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CAS No. : | 126-86-3 | MDL No. : | MFCD00008942 |
Formula : | C14H26O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | LXOFYPKXCSULTL-UHFFFAOYSA-N |
M.W : | 226.36 | Pubchem ID : | 31362 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P501-P260-P264-P280-P314-P337+P313 | UN#: | N/A |
Hazard Statements: | H319-H373 | Packing Group: | N/A |
GHS Pictogram: |
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* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With hydrazine hydrate; In ethanol; at 20 - 80℃; for 24.0h; | 2,4,7,9-tetramethyl-5-yne-4,7-decanediol (1.13 g, 5 mmol), hydrazine mass percentage concentrationThe reaction was heated to 80 C for 24 hours. The reaction was stopped, the reaction was cooled to room temperature, and the ethanol was distilled off under reduced pressure. The reaction mixture was cooled to 80 C, , With 10 ml of dichloromethane dissolved, 5 ml of water 2 washing, drying at room temperature with anhydrous sodium sulfate 2h, filter desiccant, the solvent evaporated to get viscous liquid (Z) -2,4,7,9- 4,7-decanediol; dissolving the viscous liquid with 2 mL of methylene chloride, over a silica gel column, eluting with methylene chloride / ethyl acetate (4/1 by volume)To give (Z) -2,4,7,9-tetramethyl-5-ene-4,7-decanediol as a pure product1.06 g, yield 99%. |
227 mg | With [1,3-bis(2,6-di-iso-propylphenyl)imidazol-2-ylidene]copper(I) tert-butoxide; tert-butyl alcohol; In toluene; at 40℃; for 8.0h;Inert atmosphere; Glovebox; | General procedure: 4.4 General procedure for the reduction of internal alkynes In a nitrogen-filled glovebox, a 1-dram vial was charged with a stir bar followed by the alkyne (1.00equiv, 1.00mmol), PMHS 8 (2.00equiv, 120mg, 2.00mmol), and tert-butanol (2.50equiv, 185mg, 2.50mmol). This mixture was diluted in toluene (2mL) before adding IPrCuOt-Bu 14 (0.020equiv, 11mg, 0.020mmol). The reaction mixture was stirred at 40C until complete conversion of the starting material was achieved (8h). The mixture was then diluted with hexanes (20mL), and filtered through a silica gel plug using a 1:1 ethyl acetate/hexane solution (100mL). The filtrate was concentrated under vacuum, and the crude reaction products were purified using a 10g silica gel column (see selected examples below for mobile phase used). 4.4.1.1 (Z)-2,4,7,9-Tetramethyldec-5-ene-4,7-diol (47) Compound was isolated as a white solid (227 mg, 99% yield) after a THF/NaOH workup followed by silica gel chromatography (0-40% ethyl acetate/hexanes over eight column volumes). 1H NMR (300 MHz, CDCl3) delta 5.30 (s, 2H), 4.32 (s, 2H), 1.83 (qt, J=12.9, 6.4 Hz, 2H), 1.51 (d, J=6.0 Hz, 4H), 1.34 (s, 6H), 0.96 (d, 4.7 Hz, 6H), 0.94 (d, J=6.6, 6H). 13C NMR (126 MHz, CDCl3) delta 135.4, 74.1, 52.8, 31.0, 24.9, 24.8, 24.7. HRMS calculated for [M+Na]+ 251.1987, found 251.1991. FTIR (neat, cm-1): 3219 (br), 3004 (w), 2954 (s), 1158 (s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84.1% | With potassium hydroxide; In cyclohexane; at 40 - 45℃; under 750.075 Torr; for 5.5h;Autoclave; Inert atmosphere; | The concentrated alkali liquor in Example 1 was dehydrated under reduced pressure to obtain 14 g of a paste.The paste was mixed with 10 g of a novel complex catalyst, 100 g of methyl isobutyl ketone, 40 g of cyclohexane, and 31 g of diethylene glycol divinyl ether distilled in Example 1, and put into a 500-mL autoclave.Replace air with nitrogen, control temperature 40~45C, pass acetylene into the reaction system for acetylene reaction, keep the system pressure no higher than 0.1MPa,When 11.7 g of acetylene was passed, the pressure of the system was maintained for 10 min and no longer decreased, and the reaction was stopped. At this point, the reaction had been completed for 5.5 h.After cooling down to room temperature, the reaction solution in the autoclave was transferred to a 500 mL beaker and 10 g of deionized water was added to the beaker. The system was divided into two layers.26 g of concentrated lye containing lower lye was separated and transferred to a 250 mL beaker. The organic layer was neutralized with 20% phosphoric acid solution to pH 6-7. The brine was separated to obtain 190 g of organic phase.The organic phase was transferred to a 250 mL three-necked flask, and 17 g of the semi-finished acetylene glycol product of Example 1 was introduced. 37 g of cyclohexane was distilled out at normal pressure and distilled under reduced pressure.At a vacuum of -0.098 MPa, 1.5 g of a low-boiling substance was obtained at 60C, 31 g of a fore fraction was obtained at 60 to 90C, and 28 g of diethylene glycol divinyl ether was obtained at 90 to 120C.120 g of the acetylene glycol semi-finished product was obtained at 120 to 150 C., and 85.5 g of the acetylene glycol product was collected at 150 to 155 C. The heating was stopped, and the temperature was lowered to room temperature. 2 g of the high-boiling residue was left in the beaker.The yield of finished acetylenic diol (relative to acetylene) was 84.1%. Weigh 20g of potassium hydroxide and 200 diethylene glycol divinyl ether in a 500mL three-necked flask, heat to 60C to stir the reaction, and stop the reaction when potassium hydroxide is completely dissolved.The above-prepared complex catalyst is weighed out by weighing 50 g with 100 g of methyl isobutyl ketone, 50 g of cyclohexane, and put into a 500-mL high-pressure experimental kettle to make a bottom, nitrogen is substituted for air, and the temperature is controlled at 40-45 C.Acetylene was introduced into the reaction system for acetylene reaction to maintain the pressure of the system not higher than 0.1 MPa. When acetylene was introduced to 10.4 g, the pressure of the system was maintained for 10 min and no longer decreased, and the reaction was stopped. At this time, the reaction had been performed for 6 h.After cooling down to room temperature, the reaction solution in the autoclave was transferred to a 500 mL beaker. 10 g of deionized water was added to the beaker, and the system was divided into two layers. The concentrated lye containing 23 g of the lower oxime was separated and transferred to a 250 mL beaker. The organic layer was neutralized to pH 6~7 with a 20% phosphoric acid solution, and the brine layer was separated to obtain 185 g of an organic phase.The organic phase was transferred to a 250 mL three-necked flask, and 46 g of cyclohexane was distilled off at normal pressure, followed by distillation under reduced pressure. At a pressure of -0.098 MPa, 1 g of a low-boiling substance was obtained at 60C, 18 g of a fore fraction was obtained at 60 to 90C, and 31 g of diethylene glycol divinyl ether was obtained at 90 to 120C.A acetylene glycol semi-finished product of 17 g was obtained at 120 to 150 C., 69 g of acetylene glycol product was collected at 150 to 155 C., heating was stopped, and the temperature was lowered to normal temperature, and 3 g of the high-boiling residue was left in the beaker.The yield of finished acetylenic diol (relative to acetylene) was 76.3%. |