CN102010306B - Method for preparing 3,3-dimethyl butyraldehyde - Google Patents
Method for preparing 3,3-dimethyl butyraldehyde Download PDFInfo
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- CN102010306B CN102010306B CN2010105573355A CN201010557335A CN102010306B CN 102010306 B CN102010306 B CN 102010306B CN 2010105573355 A CN2010105573355 A CN 2010105573355A CN 201010557335 A CN201010557335 A CN 201010557335A CN 102010306 B CN102010306 B CN 102010306B
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- dimethyl
- butyrylchlorine
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a method for preparing 3,3-dimethyl butyraldehyde, which comprises the following steps of: adding an acid-binding agent, a catalyst, an auxiliary catalyst and a solvent into 3,3-dimethyl butyryl chloride, and reacting under a certain pressure of H2 to obtain the 3,3-dimethyl butyraldehyde, wherein the acid-binding agent is from inorganic base or organic base; the catalyst is selected from recyclable precious metals; and the auxiliary catalyst is a metal salt. The method is suitable for the large-scale industrial production of the 3,3-dimethyl butyraldehyde; in the method, the raw materials used are cheap and readily available, the drawback that a large amount of hydrogen is discharged into the atmosphere in a normal-pressure reaction is overcome; and the method is environmentally-friendly; the reaction is compete, the product yield and product purity are high, the post treatment is simple and the production cost is low.
Description
Technical field
The present invention relates to 3, the 3-dimethyl butyraldehyde relates in particular to 3, the preparation method of 3-dimethyl butyraldehyde.
Background technology
Knob sweet (Neotame) is a kind of novel dipeptide intense sweetener, is the verivate of ASPARTAME POWDER BP/USP, and its stability and use cost all are superior to ASPARTAME POWDER BP/USP, have received the concern of world's food circle since the appearance deeply.In July, 2002, FDA official approval knob is sweet to be used in food.China ratifies in April, 2003 also that knob is sweet to be used in various food, add by the production requirement.3,3 dimethyl butyraldehydes are important intermediate of synthesizing neotame, and its purity and cost directly influence pure degree of the sweet sweet taste of knob and price,
Existing synthetic 3, the method for 3-dimethyl butyraldehyde (DMBA) mainly contains:
Method one: iso-butylene hexenoic acid aqua oxidation method (please with reference to US 6,573, No. 409 patents, Granted publication day is on June 3rd, 2003)
Though this method raw material is easy to get but quite high to the production unit requirement, side reaction is many, and product purity is lower.
Method two: palladium hydrogen catalytic reduction butyric acid method (please with reference to No. 2004/0210094 patent of US, open day is on October 21st, 2004)
The used precious metal catalyst of this method was used not recyclable, and product cost is high.
Method three: hypochlorite oxidation butanols method (please with reference to US 5,856, No. 584 patents, Granted publication day is on January 5th, 1999)
This method yield is higher, can reach 80%, but products obtained therefrom purity is lower, and the reaction very exothermic, and big production controlled than difficulty or ease.
Method four: hydrogen palladium carbon reduction chloride method (please with reference to " 3, the synthesising process research of 3-dimethyl butyraldehyde ", Xiamen University's journal (natural science edition) 2009, the 48th volume, the 4th phase, 559-563 page or leaf).
This method normal pressure leads to hydrogen reaction, and reaction conditions is gentle, but the acid gas row of a large amount of hydrogenchloride is arranged to atmosphere, and environmental pollution is serious, and all amounts of hydrogen are very big, and yield is not high.
Therefore find 3 of a kind of low-cost high-purity, the preparation method of 3-dimethyl butyraldehyde is extremely important.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, but a kind of large-scale industrial production 3 of novel practical, the method for 3-dimethyl butyraldehyde are provided.
Provided by the invention 3, the preparation method of 3-dimethyl butyraldehyde, it mainly comprises step: 3, add acid binding agent, catalyzer, cocatalyst, aprotic solvent in the 3-dimethyl-butyrylchlorine, at H
2Pressure is reaction down, obtain said 3, the 3-dimethyl butyraldehyde.Wherein said acid binding agent is selected from mineral alkali or organic bases, and catalyzer is selected from the noble metal of recyclable recycling, and cocatalyst is a metal-salt.
The consumption of said acid binding agent is 3; The 1-2 of 3-dimethyl-butyrylchlorine molar weight times, catalyst consumption is 3, the 1-10% of 3-dimethyl-butyrylchlorine weight; The consumption of cocatalyst is 3; The 3-20% of 3-dimethyl-butyrylchlorine weight, the consumption of solvent are 3, and the 2-10 of 3-dimethyl-butyrylchlorine volume doubly.Said catalyst consumption is preferably 3, the 2-5% of 3-dimethyl-butyrylchlorine weight.
Said H
2Pressure is 10-1000psi, and temperature of reaction is room temperature～200 ℃.Said H
2Pressure is preferably 20-100psi.
Said mineral alkali is selected from least a in salt of wormwood, yellow soda ash, Quilonum Retard, saleratus, the sodium-acetate; Said organic bases is selected from least a in triethylamine, diisopropyl ethyl amine, N-methylmorpholine, DBU, pyridine, picoline, the lutidine.
The noble metal of said recyclable recycling is selected from the anhydrous Pd/C of 5-20%, BaSO
4/ Pd/C, 5-20%Pt/C, PtO
2, at least a among the Ni.
Said metal-salt is selected from CeCl
3, CuCl, MgCl
2, FeCl
2In at least a.
Said aprotic solvent is selected from least a among toluene, YLENE, MTBE, glycol dimethyl ether, dioxane, ETHYLE ACETATE, methyl-phenoxide, DMF, the THF.
Preparing method of the present invention, its reaction equation is:
Method of the present invention is suitable for large-scale commercial prodn 3, the 3-dimethyl butyraldehyde, and this method low in raw material cost is easy to get; A large amount of hydrogen chloride gas were arranged to atmospheric shortcoming when no normal pressure reacted, and are environmentally friendly, react completely, and product yield is high; Purity is high, and aftertreatment is simple, and production cost is low.
For let above and other objects of the present invention, feature and advantage can be more obviously understandable, hereinafter is special lifts preferred embodiment, elaborates as follows.
Embodiment
Embodiment 1
Get 10L high-pressure hydrogenation reaction kettle and add 1L 3,3-dimethyl-butyrylchlorine, 3L dry toluene, 20g 10%Pd/C, 1.2kg salt of wormwood, 40g CeCl three times with the high pure nitrogen displacement
3, twist good reaction kettle, successively with high purity nitrogen displacement three times, High Purity Hydrogen displacement three times, control still internal pressure is 40psi, stirring velocity is 1000 rpms, slowly is warming up to 130 ℃, reacts about 2 hours, no longer inhales the bright reaction of hydrogen meter and finishes.Wait to reduce to the room temperature nitrogen replacement three times, overanxious recovery Pd/C, filtrating is collected 100-105 ℃ of cut with rectifying volumn, gets product 680g, yield 94%, GC 98.7%.
Embodiment 2
Get 10L high-pressure hydrogenation reaction kettle and add 1.5L 3 three times with the high pure nitrogen displacement, 3-dimethyl-butyrylchlorine, the anhydrous dioxane of 3L, 40g 10%Pt/C, 950g anhydrous pyridine, 60g CuCl twist good reaction kettle; With high purity nitrogen displacement three times, High Purity Hydrogen is replaced three times successively, and control still internal pressure is 25psi; Stirring velocity is 1000 rpms; Slowly be warming up to 120 ℃, reacted about 1.5 hours, no longer inhale the bright reaction of hydrogen meter and finish.Wait to reduce to the room temperature nitrogen replacement three times, overanxious recovery Pt/C, filtrating is with 10L5% salt solution flush away solvent, and gained oily matter is used rectifying volumn rectifying, collects 100-105 ℃ of cut, gets product 970g, yield 90%, GC99.2%.
Embodiment 3
Get 10L high-pressure hydrogenation reaction kettle and add 1.5L 3,3-dimethyl-butyrylchlorine, 4L glycol dimethyl ether, 60g 5%Pd/C, 1kg Quilonum Retard, 50g MgCl three times with the high pure nitrogen displacement
2, twist good reaction kettle, successively with high purity nitrogen displacement three times, High Purity Hydrogen displacement three times, control still internal pressure is 60psi, stirring velocity is 1000 rpms, slowly is warming up to 100 ℃, reacts about 4 hours, no longer inhales the bright reaction of hydrogen meter and finishes.Wait to reduce to the room temperature nitrogen replacement three times, overanxious recovery Pd/C, filtrating is with the washing of 15L 5% salt solution, and gained oily matter is collected 100-105 ℃ of cut with rectifying volumn, gets product 950g, yield 88%, GC 99.0%.
Embodiment 4
Get and add 1.5L3,3-dimethyl-butyrylchlorine, 4.55L ETHYLE ACETATE, 30g 5%Pt/C, 1.3kg 2-picoline, 30g FeCl after 10L high-pressure hydrogenation reaction kettle is replaced three times with high pure nitrogen
2, twist good reaction kettle, successively with high purity nitrogen displacement three times, High Purity Hydrogen displacement three times, control still internal pressure is 70psi, stirring velocity is 1000 rpms, slowly is warming up to 120 ℃, reacts about 5.5 hours, no longer inhales the bright reaction of hydrogen meter and finishes.Wait to reduce to the room temperature nitrogen replacement three times, overanxious recovery Pt/C, filtrating is with 10L5% salt solution flush away solvent, and the gained organic layer is used rectifying volumn rectifying, collects 100-105 ℃ of cut, gets product 965g, yield 89.4%, GC 99.4%.
Embodiment 5
Get 10L high-pressure hydrogenation reaction kettle and add 1.5L3,3-dimethyl-butyrylchlorine, 3.5L methyl-phenoxide, 20g 20%Pt/C, 1.2kg sodium-acetate, 45g CeCl three times with the high pure nitrogen displacement
3, twist good reaction kettle, successively with high purity nitrogen displacement three times, High Purity Hydrogen displacement three times, control still internal pressure is 200psi, stirring velocity is 1000 rpms, slowly is warming up to 170 ℃, reacts about 2.5 hours, no longer inhales the bright reaction of hydrogen meter and finishes.Wait to reduce to the room temperature nitrogen replacement three times, overanxious recovery Pt/C, filtrating is with 10L 5% salt solution flush away solvent, and gained oily matter is used rectifying volumn rectifying, collects 100-105 ℃ of cut, gets product 870g, yield 80.6%, GC 99.1%.
Embodiment 6
Get 10L high-pressure hydrogenation reaction kettle and add 1.5L 3,3-dimethyl-butyrylchlorine, 2L DMF (N), 25g 20%Pd/C, 1.35kg DBU (bicyclic amidine), 30gMgCl three times with the high pure nitrogen displacement
2, twist good reaction kettle, successively with high purity nitrogen displacement three times, High Purity Hydrogen displacement three times, control still internal pressure is 170psi, stirring velocity is 1000 rpms, slowly is warming up to 135 ℃, reacts about 4.5 hours, no longer inhales the bright reaction of hydrogen meter and finishes.Wait to reduce to the room temperature nitrogen replacement three times, overanxious recovery Pd/C, filtrating is with 10L 5% salt solution flush away solvent, and gained oily matter is used rectifying volumn rectifying, collects 100-105 ℃ of cut, gets product 920g, yield 85.2%, GC 99%.
Embodiment 7
Get 10L high-pressure hydrogenation reaction kettle and add 1.5L 3,3-dimethyl-butyrylchlorine, 4L THF (THF), 25g PtO three times with the high pure nitrogen displacement
2, 1.5kg diisopropyl ethyl amine, 70FeCl
2, twist good reaction kettle, successively with high purity nitrogen displacement three times, High Purity Hydrogen displacement three times, control still internal pressure is 50psi, stirring velocity is 1000 rpms, slowly is warming up to 90 ℃, reacts about 7.5 hours, no longer inhales the bright reaction of hydrogen meter and finishes.Wait to reduce to the room temperature nitrogen replacement three times, overanxious recovery Pt, filtrating is with 10L 5% salt solution flush away solvent, and gained oily matter is used rectifying volumn rectifying, collects 100-105 ℃ of cut, gets product 870g, yield 80.6%, GC 99.3%.
Embodiment 8
Get 10L high-pressure hydrogenation reaction kettle and add 1.5L 3,3-dimethyl-butyrylchlorine, 4L YLENE, 70g BaSO three times with the high pure nitrogen displacement
4/ Pd/C, 1.7kg yellow soda ash, 50g CuCl twist good reaction kettle, successively with high purity nitrogen displacement three times; High Purity Hydrogen displacement three times, control still internal pressure is 200psi, stirring velocity is 1000 rpms; Slowly be warming up to 180 ℃, reacted about 3.5 hours, no longer inhale the bright reaction of hydrogen meter and finish.Wait to reduce to the room temperature nitrogen replacement three times, overanxious recovery BaSO
4/ Pd/C, filtrating is used rectifying volumn rectifying, collects 100-105 ℃ of cut, gets product 880g, yield 81.5%, GC 98.7%.
Embodiment 9
Get 10L high-pressure hydrogenation reaction kettle and add 1L 3 three times, 3-dimethyl-butyrylchlorine, 4L THF (THF), the blue Buddhist nun Ni of 100g, 900g 2,6-lutidine, 30g CuCl with the high pure nitrogen displacement; Twist good reaction kettle, successively with high purity nitrogen displacement three times, High Purity Hydrogen displacement three times; Control still internal pressure is 75psi, and stirring velocity is 1000 rpms, slowly is warming up to 120 ℃; Reacted about 8.5 hours, and no longer inhaled the bright reaction of hydrogen meter and finish.Wait to reduce to the room temperature nitrogen replacement three times, the blue Buddhist nun Ni of overanxious recovery, filtrating is with 10L 5% salt solution flush away solvent, and gained oily matter is used rectifying volumn rectifying, collects 100-105 ℃ of cut, gets product 610g, yield 85%, GC 99.0%.
Though the present invention discloses as above with preferred embodiment; Right its is not in order to limit the present invention; Any person of ordinary skill in the field; In spirit that does not break away from the present invention and scope, when can doing a little change and improvement, so the present invention's protection domain is as the criterion when looking the claim person of defining.
Claims (7)
1.3 the preparation method of 3-dimethyl butyraldehyde is characterized in that, comprises step:, add acid binding agent, catalyzer, cocatalyst and aprotic solvent in the 3-dimethyl-butyrylchlorine, at H 3
2Pressure is reaction down, obtains saidly 3, and 3-dimethyl butyraldehyde, wherein said acid binding agent are selected from mineral alkali or organic bases, and catalyzer is selected from the noble metal of recyclable recycling, and said noble metal is the anhydrous Pd/C of 5-20%, BaSO
4/ Pd/C, 5-20%Pt/C, PtO
2Or Ni, cocatalyst is a metal-salt, said metal-salt is CeCl
3, CuCl, MgCl
2Or FeCl
2
2. preparation method according to claim 1 is characterized in that, the consumption of said acid binding agent is 3; The 1-2 of 3-dimethyl-butyrylchlorine molar weight times, catalyst consumption is 3, the 1-10% of 3-dimethyl-butyrylchlorine weight; The consumption of cocatalyst is 3; The 3-20% of 3-dimethyl-butyrylchlorine weight, the consumption of aprotic solvent are 3, and the 2-10 of 3-dimethyl-butyrylchlorine volume doubly.
3. preparation method according to claim 2 is characterized in that, said catalyst consumption is 3, the 2-5% of 3-dimethyl-butyrylchlorine weight.
4. according to each described preparation method in the claim 1 to 3, it is characterized in that said H
2Pressure is 10-1000psi, and temperature of reaction is room temperature～200 ℃.
5. preparation method according to claim 4 is characterized in that, said H
2Pressure is 20-100psi.
6. according to each described preparation method in the claim 1 to 3, it is characterized in that said mineral alkali is selected from least a in salt of wormwood, yellow soda ash, Quilonum Retard, saleratus, the sodium-acetate; Said organic bases is selected from least a in triethylamine, diisopropyl ethyl amine, N-methylmorpholine, DBU, pyridine, picoline, the lutidine.
7. according to each described preparation method in the claim 1 to 3; It is characterized in that said aprotic solvent is selected from least a among toluene, YLENE, MTBE, glycol dimethyl ether, dioxane, ETHYLE ACETATE, methyl-phenoxide, DMF, the THF.
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| CN2010105573355A CN102010306B (en) | 2010-11-23 | 2010-11-23 | Method for preparing 3,3-dimethyl butyraldehyde |
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|---|---|---|---|
| CN2010105573355A CN102010306B (en) | 2010-11-23 | 2010-11-23 | Method for preparing 3,3-dimethyl butyraldehyde |
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| CN102010306A CN102010306A (en) | 2011-04-13 |
| CN102010306B true CN102010306B (en) | 2012-12-26 |
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| CN105131081A (en) * | 2015-09-08 | 2015-12-09 | 南京工业大学 | Low-cost high-efficiency neotame preparation method |
| CN109438210B (en) * | 2018-12-05 | 2022-01-07 | 陕西理工大学 | Preparation method of pivalic aldehyde |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5059716A (en) * | 1989-08-23 | 1991-10-22 | Bayer Aktiengesellschaft | Process for the preparation of aldehydes |
| CN1078459A (en) * | 1992-03-03 | 1993-11-17 | 霍夫曼-拉罗奇有限公司 | The preparation method of aldehyde |
| CN1562931A (en) * | 2004-03-25 | 2005-01-12 | 浙江大学 | Method for synthesizing pivalaldehyde |
| CN101250095A (en) * | 2008-04-11 | 2008-08-27 | 中山大学 | Method for preparing 3,3-dimethyl butyladehyde |
-
2010
- 2010-11-23 CN CN2010105573355A patent/CN102010306B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5059716A (en) * | 1989-08-23 | 1991-10-22 | Bayer Aktiengesellschaft | Process for the preparation of aldehydes |
| CN1078459A (en) * | 1992-03-03 | 1993-11-17 | 霍夫曼-拉罗奇有限公司 | The preparation method of aldehyde |
| CN1562931A (en) * | 2004-03-25 | 2005-01-12 | 浙江大学 | Method for synthesizing pivalaldehyde |
| CN101250095A (en) * | 2008-04-11 | 2008-08-27 | 中山大学 | Method for preparing 3,3-dimethyl butyladehyde |
Non-Patent Citations (2)
| Title |
|---|
| Homogeneous Metal-Catalyzed Sequential Rosenmund-Tishchenko Reactions;Vladimir V. Grushin et al.;《The Journal of Organic Chemistry》;19911231;第56卷;第5159-5161页 * |
| Vladimir V. Grushin et al..Homogeneous Metal-Catalyzed Sequential Rosenmund-Tishchenko Reactions.《The Journal of Organic Chemistry》.1991,第56卷第5159-5161页. |
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