Structure of 37859-42-0
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Godlewska, Klaudia ; Białk-Bielińska, Anna ; Rostkowski, Pawel ; Paszkiewicz, Monika ;
Abstract: Tire wear particles are generated during driving a vehicle as a result of friction between tires and road surfaces and are released into environment. Knowledge of their environmental occurrence and fate is still limited. In this study, we investigated the presence of 16 tire wear contaminants (TWCs) and their transformation products in the surface waters, tap water and soils in Poland.The developed extraction methods were used with recoveries in the range of 71–100% (except for 2-methylthio-benzothiazole - 51%) for water samples and in the range of 62–97% for soil samples. Ten TWCs were detected in soil samples, with the highest concentration of benzothiazole (BTH)(387 ng/g). Meanwhile, all analytes were detected in water samples, also with the highest concentration of BTH (326 ng/L). N-(1,3-Dimethylbutyl)-N′-phenyl-p-phenylenediamine-quinone (6PPD-Q), 1,3-diphenylguanidine (DPG) and BTH were detected in all examined surface waters. P-phenylenediamine-quinones(PPD-Qs)were detected in higher concentrations (1.85–297 ng/l) compared to the parent compounds (0.50–58 ng/l) in surface waters. Conversely, for soil samples, PPDs (0.170–116 ng/g) were more prevalent than PPD-Qs (0.167–4.71 ng/g). 6PPD-Q showed high ecological risks at all surface water sites. This is the first report on the TWCs levels in the environment in Poland.
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Keywords: Tire wear contaminants ; Transformation products ; 6PPD-Q ; Environmental analysis ; Environmental risk assessment
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| CAS No. : | 37859-42-0 |
| Formula : | C8H7NOS |
| M.W : | 165.21 |
| SMILES Code : | OCC1=NC2=CC=CC=C2S1 |
| English Name : | 2-(Hydroxymethyl)benzothiazole |
| MDL No. : | MFCD00226293 |
| InChI Key : | PQXMQZYDBQBWNL-UHFFFAOYSA-N |
| Pubchem ID : | 268122 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 92% | With manganese(IV) oxide In dichloromethane Reflux; | Benzothiazole-2-carbaldehyde (5) A mixture of benzothiazol-2-ylmethanol (0.33 g, 1.0 mmol) and manganese dioxide (1.70 g, 10 mmol) was treated with DCM (40 mL), and the reaction mixture was stirred under reflux for 15 h. The reaction progress was followed by TLC. After the solution had cooled to r.t., the mixture was filtered with diatomite and the filtrate was evaporated in vacuo to give compound 5 as: Brown solid; yield 92%; m.p. 73 °C (lit.32 75-76 °C); IR (KBr) (ν cm-1): 3057, 2846, 2354, 1694, 1485, 1204, 775; 1H NMR (500 MHz, DMSO-d6): δ 10.11 (s, 1H), 8.27 (dt, J = 7.3, 2.1 Hz, 2H), 7.71-7.62 (m, 2H). |
| 57.2% | With Dess-Martin periodane In dichloromethane at 20℃; for 1h; | 9.2 Step 2 Preparation of Intermediate 12 The intermediate 11 (2.0 g, 12.11 mmol) was dissolved in dichloromethane, and then added to the Dess-Martin reagent (6.2 g, 14.53 mmol), and reacted at room temperature for 1 h, and the reaction was completed by TLC.Then, 20 mL of saturated sodium hydrogencarbonate and 20 mL of saturated sodium thiosulfate were added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour, and then extracted with dichloromethane, and the organic layer was washed with brine and dried over Na 2SO 4 overnight. The desiccant was filtered off and concentrated under reduced pressure to give a red brown matter, column chromatography on a kind of white solid 1.13 g, yield 57.2. |
| 56% | With Dess-Martin periodane In dichloromethane at 4℃; for 1h; |
| 40% | With phthalic acid dimethyl ester In dichloromethane at 4℃; for 1h; | 2.4. Synthesis of benzothiazole-2-carbaldehyde (compound 5) To a solution of benzothiazol-2-ylmethanol (1.650 g,10.000 mmol) in methylene chloride (40 mL) was added DMP(4.600 g, 31.000 mmol), and the reaction was allowed to proceedwith stirring at 4 °C for 1 h prior to being quenched with saturatedaqueous sodium thiosulfate solution. The subsequent mixture wasextracted three times with methylene chloride. The combined organic extracts were dried with anhydrous magnesium sulfate andconcentrated. The crude product was purified by chromatographyon a silica gel column, eluting with DCM/MeOH (100/1, v/v) to yieldthe product benzothiazole-2-carbaldehyde [41] (0.650 g,40%). 1HNMR (400 MHz, CDCl3, TMS): δH 10.18 (s, 1H), 8.25 (d, J = 7.6 Hz, 1H),8.02 (d, J = 7.6 Hz, 1H), 7.61 (m, 2H). 13C NMR (100 MHz, CDCl3) δC184.432, 164.377, 135.263, 127.359, 126.966, 124.728, 121.649. |
| With selenium(IV) oxide | ||
| 66 %Spectr. | With iodine; oxygen; trifluoroacetic acid In ethyl acetate at 70℃; for 20h; Irradiation; | |
| 1.09 g | With manganese(IV) oxide In dichloromethane at 45℃; for 12h; | 1 Example 1: 2-Hydroxymethylbenzothiazole (1.16 g, 7.0 mmol) was dissolved in 40 mL of dichloromethane,Manganese dioxide (4.87 g, 56 mmol) was added,45 reflux reaction 12h,Set aside cooling,Filtered to remove insoluble impurities,Concentrated, recrystallized from ethanol,1.09 g of solid benzothiazole-2-carbaldehyde was obtained. |
| With Dess-Martin periodane In dichloromethane | ||
| 82 % | With hydrogen bromide; oxygen at 20℃; Irradiation; | 22-23 Example 1 Preparation of benzaldehyde General procedure: In a transparent quartz bottle with a rubber stopper and a magnetic stirring rod, add the reaction substrate benzyl alcohol (0.2 mmol) and 20 mol% hydrobromic acid to 12 mL of the reaction solvent, and under light irradiation,The reaction mixture was stirred at ambient temperature under an atmosphere of oxygen. During the reaction, the progress of the reaction was monitored by GC or TLC. After the reaction was completed for 0.15 h at room temperature, the solvent was removed by vacuuming or extraction, and the residue was purified by column chromatography with petroleum ether/ethanol to obtain the desired product benzaldehyde. The yield of the target product is 90%. |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 92% | With triphenylphosphine In tetrachloromethane; benzene for 2h; Heating; | |
| 91% | With tetrachloromethane; triphenylphosphine In benzene at 20℃; Reflux; | |
| 85% | With tetrachloromethane; triphenylphosphine In toluene for 5h; Heating / reflux; | 11 Carbon tetrachloride (15. 0ml, 155mmol) is added to a stirred solution of benzothiazolyl-2-methanol (2. 50g, 15. 1mmol), triphenylphosphine (4.89g, 18. 6mmol), and anhydrous toluene (50ml). The reaction is heated to reflux under nitrogen for 5h. It is then concentrated on a rotary evaporator to give the crude product. The crude product is purified by flash chromatography on silica gel eluting with 100% dichloromethane to yield (2. 36g, 85%) of 2-chloromethyl-benzothiazole : mass spectrum (ion spray): m/z = 183.9 (M+1) : lH NMR (CDC13) : 8=8. 04-8.01 (1H, m), 7.91-7. 89 (1H, m), 7.53-7. 49 (1H, m), 7.44-7. 40 (1H, m), 4.95 (2H, s). |
| With phosphorus pentachloride | ||
| With thionyl chloride In dichloromethane Ambient temperature; |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 57% | With phosphorus tribromide In dichloromethane at 20℃; for 2h; Inert atmosphere; | 2-(Bromomethyl)benzothiazole (3) According to the Attardo’s method1, to a solution of 2 (1.00 g, 6.05 mmol) in dist. CH2Cl2 was added dropwise phosphorus tribromide (1.15 mL, 12.1 mmol). The reaction mixture was stirred at room temperature under argon for 2 hours. The solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography (hexane : AcOEt = 5 :1) to give 33 (786 mg, 57%) as a brown solid. 1H NMR (300 MHz, CDCl3) δ 4.81 (s, 2H), 7.42 (td, 1H, J = 8.1 Hz, 1.1 Hz), 7.50 (td, 1H, J = 8.1 Hz, 1.1 Hz), 7.87 (dd, 1H, J = 8.1 Hz, 1.1 Hz), 8.02 (dd, 1H, J = 8.1 Hz, 1.1 Hz). 13C NMR (75 MHz, CDCl3) δ 27.1, 121.8, 123.5, 125.9, 126.5, 136.2, 152.8, 166.2. MS (EI) 227, 229 (M)+. TLC: Rf 0.60 (hexane : AcOEt = 5 : 1). |
| 57% | With N-Bromosuccinimide; triphenylphosphine In tetrahydrofuran; dichloromethane at -78℃; for 0.0833333h; Inert atmosphere; | 3 Bromomethyl benzothiazole 66: Bromomethyl benzothiazole 66: To a stirred solution of hydroxymethyl benzothiazole 65 (1.00 g, 6.05 mmol, 1.0 equiv.) in dichloromethane/tetrahydrofuran (1 : 1, 40 mL) at -78 °C was added triphenylphosphine (1.59 g, 6.05 mmol, 1.0 equiv.), followed by A^-bromosuccinimide (1.08 g, 6.05 mmol, 1.0 equiv.). After 5 min, the reaction mixture was quenched with water (20 mL) and allowed to warm to 25 °C. The two phases were separated, and the aqueous layer was extracted with ethyl acetate (3 χ 30 mL). The combined organic layers were dried with anhydrous sodium sulfate and concentrated in vacuo. The obtained residue was purified by flash column chromatography (silica gel, 2→ 8% ethyl acetate in hexanes) to afford pure bromomethyl benzothiazole 66 (0.780 g, 3.42 mmol, 57%) as a white crystalline solid. 66: Rf = 0.48 (silica gel, 10% ethyl acetate in hexanes); m.p. 45^16 °C; FT-IR (neat) i 3059, 3028, 1594, 1557, 1505, 1456, 1430, 1313, 1278, 1242, 1190, 1157, 1125, 1090, 1061, 1013, 938, 901, 851, 756, 727, 706 cm"1; NMR (600 MHz, CDC13) δ = 8.03 (d, J = 8.4 Hz, 1 H), 7.88 (d, J = 7.8 Hz, 1 H), 7.51 (ddd, J = 7.8, 7.8, 1.2 Hz, 1 H), 7.43 (ddd, J = 7.8, 7.8, 1.2 Hz, 1 H), 4.82 (s, 2 H) ppm; 13C NMR (151 MHz, CDC13) δ = 166.2, 152.8, 136.2, 126.5, 125.9, 123.5, 121.8, 27.1 ppm; HRMS (ESI) calcd for C8H7NS2Br [M+H]+ 227.9477, found 227.9466. |
| 57% | With N-Bromosuccinimide; triphenylphosphine In tetrahydrofuran; dichloromethane at -78℃; for 0.0833333h; Inert atmosphere; |
| 57% | With N-Bromosuccinimide; triphenylphosphine In tetrahydrofuran; dichloromethane at -78℃; for 0.0833333h; | 3 2-(Bromomethyl)-l,3-benzothiazole (S31): To a stirred solution of hydroxymethyl benzothiazole S30 (1.00 g, 6.05 mmol, 1.0 equiv) in dichloro- methane/ tetrahydrofuran (1 : 1, 40 mL) at -78 °C was added triphenylphosphine (1.59 g, 6.05 mmol, 1.0 equiv), followed by -bromosuccinimide (1.08 g, 6.05 mmol, 1.0 equiv). After 5 min, the reaction mixture was quenched with water (20 mL), and allowed to warm to 25 °C. The two phases were separated, and the aqueous layer was extracted with ethyl acetate (3 x 30 mL). The combined organic layers were dried with anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was purified by flash column chromatography (silica gel, 2- > 8% ethyl acetate in hexanes) to afford pure bromomethyl benzothiazole S31 (780 mg, 3.42 mmol, 57% yield) as a white amorphous solid. S31: =0.48 (silica gel, 10% ethyl acetate in hexanes); FT-IR (film) v 3059, 3028, 1594, 1557, 1505, 1456, 1430, 1313, 1278, 1242, 1190, 1157, 1125, 1090, 1061, 1013, 938, 901, 851, 756, 727, 706 cm"1; NMR (600 MHz, CDCI3) 5 = 8.03 (d, /=8.4Hz, 1 H), 7.88 (d, /=7.8Hz, 1 H), 7.51 (ddd, /=7.8, 7.8, 1.2 Hz, 1 H), 7.43 (ddd, 7=7.8, 7.8, 1.2 Hz, 1 H), 4.82 (s, 2 H) ppm; 13C NMR (151 MHz, CDCI3) δ= 166.2, 152.8, 136.2, 126.5, 125.9, 123.5, 121.8, 27.1 ppm; HRMS (ESI) calcd for C8H7BrNS2+ [M+H]+ 227.9477, found 227.9466. |
| 57% | With phosphorus tribromide In dichloromethane at 20℃; for 2h; Inert atmosphere; | 2-(Bromomethyl)benzothiazole (3) Compound 2 (1.00 g, 6.05 mmol) was dissolved in dist. CH2Cl2 (25 mL), phosphorus tirbromide (1.15 mL, 12.1 mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours under argon atmosphere. Then, the solvent was removed by concentration under reduced pressure. The residue was purified by column chromatography (Hexane:AcOEt=5:1) to give Compound 3 (786 mg, 57%) as a brown solid. 1H NMR (300MHz, CDCl3) δ 4.81 (s, 2H), 7.42 (td, 1H, J = 8.1Hz, 1.1Hz), 7.50 (td, 1H, J = 8.1Hz, 1.1Hz), 7.87 (d, 1H, J = 8.1Hz), 8.02 (d, 1H, J = 8.1Hz). 13C NMR (75MHz, CDCl3) δ 27.1, 121.8, 123.5, 125.9, 126.5, 136.2, 152.8, 166.2. EI-MS (m/z) 227, 229 [M]+. TLC: Rf 0.60 (Hexane:AcOEt=5:1). |
| With hydrogen bromide |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With sulfuric acid; nitric acid | ||
| With nitric acid In sulfuric acid | P.2 6-Nitro-2-hydroxymethylbenzothiazole STR26 Preparation Example 2 6-Nitro-2-hydroxymethylbenzothiazole STR26 41 g of 2-hydroxymethylbenzothiazole obtained in the Preparation Example 1 was dissolved in 55 ml of concentrated sulfuric acid. 24 ml of concentrated nitric acid (specific gravity: 1.42) was added dropwise to the solution while the reaction temperature was maintained at 40° C. or below. After stirring for 1 h, the reaction mixture was poured into ice-water and extracted with ethyl acetate. The extract was dried over sodium sulfate and then concentrated under reduced pressure to give a solid, which was recrystallized from ethyl acetate to give 15 g of the titled compound. 1 H-NMR (CDCl3)δ: 2.37 (1H, s), 5.07 (2H, s), 8.05 (1 H, d), 8.35(1H, dd), 8.86 (1H, d) |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 27% | With hydrogenchloride In water at 100℃; for 6h; | Benzothiazol-2-ylmethanol (4) A mixture of 2-aminobenzenethiol (0.25 g, 2 mmol) and glycolic acid (0.46 g, 6 mmol) was treated with HCl (4 N, 6 mL). The reaction was allowed to proceed by refluxing the mixture at 100 °C for 6 h prior to being quenched with saturated aqueous sodium bicarbonate. The solution was extracted with ethyl acetate (3 × 20 mL). The combined extracts were evaporated in vacuo to give the crude product, which was subjected to PTLC purification using DCM/MeOH (100/2, v/v) as eluent to yield benzothiazol-2-ylmethanol (4) as: Orange solid; yield 27%; m.p. 91-93 °C; IR (KBr) (ν cm-1): 3161, 2831, 2361, 1745, 1552, 1350, 1184, 1077, 756; 1H NMR (500 MHz, DMSO-d6): δ 8.16-8.04 (m, 1H), 7.92 (d, J = 8.1 Hz, 1H), 7.55-7.45 (m, 1H), 7.45-7.36 (m, 1H), 6.25 (t, J = 6.0 Hz, 1H), 4.86 (d, J = 6.0 Hz, 2H). HRMS (EI) m/z calcd for C8H7NOS (M+): 165.0248; found: 165.0249. |
| 15% | With hydrogenchloride In water at 100℃; for 6h; | |
| 11% | With hydrogenchloride In water at 100℃; for 6h; | 2.3. Synthesis of benzo[d]thiazol-2-ylmethanol (compound 4) To mixture of 2-aminobenzenethiol (25.000 g, 0.200 mol) andglycolic acid (46.000 g, 0.600 mol) was added HCl (4 N, 60 mL). Thereactionwas allowed to proceed under reflux at 100 °C for 6 h priorto being quenched with saturated aqueous sodium bicarbonate.The solution was extracted three times with ethyl acetate. Thecombined extracts were evaporated in vacuum to give the crudeproduct. The crude product was purified by chromatography on asilica gel column with DCM/MeOH (100/2, v/v) as the eluent to yieldcompound 4 [41] (3.630 g, 11%). 1H NMR (400 MHz, CDCl3, TMS): δH7.97 (d, J = 8.0 Hz, 1H), 7.88 (d, J = 7.6 Hz, 1H), 7.47 (t, J = 7.2 Hz, 1H),7.38 (t, J = 7.2 Hz, 1H), 5.75 (br, 1H), 5.08 (s, 2H). 13C NMR (100 MHz,CDCl3) δC 173.635, 152.634, 134.528, 126.218, 125.099, 122.569,121.841, 62.237. |
| In neat (no solvent) at 115℃; for 14h; | ||
| at 130℃; | ||
| In ethyl acetate | P.1 2-Hydroxymethylbenzothiazole STR25 Preparation Example 1 2-Hydroxymethylbenzothiazole STR25 60 g of 2-aminothiophenol and 36.6 g of glycolic acid were heated at 130° C. in a sealed tube for 12 h. The reaction product was dissolved in ethyl acetate and dried over sodium sulfate and the solvent was concentrated under reduced pressure. The residue was crystallized from diisopropyl ether to give 55 g of the titled compound in the form of white crystals. 1 H-NMR (CDCl3)δ: 3.54 (1H, t), 5.08 (2H, d), 7.38 (1H, t), 7.47 (1H, t), 7.88 (1H, d), 7.97 (1H, d) | |
| With hydrogenchloride In water | Preparation of l ,3-benzothiazol-2-ylmethanolThe title compound was synthesized by the reaction of 2-aminothiophenol with glycolic acid using 4 hydrochloric acid as described in the literature [Journal of the Chemical Society, p.2395. ( 1 928)] ; NMR (300 MHz, CDC13) δ 5.08 (s, 2H), 7.39 (t, J = 7.5 Hz, 1 IT), 7.49 (t, J = 7.2 Hz, 1H), 7.90 (d, J = 7.8 Hz, 1H), 7.99 (d, J = 7.8 Hz, 1 H). | |
| With hydrogenchloride | ||
| 51 % | With (o-CF3PhO)3P In 1,2-dichloro-ethane at 80℃; |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 84% | With sodium tetrahydroborate In methanol for 2h; Ambient temperature; | |
| 63 %Chromat. | With [bis({2‐[bis(propan‐2‐yl)phosphanyl]ethyl})amine](borohydride)(carbonyl)(hydride)iron(II); hydrogen In tetrahydrofuran at 120℃; for 19h; Autoclave; | |
| 2 g | With methanol; sodium tetrahydroborate at 25℃; for 2h; | 54 To a solution of ethyl benzo[d]thiazole-2-carboxylate (2.5 g, 12.1 mmol) in MeOH (10 mL) was added NaBH4 (1.0 g, 26.5 mmol). The mixture was stirred at 25 °C for 2 h. The mixture was concentrated to give a residue. The pH of the residue was adjusted to 4~5 with HCl (1M) and the resultant was extracted with EtOAc (20 mL × 2). The combined organic layers were washed with brine (20 mL) and concentrated to give a residue. The residue was purified by column chromatography to give benzo[d]thiazol-2-ylmethanol (I-497) (2.0 g) as a white solid. LCMS m/z 166.0(M+1)+. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 80% | With sodium hydroxide In acetone at 60 - 70℃; for 2h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 50% | With sodium hydroxide In acetone at 60 - 70℃; for 2h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 95% | With sodium hydroxide In acetone at 60 - 70℃; for 2h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 98% | With sodium hydroxide In acetone at 60 - 70℃; for 2h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 94% | With sodium hydroxide In tetrahydrofuran; water at 20℃; for 1h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 60% | With sodium hydroxide In tetrahydrofuran; water at 20℃; for 1h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 64% | With chloro-trimethyl-silane In N,N-dimethyl-formamide for 12h; Heating; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 74% | With chloro-trimethyl-silane In N,N-dimethyl-formamide for 12h; Heating; |

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