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[ CAS No. 16112-21-3 ] {[proInfo.proName]}

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3d Animation Molecule Structure of 16112-21-3
Chemical Structure| 16112-21-3
Chemical Structure| 16112-21-3
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Product Details of [ 16112-21-3 ]

CAS No. :16112-21-3 MDL No. :MFCD00030228
Formula : C14H11NS Boiling Point : -
Linear Structure Formula :- InChI Key :JVPGYYNQTPWXGE-UHFFFAOYSA-N
M.W : 225.31 Pubchem ID :919385
Synonyms :

Calculated chemistry of [ 16112-21-3 ]

Physicochemical Properties

Num. heavy atoms : 16
Num. arom. heavy atoms : 15
Fraction Csp3 : 0.07
Num. rotatable bonds : 1
Num. H-bond acceptors : 1.0
Num. H-bond donors : 0.0
Molar Refractivity : 70.02
TPSA : 41.13 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : Yes
CYP2C9 inhibitor : Yes
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -4.39 cm/s

Lipophilicity

Log Po/w (iLOGP) : 2.94
Log Po/w (XLOGP3) : 4.62
Log Po/w (WLOGP) : 4.27
Log Po/w (MLOGP) : 3.6
Log Po/w (SILICOS-IT) : 5.18
Consensus Log Po/w : 4.12

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 0.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -4.78
Solubility : 0.00378 mg/ml ; 0.0000168 mol/l
Class : Moderately soluble
Log S (Ali) : -5.21
Solubility : 0.00139 mg/ml ; 0.00000618 mol/l
Class : Moderately soluble
Log S (SILICOS-IT) : -5.88
Solubility : 0.000296 mg/ml ; 0.00000132 mol/l
Class : Moderately soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 2.0
Synthetic accessibility : 2.31

Safety of [ 16112-21-3 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 16112-21-3 ]

* 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.

  • Downstream synthetic route of [ 16112-21-3 ]

[ 16112-21-3 ] Synthesis Path-Downstream   1~85

  • 1
  • [ 20199-06-8 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
95% With g-C3N4; air; In dimethyl sulfoxide; at 20℃; for 10h;Irradiation; In a 10mL quartz test tube, add 0.02mmol 4-methyl-N-phenylthiobenzamide,4mg g-C3N4, and 1mL DMSO,Stir at room temperature under 400-410nm LED irradiation in an air atmosphere for 10 hours. After the reaction is over, TLC plate detection,A product is formed.After the reaction,Pour the reaction mixture with g-C3N4 removed into water,Then it was extracted with ethyl acetate, the obtained organic layer was back-extracted with saturated brine, and finally the organic layer was dried with anhydrous sodium sulfate.Filter, spin dry, and pass through a silica gel column to obtain a white solid.The yield is 95%,
  • 2
  • [ 16112-21-3 ]
  • [ 24239-18-7 ]
YieldReaction ConditionsOperation in experiment
94% With N-Bromosuccinimide; In tetrachloromethane; for 4h;Reflux; 2.71 g 2-p-Tolylbenzothiazole (12 mmol) and 2.14 g N-bromosuccinimide (NBS) (12 mmol) were dissolved in 50 ml of CCl4. The solution was heated under reflux for 4 h. The precipitated succinimide was filtered, and the solvent was evaporated from the solution. The remaining gray oil was recrystallized from ethanol. The obtained white crystalline powder was dried in vacuum (3.43 g, 94%). m.p. 132-133 C refPreviewPlaceHolder[27]. 1H NMR (300 MHz, CDCl3): δppm 8.08-8.13 (d, 3H), 7.92-7.99 (d, 1H), 7.53-7.76 (m, 3H), 7.42-7.50 (t, 1H), 4.55-4.62 (s, 2H). MS(M+): 302.9717 Anal. Calc. for C14H10BrNS: C, 55.45%; H, 3.30%; N, 4.62%. Found: C, 55.38%; H, 3.40%; N, 4.57%.
94% With N-Bromosuccinimide; In tetrachloromethane; for 4h;Reflux; 2-p-Tolylbenzothiazole (2.71 g, 12 mmol) and N-bromosuccinimide (NBS) (2.14 g, 12 mmol) were dissolved in 50 mL of CCl4. The solution was refluxed for 4 h. The precipitated succinimide was filtered, and the solvent was evaporated from the solution. The remaining gray oil was recrystallized from ethanol. The obtained white crystalline powder was dried in vacuum (3.43 g, yield 94%). Mp: 132-133 C. 1H NMR (CDCl3) δ 7.928-8.132 (m, 8H, Ar-H), 4.550-4.622 (s, 2H, -CH2-).
59% With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; (1) 2-(4-Bromomethylphenyl)-1,3-benzothiazole: Refluxed for 1 hour was 150 ml of a carbon tetrachloride solution which contained 10 g of <strong>[16112-21-3]2-(4-methylphenyl)-1,3-benzothiazole</strong>, 8.0 g of N-bromosuccinimide (NBS) and 0.2 g of benzoyl peroxide. After allowing the reaction mixture to cool down, the insoluble material was filtered off and the filtrate was concentrated under reduced pressure. The residue was recrystallized from ethanol to give 8.0 g of colorless crystals having a melting point of 128-130 C. (yield: 59%). IR νmaxKBr cm-1: 1475, 1220, 965, 755, 600.
With N-Bromosuccinimide;dibenzoyl peroxide; In tetrachloromethane; cyclohexane; Synthesis of 4-(benzothiazol-2-yl) bromomethylbenzene To a solution of 45 g (0.2 mol) of 4-(benzothiazol-2-yl) toluene in 1000 ml of dry carbon tetrachloride were added 35.6 g (0.2 mol) of N-bromosuccinimide and a catalytic amount of benzoyl peroxide. The mixture was refluxed for 12 hours, and then allowed to cool down to room temperature. The precipitated succinimide was filtered off and the filtrate evaporated to dryness in vacuo, whereupon 55 g of crude crystals were obtained. Recrystallization from 1500 ml of cyclohexane gave 41 g of purified 4-(benzothiazol-2-yl) bromomethylbenzene as colorless flakes.
With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; for 9h;Reflux; <strong>[16112-21-3]2-(p-tolyl)benzothiazole</strong>(3.4 g, 15. 0 mmol), NBS (2.7 g, 15.0 mmol) and catalytic amount of benzoylperoxide (36 mg, 1 mol%) were dissolved in CCl4 (50 mL). The mixture washeated to reflux for 9 hours. The reaction was quenched by Na2SO3solution and extracted by CCl4 twice. Collected organic layers werewashed by brine, dried over Na2SO4 and concentrated togive the crude, which was recrystallized from hot EtOH to give the light purplesolid. NMR showed mono-brominated and dibrominated products were in a molarratio of 6:1. (3.2 g, 70% yield)LC-MS (ESI): [M+1]+ = 304.00, tR= 3.50 min. 1H NMR (400 MHz, CDCl3)δ 8.10-8.04 (m, 3H), 7.92-7.88 (m, 1H), 7.53-7.47 (m, 3H), 7.43-7.35 (m, 1H),4.52 (s, 1H).
8 g With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; for 12h;Reflux; Inert atmosphere; Schlenk technique; A mixture of compound 1 (9 g, 40 mmol), NBS (7.12 g, 40 mmol), and azodiisobutyronitrile (0.65 g) was refluxed in anhydrous CCl4 for 12 h. The mixture was cooled to room temperature, concentrated in vacuo, and the residue crystallized from cyclohexane yielding 8 g 1b as white solid.
With N-Bromosuccinimide; In tetrachloromethane; The solution of 1a (4.5 g, 15 mmol) in anhydrous CHCl3 (50 mL) was added dropwise to a solution (40 mL anhydrous CHCl3) of hexamethylenetetramine (2.1 g, 15 mmol). The mixture was refluxed for 5 h with vigorous stirring. The resulting precipitate was washed several times with deionized water and added to a mixture of ethanol and concentrated HCl (4:1, 100 mL). The resulting solution was kept stirring at 70 oC for 12 h and then allowed to stand at room temperature overnight. An HCl salt was obtained by filtration, washed with 10% KHCO3 (50 mL) and extracted into CHCl3 (50 mL). The organic layer was dried over anhydrous MgSO4. The solvent was removed in vacuo to give the primary amine 1b as a yellow solid (3.06 g, 85%). A mixture of 1b (1.8 g, 7.5 mmol) and paraformaldehyde (0.6 g, 19.5 mmol) in 20 mL CH2Cl2 was stirred for 5 h and treated dropwise with 2.25 mL (31 mmol) of SOCl2. After 1.5 h, the solvent and unreacted SOCl2 were removed under vacuum to give the product 1c. The generated solid was added to the THF solution of [(μ-LiS)2Fe2(CO)6], freshly prepared by the reaction of super hydride LiEt3BH (1 mol L-1 solution in THF, 8 mL) and [(μ-S)2-{Fe(CO)3}2] (2) (1.38 g, 4 mmol in 30 mL THF). The mixture was stirred for 2 h at -78 oC and then 1 h at room temperature. The solvent was removed on a rotary evaporator. The crude product was purified by column chromatography (silica, 10% dichloromethane in hexane as eluent) to give complex 4 (1.77 g, 72%) as a red solid.

  • 3
  • [ 874-60-2 ]
  • [ 137-07-5 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
55% In 1-methyl-pyrrolidin-2-one; at 100℃; for 2h; To asolution of 4-methylbenzyl chloride (3.1 g,20.0 mmol) in 50 mL of NMP, 2-aminobenzenethiol (3.1 g, 20.0mmol) was added. The mixture was heated to 100 0C for 2 hours. Themixture was cooled down to rt, and saturated Na2CO3solution was added, followed by 20 mL of water. The resulting white solid wasfiltered, washed by water and dried over high vacuum. (3.6 g, 55% yield)LC-MS(ESI): [M+1]+ = 226.13, tR = 4.59 min.1H NMR (400 MHz, CDCl3)δ 8.05 (d, J = 8.1 Hz, 1H), 7.97 (d, J = 8.1 Hz, 2H), 7.87 (d, J= 7.9 Hz, 1H), 7.47 (t, J = 7.5 Hz, 1H), 7.35 (t, J = 7.5 Hz,1H), 7.28 (d, J = 7.9 Hz, 2H), 2.41 (s, 3H).13C NMR (101 MHz, CDCl3)δ 168.27, 154.18, 141.45, 134.96, 130.96, 129.75, 127.50, 126.27, 125.02,123.06, 121.60, 21.56.
  • 4
  • [ 99-94-5 ]
  • [ 137-07-5 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
87% With diphosphorus tetraiodide; In acetonitrile; at 80℃;Sealed tube; Inert atmosphere; General procedure: To amixture of ortho-substituted (-NH 2 or -SH or -OH) anilines(1 mmol) and aryl acids (1 mmol) in acetonitrile (2 mL) in asealed tube (10 mL) was added diphosphorus tetraiodide (0.2mmol) under nitrogen atmosphere. Then, the tube was cappedand the mixture heated in an oil bath at 80 C with stirringuntil the reaction was complete as monitored by TLC. Afterbeing cooled to room temperature, the reaction was quenchedwith aqueous NaHCO 3 solution and extracted with ethyl acetatethree times. The combined organic layer was washed withwater and brine and then dried over anhydrous Na 2 SO 4 . Thesolvent was removed under reduced pressure and the residuewas purified by chromatography on silica gel, eluting withpetroleum ether/ethyl acetate, to afford the correspondingproduct. The products obtained were known compounds andwere identified by melting point and 1 H NMR spectroscopy.The spectral data were compared with the literature values.2-Phenyl-1H-benzimidazole (Table-2, entry 1): m.p.:290-293 C (Lit. [21] 292-294 C); IR (KBr, ν max , cm -1 ): 3450,3045, 1620, 1580, 1458; 1 H NMR (400 MHz, DMSO-d 6 ): δ7.08-7.14 (m, 2H), 7.31-7.5 (m, 5H), 7.96 (d, 2H), 12.80 (s,1H); 13 C NMR (DMSO-d 6 , TMS): δ 116.5, 123.1, 127.4, 128.6,129.5, 130.7, 139.0, 152.7; MS (ESI) m/z: [M+H] + 195.1.
85% With Amberlyst-15; In water; at 90℃; for 2h;Irradiation; General procedure: To a solution of o-phenylenediamine 1a, o-amino phenol 1b or o-amino thiophenol 1c (1.0 mmol) and aromatic acid (2, 1.2 mmol) in water (5 mL) was added Amberlyst-15 (10%, w/w) and the mixture was irradiated with ultrasound (40 KHz) continuously at 90 C till the completion of the reaction(monitored by TLC) as indicated in Table 3. The solid separated was filtered, washed with diethyl ether (2 x 5 mL), dried and treated with EtOAc (15 mL). After stirring for 10 min the mixture was filtered to remove the insoluble catalyst. The filtrate was collected and concentrated under vacuum. The solid obtained was purified by recrystallization (column chromatography infew cases) to afford the desired products 3, 4 or 5.
84% With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; N-ethyl-N,N-diisopropylamine; In ethyl acetate; at 100℃; for 0.166667h;Microwave irradiation; Sealed tube; General procedure: A mixture of o-aminobenzenethiol (1 mmol), carboxylic acid (1 mmol), N,N-diisopropylethylamine (1.5 mmol) and propylphosphonic anhydride (1 mmol, 50% w/w in AcOEt) was irradiated for 10 min under microwave at 100 C in a sealed tube. It was diluted with H2O, followed by alkalinization with saturated aqueous NaHCO3 solution. The precipitate was collected by filtration and washed thoroughly with H2O to afford the respective benzothiazole. If necessary, simple recrystallization was carried out in EtOH/H2O.
70% 4-methylbenzoic acid (10.24 g, 75 mmol) was added portionwise to polyphosphoric acid (30 mL) at 100 C until a smooth paste was obtained. o-aminothiophenol (9.36 g, 75 mmol) was added, and the reaction mixture was heated to 185 C. After stirring at 185 C for a further 30 min, the mixture was poured into vigorously stirred H2O. The resulting solution was extracted with CH2Cl2, and washed by Na2CO3 aqueous solution and then deionized water. The concentrated residue was further purified on silica gel (CH2Cl2 as elute), providing 1 as white solid (7.91 g, 70%). 1H NMR (400 MHz, CDCl3): d = 8.07 (d, J = 8.0 Hz,1H, NC6H4S), 7.99 (d, J = 8.0 Hz, 2H, C6H4), 7.90 (d,J = 8.0 Hz, 1H, NC6H4S), 7.50 (t, J = 7.6 Hz, 1H, NC6H4S), 7.38 (t, J = 7.6 Hz, 1H, NC6H4S), 7.31 (d,J = 8.0 Hz, 2H, C6H4), 2.43 (s, 3H, CH3) ppm; 13C NMR (100 MHz, CDCl3): d = 168.2, 154.2, 141.4, 134.9, 131.0, 129.7, 127.5, 126.3, 125.0, 123.1, 121.6, 21.5 ppm; HRMS (EI) : m/z calc. for [M+]: 225.0612; found: 225.0612.
With PPA; In water; Synthesis of 4-(benzothiazol-2-yl) toluene 125 g (1 mol) of o-aminothiophenol, 136 g (1 mol) of p-toluic acid and 600 g of polyphosphoric acid were admixed and stirred into nitrogen gas at 170-200 C. for 4 hours. After the reaction mixture was cooled to 100 C., it was poured in 5 l of water. The mixture was adjusted to pH 5 with NaOH and the resulting crystals were filtered off, whereupon 220 g of 4-(benzothiazol-2-yl) toluene was obtained as crude crystals. Recrystallization from n-hexane gave 172 g of pure product as colorless prisms melting at 84-85 C.

  • 5
  • [ 104-87-0 ]
  • [ 137-07-5 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
99% With trimethyl-(2-hydroxyethyl)ammonium chloride; tartaric acid; at 70℃; for 1h; (1) Take a 10mL Erlenmeyer flask or test tube, add 0.2mmol 2-aminothiophenol, 0.24mmol p-tolualdehyde and 2mL deep eutectic solvent (the molar ratio of choline chloride to acetamide is 1: 2) ;(2) Place the Erlenmeyer flask or test tube in step (1) into a 70 C oil bath and stir magnetically for 1 hour to obtain a crude product;(3) Separate the crude product obtained in step (2) by column chromatography. The eluent is a mixture of ethyl acetate and petroleum ether. The volume ratio is 1: 6. Dry at 30 C for 3 hours to obtain a 2-aryl group. Benzothiazole compounds.
98% With Cu(II) containing nanosilica triazine dendrimer; In neat (no solvent); at 20℃; for 0.333333h;Catalytic behavior; General procedure: A mixture of aldehyde (1 mmol), 2-aminothiophenol (1 mmol) and Cu(II)-TDnSiO2 (10 mg, containing 0.0034 mmol Cu(II)) was stirred at room temperature. The progress of the reaction was monitored by TLC (eluent: n-hexane/EtOAc, 5:1). At the end of the reaction, EtOAc (15 mL) was added; the catalyst was filtered and washed with EtOAc (10 mL). Evaporation of the filtrate and purification of the crude product by recrystallization from n-hexane/EtOAc (10:1) afforded the pure product
98.3% With aminosulfonic acid; oxygen; In ethanol; at 80℃; for 6h; General procedure: o-Aminothiophenol (5.50 mmol), aromatic aldehyde (5.50 mmol), and sulfamic acid (0.05 mmol) were added to a 100-mL three-necked flask. EtOH (20 mL) was added to the mixture followed by refluxing at 80 C for 6 h. The reaction solution was then vacuum distilled to remove EtOH. Then, 20 mL EtOAc acetate was added and dissolved by stirring and the insoluble solid was filtered off. This solid was washed twice with EtOAc (5.0 mL × 2), and the filter cake was dried under vacuum at 60 C to obtain the recovered sulfamic acid. The EtOAc solutions were combined, and dried over magnesium sulfate. 2-Arylbenzothiazole was obtained by column chromatography (EtOAc: petroleum ether = 1:40).
97% With manganese doped CdS nanoparticles; In water monomer; at 90℃; for 1.5h; General procedure: In a 50 ml round bottom flask, o-phenylenediamine/aminothiophenol (1 mmol) and aromatic aldehydes (1 mmol) in water (4 ml) were mixed and stirred at 90C. To this, catalyst was added. The progress of the reaction was checked on TLC. After completion, the reaction mixture was cooled at room temperature. Then, it was extracted with ethyl acetate; the organic layer was dried over sodium sulphate and concentrated in a vacuum to afford the crude products. The pure products were obtained by recrystallization from ethanol.
96% With AlPO4 supported ethylenediamine-chromium(III)-salen complex nanoparticles; air; In ethanol; for 2h;Green chemistry; General procedure: A mixture of 2-aminothiophenol (1.0 mmol) and arylaldehyde (1.0 mmol) was stirred in 5.0 mL of ethanol in the presence of nanocatalyst (2.0 mol%) at 50 C. After the reaction was completed, the mixture was centrifuged and rinsed with ethanol (3 × 15 mL). The solvent was evaporated to give the crude product, which was purified by silica gel column chromatography with n-hexane/ethyl acetate(10:1) to afford pure 2-arylbenzothiazole.
96% With Eosin; trypsin (bovine pancreas); In toluene; for 0.166667h;Irradiation; Green chemistry; Enzymatic reaction; General procedure: 2-aminothiophenol (0.2mmol), p-nitrobenzaldehyde (0.2mmol), Solvent Red 43 1% mol trypsin (10mg), and toluene (2mL) were added to 10mL quartz tube, at 200rpm and at λ=450nm, 20W for 10min. The reaction was completed by filtering the enzyme. The crude products were purified by silica gel column chromatography (200-300 mesh) with an eluent consisting of ethyl acetate-petroleum. Product-contained fractions were combined, concentrated, and dried to give respective product.
95% With Yb/MCM-41 molecular sieve; In ethanol; at 80℃; for 4h; A mixture of 2-aminothiophenol (1.1mmol), 4- methylbenzaldehyde (1 mmol of) and Yb / MCM-41 (0.01mmol) added to a round bottom flask was added 5ml of absolute ethanol, is heated with stirring at 80 reflux 4h.Progress of the reaction is detected by TLC, the mixture was filtered after completion of the reaction, the resulting white Yb / MCM-41 molecular sieve catalyst, recycling, and the filtrate solvent was removed by rotary evaporation, and then separated by column chromatography to give the pure product, yield 95 %.
95% With sulfated tungstate; In neat (no solvent); at 20℃;Sonication; Green chemistry; General procedure: A mixture of 2-aminothiophenol (2 mmol) and aldehydes (2 mmol), and sulfated tungstate (10 wt%) was sonicated at 20 kHz frequency and 35W power at room temperature for desired times (monitored by TLC). After completion of the reaction as indicated on TLC, the reaction mixture was cooled at room temperature and the crude product was dissolved in ethyl acetate and the catalyst was isolated by simple filtration. It was then dried and reused for another reaction. The product in ethyl acetate was washed with water and excess solvent was removed under reduced pressure. The pure products 2-substituted benzothiazoles were obtained in 88-98% yield and there is no need to purify the products by recrystallization or column chromatography.
94% With melamine trisulfonic acid; In water monomer; at 70℃; General procedure: To a mixture of an aromatic aldehyde (1 mmol) ando-aminothiophenol (1 mmol) in 5 mL water, MTSA (0.05mmol) was added and the reaction mixture stirred at 70Cfor 40-65 min. After the reaction was completed, pure products were isolated by filtration and washing with hotwater and ethanol. In some examples the aqueous mixturewas extracted with 10 mL of diethyl ether or ethylacetate and dried over anhydrous Na2SO4, and the solventwas removed under reduced pressure to give thedesired products. The product was analyzed by IR, 1HNMR, 13C NMR, mass and elemental analysis. Furtherpurification of the product was carried out by short columnchromatography on silica gel (hexane/diethyl ether)or crystallization.
93% With lithium bromide; In ethanol; at 25 - 30℃; for 0.25h;Sonication; General procedure: Aromatic aldehydes (1.0 mmol), o-aminothiophenol (1.0 mmol), and lithiumbromide (20 mol %) in ethanol (5 mL) were added into a 50-mL round-bottomedflask. The reaction flask was placed in the ultrasonic cleaner bath with the surface ofreactants slightly lower than the water level and irradiated at 25-30 C for theperiod of time indicated in Table 4. The progress of the reaction was monitored byTLC, using petroleum ether/ethyl acetate (8:2) as a solvent system. Aftercompletion of the reaction, the reaction mixture was poured into ice-cold water.The precipitate was filtered off and washed with water, dried, and purified bycrystallization from ethanol as solvent to afford pure product.
93% With nano titania supported sulfonic acid; In neat (no solvent); at 70℃; for 0.75h;Green chemistry; General procedure: In a typical experiment, 2-aminothiophenole (1 mmol), aromatic aldehyde (1 mmol),and catalyst (0.099 mmol) in solvent free condition were taken in a 25-mL round-bottomedflask and was stirred at 70 C for an appropriate time. The reaction mixture was cooled,eluted with hot ethanol (5 mL) and was centrifuged and filtrated to collect the formedprecipitate. The crude product was recrystallized from ethanol to yield pure benzothiazolederivatives.
93% With oxygen; potassium carbonate; at 80℃; for 6h; General procedure: In a 25 mL round bottomed flask, a mixture of 2-aminophenol,2-aminothiol (1.2 mmol), aldehyde (1 mmol),K2CO3(1.5 mmol), and MNPs-phenanthroline-Pd catalyst(25 mg) was stirred in PEG (3 ml) at 80 C for 6 h. Theprogress of the reaction was monitored by thin-layer chromatography(TLC). After completion of the reaction, catalystwas separated by an external magnet and the reactionmixture was extracted with H2Oand ethyl acetate and driedover anhydrous Na2SO4.After evaporation of the solvent,the desired product was isolated by silica gel flash columnchromatography with a mixture of petroleum ether/ethylacetate as eluent.
92% With cadmium sulphide; In methanol; at 20℃; for 0.5h;Irradiation;Catalytic behavior; General procedure: In the experimental procedure for catalytic reaction, amixture of aldehyde (3 mmol), 2-aminothiophenol (3 mmol) and CdSnanosphere (5 mg) was taken in a 100 ml double walled quartz beaker flaskhaving water inlet and outlet to maintain the temperature of the reactionvessel at room temperature in methanol (20 ml). The beaker was exposed tovisible light under stirring condition for the required time period (Table 3).After completion of the reaction (monitored by TLC and GC), methanol wasevaporated by rotary and the product was dissolved in dichloromethane. Thecatalyst was separated from the reaction mixture by centrifugation.Dichloromethane was then evaporated to dryness and the product waspurified by column chromatography using silica gel G60.
92% With nano-crystalline sulfated zirconia; In ethanol; for 1.41667h;Reflux; General procedure: In a 50 mL round bottom flask aldehyde (1 mmol) and 1,2-diaminobenzene, 2-aminophenol, or 2-aminothiophenol (1 mmol) were thoroughly mixed in ethanol (10 mL) then catalyst (10 mol%) was added, and the solution was refluxed for appropriate time. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was cooled to room temperature and the resulting solid was collected by filtration and dissolved in 20 mL ethyl acetate. The catalyst was recovered by filtration. After evaporation of the solvent, the resulting solid product was recrystallized from ethanol to obtain pure product.
92% With tribromide-modified silica-coated magnetic nanoparticles (Fe3O4/SiO2/(CH2)3N+Me3Br3); In neat (no solvent); at 80℃; for 0.283333h;Green chemistry; General procedure: A stirred solution of the substrate (1 mmol), aryl adehyde (1 mmol),and tribromide-modified silica-coated magnetic nanoparticles (Fe3O4/SiO2/(CH2)3N+Me3Br3-, 0.007 g) was heated 80 C. After completion of the reaction [TLC (AcOEt/hexane 1:3) monitoring], EtOH (10 mL) was added. The catalyst was recovered by an external magnet, and thereaction mixture was poured into ice-water (30 mL). The solid productwas filtered, washed with ice-water, and dried.
92% With sulfonic-acid-functionalized activated carbon made from matured tea leaf (MTLAC-SA); In ethanol; at 20℃; for 0.75h;Green chemistry;Catalytic behavior; General procedure: Aldehyde (1 mmol), ortho-phenylenediamine or 2-aminothiophenol (1.1 mmol),synthesized catalyst (10 wt%), and ethanol (3 mL) were mixed and stirred at roomtemperature for appropriate time. After reaction completion as confirmed by thinlayerchromatography (TLC), the usual work-up procedure was carried out and thecrude product was purified using column chromatography to obtain the pureproduct. Both the catalysts were recovered after reaction, washed with ethanol,dried in an oven for about 1 h, and reused for seven cycles successfully.
92% With oxygen; In neat (no solvent); at 20℃; for 0.416667h; In around bottom equipped flask 2-mercaptoaniline (1) (1 mmol), substituted aryl/heteroaryl aldehydes 2(a-o) (1 mmol) and CS-SO3H (2 mol %) is stirred at room temperature for 30 min in presence of oxygen balloon. The reaction was monitored by using TLC. Upon completion of the reaction, the reaction mass was quenched to absolute ethanol. The precipitated CS-SO3Hwas filtered and reused for subsequent reactions. The filterate was concentrated and obtained the curde product. Further thecrude product was recrystallized from ethanol and obtained pure products 3(a-o)
92% With mesoporous Cu(II)-Glycerol-MCM-41 nanocatalyst; In ethanol; at 25℃; for 3.8h; General procedure: In a 25-mL, round-bottom flask, a mixture of o-aminothiophenol(1.0 mmol), aldehyde (1.0 mmol) and Cu(II)-Glycerol-MCM-41(7 mg) in EtOH (3 mL) was stirred magnetically at room temperaturefor the appropriate time (Table 1). After completion of thereaction, as indicated by TLC, the reaction mixture was filtered toisolate the nanocatalyst and the crude product (filtrate) was purifiedby column chromatography on silica gel or recrystallization intoluene to give the desired products.
92% General procedure: All reactions were carried out in an 8 mL vial equipped with a stirring bar. Aldehyde (1 mmol), 2-aminophenol or 2-aminothiophenol(1 mmol), acetonitrile (3 mL), and a base, i.e., K2CO3 or Et3N (2 mmol) were mixed in the vial and stirred at room temperature for 30 min. The vial was then charged with eosin Y (5 mol%) and oxidant (2 mmol), capped, and purged with argon. The stirred reaction mixture was irradiated by 3 W blue LEDs (5 cm away, with a fan to maintain the reaction at room temperature) for 24-36 h. The resulting mixture was transferred to a separatory funnel, partitioned between water (15 mL)and EtOAc (3 × 15 mL). The organic extract was washed with NaHSO310% (30 mL), dried with anhydrous Na2SO4, filtered, concentrated using a rotavap, and analyzed by GCMS using naphthalene as an internal standard. The product was purified by flash column chromatography with hexane/EtOAc mixture as the eluent for NMR characterization.
92% With ruthenium silicate (Ru/Si, 1:100) zeolite; In neat (no solvent); at 90℃; General procedure: To the synthesis of 2-arylbenzothiazoles 3 (a-i) from a mixture of 2-aminothiophenol (0.001 mol), benzaldehydes (0.001 mol) and catalytic amount of (0.04 gm) RS-1 under solvent free conditions was refluxed at 90 C for the prescribed time. The reaction progress was monitored by TLC (ethyl acetate: PET ether = 3:7 as eluent), after completion of the reaction, the product and catalyst were separated by simple filtration, and catalyst was easily separated from the reaction mixture. Finally, crude product obtained was crystallized from ethanol to afford desired pure product. The representative compound was characterized by FTIR 1H, 13C NMR and HRMS.
92% With fluorescein; In methanol; at 20℃;Irradiation; General procedure: 2-Aminothiophenol derivatives 1 (1 mmol), aromatic aldehyde 2 (1mmol) and fluorescein (10 mol%) were dissolved in 20 mL methanol andplaced in a flat quartz glass jar. The open-air reaction container wasplaced under a 30 W blue LED lamp. After completion of the reaction(monitored by TLC analysis), the solvent was removed under reducedpressure. Then, water (20 mL) was added and the mixture was extractedwith ethyl acetate (3 × 20 mL). The combined organic layer was driedover anhydrous Na2SO4 and the solvent was removed in vacuo. Thecrude product was purified via silica gel column chromatography (petroleumether/ethyl acetate rations of 4:1-6:1) to generate the corresponding product 3.2-Phenylbenzothiazole (3a). 92% yield as a white solid
91% With UiO-66-NH2-TC-Cu; In neat (no solvent); at 20℃; for 0.333333h;Catalytic behavior; General procedure: A mixture of aldehyde (1mmol), 2-aminothiophenol (1mmol) and UiO-66-NH2-TC-Cu (10mg, containing 0.0032mmol Cu(II)) was stirred at room temperature. The progress of the reaction was monitored by TLC (eluent: n-hexane/EtOAc, 5:1). At the end of the reaction, EtOAc (15mL) was added; the catalyst was filtered and washed with EtOAc (10mL). Concentration of the filtrate and purification of the crude product by recrystallization from n-hexane/EtOAc (10:1) afforded the pure product.
91% With (N‑[(3‑methoxy‑2‑oxidophenyl)methylidene]pyridine‑3‑carbohydrazonato)‑bis(oxido)‑methoxo‑oxo‑vanadium(V); In ethanol; for 0.0833333h;Sonication; General procedure: 10 mol% of the catalyst, VOL or MoO2L,was added to an ethanolic solution of aryl aldehydes (1 mmol) and 1,2-phenylenediamine,2-aminophenol, or 2-aminothiophenol(1 mmol). The mixture was subjected to ultrasonic irradiation at room temperature for an appropriate period of time until the reaction was completed, as indicated by TLC (eluentn-hexane: ethyl acetate, 5:2). Then, the reaction mixturewas filtered and the product was finally recrystallized from the ethanol to achieve maximum purity.
90% With nano-TiO2-SO3H; at 70℃; for 0.75h; General procedure: In a typical experiment, aromatic aldehyde (1mmol), 2-aminothiophenol(1mmol) and n-TSA (0.032g) under solvent free conditions were taken in a 25mL round bottomed flask and were stirred at 70C for an appropriate time. The reaction mixture was cooled, eluted with hot ethanol (5mL) and was filtrated to collect the formed precipitate. The crude product was recrystallized from ethanol to yield pure benzothiazole derivatives.
90% With Ag2CO3/celite; In ethanol; at 70℃; for 3h; General procedure: To a mixture of 1,2-phenylenediamines (1.0 mmol) andaldehydes (1.1 mmol) in ethanol, 25 mol % of Ag2CO3/Celite (3 mL) was added. The resulting mixture was stirredat 70 C for 3 h. After this time, the reaction mixture wasdiluted with ethanol (50 mL) and the catalyst was separatedby filtration. Water was then added to the organic layer, andthe products were filtered and washed with water. All of theproducts are known compounds and characterized easily bycomparison with melting point, IR, [1-6] H NMR spectraldata reported in literature.
90% With ionic liquid immobilized on silica-coated cobalt-ferrite magnetic nanoparticles; In neat (no solvent); at 70℃; for 0.166667h; General procedure: CoFe2O4SiO2PAF-IL (20 mg) was added to the mixtureof aromatic aldehyde (1 mmol), o-phenylenediamine(1 mmol, 0.11 g), or 2-aminobenzenethiol (1 mmol, 0.125 g)and heated in solvent-free conditions at 70 C for an appropriatetime. After completion, the resulting mixture wasdiluted with hot ethanol (10 mL), and the catalyst was easilyseparated using an external magnet. Finally, the gainedprecipitate was recrystallized in ethanol to afford the pure product.
89% With uronium nitrate; In neat (no solvent); at 20℃; for 0.0333333h; General procedure: 2-Aminothiophenol 1 (2.0 mmol) and carbaldehyde 2 (2.0 mmol) were mixed in a conical flask and NH2CONH2.HNO3 (1.5 wt % of aldehydes) was added to it. This mixture was shaken at room temperature. An instant exothermic reaction occurred with completion of reaction (TLC) and gave yellowish orange solid that was directly chromatographed over silica gel column to afford pure 2-aryl/heteroaryl/styryl/alkylbenzothiazole 3 (Table 3). The structures of synthesized compounds were confirmed by the overlapping 1H, 13C NMR and melting points data. The spectral data of some of the synthesised compounds are given below.
88% With DL-10-camphorsulphonic acid; In ethanol; water monomer; at 20℃; for 1h;Green chemistry; General procedure: In a dry screw-cap test tube a magnetic stir bar, aromatic aldehydes (1a-1k; 1 mmol), 2-aminothiophenol (2; 1 mmol), 4 mL aqueous ethanol and a catalytic amount of camphor sulfonic acid (20 mol%) were taken sequentially. On a magnetic stirrer, the reaction mixture was then stirred vigorously at room temperature and it was monitored by TLC. After completion of the reaction, solid 2-arylbenzothiazoles (3a-3k) were isolated pure just by simple filtration and washing the crude products with aqueous ethanol (H2O:EtOH = 1:2) subsequently. By repeating the above mentioned procedure, 2-arylbenzimidazoles (5a-5c) were also synthesized from the reaction of aromatic aldehydes (1c; 1 mmol) and o-phenylenediamine (4; 1 mmol) in the presence of a catalytic amount of camphor sulfonic acid as catalyst under the same optimized conditions. The structures of all the synthesized compounds were determined by the detail spectral analysis including 1H NMR, 13C NMR and HRMS spectroscopy.
87% With copper (II) bromide; In toluene; at 111℃; for 0.583333h; General procedure for the synthesis 3-5: The catalyst (100 mg) was added to a mixture of aldehyde 2 (1.1 mmol) and o-phenylenediamine 1a, o-aminophenol 1b or o-aminothiophenol 1c (1.0 mmol). The mixture was stirred at 111 C in the presence of 5 mL toluene. Progress of the reaction was monitored by TLC (n-hexane/EtOAc 2:1). After complete conversion, the reaction mixture was filtered, the catalyst was washed, and the solvent was removed under reduced pressure. The crude material was purified by column chromatography or recrystallization to afford the pure product 3, 4 or 5.
87% With 1-butyl-3-methylimidazolium tetrachloroferrate(III); In ethanol; for 1.33333h;Reflux; General procedure: A mixture of 2-aminobenzenethiol or 2-aminobenzenthiol (1 mmol), aryl aldehyde (1mmol), [bmim][FeCl4] (0.5 mmol) and ethanol (5 mL)was placed in a round bottom flask and refluxed forthe given times recorded in Table 2. After completionof the reaction observed by TLC (using n-hexane/ethylacetate (7:3) as eluent), the mixture was cooledto room temperature, the precipitate was filtered andwashed with water for several times. The resultantproduct purified by column chromatography andcharacterized by comparison of their physical data with benzimidazole or benzthiazole derivativesreported in literature.
87% With fluorophosphoric acid; In ethanol; at 20℃; for 2.5h; General procedure: A mixture of o-substituted amino-aromatics 1(i-iii) (0.1 mol)and aldehydes 2(a-u) (0.1 mol) was added in 100 mL round bottom flask containing ethanol (10 mL). A known catalyticamount of fluorophosphoric acid was added in the abovesolution. The resulting reaction mixture was stirred at roomtemperature for an appropriate time. After completion ofthe reaction, it was monitored by TLC (hexane/ethyl acetate90:10). The work-up was performed for the reaction mixtureby diluting it with ice cold water and extracting it by ethylacetate. The organic layer was separately collected andevaporated under vacuum on rotary evaporator to obtainsolid crude product. The obtained solid product was further purified by recrystallization with hot ethanol and by passing sample through a short column of silica gel wheneverrequired.
86% With nitric acid supported on a silica gel; at 20℃; General procedure: To a mixture of 2-aminothiophenol 1 (2.0 mmol) and aryl/heteroaryl/styryl/alkylaldehyde 2 (2.0 mmol) in a vial was added SiO2-HNO3 (2 wt% to the aldehyde)and shaken at room temperature. Instantly, an exothermic reaction occurred withcompletion of the reaction (TLC) and the reaction mixture became a yellowishorangesolid that was directly chromatographed over a silica gel column to affordpure 2-aryl/heteroaryl/styryl/alkylbenzothiazole 3 (Table 3).
85.7% With oxygen; at 25 - 30℃; for 1h;Sonication; General procedure: Aromatic aldehydes (2, 1.0 mmol), o-aminothiophenol (1, 1.0 mmol), FeCl3/Montmorillonite K-10 (160 mg, 0.1 mmol, based on FeCl3) and absolute methanol (5 mL) were added into a 25 mL conical flask. The reaction flask was placed in the ultrasonic cleaner bath, where the surface of reactants was slightly lower than the water level and irradiated at 25-30 C for the period of time (sonication was continued until aromatic aldehydes disappeared as indicated by TLC) as indicated in Tables 1-4 . After completion of the reaction, the reaction mixture was dissolved in ethyl acetate and FeCl3/Montmorillonite K-10 was filtered off. The filtrate was concentrated and purified by silica-gel column chromatography (200-300 mesh) using petroleum ether or the mixture of petroleum ether and ethyl acetate as eluent to give a light yellow crystalline solid. All of the products described herein were previously reported in the literatures [16-35]. The authenticity of the products was established by spectroscopic data and by comparing their melting points with literature values. white crystals, IR (KBr, cm-1): 3058, 3023, 1608, 1484, 1457, 1434, 1312, 1286, 1253, 1227, 1122, 959, 834, 817, 761; 1H NMR: δH 8.10 (d, J = 7.9 Hz, 1H, ArH), 8.02 (d, J = 8.2 Hz, 2H, ArH), 7.91 (d, J = 8.0 Hz, 1H, ArH), 7.50-7.53 (m, 1H, ArH), 7.38-7.41 (m, 1H, ArH), 7.32 (d, J = 7.9 Hz, 2H, ArH), 2.45 (s, 3H, CH3); 13C NMR: δC 168.3, 154.2, 141.5, 134.9, 131.0, 129.7, 127.5, 125.0, 126.3, 123.1, 121.6, 21.5; m/z (ESI): 226 [M+H]+.
85% With ammonium nickel sulphate hexahydrate; at 25℃; for 1.75h;Sonication; Green chemistry; General procedure: o-amino thiophenol (1mmol), aromatic aldehyde (1.1mmol) andwater (10mL) were mixed in 25mL single neck round bottom flask, andto this Ammonium Nickel Sulphate (10 mol %) was added. The reactionmixture was sonicated at room temperature (250C) for the appropriate time(Table 2, entries 13-25), and the progress of reaction was monitored by TLC.After completion of reaction, the mixture was extracted with ethyl acetate(2×10mL). The combined organic layer was dried over anhydrous Na2SO4 andevaporated under reduced pressure; the crude material was purified by columnchromatography over silica gel to afford products 4a-4m with high purity.
85% With air; In dimethyl sulfoxide; at 60℃; for 6h; General procedure: 2-Aminothiophenol (0.5 mmol; 1.0 equiv) and aromatic aldehydes (0.6 mmol; 1.2 equiv)were dissolved in DMSO (3 mL). Then, the reaction mixture was stirred at 60 C for 6 h. Afterthe reactionH2O was added to the mixture. The mixture was extracted with AcOEt (20 mL x 3).The combined organic layers were then washed with saturated aq. NaCl (30 mL). The solutionwas dried with anhydrous Na2SO4, filtered, and concentrated in vacuo. The crude residue waspurified with silica gel chromatography (AcOEt- PE130) to give pure product.
85% With ZnCl2/SiO2; In neat (no solvent); at 50℃; for 0.75h; General procedure: To a stirred mixture of aldehyde, (10mmol), and 2-ainothiophenol (10 mmol), Silzic (0.1 g, 10 mol%) was added and the mixture was allowed to stir at 50 0C for the total recorded time. After the completion (the reaction was monitoredby TLC pet.ether-EtOAc (8:2)) of the reaction, EtOAc(20 mL) was added to the reaction mixture. Then, the solidwas filtered off. Removal of solvent under reduced pressureprovided the crude products with high purity, if required;recrystallization was performed from CH2Cl2 in some cases.The 2-aryl benzothiazoles are known compounds and allspectroscopic data were in agreement with literature reports[44, 49] (Table 5).
83.9% With montmorillonite K-10; air; In ethanol; at 20℃; for 12h; General procedure: Aldehyde (2, 1.0 mmol) and o-aminothiophenol (1, 1.0 mmol) were mixed inabsolute ethanol (10 mL) in a 50-mL three-necked flask equipped with a watercooledcondenser and a gas inlet, as reported elsewhere [45]. The solution wasstirred at room temperature, then montmorillonite K-10 (25 mg) was added. Air wasbubbled continuously through the reaction system, at a speed of 60 bubbles perminute on average, by means of a small air pump. After completion of the reaction(monitored by TLC) the catalyst was recovered by filtration and washed with EtOH.The filtrate was concentrated and purified by short column chromatography on silicagel, with petroleum ether or a mixture of petroleum ether and ethyl acetate aseluent, to give the pure product. The products (3a-r) are all known compounds andwere identified by 1H NMR spectroscopy, by comparison of their melting pointswith those reported in the literature, and by comparison of their TLC Rf values withthose of standards.
83% With 3-(2,4,6-trimethyl-3,5-bis((1,2-methyl-1H-imidazoliumbromide-3-yl)methyl)benzyl)-1,2-methyl-1H-imidazoium bromide; mesoporous silica; In neat (no solvent); at 100℃; for 0.266667h; General procedure: Required equivalents as mentioned for conventional method exceptsolvent and 5 g of silica gel (80-120 mesh) were taken and mixed andfinely grinded using mortar and pestle. The reaction mixture is kept inMuffle furnace at 100 C for completion. The progress of the reactionis monitored by TLC.
82% With tetraethylammonium L-prolinate; at 90℃; for 6h; General procedure: [N2222][AA] catalysts (0.4 mmol), benzaldehydes (1.98 mmol), o-aminothiophenol (2.28 mmol), and solvent (5 ml) were added into a round-bottom flask (25 ml) with a magnetic stirrer and condenser. The temperature of the reaction mixture was controlled by using a temperature controller with an accuracy of ±0.01 C. Then, the reactor was heated to the designated temperature in an oil bath with stirring. After the reaction was completed, deionized water (10 ml) was added to the reaction mixture. The products were precipitated out, and the aqueous phase containing [N2222][AA] ILs was isolated simply by filtration, thus were recovered and reused in the next run after heat treatment to remove water under vacuum at 90 C for 12 h.The pure products were obtained by recrystallization with EL/water or silica gel column chromatography.
82% With H3PO4/TiO2-ZrO2(1/1)-cetyl pyridinium bromide; at 20℃; for 0.25h; General procedure: A mixture of 2-aminothiophenol (1 mmol, 0.995 g), aldehyde (1 mmol), and H3PO4-TiO2- ZrO2 (1/1) (40 mg, 30 wt%H3PO4) were added in a beaker and the reaction mixture was mixed properly with the help of glass rod under solvent-free condition at room temperature. The progress of the reaction was monitored by TLC (ethylacetate-hexane, 4:6). After completion of the reaction, the reaction mixture was dispersed in ethyl acetate (5 mL) and filtered and the catalyst was washed several times with ethyl acetate and acetone. Then, the filtrate was evaporated under reduced pressure to isolate a solid residue and recrystallized from hot ethanol (10 mL) to afford the corresponding products. All of the 2-arylbenzothiazole products were characterized by IR, 1H NMR, 13C NMR, and mass spectroscopy and identified by comparison of their physical and spectral data with those of authentic samples.[34,35]
82% With [Fe3O4/SiO2/(CH2)3NPC-SO3H]Cl magnetic nanoparticles; In water monomer; at 70℃; for 0.75h; General procedure: A mixture of an aldehyde (1 mmol) with 2-aminothiophenol (1 mmol) and the catalytic amount of [MNP-PNPC-SO 3 H]Cl (30 mg) was magnetically stirred in water (5 mL) at 70C for the appropriate time (Table 1). Upon completion of the reaction, as indicated by TLC (n-hexane-ethyl acetate, 5 : 1), the catalyst was separated by an external magnet. After evaporation of the solvent, the crude product was recrystallized from ethanol-water (10 : 1) to give the corresponding pure compound.
81% With yttrium(III) chloride; In ethanol; for 0.5h;Reflux; Green chemistry; General procedure: YCl3(0.0098 g, 0.05 mmol) were dissolved in 10mL EtOH and stirred until the soliddissolved completely in refluxing, then 2-aminobenzenethiols 1a (0.118 mL, 1.1mmol) and benzaldehyde 2a (0.101 ml, 1.0 mmol) was added into thereaction mixture. After 30min, TLC showed the reaction to be complete. Thereaction mixture was cooled to r.t., and then evaporated in vacuum. The productpurified by column chromatography (PE-EtOAc= 20:1) to give white solid 3a(0.2092 g, 99%)
80% With nano silica-supported boron trifluoride (nano BF3/SiO2); In ethanol; at 20℃; for 0.416667h; General procedure: To a mixture of 2-aminothiophenol (1 mmol, 0.995 g) and aldehyde (1 mmol) in ethanol (10 ml), nano BF3/SiO2 (0.05 g, 25 mol% BF3) was added in a beaker and the reaction mixture was mixed properly with the help of a glass rod and stirred in ambient temperature for the time indicated in Table 3. The progress of the reaction was monitored by TLC (ethyl acetate:hexane, 6:4), after completion of the reaction the solvent was removed under reduced pressure, then the mixture was cooled and dichloromethane (15 ml) was added to the mixture and filtered to remove the catalyst. Then the filtrate was evaporated under reduced pressure to isolate a solid residue, and recrystallized from ethanol (10 ml) to afford the corresponding products and the catalyst residue was washed with acetone and reused. All of the 2-arylbenzothiazole products were identified by physical and spectroscopic data as follows.
79% With iron(III) trichloride hexahydrate; In water monomer; at 70℃; for 1h;Sonication; Green chemistry; General procedure: General procedure: 2-Aminothiophenol 1 (1 mmol), adehyde 2 (1.2 mmol), FeCl3•6H2O (0.02 mmol), were addedin water (5 mL) and heated at 70 C in the presence of air under ultrasound (using a laboratory ultrasonic bath SONOREX SUPER RK 510H model producing irradiationof 35 KHz) for 1 h.
79% With oxygen; C31H25BNO; In dimethyl sulfoxide; for 10h;Irradiation; In this example, 2-(p-tolyl)benzo[d]thiazolethiazole was prepared in milligram level. The quartz reaction tube was filled with oxygen first, and then 2-aminobenzenethiol (37.56mg, 0.3mmol, 1.0equiv) was added. 4-methylbenzaldehyde (54.07mg, 0.45mmol, 1.5equiv), PC (1.3mg, 0.003mmol, 1.0mol%), dimethyl sulfoxide (2.0mL) were added to the quartz reaction tube, at 10w light intensity 455nm The reaction was carried out at 25C for 10 hours under the irradiation of a blue LDE lamp with a wavelength. At the end of the reaction, the reaction mixture was filtered, washed with ethyl acetate, and the solvent was removed by rotary evaporation, and then purified by silica gel column chromatography (the specification of silica gel is 200-300 mesh, the mass ratio of silica gel to the product to be purified is 200:1, and the eluent is petroleum ether. A mixture with a volume ratio of 10:1 and ethyl acetate) to obtain the target product 2-(p-tolyl)benzo[d]thiazole with a yield of 79% (53.40 mg).
78% General procedure: The mixture of o-aminophenthiols 4a, aldehydes 2 (0.5mmol, 1 equiv) in 5mL 1,4-dioxane was stirred at 100C with oil bath for 1h. [BMIm]2[WO4] (0.1mmol, 53mg, 0.2 equiv) was added to reaction mixture for further 4h at 100C in the open air. The reaction was monitored by TLC. After completion of the reaction, the resulting solution was cooled to room temperature and pour it into the water (30mL) followed by extraction with ethyl acetate (10mL×3). The combined organic phase was washed with water three times. The solvent was removed by vacuum evaporation. The pure products were obtained by silica gel column chromatography.
70% With potassium carbonate; 3-butyl-1-methyl-1H-imidazol-3-ium iodide; In o-dimethylbenzene; para-xylene; 1,3-dimethylbenzene; at 120℃; for 10h;Green chemistry; General procedure: Into a 15x150 mm glass tube were layered o-amino phenol (1a-1d)/benzenethiol (4) (1 mmol) and corresponding aldehyde (1 mmol), xylene (3 mL; mixture of o, m, p-xylene), 0.25 mmol K2CO3 (34 mg) and NHC precursor G (0.1 mmol, 26 mg), the mixture was lowered under pre-heated oil bath, the mixture was stirred vigorously for 10 hours under air atmosphere. After reaction, the mixture was diluted with ethyl acetate, filtrated, the organic solution was concentrated under vacuum, the residue was applied on silica gel column chromatography, which afforded the corresponding oxidative cyclization product 3aa-3dd; 5a-5n.
68% With graphene oxide; In water monomer; at 60℃; for 7h;Green chemistry; General procedure: A mixture of aldehyde (1mmol) and o-phenylenediamine 1a (1mmol, 108.1 mg) in water (1 mL) were added to dispersed solution of GO (100 wt%, 108.7 mg) in water (2 mL) and the reaction mixture was stirred at 60 C forappropriate time (Table 2). After completion of the reaction(monitored by TLC using n-hexane/EtOAc 9:1 as eluent), theGO was separated by filtration and the solution was extractedwith ethyl acetate (2 5 mL). The GO was washed with warmethanol (about 75 C, 5 10 mL) and then organic layers(EtOAc and ethanol) were combined and dried over anhydroussodium sulfate. The solvents were removed under reducedpressure and the residue left out was purified by chromatographyon a short column of silica gel eluted with n-hexane/ethyl acetate (9:1) to give the corresponding benzimidazoles 2in 78-95%yield (Table 2).
68.89% With 4-methyl-2-pentanone; In methanol; for 8h;Reflux; 2-Aminothiophenol (0.03 mol, 3.76 g) was added to 4-methylbenzaldehyde (0.03 mol, 3.60 g) and 4-methylpent-3-en-2-one (0.03 mol, 2.94 g) in methanol, heated under refluxfor 8 h, and the reaction mixture allowed to stand overnightin the fume hood. The product was recrystallized andobtained as a brown solid from ethanol: acetone (1:1).Yield = 68.89%, Mp = 46-47 C, 1H NMR (DMSO-d6-400MHz) δ 8.11 (d, J = 8.0 Hz, 1H), 8.06 (m, J = 8.4 Hz, 1H),7.99 (d, J = 8.0 Hz, 02H), 7.54 (t, J = 7.6 Hz, 1H), 7.56 (t,J = 7.2, 7.6 Hz, 2H), 7.37 (t, J = 8, 10 Hz, 2H), 2.38 (s,3H). 13C NMR (DMSO-d6-100 MHz) δ 167.7 (C = N),153.8 (C), 148.3 (C), 142.0 (C), 138.0 (C), 134.8 (CH),130.8 (CH), 130.4 (CH), 129.4 (CH), 127.6 (CH), 127.1(CH), 126.0 (CH), 123.2 (123.3), 122.7 (CH), 21.3 (CH3).IR (νmax, cm-1): 3349 (N-H), 3055 (C-H), 2914 (C-H),1685 (C = N), 1610 (C = N), 1581 (C = C), 1500 (C = C),1472 (C-N). Anal. calcd. for C14H11NS: C, 74.63; H, 4.92;S, 14.23; N, 6.22. Found: C, 74.51; H, 4.84; S, 14.17; N,6.32. GC-MS (m/z, M+): Found for C14H11NS = 225.17,Expected mass = 225.31.
60% With methanol; carbon dioxide; oxygen; at 70℃; under 24752.5 Torr; for 12h;Autoclave; Sealed tube; General procedure: A stainless-steel autoclave reactor equipped with a magnetic stirrer was charged with 2-aminothiophenol (1 mmol), aromatic aldehydes (1.2 mmol) and methanol (2 mL). Then the stainless-steel autoclave was sealed and pressurized with 0.3 MPa of O2 and 3 MPa of CO2 after air was replaced at ambient temperature. And then it was heated and stirred at 70 C for 12 h. When the reaction was completed, it was cooled down to room temperature and the excessive gas was released slowly. Subsequently, the excessive aromatic aldehydes were removed by saturated sodium bisulfite aqueous solution and extracted with ethyl acetate (3x30 mL). The combined organic layers were dried over anhydrous MgSO4 and evaporated under reduced pressure. The desired products were obtained in moderate to excellent yields after purification by column chromatography on silica gel using petroleum ether/ethyl acetate as the eluent. All the desired products were identified through comparisons with the corresponding 1H NMR, 13C NMR and MS data reported in the literatures. The Supplemental Materials contains sample 1H and 13C NMR spectra of the products, 3, and the full characterization data (Figures S1-S32).
With disodium metabisulfite; In N,N-dimethyl-formamide; for 2h;Reflux; In a typical procedure, benzothiazoles 1-26 were synthesized by mixing together commercially available 2-aminothiophenol (3.12 mmol) and different aromatic aldehydes (3.16 mmol) in N,N-dimethylformamide (DMF) 10 mL, sodium metabisulfite Na2S2O5 (0.61 g) was added to a stirring mixture. The reaction mixture was refluxed for 2 h and the progress of the reaction was monitored by TLC. After completion of the reaction, mixture was allowed to cool to room temperature, addition of water (30 mL), product which precipitated as a solid, after filtration afforded the benzothiazole derivatives 1-26 in high yields. Recrystallization from methanol afforded pure product.
With disodium metabisulfite; In N,N-dimethyl-formamide; for 2h;Reflux; General procedure: In a typical reaction, benzothiazoles 1-26 were re-synthesized by dissolving 2-aminothiophenol (3.12mmol) and different aromatic aldehydes (3.16mmol) in DMF (10mL). Sodium metabisulfite (Na2S2O5, 0.61g) was also added to the above-mentioned solution with continuous stirring. The resulting reaction mixture was refluxed for 2h and the progress of the reaction was monitored by TLC analysis. After completion of the reaction, it was allowed to cool to room temperature and water (30mL) was added. The solid precipitated benzothiazoles (1-26) were collected on a filter and obtained in high yields. Recrystallization from methanol yielded pure products and their physical and spectroscopic data matched satisfactorily with previously reported literature values [21].

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  • 6
  • [ 6140-17-6 ]
  • [ 137-07-5 ]
  • [ 16112-21-3 ]
  • 7
  • [ 1155-00-6 ]
  • [ 104-85-8 ]
  • [ 16112-21-3 ]
  • 8
  • [ 615-22-5 ]
  • [ 31614-66-1 ]
  • [ 16112-21-3 ]
  • 9
  • [ 16112-21-3 ]
  • [ 34211-04-6 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: NBS, (PhCO)2O2 / CCl4 / Heating; Irradiation 2: dimethylformamide 3: N2H4*H2O / ethanol / 1 h / Heating
Multi-step reaction with 2 steps 1.1: N-Bromosuccinimide / tetrachloromethane 2.1: hexamethylenetetramine / chloroform / 5 h / Reflux 2.2: 12 h / 70 °C
  • 10
  • 2-[1-p-Tolyl-meth-(E)-ylidene]-amino}-benzenethiol [ No CAS ]
  • [ 16112-21-3 ]
  • 11
  • [ 450376-25-7 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
98% With sodium phosphate; In dimethyl sulfoxide; at 20℃; for 3h;Inert atmosphere; Irradiation; Add N-(2-bromophenyl)-4-methylthiobenzamide (0.2 mmol), Na3PO4 (0.1 mmol), and DMSO (2 mL) into a dry reaction tube with a magnetic stirrer, Then the reaction tube was replaced with N2 three times, and the reaction was stirred for 3 hours under the irradiation of a 45W household compact fluorescent lamp. After the reaction, 4 mL of water was added, and then extracted with 3×4 mL of ethyl acetate. The organic phases were combined. The organic phases were dried over anhydrous sodium sulfate and filtered. After the filtrate was concentrated by rotary evaporation, it was separated by thin layer chromatography on silica gel chromatography. , The target product was obtained with a yield of 98%.
98% With sodium phosphate; In dimethyl sulfoxide; for 3h;Inert atmosphere; Irradiation; Add N-(2-bromophenyl)-4-methylthiobenzamide (0.2 mmol),Na3PO4 (0.1 mmol) and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, and then the reaction tube was replaced with N2 three times,Under the irradiation of a 45W household compact fluorescent lamp, the reaction was stirred for 3 h. After the reaction,Add 4 mL water, then extract with 3×4 mL ethyl acetate, combine the organic phases,The organic phase was dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation.It was separated by silica gel chromatography and thin-layer chromatography to obtain the target product with a yield of 98%.
  • 12
  • [ 1043885-29-5 ]
  • [ 16112-21-3 ]
  • 13
  • [ 95-16-9 ]
  • [ 106-38-7 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
95.1% With bis(benzonitrile)palladium(II) dichloride; 1,10-Phenanthroline; 1-aza-4,6,11-trioxa-5-boratricyclo[3.3.3.0(1,5)]undecane; diisopropylamine; In water; dimethyl sulfoxide; butan-1-ol; at 60℃; for 10h; To a suitable amount of three-component solvent (dimethylsulfoxide (DMSO) in a volume ratio of 6: 1: 1, a mixture of H2O and n-butanol at room temperature) was added 100 mmol of the compound of the above formula Compound and 150 mmol of the compound of formula (II), 6 mmol of catalyst Pd (PhCN) 2 Cl2, 120 mmol of base diisopropanolamine and 15 mmol of accelerator (3 mmol of 1,10-phenanthroline and 12 mmol of triethanolamine borate ); The temperature was raised to 60 C and the reaction was stirred at this temperature for 10 hours. After the reaction, the reaction system was cooled to room temperature, sufficient deionized water sufficient to wash 2-3 times, then After sufficient chloroform was extracted and thoroughly shaken, the upper organic layer was taken, dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure. The resulting residue was subjected to silica gel column chromatography of 300 to 400 mesh in a volume ratio of 2: 1 acetone And ethyl acetate as elution solvent to give the compound of formula (III) in a yield of 95.1%.
71% With 3'-((1H-benzo[d]imidazol-2-yl)amino)-4'-(4-methoxyphenyl)-4'hspiro[indene-2,5'-isoxazole]-1,3-dione; nickel diacetate; lithium tert-butoxide; In tetrahydrofuran; for 24h;Reflux; General procedure: A 10 mL round-bottomed flask was charged with benzothiazole (19; 135 mg, 1 mmol), arylbenzene 18 (1 mmol), 14b (52.56 mg, 12 mol%), Ni(OAc)2 (17.68 mg, 10 mol%), t-BuOLi (160 mg, 2 mmol) and anhyd THF (5 mL). The mixture was stirred at reflux conditions for 24 h (TLC). The mixture was cooled to r.t. and the solvent was evaporated under reduced pressure. The mixture was diluted with EtOAc (10 mL) and successively washed with H2O and brine. The organic layer was dried (MgSO4) and concentrated under reduced pressure. The residue was purified by preparative TLC eluting with EtOAc/hexane (20:80, v/v) to afford the corresponding product 20.
62% With [(N,N'-bis-(2,6-di(isopropyl)phenyl)imidazolidin-2-ylidene)Pd(allyl)]2(μ2-pyrazine)(BF4)2; lithium tert-butoxide; In 1,2-dimethoxyethane; at 10℃; for 12h;Sealed tube;Catalytic behavior; General procedure: A sealable reaction tube was charged with azole (0.75 mmol),aryl bromide (0.50 mmol), [(NHC)Pd(h3-allyl)]2(m2-N-heterocycle)(BF4)2 (0.0025 mmol), LiOtBu (1.0 mmol) and DME (4.0 mL).The mixture was stirred at 100 C for 12 h. After completion of thereaction, the filtrate was concentrated and the residue was subjectedto purification via column chromatography to give the correspondingproduct.
51% With copper(II) oxide; potassium carbonate; triphenylphosphine; In diethylene glycol dimethyl ether; at 160℃; for 24h;Reflux; Inert atmosphere; Sealed tube; General procedure: 4.3 General procedure for CuO-catalyzed arylation and alkenylation of 1,3-azole (0012) Under argon, 0.5mmol of the bromobenzene or bromoalkene was added to the reaction mixture containing 0.25mmol of the benzoxazole, 0.5mmol K2CO3, 0.025mmol CuO, and 0.075mmol PPh3, followed by the addition of 2mL dry diglyme. The sealed reaction tube was stirred at 160C for 5-24h. After cooling, the reaction mixture was centrifuged to remove solid and separated the organic phase. Then, organic phase was extracted and dried over anhydrous MgSO4, and concentrated under reduced pressure after filtered. The residue was purified by column chromatography on silica gel eluted to afford corresponding product.
41% With 10 molpercent nickel based 2,5-dihydroxyterephthalic acid metal organic framework-74; In diethylene glycol dimethyl ether; at 160℃; for 18h;Sealed tube; General procedure: In a typical experiment, a predetermined amount of Ni-MOF-74 was added to the 8 mL vial containing a mixture of iodobenzene (0.1030 g, 0.5 mmol), benzothiazole (0.1379 g, 1.0 mmol), Li2CO3 or KCl (1.0 mmol), and diphenyl ether (0.085 g, 0.5 mmol) as standard. 1-Methoxy-2-(2-methoxyethoxy)ethane (diglyme) (1 mL) was added and vial was tightly capped. Reaction mixture was heated at 160C for 24 h. The catalyst loading was based on the molar ratio of nickel/iodobenzene. The reaction yield was monitored by withdrawing aliquots from the reaction mixture at different time intervals, diluting with ethylacetate (2 mL), quenching with an aqueous KOH solution (1%, 1 mL), and then drying over anhydrous Na2SO4 before analyzing by GC with reference to diphenyl ether (internal equation with pure product), and further confirming product identity by GC-MS and NMR. To investigatethe recycle ability of Ni-MOF-74, the catalyst was filtered from the reaction mixture after the experiment, washed with ethylacetate, water, THF, and dried at 140C under vacuum in 8 h. For the leaching test, a catalytic reaction was stopped after 12 h, analyzed by GC, and filtered to remove the solid catalyst. The reaction solution was then stirred for a further 12 h. Reaction progress, if any, was monitored by GC as previously described.

  • 14
  • [ 95-16-9 ]
  • [ 624-31-7 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
96% With copper(l) iodide; 2-(N-butyl-benzimidazol-2-yl)-6-(diphenylphosphinoxy)phenylchloropalladium(II); caesium carbonate; In N,N-dimethyl-formamide; at 120℃; for 18h;Inert atmosphere; General procedure: To a stirred solution of Cs2CO3 (0.75 mmol) and CuI (1.25 mol%)in DMF (1.0 mL) was added aryl iodide (0.75 mmol), azole (0.5mmol) and 4a (0.25 mol%) under argon atmosphere at room temperature. Then the mixture was stirred at 120 C for 18 h. After cooling, filtration, and evaporation, the residue was purified by preparative TLC on silica gel plates eluting with petroleum ether/EtOAc to afford the corresponding products.
53% With 10 molpercent nickel based 2,5-dihydroxyterephthalic acid metal organic framework-74; In diethylene glycol dimethyl ether; at 160℃; for 18h;Sealed tube; General procedure: In a typical experiment, a predetermined amount of Ni-MOF-74 was added to the 8 mL vial containing a mixture of iodobenzene (0.1030 g, 0.5 mmol), benzothiazole (0.1379 g, 1.0 mmol), Li2CO3 or KCl (1.0 mmol), and diphenyl ether (0.085 g, 0.5 mmol) as standard. 1-Methoxy-2-(2-methoxyethoxy)ethane (diglyme) (1 mL) was added and vial was tightly capped. Reaction mixture was heated at 160C for 24 h. The catalyst loading was based on the molar ratio of nickel/iodobenzene. The reaction yield was monitored by withdrawing aliquots from the reaction mixture at different time intervals, diluting with ethylacetate (2 mL), quenching with an aqueous KOH solution (1%, 1 mL), and then drying over anhydrous Na2SO4 before analyzing by GC with reference to diphenyl ether (internal equation with pure product), and further confirming product identity by GC-MS and NMR. To investigatethe recycle ability of Ni-MOF-74, the catalyst was filtered from the reaction mixture after the experiment, washed with ethylacetate, water, THF, and dried at 140C under vacuum in 8 h. For the leaching test, a catalytic reaction was stopped after 12 h, analyzed by GC, and filtered to remove the solid catalyst. The reaction solution was then stirred for a further 12 h. Reaction progress, if any, was monitored by GC as previously described.
  • 15
  • [ 85810-86-2 ]
  • [ 137-07-5 ]
  • [ 16112-21-3 ]
  • 16
  • [ 104-87-0 ]
  • [ 1141-88-4 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
97% With sodiumsulfide nonahydrate; acetic acid; In N,N-dimethyl-formamide; at 100℃; for 8h; In a parallel synthesizer reaction tube, 0.40 mmol was added 2,2' -dithio diphenylamine, 0.80 mmol of p-methylbenzaldehyde, 0.20 mmol of Na2S · 9H20 and 0.20 mmol of AcOH, Then, 3 mL of DMF was added as the reaction solvent, and the reaction was stirred at 100 C for 8 hours. LC detection found that the reaction of disulfide material completely, cooled to room temperature, The solvent was removed under reduced pressure using a rotary evaporator to give the crude product. The crude product was eluted with petroleum ether and ethyl acetate as eluant and subjected to column elution (200-300 mesh silica gel) to give 175 mg of white powder 2- (4-methylphenyl) benzothiazole having a purity of more than 99%, the separation yield was 97% and the melting point was 84-86 C.
97% General procedure: 2,2?-Disulfanediyldianiline or 5,5?-dichloro-2,2?-dithiobisaniline (0.4mmol), corresponding aryl aldehydes (0.8mmol), Na2S·9H2O (0.2mmol), and NaHCO3 or AcOH (0.2mmol) in DMF (3mL) were put into a reaction tube of parallel reactor (Wattecs). The reaction mixture was stirred at 100C under N2 atmosphere for the indicated time until the starting materials was consumed completely as monitored by TLC and LC-MS analysis. The reaction mixture was then washed with aqueous sodium bisulfite solution to remove the excess aldehyde and extracted with CH2Cl2. The organic layers were dried over anhydrous MgSO4. After filtering to remove the MgSO4, the solvent was removed under reduced pressure. The crude product was purified by column chromatography through a silica-gel column to afford the desired products.
87% With sodium hydrogen sulfide; at 190℃; for 0.333333h;Microwave irradiation; Green chemistry; General procedure: 2,2-Disulfanediyldianiline (1a) or 5,5-dichloro-2,2-dithiobisaniline (1b) (0.50 mmol), the corresponding aldehydes(2a-p) (1.1 mmol), NaSH (0.3 mmol) and PEG-300 (2 mL) wereput into a round-bottomed ask, and the reaction mixture wasirradiated for 20 min at 25 W. After completion of the reactionmonitored by TLC with a mixture of petroleum ether and ethylacetate as eluent, the mixture was allowed to cool to roomtemperature. Distilled water (25 mL) was added into the ask,and then the solid was precipitated from the aqueous phaseafter stirring by magnetic stirrers in 5 min. The solid precipitatewas isolated by fltration, washed twice by distilled water (5 mL)and dried for 3 h. The pure targetproducts3a-3o were obtaineddirectly. The pure products 3p and 3q were obtained by columnchromatography(PE/EtOAc as eluent).Complete characterization of the products (all known) is found in the SupplementalMaterials (Figures S 1-S 34).
84% With sodiumsulfide nonahydrate; carbon dioxide; In water; at 50 - 80℃; for 24h;Autoclave; (1) Synthesis of 2- (4-methylphenyl) benzothiazoleWas added to the autoclave 0.40mmol 2,2'-dithiobis aniline, 0.80mmol of methyl benzaldehyde and 0.2mmol of Na2S · 9H2O, placed magneton, then add 2mL of water as a reaction solvent, after heating to 50 2MPa charged carbon dioxide gas. And continue to heat to 80 After stirring for 24h, LC detected disulfide starting material the reaction was complete, cooled to room temperature, using a rotary evaporator to give the crude product obtained after the solvent was removed under reduced pressure. The crude product with petroleum ether and ethyl acetate as the eluent, using a gradient elution by column chromatography (200-300 mesh silica gel) was obtained with a purity greater than 99% of the white powder of 2- (4-methylphenyl ) benzothiazole 151.2mg, isolated in 84% yield,
76% With tert.-butylhydroperoxide; copper dichloride; In chloroform; water; at 80℃; for 24h;Inert atmosphere; Schlenk technique; A 25 mL reaction vessel was charged with 2,2'-disulfanediyldianiline 7 (0.483 mmol, 0.57 equiv), p-methylbenzaldehyde 2a (0.845 mmol), CuCl2 (0.254mmol, 0.3 equiv), tert-butylhydroperoxide (0.507 mmol, 0.6 equiv, 70% aqueous solution) and 0.1 mL CHCl3 under nitrogen. The reaction mixture was stirred in an ice bath for 30 min, andthen stirred at 80C for 24 h. After cooling to room temperature, the mixture was purified by column chromatography using silica gel (petroleum ether/ethylacetate) to afford the product 3a.

  • 18
  • [ 609-73-4 ]
  • [ 4498-99-1 ]
  • [ 16112-21-3 ]
  • 19
  • [ 56048-69-2 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
34 mg With sodium cyanide; oxygen; In N,N-dimethyl-formamide; at 20℃; for 8h; General procedure: 2-Aminothiophenol 7 (25 mg; 0.20 mmol; 1.0 equiv) and aldehyde 2 (0.02 mmol; 1.0 equiv), and molecular sieve (10 mg) were dissolved in DMF (1.0 mL). The reaction mixture was stirred at 60 C. After the complete consumption of the aldehyde, themixture was cooled to room temperature and NaCN (1.0 mg; 0.020 mmol; 10 mol %) was added to the above reaction mixtureand the reaction progress was monitored by TLC. On completion of the reaction, the reaction mixture was concentrated under reduced pressure. The crude product was purified by column chromatography on silica to give the corresponding benzothiazole 8.
  • 20
  • bis-(2-(4-methylbenzalamino)phenyl)disulfide [ No CAS ]
  • [ 16112-21-3 ]
  • 21
  • [ 104-82-5 ]
  • [ 137-07-5 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
55% In 1-methyl-pyrrolidin-2-one; at 100℃; for 2h; To a solution of 4-methylbenzyl chloride (3.1 g, 20.0 mmol) in 50 mL of NMP, 2-aminobenzenethiol (3.1 g, 20.0 mmol) was added. The mixture was heated to 100 C. for 2 hours. The mixture was cooled down to rt, and saturated Na2CO3 solution was added, followed by 20 mL of water. The resulting white solid was filtered, washed by water and dried over high vacuum. (3.6 g, 55% yield) LC-MS (ESI): [M+1]+=226.13, tR=4.59 min. 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J=8.1 Hz, 1H), 7.97 (d, J=8.1 Hz, 2H), 7.87 (d, J=7.9 Hz, 1H), 7.47 (t, J=7.5 Hz, 1H), 7.35 (t, J=7.5 Hz, 1H), 7.28 (d, J=7.9 Hz, 2H), 2.41 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 168.27, 154.18, 141.45, 134.96, 130.96, 129.75, 127.50, 126.27, 125.02, 123.06, 121.60, 21.56.
  • 22
  • [ 104-81-4 ]
  • [ 137-07-5 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
71% In acetonitrile;Irradiation; General procedure: A mixture of 1,2-Diaminobenzene 1 or 2-Mercaptoaniline 4(1 mmol), benzyl bromides (1 mmol) 2 and 4 % Cu:ZnS NPs (10 mol %)in 10 ml of CH3CN were irradiated in visible light (100W OSRAMTungsten Lamp, EFP 64627 HLX) with continuous stirring for the appropriatetime. Catalyst was separated by centrifugation after thecompletion of reaction. Evaporation of the above solution gave thecrude product which was purified using crystallization.
  • 23
  • [ 95-16-9 ]
  • [ 5720-05-8 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
83% With iron(III) oxide; copper(l) iodide; 1,10-Phenanthroline; di-tert-butyl peroxide; lithium tert-butoxide; In toluene; at 110℃; for 12h;Schlenk technique; Sealed tube; Green chemistry; General procedure: CuI (0.1 mmol), Fe2O3(0.1 mmol), 1,10-phenanthroline(0.1mmol) ,LiOBu-t(1.0 mmol), t-BuOOBu-t(1.0 mmol), benzooxazole(0.5 mmol) and phenylboronic acid(1.0 mmol)were weighed into an oven-dried Schlenk tube which was sealed with a plug. Then toluene(3.0 mL) was added.The reaction mixture was stirred at 110 oC for 12 h. The resulting mixture was then cooled to room temperatureand diluted with ethyl acetate. The organic layer was collected, washed with water and brine, and dried overNa2SO4. After removal of the solvent in vacuo, the residue was purified by silica gel chromatography to give thedesired 2-phenylbenzo[d]oxazole.
78% With iron(III) chloride; copper(II) acetate dihydrate; palladium dichloride; In N,N-dimethyl-formamide; at 120℃; for 24h; General procedure: Azole (0.5 mmol), arylboronic acid (1.0 mmol), PdCl2(0.05 mmol), Cu(OAc)2·H2O (0.25 mmol), FeCl3 (0.25mmol) and DMF (2.0 mL) were taken in a 25 mL two-neckflask. The mixture was heated at 120 C in air for 24 h bymagnetic stirring. After cooling to room temperature, theproduct was diluted with H2O (5 mL) and extracted withEtOAc (415 mL). The extracts were combined and washedby brine (310 mL), dried over MgSO4, filtered, and evaporated,and purified by chromatography on silica gel to obtainthe desired products with ethyl acetate/hexane(v/v=1:11:10). The products were characterized by theirspectral and analytical data and compared with those of theknown compounds.
  • 24
  • [ 5720-05-8 ]
  • [ 100498-97-3 ]
  • [ 16112-21-3 ]
  • 25
  • [ 95-16-9 ]
  • [ 380481-66-3 ]
  • [ 16112-21-3 ]
  • 26
  • [ 95-16-9 ]
  • [ 824-79-3 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
71% General procedure: Under nitrogen atmosphere, a sealable reaction tube equipped with a magnetic stirrer bar was charged with azole (0.50 mmol), sodium arylsulfinate (1.0 mmol), Pd(OAc)2 (0.025 mmol), Cu(OAc)2 (1.0 mmol), CF3COOH (0.50 mmol), and dimethylglycol (2.0 mL). The rubber septum was then replaced by a Teflon-coated screw cap, and the reaction vessel placed in an oil bath at 120 C for 24 h. After the reaction was completed, it was cooled to room temperature and the mixture was treated with K2CO3 solution (1.0 mol/L, 3.0 mL), then extracted with ethyl acetate. The resulting solution was dried by Na2SO4 then concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (eluant: petroleum ether/ethyl acetate=12:1, v/v) to give the desired product.
  • 28
  • [ 95-16-9 ]
  • [ 106-43-4 ]
  • [ 16112-21-3 ]
  • 29
  • [ 95-16-9 ]
  • [ 25563-06-8 ]
  • [ 16112-21-3 ]
  • 30
  • [ 615-43-0 ]
  • [ 104-87-0 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
93% With potassium thioacyanate; sodium hydroxide; In water; at 100℃; for 0.5h;Microwave irradiation; In the reaction vessel, 2-iodoaniline (1 mmol), 4-methylbenzaldehyde (1 mmol), potassium thiocyanate (2.4 mmol), nickel/proline lithium complex (0.05 mmol), sodium hydroxide (1 mmol), and water (3 mL) were added.After being placed under the microwave reactor,Set in a microwave reactor to 100 C was heated for 30 minutes at 150 W power, cooled to room temperature.The product was extracted with ethyl acetate and concentrated under reduced pressure. The product was purified by column chromatography to give a white solid in 93% yield.
81% With potassium carbonate; thiourea; In water; at 100℃; for 6.5h;Green chemistry; General procedure: To a mixture of 2-iodoaniline (1 mmol), aryl aldehyde (1.2 mmol), thiourea (3 mmol), K2CO3 (3 mmol) and Cu(0)-Fe3O4SiO2/NH2cel (0.05 g, 0.25 mol% Cu) in a round-bottom flask (25 mL), water (5 mL) was added, and the reaction mixture was stirred at 100 C for an appropriate time (Scheme 3). After completion of the reaction (monitored by TLC), the catalyst was separated using an external magnet and the reaction mixture was diluted with ethyl acetate. The organic layer was washed with water (3 x 10 mL) followed by brine solution (2 x 10 mL) and dried over anhyd. Na2SO4. Finally the product was obtained after removal of the solvent under reduced pressure followed by crystallization with EtOAc-pet. ether. The recovered catalyst was washed with EtOAc (3 x 10 mL) followed by double distilled water (3 x 10 mL) which was dried and reused for subsequent reactions.
  • 32
  • [ 95-16-9 ]
  • [ 104-87-0 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
82% With silver(I) 4-methylbenzenesulfonate; In water; at 100℃; for 12h;Sealed tube; Inert atmosphere; Green chemistry; General procedure: A sealed pressure vessel was charged with benzothiazole (68 mg, 0.5 mmol), AgOTs (280 mg, 1 mmol),aldehyde (0.6 mmol) and 2.0 mL of H2O. The resulting solution was stirred at 100 C for 12 h under N2.Upon completion of the reaction, H2O (8.0 mL) was added, then extracted with EtOAc (5 mL × 3), driedover Na2SO4, and concentrated under reduced pressure. The residue was further purified with flashcolumn chromatography.
80% With tert.-butylhydroperoxide; copper dichloride; In water; at 80℃; for 24.5h;Inert atmosphere; Schlenk technique; General procedure: A 25 mL reaction vessel was charged with benzothiazole 1 (1.86 mmol, 1.1 equiv), aldehyde 2 (1.69 mmol), CuCl2 (0.51mmol, 0.3 equiv), and tert-butylhydroperoxide (2.36 mmol, 1.4 equiv, 70% aqueous solution) under nitrogen. The reactionmixture was stirred in an ice bath for 30 min, and then stirred at 80C for 24 h. After cooling to room temperature, the mixture was purified by column chromatography using silica gel (petroleum ether/ethyl acetate) to afford the products 3.
53% With tert.-butylhydroperoxide; N-chloro-succinimide; In decane; dimethyl sulfoxide; at 120℃; for 10h;Schlenk technique; Weigh 4-methylbenzaldehyde (0.37 mmol, 44.8 mg) benzothiazole (2.0 eq., 0.74 mmol, 99.9 mg), NCS (20 mol%, 0.07 mmol, 9.4 mg) and 5.5 M TBHP in decane (2.0 eq., 0.74 mmol, 135 μL) in a 25 mL Schlenk reaction tube, and then added DMSO (15 eq., 5.55 mmol, 0.43 g), placed at 120 reaction, after 10 h the reaction was completed, the reaction solution was extracted with DCM The organic layer was concentrated to remove the solvent, and the concentrated solution was separated by column chromatography (eluent is a petroleum ether-ethyl acetate mixed solvent with a volume ratio of 1: 0.05) to obtain a white solid, namely the derivative Ia. The yield is 53%.
  • 33
  • [ 137-07-5 ]
  • [ 104-84-7 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
83% With acide 2,4,6-trihydroxybenzoique; oxygen; In para-xylene; at 140℃; under 750.075 Torr; for 24h;Green chemistry; General procedure: To a two-necked flask, benzylamine derivatives 1 (4.0 mmol), o-aminothiophenol (8a) (3.0 mmol), 4,6-dihydroxysalicylic acid (10 mol%), and distilled p-xylene (2.0 mL) were added, and then the reaction vessel was connected to an O2 balloon at room temperature. The mixture was stirred in 140 C under O2 atmosphere for 24 h. The resulting mixture was transferred into a round-bottom flask using ethyl acetate (EtOAc) and concentrated under reduced pressure. The residue was purified by silica gel chromatography (eluent: hexane/EtOAc) to give product 9.
69% With 2,8-dibromo-10-(4-bromophenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-dipyrrolo[1,2-c:2′,1′-f ][1,3,2]diazaborinin-4-ium-5-uide; In acetonitrile; at 50℃; under 1500.15 Torr; for 5h;Irradiation; Green chemistry; General procedure: Amine (1 mmol), 2-aminothiophenol (2 mmol), BODIPY photosensitizer (0.01 mmol, 1.0 mol%), and acetonitrile (5 mL) were added to a dry 10-mL flask. The flask was pressurized with air (2 bar) and then heated to 50 C. The solution was then irradiated using a 35-W xenon lamp through a cutoff filter (0.72M NaNO2 aqueous solution, which is transparent for light >385nm, because lamps could emit a small amount of ultraviolet light). After the reaction was completed, the solvent was evaporated under reduced pressure. The crude product was further purified using column chromatography.
  • 35
  • [ 16112-21-3 ]
  • [ 56048-54-5 ]
YieldReaction ConditionsOperation in experiment
85% With [bis(acetoxy)iodo]benzene; palladium diacetate; acetic acid; at 110℃; for 4h; General procedure: An oven-dried flask was charged with Pd(OAc)2 (0.05 mmol), diacetoxyiodobenzene (DIB) (1.0 mmol), substituted 2-phenylbenzo[d]thiazole (1-18) (1.0 mmol), and acetic acid (2 mL). Then the reaction vessel was kept in an oil bath preheated to 110 C and allowed to stir for the stipulated period of time. The progress of the reaction was monitored by TLC. During this period complete disappearance of substituted 2-phenylbenzo[d]thiazole was observed with the appearance of one major product having higher Rf [in some cases (1b, 4b, 16b, 15c, 18c)] another product was also observed having lower Rf with respect to the substrate. The reaction mixture was then cooled and admixed with water (5 mL). The product was extracted with ethyl acetate (2×10 mL) and the combined organic layer was washed with saturated sodium bicarbonate (NaHCO3) solution. Organic layer was dried over anhydrous sodium sulfate (Na2SO4) and evaporated under reduced pressure. The crude product so obtained was further purified through silica gel column chromatography (EtOAc/hexane) to yield the pure product. The identity and purity of the products were confirmed by spectroscopic analysis.
  • 36
  • [ 16112-21-3 ]
  • [ 100-52-7 ]
  • (2-(benzo[d]thiazol-2-yl)-5-methylphenyl)(phenyl)methanone [ No CAS ]
  • 37
  • [ 137-07-5 ]
  • [ 155164-67-3 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
80% In toluene; at 20℃; for 1.5h;Green chemistry; General procedure: A mixture of 2-acyl-4,5-dichloropyridazin-3(2H)-one (5, 1 equiv, 2.4 mmol), 2-aminothiophenol (1, 1.2 equiv, 0.3 mmol), and toluene (25 mL) was stirred at room temperature (or at reflux conditions) until 5 was disappeared as determined by TLC. Water (50 mL) and dichloromethane (150 mL) were added with stirring to the reaction mixture. The organic layer was extracted and dried over anhydrous magnesium sulfate, and the solvent was evaporated under the reduced pressure. The resulting residue was transferred to an open-bed silica gel column (3×6 cm). The column was eluted with n-hexane/tetrahydrofuran (5:1, v/v) for 3 and then ethyl acetate for 4,5-dichloropyridazin-3(2H)-one. Fractions containing compound 3 were combined and evaporated under reduced pressure to give the product. Fractions containing 4,5-dichloropyridazin-3(2H)-one were also combined and evaporated under reduced pressure to afford quantitatively the recyclable 4,5-dichloropyridazin-3(2H)-one.; Light yellow solid. Mp 77-79 C (lit.15 79.3-81.2 C). IR (KBr) 2949, 2916, 2846, 1693, 1604, 1546, 1478, 1427, 1402, 1306, 1269, 1253, 1221, 955, 811, 750, 721, 703, 685, 662 cm-1. 1H NMR (DMSO-d6, δ ppm) 2.39 (s, 3H), 7.38 (d, 2H, J=8.09 Hz), 7.45 (t, 1H, J1=7.21 Hz, J2=7.87 Hz), 7.54 (t, 1H, J1=7.97 Hz, J2=7.13 Hz), 7.99 (d, 2H, J=8.03 Hz), 8.04 (d, 1H, J=8.09 Hz), 8.14 (d, 1H, J=7.96 Hz). 13C NMR (DMSO-d6, δ ppm) 21.52, 122.78, 123.17, 125.85, 127.07, 127.61, 130.42, 130.69, 134.76, 141.98, 154.04, 167.81. HRMS (m/z): [M]+ calcd for C14H11NS; 225,0612. Found: 225,0611.
  • 38
  • [ 609-73-4 ]
  • [ 104-87-0 ]
  • [ 16112-21-3 ]
  • 39
  • [ 104-85-8 ]
  • [ 137-07-5 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
91% With zinc(II) oxide; In neat (no solvent); at 70℃;Green chemistry; General procedure: To a mixture of 2-aminothiophenol (1a) or 4-chloro-2-aminothiophenol (1b) (1 mmol) andaryl/alkyl nitriles (2a-2z and 4a-4g) (1mmol), ZnO-NPs (10 mg) were added. Then resulting reaction mixture was heated at 70C in oil bath with constant stirring till the reaction wascompleted. After completion of the reaction as indicated on TLC, the reaction mixture was cooled at room temperature and the crude product was dissolved in ethyl acetate and catalyst was isolated by simple filtration. The product in ethyl acetate was washed with water and excess of solvent removed under reduced pressure. The solid product was washed with cold diethyl ether and dried. The pure products (3a-3z and 5a-5g) were obtained in 86-96% yield and there is no need to purify the products recrystallization or column chromatography.
75% With trifluorormethanesulfonic acid; In neat (no solvent); at 100℃; for 12h; General procedure: A reaction flask was charged with a mixture of 1a (3.0 mmol), 2a (3.0 mmol), TfOH (0.06 mmol). The reaction mixture was stirred at 100 oC for 12 h, and then was cooled to room temperature. Water (10 mL) was added to the resultant mixture. The product was extracted with CH2Cl2 (10 mL × 2). The solvent was removed under reduced pressure, and the residue obtained was purified via silica gel chromatography (eluent: petroleum ether/ethyl acetate = 50:1) to afford the product 3a (595.8mg, 94% yield) as a white solid.
  • 40
  • [ 95-16-9 ]
  • [ 104-84-7 ]
  • [ 16112-21-3 ]
  • 41
  • [ 50684-43-0 ]
  • [ 77116-72-4 ]
  • [ 16112-21-3 ]
  • 42
  • [ 865077-50-5 ]
  • [ 16112-21-3 ]
  • 43
  • [ 615-43-0 ]
  • [ 104-84-7 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
84% With 1,4-diaza-bicyclo[2.2.2]octane; 1,10-Phenanthroline; copper(II) acetate monohydrate; sulfur; In dimethyl sulfoxide; at 100℃; General procedure: A mixture of 2-iodoaniline 1 (1 mmol), benzylamine 2 (1.2 mmol), sulfur powder (6 mmol), DABCO (2 mmol), Cu(OAc)2·H2O (0.02 mmol), and 1,10-phenanthroline (0.02 mmol) was stirred in DMSO (5mL) at 100 C. After completion of the reaction as indicated by TLC, the mixture was cooled to room temperature, water (20 mL) was added, and then the aqueous solution was extracted with ethyl acetate (3×15 mL). The organic layers were combined, dried over anhydrous MgSO4, the filtrate was concentrated under vacuum and then the residue was purified by column chromatography (eluent: petroleum ether/ethyl acetate (10:1 to 14:1) on silica gel to provide the desired product.
84% With 1,4-diaza-bicyclo[2.2.2]octane; 1,10-Phenanthroline; copper(II) acetate monohydrate; sulfur; In dimethyl sulfoxide; at 100℃; General procedure: A mixture of 2-iodoaniline 1 (1 mmol), benzylamine 2 (1.2 mmol), sulfur powder (6 mmol), DABCO (2 mmol), Cu(OAc)2.H2O (0.02 mmol), and 1,10-phenanthroline (0.02 mmol) was stirredin DMSO (5 mL) at 100 C. After completion of the reaction as indicated by TLC, the mixture was cooled to room temperature, water (20 mL) was added, and then the aqueous solution was extracted with ethyl acetate (3 15 mL). The organic layers were combined, dried over anhydrous MgSO4, the filtrate was concentrated under vacuum and then the residue was purified by column chromatography (eluent: petroleum ether/ethyl acetate (10:1 to 14:1) on silicagel to provide the desired product.
  • 44
  • [ 95-16-9 ]
  • [ 122-00-9 ]
  • [ 33429-09-3 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
With dipotassium peroxodisulfate; iron(III) chloride hexahydrate; In water; dimethyl sulfoxide; at 100℃; for 12h; General procedure: A dried reflux tube equipped witha magnetic stir bar charged with benzothiazole derivative (1 mmol 2.0 equiv), acetophenone derivative (0.5 mmol 1.0equiv),FeCl3·6H2O (0.2equiv), K2S2O8 (3.0 equiv), DMSO/H2O (2:1 mL)and the reaction vessel was placed in a 100C oil bath for 12 h under air.After cooling to room temperature, the mixture was diluted with ethyl acetateand directly filtered through a pad of celite and washed with water. Theorganic phase was dried over NaSO4 and removed under reduced vacuum.The residue was purified by column chromatography eluting with ethyl acetateand hexane to afford the desired product
  • 45
  • [ 95-16-9 ]
  • [ 589-18-4 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
47% With dipotassium peroxodisulfate; iron(III) chloride hexahydrate; In water; dimethyl sulfoxide; at 100℃; for 12h; A dried reflux tube equipped witha magnetic stir bar charged with benzothiazole derivative (0.5 mmol 1.0equiv), benzylalcohol derivative (1.5mmol 3.0equiv), FeCl3·6H2O (0.1equiv), K2S2O8 (2.0 equiv), DMSO/H2O (2:1 mL) and the reaction vessel was placedin a 100C oil bath for 12 h under air. After cooling to room temperature,the mixture was diluted with ethyl acetate and directly filtered through a padof celite and washed with water. The organic phase was dried over NaSO4and removed under reduced vacuum. The residue was purified by columnchromatography eluting with ethyl acetate and hexane to afford thedesired product.
37% With tert.-butylhydroperoxide; copper dichloride; In water; at 80℃; for 24.5h;Inert atmosphere; Schlenk technique; General procedure: A 25 mL reaction vessel was charged with benzothiazole 1 (1.86 mmol, 1.1 equiv), benzylic alcohol 4 (1.69 mmol), CuCl2 (0.51 mmol, 0.3 equiv), and tert-butyl hydroperoxide (4.06mmol, 2.4equiv, 70% aqueous solution) under nitrogen. The reaction mixture was stirred in an ice bath for 30 min, and then stirred at 80C for 24 h. After cooling to room temperature, the mixture was purified by column chromatography using silica gel (petroleum ether/ethyl acetate) to afford the products 3.
  • 46
  • [ 1040308-59-5 ]
  • [ 16112-21-3 ]
  • 47
  • [ 875238-80-5 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
88% With tert.-butylhydroperoxide; copper dichloride; In water; tert-butyl alcohol; at 80℃; for 24h;Inert atmosphere; Schlenk technique; To a solution of compound 6(25 mg,0.051 mmol) and CuCl2(2.1mg,0.015 mmol) in t-BuOH(0.3 mL) was added tert-Butyl hydroperoxide (9.4 μL,0.072 mmol, 70% aqueous solution) under nitrogen and the mixture was stirred at 80C for 24 h. After cooling to room temperature, the mixture was purified by column chromatography using silica gel (petroleum ether/ethyl acetate=50:1) to afford 3aa in 88% yield (20.3 mg).
  • 48
  • [ 95-16-9 ]
  • [ 123726-16-9 ]
  • [ 16112-21-3 ]
  • 49
  • [ 88-73-3 ]
  • [ 104-84-7 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
75% With sulfur; In neat (no solvent); at 130℃; for 24h;Sealed tube; Inert atmosphere; General procedure: A mixture of 2-chloronitrobenzene (1 mmol), amine (3 mmol), and elemental sulfur (2 mmol) was stirred in a sealed tube under nitrogen atmosphere at indicated temperature for 24 h (See Table 2). After being cooled to room temperature, the crude reaction mixture was triturated and dissolved in ethylacetate, then filtered and the filtrate was concentrated, and the residue was purified by column chromatography on silica gel to afford the desired product.
  • 50
  • [ 1073-67-2 ]
  • [ 16112-21-3 ]
  • C21H14ClNOS [ No CAS ]
  • 51
  • [ 100-42-5 ]
  • [ 16112-21-3 ]
  • (2-(benzo[d]thiazol-2-yl)-5-methylphenyl)(phenyl)methanone [ No CAS ]
  • 52
  • [ 16112-21-3 ]
  • [ 65-85-0 ]
  • 2-(benzo[d]thiazol-2-yl)-5-methylphenyl benzoate [ No CAS ]
  • 53
  • [ 16112-21-3 ]
  • [ 611-73-4 ]
  • (2-(benzo[d]thiazol-2-yl)-5-methylphenyl)(phenyl)methanone [ No CAS ]
  • 54
  • [ 128-08-5 ]
  • [ 16112-21-3 ]
  • 2-(2,6-dibromo-4-methylphenyl)benzo[d]thiazole [ No CAS ]
  • 55
  • [ 516-12-1 ]
  • [ 16112-21-3 ]
  • C14H9I2NS [ No CAS ]
  • 56
  • [ 128-09-6 ]
  • [ 16112-21-3 ]
  • 2-(2,6-dichloro-4-methylphenyl)benzo[d]thiazole [ No CAS ]
  • 57
  • [ 622-47-9 ]
  • [ 88-73-3 ]
  • [ 16112-21-3 ]
  • 58
  • [ 100-52-7 ]
  • [ 137-07-5 ]
  • [ 16112-21-3 ]
  • 59
  • [ 589-18-4 ]
  • [ 137-07-5 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
97% With tetrabutylammonium bromide; In N,N-dimethyl-formamide; at 80℃; for 1.83333h; General procedure: A mixture of alcohol (1 mmol), 1,2-phenylenediamine or 2-aminothiophenol(1 mmol), Pd(II)Cl2-BTPMNPs (0.019 g, containing 0.09mol% Pd) and (1 mmol) tetrabutylammonium bromide (TBAB, 0.01 g)in DMF (5 mL) in a round-bottomed flask equipped with a condenser wasstirred at 80 C. The progress of the reaction was monitored by TLC(eluent: n-Hexane/EtOAc, 4: 1 for benzimidazoles and n-Hexane/EtOAc, 6: 1 for benzothiazoles). The catalyst was separated by permanentmagnet and washed with EtOAc (10 mL). The crude product waspurified by recrystallization from EtOAc or EtOH to afford the purebenzimidazole. The benzothiazoles was obtained by recrystallizationfrom n-hexane/EtOAc (10: 1).
79% With anhydrous sodium carbonate; In neat (no solvent); at 120℃;Green chemistry; General procedure: Typically, o-phenylenediamine (1.3 mmol) or 2-aminothiophenol (1 mmol), benzyl alcohols (1 mmol), Na2CO3 (20 mol%), and Pd-NPs/Cu2(BDC)2(DABCO) (20 mg, 0.01 mol%) were added to a round-bottom flask. The reaction mixture was heated to 120 Cand stirred at for the appropriate time in air (TLC monitoring). Ethyl acetate was added to the reaction mixture and catalyst was filtered. For the purification of impure products, chromatography on silica gel was performed (EtOAc:Hep. (1:6)). The entire products characterized by melting point, CHN, 1H-NMR and13C-NMR spectroscopy.
79% With potassium-t-butoxide; In toluene; at 20 - 110℃; for 48h; At room temperature, add o-aminothiophenol 1a (0.6 mmol), toluene solvent and 4-methylbenzyl alcohol 2e (0.2 mmol) to the reactor in turn, stir at room temperature to fully dissolve them, and add to Example 1 in turn The prepared HKUST-1-400 catalyst (20mg), potassium tert-butoxide (0.2mmol), after dissolving, continue the reaction and place it at 110C for 2 days. After the completion of the reaction is detected by TLC, the Cu-MOF derivative material is filtered out first The HKUST-1-400 catalyst was then subjected to column chromatography to obtain the target compound 3e with a yield of 79%.
73% With [Pd(COD)Cl(SnCl3)]; In o-dimethylbenzene; at 140℃; for 24h; General procedure: A mixture of aniline 1 (23.28 mg, 0.25 mmol), benzyl alcohol 2 (27 mg, 0.25 mmol), [Pd(COD)Cl(SnCl3)] (3.5 mg, 0.007 mmol) in 3mL of o-xylene was stirred at 140 C for 24h. Then, solvent was removed under reduced pressure, and the mixture was subjected to column chromatography over silica gel (100-200 mesh, eluent: petroleum ether 60-80 C/ethylacetate 20:1 v/v) to afford a corresponding product 3 as a yellow color oil in 90% (41.5 mg) isolated yield.
With oxygen; In acetonitrile; under 760.051 Torr; for 10h;Schlenk technique; Sealed tube; Irradiation; Green chemistry; General procedure: The synthesis of 2-substituted benzothiazoles from oaminothiophenols and alcohols was performed in a sealed Schlenk tube under visible light irradiation. Typically, a mixture of oaminothiophenol(0.1 mmol) and alcohol (0.3 mmol) in acetonitrile(CH3CN, 2 mL) was saturated with O2 before the mixture wastransferred into a 10 mL tube containing 10 mg of MOFs. The suspensionwas irradiated with a 300WXe lamp equipped with a UVcutfilter to remove all irradiations with wavelengths less than420 nm and an IR-cut filter to remove all irradiations with wavelengthsgreater than 800 nm. After the reaction, the suspensionwas filtered through a porous membrane (diameter 20 μm) andthe products were analyzed by GC-MS and GC-FID (ShimadzuGC-2014) with an HP-5 capillary column. The reaction, scaled upby 10 times, was conducted under similar conditions in a homemadereactor. A mixture of o-aminothiophenol (1 mmol) and benzylalcohol (3 mmol) in CH3CN (20 ml) saturated with O2 wastransferred to the homemade reactor containing 100 mg of MIL-100(Fe). The reactor was irradiated with a 300W Xe lampequipped with both a UV-cut filter and an IR-cut filter.

  • 60
  • [ 95-16-9 ]
  • [ 623-13-2 ]
  • [ 16112-21-3 ]
  • 61
  • [ 99-94-5 ]
  • [ 1141-88-4 ]
  • [ 16112-21-3 ]
  • C22H19NO2S [ No CAS ]
YieldReaction ConditionsOperation in experiment
59% General procedure: 2,2'-Disulfanediyldianiline 1a or 6,6'-disulfanediylbis(3-chloroaniline) 1b (0.5 mmol) and carboxylic acid (1.0 mmol, except 0.5mmol for 2k) were added to a three-neck flask under an atmosphere of Ar, and 5 mL dry toluene was added, then the mixture was stirred for 2.5 h at 70 C to allow the solid to dissolve in toluene solvent completely. After the reaction solution was cooled down to 30 C, PCl3 (1.2 mmol, 0.165 g) was added dropwise. When the PCl3 was added completely, the reaction mixture was further stirred for 4 - 6 h at 100C until no 2,2'-disulfanediyldianiline or 6,6'-disulfanediylbis(3-chloroaniline) was detected by TLC analysis. The reaction solution was washed with saturated aqueous sodium bicarbonate solution and extracted with CH2Cl2. The collected organic layers were dried over anhydrous MgSO4. After filtered toremove the MgSO4 and the solvent was removed under reduced pressure. The crude product was purifiedby flash chromatography on silica gel using PE / EtOAc.
  • 62
  • [ 615-20-3 ]
  • [ 14338-21-7 ]
  • [ 16112-21-3 ]
  • 63
  • [ 16112-21-3 ]
  • copper(l) cyanide [ No CAS ]
  • 2-(benzo[d]thiazol-2-yl)-5-methylisophthalonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% General procedure: A solution of 2-arylbenzothiazole 1 (0.2mmol), I2 (0.22mmol), PhI(OAc)2 (0.22mmol), [RhCp*Cl2]2 (1mol%), and AgSbF6 (4mol%) in DCE (2.0mL) was stirred at 80C. After completion of the reaction as detected by TLC, the reaction mixture was cooled to room temperature. Then CuCN (0.6mol) and l-proline (0.2mmol) were added into the solution. The reaction mixture was stirred at 80C. After the completion of the reaction (monitored by TLC), the solvent was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel with petroleum ether/ethyl acetate (10:1) as the eluent to give the desired product 2.
  • 64
  • [ 16112-21-3 ]
  • 3-acetyl-3-(tert-butylperoxy)-4-cyclohexylchroman-2-one [ No CAS ]
  • 1-(2-(benzo[d]thiazol-2-yl)-5-methylphenyl)ethanone [ No CAS ]
  • 65
  • [ 16112-21-3 ]
  • 3-benzoyl-3-(tert-butylperoxy)-4-cyclohexylchroman-2-one [ No CAS ]
  • (2-(benzo[d]thiazol-2-yl)-5-methylphenyl)(phenyl)methanone [ No CAS ]
  • 66
  • [ 16112-21-3 ]
  • 2-(2,6-dibromo-4-methylphenyl)benzo[d]thiazole [ No CAS ]
  • 67
  • [ 16112-21-3 ]
  • 2-(2,6-dichloro-4-methylphenyl)benzo[d]thiazole [ No CAS ]
  • 68
  • [ 7163-50-0 ]
  • [ 137-07-5 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
75% With trimethyl-(2-hydroxyethyl)ammonium chloride; tartaric acid; at 60℃; for 0.5h; 1) Take a 10mL Erlenmeyer flask or test tube, add 0.2mmol 2-aminothiophenol, 0.4mmol p-toluoyl formic acid and 2mL deep eutectic solvent (the molar ratio of choline chloride to tartaric acid is 2: 1 );(2) Place the Erlenmeyer flask or test tube in step (1) into a 60 C oil bath and stir magnetically for 30 min to obtain the crude product;(3) Separate the crude product obtained in step (2) by column chromatography. The eluent is a mixture of ethyl acetate and petroleum ether.The volume ratio is 1: 6, and it is dried at 30 C for 3 hours to obtain a 2-arylbenzothiazole compound.
73% at 60℃; for 0.5h;Green chemistry; General procedure: (a) Deep eutectic solvent synthesis: Choline chloride and the hydrogen bond donor (urea, oxalic acid, zinc chloride, etc.) were placed into a 10 mL plugged test tube. The reagents were mixed evenly, then heated and stirred in an 80 C oil bath until a uniform and transparent liq- uid was ready for use (generally 30 min). (b) Synthesis of cyclization product: o-Substituted aniline (0.30 mmol) and -keto acid (0.45 mmol) and DES (1 mL) were allowed to react in an oil bath at 80 C for 2.0 h. The reaction mixture was then extracted with EtOAc (5 ×), organic phases were combined, distilled and con- centrated to obtain the crude product, and then separated by column chromatography to obtain the pure product.
  • 69
  • [ 95-16-9 ]
  • [ 5142-75-6 ]
  • [ 16112-21-3 ]
  • 70
  • [ 1218-89-9 ]
  • [ 137-07-5 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
85.7% With silica gel-supported chlorosulfonic acid; In 2-methyltetrahydrofuran; at 120℃; for 4h; At room temperature, to the reaction vessel in an organic solvent, 2-MeTHF was added the above formula (II) Compound of formula (III) compound and silica-supported chlorosulfonic acid. Wherein, the formula (II) and the formula (III) The molar ratio of the compound of 1: 2 molar ratio of formula (II) compound with chlorosulfonic acid is 1: 0.1; stir Mix warmed up to 120 C, and incubated for 4 hours.After post-processing, as a yellow crystalline product of the formula (the I), in a yield of 85.7%, Purity 98.4% (HPLC).
  • 71
  • [ 16112-21-3 ]
  • [ 108-88-3 ]
  • (2-(benzo[d]thiazol-2-yl)-5-methylphenyl)(phenyl)methanone [ No CAS ]
  • 72
  • [ 615-43-0 ]
  • [ 104-82-5 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
67% With copper(II) acetate monohydrate; sodium carbonate; sulfur; In dimethyl sulfoxide; at 130℃; for 24h;Schlenk technique; Inert atmosphere; General procedure: 2-Iodoaniline 1a (0.5 mmol), benzyl chloride 2a (1 mmol, 126 mg), sulfur powder (2 mmol, 64 mg), Cu(OAc)2·H2O (20 mg) and Na2CO3 (1 mmol, 106 mg) in DMSO (3 mL) were put into a Schlenk tube. The reaction mixture was stirred at 130 C for 24 h and cooled to room temperature, filtered and extracted with ethyl acetate, washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified by chromatography on silica gel (300-400 mesh) to afford desired product 3aa as a light yellow solid; yield : 102 mg (97%);
  • 73
  • [ 7163-50-0 ]
  • [ 1141-88-4 ]
  • [ 16112-21-3 ]
  • 74
  • [ 104-82-5 ]
  • [ 88-73-3 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
87% With N-methylcyclohexylamine; sulfur; at 110℃; for 24h;Sealed tube; Inert atmosphere; General procedure: A mixture of o-chloronitrobenzene (0.5 mmol), benzyl chloride (1.0 mmol), elemental sulfur (1.5 mmol) and N-methylpiperidine (1.5 mL) was placed in a sealed pressure vessel (25 mL) containing a magnetic stirring bar. The The tube was purged with nitrogen three times, and then capped and stirred in a preheated oil bath at 110 C for 24 h. After the mixture was cooled to room temperature, concentrated in vacuum and purified by silica gel column chromatography by using petroleum ether and ethyl acetate (PE:EA=1:500) as eluent.
  • 75
  • [ 95-16-9 ]
  • [ 106-42-3 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
74% General procedure: Under an air atmosphere, a sealable reaction tube with a Teflon-coated screw cap equipped with a magnetic stir bar was charged with benzothiazole 1 (1.0 mmol), toluene derivative 2 (3.0 mmol), and Cu(OTf)2 (0.10 mmol) in DCE/DMSO (5:1, 2.0 mL). To this was added 70% aq TBHP (6.0 equiv) at r.t. The rubber septum was then replaced by a Teflon-coated screw cap, and the reaction vessel placed in an oil bath at 90 C for 24 or 36 h. When the reaction was complete, it was cooled to r.t. and monitored by TLC. To the resulting solution was added 98% hydrazine hydrate (0.5 or 1.0 mL), K2CO3 (3.0 mmol), and EtOH(2.0 mL), the mixture was stirred for 5 min and then poured into 10% HCl (15 mL); the mixture was extracted with EtOAc (2 ×). The combined organic layers were dried (anhyd Na2SO4) and the solvents were removed in vacuo. The residue was purified by flash chromatography (silica gel, petroleum ether/EtOAc 20:1) to give the product.
  • 76
  • [ 106-42-3 ]
  • [ 137-07-5 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
82% With Manganese dioxide nanostructures coated on natural silk; for 10h;Reflux; General procedure: In a two-necked flask, to a solution of amine source (1.0 mmol)in toluene or xylene (5.0 mL), MnO2silk (the amount of catalystwas listed in Table 4) was added and the mixture was stirred magneticallyunder reflux conditions and air blowing for the indicatedtime in Table 4. The progress of the reaction was monitored by TLC.After completion, the reaction mixture was filtered and washedwith ethanol. After removing of the organic solvents, the crudeproduct was separated on a silica gel column to give final product.
53% With methanesulfonic acid; di-tert-butyl peroxide; copper(II) oxide; at 120℃; for 20h; 0.06 mmol of cuprous oxide, 0.3 mmol of o-aminothiophenol, 1.2 mmol of di-tert-butyl peroxide, and 0.3 mmol of methanesulfonic acid were added to 2 mL of 4-methyltoluene, and refluxed at 120 C for 20 hours.After the reaction is completed, it is cooled to room temperature.The reaction mixture was diluted with 30 mL of ethyl acetate.Then use 8 mL of saturated brine,8mL of NaHSO3 solution,Wash with 8 mL of saturated saline solution.Dry with anhydrous Na2SO4, suction filtration, spin dry,Finally, using thin layer chromatography or column chromatography(Petroleum ether / ethyl acetate) isolated product 35.8 mg,The yield was 53%.
  • 77
  • [ 136620-24-1 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
60% With di-tert-butyl peroxide; iron; In toluene; at 110℃; for 16h; General procedure: 1 mmol of o-aminobenzyl benzyl sulfide 4,10 mol% of iron catalyst, 3 mmol of di-tert-butyl peroxide and 5 mL of toluene were successively added to a 25 mL single-necked flask and reacted at 110 C. for 16 h.After the reaction was completed, the mixture was cooled to room temperature and the solvent was removed by rotary evaporation. Finally, the target product 5a-5g was obtained by column chromatography on silica gel with the yield shown below.Which GW610 (5g) is an antineoplastic drug.
  • 78
  • [ 615-43-0 ]
  • [ 766-97-2 ]
  • [ 16112-21-3 ]
  • 79
  • [ 622-47-9 ]
  • [ 615-43-0 ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
74% With copper(II) acetate monohydrate; sulfur; sodium hydroxide; In dimethyl sulfoxide; at 130℃; for 24h;Sealed tube; Inert atmosphere; General procedure: A mixture of o-iodoaniline (0.5 mmol, 1 equiv), arylacetic acid (0.6 mmol), elemental sulfur (1.5mmol), Cu(OAc)2·H2O (20 mmol%), and NaOH (1.0 mmol) in DMSO (3 mL) was put into a sealed pressure vessel (25 mL) containing a magnetic stirring bar. The tube was purged with nitrogen three times, and then capped and stirred in a preheated oil bath at 130 C for 24 h. The reaction mixture then cooled to room temperature and extracted with ethyl acetate (3x10 mL), the organic layer was washed with saturated NaCl (2x10 mL), dried over anhydrous Na2SO4, evaporated under vacumm and then purified by silica gel column chromatography by using petroleum ether and ethyl acetate (PE:EA=200:1) as eluent.
  • 80
  • [ 5720-05-8 ]
  • [ 175694-99-2 ]
  • [ 16112-21-3 ]
  • 81
  • [ 95-16-9 ]
  • [ 1900-85-2 ]
  • [ 16112-21-3 ]
  • 82
  • [ 104-87-0 ]
  • [ 137-07-5 ]
  • (CuII-NHCs)n*nSiO2 [ No CAS ]
  • [ 16112-21-3 ]
YieldReaction ConditionsOperation in experiment
90% In neat (no solvent); at 20℃; for 0.283333h; General procedure: After observing the high activity of the (CuII-NHCs)nnSiO2 in the synthesis of benzimidazoles, we were encouraged to apply this catalyst in the synthesis of benzothiazoles. In this manner, the reaction between 3-bromobenzaldehyde and 2-ATP was used as model reaction for optimization of reaction conditions. In this situation, the effect of important parameters such as solvent type, catalyst amount and reaction temperature were investigated (Table 2). The obtained results showed that the highest benzothiazole was produced by 0.020mol% of (CuII-NHCs)nnSiO2 catalyst at room temperature and under solvent free conditions Table 2, entries 12-19). To investigate the scope and generality of the catalyst, different substituted benzaldehydes were reacted with 2-aminothiophenol and the corresponding 2-sunstituted benzothiazoles were produced in 85-95% (Table 4 , entries 1-8). The benefits of this catalytic system include high catalyst activity, short reaction time and easy separation of the catalyst from the product.
  • 83
  • [ 16112-21-3 ]
  • [ 24239-18-7 ]
  • C14H9Br2NS [ No CAS ]
YieldReaction ConditionsOperation in experiment
With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; for 9h;Reflux; <strong>[16112-21-3]2-(p-tolyl)benzothiazole</strong> (3.4 g, 15.0 mmol), NBS (2.7 g, 15.0 mmol) and catalytic amount of benzoyl peroxide (36 mg, 1 mol %) were dissolved in CCl4 (50 mL). The mixture was heated to reflux for 9 hours. The reaction was quenched by Na2SO3 solution and extracted by CCl4 twice. Collected organic layers were washed by brine, dried over Na2SO4 and concentrated to give the crude, which was recrystallized from hot EtOH to give the light purple solid. NMR showed mono-brominated and dibrominated products were in a molar ratio of 6:1. (3.2 g, 70% yield) LC-MS (ESI): [M+1]+=304.00, tR=3.50 min. 1H NMR (400 MHz, CDCl3) δ 8.10-8.04 (m, 3H), 7.92-7.88 (m, 1H), 7.53-7.47 (m, 3H), 7.43-7.35 (m, 1H), 4.52 (s, 1H).
  • 84
  • [ 773837-37-9 ]
  • [ 16112-21-3 ]
  • [ 2548-64-3 ]
YieldReaction ConditionsOperation in experiment
50% To a solution of 2-(4-(bromomethyl)phenyl)benzothiazole (2.8 g, 9.2 mmol) dissolved in 30 mL of DMF were added by NaCN (540 mg, 11.0 mmol) and water (3 mL). The mixture was stirred at rt for 1 h. The mixture was diluted with EA (50 mL), washed by 1 M of NaOH, 1 M of HCl and brine, extracted by EA (50 mL). Collected organic layers were dried over Na2SO4, concentrated and purified by silica gel (PE/EA=2/1 to 1/2) to get off-white powder. (1.3 g, 50% yield) LC-MS (ESI): [M+1]+=251.22, tR=4.05 min. 1H NMR (400 MHz, CDCl3) δ 8.11-8.05 (m, 3H), 7.90 (d, J=8.0 Hz, 1H), 7.50 (t, J=7.7 Hz, 1H), 7.44 (d, J=8.1 Hz, 2H), 7.39 (t, J=7.6 Hz, 1H), 3.80 (s, 2H). 3C NMR (101 MHz, CDCl3) δ 166.89, 154.08, 135.07, 133.55, 132.65, 128.59, 128.22, 126.50, 125.47, 123.36, 121.69, 117.30, 23.57.
  • 85
  • [ 16112-21-3 ]
  • [ 19226-36-9 ]
  • N-(2-(benzo[d]thiazol-2-yl)-5-methylphenyl)benzamide [ No CAS ]
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