CN102241573A - Preparation method of 3,3-methyl butyraldehyde - Google Patents
Preparation method of 3,3-methyl butyraldehyde Download PDFInfo
- Publication number
- CN102241573A CN102241573A CN201010172981XA CN201010172981A CN102241573A CN 102241573 A CN102241573 A CN 102241573A CN 201010172981X A CN201010172981X A CN 201010172981XA CN 201010172981 A CN201010172981 A CN 201010172981A CN 102241573 A CN102241573 A CN 102241573A
- Authority
- CN
- China
- Prior art keywords
- dimethyl
- water
- add
- drop
- butyraldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 3,3-methyl butyraldehyde, which comprises the following steps: (1) reacting to generating ester: putting 3,3-dimethyl butyric acid, ethanol and concentrated sulfuric acid into an enamel still for reacting, separating concentrated sulfuric acid at the lower layer after finishing the reaction, then performing a decompression distillation; (2) reacting to generating alcohol: putting tetrahydrofuran, potassium borohydride, anhydrous lithium chloride and anhydrous aluminium chloride, heating and dropping 3,3-dimethyl ethyl butyrate, refluxing, cooling and stirring by adding water, distilling once again; (3) reacting to generating aldehyde: putting dichloromethane, water, potassium bromide and 3,3-dimethylbutyrate, cooling, then dropping sodium hypochlorite and water, separating a crude 3,3-methyl butyraldehyde solution at the lower layer; (4) purifying aldehyde: putting water and sodium bisulfite into the enamel still, putting the crude 3,3-dimethylutyraldehyde solution, dichloromethane extract and sodium bicarbonate after stirring and dissolving, distilling to obtain the product. The invention has the advantages of simple reaction mechanism, easy control, easy raw material acquisition and low preparation cost.
Description
Technical field
The present invention relates to a kind of 3, the preparation method of 3-dimethyl butyraldehyde.
Background technology
At present, 3, the preparation method of 3-dimethyl butyraldehyde has a variety of, and all there is certain defective in they: raw material is not easy to obtain and preserve, the reaction mechanism more complicated, need high-temperature and high-pressure conditions, therefore have certain danger, reaction process to be difficult to control, be easy to generate by product, cause the waste of the material and the energy, it is higher that high-temperature and high-pressure conditions has also caused the cost of preparation in addition, do not utilize to expand the scale of production.
Summary of the invention
The purpose of this invention is to provide a kind of 3, the preparation method of 3-dimethyl butyraldehyde, the reaction conditions gentleness, preparation cost is lower, and safety relatively.
The object of the present invention is achieved like this: a kind of 3, the preparation method of 3-dimethyl butyraldehyde may further comprise the steps:
(1) reaction generates ester: with 3,3-acid dimethyl, ethanol, the vitriol oil drop into the enamel still reaction, after finishing, reaction tells lower floor's vitriol oil, distill out unnecessary ethanol, carry out underpressure distillation again and obtain 3,3-dimethyl butyrate acetoacetic ester, wherein 3,3-acid dimethyl, ethanol are raw material, and the vitriol oil is a catalyzer;
(2) reaction generates alcohol: in enamel still, drop into tetrahydrofuran (THF), POTASSIUM BOROHYDRIDE, Lithium chloride (anhydrous), Aluminum chloride anhydrous, heat up, drip simultaneously that step (1) obtains 3,3-dimethyl butyrate acetoacetic ester, reflux, distill out tetrahydrofuran (THF) then, cooling adds water and stirs, branch vibration layer, obtain 3,3-dimethyl butyrate alcohol, wherein tetrahydrofuran (THF), 3 after the distillation once more, 3-dimethyl butyrate acetoacetic ester, POTASSIUM BOROHYDRIDE are raw material, and Lithium chloride (anhydrous), Aluminum chloride anhydrous are catalyzer;
(3) reaction generates aldehyde: drop in enamel still that methylene dichloride, water, Potassium Bromide, step (2) obtain 3, the 3-dimethyl butyrate alcohol, the cooling back drips clorox, controlled temperature is below 13 ℃, with dilute acetic acid pH value is regulated in 7～9 simultaneously, added entry, layering after dripping clorox, tell lower coarse 3,3-dimethyl butyraldehyde solution, wherein methylene dichloride, water, 3, the 3-dimethyl butyrate alcohol is a raw material, Potassium Bromide is a catalyzer, and clorox is a chlorizating agent;
(4) purification of aldehyde: in enamel still, drop into water, sodium bisulfite, drop into after the stirring and dissolving that step (3) obtains thick 3,3-dimethyl butyraldehyde solution restir, leave standstill and tell lower floor's waste water, add dichloromethane extraction and stir the back static layering, in enamel still, drop into sodium bicarbonate, obtain 3 after the distillation, the 3-dimethyl butyraldehyde.
In the step of the present invention (1), 3, the mol ratio of 3-acid dimethyl, ethanol, the vitriol oil is 1: 1.11～1.75: 0.005～0.018, described 3, the concentration of 3-acid dimethyl is not less than 99%, and described concentration of ethanol is not less than 95%, and the concentration of the described vitriol oil is not less than 98%; In the described step (2), tetrahydrofuran (THF), POTASSIUM BOROHYDRIDE, Lithium chloride (anhydrous), Aluminum chloride anhydrous, 3, the mol ratio of 3-dimethyl butyrate acetoacetic ester is 2.4～2.6: 0.76～0.97: 0.68～0.86: 0.000004～0.000012: 1; In the described step (3), the methylene dichloride that in enamel still, drops into, water, Potassium Bromide, 3, the mol ratio of 3-dimethyl butyrate alcohol, clorox is 4.2～4.7: 2.2～2.8: 0.5～0.8: 1: 9.3～10.8; In the described step (4), the mol ratio of the water that drops in enamel still, sodium bisulfite, methylene dichloride, sodium bicarbonate is 50～59,1.2～1.42,0.79～1.25,1.26～1.58.
Preferably, when the input raw material reacts in enamel still in the step of the present invention (1), drop into 1 part 3 earlier, the 3-acid dimethyl, 1.11～1.4 parts of ethanol, 0.005～0.009 part of vitriol oil, be warming up to more than 80 ℃ and refluxed 2 hours, leave standstill the branch sub-cloud vitriol oil after the cooling, add 0.005～0.009 part of vitriol oil again, 0.15～0.35 part of ethanol, standing demix after refluxing again 3 hours, tell lower floor's sulfuric acid, being warming up to the still temperature after the layering is 110 ℃～120 ℃, distills out unnecessary ethanol, underpressure distillation to 115 ℃, the vacuum tightness during underpressure distillation be-0.08～-0.09MPa.
Preferably, when the input raw material reacts in enamel still in the step of the present invention (2), drop into 2.4～2.6 parts of content tetrahydrofuran (THF)s earlier, 0.76～0.97 part of POTASSIUM BOROHYDRIDE, 0.68～0.86 part of Lithium chloride (anhydrous), add Aluminum chloride anhydrous again, add for the first time 0.000004 part of Aluminum chloride anhydrous, add 0.000012 part of Aluminum chloride anhydrous after spending 10 minutes again, add 0.000008 part of Aluminum chloride anhydrous after spending 10 minutes again, drip 1 part of ethyl butyrate when being warming up to 50 ℃, when rising to 70 ℃ naturally, temperature refluxes, until recording ethyl butyrate＜5%, taking off tetrahydrofuran (THF) to still temperature then is 85 ℃, vacuumize again that (vacuum tightness is 0.06～0.092MPa), be cooled to 50 degree and drip 8～13.2 parts of water, be stirred to branch vibration layer when not having solid, add 1.3～2.5 parts of water again and 0.07～0.18 part of hydrochloric acid carries out pickling from header tank, intensification is distilled to 120 ℃, and vacuum is deviate from preceding gold-plating again.
Preferably, when the input raw material reacts in enamel still in the step of the present invention (3), drop into when cooling to 5～8 ℃ behind the raw material and begin to drip clorox, the concentration that is used to regulate the dilute acetic acid of pH value is 50%, and the umber that drips clorox is 9.3～10.8, up to recording 3, the mass percent of 3-dimethyl butyrate alcohol＜2% adds layering behind 16.7 parts of water, and wherein lower floor is thick 3,3-dimethyl butyraldehyde solution, upper strata are waste water.
Preferably, when in enamel still, dropping into raw material reaction in the step of the present invention (4), drop into that step (3) obtains thick 3, temperature rises 1～2 ℃ behind the 3-dimethyl butyraldehyde solution, and the time of restir is 1.5 hours, and temperature is 30～35 ℃ of stirrings, the methylene dichloride that adds extraction is 0.79～1.25 part, the time of stirring is 30 minutes, tells lower floor's methylene dichloride after the static layering, with 3, after the aqueous solution of 3-dimethyl butyraldehyde is emitted 450L, in enamel still, drop into 1.26～1.58 parts of sodium bicarbonates, be warmed up to 60 ℃, have carbonic acid gas to emit, with 3,3-dimethyl butyraldehyde suction header tank drips, and rate of addition 100L/10 minute, slowly adds 30～50L water again, stir after all adding and begin to add thermal distillation half an hour, distill out 3 under 80 ℃, the 3-dimethyl butyraldehyde obtains qualified product through after the rectifying again.
Therefore compared with prior art, the present invention has following beneficial effect:
(1) reaction conditions of the present invention is relatively gentleer, do not need high-temperature and high-pressure conditions, so security is higher, and preparation cost is lower, is easy to large-scale production;
(2) raw material ratio of the present invention is easier to obtain and preserve, and reaction mechanism is fairly simple, and reaction process is easy to control, and can not produce by product, can not cause the waste of the material and the energy.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiment, be used for explaining the present invention in this illustrative examples of the present invention and explanation, but not as a limitation of the invention.
Embodiment one
According to the following step preparation 3, the 3-dimethyl butyraldehyde:
(1) reaction generates ester: drop into 1 part 3 earlier, the 3-acid dimethyl, 1.11 part ethanol, 0.005 part sulfuric acid, be warming up to more than 80 ℃ and refluxed 2 hours, leave standstill the branch sub-cloud vitriol oil after the cooling, add 0.005 part of vitriol oil again, 0.15 part ethanol, standing demix after refluxing again 3 hours, tell lower floor's vitriol oil, being warming up to the still temperature after the layering is 110 ℃, distills out unnecessary ethanol, underpressure distillation to 115 ℃ obtains 3,3-dimethyl butyrate acetoacetic ester, the vacuum tightness during underpressure distillation be-0.08Mpa, wherein 3, the concentration of 3-acid dimethyl is not less than 99%, concentration of ethanol is not less than 95%, and the concentration of the vitriol oil is not less than 98%, 3, the 3-acid dimethyl, ethanol is raw material, and the vitriol oil is a catalyzer;
(2) reaction generates alcohol: drop into 2.4 parts of content tetrahydrofuran (THF)s in enamel still, 0.76 part POTASSIUM BOROHYDRIDE, 0.68 part Lithium chloride (anhydrous), add Aluminum chloride anhydrous again, add for the first time 0.000004 part of Aluminum chloride anhydrous, add 0.000012 part of Aluminum chloride anhydrous after spending 10 minutes again, add 0.000008 part of Aluminum chloride anhydrous after spending 10 minutes again, drip 1 part of ethyl butyrate when being warming up to 50 ℃, when rising to 70 ℃ naturally, temperature refluxes, until recording ethyl butyrate＜5%, taking off tetrahydrofuran (THF) to still temperature then is 85 ℃, vacuumize (vacuum tightness is 0.06MPa) again, be cooled to 50 degree and drip 8 parts of water, be stirred to branch vibration layer when not having solid from header tank, add 1.3 parts of water again and 0.07 part of hydrochloric acid carries out pickling, intensification is distilled to 120 ℃, heats up in a steamer before vacuum is deviate from again, obtains 3, the 3-dimethyl butyrate alcohol, tetrahydrofuran (THF) wherein, 3,3-dimethyl butyrate acetoacetic ester, POTASSIUM BOROHYDRIDE is a raw material, Lithium chloride (anhydrous), Aluminum chloride anhydrous is a catalyzer;
(3) reaction generates aldehyde: drop into 4.2 parts of methylene dichloride in enamel still, 2.2 part water, 0.5 part Potassium Bromide, 1 part 3, the 3-dimethyl butyrate alcohol, begin to drip clorox when cooling to 5 ℃, controlled temperature is below 13 ℃, be that 50% dilute acetic acid is adjusted to 7 with pH value with concentration simultaneously, the umber that drips clorox is 9.3, up to recording 3, the mass percent of 3-dimethyl butyrate alcohol＜2%, water stratification after adding 16.7 parts, wherein lower floor is thick 3,3-dimethyl butyraldehyde solution, and the upper strata is a waste water, methylene dichloride wherein, water, 3, the 3-dimethyl butyrate alcohol is a raw material, and Potassium Bromide is a catalyzer, and clorox is a chlorizating agent;
(4) purification of aldehyde: in enamel still, drop into 50 parts of water, 1.2 part sodium bisulfite, drop into after the stirring and dissolving that step (3) obtains thick 3, temperature rises 1 ℃ behind the 3-dimethyl butyraldehyde solution, restir was 1.5 hours when temperature was controlled at 30 ℃ then, tell lower floor's waste water after leaving standstill, add 0.79 part of dichloromethane extraction again and stirred 30 minutes, tell lower floor's methylene dichloride after the static layering, 3, after the aqueous solution of 3-dimethyl butyraldehyde is emitted 450L, in enamel still, drop into 1.26 parts of sodium bicarbonates, be warmed up to 60 ℃, have carbonic acid gas to emit, with 3,3-dimethyl butyraldehyde suction header tank drips, and rate of addition 100L/10 minute, slowly adds 30L water again, stir after all adding and begin to add thermal distillation half an hour, distill out 3 under 80 ℃, the 3-dimethyl butyraldehyde obtains qualified product through after the rectifying again.
Embodiment two
According to the following step preparation 3, the 3-dimethyl butyraldehyde:
(1) reaction generates ester: drop into 1 part 3 earlier, the 3-acid dimethyl, 1.14 part ethanol, 0.009 part sulfuric acid, be warming up to more than 80 ℃ and refluxed 2 hours, leave standstill the branch sub-cloud vitriol oil after the cooling, add 0.005 part of vitriol oil again, 0.35 part ethanol, standing demix after refluxing again 3 hours, tell lower floor's vitriol oil, being warming up to the still temperature after the layering is 120 ℃, distills out unnecessary ethanol, underpressure distillation to 115 ℃ obtains 3,3-dimethyl butyrate acetoacetic ester, the vacuum tightness during underpressure distillation be-0.09Mpa, wherein 3, the concentration of 3-acid dimethyl is not less than 99%, concentration of ethanol is not less than 95%, and the concentration of the vitriol oil is not less than 98%, 3, the 3-acid dimethyl, ethanol is raw material, and the vitriol oil is a catalyzer;
(2) reaction generates alcohol: drop into 2.6 parts of content tetrahydrofuran (THF)s in enamel still, 0.97 part POTASSIUM BOROHYDRIDE, 0.86 part Lithium chloride (anhydrous), add Aluminum chloride anhydrous again, add for the first time 0.000004 part of Aluminum chloride anhydrous, add 0.000012 part of Aluminum chloride anhydrous after spending 10 minutes again, add 0.000008 part of Aluminum chloride anhydrous after spending 10 minutes again, drip 1 part of ethyl butyrate when being warming up to 50 ℃, when rising to 70 ℃ naturally, temperature refluxes, until recording ethyl butyrate＜5%, taking off tetrahydrofuran (THF) to still temperature then is 85 ℃, vacuumize (vacuum tightness is 0.06MPa) again, be cooled to 50 degree and drip 13.2 parts of water, be stirred to branch vibration layer when not having solid from header tank, add 2.5 parts of water again and 0.18 part of hydrochloric acid carries out pickling, intensification is distilled to 120 ℃, heats up in a steamer before vacuum is deviate from again, obtains 3, the 3-dimethyl butyrate alcohol, tetrahydrofuran (THF) wherein, 3,3-dimethyl butyrate acetoacetic ester, POTASSIUM BOROHYDRIDE is a raw material, Lithium chloride (anhydrous), Aluminum chloride anhydrous is a catalyzer;
(3) reaction generates aldehyde: drop into 4.7 parts of methylene dichloride in enamel still, 2.8 part water, 0.8 part Potassium Bromide, 1 part 3, the 3-dimethyl butyrate alcohol, begin to drip clorox when cooling to 8 ℃, controlled temperature is below 13 ℃, be that 50% dilute acetic acid is adjusted to 9 with pH value with concentration simultaneously, the umber that drips clorox is 10.8, up to recording 3, the mass percent of 3-dimethyl butyrate alcohol＜2%, water stratification after adding 16.7 parts, wherein lower floor is thick 3,3-dimethyl butyraldehyde solution, and the upper strata is a waste water, methylene dichloride wherein, water, 3, the 3-dimethyl butyrate alcohol is a raw material, and Potassium Bromide is a catalyzer, and clorox is a chlorizating agent;
(4) purification of aldehyde: in enamel still, drop into 59 parts of water, 1.42 part sodium bisulfite, drop into after the stirring and dissolving that step (3) obtains thick 3, temperature rises 2 ℃ behind the 3-dimethyl butyraldehyde solution, restir was 1.5 hours when temperature was controlled at 35 ℃ then, tell lower floor's waste water after leaving standstill, add 1.25 parts of dichloromethane extractions again and stirred 30 minutes, tell lower floor's methylene dichloride after the static layering, 3, after the aqueous solution of 3-dimethyl butyraldehyde is emitted 450L, in enamel still, drop into 1.58 parts of sodium bicarbonates, be warmed up to 60 ℃, have carbonic acid gas to emit, with 3,3-dimethyl butyraldehyde suction header tank drips, and rate of addition 100L/10 minute, slowly adds 50L water again, stir after all adding and begin to add thermal distillation half an hour, distill out 3 under 80 ℃, the 3-dimethyl butyraldehyde obtains qualified product through after the rectifying again.
Embodiment three
According to the following step preparation 3, the 3-dimethyl butyraldehyde:
(1) reaction generates ester: drop into 1 part 3 earlier, the 3-acid dimethyl, 1.12 part ethanol, 0.006 part sulfuric acid, be warming up to more than 80 ℃ and refluxed 2 hours, leave standstill the branch sub-cloud vitriol oil after the cooling, add 0.006 part of vitriol oil again, 0.2 part ethanol, standing demix after refluxing again 3 hours, tell lower floor's vitriol oil, being warming up to the still temperature after the layering is 115 ℃, distills out unnecessary ethanol, underpressure distillation to 115 ℃ obtains 3,3-dimethyl butyrate acetoacetic ester, the vacuum tightness during underpressure distillation be-0.085Mpa, wherein 3, the concentration of 3-acid dimethyl is not less than 99%, concentration of ethanol is not less than 95%, and the concentration of the vitriol oil is not less than 98%, 3, the 3-acid dimethyl, ethanol is raw material, and the vitriol oil is a catalyzer;
(2) reaction generates alcohol: drop into 2.5 parts of content tetrahydrofuran (THF)s in enamel still, 0.8 part POTASSIUM BOROHYDRIDE, 0.7 part Lithium chloride (anhydrous), add Aluminum chloride anhydrous again, add for the first time 0.000004 part of Aluminum chloride anhydrous, add 0.000012 part of Aluminum chloride anhydrous after spending 10 minutes again, add 0.000008 part of Aluminum chloride anhydrous after spending 10 minutes again, drip 1 part of ethyl butyrate when being warming up to 50 ℃, when rising to 70 ℃ naturally, temperature refluxes, until recording ethyl butyrate＜5%, taking off tetrahydrofuran (THF) to still temperature then is 85 ℃, vacuumize (vacuum tightness is 0.07MPa) again, be cooled to 50 degree and drip 9 parts of water, be stirred to branch vibration layer when not having solid from header tank, add 2 parts of water again and 0.1 part of hydrochloric acid carries out pickling, intensification is distilled to 120 ℃, heats up in a steamer before vacuum is deviate from again, obtains 3, the 3-dimethyl butyrate alcohol, tetrahydrofuran (THF) wherein, 3,3-dimethyl butyrate acetoacetic ester, POTASSIUM BOROHYDRIDE is a raw material, Lithium chloride (anhydrous), Aluminum chloride anhydrous is a catalyzer;
(3) reaction generates aldehyde: drop into 4.5 parts of methylene dichloride in enamel still, 2.5 part water, 0.6 part Potassium Bromide, 1 part 3, the 3-dimethyl butyrate alcohol, begin to drip clorox when cooling to 6 ℃, controlled temperature is below 13 ℃, be that 50% dilute acetic acid is adjusted to 8 with pH value with concentration simultaneously, the umber that drips clorox is 10, up to recording 3, the mass percent of 3-dimethyl butyrate alcohol＜2%, water stratification after adding 16.7 parts, wherein lower floor is thick 3,3-dimethyl butyraldehyde solution, and the upper strata is a waste water, methylene dichloride wherein, water, 3, the 3-dimethyl butyrate alcohol is a raw material, and Potassium Bromide is a catalyzer, and clorox is a chlorizating agent;
(4) purification of aldehyde: in enamel still, drop into 55 parts of water, 1.3 part sodium bisulfite, drop into after the stirring and dissolving that step (3) obtains thick 3, temperature rises 1.5 ℃ behind the 3-dimethyl butyraldehyde solution, restir was 1.5 hours when temperature was controlled at 32 ℃ then, tell lower floor's waste water after leaving standstill, add 1 part of dichloromethane extraction again and stirred 30 minutes, tell lower floor's methylene dichloride after the static layering, 3, after the aqueous solution of 3-dimethyl butyraldehyde is emitted 450L, in enamel still, drop into 1.3 parts of sodium bicarbonates, be warmed up to 60 ℃, have carbonic acid gas to emit, with 3,3-dimethyl butyraldehyde suction header tank drips, and rate of addition 100L/10 minute, slowly adds 40L water again, stir after all adding and begin to add thermal distillation half an hour, distill out 3 under 80 ℃, the 3-dimethyl butyraldehyde obtains qualified product through after the rectifying again.
Embodiment four
According to the following step preparation 3, the 3-dimethyl butyraldehyde:
(1) reaction generates ester: drop into 1 part 3 earlier, the 3-acid dimethyl, 1.3 part ethanol, 0.008 part sulfuric acid, be warming up to more than 80 ℃ and refluxed 2 hours, leave standstill the branch sub-cloud vitriol oil after the cooling, add 0.008 part of vitriol oil again, 0.25 part ethanol, standing demix after refluxing again 3 hours, tell lower floor's vitriol oil, being warming up to the still temperature after the layering is 112 ℃, distills out unnecessary ethanol, underpressure distillation to 115 ℃ obtains 3,3-dimethyl butyrate acetoacetic ester, the vacuum tightness during underpressure distillation be-0.088Mpa, wherein 3, the concentration of 3-acid dimethyl is not less than 99%, concentration of ethanol is not less than 95%, and the concentration of the vitriol oil is not less than 98%, 3, the 3-acid dimethyl, ethanol is raw material, and the vitriol oil is a catalyzer;
(2) reaction generates alcohol: drop into 2.55 parts of content tetrahydrofuran (THF)s in enamel still, 0.9 part POTASSIUM BOROHYDRIDE, 0.8 part Lithium chloride (anhydrous), add Aluminum chloride anhydrous again, add for the first time 0.000004 part of Aluminum chloride anhydrous, add 0.000012 part of Aluminum chloride anhydrous after spending 10 minutes again, add 0.000008 part of Aluminum chloride anhydrous after spending 10 minutes again, drip 1 part of ethyl butyrate when being warming up to 50 ℃, when rising to 70 ℃ naturally, temperature refluxes, until recording ethyl butyrate＜5%, taking off tetrahydrofuran (THF) to still temperature then is 85 ℃, vacuumize (vacuum tightness is 0.07MPa) again, be cooled to 50 degree and drip 10 parts of water, be stirred to branch vibration layer when not having solid from header tank, add 1.5 parts of water again and 0.15 part of hydrochloric acid carries out pickling, intensification is distilled to 120 ℃, heats up in a steamer before vacuum is deviate from again, obtains 3, the 3-dimethyl butyrate alcohol, tetrahydrofuran (THF) wherein, 3,3-dimethyl butyrate acetoacetic ester, POTASSIUM BOROHYDRIDE is a raw material, Lithium chloride (anhydrous), Aluminum chloride anhydrous is a catalyzer;
(3) reaction generates aldehyde: drop into 4.4 parts of methylene dichloride in enamel still, 2.4 part water, 0.7 part Potassium Bromide, 1 part 3, the 3-dimethyl butyrate alcohol, begin to drip clorox when cooling to 7 ℃, controlled temperature is below 13 ℃, be that 50% dilute acetic acid is adjusted to 8.5 with pH value with concentration simultaneously, the umber that drips clorox is 10.5, up to recording 3, the mass percent of 3-dimethyl butyrate alcohol＜2%, water stratification after adding 16.7 parts, wherein lower floor is thick 3,3-dimethyl butyraldehyde solution, and the upper strata is a waste water, methylene dichloride wherein, water, 3, the 3-dimethyl butyrate alcohol is a raw material, and Potassium Bromide is a catalyzer, and clorox is a chlorizating agent;
(4) purification of aldehyde: in enamel still, drop into 56 parts of water, 1.4 part sodium bisulfite, drop into after the stirring and dissolving that step (3) obtains thick 3, temperature rises 1.8 ℃ behind the 3-dimethyl butyraldehyde solution, restir was 1.5 hours when temperature was controlled at 33 ℃ then, tell lower floor's waste water after leaving standstill, add 1.2 parts of dichloromethane extractions again and stirred 30 minutes, tell lower floor's methylene dichloride after the static layering, 3, after the aqueous solution of 3-dimethyl butyraldehyde is emitted 450L, in enamel still, drop into 1.5 parts of sodium bicarbonates, be warmed up to 60 ℃, have carbonic acid gas to emit, with 3,3-dimethyl butyraldehyde suction header tank drips, and rate of addition 100L/10 minute, slowly adds 35L water again, stir after all adding and begin to add thermal distillation half an hour, distill out 3 under 80 ℃, the 3-dimethyl butyraldehyde obtains qualified product through after the rectifying again.
More than the technical scheme that the embodiment of the invention provided is described in detail, used specific case herein the principle and the embodiment of the embodiment of the invention are set forth, the explanation of above embodiment only is applicable to the principle that helps to understand the embodiment of the invention; Simultaneously, for one of ordinary skill in the art, according to the embodiment of the invention, the part that on embodiment and range of application, all can change, in sum, this description should not be construed as limitation of the present invention.
Claims (9)
1. one kind 3, the preparation method of 3-dimethyl butyraldehyde is characterized in that may further comprise the steps:
(1) reaction generates ester: with 3,3-acid dimethyl, ethanol, the vitriol oil drop into the enamel still reaction, after finishing, reaction tells lower floor's vitriol oil, distill out unnecessary ethanol, carry out underpressure distillation again and obtain 3,3-dimethyl butyrate acetoacetic ester, wherein 3,3-acid dimethyl, ethanol are raw material, and the vitriol oil is a catalyzer;
(2) reaction generates alcohol: in enamel still, drop into tetrahydrofuran (THF), POTASSIUM BOROHYDRIDE, Lithium chloride (anhydrous), Aluminum chloride anhydrous, heat up, drip simultaneously that step (1) obtains 3,3-dimethyl butyrate acetoacetic ester, reflux, distill out tetrahydrofuran (THF) then, cooling adds water and stirs, branch vibration layer, obtain 3,3-dimethyl butyrate alcohol, wherein tetrahydrofuran (THF), 3 after the distillation once more, 3-dimethyl butyrate acetoacetic ester, POTASSIUM BOROHYDRIDE are raw material, and Lithium chloride (anhydrous), Aluminum chloride anhydrous are catalyzer;
(3) reaction generates aldehyde: drop in enamel still that methylene dichloride, water, Potassium Bromide, step (2) obtain 3, the 3-dimethyl butyrate alcohol, the cooling back drips clorox, controlled temperature is below 13 ℃, with dilute acetic acid pH value is regulated in 7～9 simultaneously, added entry, layering after dripping clorox, tell lower coarse 3,3-dimethyl butyraldehyde solution, wherein methylene dichloride, water, 3, the 3-dimethyl butyrate alcohol is a raw material, Potassium Bromide is a catalyzer, and clorox is a chlorizating agent;
(4) purification of aldehyde: in enamel still, drop into water, sodium bisulfite, drop into after the stirring and dissolving that step (3) obtains thick 3,3-dimethyl butyraldehyde solution restir, leave standstill and tell lower floor's waste water, add dichloromethane extraction and stir the back static layering, in enamel still, drop into sodium bicarbonate, obtain 3 after the distillation, the 3-dimethyl butyraldehyde.
2. according to claim 13, the preparation method of 3-dimethyl butyraldehyde, it is characterized in that: in the described step (1), 3, the mol ratio of 3-acid dimethyl, ethanol, the vitriol oil is 1: 1.11～1.75: 0.005～0.018, and is described 3, and the concentration of 3-acid dimethyl is not less than 99%, described concentration of ethanol is not less than 95%, and the concentration of the described vitriol oil is not less than 98%.
3. according to claim 23, the preparation method of 3-dimethyl butyraldehyde, it is characterized in that: in the described step (2), tetrahydrofuran (THF), POTASSIUM BOROHYDRIDE, Lithium chloride (anhydrous), Aluminum chloride anhydrous, 3, the mol ratio of 3-dimethyl butyrate acetoacetic ester is 2.4～2.6: 0.76～0.97: 0.68～0.86: 0.000004～0.000012: 1.
4. claim 1 described 3, the preparation method of 3-dimethyl butyraldehyde, it is characterized in that: in the described step (3), the methylene dichloride that drops in enamel still, water, Potassium Bromide, 3, the mol ratio of 3-dimethyl butyrate alcohol, clorox are 4.2～4.7: 2.2～2.8: 0.5～0.8: 1: 9.3～10.8.
5. according to claim 13, the preparation method of 3-dimethyl butyraldehyde, it is characterized in that: in the described step (4), the mol ratio of the water that drops in enamel still, sodium bisulfite, methylene dichloride, sodium bicarbonate is 50～59,1.2～1.42,0.79～1.25,1.26～1.58.
6. according to claim 13, the preparation method of 3-dimethyl butyraldehyde, it is characterized in that: when the input raw material reacts in enamel still in the described step (1), drop into 1 part 3 earlier, the 3-acid dimethyl, 1.11～1.4 parts of ethanol, 0.005～0.009 part of vitriol oil, be warming up to more than 80 ℃ and refluxed 2 hours, leave standstill the branch sub-cloud vitriol oil after the cooling, add 0.005～0.009 part of vitriol oil again, 0.15～0.35 part of ethanol, standing demix after refluxing again 3 hours is told lower floor's sulfuric acid, being warming up to the still temperature after the layering is 110 ℃～120 ℃, distill out unnecessary ethanol, underpressure distillation to 115 ℃, the vacuum tightness during underpressure distillation is-0.08～-0.09MPa.
7. according to claim 13, the preparation method of 3-dimethyl butyraldehyde, it is characterized in that: when the input raw material reacts in enamel still in the described step (2), drop into 2.4～2.6 parts of content tetrahydrofuran (THF)s earlier, 0.76～0.97 part of POTASSIUM BOROHYDRIDE, 0.68～0.86 part of Lithium chloride (anhydrous), add Aluminum chloride anhydrous again, add for the first time 0.000004 part of Aluminum chloride anhydrous, add 0.000012 part of Aluminum chloride anhydrous after spending 10 minutes again, add 0.000008 part of Aluminum chloride anhydrous after spending 10 minutes again, drip 1 part of ethyl butyrate when being warming up to 50 ℃, when rising to 70 ℃ naturally, temperature refluxes, until recording ethyl butyrate＜5%, taking off tetrahydrofuran (THF) to still temperature then is 85 ℃, vacuumize again (vacuum tightness is 0.06～0.092MPa), be cooled to 50 the degree drip 8～13.2 parts of water from header tank, be stirred to branch vibration layer when not having solid, add 1.3～2.5 parts of water again and 0.07～0.18 part of hydrochloric acid carries out pickling, heat up and be distilled to 120 ℃, heat up in a steamer before vacuum is deviate from again.
8. according to claim 13, the preparation method of 3-dimethyl butyraldehyde, it is characterized in that: when the input raw material reacts in enamel still in the described step (3), begin to drip clorox when cooling to 5～8 ℃ behind the input raw material, the concentration that is used to regulate the dilute acetic acid of pH value is 50%, the umber that drips clorox is 9.3～10.8, up to recording 3, the mass percent of 3-dimethyl butyrate alcohol＜2%, add layering behind 16.7 parts of water, wherein lower floor is thick 3,3-dimethyl butyraldehyde solution, and the upper strata is a waste water.
9. according to claim 13, the preparation method of 3-dimethyl butyraldehyde, it is characterized in that: when in enamel still, dropping into raw material reaction in the described step (4), drop into that step (3) obtains thick 3, temperature rises 1～2 ℃ behind the 3-dimethyl butyraldehyde solution, the time of restir is 1.5 hours, temperature is 30～35 ℃ of stirrings, and the methylene dichloride that adds extraction is 0.79～1.25 part, and the time of stirring is 30 minutes, tell lower floor's methylene dichloride after the static layering, with 3, after the aqueous solution of 3-dimethyl butyraldehyde is emitted 450L, in enamel still, drop into 1.26～1.58 parts of sodium bicarbonates, be warmed up to 60 ℃, have carbonic acid gas to emit, with 3,3-dimethyl butyraldehyde suction header tank drips, rate of addition 100L/10 minute, slowly add 30～50L water again, all add back the stirring and begin to add thermal distillation half an hour, under 80 ℃, distill out 3, the 3-dimethyl butyraldehyde obtains qualified product through after the rectifying again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010172981.XA CN102241573B (en) | 2010-05-10 | 2010-05-10 | Preparation method of 3,3-methyl butyraldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010172981.XA CN102241573B (en) | 2010-05-10 | 2010-05-10 | Preparation method of 3,3-methyl butyraldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102241573A true CN102241573A (en) | 2011-11-16 |
| CN102241573B CN102241573B (en) | 2014-06-11 |
Family
ID=44959855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010172981.XA Active CN102241573B (en) | 2010-05-10 | 2010-05-10 | Preparation method of 3,3-methyl butyraldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102241573B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104649874A (en) * | 2013-11-15 | 2015-05-27 | 中国科学院大连化学物理研究所 | Method for preparing 3,3-dimethyl-1-butyraldehyde by 3,3-dimethyl-1-butanol through dehydrogenation |
| CN104974012A (en) * | 2015-07-01 | 2015-10-14 | 广西科技大学 | Preparation method of 3,3-dimethyl butanol |
| CN111450857A (en) * | 2020-05-13 | 2020-07-28 | 江苏帕睿尼新材料科技有限公司 | Catalyst and preparation process of tert-butyl isothiocyanate |
| CN111704912A (en) * | 2020-06-29 | 2020-09-25 | 烟台丰蓬液晶材料有限公司 | Novel preparation method of 3-alkenyl benzyne liquid crystal compound |
| CN112934919A (en) * | 2021-02-05 | 2021-06-11 | 云南大地丰源环保有限公司 | Method for treating waste anhydrous aluminum chloride |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0285786A2 (en) * | 1987-03-03 | 1988-10-12 | Japan Tobacco Inc. | Method of producing alcohols |
| CN1360563A (en) * | 1999-07-02 | 2002-07-24 | 纳特拉斯维特公司 | Process for preparation of 3,3-dimethylbutanal |
| US6825384B1 (en) * | 2004-01-29 | 2004-11-30 | The Nutrasweet Company | Bromine free TEMPO based catalyst system for oxidation of primary and secondary alcohols using NaOCl as an oxidant |
| CN1238320C (en) * | 1997-08-06 | 2006-01-25 | 纽特拉斯威特公司 | Preparation of 3,3-dimethylbutyraldehyde by oxidation of 3,3-dimethylbutanol |
-
2010
- 2010-05-10 CN CN201010172981.XA patent/CN102241573B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0285786A2 (en) * | 1987-03-03 | 1988-10-12 | Japan Tobacco Inc. | Method of producing alcohols |
| CN1238320C (en) * | 1997-08-06 | 2006-01-25 | 纽特拉斯威特公司 | Preparation of 3,3-dimethylbutyraldehyde by oxidation of 3,3-dimethylbutanol |
| CN1360563A (en) * | 1999-07-02 | 2002-07-24 | 纳特拉斯维特公司 | Process for preparation of 3,3-dimethylbutanal |
| US6825384B1 (en) * | 2004-01-29 | 2004-11-30 | The Nutrasweet Company | Bromine free TEMPO based catalyst system for oxidation of primary and secondary alcohols using NaOCl as an oxidant |
Non-Patent Citations (3)
| Title |
|---|
| PIER LUCIO ANELLI ET AL.: "Fast and Selective Oxidation of Primary Alcohols to Aldehydes or to Carboxylic Acids and of Secondary Alcohols to Ketones Mediated by Oxoammonium Salts under Two-Phase Conditions", 《J. ORG. CHEM.》 * |
| TSUTOMU INOKUCHI ET AL.: "A Selective and Efficient Method for Alcohol Oxidations Mediated by N-Oxoammonium Salts in Combination with Sodium Bromite", 《J. ORG. CHEM.》 * |
| 魏志勇等: "纽甜的应用及研究进展", 《食品工业科技》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104649874A (en) * | 2013-11-15 | 2015-05-27 | 中国科学院大连化学物理研究所 | Method for preparing 3,3-dimethyl-1-butyraldehyde by 3,3-dimethyl-1-butanol through dehydrogenation |
| CN104974012A (en) * | 2015-07-01 | 2015-10-14 | 广西科技大学 | Preparation method of 3,3-dimethyl butanol |
| CN111450857A (en) * | 2020-05-13 | 2020-07-28 | 江苏帕睿尼新材料科技有限公司 | Catalyst and preparation process of tert-butyl isothiocyanate |
| CN111450857B (en) * | 2020-05-13 | 2023-06-13 | 江苏帕睿尼新材料科技有限公司 | Catalyst and preparation process of tert-butyl isothiocyanate |
| CN111704912A (en) * | 2020-06-29 | 2020-09-25 | 烟台丰蓬液晶材料有限公司 | Novel preparation method of 3-alkenyl benzyne liquid crystal compound |
| CN112934919A (en) * | 2021-02-05 | 2021-06-11 | 云南大地丰源环保有限公司 | Method for treating waste anhydrous aluminum chloride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102241573B (en) | 2014-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102241573B (en) | Preparation method of 3,3-methyl butyraldehyde | |
| CN102276464B (en) | Method for producing methyl acetoacetate | |
| CN102675359B (en) | Preparation method of triethyl phosphate | |
| CN101643397B (en) | Preparation method of cyclopropyl methyl ketone and bicyclo-propyl ketone | |
| CN106699511A (en) | Method for recycling inorganic/organic matters from glycerin chlorination distillate | |
| CN105037139A (en) | Preparation method for 2-phenylpropionic acid | |
| CN104478719B (en) | A kind of preparation method of 4-methoxyl group methyl acetoacetate | |
| CN105037138A (en) | Preparation method for 2,9-dibutyl sebacate | |
| CN104892389B (en) | Technique for preparing oxalic acid by performing continuous reaction rectification hydrolysis on dimethyl oxalate | |
| CN104311399A (en) | Method for converting estragole into trans-anethole | |
| CN103951547B (en) | M-fluorophenol preparation method | |
| CN204303239U (en) | A kind ofly promote the chemical experiment device that Synthesis Diethyl ether reaction forward is carried out | |
| CN103012059A (en) | Novel process for reducing consumption of formaldehyde in production of neopentyl glycol | |
| CN103664835A (en) | Preparation method of biological plasticizing agent epoxidized fatty acid methyl ester | |
| CN102718654A (en) | Preparation method of a-cyclopentyl methyl mandelate | |
| CN105523902B (en) | The preparation method of 2 chloroethyl propyl ethers | |
| CN103848879B (en) | A kind of with Isosorbide-5-Nitrae-Androstenedione for the method for Progesterone prepared by raw material | |
| CN104649866A (en) | Safe, reliable and low-cost preparation method of 9-fluorenylmethanol | |
| CN103641735B (en) | The co-production of Paracetamol and butylacetate | |
| CN101817507B (en) | Method for recovering hydrogen chloride gas during production of triethyl orthoformate | |
| CN103319447B (en) | Xanthene-9-carboxylic acid preparation method | |
| CN103709043A (en) | Method for preparing 2-(4-chlorophenyl)ethylamine | |
| CN112408327A (en) | Method and device for preparing electronic-grade germane and co-producing electronic-grade tetrafluorogermane | |
| CN103387556A (en) | Synthetic method for alpha-acetyl-gamma-butyrolactone | |
| CN103554019A (en) | Synthetic method of tilbroquinol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: SHAANXI TIANHAN BIOTECH CO., LTD. Free format text: FORMER OWNER: SHAANXI TANGZHENG SCI-TECH DEVELOPMENT CO., LTD. Effective date: 20120913 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20120913 Address after: 723300 people's road, Chengxi, Yangxian County, Shaanxi, Hanzhoung Applicant after: SHAANXI TANGZHENG TECHNOLOGY DEVELOPMENT CO.,LTD. Address before: 723300 people's road, Chengxi, Yangxian County, Shaanxi, Hanzhoung Applicant before: Shaanxi Tangzheng Technology Development Co.,Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |