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CAS No. : | 10387-40-3 |
Formula : | C2H3KOS |
M.W : | 114.21 |
SMILES Code : | O=C(C)[S-].[K+] |
MDL No. : | MFCD00137704 |
GHS Pictogram: |
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Signal Word: | Danger |
Hazard Statements: | H302-H315-H318-H335-H410 |
Precautionary Statements: | P261-P264-P270-P271-P280-P302+P352-P304+P340-P305+P351+P338-P310-P330-P362+P364-P403+P233-P501 |
Class: | 9 |
UN#: | 3077 |
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 |
---|---|---|
97% | In acetone; | e. Methyl 4-[3-(acetylthio)propyl]benzoate Five (5) mmol (1.29 grams) of <strong>[113100-86-0]methyl 4-(3 bromopropyl) benzoate</strong> was dissolved in 40 ml of acetone and vigorously agitated while 10 mmol (1.14 grams) of potassium thioacetate was added in a single portion. The mixture was heated at reflux for 35 minutes, then returned to room temperature and filtered. The filter cake was washed twice with acetone. The filtrate and washings were combined and concentrated under vacuum. The residue was partitioned between ether and water (25 ml each). The layers were separated and the aqueous phase extracted with 25 ml of ether. The organic extracts were combined, dried over Na2 SO4, and concentrated in vacuo, yielding a red oil. This oil was purified by flash chromatography. Elution with hexane/ethyl acetate (9 to 1 V:V) yielded 1.22 g (97% yield) of an amber colored oil. The following analyses were obtained for this material indicating that it was methyl 4-[3-(acetylthio)propyl]benzoate: NMR (CDCl3) delta=7.95 (2H, d, J=8.3 Hz), 7.24 (2H, d, J=8.3 Hz), 3.90 (3H, s), 2.88 (2H, t, J=7.2 Hz), 2.74 (2H, t, J=7.7 Hz), 2.34 (3H, s), 1.91 (2H, tt, J=7.2, 7.7 Hz) |
97% | In acetone; | e. Methyl 4-[3-(acetylthio)propyl]benzoate Five (5) mmol (1.29 grams) of <strong>[113100-86-0]methyl 4-(3 bromopropyl) benzoate</strong> was dissolved in 40 ml of acetone and vigorously agitated while 10 mmol (1.14 grams) of potassium thioacetate was added in a single portion. The mixture was heated at reflux for 35 minutes, then returned to room temperature and filtered. The filter cake was washed twice with acetone. The filtrate and washings were combined and concentrated under vacuum. The residue was partitioned between ether and water (25 ml each). The layers were separated and the aqueous phase extracted with 25 ml of ether. The organic extracts were combined, dried over Na2 SO4, and concentrated in vacuo, yielding a red oil. This oil was purified by flash chromatography. Elution with hexane/ethyl acetate (9 to 1 V:V) yielded 1.22 g (97% yield) of an amber colored oil. The following analyses were obtained for this material indicating that it was methyl 4-[3-(acetylthio)propyl] benzoate: NMR (CDCl3) delta=7.95 (2H, d, J=8.3 Hz), 7.24 (2H, d, J=8.3 Hz), 3.90 (3H, s), 2.88 (2H, t, J=7.2 Hz), 2.74 (2H, t, J=7.7 Hz), 2.34 (3H, s), 1.91 (2H, tt, J=7.2, 7.7 Hz) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In ethyl acetate; N,N-dimethyl-formamide; | Methyl 3-(4-acetylthio-1-methoxycarbonyl-butoxy)-benzoate XV To a solution of <strong>[50995-48-7]methyl 2,5-dibromopentanoate</strong> XIII (22.00 g, 80.3 mmol) and methyl 3-hydroxybenzoate XIV (10.18 g, 66.9 mmol) in DMF (80 mL) was added K2CO3 (12.94 g, 93.7 mmol) at room temperature. The mixture was stirred at room temperature under N2 for 12 hours, then heated at 70° C. for 1 hour. Potassium thioacetate (22.93 g, 200.8 mmol) was added to the mixture, which was heated at 70° C. for 2 hours. The mixture was allowed to cool to room temperature and was diluted with EtOAc (1000 mL). The mixture was washed with H2O (3*300 mL) and brine (2*300 mL). The organic layer was dried over MgSO4, filtered and concentrated. The crude product was purified by flash chromatography (gradient elution: 10percent to 20percent EtOAc/hexanes) to afford methyl 3-(4-acetylthio-1-methoxycarbonyl-butoxy)-benzoate XV (8.40 g, 24.7 mmol, 37percent) as a yellow oil: Rf 0.26 (hexanes/EtOAc, 4:1): 1H NMR (CDCl3) delta1.73-1.88 (m, 2H), 2.01-2.08 (m, 2H), 2.32 (s, 3H), 2.93 (t, J=7.2 Hz, 2H), 3.75 (s, 3H), 3.89 (s, 3H), 4.69 (t, J=6.2 Hz, 1H), 7.07 (dm, J=8.0 Hz, 1H), 7.33 (t, J=7.9 Hz, 1H) 7.50 (m, 1H), 7.65 (dm, J=7.7 Hz, 1H); 13C NMR (CDCl3) delta25.3, 28.3, 30.5, 31.4, 52.1, 52.2, 75.8, 115.4, 120.0, 122.8, 129.5, 131.4, 157.5, 166.4, 171.3, 195.4. | |
With potassium carbonate; In ethyl acetate; N,N-dimethyl-formamide; | Methyl 3-(4-acetylthio-1-methoxycarbonyl-butoxy)-benzoate XV To a solution of <strong>[50995-48-7]methyl 2,5-dibromopentanoate</strong> XIII (22.00 g, 80.3 mmol) and methyl 3-hydroxybenzoate XIV (10.18 g, 66.9 mmol) in DMF (80 mL) was added K2CO3 (12.94 g, 93.7 mmol) at room temperature. The mixture was stirred at room temperature under N2 for 12 hours, then heated at 70° C. for 1 h. Potassium thioacetate (22.93 g, 200.8 mmol) was added to the mixture, which was heated at 70° C. for 2 hours. The mixture was allowed to cool to room temperature and was diluted with EtOAc (1000 mL). The mixture was washed with H2O (3*300 mL) and brine (2*300 mL). The organic layer was dried over MgSO4, filtered and concentrated. The crude product was purified by flash chromatography (gradient elution: 10percent to 20percent EtOAc/hexanes) to afford methyl 3-(4-acetylthio-1-methoxycarbonyl-butoxy)-benzoate XV (8.40 g, 24.7 mmol, 37percent) as a yellow oil: Rf 0.26 (hexanes/EtOAc, 4:1): 1H NMR (CDCl3) delta1.73-1.88 (m, 2H), 2.01-2.08 (m, 2H), 2.32 (s, 3H), 2.93 (t, J=7.2 Hz, 2H), 3.75 (s, 3H), 3.89 (s, 3H), 4.69 (t, J=6.2 Hz, 1H), 7.07 (dm, J=8.0 Hz, 1H), 7.33 (t, J=7.9 Hz, 1H), 7.50 (m, 1H), 7.65 (dm, J=7.7 Hz, 1H); 13C NMR (CDCl3) delta25.3, 28.3, 30.5, 31.4, 52.1, 52.2, 75.8, 115.4, 120.0, 122.8, 129.5, 131.4, 157.5, 166.4, 171.3, 195.4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | Triton-X 405; at 130.0℃; for 3.0h;Product distribution / selectivity; | Surfactant mediated solvent-free protocols were also successfully extended to the conversion of aryl nitro compounds to aryl acetamides. Thus, solvent-free acetamidation reactions involved treating a mixture of the aryl nitro compound (1 eq) with potassium thioacetate (4 eq.) in presence of dry Triton-X 405 (cat) at about 130 DEG C for about 3 hours producing the corresponding arylacetamide in greater than about 95% conversion (HPLC and GC) and selectivity. Representative results for acetamidation of aryl nitro compounds are summarized in Table 2. The general reaction for the acetamidation of the aryl nitro compound is as follows: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In ethyl acetate; acetonitrile; sodium chloride; | EXAMPLE 28 STR61 tert.-Butyl 4-acetylthioacetoacetate 2.40 g (21.0 mmols) of dry potassium thioacetate were added to a solution, cooled to 0 C., of 3.85 g (20.0 mmols) of tert.-butyl 4-chloroacetoacetate in 40 ml of anhydrous acetonitrile and the mixture was stirred at this temperature for 30 minutes. Thereafter, the mixture was poured into a mixture of NaCl solution and ethyl acetate, the organic phase was separated off and extracted with 2*30 ml of ethyl acetate and the extracts were washed with water and dried over MgSO4. After the solvent had been evaporated off in vacuo and the residue had been chromatographed on 60 g of silica gel (toluene:ethyl acetate 95:5), 3.87 g (83%) of the title compound were obtained as a colorless oil, RF:0.2 (toluene:ethyl acetate 95:5). IR (CHCl3) 1740-1710 cm-1 (C=0). 1 H-NMR (250 MHz, CDCl3) 1.50 (s. 9H, C(CH3)3), 2.42 (s. 3H, CH3 CO3), 3.53 (s. 2H, CH2) and 3.90 (s, 2H, CH2). | |
In ethyl acetate; acetonitrile; sodium chloride; | PREPARATION EXAMPLE 6 STR58 tert.-Butyl 4-acetylthioacetoacetate 2.40 g (21.0 mmol) of dry potassium thioacetate were added to a solution, which had been cooled to 0 C., of 3.85 g (20.0 mmol) of tert.-butyl 4-chloroacetoacetate in 40 ml of anhydrous acetonitrile, and the mixture was stirred at this temperature for 30 min. It was then poured into a mixture of NaCl solution and ethyl acetate, the organic phase was separated off, extraction with 2*30 ml of ethyl acetate was carried out, and the extract was washed with water and dried over MgSO4. After evaporation of the solvent in vacuo and chromatography of the residue on 60 g of silica gel (toluene:ethyl acetate 95:5), 3.87 g (83%) of the title compound were obtained as a colorless oil, Rf: 0.24 (toluene:ethyl acetate 95:5). IR (CHCl3) 1740-1710 cm-1 (C=O). 1 H-NMR (250 MHz, CDCl3) δ 1.50 (s, 9H, C(CH3)3), 2.42 (s, 3H, CH3 CO), 3.53 (s, 2H, CH2), 3.90 (s, 2H, CH2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water; N,N-dimethyl-formamide; | 1) Synthesis of S-(diethoxyphosphorylmethyl) thioacetate To a solution of 17.527 g (93.938 mM) of <strong>[3167-63-3]diethyl chloromethylphosphonate</strong> in 50 ml of N,N-dimethylformamide was added 12.9 g (113 mM) of potassium thioacetate and the mixture was stirred at 100 C. for 3 hours. This reaction mixture was poured in water, saturated with sodium chloride, and extracted with 4 portions of ethyl acetate. The organic layers were pooled and dried over MgSO4 and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane-ethyl acetate:3/1 to 1/1) to provide the title compound. Orange-colored liquid. Yield 13.059 g (61%) 1H-NMR (CDCl3, 200 MHz) delta: 1.330 (6H, t, 7.2 Hz), 2.398 (3H, s), 3.231 (2H, d, 14.0 Hz), 4.141 (4H, quint, 7.4 Hz). IR (neat): 2983, 1701, 1252, 1051,.1024, 968, 623 cm-1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methanol; at 0 - 20℃; | Dimethyl-2,4-bis(acetylthio)glutarate was prepared by a modificationof the literature method [17]. A solution of potassium thioacetate(11.85 g, 103.8 mmol) in methanol (ca. 50 mL) was added slowly to a solution of <strong>[31358-13-1]dimethyl-2,4-dibromoglutarate</strong> (15.28 g,48.0 mmol) in methanol (ca. 50 mL) at C, thereby resulting in acolor change from red to yellow, accompanied by precipitation of KBr. After the addition was complete, the reaction was allowed to warm to room temperature, and the mixture was stirred overnight. The mixture was filtered and the volatile components were removed from the filtrate in vacuo. The residue obtained was extracted into Et2O and washed with H2O. The organic layer was isolated and dried with MgSO4, after which the volatile components were removed in vacuo to give dimethyl 2,4-bis(acetylthio)glutarate as a dark yellow oil (12.58 g, 85.0%) as a mixture ofisomers of sufficient purity to be used directly for the synthesis of the 1,2-dithiolane-3,5-dicarboxylic acids (see below). 1H NMR (d6-acetone): Meso-isomer: delta 2.05 [m, 1H, CH2{(CHSAc)(CO2CH3)}2], 2.39 [s, 6H, CH2{(CHSAc)(CO2CH3)}2], 2.66 [m, 1H,CH2{(CHSAc)(CO2CH3)}2], 3.69 (overlap with rac-isomer) [s, 6H,CH2{(CHSAc)(CO2CH3)}2], 4.28 (overlap with rac-isomer) [m, 2H,CH2{(CHSAc)(CO2CH3)}2]; rac-isomer: delta 2.35 [s, 6H, CH2{(CHSAc)(CO2CH3)}2], 2.83 [s, 2H, CH2{(CHSAc)(CO2CH3)}2], 3.69 (overlapwith meso-isomer) [s, 6H, CH2{(CHSAc)(CO2CH3)}2], 4.28 (overlapwith meso-isomer) [m, 2H, CH2{(CHSAc)(CO2CH3)}2]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
12 g | With potassium carbonate; In dimethyl sulfoxide; at 15℃; for 2h; | In a reaction flask, 2-[(tert-butoxycarbonyl)amino]ethyl 4-methylbenzensulphonate (18.00 g, 0.057 mol), dimethyl sulfoxide (95.00 ml) were loaded, the temperature was cooled to about 15 C., potassium carbonate (12.60 g, 0.091 mol) was added, potassium thioacetate (8.46 g, 0.074 mol) and the reaction mixture was maintained under these conditions for about two hours. Once the reaction is finished, a mixture of water and ice (114 g) was added at the temperature of about 10 C. and the aqueous phase was extracted with toluene (2*72 ml). The organic phase was washed with water (4*36 ml) and the collected organic phase were concentrated till residue through vacuum distillation to give 12 g di S-2-(tert-butoxycarbonyl amino)ethyl-ethantionate. 1H-NMR (CDCl3, 300 MHz): δ 3.25 (t, 2H), 2.97 (t, 2H), 2.31 (s, 3H), 1.43 (s, 9H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With copper(II) acetate monohydrate; In acetonitrile; at 80℃; for 18h;Sealed tube; | General procedure: Under air atmosphere, anilines or phenols (0.5 mmol), potassium thioacetate (3.0 eq.),Cu(OAc)2H2O (0.2 eq.), MeCN (3 mL) were added to a screw-capped vial. Thereaction vial was placed in a temperature-controlled oil bath pot set at 80 °C. Thereaction progress was monitored by TLC. After the completion of the reaction, thevial was removed from the oil bath pot and was left to cool to the ambient temperature.The solution was filtered though a short column of silica gel and washed with EtOAc.The filtrate was concentrated under reduced pressure to leave a crude product, whichwas purified by flash column chromatography on silica gel with Petroleumether/EtOAc as an eluent to give the desired product. |
Tags: Potassium ethanethioate | Carboxylic Acid Salts | Inorganic Salts | Thiols | Organic Building Blocks | Synthetic Reagents | 10387-40-3
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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 |
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