supplementary material - csiro publishing · s1 synthesis of dichlorides 1a-c the dichlorides 1a-c...
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S0
10.1071/CH17255_AC
CSIRO 2018
Australian Journal of Chemistry 2018, 71(1), 58-69
Supplementary Material
N,N-Dialkyl-N’-Chlorosulfonyl Chloroformamidines in Heterocyclic Synthesis. Part XIV. Synthesis and Reactivity of the New
Benzo[4,5]imidazo[1,2-b][1,2,6]thiadiazine Ring System
Dylan Innes,A Michael V. Perkins,A Andris J. Liepa,B and Craig L. FrancisB,C
ASchool of Chemical and Physical Sciences, Flinders University, Bedford Park, SA 5042, Australia. BBiomedical Synthetic Chemistry Group, CSIRO, Clayton, Vic. 3168, Australia.
CCorresponding author. Email: [email protected]
S1 Synthesis of dichlorides 1a-c
S1-S3 Synthesis and spectral data for benzimidazole derivatives 4, 8, 11, 13, and 16
S3-S4 Crystal structures for compounds 6c, 6d, and 15b
S5-S9 1H NMR and 13C NMR spectra for benzimidazol-2-ylacetonitriles 4b-d
S10-S24 1H NMR and 13C NMR and 19F NMR spectra for benzimidazo-thiadiazines 6
S25-S26 1H NMR and 13C NMR spectra for ethyl benzimidazol-2-yl-acetate 8
S27-S32 1H NMR and 13C NMR spectra for ethyl benzimidazo-thiadiazine carboxylates 9
S33 1H NMR spectrum for 2-(4-chlorophenacyl)benzimidazole 11
S34-S35 1H NMR and 13C NMR spectra for 4-chlorophenyl benzimidazo-thiadiazine 12
S36-S37 1H NMR and 13C NMR spectra for 2-tosylmethyl-benzimidazole 13
S38-S48 1H NMR and 13C NMR spectra for tosyl benzimidazo compounds 14 and 15
S49-S51 1H NMR, 13C NMR and 19F NMR spectra for trifluoromethyl-benzimidazole 16
S52-S57 1H NMR, 13C NMR and 19F NMR spectra for trifluoromethyl benzimidazo-pyrimidines 19 and 20
S58-S59 1H NMR and 13C NMR spectra for 2-methyl benzimidazo compounds 22 or 23
S60-S67 1H NMR and 13C NMR spectra for N5-alkyl substituted benzimidazo-thiadiazines 26
S68-S69 1H NMR and 13C NMR spectra for N5-acyl substituted benzimidazo-thiadiazine 28
S70-S71 1H NMR and 13C NMR spectra for 4,5-dimethyl benzimidazo-thiadiazine 29
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S1
Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as previously described (Scheme S1).[6]
Scheme S1
Synthesis of benzimidazole derivatives 4. 5,6-Dimethylbenzimidazole 4b[7] was prepared following published procedures,[7,8] in which 4,5-dimethyl-1,2-diaminobenzene 5b was heated with ethyl cyanoacetate. However, attempts to employ this procedure for preparation of the 5,6-dihalogenated derivatives 4c and 4d[9] were unsuccessful, requiring the use of the relatively more reactive 2-cyanoacetimidic acid ethyl ester.[10]
NH
N
CN
R1
R1
4
R1
H 4a
Me 4bCl 4c
F 4d
2-(5,6-Dichloro-1H-benzo[d]imidazol-2-yl)acetonitrile 4c
A stirred mixture of 4,5-dichlorobenzene-1,2-diamine 5c (1.0 g, 5.7 mmol) and 2-cyanoacetimidic acid ethyl ester hydrochloride[9] (1.1 g, 7.6 mmol) in CH2Cl2 (30 mL) was heated at reflux overnight. The reaction mixture was cooled to room temperature and the precipitate was collected, washed with water and purified by column chromatography. Elution with 60% EtOAc in hexanes provided the title compound 4c (0.63 g, 49%) as a white solid; mp 200 °C dec.; (Found: [M + H]+ 225.9935; C9H6Cl2N3, requires [M + H]+ 225.9939); 1H NMR (600 MHz, DMSO-d6 + 1 drop conc. HCl) 7.98 (2H, s, ArH), 4.64 (2H, s, CH2). 13C NMR (150 MHz, DMSO-d6 + 1 drop conc. HCl) 147.63, 134.85, 126.92, 116.46, 115.31, 18.20.
2-(5,6-Difluoro-1H-benzo[d]imidazol-2-yl)acetonitrile 4d[9]
A mixture of 4,5-difluorobenzene-1,2-diamine 5d (195 mg, 1.4 mmol) and 2-cyanoacetimidic acid ethyl ester hydrochloride[10] (250 mg, 1.7 mmol) in CH2Cl2 (7 mL) was stirred at 40 °C overnight. After cooling, the precipitate was collected, washed with water and with CH2Cl2 (3 × 10 mL) to give the title
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S2
compound 4d (184 mg, 70%) as a tan solid; mp 202–203 °C (lit[9] 210–212 °C); (Found: [M + H]+ 194.0525; C9H6N3F2 requires [M + H]+ 194.0530); 1H NMR (400 MHz, DMSO-d6) 7.62 (2H, t, J 10.9 Hz, ArH), 4.37 (2H, s, CH2); 13C NMR (150 MHz, DMSO-d6 + 1 drop conc. HCl) 149.56 (d, J 17.0 Hz), 147.93 (d, J 17.0 Hz), 146.54, 128.86 (t, J 6.1 Hz), 114.76, 103.37 (dd, J 17.0, 7.2 Hz), 17.94.
Ethyl 2-(1H-benzo[d]imidazol-2-yl)acetate 8[8]
Prepared by a literature procedure.[11] Thus, acetyl chloride (1 mL, 14 mmol) was added dropwise to a stirred solution of benzimidazole acetonitrile 4a (500 mg, 3.18 mmol) in EtOH (8 mL) at 0 °C. The reaction mixture was heated at reflux for 2 h, cooled to room temperature and the remaining solvent removed in vacuo. The hydrochloride salt was dissolved in water and neutralised with a saturated solution of NaHCO3. Extraction with CH2Cl2 (3 × 20 mL) provided the title compound 8 (605 mg, 93%) as a brown solid; mp 106–108 °C (lit.[8] 128.5–129.5 °C); 1H NMR (600 MHz, DMSO-d6) 7.56–7.48 (2H, m, ArH), 7.20–7.12 (2H, m, ArH), 4.13 (2H, q, J 7.1 Hz, CH2CH3), 3.97 (2H, s, ArCH2), 1.20 (3H, t, J 7.1 Hz, CH2CH3); 13C NMR (150 MHz, DMSO-d6) 168.72, 147.75, 138.71, 121.54, 114.75, 60.81, 35.10, 14.03.
2-(1H-Benzo[d]imidazol-2-yl)-1-(4-chlorophenyl)ethan-1-one 11[12]
Prepared by a literature procedure[12] using acetonitrile as solvent in the first step with the modification of heating the tri-benzoylated intermediate in n-BuOH at 110 °C for 2 h rather than in 2-propanol at reflux. The title compound 11 (60% yield) was obtained as a bright yellow solid; mp 225–228 °C (lit.[12] 226–228 °C). 1H NMR (600 MHz, DMSO-d6) 12.32 and 12.24 (1H, 2 x br s, NH), 8.09 (0.30H, d, J 8.5 Hz, ArH), 7.87 (1.6H, d, J 8.5 Hz, ArH), 7.64 (0.32H, d, J 8.6 Hz, ArH), 7.51 (1.6H, d, J 8.6 Hz, ArH), 7.56 and 7.37 (2H, 2 x m, H-4,7), 7.15-7.18 (2H, m, H-5,6), 6.03 (1H, s, C=CH-C=O), 4.67 (0.41H, s, CH2).
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S3
2-Tosylmethyl-1H-benzo[d]imidazole 13[13,14]
A solution of 2-chloromethylbenzimidazole (0.57 g, 3.4 mmol) and sodium p-toluenesulfinate (1.6 g, 9 mmol) in freshly distilled DMSO (20 mL) was stirred at room temperature overnight. The reaction mixture was diluted with EtOAc (100 mL) and washed with brine (4 × 50 mL) to remove the DMSO and excess sulfinate salts. The organic phase was dried (Na2SO4), and the solvent was removed in vacuo to provide the title compound 13 (0.81 g, 83%) as a tan solid; mp 206–208 °C (lit.[13] 202 °C); 1H NMR (600 MHz, DMSO-d6) 12.63 (1H, br. s, NH), 7.65 (2H, d, J 8.0 Hz, ArH), 7.53 (2H, dd, J 6.2, 2.9 Hz, ArH), 7.40 (2H, d, J 8.0 Hz, ArH), 7.18 (2H, dd, J 6.2, 2.9 Hz, ArH), 4.94 (2H, s, CH2), 2.39 (3H, s, CH3); 13C NMR (150 MHz, DMSO-d6) 144.68, 142.52, 135.80, 129.75, 127.93, 122.09, 55.84, 21.09.
3-(1H-Benzo[d]imidazol-2-yl)-1,1,1-trifluoropropan-2-one (3-(1,3-dihydro-2H-benzo[d]imidazol-2-ylidene)-1,1,1-trifluoropropan-2-one) 16
Prepared by a literature procedure.[15] The title compound 16 (300 mg, 44%) was obtained as a white powder; mp 280–282 °C (lit.[15] 279–280 °C dec.); 1H NMR (600 MHz, DMSO-d6) 12.68 (2H, br s, 2 x NH), 7.51 (2H, br s, ArH), 7.25−7.22 (2H, m, ArH), 5.41 (1H, s, C=CHCOCF3); 13C NMR (150 MHz, DMSO-d6) 167.96 (q, J 30.5 Hz), 151.94 , 130.30 , 123.13 , 118.83 (q, J 288.9 Hz), 111.70 (m), 71.69; 19F (565 MHz MHz; DMSO-d6) −74.48.
References
[6] C. M. Forsyth, C. L. Francis, S. Jahangiri, A. J. Liepa, M. V. Perkins, A. P. Young, Aust. J. Chem. 2010, 63, 659–668. doi: 10.1071/CH09581
[7] H. S. A. Elzahabi, Eur. J. Med. Chem. 2011, 46, 4025–4034. doi: 10.1016/j.ejmech.2011.05.075
[8] R. A. B. Copeland, A. R. Day, J. Am. Chem. Soc. 1943, 65, 1072–1075. doi: 10.1021/ja01246a019
[9] H. Ben Ammar, M. T. Kaddachi, P. H. Kahn, Phys. Chem. News 2003, 9, 137–139.S. K.
[10] Kotovskaya, Z. M. Baskakova, V. N. Charushin, O. N. Chupakhin, E. F. Belanov, N. I. Bormotov, S. M. Balakhnin, O. A. Serova, Pharm. Chem. J. 2005, 39, 574–578. doi:10.1007/s11094-006-0023-9
[11] S. M. Rida, F. S. G. Soliman, E.-S. A. M. Badawey, E. El-Ghazzawi, O. Kader, T. Kappe, J. Heterocycl. Chem. 1988, 25, 1087–1093. doi: 10.1002/jhet.5570250408
[12] I. B. Dzvinchuk, A. M. Nesterenko, V. V Polovinko, A. B. Ryabitskii, M. O. Lozinskii, Chem. Heterocycl. Compd. 2011, 47, 953–963. doi: 10.1007/s10593-011-0860-7
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[13] P. K. Dubey, P. V. V. P. Reddy, K. Srinivas, Indian J. Chem. 2007, 46, 488–491.
[14] S. Liang, R. Y. Zhang, L. Y. Xi, S. Y. Chen, X. Q. Yu, J. Org. Chem. 2013, 78, 11874–11880. doi: 10.1021/jo401828b
[15] M. Kawase, M. Teshima, S. Saito, S. Tani, Heterocycles 1998, 48, 2103–2109. doi: 10.3987/COM-98-8268
Additional Crystal Structures
6c
6d
Figure S1. ORTEP diagrams of 6c and 6d. A molecule of DMSO is omitted from the crystal structure of 6d for clarity.
15b
Figure S2. ORTEP diagram of 15b.
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S5
1H NMR spectrum for 4b (600 MHz; DMSO-d6)
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S6
1H NMR spectrum for 4c (600 MHz; DMSO-d6 + 1 drop conc. HCl)
NH
N
CN
Cl
Cl
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S7
13C NMR spectrum for 4c (150 MHz; DMSO-d6 + 1 drop conc. HCl)
NH
N
CN
Cl
Cl
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S8
1H NMR spectrum for 4d (400 MHz; DMSO-d6)
NH
N
CN
F
F
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S9
13C NMR spectrum for 4d (150 MHz; DMSO-d6 + 1 drop conc. HCl)
NH
N
CN
F
F
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S10
1H NMR spectrum for 6a (600 MHz; DMSO-d6)
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S11
13C NMR spectrum for 6a (150 MHz; 55 °C; DMSO-d6)
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S12
1H NMR spectrum for 6b (600 MHz; DMSO-d6)
NH
N
NS
OO
N
CN
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S13
13C NMR spectrum for 6b (150 MHz; DMSO-d6)
NH
N
NS
OO
N
CN
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S14
1H NMR spectrum for 6c (600 MHz; DMSO-d6)
NH
N
NS
OO
N
CN
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S15
13C NMR spectrum for 6c (100 MHz; DMSO-d6)
NH
N
NS
OO
N
CN
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S16
1H NMR spectrum for 6d (600 MHz; DMSO-d6)
NH
N
NS
OO
N
CN
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S17
13C NMR spectrum for 6d (150 MHz; DMSO-d6)
NH
N
NS
OO
N
CN
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S18
1H NMR spectrum for 6e (600 MHz; DMSO-d6)
NH
N
NS
OO
N
CN
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S19
13C NMR spectrum for 6e (100 MHz; 55 °C; DMSO-d6)
NH
N
NS
OO
N
CN
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S20
1H NMR spectrum for 6f (600 MHz; DMSO-d6)
NH
N
NS
OO
N
CN
Cl
Cl
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S21
13C NMR spectrum for 6f (150 MHz; DMSO-d6)
NH
N
NS
OO
N
CN
Cl
Cl
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S22
1H NMR spectrum for 6g (600 MHz; DMSO-d6)
NH
N
NS
OO
N
CN
F
F
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S23
13C NMR spectrum for 6g (150 MHz; DMSO-d6)
NH
N
NS
OO
N
CN
F
F
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S24
19F NMR spectrum for 6g (565 MHz, DMSO-d6)
NH
N
NS
OO
N
CN
F
F
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S25
1H NMR spectrum for 8 (600 MHz; DMSO-d6)
NH
NO
OEt
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S26
13C NMR spectrum for 8 (150 MHz; DMSO-d6)
NH
NO
OEt
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S27
1H NMR spectrum for 9a (600 MHz; DMSO-d6)
NH
N
NS
OO
N
EtO
O
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S28
13C NMR spectrum for 9a (150 MHz; DMSO-d6)
NH
N
NS
OO
N
EtO
O
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S29
1H NMR spectrum for 9b (600 MHz; DMSO-d6)
NH
N
NS
OO
N
EtO
O
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S30
13C NMR for spectrum 9b (150 MHz; DMSO-d6)
NH
N
NS
OO
N
EtO
O
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S31
1H NMR spectrum for 9c (600 MHz; DMSO-d6)
NH
N
NS
OO
N
EtO
O
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S32
13C NMR spectrum for 9c (150 MHz; DMSO-d6)
NH
N
NS
OO
N
EtO
O
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S33
1H NMR spectrum for 11 (600 MHz; DMSO-d6)
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S34
1H NMR spectrum for 12 (600 MHz; DMSO-d6)
NH
N
NS
OO
N
O
Cl
![Page 36: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/36.jpg)
S35
13C NMR spectrum for 12 (150 MHz; DMSO-d6)
NH
N
NS
OO
N
O
Cl
![Page 37: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/37.jpg)
S36
1H NMR spectrum for 13 (600 MHz; DMSO-d6)
NH
N
S MeO
O
![Page 38: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/38.jpg)
S37
13C NMR spectrum for 13 (150 MHz; DMSO-d6)
NH
N
S MeO
O
![Page 39: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/39.jpg)
S38
1H NMR spectrum for 14a (600 MHz; DMSO-d6)
![Page 40: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/40.jpg)
S39
13C NMR spectrum for 14a (150 MHz; DMSO-d6)
![Page 41: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/41.jpg)
S40
1H NMR spectrum for 14a (600 MHz; CDCl3)
![Page 42: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/42.jpg)
S41
13C NMR spectrum for 14a (150 MHz; CDCl3)
![Page 43: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/43.jpg)
S42
HMQC NMR spectrum for 14a (600 × 150 MHz; CDCl3)
![Page 44: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/44.jpg)
S43
1H NMR spectrum for 15a (600 MHz; DMSO-d6)
![Page 45: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/45.jpg)
S44
13C NMR spectrum for 15a (150 MHz; DMSO-d6)
![Page 46: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/46.jpg)
S45
1H NMR spectrum for 14b (600 MHz; DMSO-d6)
NH
N
NS
OO
N
S OO
![Page 47: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/47.jpg)
S46
13C NMR spectrum for 14b (150 MHz; DMSO-d6)
NH
N
NS
OO
N
S OO
![Page 48: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/48.jpg)
S47
1H NMR spectrum for 15b (600 MHz; DMSO-d6)
![Page 49: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/49.jpg)
S48
13C NMR spectrum for 15b (150 MHz; DMSO-d6)
![Page 50: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/50.jpg)
S49
1H NMR spectrum for 16 (600 MHz; DMSO-d6)
![Page 51: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/51.jpg)
S50
13C NMR spectrum for 16 (150 MHz; DMSO-d6)
![Page 52: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/52.jpg)
S51
19F NMR spectrum for 16 (565 MHz; DMSO-d6)
NH
N CF3
O
NH
N CF3
OH
~100%
![Page 53: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/53.jpg)
S52
1H NMR spectrum for 19 (600 MHz; DMSO-d6)
![Page 54: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/54.jpg)
S53
13C NMR spectrum for 19 (150 MHz; DMSO-d6)
![Page 55: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/55.jpg)
S54
19F NMR spectrum for 19 (565 MHz, DMSO-d6)
![Page 56: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/56.jpg)
S55
1H NMR spectrum for 20 (600 MHz; DMSO-d6)
![Page 57: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/57.jpg)
S56
13C NMR spectrum for 20 (150 MHz; 60 °C; D1 = 5s; DMSO-d6)
![Page 58: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/58.jpg)
S57
19F NMR spectrum for 20 (565 MHz, DMSO-d6)
![Page 59: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/59.jpg)
S58
1H NMR spectrum for 22/23 (600 MHz; CDCl3)
N
NS N
Cl
NEt2OO
N
N
NEt2N
S
O
Cl
Oor
![Page 60: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/60.jpg)
S59
13C NMR spectrum for 22/23 (150 MHz; CDCl3)
N
NS N
Cl
NEt2OO
N
N
NEt2N
S
O
Cl
Oor
![Page 61: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/61.jpg)
S60
1H NMR spectrum for 26a (600 MHz; DMSO-d6)
![Page 62: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/62.jpg)
S61
13C NMR spectrum for 26a (150 MHz; DMSO-d6)
![Page 63: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/63.jpg)
S62
1H NMR spectrum for 26b (600 MHz; CDCl3)
N
N
NS
OO
N
CN
Cl
![Page 64: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/64.jpg)
S63
13C NMR spectrum for 26b (150 MHz; DMSO-d6)
N
N
NS
OO
N
CN
Cl
![Page 65: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/65.jpg)
S64
1H NMR spectrum for 26c (600 MHz; DMSO-d6)
N
N
NS
OO
N
CN
![Page 66: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/66.jpg)
S65
13C NMR spectrum for 26c (150 MHz; DMSO-d6)
N
N
NS
OO
N
CN
![Page 67: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/67.jpg)
S66
1H NMR spectrum for 26d (600 MHz; DMSO-d6)
N
N
NS
OO
N
CN
O
![Page 68: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/68.jpg)
S67
13C NMR spectrum for 26d (150 MHz; DMSO-d6)
N
N
NS
OO
N
CN
O
![Page 69: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/69.jpg)
S68
1H NMR spectrum for 28 (600 MHz; DMSO-d6)
N
N
NS
OO
N
CN
OO
![Page 70: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/70.jpg)
S69
13C NMR spectrum for 28 (150 MHz; DMSO-d6)
N
N
NS
OO
N
CN
OO
![Page 71: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/71.jpg)
S70
1H NMR spectrum for 29 (600 MHz; CDCl3)
N
N
NSN
OO
![Page 72: Supplementary Material - CSIRO Publishing · S1 Synthesis of dichlorides 1a-c The dichlorides 1a-c were prepared from sulfuryl chloride and the corresponding dialkyl cyanamide as](https://reader034.vdocument.in/reader034/viewer/2022050517/5fa0aec09c421f2cb96899b8/html5/thumbnails/72.jpg)
S71
13C NMR spectrum for 29 (150 MHz; CDCl3)
N
N
NSN
OO