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Structure of 78-39-7
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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
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Chen, Jing ; Ji, Peng ; Gnawali, Giri ; Chang, Mengyang ; Gao, Feng ; Xu, Hang , et al.
Abstract: The current targeting drug delivery mainly relies on cancer cell surface receptors. However, in many cases, binding affinities between protein receptors and homing ligands is relatively low and the expression level between cancer and normal cells is not significant. Distinct from conventional targeting strategies, we have developed a general cancer targeting platform by building artificial receptor on cancer cell surface via a chemical remodeling of cell surface glycans. A new tetrazine (Tz) functionalized chemical receptor has been designed and efficiently installed on cancer cell surface as "overexpressed" biomarker through a metabolic glycan engineering. Different from the reported bioconjugation for drug targeting, the tetrazine labeled cancer cells not only locally activate TCO-caged prodrugs but also release active drugs via the unique bioorthogonal Tz-TCO click-release reaction. The studies have demonstrated that the new drug targeting strategy enables local activation of prodrug, which ultimately leads to effective and safe cancer therapy.
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Keywords: Artificial receptor ; Click and release ; Local activation ; Protein degradation
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Purchased from AmBeed: 3212-75-7 ; 5505-63-5 ; 25316-40-9 ; 1345866-66-1 ; 2645443-13-4 ; 67131-33-3 ; 501-52-0 ; 1949837-12-0 ; 107-96-0 ; 78-39-7 ; 2915291-31-3
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CAS No. : | 78-39-7 |
Formula : | C8H18O3 |
M.W : | 162.23 |
SMILES Code : | CC(OCC)(OCC)OCC |
MDL No. : | MFCD00009223 |
GHS Pictogram: |
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Signal Word: | Danger |
Hazard Statements: | H225 |
Precautionary Statements: | P210-P403+P235 |
Class: | 3 |
UN#: | 3272 |
Packing Group: | Ⅲ |
* 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 |
---|---|---|
65.8% | Stage #1: at 120℃; for 4 h; Stage #2: Cooling |
80 mL of ethyl orthoacetate was added to 15 g (136 mmol) of 2-amino-3-hydroxypyridine, followed by addition of p-toluenesulfonic acid in a catalytic amount, and the mixture was reacted at 120° C. for 4 hours. After the reaction solution was cooled, triethylamine was added to the solution, to neutralize p-toluenesulfonic acid. Then, the solution was subjected to distillation under reduced pressure by using an evaporator, and then purified by silica gel column chromatography.Amount of the product: 12.0 g, Yield: 65.8percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With acetic acid In ethanol at 110℃; for 24 h; Inert atmosphere; Sealed tube | General procedure: The 2-aminobenzamide (1 equiv), the orthoester (2–3 equiv) and absolute ethanol (2–3 mL) wereplaced in a 15-mL Chemglass screw-cap pressure tube (No. CG-1880-01, Chemglass, Vineland, NJ,USA). Glacial acetic acid (3 equiv) was added, N2 was introduced to the vessel and the cap wastightened. The vessel was heated at 110 °C for 12–72 h, then cooled and concentrated to give thequinazolinone, which was purified by crystallization from absolute ethanol or trituration from 5percentether in pentane. The following compounds were prepared: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
2 g | Reflux | Step 2: 8-chloro-3-methyl-[l,2,4]triazolo[4,3-a]pyrazine [0197] To a stirred solution of 2-chloro-3-hydrazinylpyrazine (2.0 g, 14 mmol) in xylene (20 mL) was added triethyl orthoformate (5.8 mL, 32 mmol). The mixture was heated under reflux overnight and then cooled to room temperature. The resulting precipitate was collected by filtration to afford the title compound as a brown powder (2.0 g, 87percent). MS (ESI) calcd forC6H5CIN4: 168.0 ; found: 169.2 [M+H]. *H NM (400 MHz, CDCI3) δ 7.80 (d, J = 4.8 Hz, 1H), 7.71 (d, J = 4.8 Hz, 1H), 2.83 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69.8% | With acetic anhydride; zinc(II) chloride; at 170℃; for 5h; | The compound 1,1,1-triethoxyethane (62.6 mL, 341 mmol),Compound diethyl malonate (224.4 mL, 990.1 mmol),Acetic anhydride (1.4 mL, 10.1 mmol) and a catalytic amount of zinc chloride (0.1 g) were placed in a reaction flask and heated to 170 C for 5.0 h.Evaporating unreacted diethyl malonate under reduced pressure,The residue was purified by column (eluent: PE/EtOAc (v/v) = 20/1).40.0 g of yellow oil were obtained.The yield was 69.8%. |
With acetic anhydride; | EXAMPLE 8 160 g (1 mol) of diethyl malonate, 649 g (4 mol) of triethyl orthoacetate and 0.5 g of catalyst from Example 1 were heated to 130 C. in a glass apparatus having a distillation column. The metering-in of 102 g of acetic anhydride over the course of 7 h was then begun. The bottom temperature was increased to 159 C. with the distillation of low-boiling components at a head temperature of 72 to 73 C. After the end of the reaction, the residual low-boiling components were distilled off under a low vacuum and the excess triethyl orthoacetate was removed at 15 mbar. The desired product was then distilled over at 0.3 mbar and a head temperature of 100 to 102 C. Ethyl 2-carboethoxy-3-ethoxy-2-butenoate was obtained in a yield of 73% of the theoretical yield. | |
With acetic anhydride; zinc(II) chloride; at 140℃; | Reference Example 196 Ethyl 4-hydroxy-6-methylpyrimidine-5-carboxylate A mixture of diethyl malonate (4.8 mL), triethyl orthoacetate (17 mL), acetic anhydride (0.11 mL) and zinc chloride (1.2 g) was stirred at 140C. To the mixture was added acetic anhydride (0.11 mL) each after 30, 90 and 120 minutes, and then stirred at the same temperature overnight. The reaction mixture was cooled to room temperature, and the insoluble material was removed by filtration. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate = 4/1 - 7/3) to give diethyl 2-(1-ethoxyethylidene)malonate (5.02 g). To a solution of diethyl 2-(1-ethoxyethylidene)malonate (4.13 g) in ethanol (15 mL) were added formamidine hydrochloride (1.73 g) and a solution of potassium hydroxide (2.21 g) in water (7.5 mL), and the mixture was stirred at room temperature for 2 days. The reaction mixture was neutralized by adding acetic acid. To the mixture was added ethyl acetate (30 mL), and the mixture was stirred at room temperature for 30 minutes. The insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (eluent: ethyl acetate - ethyl acetate/methanol = 9/1) to give the title compound (1.5 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With toluene-4-sulfonic acid; In toluene; for 3h;Reflux; | Example 2 5,6-Dichloro-1,2-Dimethyl-Benzoimidazole (2) Triethyl orthoacetate (4.6 g, 1 eq) was added drop wise to a refluxing mixture of 4,5-dichloro-1,2-phenylenediamine (5 g, 1 eq) and a catalytic amount of p-toluenesulfonic acid in toluene (40 mL). The mixture was refluxed for 3 hrs and 5.7 g black solid was collected after evaporation of the solvents under reduced pressure and used directly in the following step without further purification. ESI-MS (m/z) calcd (found): 200.0 (201.1) for [M+H]+. To the crude 5,6-dichloro-2-methyl-benzoimidazole (5.7 g, 1 eq) (see ) and grinded potassium hydroxide (4.8 g, 3 eq) in acetone (50 mL) was added iodomethane (5.2 g, 1.4 eq) drop wise and the mixture was stirred overnight. The solvent was evaporated under reduced pressure and the residue was partitioned between dichloromethane (200 mL) and water (200 mL). The aqueous phase was washed two times with dichloromethane (200 mL) and the combined organic phase was dried over Na2SO4 and evaporated to dryness. The crude product was recrystallized from ethyl acetate. 5.5 g product was collected as pale flakes with 90.6% yield for two steps. 1H NMR: (CDCl3) 2.55 (s, 3H), 3.63 (s, 3H), 7.28 (s, 1H), 7.68 (s, 1H). 13C NMR: (CDCl3): 13.82, 30.05, 110.20, 120.00, 125.58, 125.75, 134.97, 141.83, 153.93. ESI-MS (m/z) calcd (found): 214.0 (215.1) for [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With Montmorillonite KSF clay; In toluene;Heating / reflux; | To a solution of <strong>[603-87-2]2-amino-6-nitrophenol</strong> (Description 34,8 g, 51.9 mmol) in anhydrous toluene (150 ml) was added triethyl orthoacetate (9.51 ml, 51.9 mmol) and Montmorillonite KSF clay (2 g). The resulting mixture was then heated at reflux overnight. The cooled reaction mixture was filtered through CELITE AND the filtrate evaporated to dryness. The residue was triturated with diethyl ether and the solid collected by filtration and dried to give the title compound (2. 96 g, 32%). 1H NMR (400 MHz, CDC13) 8 2.77 (3H, s), 7.45 (1H, T, J8. 1), 7.98 (1H, dd, J7. 9 and 0.9), 8.14 (1 H, dd, J 8. 4 and 0.9). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | at 100℃; for 3.0h; | Example 59; 2-(2, 6-Dichloro-phenylimino)-5- (2-methyl-benzooxazol-6-yl-methylene)-thiazolidin-4-one; a) 2-Methvl-benzooxazole-6-carboxvlic acid methyl ester; A suspension of methyl 4-amino-3-hydroxy-benzoate (30 g, 0.18 mol) in triethylorthoacetate (90 mL) was heated to 100 oC for 3 hours. Ethanol (150 mL) was added followed by water (50 mL). The reaction mixture was filtered to yield 25 g (72 % yield) of pure 2-methyl-benzooxazole-6-carboxylic acid methyl ester. 1H-NMR (CDC13) : 5 2. 67 (s, 3H), 3.94 (s, 3H), 7.65 (d, 1H, J=8.1 Hz), 8.02 (dd, 1H, J=8.1 Hz, J'=1.5 Hz), 8.15 (d, 1H, J=1.5 Hz). LC MS (m/e) = 192.2 (MH+). Rt = 1.70 min |
72% | at 100℃; for 3.0h; | A suspension of methyl 4-amino-3-hydroxy-benzoate (30 g, 0.18 mol) in triethylorthoacetate (90 ml.) was heated to 100 0C for 3 hours. Ethanol (150 ml.) was added followed by water (50 ml_). The reaction mixture was filtered to yield 25 g (72 % yield) of pure 2-methyl-benzooxazole-6-carboxylic acid methyl ester. 1H- NMR (CDCI3): D2.67 (s, 3H), 3.94 (s, 3H), 7.65 (d, 1 H, J=8.1 Hz), 8.02 (dd, 1 H, J=8.1 Hz, J'=1.5 Hz), 8.15 (d, 1 H, J=1.5 Hz). LC MS (m/e) = 192.2 (MH+). Rt = 1.70 min |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
(A) In the same manner as described in the step (B) of Reference Example 11, 4.5 g of N-(4-n-propyl-1H-pyrazol-3-yl)acetamidoxime was obtained from 7.2 g of <strong>[151521-41-4]3-amino-4-n-propyl-1H-pyrazole</strong> and 9.3 g of triethyl orthoacetate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
EXAMPLE 2 Ethyl <strong>[13054-02-9]6-iodonicotinate</strong> Using the same procedure for ethyl 6-chloronicotinate but instead using 6-iodonicotinic acid (7.14 g, 28.67 mmol) and triethylorthoacetate (13.96 g, 86.02 mmol) gave the titled compound as a white solid (7.340 g, 26.49 mmol, 92.4%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane; water; | EXAMPLE 55 2-(3,4-Difluorobenzoyl)-3-hydroxycrotononitrile A solution of 10.2 g. of <strong>[71682-97-8]3,4-difluorobenzoylacetonitrile</strong>, 9.2 g. of triethyl orthoacetate and 20 ml. of acetic anhyride is heated on a steam bath for 0.5 hour and then poured into 200 ml. of water which is then heated on the steam bath for 2 hours. On cooling, the solid is filtered and then dissolved in methylene chloride. This solution is extracted with two portions of aqueous sodium bicarbonate and the aqueous extracts are combined and acidified with concentrated hydrochloric acid. The precipitate is extracted into methylene chloride, passed through a pad of Magnesol.(R)., heated and diluted with hexane. Upon cooling, colorless crystals result, yielding the title compound, m.p. 51°-54° C. Similarly prepared are 2-(2,5-difluorobenzoyl)-3-hydroxycrotononitrile, 2-(3,4,5-trimethoxybenzoyl)-3-hydroxycrotononitrile, 2-(2,4,6-trimethylbenzoyl)-3-hydroxycrotononitrile, and 2-(2,5-dichlorobenzoyl)-3-hydroxycrotononitrile. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With toluene-4-sulfonic acid; at 130.0℃; for 1.0h; | Example A1; 6-Bromo-2-methyl-oxazolo[4,5-b]pyridine; A solution of 20 g (106 mmol) 2-amino-6-bromo-3-hydroxy-pyridine and 0.05 g p-toluenesulfonic acid monohydrate in 22 ml triethyl orthoacetate is stirred at 13O0C for 1 h. After cooling to room temperature the reaction solution is diluted with ethyl acetate (150 ml) and extracted with water (3 x 150 ml). The combined organic phases are dried over MgSO4, filtered and concentrated in vacuo. Subsequent purification by crystallization from ethanol affords the title compound (19 g) as yellow-orange crystals. The mass spectrum shows the molecular peak MH+ at 213.2 and 215.2 Da. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | for 5h;Heating / reflux; | A mixture of commercially available 49 (2 g, 0.009 mol) and 1,1,1-triethoxy-ethane (5.2 mL, 0.028 mol) were heated for 5 hours. The reaction mixture was poured into water, washed with water yielding 50 (70%). After recrystallization from EtOH the crude material was used in next step without further purification. |
for 5h;Heating; | 2-Methyl-3-m-tolyl-3H-quinazolin-4-one (50): A mixture of commercially available 49 (2 g, 0.009 mol) and 1,1,1-triethoxy-ethane (5.2 mL, 0.028 mol) were heated for 5 hours. The reaction mixture was poured into water, washed with water yielding 50 (70%). After recrystallization from EtOH the crude material was used in next step without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 140℃; for 38.5h; | A solution of 5-bromo-N*2*-methyl-pyridine-2 3-diamine (Stage 67.1.4, 960 mg, 4 75 mmol) in triethylorthoacetate (Aldrich, Buchs, Switzerland, 25 ml) was stirred for 38 5 h at 140C. The reaction mixture was evaporated to dryness. The residue was dissolved in EtOAc and washed with saturated aqueous NaHCO3. The aqueous layer was extracted with EtOAc and the combined organic layers washed with brine, dried over Na2SO4, filtered and evaprated. The crude product was dry loaded on silica gel and purified by MPLC (DCM/MeOH 0% - 4%) to give the title compound as a brown solid (HPLC. tR 1 95 mm (Method A); M+H = 226, 228 MS-ES). | |
With acetic acid; at 80℃; for 2h; | To a suspension of <strong>[89415-54-3]5-bromo-N2-methylpyridine-2,3-diamine</strong> (510 mg, 2.51 mmol) in AcOH (20 mL) was added MeC(OEt)3 (1 mL) and the solution was warmed to 80 C. for 2 hours. The reaction mixture was allowed to cool to room temperature and was concentrated in vacuo. The crude residue was purified by silica gel column chromatography (0-25% THF/CH2Cl2 gradient) to afford the desired product. 1H NMR (400 MHz, CDCl3) delta 8.36 (d, J=1.8 Hz, 1H), 8.06 (d, J=1.9 Hz, 1H), 3.80 (s, 3H), 2.65 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88.5% | With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione; at 25.0℃; for 0.166667h; | 2-Amino-5-bromophenol (561 mg, 3.00 mmol)Was added to triethyl orthoacetate (656 muL, 3.6 mmol),1,3-Dibromo-5,5-dimethylhydantoin (17.2 mg, 6.00 × 10 -2 mmol) was added,And the mixture was stirred at room temperature for 10 minutes.And extracted with ethyl acetate (50 mL × 2).The organic layer was washed with saturated brine,After dehydration with anhydrous magnesium sulfate,The solvent was distilled off under reduced pressure,The residue was subjected to silica gel column chromatography using ethyl acetate / hexane (1/4 (volume ratio)) as an elution solvent,Compound 16 was obtained in a yield of 560 mg (88.5%). |
65% | With acetic acid; for 0.5h;Reflux; | To 2-amino-5- bromophenol ( l .OOg, 5.32 mmol) , acetic acid ((0.006 ml) and triethylorthoacetate ( 1.75 ml, 9.58 mmol) were added and refluxed for 3o min. The reaction mixture was quenched with water, extracted with ethyl acetate, dried over sodium sulphate and concentrated. The crude product was column chromatographed with ethyl acetate : petroleum ether to afford the title compound as a orange solid ((0.756 g, 65%). -NMR (delta ppm, CDC13, 400 MHz): delta 7.64 (d, 7 = 1.7 Hz, 1 H), 7.51 (d, 7 = 8.4 Hz, 1 H), 7.43 (dd, 7 = 8.4, 1.7 Hz, 1 H), 2.67 (s, 3H). |
65% | With acetic acid; for 0.5h;Reflux; | Intermediate 126 6-bromo-2-methylbenzo[d]oxazole: To 2-amino-5-bromophenol (1.00 g, 5.32 mmol), acetic acid ((0.006 ml) and triethylorthoacetate (1.75 ml, 9.58 mmol) were added and refluxed for 30 min. The reaction mixture was quenched with water, extracted with ethyl acetate, dried over sodium sulphate and concentrated. The crude product was column chromatographed with ethyl acetate: petroleum ether to afford the title compound as a orange solid ((0.756 g, 65%). 1H-NMR (delta ppm, CDCl3, 400 MHz): delta 7.64 (d, J=1.7 Hz, 1H), 7.51 (d, J=8.4 Hz, 1H), 7.43 (dd, J=8.4, 1.7 Hz, 1H), 2.67 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With zinc(II) chloride; at 95℃; for 4h;Inert atmosphere; | a) diethyl 2-(1-ethoxyethylidene)malonate. A mixture of diethyl 2-acetylmalonate (10 g, 0.049 mol), 1 , 1 ,1 -triethoxyethane (24 g, 0.15 mol) and ZnCI2 (70 mg, 0.0049 mol) was stirred at 95 C for 4 h under an inert atmosphere. The mixture was concentrated and the residue was purified by silica gel chromatography (10% pet. ether in ethyl acetate) to give the desired product as an oil (6.4 g, 56%). LC/MS: MS (ES+) m/e 231 (MH+); 1H NMR (300 MHz, CDCI3) delta ppm 1.22-1.33 (m, 9 H), 2.43 (s, 3H), 4.06 (q, J = 6.9 Hz, 2 H), 4.16 (q, J = 7.2 Hz, 2 H), 4.26 (q, J = 7.2 Hz, 2 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91.8% | To a 250 ml four-necked flask, 30 g of ethanol, 7.0 g (0.1 mol) of 3-aminopropionitrile, 16.2 g(? 1 mol) of triethyl orthoacetate,50 ~ 55 C reaction for 2 hours. Then, 5.0 g (0.12 mol) of cyanamide was added and reacted at 55 to 60 C for 3 hours.6 g of a 27 wt% ethanolic sodium ethoxide solution was added,35 ~ 45 C for 2 hours;Add about 5 grams of acetic acid adjusted pH value of 3-4, 17 grams of 30% hydrogen peroxide,40 ~ 45 C stirring reaction, the use of gas detection reaction, about 4 hours to complete conversion. Then 100 grams of water were added,Filtration gave 12.3 g of 2-methyl-4-amino-5-cyanopyrimidine as an off-white solid with a GC purity of 99.8% and a yield of 91.8% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With acetic acid; In ethanol; at 110℃; for 24h;Inert atmosphere; Sealed tube; | General procedure: The 2-aminobenzamide (1 equiv), the orthoester (2?3 equiv) and absolute ethanol (2?3 mL) wereplaced in a 15-mL Chemglass screw-cap pressure tube (No. CG-1880-01, Chemglass, Vineland, NJ,USA). Glacial acetic acid (3 equiv) was added, N2 was introduced to the vessel and the cap wastightened. The vessel was heated at 110 °C for 12?72 h, then cooled and concentrated to give thequinazolinone, which was purified by crystallization from absolute ethanol or trituration from 5percentether in pentane. The following compounds were prepared:2,7-Dimethylquinazolin-4(3H)-one (8a). This compound was prepared from<strong>[39549-79-6]2-amino-4-methylbenzamide</strong> (100 mg, 0.67 mmol), triethyl orthoacetate (217 mg, 245 L, 1.34 mmol)and acetic acid (121 mg, 115 L, 2.01 mmol) in absolute ethanol (2 mL) at 110 °C for 24 h to give105 mg (90percent) as a white solid, m.p. 260?262 °C (lit [49] m.p. 263?264 °C); IR (CHCl3): 3169, 1677 cm-1;1H-NMR (400 MHz, CDCl3): delta 11.6 (br s, 1H), 8.16 (d, J = 8.1 Hz, 1H), 7.47 (br s, 1H), 7.29 (dd, J =8.1, 1.0 Hz, 1H), 2.57 (s, 3H), 2.51 (s, 3H); 13C-NMR (101 MHz, CDCl3): delta 163.9, 153.2, 149.5, 146.0,128.0, 126.8, 126.1, 117.9, 22.1, 22.0; HRMS (ESI): m/z for C10H10N2O [M + 1]+: calcd.: 175.0871; found:175.0867. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With acetic acid; In ethanol; at 110℃; for 24h;Inert atmosphere; Sealed tube; | General procedure: The 2-aminobenzamide (1 equiv), the orthoester (2?3 equiv) and absolute ethanol (2?3 mL) wereplaced in a 15-mL Chemglass screw-cap pressure tube (No. CG-1880-01, Chemglass, Vineland, NJ,USA). Glacial acetic acid (3 equiv) was added, N2 was introduced to the vessel and the cap wastightened. The vessel was heated at 110 °C for 12?72 h, then cooled and concentrated to give thequinazolinone, which was purified by crystallization from absolute ethanol or trituration from 5percentether in pentane. The following compounds were prepared: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 120℃; for 16h; | A solution of 563 <strong>[17672-21-8]methyl 2-amino-3-hydroxybenzoate</strong> (1 g, 5.98 mmol) in 564 1,1,1-triethoxyethane (17.7 g, 109 mmol) was heated at 120 C. for 16 hours. The mixture was concentrated. The residue was purified by flash silica gel chromatography (ethyl acetate/petroleum ether gradient 030%) to afford 565 methyl 2-methylbenzo[d]oxazole-4-carboxylate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | at 100℃; for 6h; | [0339] Compound 8e: A solution of Comp-8d (15 g, 79.78 mmol) in 1,1,1-triethoxy ethane (75 mL) was heated at 100C for 6h. Progress of the reaction was monitored by TLC and LCMS. After completion, the reaction mixture was concentrated in vacuo and the crude obtained was purified by column chromatography (silica, 100-200 mesh, 10% Ethyl acetate in Hexane) to afford 5-bromo-2-methylbenzo[d]oxazole (8e; 10 g, 59%) as a yellow solid. (0602) [0340] MS (ESI) m/e [M+H]+ Rt %: 211.95/1.93/93.3%. (0603) [0341] XH NMR (400 MHz, CDCl3) delta 2.65 (s, 3H) 7.33 - 7.37 (m, 1H) 7.39 - 7.44 (m, 1H) 7.79 (s, l |
Tags: 78-39-7 synthesis path| 78-39-7 SDS| 78-39-7 COA| 78-39-7 purity| 78-39-7 application| 78-39-7 NMR| 78-39-7 COA| 78-39-7 structure
A411107 [1607-37-0]
4-[(2,3-Epoxypropoxy)methyl]-2,2-dimethyl-1,3-dioxolane
Similarity: 0.52
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P202 | Do not handle until all safety precautions have been read and understood. |
P210 | Keep away from heat/sparks/open flames/hot surfaces. - No smoking. |
P211 | Do not spray on an open flame or other ignition source. |
P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
P223 | Keep away from any possible contact with water, because of violent reaction and possible flash fire. |
P230 | Keep wetted |
P231 | Handle under inert gas. |
P232 | Protect from moisture. |
P233 | Keep container tightly closed. |
P234 | Keep only in original container. |
P235 | Keep cool |
P240 | Ground/bond container and receiving equipment. |
P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
P242 | Use only non-sparking tools. |
P243 | Take precautionary measures against static discharge. |
P244 | Keep reduction valves free from grease and oil. |
P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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