 mL), extracted with CH2Cl2 (3 × 100 mL),

combined organic layers were washed with H2O (250 mL), dried over Na2SO4 and

concentrated under reduced pressure to afford a yellowish syrup (594 mg), containing

amidines 13 (244 mg, 42% yield) and 18 (320 mg, 40% yield) by 1H NMR using CH2Br2 as an

internal standard. Purified 18 was obtained as a yellowish syrup by preparative TLC on

silicagel using CH2Cl2-MeOH (9:1) with 1% of Et3N (Rf ~ 0.18). NMR spectra of 13 are given

above. 18: 1H NMR (500 MHz, CDCl3, 323 K): δ = 7.41 (br s, 3 H), 7.36-7.34 (m, 2 H), 5.06

(br m, 1 H), 4.05-4.02 (m, 1 H), 3.75-3.73 (m, 1 H), 2.88 (s, 3 H), 2.11-2.05 (m, 1 H), 1.96 (br

s, 1 H), 1.82 (br s, 2 H) ppm. 13C NMR (125 MHz, CDCl3, 323 K): δ = 161.1, 135.0, 129.2,

128.3, 127.5, 91.1, 67.1, 33.9, 28.5, 25.6 ppm. IR (ATR) ν = 3326, 3058, 2942, 2870, 1613,

1597, 1573, 1526, 1444, 1412, 1319, 1201, 1159, 1043, 922, 772, 702 cm-1. HRMS (ESI+)

m/z calcd for C12H17N2O [M + H]+ 205.1341, found 205.1335.

S7

Figure S1. 1H NMR (300 MHz, CDCl3) spectrum of diaziridine 4

Figure S2. 13C NMR (75 MHz, CDCl3) spectrum of diaziridine 4

N NH

HPh

4t-Bu

N NH

HPh

4t-Bu

S8

Figure S3. 1H NMR (300 MHz, CDCl3) spectrum of diaziridine 5

Figure S4. 13C NMR (75 MHz, CDCl3) spectrum of diaziridine 5

HN NH

HPh

5

HN NH

HPh

5

S9

Figure S5. 1H NMR (500 MHz, CDCl3, 323 K) spectrum of amidine 12

Figure S6. 1H NMR (500 MHz, DMSO-d6, 373 K) spectrum of amidine 12

NHn-BuPh

Nn-Bu

12

NHn-BuPh

Nn-Bu

12

S10

Figure S7. 13C APT NMR (125 MHz, CDCl3, 323 K) spectrum of amidine 12

Figure S8. 13C APT NMR (125 MHz, DMSO-d6, 373 K) spectrum of amidine 12

NHn-BuPh

Nn-Bu

12

NHn-BuPh

Nn-Bu

12

S11

Figure S9. 1H NMR (300 MHz, CDCl3) spectrum of amidine 13

Figure S10. 13C NMR (75 MHz, CDCl3) spectrum of amidine 13

NHMePh

NMe

13

NHMePh

NMe

13

S12



NHt-BuPh

Nt-Bu

14

NHt-BuPh

Nt-Bu

14

S13

Figure S13. 1H NMR (500 MHz, DMSO-d6, 373 K) spectrum of amidine 16

Figure S14. 13C APT NMR (125 MHz, DMSO-d6, 373 K) spectrum of amidine 16

NHiPrPh

NiPr

16

NHiPrPh

NiPr

16

S14



HNPh

NMe

O

18

HNPh

NMe

O

18

S15

Figure S17. 1H-13C HMQC NMR (125 MHz, CDCl3, 323 K) spectrum of amidine 18

HNPh

NMe

O

18

S16

Figure S18. IR (ATR) spectrum of diaziridine 4

Figure S19. IR (ATR) spectrum of diaziridine 5

N NH

HPh

4t-Bu

HN NH

HPh

5

S17

Figure S20. IR (ATR) spectrum of amidine 12


NHn-BuPh

Nn-Bu

12

NHMePh

NMe

13

S18



NHt-BuPh

Nt-Bu

14

NHiPrPh

NiPr

16

S19


HNPh

NMe

O

18

S20

EPR Experiment

The EPR experiment was performed on EMXplus-10/12 CW (continuous wave)

spectrometer (Bruker, Germany) equipped with the Premium-X band microwave bridge. The

EPR spectrum of the 3-phenyldiazirinyl radical (7) was recorded in special dielectric mixing

cell cavity (ER4117DMX, Bruker) enabling the detection of transient radicals generated in a

continuous-flow system. For this purpose two Hamilton syringes were filled with solutions of

diazirine 1a (8.5 × 10–2 M) and MeLi (5.1 × 10–1 M) in THF. Afterwards, they were connected

by the Luer-lock system with teflon tubes coming to mixing cell cavity. The sampling of both

reactants was performed by dual syringe-pump (kdScientific, US), which was positioned

outside of the EPR magnet. The sampling flow was kept constant at 2 × 10–2 mL.min–1. When

both reactant solutions reached the cavity, the recording of EPR spectrum (accumulation of

70 sweeps) was started and recording continued in situ during the whole mixing time of both

reactants (ca. 60 min). The EPR spectrum-sweeps were recorded using the following experi-

mental parameters: sweep width = 60 mT, modulation amplitude = 1.0 × 10–1 mT, resolution

= 3.0 × 10–2 mT, modulation frequency = 100 kHz, time constant = 10.2 ms, conversion time

= 24 ms, receiver gain = 1 × 105, microwave power = 8.0 × 10–1 mW. The g-factor was

determined using a built-in spectrometer frequency counter and an ER 036TM NMR-Tesla-

meter (both Bruker, Germany).

Theoretical calculations and EPR simulations

All calculations have been carried out within the Gaussian 09/Revision D.01 package.S7

The geometry optimization of radical 7 in THF was performed by the hybrid functional

B3LYPS8 with the triple-ζ 6-311+G(d,p) basis set. Afterwards, the harmonic vibrational

analysis confirmed the potential energy minimum of the geometry. The EPR hyperfine

coupling (A) / splitting (a) constants (HFCCs/HFSCs) as well as the g-factor and the spin

density were calculated by B3LYP using the triple-ζ basis sets: EPR-III for all atoms.S9 All

computations for the open-shell diazirine radical were performed in unrestricted fashion (i.e.

by UB3LYP) and the resulting spin contamination, after the geometry- or single-point energy

calculation, was small and the eigenvalue of Ŝ2 did not exceed 0.777.

Solvent (THF) effects in all calculations were incorporated by the self-consistent

reaction field theory at the level of conductor-like polarizable continuum model CPCM.S10 The

equilibrium geometry and spin density of the radical were visualized by VMD software

package.S11

S21

Simulations of EPR spectra were done within the EasySpin 5.0.20 packageS12 and

treated by the Origin data analysis software (OriginLab, Northhampton, MA). Experimental

parameters such as modulation amplitude, central field, sweep width, microwave frequency

and the spectral resolution (number of points) were included in the simulation.

Figure S25. Spin density (iso value = 0.0024 e/Å3) of radical 7 calculated at the B3LYP/

EPR-III//B3LYP/6-311+G(d,p)/CPCM(THF) level. Blue surfaces: positive values (alpha

spins), red surfaces: negative values (beta spins).

Table S1. DFT calculated EPR parameters compared to those obtained by EPR spectrum

simulation. A (MHz)/a (mT): hyperfine coupling/splitting constants (those for 13C nuclei are

not presented) and g-factors.

A/a (14N1,14N2) A/a (1H10,1H14) A/a (1H11,1H13) A/a (1H12) g

DFT 21.40 / 0.764 1.92 / 0.069 –0.94 / –0.034 1.93 / 0.069 2.0043

simul. 21.00 / 0.749 2.00 / 0.071 –1.00 / –0.036 2.00 / 0.071 2.0039

S22

Table S2. Geometry of radical 7 calculated at the B3LYP/6-311+G(d,p)/CPCM(THF) level.

--------------------------------------------------------------

coordinates (Ångstroms)

atom X Y Z

--------------------------------------------------------------

N1 15.363248 -15.847203 -0.454507

N2 15.975553 -17.202794 -0.063869

C3 16.644663 -16.107221 -0.338193

C4 17.964590 -15.541984 -0.445066

C5 19.086577 -16.343578 -0.187066

C6 20.358339 -15.793636 -0.291498

C7 20.509439 -14.452319 -0.651089

C8 19.392288 -13.654049 -0.908005

C9 18.116443 -14.194952 -0.806186

H10 18.953867 -17.382410 0.090874

H11 21.230420 -16.404996 -0.094150

H12 21.503079 -14.026856 -0.731532

H13 19.519166 -12.614951 -1.186228

H14 17.240627 -13.587952 -1.002483

--------------------------------------------------------------

S23

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