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[ CAS No. 927-74-2 ] {[proInfo.proName]}

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Chemical Structure| 927-74-2
Chemical Structure| 927-74-2
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Product Details of [ 927-74-2 ]

CAS No. :927-74-2 MDL No. :MFCD00002955
Formula : C4H6O Boiling Point : -
Linear Structure Formula :HC2CH2CH2OH InChI Key :OTJZCIYGRUNXTP-UHFFFAOYSA-N
M.W : 70.09 Pubchem ID :13566
Synonyms :

Calculated chemistry of [ 927-74-2 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 5
Num. arom. heavy atoms : 0
Fraction Csp3 : 0.5
Num. rotatable bonds : 1
Num. H-bond acceptors : 1.0
Num. H-bond donors : 1.0
Molar Refractivity : 20.67
TPSA : 20.23 Ų

Pharmacokinetics

GI absorption : Low
BBB permeant : No
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -6.64 cm/s

Lipophilicity

Log Po/w (iLOGP) : 1.45
Log Po/w (XLOGP3) : 0.12
Log Po/w (WLOGP) : 0.08
Log Po/w (MLOGP) : 0.6
Log Po/w (SILICOS-IT) : 0.27
Consensus Log Po/w : 0.5

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 3.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -0.28
Solubility : 36.4 mg/ml ; 0.52 mol/l
Class : Very soluble
Log S (Ali) : -0.1
Solubility : 55.6 mg/ml ; 0.793 mol/l
Class : Very soluble
Log S (SILICOS-IT) : -0.05
Solubility : 62.0 mg/ml ; 0.885 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 1.93

Safety of [ 927-74-2 ]

Signal Word:Danger Class:3
Precautionary Statements:P261-P305+P351+P338 UN#:1987
Hazard Statements:H225-H315-H319-H335 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 927-74-2 ]

* 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.

  • Upstream synthesis route of [ 927-74-2 ]
  • Downstream synthetic route of [ 927-74-2 ]

[ 927-74-2 ] Synthesis Path-Upstream   1~35

  • 1
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YieldReaction ConditionsOperation in experiment
98% With hydrogenchloride In water at 5 - 50℃; for 3 h; A mixture of 4-dihydro-2H-pyridine (293.2 g 3.5 mol) and concentrated HCl (1. 1 mL) was cooled to 5 °C. While continuing to cool externally, 3-BUTYN-1-OL (231.5 g, 3.3 mol) was added over a period of 30 min allowing the temperature to reach 50 °C. Reaction was held with mixing at room temperature for 2.5 hr before it was diluted with MTBE (1.0 L). The resulting mixture was washed with saturated sodium bicarbonate (2X150 mL). The organic phase was dried over sodium sulfate and concentrated under reduced pressure to afford 500 g (98percent crude yield) of product; GC areapercent of 96percent.
86% With pyridinium p-toluenesulfonate In dichloromethane 2-But-3-ynyloxy-tetrahydro-pyran (2)A solution of 3-butyn-l-ol 1 (1.0Og, 14.3 mmol) and PPTS (0.72g, 2.9 mmol) in CH2Cl2 (20 niL) was treated dropwise with dihydopyran (1.7 mL, 19 mmol) and the resulting mixture was stirred for overnight. The reaction mixture was diluted with CH2Cl2 (80 mL) and washed with 0.02 N NaOH (50 mL) and brine (100 mL). The organic layer was dried over MgSC>4 and concentrated and the residue was purified with 3~5percent EtOAc in hexane on silica gel to give 1.9Og of compound 2 (12.3 mmol, 86percent yield): 1H NMR (CDCl3) δ 4.63 (t, J= 3.4 Hz, IH)5 3.92-3.77 (m, 2H), 3.59-3.45 (m, 2H), 2.47 (td, J = 7.1, 2.8 Hz, 2H), 1.96 (t, J= 2.5 Hz, IH), 1.90-1.44 (m, 6H).
84% With pyridinium p-toluenesulfonate In dichloromethane at 0 - 20℃; for 3.5 h; Inert atmosphere Pyridinium p-toluene sulfonate (10.43 g, 41.5 mmol) was added to a solution of 3-butyn-1-ol (30.0 mL, 396 mmol) and 3,4-dihydro-2H-pyran (37.9 mL, 415 mmol) in CH2Cl2 (150 mL), and the whole was stirred at 0 C for 2 h and then at room temperature for a further 1.5 h. The reaction was quenched with saturated aqueous NaHCO3 solution (150 mL) and the aqueous layer extracted with CH2Cl2 (150 mL). The combined organic extracts were dried (MgSO4), and the solvent removed in vacuo. The residue was purified by distillation (bp 70–102C,24 mm Hg; 96–104 C, 24 mm Hg) to yield the title compound as a pale yellow oil (51.26 g, 84percent); Rf 0.42 [petroleum ether (40–60C)–EtOAc, 5:1]. IR (neat, max, cm-1): 3291, 2941, 2870. 1H NMR (400 MHz, CDCl3, , ppm, J/Hz): 4.54 (1H, t, J = 3.5,H-2), 3.78 (1H, ddd, J = 11.7, 8.4, 3.1, H-6), 3.72 (1H, td, J = 9.7, 7.0, H-6), 3.46 (1H, td, J = 9.7, 7.0, H-1), 3.43–3.38 (1H,m, H-1), 2.38 (2H, td, J = 7.0, 2.6, H-2), 1.89 (1H, t, J = 2.6, H-4), 1.78–1.69 (1H, m, H-3), 1.62 (1H, dt, J = 11.6, 3.5, H-3),1.54–1.38 (4H, m, H-4, 5). 13C NMR (100 MHz, CDCl3, , ppm): 98.6 (CH), 81.3 (C), 69.2 (CH), 65.4 (CH2), 62.0 (CH2),30.4 (CH2), 25.3 (CH2), 19.8 (CH2), 19.3 (CH2). LC-MS (ES+) m/z 155 [M + H]+, [M]+ C9H14O2. Spectral data were consistent with literature values [18].
82% With toluene-4-sulfonic acid In dichloromethane at 25℃; for 24 h; A solution of 3-butyn-1-ol (50 g, 1 equiv, 713 mmol), p-toluenesulfonic acid monohydrate (1.36 g, 0.01 equiv, 7.13 mmol), and dihydropyran (71.7 mL, 1.10 equiv, 785 mmol) in dichloromethane (500 mL) is stirred at 25° C. for 24 hours.
Saturated sodium bicarbonate solution (500 mL) is then slowly added, and the mixture is extracted with dichloromethane (500 mL).
The organic extract is dried over anhydrous sodium sulfate, filtered, and concentrated to afford the crude product, which is purified by vacuum distillation to afford the title compound (90 g, 82percent): b.p.: 65° C., 1 mm Hg.
68% With pyridinium p-toluenesulfonate In dichloromethane at 20℃; for 16 h; To but-3-yn-1-ol (40.0 g, 570.0 mmol) and 3,4-dihydro-2H-pyran (48.0 g, 570.0 mmol) in anhydrous dichloromethane (350 mL) was added pyridium p-toluenesulfonate (0.45 g, 1.80 mmol). The mixture was stirred at room temperature for 16 hours. Solvent was evaporated, and the residue was purified by vacuum distillation to give 2-but-3-ynyloxy-tetrahydro-pyran as a light yellow liquid. Yield: 60.0 g (68percent)
68% With pyridinium p-toluenesulfonate In dichloromethane at 20℃; for 16 h; To but-3-yn-1-ol (40.0 g, 570.0 mmol) and 3,4-dihydro-2H-pyran (48.0 g, 570.0 mmol) in anhydrous dichloromethane (350 mL) was added pyridium p-toluenesulfonate (0.45 g, 1.80 mmol).
The mixture was stirred at room temperature for 16 hours.
Solvent was evaporated, and the residue was purified by vacuum distillation to give 2-but-3-ynyloxy-tetrahydro-pyran as a light yellow liquid. Yield: 60.0 g (68percent).
21.8 g With pyridinium p-toluenesulfonate In dichloromethane at 20℃; for 6 h; Cooling with ice 10.0 g (0.14 mol) of a compound represented by the formula (I-9a) and 1.79 g (7.1 mmol) of pyridinium p-toluenesulfonate were added to a flask and dissolved in 50 mL of dichloromethane. While ice-cooling, a dichloromethane solution of 15.6 g (0.19 mol) of 3,4-dihydro-2H-pyran was added dropwise. After stirring at room temperature for 6 hours, it was washed with saturated aqueous sodium bicarbonate solution and brine. By distilling off the solvent, the compound represented by the formula (I-9b) 21.8 g (0.14 mol) was obtained.

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YieldReaction ConditionsOperation in experiment
76% With sodium periodate; sodium dichromate; nitric acid In waterCooling with ice Preparation 1: Synthesis of 3-butynoic acidOH03-butynoic acid was prepared from the oxidation of 3-butyn-1-oI and following the reported procedure (Schmieder-van de Vondervoort, L. et a., P. L. SynIett2002, 2002, 0243). Water (45 mL) was added to a 150 mL single neck RBF fitted with a magnetic. stirrer bar. 65percent HNO3 (0.17 mL, 5 molpercent, 2.5 mmol), Na2Cr2O7 (0.15 g, I molpercent, 0.5 mmol) and NaIO4 (23.53 g, 2.2 eq., 110 mmol) were subsequently added to the RBF and the mixture was stirredvigorously on an ice bath for 15 mm. 3.78 mL of 3-butyn-1-ol (1 eq., 50 mmol) dissolved in45 mL of chilled water was added to this mixture slowly and the reaction mixture was left for18 — 24 hrs (ice bath was not removed to let the ice melt and temperature of reaction mixturerise slowly to rt). After this time, the product was extracted in diethyl ether (80 mL X 6). All ofthe fractions were combined and dried over anhydrous magnesium sulphate. The solventwas removed usinga rotary evaporator to give an orange/yellowish viscous liquid.Subsequent addition of dichloromethane and removal of solvent on a rotary evaporator (under vacuum) 4-5 times gave 3.20 g of an off white/yellowish solid (38 mmol, yield 76percent).1H NMR (400 MHz, CDCI3) 6 3.38 (d, 2H, J 2.7 Hz), 2,25 (t, IH, J = 2.7 Hz); 13C NMR(400 MHz, CDCI3) 6 173.8, 74.8, 72.4, 25.6
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YieldReaction ConditionsOperation in experiment
95%
Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78 - 0℃; for 0.583333 h; Inert atmosphere
Stage #2: at 0℃; for 0.5 h; Inert atmosphere
A solution of n-BuLi (2.80 mL, 2.60 M, 7.27 mmol) in hexanes was added dropwise to a solution of 6 (0.50 mL, 6.61 mmol) in THF (7.5 mL) at -78 °C. After 5 min at -78 °C, stirring was continued for 30 min at 0 °C. p-TsCl (1.51 g, 7.93 mmol) in THF (8 mL) was added, and the reaction was stirred for 30 min at 0 °C. H2O (2 mL) was added, and the mixture was extracted with Et2O (3.x.10 mL). The combined organic phases were dried (Na2SO4), and the solvent was removed under reduced pressure to give 1.41 g (95percent) of 12 as a pale yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.78 (d, J=8.0 Hz, 2H), 7.33 (d, J=8.0 Hz, 2H), 4.08 (t, J=7.1 Hz, 2H), 2.53 (dt, J=7.1, 2.6 Hz, 2H), 2.43 (s, 3H), 1.95 (t, J=2.6 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 145.0, 132.7, 129.9, 127.9, 78.3, 70.7, 67.4, 21.6, 19.4; IR (neat) 3290, 2962, 2919, 1598, 1359, 1190, 1176, 980, 904, 815 cm-1; mass spectrum (ESI) m/z 247.0399 [C11H12O3S (M+23) requires 247.0400], 471 (base), 247, 225.
95% With dmap; triethylamine In dichloromethane at 0℃; for 4 h; To a stirred solution of 3-butynol (1.47 g, 21.05 mmol), triethylamine (3.5 mL, 25.26 mmol) and 4-dimethylaminopyridine (25 mg, 0.210 mmol) in CH2Cl2 (20 mL) was added p-toluenesulfonyl chloride (4.0 g, 21.05 mmol) at 0 oC. After 4 h, the reaction mixture was quenched with H2O and extracted with CH2Cl2 (2.x.10 mL) and the combined organic extracts were dried over Na2SO4 and concentrated in vacuo. Purification by column chromatography on silica gel (PE/EtOAc, 15:1) gave the product 23 (4.48 g, 95percent) as a pale yellow oil. 1H NMR (300 MHz, CDCl3, d): 7.78 (d, J = 8.1 Hz, 2H), 7.34 (d, J = 7.8 Hz, 2H), 4.08 (t, J = 7.2 Hz, 2H), 2.53 (td, J = 6.9, 2.1 Hz, 2H), 2.43 (s, 3H), 1.96 (d, J = 2.1 Hz, 1H); 13C NMR (75 MHz, CDCl3, d): 145.1, 132.8, 129.9, 128.0, 78.4, 70.8, 67.5, 21.7, 19.4; IR (neat): 3292, 3055, 2962, 2125, 1599, 1359 cm-1; HRMS (ESI) (M + Na)+ calcd for C11H12O3SNa+, 247.0405; found 247.0408.
91% With triethylamine In dichloromethane at 10 - 20℃; Large scale Add 1 (1400g, 19.97mol) and 7L DCM to a 20L four-neck flask; TEA (11038 ml, 27.6 mol) was added at 10° C.,and TsCl (7254 g, 38.04 mol) was added in portions, and the mixture was stirred at room temperature overnight. The NMR showed that 2.33 L of water was added without raw materials, and the aqueous phase was back-extracted once with DCM (1.17 L). The organic phase was combined, washed twice (2*2.73 L), dried over anhydrous magnesium sulfate for 10 minutes, filtered, and spin-dried at 50°C. to obtain a brown-yellow oily liquid 2 of 4081 g in a yield of 91percent.
90% With lithium hydroxide monohydrate In tetrahydrofuran at 20 - 30℃; for 16 h; To a solution of but-3-yn-l-ol (100 g, 1.42 mol) in THF (500 mL) was added L1OH.H2O (89.5 g, 2.13mol) in four portions, followed by the portionwise addition of 4- methylbenzene- 1 -sulfonyl chloride (270 g, 1.42 mol) while maintaining a temperature between 20-30 °C. The resulting mixture was stirred at RT for 16 h, diluted with water (300 mL) and extracted with EtOAc (2 x 300 mL). The combined organic layers were washed with brine (100 ml), dried ( a2S04), filtered and concentrated under reduced pressure to give the title compound as an oil (286 g, 90percent).
88% With dmap; triethylamine In dichloromethane at 0 - 20℃; for 16 h; Inert atmosphere p-TsCl (598 mg, 3.14 mmol was added with stirring to 3-butyn-1-ol (0.22 mL, 2.85 mmol), NEt3 (0.5mL, 3.70 mmol) and 4-(dimethylamino)pyridine (34 mg, 0.28 mmol) in CH2Cl2 (11.5 mL) at 0 °C. After16 h at room temperature, aqueous NaOH (1.0 M; 10 mL) was added and the mixture stirred for a further15 min. The phases were separated and the organic layer diluted with CH2Cl2 (20 mL), washedsequentially with brine (20 mL) and H2O (20 mL), and dried (MgSO4), rotary evaporated andchromatographed (30percent EtOAc in hexanes) to yield sulfonate 39 as a clear colorless oil (564 mg, 88percent).
85% at 15 - 20℃; for 20.3333 h; Butynyl-1-tosylate (24). Method I: A mixture of p-toluenesulfonyl chloride (62.21 g, 0.323 mol) and pyridine (31 mL, 0.383 mol) was warmed to get a colorless solution, and then cooled to get small crystals. 3-Butyn-1-ol (23) (23 mL, 0.29 mol) was added dropwise by syringe during about 20 min with stirring at 15° C. The resulting mixture was stirred below 20° C. under nitrogen atmosphere for 20 h. Water was added with cooling. The mixture was extracted with ethyl acetate (4.x.120 mL). The organic solution was washed with 5percent aqueous sulfuric acid (3.x.120 mL), water (100 mL), 10percent aqueous sodium hydrogen carbonate, brine, dried over sodium sulfate and concentrated. The crude product was purified by flash column chromatography on silica gel (800 g), eluting with ethyl acetate-hexanes (0-10percent) to afford the tosylate 24 (56.13 g) as colorless oil in 85percent yield.11 1H NMR (300 MHz, CDCl3) δ 7.79 (d, J=8.4 Hz, 2H), 7.33 (d, J=8.1 Hz, 2H), 4.08 (t, J=6.9-7.2 Hz, 2H), 2.54 (dt, J=2.7 Hz, J=6.9-7.2 Hz, 2H), 2.43 (s, 3H), 1.94 (t, J=2.7 Hz, 1H).
81% With triethylamine In dichloromethane at 0 - 20℃; for 12 h; Step-1:
Synthesis of but-3-yn-1-yl 4-methylbenzenesulfonate
To a stirred solution of but-3-yn-1-ol (5 g, 0.0714 mmol) in dichloromethane (50 mL) at 0° C. was added triethylamine (10.82 g, 0.107 mmol) and tosyl chloride (13.61 g, 0.0714 mmol).
The reaction mixture was stirred at room temperature for 12 h, after completion of reaction (monitored by TLC), reaction mixture was diluted with dichloromethane.
The organic layer was washed with water, brine and dried over anhydrous Na2SO4 and concentrated under reduced pressure to afford but-3-yn-1-yl 4-methylbenzenesulfonate (13 g, 81percent).
77% With sodium hydroxide In tetrahydrofuran; water at 20℃; for 50.5 h; Method II: A solution of sodium hydroxide (22.53 g, 0.563 mol) in water (200 mL) was added to a mixture of 3-butyn-1-ol (23) (26.76 g, 0.370 mol) and p-toluenesulfonyl chloride (86.3 g, 0.448 mol) in THF (500 mL). The resulting mixture was stirred at room temperature for 50.5 h and concentrated to remove the organic solvent. The residue was extracted with ethyl acetate (3.x.100 mL). The combined organic solution was washed with brine, dried over Na2SO4 and concentrated to afford a residue. The residue was purified by column chromatography on silica gel (200 g), eluting with 0-10percent EtOAc in hexanes, to afford the tosylate 24 (68.70 g) as an oil in 77percent yield.
62% With pyridine In dichloromethane for 12 h; To compound 206A (2.16mL. 28.5mmol) was added CH2Cl2 (95mL), pyridine (3.5mL, 42.8mmol) and TsCl (8.2g, 42.8mmol) and the solution was stirred for 12 hours. Purified solution by flash column chromatography using (30percentEtOAc/hexanes) to yield compound 206B (3.9g, 62percent).
16% With pyridine In dichloromethane at 20℃; for 16 h; Example 78A
but-3-ynyl 4-methylbenzenesulfonate
To a mixture of 3-butyn-1-ol (0.5 g, 8.3 mmol) in CH2Cl2 (20 mL) and pyridine (1.7 mL, 33.2 mmol) was added p-toluenesulfonyl chloride (1.7 g, 8.7 mmol).
This mixture was stirred at ambient temperature for 16 h then diluted with CH2Cl2 (20 mL) and quenched with aqueous 1percent HCl (5 mL).
The layers were separated and the organic layer was washed with aqueous 1percent HCl (5 mL) and brine (5 mL).
The organic layer was dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure and purified via column chromatography (4:1 hexanes:EtOAc) to provide the title compound (0.30 g, 1.3 mmol, 16percent yield). MS (DCI/NH3) m/z 242 (M+NH4)+.
13.52 g With triethylamine In dichloromethane at 0 - 20℃; To 500 ml of dichloromethane, 10.00 g of 3-butyn-1-ol and triethylamine (40 ml) was added and the resulting solution was cooled to 0° C. To the cooled solution, 30.00 g of p-toluenesulfonyl chloride was slowly added and following stifling overnight at room temperature, water was added to the reaction mixture, which was extracted twice with 200 ml of dichloromethane. The organic layer was washed twice with 200 ml of water and dried over magnesium sulfate. After filtering the magnesium sulfate, the organic layer was concentrated and the residue was purified by column chromatography (Wakogel C-200; hexane:ethyl acetate=6:1) to give 13.52 g of an O-tosyl compound.

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  • [ 98-59-9 ]
  • [ 927-74-2 ]
  • [ 23418-85-1 ]
  • [ 554-68-7 ]
YieldReaction ConditionsOperation in experiment
97% at 0 - 20℃; for 21 h; 3-Butyn-1-ol (1.8 g, 25 mmol) was dissolved in methylene chloride (CH2CL2) (40 mL) and triethylamine (ET3N) (4.18 mL, 30 mmol). The solution was stirred at 0°C followed by addition of p-toluenesulfonyl chloride (5.05 g, 26.25 mmol). The reaction was allowed to warm to room temperature over a period of 1 hour and stirring was continued overnight. Thin layer chromatography (TLC) analysis (hexanes/ethyl acetate (EtOAc) 6: 1) after 20 hours of reaction showed a complete consumption OF 3-BUTYN-1-OL. The precipitated triethylamine HYDROCHLORIDC was filtered off and the filtrate washed with water (H20) (30 mL) and brine (30 mL). The organic layer was dried over sodium sulfate (NA2S04) and the solvent evaporated away to give 155 as a light-yellow oil (5.45 g, 97percent). The crude oil was used without further purification; however, it could be purified on a silica gel column, first eluting with 8percent EtOAc in hexanes followed by 40percent EtOAc in hexanes.
Reference: [1] Patent: WO2004/29066, 2004, A2, . Location in patent: Page/Page column 215
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Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2009, vol. 19, # 24, p. 7003 - 7006
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Reference: [1] Organic Letters, 2009, vol. 11, # 20, p. 4548 - 4551
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Reference: [1] Synthesis, 1992, # 1-2, p. 146 - 150
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YieldReaction ConditionsOperation in experiment
67% With potassium phosphate In water; isopropyl alcohol at 80℃; for 20 h; Sealed tube General procedure: In a sealed tube, aryl iodide (1 mmol, 1 equiv.), K3PO4(2 mmol,2 equiv.), catalyst (2 molpercent Pd) were suspended in i-PrOH (3 mL)and H2O (3 mL). The acetylene derivative (1.2 mmol, 1.2 equiv.)was added and the resulting mixture was stirred at 80C for 20 h.After cooling to room temperature, EtOAc (20 mL) and H2O (20 mL)were added and the mixture was filtered over a pad of Celite®.The aqueous layer was extracted twice with EtOAc (2 × 20 mL). Thecollected organics extracts were washed by brine (60 mL), driedon MgSO4, filtered and concentrated under reduced pressure. Thecrude product was purified by flash chromatography.
Reference: [1] Applied Catalysis A: General, 2014, vol. 482, p. 157 - 162
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YieldReaction ConditionsOperation in experiment
90% With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In 1,4-dioxane at 20℃; Inert atmosphere Under nitrogen atmosphere, and at r.t., CuT (0.06 g, 0.31 mmol), dry Et3N (1.32 mL, 9.49 mmol) and bis-(triphenylphosphine)-palladium chloride (0.13 g, 0.18 mmol) were sequentially added to a solution of 2-bromopyridine (0.60 mL, 6.33 mmol) in 1,4-dioxane (10 mL). Then, but-3-yn-1-ol (0.57 mL, 7.59 mmol) was added dropwise at the same temperature.The resulting reaction mixture was left stirred overnight, then concentrated under reduced pressure, dissolved in EtOAc (80 mL) and washed with H20 (3 x 10 mL). The organic layer was dried over Na2504 and concentrated to dryness to give an oily crude (1.1 g). Purification by typical silica gel flash chromatography using a Teledyne ISCO apparatus (Cy/EtOAc from 90:10 to 30:70) afforded the pure title compound (0.84 g, 90percent), as a white solid. R= 1.25 mm. MS(ESI) m/z: 148 EM-H], 170 EM-Na], 186 EM-K]. ‘H NMR (DMSO-d6): ö 8.55—8.49 (m, 1H),7.76 (td, 1H, J= 7.8, 1.8 Hz), 7.44 (d, 1H, J= 7.8 Hz), 7.33 (ddd, 1H, J= 7.8, 4.9, 1.8 Hz), 4.92 (t, 1H, J= 5.2 Hz), 3.62-3.58 (m, 2H), 2.58 (t, 2H, J= 6.8 Hz).
77% at 0 - 70℃; Example 199 ;3 -Methoxy- N -methyl- N -( 4-(pyridin- 2-yl)but - 3 -ynyl)benzamide; 199(A) 4-(Pyridin-2-yl)but-3-yn-1-01; To a suspension of CuI (301 mg, 1.58 mmol) in TEA (40 mL) were added 2- bromopyridine (5 g, 31.6 mmol), followed by Pd2Cl2(PPh3)2 (1.11 g, 1.58 mmol) to give a yellow orange suspension. After cooling down to 0°C under N2, 3-butyn-l-ol (2.28 g, 31.6 mmol) was added. The resulting reaction mixture turned black and it was stirred overnight at 70°C. The reaction mixture was quenched at 0°C with water, TEA was removed under low pressure, and the organic layer was extracted 3x using DCM, washed with Ammonia, water, brine, dried over MgS04, filtered and concentrated. The crude residue was purified over silicagel chromatography (prepacked 250 g silicagel column, DCM/MeOH : from 99/1 to 95/5 as eluent) to afford 3.60 g of 4- (pyridin-2-yl)but-3-yn-1-ol as a brown oil (Yield : 77percent). LCMS (RT) : 1.58min; MS (ES+) gave m/z : 148 Rf (DCM/MeOH : 95/5) =0.23
Reference: [1] Tetrahedron Letters, 2005, vol. 46, # 10, p. 1717 - 1720
[2] Journal of Organic Chemistry, 2003, vol. 68, # 3, p. 762 - 769
[3] Patent: WO2014/144836, 2014, A2, . Location in patent: Paragraph 0526; 0527
[4] European Journal of Organic Chemistry, 2011, # 2, p. 271 - 279
[5] Patent: WO2005/123703, 2005, A2, . Location in patent: Page/Page column 207
[6] Molecules, 2010, vol. 15, # 12, p. 9157 - 9173
[7] Journal of Organic Chemistry, 2003, vol. 68, # 8, p. 3327 - 3329
[8] Bioorganic and Medicinal Chemistry Letters, 2001, vol. 11, # 8, p. 1077 - 1080
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YieldReaction ConditionsOperation in experiment
74%
Stage #1: at 20℃;
Stage #2: at 20 - 80℃; for 20.5 h;
Example 32; 2-(4-(5-PhgpEl-2H-tetrazol-2-yl)but-1-3TY1)pyLidine; 32(A) 4-(Pyridin-2- )but-3-yn-1-ol; In a dry reaction tube containing in suspension iodide copper (38 mg, 0.2 mmol) and triethylamine (11 mL, 80 mmol), were added 2-bromopyridine (632 mg, 4 mmol) and Pd (PPh3)2Cl2 (140 mg, 0.2 mmol). A yellow suspension is obtained and after a few minutes of stirring at room temperature, was added a solution of but-3-yn-1-ol (280 mg, 4 mmol) in triethylamine (2.2 mL). Immediatly the color of the reaction turns to black. The mixture was stirred at room temperature for 30 min and then at 80°C for 20h. Triethylamine was concentrated under reduced pressure and the residue was dissolved in DCM. The organic layer was washed with saturated NH4CI, water and brine, dried (MgS04) and concentrated. The product was purified by flash chromatography (prepacked 15 g silicagel column, from DCM 100percent to DCM/MeOH : 98/2 as eluent) to afford 440 mg of 4-(pyridin-2-yl)but-3-yn-l-ol (Yield : 74percent) as brown oil. Rf:(DCM/MeOH : 95/5) = 0.5 LCMS (RT) : 0.60min; MS (ES+) gave m/z : 148.1
Reference: [1] Patent: WO2005/123703, 2005, A2, . Location in patent: Page/Page column 103-104
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Reference: [1] Green Chemistry, 2018, vol. 20, # 21, p. 4859 - 4864
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Reference: [1] Tetrahedron Letters, 2005, vol. 46, # 10, p. 1717 - 1720
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Reference: [1] Australian Journal of Chemistry, 2008, vol. 61, # 12, p. 930 - 940
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Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2001, vol. 11, # 8, p. 1077 - 1080
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