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CAS No. : | 75318-43-3 | MDL No. : | MFCD03426194 |
Formula : | C2Cl3NS2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | NIZMCFUMSHISLW-UHFFFAOYSA-M |
M.W : | 208.52 | Pubchem ID : | 11095847 |
Synonyms : |
|
Num. heavy atoms : | 8 |
Num. arom. heavy atoms : | 5 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 0 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 40.27 |
TPSA : | 69.37 Ų |
GI absorption : | High |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.17 cm/s |
Log Po/w (iLOGP) : | 0.0 |
Log Po/w (XLOGP3) : | 3.39 |
Log Po/w (WLOGP) : | -0.2 |
Log Po/w (MLOGP) : | 1.0 |
Log Po/w (SILICOS-IT) : | 2.41 |
Consensus Log Po/w : | 1.32 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -3.73 |
Solubility : | 0.0387 mg/ml ; 0.000186 mol/l |
Class : | Soluble |
Log S (Ali) : | -4.53 |
Solubility : | 0.00621 mg/ml ; 0.0000298 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -1.9 |
Solubility : | 2.63 mg/ml ; 0.0126 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 3.05 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P301+P312-P302+P352-P304+P340-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With disulfur dichloride In dichloromethane at 20℃; for 51h; Inert atmosphere; | |
85% | With disulfur dichloride In dichloromethane for 16h; | |
85% | With disulfur dichloride In dichloromethane at 20℃; for 18h; | Disulfur dichloride (10 mL, 158 mmol) was added to a solution of 2- chloroacetonitrile (4.0 mL, 64 mmol) in CH2Cl2 (13 mL) at room temperature under an inert atmosphere of argon. The resulting mixture was stirred at room temperature for 18 h. The precipitate was collected by filtration, washed with CH2Cl2 copiously, and then dried to afford 4,5-dichloro-l ,2,3-dithiazol-l-ium chloride (1 1.1 g, yield: 85%). MS (ESI) calcd for C2Cl3NS2 (m/z): 208.52, found: 248.0 [M+K]+, 206.8 [M-2] |
85% | With disulfur dichloride In dichloromethane at 20℃; for 18h; | 1 Preparation of 4,5-dichIoro-l,2,3-dithiazol-l-ium chloride (Appel's salt):Disulfur dichloride (10 mL, 158 mmol) was added to a solution of 2- chloroacetonitrile (4.0 mL, 64 mmol) in CH2Cl2 (13 mL) at room temperature under an inert atmosphere of argon. The resulting mixture was stirred at room temperature for 18 h. The precipitate was collected by filtration, washed with CH2Cl? copiously, and then dried to afford 4,5-dichloro-l ,2,3-dithiazol-l -ium chloride (1 1.1 g, yield: 85%). MS (ESI) calcd for C2Cl3NS2 (m/z): 208.52, found: 248.0 [M+K]+, 206.8 [M- 2]-- |
85% | With sulfur dichloride In dichloromethane for 18h; Cooling; Inert atmosphere; | Appel salt was prepared according to literature procedure,6d by addition of chloroacetonitrile (1 equiv) to a solution of sulfur dichloride (5 equiv) in dichloromethane (50 mL). Adogen (3-4 drops) was then added and the reaction was placed in a bowl of cold water.6b,c The mixture was left for 18 h without stirring under CaCl2 tube protection: The dark olive green solid was removed from the wall of the flask, filtered off under a blanket of argon, washed abundantly with dichloromethane and dried under vacuum for 2-3 h (average yield: 85%) |
80% | With disulfur dichloride In dichloromethane at 20℃; for 18h; | Synthesis of 4,5-dichioro- 1,2,3-dithiazol- 1-lum chloride (Appel’s Salt) To a solution of chloroacetonitrile (2 mL, 31.60 mmol, 1.0 eq) in DCM (15 mL) at ambienttemperature was added sulphur monochloride (13 mL, 158.01 mmol, 5.0 eq). Thereafter, thereaction mixture was allowed to stir for a minute and then left to stand for 18 h. The resulting brown precipitate that had formed was filtered under vacuum, and washed with DCM. The brown- green solid was then dried under vacuum (5.30 g, 80%). Mp: 117-130 00. |
80% | With disulfur dichloride In dichloromethane at 20℃; for 24h; Inert atmosphere; | 4,5-Dichloro-1,2,3-dithiazol-1-ium chloride (Appel’s Salt). 4,5-Dichloro-1,2,3-dithiazol-1-ium chloride (Appel’s Salt).24 Sulfur monochloride (13 mL, 158 mmol, 5 eq) was added to a solution of chloroacetonitrile (2 mL, 31.6 mmol, 1 eq) in anhydrous DCM (15 mL) in an oven-dried flask equipped with a gas outlet. Thereafter, the reaction mixture was swirled for a few seconds and then left to stand, without further agitation, for 24 h at room temperature under a nitrogen atmosphere. The resulting brown precipitate that had formed was filtered under vacuum and washed copiously with DCM (3 x 200 mL) to afford Appel’s salt as a brown-green solid (5.30 g, 80%). Mp 117-130 oC. MS (ESI+): m/z Calculated for C2Cl3NS2 [M+H] 207.8616, found 207.8610. |
77% | With disulfur dichloride; Adogen(R) 464 In dichloromethane at 20℃; | |
75% | With sulfur monochloride In dichloromethane for 72h; Inert atmosphere; | 1.1 1. Preparation of Appel SaltA 500-mL round-bottomed flask was charged with chloroacetonitrile (20 mL), sulfur monochloride (120 mL), and CH2CI2 (110 mL) under argon. The reaction stirred under argon for 3 days while a brown precipitate formed. The precipitate was collected by suction filtration and washed with CH2CI2 (300 mL) and hexanes (300 mL). The washed solid was vacuum dried to give the product as a brown solid (75% yield). |
75% | With disulfur dichloride In dichloromethane at 20℃; for 72h; Inert atmosphere; | 1 Example 1 Under nitrogen,Add 20 mL of chloroacetonitrile and 120 mL of dithio-dichloride to the vial110 mL of methylene chloride in a 500 mL flask and reacted at room temperature for about 72 hours. Upon completion of the reaction, a brown solid precipitated. The solid was collected by suction filtration and the filter cake was washed with methylene chloride and n-hexane, respectively, and dried in vacuo to give a brown solid49.7 g of 4,5-dichloro-1,2,3-dithiazole chloride was used for the next reaction in a yield of 75%. |
65% | With disulfur dichloride In dichloromethane at 20℃; for 12h; | |
With disulfur dichloride | ||
With disulfur dichloride In dichloromethane at 20℃; for 18h; Inert atmosphere; | 49.A Example 49 9-[4-(l-Amino-cvclobutyl -phenyn-2-phenyl-9H-purine-8-carbonitrile Step A: Disulfurdichloride (6.6 mL, 101 mmol) was added to a solution of 2- chloroacetonitrile (3.0 g, 40.2 mmol) in CH2C12 (10 mL) at room temperature, under an insert atomosphere of nitrogen, the resulting mixture was stirred at room temperature for 18 hours.the reaction mixture was concentrated in vacuo to get crude product 4,5-Dichloro-[l,2,3]dithiazol-l- ylium chloride (8 g crude) which was used without purification. | |
With disulfur dichloride |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With water; dimethyl sulfoxide In acetonitrile at 20℃; for 2h; | |
89% | With formic acid In neat (no solvent) at 20℃; for 2h; | 3.4.1. Reaction of 4,5-Dichloro-1,2,3-dithiazolium Chloride (2) with Formic Acid Appel’s salt 2 (208 mg, 1.00 mmol) was added to a stirred solution of HCO2H (98%, 1 mL), and the solution was stirred at ca. 20 °C, protected with a CaCl2 drying tube, until complete consumption of the starting material (2 h). The mixture was then adsorbed onto silica, and chromatography (n-hexane/DCM, 60:40) gave 4-chloro-5H-1,2,3-dithiazol-5-one (9) (137 mg, 89%) as pale yellow plates, mp 35-36 °C (from pentane, lit. [17] 39 °C); Rf 0.48 (n-hexane/DCM, 60:40); δC (75 MHz; CDCl3) 183.3 (s), 147.0 (s); νmax/cm-1 1651s (C=O), 1612m, 1501m, 1337w, 1142w, 1021m, 1080w, 847m, 837m, 806w, 785m, identical to an authentic sample [17]. |
84% | With dimethyl sulfoxide In acetonitrile at 20℃; for 1h; |
72% | With sodium nitrate In dichloromethane for 16h; Heating; | |
With formic acid at 20℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With pyridine In dichloromethane for 0.5h; Ambient temperature; | |
76% | With pyridine In dichloromethane Ambient temperature; | |
With pyridine In dichloromethane Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With pyridine 1) CH2Cl2, 2 h, room temperature; 2) CH2Cl2, 2 h, room temperature; Yield given. Multistep reaction; | ||
With pyridine 1) CH2Cl2, rt, 2 h; 2) CH2Cl2, rt, 2 h; Multistep reaction; | ||
In dichloromethane at 20℃; for 2h; |
Stage #1: 4,5-dichloro-1,2,3-dithiazol-1-ium chloride; 4-fluoroaniline In dichloromethane at 20℃; for 1h; Stage #2: With pyridine In dichloromethane at 20℃; for 2h; | General method for the synthesis of 4-chloro-1,2,3-dithiazoles (8-39). General procedure: To a stirred suspension of 4,5-dichloro-1,2,3-dithiazolium chloride (Appel’s salt) (6)51a (100 mg, 0.48 mmol) in dichloromethane (4 mL) at ca. 20°C, the corresponding arylamine (0.48 mmol) was added. After 1 h, pyridine (77.3 μL, 0.96 mmol) was added to the reaction mixture dropwise. After a further 2 h the reaction mixture was adsorbed onto silica and purified by dry flash chromatography to afford the corresponding (Z)-4-chloro-N-aryl-5H-1,2,3-dithiazol-5-imine. Compounds 7-9,45 and 11-15,45 25-2645 and 35-3851l were consistent with literature reports. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With pyridine In dichloromethane for 2h; Ambient temperature; | |
76% | Stage #1: 2-amino-4,5-dimethoxybenzonitrile; 4,5-dichloro-1,2,3-dithiazolium chloride In dichloromethane at 20℃; for 1h; Stage #2: With pyridine In dichloromethane at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | In dichloromethane for 0.3h; Ambient temperature; | |
95% | Stage #1: 4,5-dichloro-1,2,3-dithiazolium chloride; 2-amino-phenol In dichloromethane at 20℃; for 1h; Stage #2: With pyridine In dichloromethane at 20℃; for 2h; | |
76% | With pyridine In dichloromethane at 20℃; Inert atmosphere; | 4.4. Synthesis of benzo[d]oxazole-2-carbonitriles (13 and 14) General procedure: 4.4. Synthesis of benzo[d]oxazole-2-carbonitriles (13 and 14)4,5-Dichloro-1,2,3-dithiazolium chloride (4.066 g, 19.5 mmol)was added portionwise to a stirred solution of the appropriateaminophenol (15 mmol) in freshly distilled methylene chloride(115 mL) at room temperature. The dark mixture was vigorouslyagitated for 3 h. Pyridine (30 mmol, 2.42 mL) was added dropwiseto the solution, which was further agitated for another 2 h. Thereaction mixture was quenched with water. The organic layer wasseparated and dried over magnesium sulfate and evaporated todryness in vacuo. (Z)-2-(4-chloro-5H-1,2,3-dithiazol-5-ylideneamino)phenol was purified by flash chromatography usingpetroleum ether/methylene chloride (100:0 to 0:100, v/v) or directlyengaged in the cyclization step.(Z)-2-(4-Chloro-5H-1,2,3-dithiazol-5-ylideneamino)phenol wasdissolved in toluene (50 mL) and vigorously refluxed for 3 h. Thereaction mixture was evaporated in vacuo. Purification of the residueby flash chromatography using petroleum ether/methylenechloride (100:0 to 0:100, v/v) afforded the corresponding benzo[d]oxazole-2-carbonitriles.4.4.1. (Z)-2-(4-Chloro-5H-1,2,3-dithiazol-5-ylideneamino)phenol(11). Yield 76% (3.71 g), yellow solid, mp183e185 C; IR (cm1)ymax 3385,1661,1608,1583,1472,1444,1339,1286,1254,1219,1135,1033, 951, 854, 807, 744, 730, 674; 1H NMR (300 MHz, DMSO-d6)d 9.46 (br s, 1H, OH), 7.12e7.03 (m, 1H, Har), 7.02e6.94 (m, 2H, Har),6.87 (td, J7.8,1.4 Hz, 1H, Har); 13C NMR (75 MHz, DMSO-d6) d 160.7,148.0, 147.2, 139.4, 127.4, 120.3, 119.8, 117.3; HRMS calcd forC8H5N2O [MH] 244.9610, found 244.9607.4.4.2. Benzo[d]oxazole-2-carbonitrile (13). Yield 61% (1.317 g), colourlesssolid, mp102e104 C; IR (cm1) ymax 2249, 1530, 1475,1443, 1338, 1256, 1169, 1102, 950, 893, 817, 759, 748, 685, 620; 1HNMR (300 MHz, DMSO-d6) d 8.00 (d, J8.0 Hz, 1H, Har), 7.94 (d,J8.3 Hz, 1H, Har), 7.74e7.67 (m, 1H, Har), 7.63e7.56 (m, 1H, Har); 13CNMR (75 MHz, DMSO-d6) d 150.6, 139.4, 137.8, 129.9, 127.2, 122.0,112.4, 110.2. This compound was already described2b,5, spectrometricdata are consistent with the assigned structure. |
69% | Stage #1: 4,5-dichloro-1,2,3-dithiazolium chloride; 2-amino-phenol In dichloromethane at 20℃; for 3h; Inert atmosphere; Stage #2: With pyridine In dichloromethane at 20℃; for 2h; | |
In dichloromethane at 20℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With pyridine In dichloromethane at 20℃; Inert atmosphere; | 4.2. Synthesis of ortho-halogenated N-aryliminodithiazolesusing 4,5-dichloro-1,2,3-dithiazolium chloride (Appel salt) General procedure: 4.2. Synthesis of ortho-halogenated N-aryliminodithiazolesusing 4,5-dichloro-1,2,3-dithiazolium chloride (Appel salt)4,5-Dichloro-1,2,3-dithiazolium chloride (5.421 g, 26 mmol)was added portionwise to a stirred solution of the appropriateamine (20 mmol) in freshly distilled methylene chloride (150 mL)at room temperature. The dark mixture was vigorously agitated for3 h. Pyridine (40 mmol, 3.23 mL) was added dropwise to the solution,which was further agitated for another 2 h. The reactionmixture was quenched with water. The organic layer was separatedand dried over magnesium sulfate and evaporated to drynessin vacuo. Purification of the dark brown residue by flashchromatography using petroleum ether/methylene chloride (100:0to 0:100, v/v) as eluent afforded the correspondingaryliminodithiazoles.4.2.1. (Z)-2-Bromo-N-(4-chloro-5H-1,2,3-dithiazol-5-ylidene) aniline(1). Yield 97% (5.968 g), yellow solid, mp80e82 C; IR (cm1) ymax3065, 1691, 1661, 1596, 1583, 1540, 1503, 1463, 1433, 1223, 1150,1042, 1024, 856, 848, 771, 720, 673; 1H NMR (300 MHz, DMSO-d6)d 7.76 (dd, J8.0, 0.9 Hz, 1H, H-3), 7.55e7.43 (m, 1H, Har), 7.27e7.13(m, 2H, Har); 13C NMR (75 MHz, DMSO-d6) d 163.0, 150.9, 146.8, 134.1, 130.1, 127.7, 119.2, 114.8; HRMS calcd for C8H579BrClN2S2[MH] 306.8771, found 306.8766. |
91% | In dichloromethane for 1h; Ambient temperature; | |
Stage #1: 4,5-dichloro-1,2,3-dithiazol-1-ium chloride; 2-bromoaniline In dichloromethane at 20℃; for 1h; Stage #2: With pyridine In dichloromethane at 20℃; for 2h; | General method for the synthesis of 4-chloro-1,2,3-dithiazoles (8-39). General procedure: To a stirred suspension of 4,5-dichloro-1,2,3-dithiazolium chloride (Appel’s salt) (6)51a (100 mg, 0.48 mmol) in dichloromethane (4 mL) at ca. 20°C, the corresponding arylamine (0.48 mmol) was added. After 1 h, pyridine (77.3 μL, 0.96 mmol) was added to the reaction mixture dropwise. After a further 2 h the reaction mixture was adsorbed onto silica and purified by dry flash chromatography to afford the corresponding (Z)-4-chloro-N-aryl-5H-1,2,3-dithiazol-5-imine. Compounds 7-9,45 and 11-15,45 25-2645 and 35-3851l were consistent with literature reports. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 30% 2: 36% | With N-ethyl-N,N-diisopropylamine In dichloromethane at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | Stage #1: 4-amino-5-fluoro-2-[(2,2,2-trifluoroethyl)thio]benzonitrile; 4,5-dichloro-1,2,3-dithiazolium chloride In dichloromethane at 20℃; for 2h; Stage #2: With pyridine In dichloromethane at 20℃; for 1h; | 5.1 To a 50 ml dichloromethane solution of 3.2 g (12.8 mmol) of4-amino-5-fluoro-2- [ (2,2, 2-trifluoroethyl) thio] benzonitrile was added 3.O g (14.4 mmol) of4, 5-dichloro-l, 2, 3-dithiazol-l-ium chloride and the mixture was stirred at room temperature for 2 hours. Then, at room temperature, a 20 ml dichloromethane solution of 2.2 g (27.8 mmol) of pyridine was dropped, and the mixture was stirred at room temperature for 1 hour without any other operation. After completion of the reaction, the reaction solution was washed with saturated saline, the solvent was distilled off under reduced pressure, then, the residue was purified by silica gel column chromatography, to obtain 4.1 g of the aimed compound in the form of yellow crystal (yield: 83%) . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | Stage #1: 4-amino-3-bromo-N-[2-ethyl-6-methyl-4-(1,1,1,2,3,3,4,4,4-nonafluorobutan-2-yl)phenyl]benzamide; 4,5-dichloro-1,2,3-dithiazolium chloride In tetrahydrofuran at 18 - 30℃; for 2h; Stage #2: With pyridine In tetrahydrofuran; dichloromethane at 18 - 30℃; for 1h; | 12.12-1 4-amino-3-bromo-N-[2-ethyl-6-methyl^-(l , 1 , 1 ,2,3,3,4,4,4-nonafluorobιitan-2-yl)phenyl]benzamide(0.254 g) was dissolved in tetrahydrofiιran(20 ml). To the mixture was added 4,5-dichJoro-l,2,3-dithiazol-l-iurn chloride (0.106 g), and stirred at room temperature for 2 hours. To the reaction mixture was added pyridine (0.091 g) in dichloromethane, and stirred at room temperature for 1 hour. The solvent was removed under reduced pressure. To the residue was added water and extracted twice with ethyl acetate. The organic phases were combined and washed with water, and dried over anhydrous magnesium sulfate. The drying agent (anhydrous magnesium sulfate) was removed by filtration and the solvent was distilled off under the reduced pressure. The residue was purified by column chromatography to obtain3-bromo-4-[4κ;Woro-5H-l^,3κlitrazDl-5-ylidene]arrdno}-N-[2-eihyl-6-me%14-(l,l,l^,3,3,4,4,4-nonafl uorobutan-2-yl)phenyl]benzamide (0.270 g, 85%).(ref. Frere, S. et al, Tetrahedron 2003, 59, 773-779.) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With triethylamine In N,N-dimethyl-formamide at 0 - 20℃; Inert atmosphere; | 3 Example 3 Under nitrogen atmosphere, 10.5 g (76.0 mmol) of 4-methoxy-o-phenylenediamine was dissolved in 200 ml of N, N-(DMF), 31 ml (228 mmol) of triethylamine was added, the mixture was cooled to 0 ° C in ice-water and 10.4 g (50.1 mmol) of 4,5-dichloro-1,2,3-dithiazole Chloride, added after the reaction was continued under nitrogen for 1 hour, then slowly warmed to room temperature and stirred overnight. The reaction mixture was poured into 2 liters of ice water mixture, the solid precipitated, and the solid was collected by suction filtration. The crude product was recrystallized from a 3/1 volume ratio of ethyl acetate / cyclohexane solvent,There was obtained 5.3 g of 2-cyano-6-methoxybenzimidazole as a red-brown solid in a yield of 61%. |
3.34 g | With pyridine at 0 - 20℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With pyridine In dichloromethane at 20℃; for 3h; | |
56% | With pyridine In dichloromethane at 20℃; for 3h; | |
51% | Stage #1: 4,5-dichloro-1,2,3-dithiazolium chloride; 6-amino-3-benzyl-5-bromoquinazolin-4(3H)-one In dichloromethane at 20℃; for 1h; Inert atmosphere; Stage #2: With pyridine In dichloromethane at 20℃; for 2h; Inert atmosphere; | 5 4.2.5.3-Benzyl-5-bromo-6-(4-chloro-5H-1,2,3-dithiazol-5-ylideneamino)quinazolin-4(3H)-one (10). 4.2.5 3-Benzyl-5-bromo-6-(4-chloro-5H-1,2,3-dithiazol-5-ylideneamino)quinazolin-4(3H)-one (10) A suspension of 9 (4.0 g, 12.1 mmol) and 4,5-dichloro-1,2,3-dithiazolium chloride (Appel salt) (3.78 g, 18.5 mmol) in dichloromethane (120 mL) was stirred at room temperature under an argon atmosphere. After 1 h of stirring at room temperature, pyridine (2 equiv) was added and the mixture was stirred again 2 h at room temperature. The resulting solution was concentrated under reduced pressure. The crude residue was purified by chromatography on silica gel with ethyl acetate/dichloromethane (5:95 then 10:90, v/v) to give the expected compound 10 (2.90 g, yield 51%) as a yellow powder: mp 210 °C (lit. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With pyridine In dichloromethane at 20℃; Inert atmosphere; | Methyl-4-bromo-5-[(5E)-4-chloro-5H-1,2,3-dithiazol-5-ylidene]amino}-2-[(trifluoroacetyl)amino]benzoate (10) General procedure: A suspension of 9 (10.0 g, 29.3 mmol) and 4,5-dichloro-1,2,3-dithiazoliumchloride (9.16 g, 35.2 mmol, 1.2 equiv) in DCM (180 mL) was stirred at room temperature under an argon atmosphere. After 1 h of stirring at room temperature, pyridine (4.8 mL, 58.6 mmol, 2.0 equiv) was added and the mixture was stirred again 2 h at room temperature. The resulting solution was concentrated in vacuo to give a crude residue, which was purified by flash chromatographyon silica gel with PE/DCM (1:0 to 5:5, v/v) to give 10 (10.3 g, 74%) as an orange solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With pyridine In dichloromethane at 20℃; for 2h; Inert atmosphere; | Methyl-4-bromo-5-[(5E)-4-chloro-5H-1,2,3-dithiazol-5-ylidene]amino}-2-[(trifluoroacetyl)amino]benzoate (10) A suspension of 9 (10.0 g, 29.3 mmol) and 4,5-dichloro-1,2,3-dithiazoliumchloride (9.16 g, 35.2 mmol, 1.2 equiv) in DCM (180 mL) was stirred at room temperature under an argon atmosphere. After 1 h of stirring at room temperature, pyridine (4.8 mL, 58.6 mmol, 2.0 equiv) was added and the mixture was stirred again 2 h at room temperature. The resulting solution was concentrated in vacuo to give a crude residue, which was purified by flash chromatographyon silica gel with PE/DCM (1:0 to 5:5, v/v) to give 10 (10.3 g, 74%) as an orange solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With pyridine In dichloromethane at 20℃; Inert atmosphere; | 4.2. Synthesis of ortho-halogenated N-aryliminodithiazolesusing 4,5-dichloro-1,2,3-dithiazolium chloride (Appel salt) General procedure: 4.2. Synthesis of ortho-halogenated N-aryliminodithiazolesusing 4,5-dichloro-1,2,3-dithiazolium chloride (Appel salt)4,5-Dichloro-1,2,3-dithiazolium chloride (5.421 g, 26 mmol)was added portionwise to a stirred solution of the appropriateamine (20 mmol) in freshly distilled methylene chloride (150 mL)at room temperature. The dark mixture was vigorously agitated for3 h. Pyridine (40 mmol, 3.23 mL) was added dropwise to the solution,which was further agitated for another 2 h. The reactionmixture was quenched with water. The organic layer was separatedand dried over magnesium sulfate and evaporated to drynessin vacuo. Purification of the dark brown residue by flashchromatography using petroleum ether/methylene chloride (100:0to 0:100, v/v) as eluent afforded the correspondingaryliminodithiazoles. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With pyridine; In dichloromethane; at 20℃;Inert atmosphere; | General procedure: 4.2. Synthesis of ortho-halogenated N-aryliminodithiazolesusing 4,5-dichloro-1,2,3-dithiazolium chloride (Appel salt)4,5-Dichloro-1,2,3-dithiazolium chloride (5.421 g, 26 mmol)was added portionwise to a stirred solution of the appropriateamine (20 mmol) in freshly distilled methylene chloride (150 mL)at room temperature. The dark mixture was vigorously agitated for3 h. Pyridine (40 mmol, 3.23 mL) was added dropwise to the solution,which was further agitated for another 2 h. The reactionmixture was quenched with water. The organic layer was separatedand dried over magnesium sulfate and evaporated to drynessin vacuo. Purification of the dark brown residue by flashchromatography using petroleum ether/methylene chloride (100:0to 0:100, v/v) as eluent afforded the correspondingaryliminodithiazoles. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20% | 4.4. Synthesis of benzo[d]oxazole-2-carbonitriles (13 and 14)4,5-Dichloro-1,2,3-dithiazolium chloride (4.066 g, 19.5 mmol)was added portionwise to a stirred solution of the appropriateaminophenol (15 mmol) in freshly distilled methylene chloride(115 mL) at room temperature. The dark mixture was vigorouslyagitated for 3 h. Pyridine (30 mmol, 2.42 mL) was added dropwiseto the solution, which was further agitated for another 2 h. Thereaction mixture was quenched with water. The organic layer wasseparated and dried over magnesium sulfate and evaporated todryness in vacuo. (Z)-2-(4-chloro-5H-1,2,3-dithiazol-5-ylideneamino)phenol was purified by flash chromatography usingpetroleum ether/methylene chloride (100:0 to 0:100, v/v) or directlyengaged in the cyclization step.(Z)-2-(4-Chloro-5H-1,2,3-dithiazol-5-ylideneamino)phenol wasdissolved in toluene (50 mL) and vigorously refluxed for 3 h. Thereaction mixture was evaporated in vacuo. Purification of the residueby flash chromatography using petroleum ether/methylenechloride (100:0 to 0:100, v/v) afforded the corresponding benzo[d]oxazole-2-carbonitriles. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With pyridine In dichloromethane at 20℃; Inert atmosphere; | 4.2. Synthesis of ortho-halogenated N-aryliminodithiazolesusing 4,5-dichloro-1,2,3-dithiazolium chloride (Appel salt) General procedure: 4.2. Synthesis of ortho-halogenated N-aryliminodithiazolesusing 4,5-dichloro-1,2,3-dithiazolium chloride (Appel salt)4,5-Dichloro-1,2,3-dithiazolium chloride (5.421 g, 26 mmol)was added portionwise to a stirred solution of the appropriateamine (20 mmol) in freshly distilled methylene chloride (150 mL)at room temperature. The dark mixture was vigorously agitated for3 h. Pyridine (40 mmol, 3.23 mL) was added dropwise to the solution,which was further agitated for another 2 h. The reactionmixture was quenched with water. The organic layer was separatedand dried over magnesium sulfate and evaporated to drynessin vacuo. Purification of the dark brown residue by flashchromatography using petroleum ether/methylene chloride (100:0to 0:100, v/v) as eluent afforded the correspondingaryliminodithiazoles. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With pyridine In dichloromethane at 20℃; for 2h; Inert atmosphere; | 2.2.8. Methyl 2-[(tert-butoxycarbonyl)amino]-4-[(4-chloro-5H-1,2,3-dithiazol-5-ylidene)-amino]benzoate (27). A mixture of compound 22 (6.0 g, 22.5 mmol), Appel’s salt (5.6 g, 27.0mmol, 1.2 equiv) and pyridine (3.6 mL, 45.0 mmol, 2.0 equiv) in dichloromethane (220 mL),was stirred at room temperature for 2 h, gave product 27 (6.7 g, 74%) as a yellow powder: mp= 166-168 °C; IR (cm-1) max 2988, 1775, 1695, 1556, 1513, 1502, 1274, 1245, 1111, 796; 1HNMR (300 MHz, DMSO-d6) δ 10.36 (s, 1H, NHBoc), 8.11 (d, J = 1.6 Hz, 1H, H3), 8.04 (d, J= 8.5 Hz, 1H, H6), 6.89 (dd, J = 8.5, 1.8 Hz, 1H, H5), 3.85 (s, 3H, OCH3), 1.48 (s, 9H, 3 ×CH3); 13C NMR (75 MHz, DMSO-d6) δ 167.5, 161.3, 156.0, 152.0, 146.8, 133.0, 113.1, 111.8, 108.1, 80.6, 52.5, 27.9 (3C); HRMS calcd for C15H17N3O4S235Cl [M+H]+ 402.0349found 402.0333. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With pyridine In dichloromethane at 20℃; for 3h; Inert atmosphere; | 2.2.4. Methyl 5-bromo-2-[(tert-butoxycarbonyl)amino]-4-[(4-chloro-5H-1,2,3-dithiazol-5-ylidene)amino]benzoate (24). According to the procedure described for 16, a mixture of 23(4.5 g, 13.1 mmol), Appel’s salt (3.3 g, 15.7 mmol, 1.2 equiv) and pyridine (2.1 mL, 26.2mmol, 2.0 equiv) in dichloromethane (260 mL), was stirred at room temperature for 3 h. Theresulting solution was concentrated under vacuo to give a crude residue which was purified bychromatography on silica gel with methylene chloride/petroleum ether (0:100 to 100:0, v/v) togive 24 (5.2 g, 82%) as an yellow powder: mp = 192-194 °C; IR (cm-1) max 3309, 3117,2986, 1786, 1694, 1568, 1533, 1502, 1272, 1245, 1111, 796; 1H NMR (300 MHz, DMSO-d6)δ 10.25 (s, 1H, NHBoc), 8.21 (s, 1H, H6), 8.12 (s, 1H, H3), 3.87 (s, 3H, OCH3), 1.48 (s, 9H, 3× CH3); 13C NMR (75 MHz, DMSO-d6) δ 166.3, 162.9, 154.3, 151.8, 146.2, 142.1, 135.3,113.3, 107.8, 106.2, 80.9, 52.7, 27.8 (3C); HRMS calcd for C15H16N3O4S279Br35Cl [M+H]+479.9454 found 479.9463. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With pyridine In dichloromethane at 20℃; for 1h; Inert atmosphere; | 2.1.6. Methyl 2-bromo-6-[(tert-butoxycarbonyl)amino]-3-[(4-chloro-5H-1,2,3-dithiazol-5-ylidene)amino]benzoate To a stirred solution of 14 (0.250 g, 0.56 mmol) and pyridine(0.09 mL, 1.12 mmol, 2.0 equiv) in dichloromethane (1.1 mL) was added 4,5-dichloro-1,2,3-dithiazolium chloride (Appel salt, 0.140 g, 0.67 mmol, 1.2 equiv) at room temperature. After1 h of stirring at room temperature under an argon atmosphere, the resulting solution wasconcentrated under vacuo to give a crude residue which was purified by chromatography onsilica gel with methylene chloride/petroleum ether (0:100 to 100: 0, v/v) to give 16 (0.166 g,62%) as an orange powder: mp = 134-136 °C; IR (cm-1) max 3416, 2978, 1732, 1598, 1571,1506, 1387, 1218, 1149, 1111, 984, 865, 661; 1H NMR (300 MHz, DMSO-d6) δ 9.17 (s, 1H,NHBoc), 7.49 (d, J = 8.7 Hz, 1H, H5), 7.32 (d, J = 8.7 Hz, 1H, H4), 3.83 (s, 3H, OCH3), 1.45(s, 9H, 3 × CH3); 13C NMR (75 MHz, DMSO-d6) δ 165.5, 162.7, 153.4, 147.0, 146.1, 134.0,131.1, 125.9, 119.6, 112.4, 79.6, 52.5, 28.0 (3C); HRMS calcd for C15H16N3O4S279Br35Cl[M+H]+ 479.9454 found 479.9438. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With copper In acetonitrile at 20℃; for 1h; Inert atmosphere; | 4,4'-Dichloro-5,5'-bi-1,2,3-dithiazole 1a. 4,4'-Dichloro-5,5'-bi-1,2,3-dithiazole 1a. Copper powder (256 mg,4 mmol) was added to a slurry of 4,5-dichloro-1,2,3-dithiazol-1-iumchloride 2a (416 mg, 2 mmol) in acetonitrile (10 ml). The mixture wasstirred at room temperature for 1 h, poured into ice water (100 ml), theprecipitate was filtered, washed thoroughly with water (2×10 ml), MeCN(2×5 ml), CH2Cl2 (2×5 ml) and dried to afford black crystals of compound1a, yield 98%, mp 144-145 °C (lit.,13 mp 120-121 °C). The IR, UV andmass spectra are similar to those of the sample prepared by the literaturemethod.13 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With pyridine In dichloromethane at 20℃; for 3h; Inert atmosphere; | 6-[(4-Chloro-5H-1,2,3-dithiazol-5-yl)amino]-3-cyclopropylquinazolin-4(3H)-one (5). A suspension of6-amino-3-cyclopropylquinazolin-4(3H)-one (3, 300 mg, 1.49 mmol) and 4,5-dichloro-1,2,3-dithiazoliumchloride (1.2 equiv.) in DCM (0.1 M solution) was stirred for 1 h at room temperature under an argonatmosphere. Pyridine (2.0 equiv.) was added and the mixture was stirred again for 2 h at roomtemperature. The resulting solution was concentrated under vacuo to give a crude residue which waspurified by chromatography on silica gel with EtOAc/DCM (5/95 then 50/50, v/v) to give the expectediminodithiazole as a yellow solid (382 mg, 76%), mp. 190-192 °C; 1H-NMR (DMSO-d6) δ 8.29 (s, 1H,H2), 7.97 (d, J = 2.4 Hz, 1H, H5), 7.78 (d, J = 8.7 Hz, 1H, H8), 7.65 (dd, J = 8.7, 2.4 Hz, 1H, H7), 3.20-3.16(m, 1H, NCH), 1.09-0.94 (m, 4H, CH); 13C-NMR (DMSO-d6) δ 161.0, 160.4, 149.0, 147.7, 147.0, 145.4,129.1, 128.2, 122.3, 114.2, 29.3, 5.9; νmax 3073, 1659, 1592, 1530, 1454, 1305, 951, 842, 581 cm-1; HRMScalcd for C13H10N4OS2Cl2 [M + H]+ 336.9985 found 336.9974. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With pyridine In dichloromethane at 20℃; for 3h; | (Z)-5-Bromo-6-[(4-chloro-5H-1,2,3-dithiazol-5-ylidene)amino]-3-cyclopropylquinazolin-4(3H)-one (15). A suspension of 6-amino-5-bromo-3-cyclopropylquinazolin-4(3H)-one (11, 2.0 g, 1.0 equiv.) and 4,5-dichloro-1,2,3-dithiazolium chloride (1.2 equiv.) in DCM (0.1 M solution) was stirred for 1 h at room temperature under an argon atmosphere. Pyridine (2.0 equiv.) was added and the mixture was stirred again for 2 h at room temperature. The resulting solution was concentrated under vacuo togive a crude residue which was purified by chromatography on silica gel with EtOAc/DCM (5/95then 50/50, v/v) to give the desired iminodithiazole as an orange solid (2.3 g, 76%), mp. 204-206 °C; 1H-NMR (DMSO-d6) δ 8.33 (s, 1H, H2), 7.75 (d, J = 8.7 Hz, 1H, H7), 7.58 (d, J = 8.7 Hz, 1H, H8), 3.24-3.17(m, 1H, NCH), 1.06-1.00 (m, 2H, CH), 0.97-0.94 (m, 2H, CH); 13C-NMR (DMSO-d6) δ 163.2, 159.6,150.5, 147.9, 146.8, 145.8, 129.0, 124.6, 120.3, 111.3, 29.7, 6.0 (2C); νmax 3003, 1862, 1675, 1593, 1452, 1325,1293, 1148, 826, 759 cm-1; HRMS calcd for C13H9N4OS279BrCl [M + H]+ 414.9090 found 414.9088. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | In dichloromethane at 20℃; for 18h; Inert atmosphere; | 3.2.1. General Procedure for the Synthesis of 3-(4-Chloro-5H-1,2,3-Dithiazol-5-Ylidene)Indolin-2-oneDerivatives (Table 2, 3a-d). General procedure: Appel’s salt (Scheme 2, 1; 4,5-dichloro-1,2,3-dithiazolium chloride; 15.76 mmol) was added to asolution of each appropriate 2-oxindole derivative (Scheme 2, 2a-d; 14.33 mmol) in CH2Cl2 (20 mL).After a few minutes, the uncolored mixture turned to a dark red color, and was stirred at roomtemperature for 18 h. The solvent was evaporated under reduced pressure, and the crude productwas dissolved with acetone (a minimum of 30 mL), and then precipitated with water (300 mL).The heterogeneous mixture was filtered in a vacuum, and the red solid was washed three times withwater (25 mL). This solid was finally dried over phosphorus pentoxide in a vacuum in a desiccator. (Z)-3-(4-Chloro-5H-1,2,3-dithiazol-5-ylidene)indolin-2-one (Table 2, 3a). Yield: 96%. Red solid; melting point (m.p.): 271-273 °C. νmax (cm-1): 3244, 1693, 1613, 1462, 1336, 1221, 1203, 1080, 743. 1H-NMR (400 MHz, DMSO-d6) = 11.22 (s, 1H), 8.19 (d, J = 8.0 Hz, 1H), 7.17 (t, J = 7.9 Hz, 1H), 6.91-6.97 (m, 2H).13C-NMR (400 MHz, DMSO-d6) = 169.5, 149.0, 143.8, 139.8, 127.4, 126.5, 120.8, 120.1, 115.7, 110.2.HRMS (ES) m/z calculated for C10H5ClN2OS2 [M + H]+ 267.9538, found 267.9545. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | In dichloromethane at 20℃; for 18h; Inert atmosphere; | 3.2.1. General Procedure for the Synthesis of 3-(4-Chloro-5H-1,2,3-Dithiazol-5-Ylidene)Indolin-2-oneDerivatives (Table 2, 3a-d). General procedure: Appel’s salt (Scheme 2, 1; 4,5-dichloro-1,2,3-dithiazolium chloride; 15.76 mmol) was added to asolution of each appropriate 2-oxindole derivative (Scheme 2, 2a-d; 14.33 mmol) in CH2Cl2 (20 mL).After a few minutes, the uncolored mixture turned to a dark red color, and was stirred at roomtemperature for 18 h. The solvent was evaporated under reduced pressure, and the crude productwas dissolved with acetone (a minimum of 30 mL), and then precipitated with water (300 mL).The heterogeneous mixture was filtered in a vacuum, and the red solid was washed three times withwater (25 mL). This solid was finally dried over phosphorus pentoxide in a vacuum in a desiccator. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | In dichloromethane at 20℃; for 18h; Inert atmosphere; | 3.2.1. General Procedure for the Synthesis of 3-(4-Chloro-5H-1,2,3-Dithiazol-5-Ylidene)Indolin-2-oneDerivatives (Table 2, 3a-d). General procedure: Appel’s salt (Scheme 2, 1; 4,5-dichloro-1,2,3-dithiazolium chloride; 15.76 mmol) was added to asolution of each appropriate 2-oxindole derivative (Scheme 2, 2a-d; 14.33 mmol) in CH2Cl2 (20 mL).After a few minutes, the uncolored mixture turned to a dark red color, and was stirred at roomtemperature for 18 h. The solvent was evaporated under reduced pressure, and the crude productwas dissolved with acetone (a minimum of 30 mL), and then precipitated with water (300 mL).The heterogeneous mixture was filtered in a vacuum, and the red solid was washed three times withwater (25 mL). This solid was finally dried over phosphorus pentoxide in a vacuum in a desiccator. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In dichloromethane; at 20℃; for 18h;Inert atmosphere; | General procedure: Appel?s salt (Scheme 2, 1; 4,5-dichloro-1,2,3-dithiazolium chloride; 15.76 mmol) was added to asolution of each appropriate 2-oxindole derivative (Scheme 2, 2a-d; 14.33 mmol) in CH2Cl2 (20 mL).After a few minutes, the uncolored mixture turned to a dark red color, and was stirred at roomtemperature for 18 h. The solvent was evaporated under reduced pressure, and the crude productwas dissolved with acetone (a minimum of 30 mL), and then precipitated with water (300 mL).The heterogeneous mixture was filtered in a vacuum, and the red solid was washed three times withwater (25 mL). This solid was finally dried over phosphorus pentoxide in a vacuum in a desiccator. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With pyridine In dichloromethane at 20℃; Inert atmosphere; | General procedure for the synthesis of imino-1,2,3-dithiazoles 3, 9, 11 and 12 from starting amino ester derivatives. General procedure: Under an inert atmosphere (argon), dithiazolium salt 1 (0.208 g,1 mmol) was added to a solution of amino ester (1 mmol) in dichloromethane (5 mL). Pyridine (2 mmol) was slowly added. The mixture was stirred until all of the amine had been consumed (tlc control). The mixture was warmed to room temperature and the reaction mixture filtered through acidic alumina and pour into ice water and the organic layer was separated and the aqueous phase extracted with dichloromethane. The crude product was purified by column chromatography using petroleum ether/DCM as the eluent.Orange solid; Yield: 68% ; mp 130 °C ; 1H NMR (400 MHz, CDCl3) d : 4.38 (q, 2H, J 7.2 Hz, CH2),2.72-2.92 (m, 4H, 2 CH2), 1.73-2.00 (m, 4H, 2 CH2), 1.41 (t, 3H, J 7.2 Hz, CH3).13C NMR (100 MHz, CDCl3) d :164.0; 152.0; 149.2; 148.9; 136.4; 133.1; 127.2; 60.8; 25.7; 25.6; 22.9; 22.3; 14.3. υmax (ATR) / cm-1 : 2929,1665, 1545, 1268, 1146, 779. HRMS (ESI) m/z [M+H]+: calcd for C13H1335ClN2O2S3 : 359.98277; found :359.9853. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | General procedure: Appel?s salt and an aniline were allowed to stir in CH2CI2 (DCM) for 1 h at room temperature under a nitrogen atmosphere. The solution was then cooled to below 5 00 and base (preferably DBU orDBN) was added, dropwise over 30 mm, to the stirring solution maintained at 5 00 all under a nitrogen atmosphere. After the addition, the resulting mixture was stirred for 30 mm while allowing it to warm to room temperature, after which it was ref luxed at 40 C for 4 h. Upon cooling to room temperature (rt), ethyl acetate (EtOAc) was added. The reaction mixture was then washed with saturated NH4CIaq solution, and H20. The organic phase was dried over Na2SO4 and concentratedin vacuo. The crude material was purified by silica gel chromatography to provide the corresponding benzothiazoles. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | Stage #1: benzyl (E)-3-((4-aminophenyl)thio)acrylate; 4,5-dichloro-1,2,3-dithiazolium chloride In N,N-dimethyl-formamide at 20℃; for 1h; Inert atmosphere; Stage #2: With pyridine In N,N-dimethyl-formamide for 2h; Inert atmosphere; | Synthesis of benzyl (E)-3-((4-(((Z)-4-chloro-5H- 1,2,3-dithiazol-5-ylidene)amino)phenyl)thio)acrylate Appel’s salt (0.220 g, 1.08 mmol, 2 eq) and benzyl (E)-3-((4-aminophenyl)thio)acrylate (0.150 g,0.540 mmol, 1 eq) were dissolved in DMF (4 mL). The resulting solution was stirred at roomtemperature under a nitrogen atmosphere for 1 h. Thereafter, anhydrous pyridine (0.05 mL, 1 .08 mmol, 2 eq) was slowly added to the solution, after which it was left to stir for an additional 2 h.The mixture was then concentrated in vacuo and purified by silica column chromatography, eluting with 1:9 EtOAc:Pet. ether, to afford the title compound as a bright yellow solid (0.225 g, 99 %). Mp: 130-1 52 C. 1H-NMR (300 MHz, DMSO) O 7.66 (3H, m, H-8,5), 7.41 (5H, m, H-12,13,14), 7.28 (2H, d, J= 8.5 Hz, H-4), 6.07 (iH, d, J= 10.0 Hz, H-7), 5.20 (2H, s, H-b). 13C-NMR (100.6 MHz, DMSO) O 165.8 (C-9), 160.6 (C-2), 151.2 (C-i), 150.3 (C-7), 147.2 (C-3), 136.6 (C-6), 132.7 (C-i 1), 132.3 (C-5), 128.9 (C-i 3), 128.6 (C-i4), 128.5 (C-i2), 121.1 (C-4), 113.4 (C- 8), 65.9 (C-i 0). MS (ESI+): m/z Calculated for C18H13C1N202S3 [M+H] 420.9905, found 420.9899. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | Stage #1: 2-amino-5-bromobenzonitrile; 4,5-dichloro-1,2,3-dithiazolium chloride With hydrogenchloride In dichloromethane at 20℃; Stage #2: With 2,6-dimethylpyridine In dichloromethane at 0.2℃; | General procdure for [(4-chloro-5 H-1,2,3-dithiazol-5-ylidene)amino]arenes: General procedure: Aminoarene (0.48 mmol) was added to a stirred suspension of 4,5-dichloro-1,2,3-dithiazolium chloride (100 mg, 0.48 mmol) in dichloromethane (4 mL) at ca. 20 °C. After 1 hour 2,6-lutidine (111.2 μL, 0.96 mmol) was added dropwise. The reaction mixture was adsorbed onto silica after a further 2 hours and purified by flash chromatography to afford the corresponding [(4-chloro-5H-1,2,3-dithiazol-5-ylidene)amino]arene. Represenative example: (Z)-5-Bromo-2-[(4-chloro-5H-1,2,3-dithiazol-5-ylidene)amino]benzonitrile (32). Yellow needles (72%), mp (DSC) onset: 167.5 °C, peak max: 168.3 °C (from cyclohexane/DCE); (found: C, 32.6; H, 1.0; N, 12.6. C9H3BrClN3S2 requires C, 32.5; H, 0.9; N, 12.6%); λmax(DCM)/nm 230 (log ε 3.14), 250 (3.08), 314 (2.50), 383 (2.88), 419 inf (2.65); νmax/cm-1 3080w (Ar CH), 3063w, 2232w (C≡N), 1585m, 1560s, 1545m, 1489s, 1476s, 1458m, 1389w, 1269w, 1233w, 1182w, 1148m, 1126m, 1074m, 880m, 864s, 812m, 795m, 770m; 1H NMR (500 MHz, CDCl3) δ 7.87 (1H, d, J 2.0, H-6), 7.78 (1H, dd, J 8.5, 2.0, H-4), 7.21 (1H, d, J 9.0, H-3); 13C NMR (125 MHz, CDCl3) δ 161.9 (s), 125.1 (s), 148.2 (s), 137.5 (d), 136.4 (d), 119.1 (d), 118.8 (s), 114.9 (s), 108.1 (s); m/z (EI) 335 (M++4, 7%), 333 (M++2, 24), 331 (M+, 17), 272 (22), 270 (22), 240 (4), 238 (4), 234 (3), 232 (3), 208 (3), 206 (3), 182 (3), 180 (3), 159 (8), 127 (12), 125 (6), 115 (4), 100 (20), 93 (5), 88 (4), 75 (9), 70 (4), 66 (9), 64 (100), 50 (8). |
Tags: 75318-43-3 synthesis path| 75318-43-3 SDS| 75318-43-3 COA| 75318-43-3 purity| 75318-43-3 application| 75318-43-3 NMR| 75318-43-3 COA| 75318-43-3 structure
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P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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