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CAS No. : | 56012-38-5 | MDL No. : | MFCD12912988 |
Formula : | C5H7NOS | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | UGNOVENEUBRGNI-UHFFFAOYSA-N |
M.W : | 129.18 | Pubchem ID : | 12808792 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
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* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With thionyl chloride; In dichloromethane; at 0 - 20℃; for 1h; | To a stirred solution of <strong>[56012-38-5](2-methylthiazol-5-yl)methanol</strong> (2, 0.2 g, 1.55 mmol) in DCM (5 mL), was added SOCl2(0.23 mL, 3.10 mmol) drop wise at 0 C and the reaction mixture was stirred at rt for 1 h. The reaction mixture was neutralized using cold NaHC03(5 mL) solution and extracted with DCM (2 X 25 mL). Organic layer was washed with brine (5mL) solution, dried over anhydrous Na2S04 and evaporated to afford the product as yellow oil. (0.2 g, 90%, Yield). MS (ESI): Mass calcd. for C5H6C1NS , 146.99; m/z found 148.1 (M+H)+. |
87% | With methanesulfonyl chloride; triethylamine; In dichloromethane; at 0 - 20℃; for 4h;Inert atmosphere; | To a stirred solution of compound 64 (5 g, 38.75 mmol) in CH2C12 (150 mL) under inert atmosphere were added triethyl amine (8.3 mL, 58.13 mmol), methanesulfonyl chloride (4.6 mL, 46.51 mmol) at 0 C; warmed to RT and stirred for 4 h. The reaction was monitored by TLC; after completion of the reaction, the reaction mixture was diluted with water (50 mL) andextracted with CH2C12 (2 x 100 mL). The combined organic extracts were dried over sodium sulfate, filtered and concentrated in vacuo to afford compound 65 (5 g, 87%) as a pale-yellow syrup. TLC: 30% EtOAc/ hexanes (Rf: 0.8); LC-MS: 77.92%; 147.7 (M+1) (column; Ascentis Express C18, (50 x 3.0 mm, 2.7 jim); RT 1.71 mm. 0.025% Aq. TFA + 5% ACN: ACN + 5% 0.025% Aq. TFA, 1.2 mL/min). |
82.32% | With thionyl chloride; In dichloromethane; for 4h; | (2-methylthiazol-5-yl) methanol (304 mg, 2.35 mmol) and thionyl chloride (0.9 mL,10mmol) was dissolved in dichloromethane (15mL), the reaction 4h. The reaction mixture was poured into water (30 mL) and extracted with ethyl acetate (30 mL × 3)The residue was washed with saturated brine (15 mL) and dried over anhydrous sodium sulfate. The solvent was removed and the residue was subjected to column chromatography (eluent: PE /EtOAc (v / v) = 10/1) to give 286 mg of a light yellow oil, yield: 82.32%. |
With thionyl chloride; In dichloromethane; at 0℃;Inert atmosphere; | To a solution of <strong>[56012-38-5](2-methylthiazol-5-yl)methanol</strong> (1 eq) in DCM (10 mL) at 0C under N2 was added thionyl chloride (3 eq), dropwise. The reaction mixture was stirred at 0C for 2h. The reaction progress was monitored by TLC. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to afford 5-(chloromethyl)-2- methylthiazole as a brown liquid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With lithium aluminium tetrahydride; In tetrahydrofuran; at 0 - 20℃; for 16.25h;Inert atmosphere; | To a stirred suspension of lithium aluminium hydride (3.1 g, 93.56 mmol) in dry THF (10 mL) under inert atmosphere was added compound 63 (8 g, 46.78 mmol) in dry THF (50 mL) dropwise for 15 mm at 0 °C; warmed to RT and stirred for 16 h. The reaction was monitored by TLC; after completion of the reaction, the reaction mixture was cooled to 0 °C, quenched with15percent aqueous sodium hydroxide solution (10 mL), filtered through celite and washed withEtOAc (3 x 100 mL). The filtrate was dried over sodium sulfate, filtered and concentrated invacuo to afford compound 64 (5 g, 83percent) as an off-white solid. TLC: 50percent EtOAc/ hexanes (Rf:0.3). LC-MS: 97.32percent; 130.22 (M+1) (column; X-select CSH C18, (50 x 3.0 mm, 2.5 jim); RT0.65 mm. 2.5 mM Aq. NH4OAc: ACN: 0.8 mL/min). |
78% | In chloroform; | B. 5-(Hydroxymethyl)-2-methylthiazole Using the procedure of Example 1P, but replacing ethyl thiazole-5-carboxylate with crude ethyl 2-methylthiazole-5-carboxylate provided, after silica gel chromatography using 3percent then 5percent methanol in chloroform, the desired compound, Rf 0.27, (4percent methanol in chloroform) in 78percent yield. 1 H NMR (CDCl3)delta2.32 (br, 1H), 2.70 (s, 3H), 4.80 (s, 2H), 7.46 (s, 1H). Mass spectrum: (M+H)+ =130. |
Step 1: Intermediate 15-a To a solution of ethyl 2-methylthiazole-5-carboxylate (5.82 g, 34.0 mmol) in THF (170 ml), cooled to 0 °C, was added a 1.0M solution of LiAIH4 in THF (34.0 ml, 34.0 mmol) and the reaction was slowly warmed to room temperature and stirred overnight. Water (1.3 ml) was slowly added, followed by 15percent NaOH (1.3 ml_). The solution was stirred for 2 hours at room temperature then filtered over celite. The filtrate was concentrated under reduced pressure to provide intermediate 15-a as a yellow oil. |
With lithium aluminium tetrahydride; In tetrahydrofuran; at 0 - 20℃; for 2h; | To a solution of intermediate 7-c (22.2 g, 130.0 mmol) in THF (430 ml) cooled to 0°C was added a 1.0 M solution LiAIH4 in THF (91.0 ml, 91.0 mmol). The solution was slowly warmed to room temperature and stirred for 2 hours. Water (3.5 ml) was slowly added, followed by 3.5 ml 15percent NaOH (3.5 ml) and water (10.5 ml) and the mixture was stirred for 1 hour. The reaction was filtered through celite and the filtrate collected. Volatiles were removed in vacuo to provide intermediate 7-d as a yellow oil. | |
Step 3: Intermediate 5-d; To a solution of intermediate 5-c (22.2 g, 130.0 mmol) in THF (430 ml) cooled to 0°C was added a 1.0 M solution LiAIH4 in THF (91.0 ml, 91.0 mmol) and the solution was slowly warmed to room temperature and stirred for 2 hours. Water (3.5 ml) was slowly added, followed by 3.5 ml lSpercent NaOH (3.5 ml) and water (10.5 ml) and the mixture was stirred for 1 hour. The reaction was filtered over celite and volatiles were removed under reduced pressure to provide intermediate 5-d as yellow oil. | ||
With lithium aluminium tetrahydride; In tetrahydrofuran; at 0 - 20℃;Inert atmosphere; | To a stirred solution of ethyl 2-methylthiazole-5-carboxylate (1 eq) in dry THF (5 mL) at 0 <C ) under N2 was added LiAIH4 (1 .1 eq., 2.0 M solution in THF) dropwise. The reaction mixture was stirred at RT for 1 h. The reaction progress was monitored by TLC. After completion of the reaction, the reaction mixture was cooled to -10°C to 0 < and then quenched by the dropwise addition of 10percent NaOH aqueous solution (5 mL). After 10 min of stirring, the mixture was filtered through a pad of Celite and the filtrate was concentrated under reduced pressure to afford (2-methylthiazol-5-yl)methanol (6 g) as a pale yellow solid. The crude product used in the next step without purification. LC/MS: (Method A) 130.0 (M+H). H NMR (DMSO-de, 400 MHz): delta 7.4 (s, 1 H), 5.5 (s, 1 H), 4.6 (d, J = 4.0 Hz, 2H), 2.6 (s, 3H). | |
With lithium aluminium tetrahydride; In tetrahydrofuran; at 0 - 20℃; for 2h; | Step 4: Intermediate 29-d [0172] To a solution of intermediate 29-c (22.2 g, 130.0 mmol) in THF (430 ml) cooled to 0° C. was added a 1.0 M solution of LiAlH4 in THF (91.0 ml, 91.0 mmol) and the solution was slowly warmed to room temperature and stirred for 2 hours. Water (3.5 ml) was slowly added, followed by 3.5 ml 15percent NaOH (3.5 ml) and water (10.5 ml) and the mixture was stirred for 1 hour. The reaction was filtered over celite and volatiles were removed in vacuo to provide intermediate 29-d as yellow oil. | |
12g | With lithium aluminium tetrahydride; In tetrahydrofuran; at 0 - 20℃; for 18h; | Step 1: Synthesis of 2-methyl-5-hydroxymethylthiazole: At room temperature, lithium aluminum hydride (8.88g, 234mmol) was dispersed in anhydrous tetrahydrofuran (THF, 100mL). The resulting mixture was cooled to 0-5°C in an ice-water bath. To the cooled mixture was dropwise added a solution of 2-methyl-5-ethoxyformylthiazole (20g,117mmol) in anhydrous tetrahydrofuran (THF, 100mL). After the completion of the dropwise addition, the reaction mixture was naturally warmed to room temperature, and was stirred for 18 hours at room temperature. To the reaction mixture was dropwise added water (10mL) at 0-5°C. After the completion of the dropwise addition, the resulting mixture was filtered. The filtrate was concentrated to produce a yellow oily substance (12g), which was directly used in the next step. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | 5-(Azidomethyl)-2-methylthiazole. A solution of <strong>[56012-38-5](2-methylthiazol-5-yl)methanol</strong> (3.99 g, 30.9 mmol) in tetrahydrofuran (100 ml) was cooled to 0 C. and treated with methanesulfonyl chloride (2.40 ml, 30.9 mmol) followed by triethylamine (4.3 ml, 30.9 mmol) added dropwise over 10 min. The resulting mixture was stirred for 20 min, diluted with N,N-dimethylformamide (50 ml) and then treated with sodium azide (3.20 g, 49.2 mmol). After 18 h at 22 C., the reaction mixture was diluted with ethyl acetate, washed with saturated sodium bicarbonate, brine and dried over anhydrous magnesium sulfate. Evaporation of the solvent under reduced pressure followed by chromatography of the residue on silica gel (elution toluene-ethyl acetate 0-20%) gave 4.42 g (92% yield) of the title azide as a clear oil. 1HNMR 400 MHz (CDCl3) delta (ppm) : 2.74 (3H, s, CH3), 4.50 (2H, s, CH2), 7.56 (1H, s, CH). MS (ESI+) m/e 155 [M+H+]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water; ethyl acetate; isopropyl alcohol; | EXAMPLE 2 2-methyl-5-[(N,N-dimethylcarbamoyloxy)-methyl]-thiazole hydrochloride A mixture of 50 ml of deperoxidized and anhydrous tetrahydrofuran and 1.9 g of sodium hydride suspended in oil was stirred and then 5.2 g of 2-methyl-5-hydroxymethyl-thiazole were added thereto followed by 8.8 g of dimethylcarbamic acid chloride while holding the temperature between 15 and 20 C. The mixture was stirred for 4 hours at room temperature and was vacuum filtered. The filter was washed with tetrahydrofuran and the filtrate was evaporated to dryness under reduced pressure. The residue was taken up in water and the aqueous phase was washed with ethyl ether. The ether extracts were dried over magnesium sulfate and evaported to dryness to obtain 10 g of raw product which was dissolved in ethyl acetate. The pH of the solution was adjusted to 1 with ethyl acetate saturated with hydrochloric acid and the mixture was vacuum filtered. The recovered crystals were washed with ethyl acetate and dissolved in 50ml of refluxing isopropanol. The solution was iced and vacuum filtered and the product was dried to obtain 6.8 g of 2-methyl-5-[N,N-dimethylcarbamoyloxy)-methyl] -thiazole hydrochloride melting at 130 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; In tetrahydrofuran; ethyl acetate; | EXAMPLE 3 2-methyl-5-(N-phenylcarbamoyloxymethyl)-thiazole hydrochloride A mixture of 2.6 g of 2-methyl-5-hydroxymethyl-thiazole, 2.6 g of phenyl isocyanate, 26 ml of anhydrous tetrahydrofuran and 1 ml of triethylamine was refluxed for one hour, cooled to room temperature and then evaporated to dryness under reduced pressure. The residue was dissolved in hot ethyl acetate and the solution was added to ethyl acetate saturated with hydrochloric acid. The mixture was filtered and the crystals were dried to obtain 5 g of crystals which were crystallized from ethanol to obtain 3.2 g of 2-methyl-5-(N-phenylcarbamoyloxy-methyl)-thiazole hydrochloride melting at 160 C. Analysis: C12 H13 N2 O2 SCl Calculated: %C, 50.60; %H, 4.60; %N, 9.83; %Cl, 12.44; %S, 11.25; Found: %C, 50.5; H, 4.6; N, 9.8; Cl, 12.7; S, 11.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
STEP B: 2-methyl-5-[(N-methylcarbamoyloxy)-methyl]-thiazole A mixture of 3.85 g of <strong>[56012-38-5]2-methyl-5-hydroxymethylthiazole</strong> and 10 ml of methyl isocyanate stood for 24 hours and was then evaporated to dryness. The oily residue was chromatographed over silica gel and elution with a 3-7 benzene-ethyl acetate mixture yielded 5.03 g of product. The product was crystallized from a methylene chloride-isopropyl ether mixture to obtain 4.16 g of 2-methyl-5-[(N-methylcarbamoyloxy)-methyl] -thiazole in the form of colorless crystals melting at 80 C. Analysis: C7 H10 N2 O2 S Calculated: %C, 45.14; %H, 5.41 %N, 15.04; %S, 17.21; Found: %C, 45.2; H, 5.5; N, 15.0; S, 17.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In tetrahydrofuran; methanol; ethyl acetate; | STEP A 2-methyl-5-hydroxymethyl-thiazole 2.54 g of lithium aluminum hydride were added at 20-25 C. under a nitrogen atmosphere to a solution of 10.5 g of methyl 2-methyl-5-thiazolecarboxylate in 105 ml of anhydrous tetrahydrofuran and the mixture was refluxed for one hour and then cooled. Addition of ethyl acetate and then methanol destroyed excess hydride and the mixture was filtered. The filtrate was evaporated to dryness and the residue was chromatographed over silica gel to obtain 7.6 g of product which was crystallized from isopropyl ether to obtain 5.28 g of 2-methyl-5-hydroxymethyl-thiazole melting at 50 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With di-isopropyl azodicarboxylate; triphenylphosphine; In tetrahydrofuran; at 20℃; | Step 7: Intermediate 29-h To a solution of intermediate 29-g (8.0 g, 33.1 mmol) and intermediate 29-d (4.70 g, 36.4 mmol) in THF (20 ml) were sequentially added triphenylphosphine (12.15 g, 46.3 mmol) and DIAD (9.0 ml, 46.3 mmol) at room temperature and the reaction was then stirred at room temperature overnight. Volatiles were removed under reduced pressure. Purification by silica gel chromatography provided intermediate 29-h as a yellow oil. | |
With di-isopropyl azodicarboxylate; triphenylphosphine; In tetrahydrofuran; at 20℃; for 1h; | To a solution of intermediate 8-c (1.0 g, 105.0 mmol) and intermediate 7-d (352 mg, 2.73 mmol) in THF (20 ml) were sequentially added triphenylphosphine (1.07 g, 4.1 mmol) and DIAD (796 p1, 4.1 mmol) at room temperature. The reaction was then stirred at room temperature for 1 hour. Volatiles were removed under reduced pressure. Purification by silica gel chromatography provided intermediate 8-d as a yellow oil. | |
With di-isopropyl azodicarboxylate; triphenylphosphine; In tetrahydrofuran; at 20℃; for 1h; | Step 6: Intermediate 5-h: To a solution of intermediate 5-g (1.0 g, 105.0 mmol) and intermediate 5-d (352 mg, 2.73 mmol) in THF (20 ml) were sequentially added triphenylphosphine (1.07 g, 4.1 mmol) and DIAD (796 p1, 4.1 mmol) at room temperature and the reaction was then stirred at room temperature for 1 hour. Volatiles were removed under reduced pressure. Purification by silica gel chromatography provided intermediate 5-h as yellow oil. |
With di-isopropyl azodicarboxylate; triphenylphosphine; In tetrahydrofuran; at 20℃; | Step 7: Intermediate 29-h [0175] To a solution of intermediate 29-g (8.0 g, 33.1 mmol) and intermediate 29-d (4.70 g, 36.4 mmol) in THF (20 ml) were sequentially added triphenylphosphine (12.15 g, 46.3 mmol) and DIAD (9.0 ml, 46.3 mmol) at room temperature and the reaction was then stirred at room temperature overnight. Volatiles were removed under reduced pressure. Purification by silica gel chromatography provided intermediate 29-h as a yellow oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With di-isopropyl azodicarboxylate; triphenylphosphine; In tetrahydrofuran; at 20℃; for 18h; | Step 2: Intermediate 15-b To a solution of intermediate 15-a (7.75 g, 34.5 mmol) and intermediate 11- a (4.25 g, 32.9 mmol), in THF (33 ml_), were sequentially added triphenylphosphine (10.35 g, 39.5 mmol) and DIAD (7.68 ml, 39.5 mmol) drop wise at room temperature. The reaction was then stirred for 18 hours. Volatiles were removed in vacuo. Purification by silica gel chromatography provided intermediate 15-b as a colorless oil. | |
With di-isopropyl azodicarboxylate; triphenylphosphine; In tetrahydrofuran; at 20℃; for 18h; | Step 2: Intermediate 15-b [0132] To a solution of intermediate 15-a (7.75 g, 34.5 mmol) and intermediate 11-a (4.25 g, 32.9 mmol), in THF (33 mL), were sequentially added triphenylphosphine (10.35 g, 39.5 mmol) and DIAD (7.68 ml, 39.5 mmol) drop wise at room temperature. The reaction was then stirred for 18 hours. Volatiles were removed in vacuo. Purification by silica gel chromatography provided intermediate 15-b as a colorless oil. |
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