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CAS No. : | 37614-58-7 | MDL No. : | MFCD01250510 |
Formula : | C9H7BrO | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | XXVUZDYGEDBOHT-UHFFFAOYSA-N |
M.W : | 211.06 | Pubchem ID : | 4048181 |
Synonyms : |
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P280-P301+P312-P302+P352-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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 |
---|---|---|
78% | With manganese(IV) oxide; potassium hydroxide In diethyl ether at 20℃; for 0.5h; | |
With manganese(IV) oxide; potassium hydroxide In diethyl ether |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; | |
99% | With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; Inert atmosphere; | Representative procedure: preparation of 1a General procedure: A round-bottomed flask containing a magentic stirbar and iodobenzene (911.5 mg, 4.468 mmol,1.0 equiv) was added with PdCl2(PPh3)2 (62.9 mg, 0.0896 mmol, 0.02 equiv), CuI (34.9 mg, 0.183mmol, 0.04 equiv) and 5.0 mL of Et3N. The resulted mixture was thoroughly degassed by a steadystream of argon for 15 min before propargyl alcohol (0.14 mL, 270.2 mg, 4.820 mmol, 1.1 equiv)was added via syringe. Ther resulted reaction mixture was allowed to stir at room temperatureunder argon overnight. The reaction mixture was diluted with saturated aqueous NH4Cl and theseparated aqueous layer was extracted with 3xEtOAc. Combined organic phases were washed withsaturated aqueous NaCl, dried over anhydrous Na2SO4, filtered and concentrated in vacuo to givea crude material. The crude material was purified by SiO2 column chromatography eluting with10% EtOAc-hexane to give the desired product 1a as a brown oil (451.5 mg, 76%);. |
98% | Stage #1: 1,4-bromoiodobenzene With piperidine; copper (I) iodide; bis (triortho-tolylphosphine)palladium(II) chloride In toluene at 20℃; for 0.0333333h; Inert atmosphere; Stage #2: Prop-2-ynyl alcohol In toluene at 35℃; Inert atmosphere; |
95% | With piperidine; [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide In toluene at 60℃; for 2h; Inert atmosphere; | |
94% | With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 12h; Inert atmosphere; | |
93% | ||
92% | With piperidine; copper (I) iodide In benzene at 30 - 35℃; | |
88% | With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In benzene at 50℃; for 0.333333h; | |
82% | Stage #1: 1,4-bromoiodobenzene With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; for 0.0833333h; Inert atmosphere; Stage #2: Prop-2-ynyl alcohol In tetrahydrofuran at 20℃; Inert atmosphere; | |
80% | With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide at 60℃; for 22h; Inert atmosphere; | |
74% | With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere; | |
65% | With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In toluene at 50℃; for 16h; | |
With piperidine; [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide In tetrahydrofuran at 0 - 20℃; | ||
With diethylamine for 5h; Ambient temperature; | ||
With N-ethyl-N,N-diisopropylamine; triphenylphosphine In tetrahydrofuran at 20℃; for 13h; | 41-1 (41-1) Synthesis of 3-(4-bromophenyl)-2-propyne-1-ol (compound 41-1) [Show Image] A mixture of 4-bromoiodobenzene (8.00 g), copper(I) iodide (108 mg), triphenylphosphine (372 mg), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (586 mg), propargyl alcohol (1.84 ml), diisopropylethylamine (19.7 ml) and tetrahydrofuran (100 ml) was stirred at room temperature for 13 hr. The reaction mixture was added to water, and the mixture was extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=98:2 - 90:10) to give the object product (4.34 g) as a brown oil. 1H-NMR(CDCl3) δ (ppm): 1.64(1H, t, J=6.2Hz), 4.48(2H, d, J=6.2Hz), 7.30(2H, d, J=8.4Hz), 7.45(2H, d, J=8.4Hz). | |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 15h; | ||
Inert atmosphere; | ||
With piperidine; copper (I) iodide; trans-bis(triphenylphosphine)palladium(II) dichloride In toluene at 30℃; for 3h; Inert atmosphere; | ||
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; Inert atmosphere; Schlenk technique; | ||
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In N,N-dimethyl-formamide at 20℃; Inert atmosphere; | ||
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 5h; Inert atmosphere; | ||
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In N,N-dimethyl-formamide at 20℃; for 10h; Inert atmosphere; | ||
With copper (I) iodide; trans-bis(triphenylphosphine)palladium(II) dichloride; triethylamine at 20℃; for 12h; | ||
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; Inert atmosphere; | ||
Stage #1: 1,4-bromoiodobenzene With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 0.166667h; Inert atmosphere; Stage #2: Prop-2-ynyl alcohol Inert atmosphere; | ||
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 12h; Inert atmosphere; | ||
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 8h; Inert atmosphere; | ||
Stage #1: 1,4-bromoiodobenzene With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 25℃; for 0.166667h; Inert atmosphere; Stage #2: Prop-2-ynyl alcohol at 25℃; for 10h; Inert atmosphere; | ||
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 24h; Inert atmosphere; | ||
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | With copper(I) tetrakis(acetonitrile) hexafluorophosphate; tributylphosphine In lithium hydroxide monohydrate; benzene at 70℃; for 16h; Sealed tube; | |
(i) EtMgBr, (ii) /BRN= 1209228/; Multistep reaction; | ||
With ethynylmagnesium bromide 1.) THF, 45 deg C, 1 h, 2.) THF, 45 deg C, 1 h; Yield given. Multistep reaction; |
Stage #1: 4-bromo-1-ethynylbenzene With n-butyllithium In tetrahydrofuran at -78 - 20℃; for 1h; Inert atmosphere; Stage #2: formalin In tetrahydrofuran at -78 - 20℃; for 1.5h; Inert atmosphere; | ||
Stage #1: 4-bromo-1-ethynylbenzene With n-butyllithium In tetrahydrofuran; hexane at -78 - 0℃; for 1.16h; Inert atmosphere; Stage #2: formalin In tetrahydrofuran; hexane at -78 - 20℃; for 12h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With bromine; triphenylphosphine In dichloromethane at 0℃; | |
With pyridine; phosphorus tribromide In diethyl ether for 2.5h; Ambient temperature; | ||
With phosphorus tribromide at 0℃; for 0.5h; |
With pyridine; phosphorus tribromide In diethyl ether at 0 - 20℃; for 2.5h; | ||
With bromine; triphenylphosphine In dichloromethane at 0℃; for 1h; | ||
With carbon tetrabromide; triphenylphosphine In dichloromethane for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With manganese(IV) oxide In ethyl acetate for 1h; Reflux; | |
79% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; [bis(acetoxy)iodo]benzene In dichloromethane at 20℃; for 2h; | |
76% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; copper(II) nitrate trihydrate; oxygen In acetonitrile at 25℃; for 8h; | 35-36 Example 1 General procedure: Insert an oxygen balloon on the dry reaction tube, ventilate 3 times, add Cu(NO3)2·3H2O (24.6mg, 0.1mmol), TEMPO (16.2mg, 0.1mmol), 1b (146.4mg, 1.0mmol) in sequenceMeCN (4mL) solution.The reaction tube was stirred at 25°C for 6 hours. The reaction solution was filtered with a short silica gel column (2cm),Wash with ether and remove the solvent by rotary evaporation. Use silica gel column chromatography for separation and purification (eluent:Petroleum ether/diethyl ether=60/1) to obtain product 2b (130.7 mg, 91%): a white solid. |
66% | With manganese (IV) dioxide In dichloromethane at 20℃; | |
61% | With silica gel; pyridinium chlorochromate In dichloromethane at 20℃; for 12h; Inert atmosphere; | |
46% | With pyridinium chlorochromate In dichloromethane at 20℃; for 2h; Inert atmosphere; | |
With pyridinium chlorochromate | ||
2.46 g | With manganese(IV) oxide In dichloromethane at 20℃; for 15h; | |
With manganese(IV) oxide In dichloromethane at 20℃; Inert atmosphere; Schlenk technique; | ||
With manganese(IV) oxide In dichloromethane at 20℃; | ||
With pyridinium chlorochromate In dichloromethane at 20℃; for 1h; Inert atmosphere; | ||
With Dess-Martin periodane In dichloromethane at 0℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 20℃; for 0.25h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | Stage #1: 3-(4-bromophenyl)prop-2-yn-1-ol With lithium aluminium tetrahydride In tetrahydrofuran at 0℃; Stage #2: With ethyl acetate In tetrahydrofuran Stage #3: 4-fluoro-1-iodobenzene With tris-(dibenzylideneacetone)dipalladium(0); trifuran-2-yl-phosphane; zinc(II) chloride at 65℃; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With iodine In tetrahydrofuran; ethyl acetate; toluene at -80 - 20℃; | |
84% | Stage #1: 3-(4-bromophenyl)prop-2-yn-1-ol With lithium aluminium tetrahydride; sodium methylate In tetrahydrofuran at 0℃; for 3h; Stage #2: With carbonic acid dimethyl ester In tetrahydrofuran for 1h; Stage #3: With iodine In tetrahydrofuran at 0℃; Further stages.; | |
84% | Stage #1: 3-(4-bromophenyl)prop-2-yn-1-ol With lithium aluminium tetrahydride; sodium methylate In tetrahydrofuran for 3h; Stage #2: With carbonic acid dimethyl ester In tetrahydrofuran at 0℃; for 1h; Stage #3: With methanol; iodine more than 3 stages; | 27.D.C Step C. (Z)-3- (4-BROMOPHENYL)-3-IODOPROP-2-EN-1-OL A solution of the above ALKYNE (2.0 g, 10 MMOL) in dry tetrahydrofuran (25 mL) was added dropwise to an ice-cooled solution of lithium aluminum hydride (600 mg, 15 MMOL) and sodium methoxide (2 mg, 0.5%) in dry tetrahydrofuran (10 ML). Reaction mixture was stirred for 3 h under nitrogen atmosphere, a solution of dimethyl carbonate (1.2 g, 20 MMOL) in dry tetrahydrofuran (10 mL) was added dropwise at 0 °C and the reaction mixture was stirred for further 1 h. Subsequently, a solution of iodine (5.0 g, 20 MMOL) in tetrahydrofuran (20 mL) was added and the mixture was allowed to stand overnight in a fridge. Methanol (10ML) was added and the reaction mixture was stirred for further 0.5 h. A saturated solution of sodium thiosulfate (50 mL) and subsequently brine (150 mL) were added and it was extracted with ether (4X150 mL). The collected organic solutions were dried with anhydrous magnesium sul- fate and subsequently evaporated in vacuo. The residue was purified by column chromatog- raphy (silica gel Fluka 60, HEXANE/METHYLENE chloride 9: 1-methylene chloride-methylene chloride/methanol 3: 1) yielding 2.7 G of the product. Yield : 2. 7G (84%). RF = 0. 50 (SIO2, HEXANE/ETHYL acetate 8: 2). |
84% | Stage #1: 3-(4-bromophenyl)prop-2-yn-1-ol With lithium aluminium tetrahydride; sodium methylate In tetrahydrofuran at 0℃; for 3h; Stage #2: With carbonic acid dimethyl ester In tetrahydrofuran at 0℃; for 1h; Stage #3: With iodine In tetrahydrofuran | 27.C A solution of the above alkyne (2.0 g, 10 mmol) in dry tetrahydrofuran (25 mL) was added dropwise to an ice-cooled solution of lithium aluminum hydride (600 mg, 15 mmol) and sodium methoxide (2 mg, 0.5%) in dry tetrahydrofuran (10 mL). Reaction mixture was stirred for 3 h under nitrogen atmosphere, a solution of dimethyl carbonate (1.2 g, 20 mmol) in dry tetrahydrofuran (10 mL) was added dropwise at 0° C. and the reaction mixture was stirred for further 1 h. Subsequently, a solution of iodine (5.0 g, 20 mmol) in tetrahydrofuran (20 mL) was added and the mixture was allowed to stand overnight in a fridge. Methanol (10 mL) was added and the reaction mixture was stirred for further 0.5 h. A saturated solution of sodium thiosulfate (50 mL) and subsequently brine (150 mL) were added and it was extracted with ether (4×150 mL). The collected organic solutions were dried with anhydrous magnesium sulfate and subsequently evaporated in vacuo. The residue was purified by column chromatography (silica gel Fluka 60, hexane/methylene chloride 9:1-methylene chloride-methylene chloride/methanol 3:1) yielding 2.7 g of the product. Yield: 2.7g (84%). RF=0.50 (SiO2, hexane/ethyl acetate 8:2). |
Stage #1: 3-(4-bromophenyl)prop-2-yn-1-ol With lithium aluminium tetrahydride In tetrahydrofuran at 0℃; Stage #2: With ethyl acetate In tetrahydrofuran Stage #3: With iodine In tetrahydrofuran Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | ||
With wilkinson's In ethanol; toluene | 3-(4-bromophenyl)-propanol 3-(4-bromophenyl)-propanol To a solution under inert gas of 36.4 g of 3-(4-bromophenyl)-2-propynol (stage A) in 200 ml of ethanol at 5% of toluene, is added 200 ml of toluene, 7.9 g of Wilkinson's reagent and hydrogen at 1900 mbar for 5 hours. It is evaporated at reduced pressure until the obtainment of 45.9 g of raw product that is purified by chromatography on silica by eluding with the compound CH2Cl2/AcOEt 95/5. 30.1 g of expected product is obtained. Rf (CH2Cl2/AcOEt 95/5): 0.28 IR (CHCl3) | |
With hydrogen In toluene at 60℃; for 7h; | 41-2 (41-2) Synthesis of 3-(4-bromophenyl)-1-propanol (compound 41-2) A suspension of compound 41-1 (4.34 g) and chlorotris(triphenylphosphine)rhodium(I) (2.50 g) in toluene (170 ml) was stirred under a hydrogen atmosphere at 60°C for 7 hr. The reaction mixture was filtered through celite and concentrated. The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate=98:2 - 70:30) to give the object product (3.62 g) as a brown oil. 1H-NMR(CDCl3) δ (ppm): 1.28(1H, brs), 1.83-1.90(2H, m), 2.67(2H, t, J=7.7Hz), 3.67(2H, t, J=6.3Hz), 7.08(2H, d, J=8.2Hz), 7.40(2H, d, J=8.2Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | In triethylamine | 1 Example 1 Example 1 1-(4-Bromophenyl)prop-1-yne-3-ol (Intermediate B): To a solution of 4-bromoiodobenzene (10.0 g, 35.3 mmol) in triethylamine (Et3N, 100 mL) was added propargyl alcohol (2.7 mL, 2.57 g, 45.9 mmol), Cul (0.81 g, 4.24 mmol), and Pd(PPh3)4 (1.63 g, 1.41 mmol). The mixture was stirred overnight, then the reaction mixture was concentrated. Column chromatography (20-35% EtOAc/hexanes) provided 1-(4-bromophenyl)-1-propyne-3-ol B (6.58 g, 88%) as a yellow/orange solid. 1H NMR (300 MHz, CDCl3) 1.77 (t, 1H), 4.48 (d, 2H), 7.29 (d, 2H), 7.45 (d, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethanolamine In N,N-dimethyl-formamide | 1 3-(4-bromophenyl)-2-propynol 3-(4-bromophenyl)-2-propynol To a solution under inert gas of 55.2 g of 4-bromo iodo benzene at 97% in 230 ml of DMF, 56 ml of TEA is added, 12.2 ml of propargylic alcohol, 1 g of copper iodide and 1.1 g of PdCl2 (PPh3)2 whilst maintaining the temperature at 47° C. After stirring for 3 hours 15 minutes at ambient temperature, it is poured into water, drawn off, washed dried and evaporated under reduced pressure until 48.3 g of raw product is obtained that is purified by chromatography on silica by eluding with the compound CH2Cl2/AcOEt 95/5. 36, 37 g of expected pure product is obtained. (F=80° C.) Rf (CH2Cl2/AcOEt 95/5): 0.32 IR (CHCl3) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With n-butyllithium In tetrahydrofuran; methanol | 43.B 3-[4-(benzoxazol-2-yl)phenyl]propargyl alcohol Step B 3-[4-(benzoxazol-2-yl)phenyl]propargyl alcohol To a solution of 3-(4-bromophenyl)propargyl alcohol (11.2 g; 53.1 mmol) in dry THF (260 ml) at -78° C. is added a solution of butyllithium in hexanes (70 ml; 110 mmol) dropwise over 45 minutes. The reaction is allowed to stir an additional 30 minutes and a solution of 2-chlorobenzoxazole (6.7 ml; 58 mmol) in THF (30 ml) is added dropwise over 15 minutes. The bath is removed and the mixture is allowed to warm to 0° C. and stirred 20 minutes. MeOH (20 ml) is added slowly followed by H2 O (250 ml). The mixture is extracted with ether and the organic phase is concentrated and washed with hexane and CH2 Cl2 to give 3-[4-(benzoxazol-2-yl)phenyl]propargyl alcohol which is used directly in Step C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44.A Step A Step A When 1-bromo-4-iodobenzene in Example 43, Step A is replaced by 1-bromo-3-methyl-4-iodobenzene or 1-bromo-3,6-dimethyl-4-iodobenzene, then the corresponding products are obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | With copper(l) iodide In tetrahydrofuran at 0 - 50℃; for 5h; | 2 A solution of 1 ,4-dibromobenzene (23.6 g, 100.0 mmol) in dry tetrahydrofuran (100 mL) was degassed and copper(l)iodide (570 mg, 3.0 mmol), tetrakis(triphenylphosphine)- palladium (3.4 g, 3.0 mmol) and diazobicycloundecene (18.2 g, 120.0 mmol) were added. The reaction solution was degassed again and propargyl alcohol (6.7 g, 120.0 mmol) was added dropwise under inert atmosphere at 0 °C. The reaction was stirred at 0 °C for 1 h and next 4 h at 50 °C. The solution was then treated with brine (20 mL) and acidified with 2 M hydrochloric acid (20 mL). The organic phase was isolated and the aqueous phase was ex- tracted with ether (4 x 30 mL). The combined organic phases were dried with magnesium sulfate and concentrated in vacuo yielding brown solid. Product was purified by crystallization from hexane yielding yellowish dust of 3-(4-bromophenyl)prop-2-yn-1-ol.Yield: 10 g (49%).M. p.: 65-68 °C (hexane). Rf (hexane/ethyl acetate 90:10): 0.10. |
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 80℃; Inert atmosphere; | ||
With bis-triphenylphosphine-palladium(II) chloride |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With tri-tert-butyl phosphine In cyclohexane; N,N-dimethyl-formamide at 50℃; for 2h; | 17 In nitrogen atmosphere, 0.15 M solution of tri(tert-butyl)phosphine in cyclohexane (6.60 ml_, 0.990 mmol) and tris(dibenzylideneacetone)dipalladium chloroform complex (252 mg, 0.243 mmol) were added to a degassed solution of 3-(4-bromophenyl)propargyl alcohol (1.82 g, 8.62 mmol; example 2) and tributyl-(5-methylthiophen-2-yl)tin (4.18 g, 10.8 mmol; prepared according to J. Med. Chem. 2001 , 44, 3355) in dry N,N-dimethylformamide (50 ml_). The reaction mixture was stirred at 50 °C for 2 h, cooled down and 10 % aqueous solution of potassium fluoride (5 ml.) was added. The formed suspension was stirred for 15 min, filtered through a paddle of silica gel and the solid mass was thoroughly washed with ethyl acetate (180 ml_). The combined filtrates were washed with brine (3 x 50 ml_), 10 % aqueous solution of potassium fluoride (2 x 50 ml_), water (50 ml.) and brine (2 x 50 ml_). The organic solution was dried with anhydrous magnesium sulfate and its evaporation gave oil that was purified by flash column chromatography (silica gel Fluka 60, hexanes/ethyl acetate 5:1 ) yielding 3-[4-(5-methylthiophen-2-yl)phenyl]propargyl alcohol as brownish solid mass. Yield: 1.16 g (59 %). RF (SiO2, hexanes/ethyl acetate 4:1 ): 0.15.1H NMR spectrum (300 MHz, CDCI3, δH): 7.49 (dm, J=8.5 Hz, 2 H); 7.41 (dm, J=8.6 Hz, 2 H); 7.14 (d, J=3.6 Hz, 1 H); 6.73 (dd, J=3.6 and 1.0 Hz, 1 H); 4.51 (d, J=5.9 Hz, 2 H); 2.51 (d, J=0.9 Hz, 1 H); 1.67 (bt, J=5.6 Hz, 1 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With potassium <i>tert</i>-butylate In dimethyl sulfoxide at 40℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | Stage #1: 1-bromo-4-(2,2-dibromovinyl)benzene With lithium diisopropyl amide In tetrahydrofuran at -78℃; for 2h; Stage #2: formaldehyd In tetrahydrofuran at -78 - 20℃; for 3h; | 27.D.B Step B, 3-(4-BROMOPHENEL) PROP-2-VN-1-OL The above bromo derivative (8.0 g, 23 MMOL) was dissolved in dry tetrahydrofuran (120 mL) and cooled TO-78°C under inert atmosphere. 2M Solution of lithium diisopropyla- mide in tetrahydrofuran (38 mL, 75 MMOL) was added dropwise to the reaction mixture and it was stirred for 2 h under cooling. Finely powdered paraformaldehyde (7.0 g, 230 MMOL) was added to the mixture and it was stirred for further 3 h warming up the reaction mixture slowly to the room temperature. Brine (50 mL) was added and the mixture was extracted with ether (4X50 mL). The collected organic layers were dried with anhydrous magnesium sulfate and subsequently evaporated in vacuo. The residue was pre-purified by column chromatography (silica gel Fluka 60, hexane/ethyl acetate 1: 0-3: 1) and the obtained crude product was fur- ther purified by crystallization from ethyl acetate and hexane yielding 3.0 G of the desired product. Yield : 3.0 G (66%). RF = 0. 10 (SIO2, HEXANE/ETHYL acetate 9: 1). 'H NMR spectrum (250 MHz, CDC13) : 7.24-7. 49 (m, 4 H); 4.48 (s, 2 H). |
66% | Stage #1: 1-bromo-4-(2,2-dibromovinyl)benzene With lithium diisopropyl amide In tetrahydrofuran at -78℃; for 2h; Stage #2: formaldehyd In tetrahydrofuran at 20℃; for 3h; | 27.B The above bromo derivative (8.0 9, 23 mmol) was dissolved in dry tetrahydrofuran (120 mL) and cooled to -78° C. under inert atmosphere. 2M Solution of lithium diisopropylamide in tetrahydrofuran (38 mL, 75 mmol) was added dropwise to the reaction mixture and it was stirred for 2 h under cooling. Finely powdered paraformaldehyde (7.0 g, 230 mmol) was added to the mixture and it was stirred for further 3 h warming up the reaction mixture slowly to the room temperature. Brine (50 mL) was added and the mixture was extracted with ether (4×50 mL). The collected organic layers were dried with anhydrous magnesium sulfate and subsequently evaporated in vacuo. The residue was pre-purified by column chromatography (silica gel Fluka 60, hexane/ethyl acetate 1:0-3:1) and the obtained crude product was further purified by crystallization from ethyl acetate and hexane yielding 3.0 g of the desired product. Yield: 3.0 g (66%). RF=0.10 (SiO2, hexane/ethyl acetate 9: 1). 1H NMR spectrum (250 MHz, CDCl3): 7.24-7.49 (m, 4 H); 4.48 (s, 2 H). |
66% | Stage #1: 1-bromo-4-(2,2-dibromovinyl)benzene With lithium diisopropyl amide In tetrahydrofuran at -78℃; for 2h; Stage #2: formaldehyd In tetrahydrofuran at -78 - 20℃; for 3h; | 1; A.B Step B:; 3-(4-Bromophenyl)prop-2-yn-1-ol:; 1-Bromo-4-(2,2-dibromovinyl)benzene (8.0 g, 23 mmol) was dissolved in dry tetra- hydrofuran (120 mL) and cooled to -78°C under inert atmosphere. 2M Solution of lithium diisopropylamide in tetrahydrofuran (38 mL, 75 mmol) was added dropwise to the reaction mixture and it was stirred for 2 h under cooling. Finely powdered paraformaldehyde (7.0 g, 230 mmol) was added to the mixture and it was stirred for further 3 h warming up the reac- tion mixture slowly to the room temperature. Brine (50 mL) was added and the mixture was extracted with ether (4x50 mL). The collected organic layers were dried with anhydrous magnesium sulfate and subsequently evaporated in vacuo. The residue was pre-purified by column chromatography (silica gel Fluka 60, hexane/ethyl acetate 1:0 - 3:1) and the obtained crude product was further purified by crystallization from ethyl acetate and hexane yielding 3.0 g of the desired product. Yield: 3.0 g (66%). RF = 0.10 (Si02, hexane/ethyl acetate 9 : 1 ). ¹H NMR spectrum (250 MHz, CDCI3, On): 7.24 - 7.49 (m, 4 H) ; 4.48 (s, 2 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | Stage #1: 3-(4-bromophenyl)prop-2-yn-1-ol With lithium aluminium tetrahydride; sodium methylate In tetrahydrofuran at 0℃; for 3h; Stage #2: carbonic acid dimethyl ester In tetrahydrofuran at 0℃; for 1h; Stage #3: With methanol; iodine more than 3 stages; | 1; A.C Step C:; (Z)-3-(4-Bromophenyl)-3-iodoprop-2-en-1-ol:; A solution of 3-(4-bromophenyl)prop-2-yn-1-ol (2.0 g, 10 mmol) in dry tetrahydrofu- ran (25 mL) was added dropwise to an ice-cooled solution of lithium aluminum hydride (600 mg, 15 mmol) and sodium methoxide (2 mg, 0.5%) in dry tetrahydrofuran (10 mL). Reaction mixture was stirred for 3 h under nitrogen atmosphere, a solution of dimethyl carbonate (1.2 g, 20 mmol) in dry tetrahydrofuran (10 mL) was added dropwise at 0 °C and the reaction mix- ture was stirred for further 1 h. Subsequently, a solution of iodine (5.0 g, 20 mmol) in tetrahy- drofuran (20 mL) was added and the mixture was allowed to stand overnight in a fridge. Methanol (lOmL) was added and the reaction mixture was stirred for further 0.5 h. A satu- rated solution of sodium thiosulfate (50 mL) and subsequently brine (150 mL) were added and it was extracted with ether (4x150 mL). The collected organic solutions were dried with anhydrous magnesium sulfate and subsequently evaporated in vacuo. The residue was puri- fied by column chromatography (silica gel Fluka 60, hexane/methylene chloride 9: 1 - methyl- ene chloride - methylene chloride/methanol 3:1) yielding 2.7 g of the product. Yield: 2.7g (84%). RF = 0.50 (Si02, hexane/ethyl acetate 8:2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With toluene-4-sulfonic acid In toluene for 24h; Reflux; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With (2S)-2-{diphenyl[(trimethylsilyl)oxy]methyl}pyrrolidine; tetrapropylammonium perruthennate; 4-methylmorpholine N-oxide In dichloromethane at 20℃; for 18h; Inert atmosphere; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride In tetrahydrofuran; water; ethyl acetate | 11.1 11.1 11.1 6-[4-(3-Hydroxyprop-1-ynyl)phenyl]naphthalen-2-ol 13.0 g (0.047 mol) of sodium metaborate octahydrate are initially introduced in 100 ml of water, and a solution of 7.00 g (33.1 mmol) of 3-(4-bromophenyl)prop-2-yn-1-ol (CAS No. 37614-58-7) and 9.00 g (33.3 mmol) of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-2-ol (CAS No. 269410-21-1) in 200 ml of THF is added. After addition of 1.00 g (1.40 mmol) of bis(triphenylphosphine)palladium(II) chloride, the batch is heated under reflux for 5 h, 100 ml of ethyl acetate are subsequently added, and the mixture is acidified using 2 M hydrochloric acid. The org. phase is separated off, dried over sodium sulfate and evaporated. The residue is filtered through silica gel with toluene/ethyl acetate (3:2), and the crude product is recrystallised from toluene/ethyl acetate, giving 6-[4-(3-hydroxyprop-1-ynyl)phenyl]naphthalen-2-ol as a colourless solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With sodium hydride In tetrahydrofuran at 0 - 55℃; for 5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | Stage #1: 3-(4-bromophenyl)prop-2-yn-1-ol With potassium <i>tert</i>-butylate; copper(II) acetate monohydrate; 1,3-bis[2,6-diisopropylphenyl]imidazolium chloride; <i>tert</i>-butyl alcohol In toluene at 25℃; for 6h; Inert atmosphere; Stage #2: With tetrabutyl ammonium fluoride In tetrahydrofuran; toluene at 0℃; diastereoselective reaction; | General procedure for the copper-catalyzed semihydrogenation of alkynes: for solid substrates (1d, f, g, h, i, j, l, m, q, r, w, z, and CA-4) General procedure: In air, Cu(OAc)2·H2O (5.0mg, 5mol%), IPr·HCl (10.6mg, 5mol%), and solid substrates (0.5mmol) were placed in a screw-capped reaction vial. The vial was moved into a glove box and t-BuOK (5.6mg, 10mol%) and solvent (1.0ml) were added. The vial was moved out of the glove box and connected to an argon line through a needle. The mixture was raised to 50°C and stirred for 1h. The mixture was then treated in two different manners: (1) if reaction temperature ≥50°C (1d, i, j, q, r, w and CA-4), PMHS (131mg, 4.0equiv) was then added dropwise with a microsyringe at 50°C and the solution was stirred for an additional 30min. After t-BuOH (74mg, 2.0equiv) was added, the mixture was raised to required reaction temperature and stirred for a specified period of time; (2) if reaction temperature 1f, g, h, l, m, z), the mixture was first cooled to the required temperature and PMHS (131mg, 4.0equiv) was then added and the solution was stirred for an additional 30min. After t-BuOH (74mg, 2.0equiv) was added, the mixture was stirred for a specified period of time. The reaction mixture was subsequently hydrolyzed by adding 1M NaOH aqueous (2ml) (for substrates with no hydroxyl group) or 1M TBAF in THF (2ml) at 0°C (for substrates with a hydroxyl group) for several hours. The mixture was extracted with ether (2ml×3). Crude products were obtained after evaporation and purified by silica gel chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With bis(η3-allyl-μ-chloropalladium(II)) In dichloromethane at 20℃; for 1h; Inert atmosphere; Molecular sieve; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With silver hexafluoroantimonate; 2-(di-tert-butylphosphino)-1,1'-biphenylgold(I) chloride In 1,2-dichloro-ethane at 20℃; for 0.5h; | |
50% | With bis(η3-allyl-μ-chloropalladium(II)) In dichloromethane at 20℃; for 1h; Inert atmosphere; Molecular sieve; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dmap; triethylamine In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere; | Preperation of Propargyl Esters General procedure: To the solution of 3-phenyl-2-propyn-1-ol (1.32 g, 10.0 mmol),NEt3 (7.0 mL, 50.0 mmol) and 4-(dimethylamino)pyridine (DMAP) (127.5 mg, 1.05 mmol) in methylene chloride(CH2Cl2) (50 mL) at 0°C was added pivaloyl chloride (1.35 mL,11.0 mmol) slowly under Ar and the mixure was warmed toroom temperature. After stirring for 2 h, the mixture wasquenched with water and extracted with chloroform (CHCl3).The combined extracts were washed with 1.0 M aqueoussolution of HCl and 3.0 M aqueous solution of NaOH, driedover Na2SO4 and concentrated under reduced pressure. Theobtained residue was purified by silica gel column chromatography(hexane/CH2Cl2=75/25) to give 11a (1.89 g, 88%) asa colorless oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane at 20℃; stereoselective reaction; | General procedure for the synthesis of chlorothiolated adducts of alkynes: General procedure: To a solution of aryl/heteroaryl thiols (0.55 mmol) in CH2Cl2 (4 mL) was added N-chlorosuccinimde(0.55 mmol) and the reaction mixture was allowed to stir for 5 minutes to form sulphenylchlorides as yellow colored solution. To this stirred solution of sulphenylchloride was added internal alkynoate (0.5mmol) and the reaction mixture was again stirred for 2-5 h. After completion of the reaction (monitored by TLC) water (10 mL) was added to the reaction mixture and extracted with CH2Cl2 (3 x 10 mL). The combined organic layers were washed with brine (10 mL) and dried over anh. sodium sulphate. The organic layer was concentrated using a rotary evaporator and chromatographed on silica gel (100-200 mesh) using 1:9 ethyl acetate-hexane as the eluent to give pure chloroalkenyl sulphides (4a-4n). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane at 20℃; stereoselective reaction; | General procedure for the synthesis of chlorothiolated adducts of alkynes: General procedure: To a solution of aryl/heteroaryl thiols (0.55 mmol) in CH2Cl2 (4 mL) was added N-chlorosuccinimde(0.55 mmol) and the reaction mixture was allowed to stir for 5 minutes to form sulphenylchlorides as yellow colored solution. To this stirred solution of sulphenylchloride was added internal alkynoate (0.5mmol) and the reaction mixture was again stirred for 2-5 h. After completion of the reaction (monitored by TLC) water (10 mL) was added to the reaction mixture and extracted with CH2Cl2 (3 x 10 mL). The combined organic layers were washed with brine (10 mL) and dried over anh. sodium sulphate. The organic layer was concentrated using a rotary evaporator and chromatographed on silica gel (100-200 mesh) using 1:9 ethyl acetate-hexane as the eluent to give pure chloroalkenyl sulphides (4a-4n). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | Stage #1: 1-(4-methylbenzensulfonyl)-4-phenyl-1H-1,2,3-triazole; 3-(4-bromophenyl)prop-2-yn-1-ol With rhodium(II) pivalate In toluene at 100℃; for 0.666667h; Glovebox; Stage #2: With [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In toluene at 100℃; for 4h; Glovebox; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bis-triphenylphosphine-palladium(II) chloride In tetrahydrofuran; water for 5h; Reflux; | 11.1 13. 0g (0. 047mol) of sodium metaborate in 100 ml of water to first water triuranium octoxide introduced into hydrate, 200 ml of THF in 7. 00g (33. 1mmol) of 3-(4-bromophenyl) [...] -2--1-ol (CAS No. 37614-58-7) and 9. 00g (33. 3mmol) of 6-(4, 4, 5, 5-tetramethyl -1, 3, 2-dioxaborolane-2-yl)-2-ol (CAS No. 269410-21-1) applying a solution. 1. 00g (1. 40mmol) of bis (triphenylphosphine) palladium (II) chloride is added, the batch is heated under reflux for 5 hours in, which successively added to 100 ml of ethyl acetate, 2M of hydrochloric acid and a mixture is used. The organic phase is separated, dried over sodium sulfate, and is evaporated. Residue through silica gel, toluene/ethyl acetate (3:2) by filtering, re-crystallization toluene/crude product from ethyl acetate, colorless as solid, 6-[ 4-(3- [...] -1-ynyl) phenyl]-2-ol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 80℃; Inert atmosphere; | 4.2 Preparation of 1a-1o and 1q General procedure: To a mixture of aryl halide (1 mmol) in Et3N (4 mL), PdCl2(PPh3)2 (0.1 mmol), CuI (0.05 mmol), and propargyl alcohol (1.2mmol) were added. The mixture was stirred at 80°C under nitrogen until the starting halide disappeared completely monitored by TLC. Then the reaction was quenched by saturated NH4Cl solution and extracted with ethyl acetate. The combined organic phases were washed with brine, dried over anhydrous Na2SO4 and concentrated under reduced pressure to give a residue. Finally the residue was purified through column chromatography on silica gel (200-300 mesh) with hexane/EtOAc as eluent to afford the products 1a-1o and 1q. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With iron(III) trifluoromethanesulfonate at 110℃; for 21h; | 4.4 Preparation of 2a, 2d-2p, and 3a-3e General procedure: To a mixture of propargyl alcohol 1 (0.2mmol) in dioxane (1mL), Fe(OTf)3 (0.04mmol) and nucleophile (0.4 mmol) were added. The mixture was stirred at refluxing temperature until 1 disappeared completely monitored by TLC. Then the reaction was quenched by saturated NaHCO3 solution and extracted with ethyl acetate. The combined organic phases were washed with brine, dried over anhydrous Na2SO4 and concentrated under reduced pressure to give a residue. Finally the residue was purified through column chromatography on silica gel (200-300 mesh) with hexane/EtOAc as eluent to afford the products 2a, 2d-2p, and 3a-3e. |
With bismuth(lll) trifluoromethanesulfonate In 1,4-dioxane Sealed tube; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | Stage #1: n-<(trimethylsiloxy)methyl>phthalimide; (4-bromophenyl)(trimethylsilyl)acetylene With sodium phenoxide In N,N-dimethyl-formamide at 20℃; Inert atmosphere; Stage #2: With potassium carbonate In methanol; N,N-dimethyl-formamide at 20℃; for 0.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | Stage #1: formaldehyd; (4-bromophenyl)(trimethylsilyl)acetylene With sodium phenoxide In N,N-dimethyl-formamide at 20℃; Inert atmosphere; Stage #2: With potassium carbonate In methanol; N,N-dimethyl-formamide at 20℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With bis{rhodium[3,3'-(1,3-phenylene)bis(2,2-dimethylpropanoic acid)] In 1,2-dichloro-ethane at 25℃; Molecular sieve; Inert atmosphere; | |
73% | With bis{rhodium[3,3'-(1,3-phenylene)bis(2,2-dimethylpropanoic acid)] In 1,2-dichloro-ethane at 25℃; Inert atmosphere; Molecular sieve; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With dmap; dicyclohexyl-carbodiimide In dichloromethane at 0 - 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine In acetonitrile at 85℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bismuth(lll) trifluoromethanesulfonate In 1,4-dioxane at 110℃; for 3h; | 4. Preparation of 3a-3i, 4b-4d, and 4g-4q General procedure: To a mixture of propargyl alcohol 1 (0.2 mmol) in dioxane (1 mL), Bi(OTf)3 (0.03 mmol) and nucleophile 2 (0.22 mmol) were added. The mixture was stirred at refluxing temperature until 1 disappeared monitored by TLC. Then the reaction was quenched by saturated NaHCO3 solution and extracted with ethyl acetate. The combined organic phases were washed with brine, dried over anhydrous Na2SO4 and concentrated under reduced pressure to give a residue. Finally the residue was purified through column chromatography on silica gel (200-300 mesh) with hexane/EtOAc as eluent to afford the products 3a-3i, 4b-4d, and 4g-4q. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 80℃; Inert atmosphere; | 2. Preparation of 1a-1o and 1q. General procedure: To a mixture of aryl halide (1 mmol) in Et3N (4 mL), PdCl2(PPh3)2 (0.1 mmol), CuI (0.05 mmol), and propargyl alcohol (1.2 mmol) were added. The mixture was stirred at 80oC under nitrogen until the starting halide disappeared monitored by TLC. Then the reaction was quenched by saturated NH4Cl solution and extracted with ethyl acetate. The combined organic phases were washed with brine, dried over anhydrous Na2SO4 and concentrated under reduced pressure to give a residue. Finally the residue was purified through column chromatography on silica gel (200-300 mesh) with hexane/EtOAc as eluent to afford the products 1a-1n and 1p. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; [bis(acetoxy)iodo]benzene; ammonium acetate In water; acetonitrile at 20℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With 2,2'-bis[di(3,5-dimethylphenyl)phosphino]-1,1'-binaphthyl; silver hexafluoroantimonate; calcium hydride In dichloromethane at 25℃; for 49h; Inert atmosphere; Darkness; Molecular sieve; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With iron(II) triflate; N-iodo-succinimide In benzene at 80℃; Sealed tube; | 7 Preparation process Add 1,3-substituted propargyl alcohol, halogen source and acid in a sealed tube, and carry out the reaction under heating and reflux at 80 ° C;The complete disappearance of 1,3-substituted propargyl alcohol was monitored by TLC and quenched by the addition of saturated brine. The organic phase was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated.The obtained concentrated liquid was purified by column chromatography to obtain α-halo unsaturated aldehyde ketone, and the calculated yield was 82%.Among them, propargyl alcohol, halogen source, solvent and acid were added as 3- (4-bromophenyl) prop-2-yn-1-ol (2 mmol), NIS (2.2 mmol),Benzene (25mL)And ferrous triflate (0.08 mmol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35%; 53% | With N-iodo-succinimide; hydroxylamine hydrochloride; copper(II) bis(trifluoromethanesulfonate); In 1,4-dioxane; at 101℃; for 5h;Sealed tube; | The preparation process is: adding propargyl alcohol derivative, halogen source and acid in a sealed tube,The reaction was carried out at 101 C under heating and reflux, and hydroxylamine was added after the disappearance of the propargyl alcohol derivative was monitored by TLC.After 5 hours of reaction, saturated brine was added to quench the reaction. The organic phase was extracted with ethyl acetate and dried over anhydrous sodium sulfate.Concentration yields the isoxazole derivative, which can be purified by column chromatography to calculate the yield:The yield of isoxazole derivative I was 35%; the yield of isoxazole derivative II was 53%, and the total yield of isoxazole derivatives was 88%.Among them, propargyl alcohol, halogen source, hydroxylamine,Solvent and acid loading was 3- (4-bromophenyl) prop-2-yn-1-ol (2 mmol),NIS (2.2 mmol), hydroxylamine hydrochloride (3.2 mmol),Dioxane (20 mL) and copper triflate (0.3 mmol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With Jones reagent In acetone at 0 - 20℃; for 3.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With N-iodo-succinimide; copper(II) bis(trifluoromethanesulfonate); hydrazine hydrate; In 1,4-dioxane; at 101℃; for 5h;Sealed tube; | The preparation process is as follows: adding a propargyl alcohol derivative, a halogen source and an acid in a sealed tube, and carrying out the reaction under heating at 101 C; and monitoring the TLC to detect that the propargyl alcohol derivative has completely disappeared, and then adding hydrazine, after 5 hours of reaction, saturated brine was added to quench the reaction. The organic phase was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated to obtain a pyrazole derivative. The purity of the product was improved by column chromatography, and the calculated yield was 89%. Among them, propargyl alcohol, halogen source, hydrazine, solvent and acid were added as follows: 1,3-diphenylprop-2-yn-1-ol (2 mmol), NIS (2.2 mmol), hydrazine hydrate (3.2 mmol), dioxane (20 mL) and copper triflate (0.3 mmol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | Stage #1: 3-(4-bromophenyl)prop-2-yn-1-ol With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 0.5h; Stage #2: 2-methyl-3-bromo-1-propene In tetrahydrofuran; mineral oil at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With lithium aluminium tetrahydride In tetrahydrofuran at 0 - 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine In N,N-dimethyl-formamide at 0 - 20℃; | General procedure for the preparation of3-substituted-4H-[1,2,3]triazolo[5,1-c][1,4]oxazin-6(7H)-ones General procedure: Propargyl alcohol 1a-l (1.0 mmol) was dissolved in dryDMF (10 mL) and then cooled to 0 °C. Anhydrous Et3N(0.3 g, 3 equiv.) and chloroacetyl chloride (0.14 g; 1.2mmol) were added, and the reaction mixture was allowedto stir at room temperature. After the disappearance of thestarting materials (monitored by TLC), sodium azide(0.13 g, 2.0 mmol) was added to the reaction mixture. Thereaction was heated to 100 °C, stirred for 5 h and thencooled to room temperature. The reaction mixture wastreated with water (10 mL) and extracted with ethyl acetate(3 × 10 mL). The combined organic extract waswashed with brine, dried over anhydrous sodium sulfate,filtered and concentrated in vacuo. The residue was subjectedto flash column chromatography with petroleumether/ethyl acetate (5/1) as eluent to afford the desiredproduct 3a-l. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With bismuth(lll) trifluoromethanesulfonate; N-Bromosuccinimide In tetrahydrofuran | 10 N-((2-Amino-4-(4-bromophenyl)thiazol-5-yl)methyl)-4-methylbenzenesulfonamide Aryl-substituted propargyl alcohol, N-protected amine, N-halogenated succinimide, catalyst acid, solvent, thiourea types and their amounts are: 4-bromophenylpropargyl alcohol (0.10 mmol),P-toluenesulfonamide (0.12mmol), N-bromosuccinimide (0.15mmol), bismuth trifluoromethanesulfonate (0.02mmol),Tetrahydrofuran (1.00mL)And thiourea (0.20 mmol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 80% 2: 18% | With hydrogenchloride; N-chloro-succinimide In 1,4-dioxane; water monomer at 20℃; for 5h; | Representative procedure: 2,2-dichlorooxygenation of alkynol 1a General procedure: A solution of alkynol 1a (95.8 mg, 0.725 mmol, 1.0 equiv) in 3.6 mL of 1,4-dioxane was addedwith NCS (193.3 mg, 1.448 mmol, 2.0 equiv) and 1 M aqueous HCl (0.38 mL, 0.38 mmol, 0.5equiv). The resulted solution was allowed to stir at room temperature until the reaction was judgedcomplete by TLC (typically 5 h). Upon completion, the reaction mixture was diluted with water.The separated aqueous phase was extracted with 3xEtOAc. The combined organic phases werewashed with saturated aqueous NaCl, dried over anhydrous Na2SO4, filtered and concentrated toa crude material. The crude material was purified by SiO2 column chromatography eluting 10%EtOAc-hexane to give the corresponding 2,2-dichloroketone 2a-Cl as a yellow oil (117.2 mg,74%); |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 3-(4-bromophenyl)propargyl alcohol With 4-methylbenzenesulfonyl chloride; potassium hydroxide In diethyl ether at 0℃; for 1h; Inert atmosphere; Stage #2: toluene-4-sulfonic acid hydrazide With sodium hydride at 0 - 20℃; for 16h; | N-(3-Phenyl-2-propyn-1-yl)-N′-tosylhydrazine (1A); Typical Procedure General procedure: To a solution of 3-phenyl-2-propyn-1-ol (1322.0 mg, 10.0 mmol) inEt2O (20.0 mL) were added KOH (2801.0 mg, 50.0 mmol) and p-TsCl(2097.0 mg, 11.0 mmol). The obtained mixture was stirred for 1 h at 0°C under argon atmosphere. Sat. aq NH4Cl (30.0 mL) was added to themixture and extracted with EtOAc (3 × 15.0 mL). The combined organiclayers were dried (Na2SO4). After filtration and removal of thesolvent under reduced pressure, the residue was added to a solutionof p-toluenesulfonyl hydrazide (9312.0 mg, 50.0 mmol) and NaH(480.0 mg, 20.0 mmol) at 0 °C. The obtained mixture was stirred for16 h at r.t. H2O (30.0 mL) was added to the mixture, and the productwas extracted with CHCl3 (3 × 15.0 mL). The combined organic layerswere dried (Na2SO4). After filtration and removal of the solvent underreduced pressure, the residue was purified by silica gel column chromatography(eluent: n-hexane/EtOAc 2:1); yield: 2163.0 mg (72%); |
Precautionary Statements-General | |
Code | Phrase |
P101 | If medical advice is needed,have product container or label at hand. |
P102 | Keep out of reach of children. |
P103 | Read label before use |
Prevention | |
Code | Phrase |
P201 | Obtain special instructions before use. |
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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