CN103664553A - Preparation method for 3,3-dimethylbutyraldehyde - Google Patents
Preparation method for 3,3-dimethylbutyraldehyde Download PDFInfo
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- CN103664553A CN103664553A CN201310680405.XA CN201310680405A CN103664553A CN 103664553 A CN103664553 A CN 103664553A CN 201310680405 A CN201310680405 A CN 201310680405A CN 103664553 A CN103664553 A CN 103664553A
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- dimethyl butyrate
- butyrate alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
Abstract
The invention discloses a preparation method for 3,3-dimethylbutyraldehyde. According to the method, under the effect of a catalyst 2,2,6,6-tetramethyl-1-piperidinyloxy free radicals or salts thereof, 3,3-dimethyl-1-butanol and sodium chlorite are subjected to oxidation reaction, so that 3,3-dimethylbutyraldehyde is obtained. The product (3,3-dimethylbutyraldehyde) prepared through the method disclosed by the invention has the advantages that the purity is high, and can reach more than 98.5%, and the yield is high, and can reach more than 80%, and the preparation method is an ideal preparation method for 3,3-dimethylbutyraldehyde, and is suitable for scale production.
Description
Technical field
The present invention relates to technical field of organic synthesis, relate in particular to a kind of 3, the preparation method of 3-dimethyl butyraldehyde.
Background technology
Knob sweet (Neotame) is a kind of novel dipeptide intense sweetener, is the derivative of aspartame, and its stability and use cost are all better than aspartame, has deeply been subject to the concern of World of Food since appearance.In July, 2002, FDA official approval knob is sweet to be used in food.China also ratifies in April, 2003 that knob is sweet to be used in various food, by need of production amount, adds.3,3-dimethyl butyraldehyde is the important intermediate of synthesizing neotame, and its purity and cost directly affect the pure degree of sweet taste and the price that knob is sweet.
The method of existing synthetic 3,3-dimethyl butyraldehyde (DMBA) mainly contains:
Method one: iso-butylene hexenoic acid aqua oxidation method (with reference to US6,573, No. 409 patents, Granted publication day is on June 3rd, 2003), its synthetic route is as follows:
Although the method raw material is easy to get but quite high to production unit requirement, side reaction is many, and product purity is lower.
Method two: palladium hydrogen catalytic reduction butyric acid method (with reference to US2004/0210094 patent, open day is on October 21st, 2004), its synthetic route is as follows:
The method precious metal catalyst used was used not recyclable, and product cost is high.
Method three: hydrogen palladium carbon reduction chloride method (with reference to " synthesising process research of 3,3-dimethyl butyraldehyde ", Xiamen University's journal (natural science edition) 2009, the 48th volume, the 4th phase, 559-563 page), its synthetic route is as follows:
The method normal pressure leads to hydrogen reaction, and reaction conditions is gentleer, but has the acid gas of a large amount of hydrogenchloride discharged to atmosphere, and environmental pollution is serious, and all amounts of hydrogen are very large, and yield is not high.
Method four: hypochlorite oxidation butanols method (with reference to US5,856, No. 584 patents, Granted publication day is on January 5th, 1999), its synthetic route is as follows:
The method yield is higher, can reach 80%, but products obtained therefrom purity is lower, and reaction very exothermic, the more difficult control of large production.
Therefore, find a kind of desirablely 3, the preparation method of 3-dimethyl butyraldehyde is extremely important.
Summary of the invention
For above-mentioned the deficiencies in the prior art, technical problem to be solved by this invention is to provide a kind of high yield, highly purified 3, the preparation method of 3-dimethyl butyraldehyde, the method prepared 3, the yield of 3-dimethyl butyraldehyde can reach more than 80%, purity reaches more than 98.5%, facilitates suitability for industrialized production.
For reaching this object, the present invention by the following technical solutions:
A kind of 3, the preparation method of 3-dimethyl butyraldehyde, the method comprises: under the existence of catalyzer, 3,3-dimethyl butyrate alcohol and Textone generation oxidizing reaction and obtain;
Described catalyzer comprises 2,2,6,6-tetramethyl--piperidino oxyradical or its salt.
In above-mentioned preparation method, as preferably, described 3, the mol ratio of 3-dimethyl butyrate alcohol and Textone is (0.1～1): 1, be preferably (0.3～1): and 1, more preferably (0.5～1): 1.
As preferably, described 2,2,6, the mol ratio of 6-tetramethyl--piperidino oxyradical or its salt and 3,3-dimethyl butyrate alcohol is (0.5～10): 100, be preferably (1～10): and 100, more preferably (3～10): 100.
As preferably, described catalyzer comprises the composite salt of 2,2,6,6-tetramethyl--piperidino oxyradical and Potassium Bromide.
As preferably, described oxidizing reaction is carried out in organic solvent; More preferably, described organic solvent is any one or a few the mixture in heptane, toluene, ethyl acetate or methylene dichloride.
As preferably, the temperature of described oxidizing reaction is-20～30 ℃, more preferably 0～30 ℃, be further preferably 10～30 ℃.
As preferably, the time of described oxidizing reaction is 1～100h, is preferably 2～48h, more preferably 5～24h.
As preferably, described catalyzer also comprises phase-transfer catalyst; More preferably, described phase-transfer catalyst is butyl brometo de amonio.
In preferred specific embodiments, preparation method of the present invention comprises the steps:
(1), by 3,3-dimethyl butyrate alcohol and catalyst mix, be cooled to-15～0 ℃, be preferably-10 ℃; Described catalyzer comprises the composite salt of 2,2,6,6-tetramethyl--piperidino oxyradical and Potassium Bromide, and optionally comprises butyl brometo de amonio;
Preferably, described mixing also comprises the mixing with organic solvent;
(2) in the described mixed solution of step (1), drip NaClO
2the aqueous solution, preferred mass per-cent are 8%～12%, more preferably 10% NaClO
2the aqueous solution, in dropping process, envrionment temperature remains between 0～-5 ℃;
(3) drip and to finish rear continuation and stir, and make temperature remain on-20～30 ℃, be preferably 0～30 ℃, more preferably 10～30 ℃, make 3,3-dimethyl butyrate alcohol and NaClO
2carry out oxidizing reaction, while detecting 3,3-dimethyl butyrate alcohol content≤1% to GC, reaction finishes.
Above-mentioned preparation method also comprise reaction finish after with an organic solvent preferably methylene dichloride extract, then to organic layer wash, concentrate, the step of underpressure distillation.
Of the present invention 3, the preparation method of 3-dimethyl butyraldehyde in the situation as catalyzer, be take Textone as oxygenant at 2,2,6,6-tetramethyl--piperidino oxyradical or its salt, makes 3,3-dimethyl butyrate alcohol generation oxidizing reaction and obtains; Described preparation method's 3, the yield of 3-dimethyl butyraldehyde reaches more than 80%, and purity reaches more than 98.5%, is suitable for suitability for industrialized production.
Embodiment
Embodiment further illustrates technical scheme of the present invention below.In following examples, the method for calculation of yield are: yield=(3 of actual generation, 3-dimethyl butyraldehyde mole number/3, the mole number that feeds intake of 3-dimethyl butyrate alcohol) * 100%.
Embodiment 1
In 2000ml four-hole boiling flask, add 3,3-dimethyl butyrate alcohol 51g(0.5mol) and the composite salt 9.8g(0.05mol of 2,2,6,6-tetramethyl--piperidino oxyradical and Potassium Bromide), be cooled to-10 ℃, start to drip mass percent and be 10% NaClO
2aqueous solution 1357ml(is containing 1.5mol NaClO
2), in dropping process, temperature remains between 0～-5 ℃, drips and finishes rear continuation stirring, is slowly warming up to 25 ℃ and carries out oxidizing reaction, and while detecting 3,3-dimethyl butyrate alcohol content≤1% to GC, reaction finishes; After reaction finishes, to adding methylene dichloride 300ml extraction in reaction solution, then to organic layer wash, concentrate, underpressure distillation, obtain target product 40g, in target product 3,3-dimethyl butyrate aldehyde is 98.5%, yield is 80%.
Embodiment 2
In 5000ml four-hole boiling flask, add 3,3-dimethyl butyrate alcohol 102g(1.0mol), THF500ml and 2,2,6, the composite salt 19.6g(0.1mol of 6-tetramethyl--piperidino oxyradical and Potassium Bromide), be cooled to-10 ℃, start to drip mass percent and be 10% NaClO
2aqueous solution 2714ml(is containing 3molNaClO
2), in dropping process, temperature remains between 0～-5 ℃, drips and finishes rear continuation stirring, is slowly warming up to 25 ℃ and carries out oxidizing reaction, and while detecting 3,3-dimethyl butyrate alcohol content≤1% to GC, reaction finishes; After reaction finishes, to adding methylene dichloride 600ml extraction in reaction solution, then to organic layer wash, concentrate, underpressure distillation, obtain target product 85g, in target product 3,3-dimethyl butyrate aldehyde is 98.5%, yield is 85%.
Embodiment 3
In 5000ml four-hole boiling flask, add 3,3-dimethyl butyrate alcohol 102g(1.0mol), 2,2,6, the composite salt 19.6g(0.1mol of 6-tetramethyl--piperidino oxyradical and Potassium Bromide) and butyl brometo de amonio 10g, be cooled to-10 ℃, start to drip mass percent and be 10% NaClO
2aqueous solution 2714ml(is containing 3molNaClO
2), in dropping process, temperature remains between 0～-5 ℃, drips and finishes rear continuation stirring, is slowly warming up to 25 ℃ and carries out oxidizing reaction, and while detecting 3,3-dimethyl butyrate alcohol content≤1% to GC, reaction finishes; After reaction finishes, to adding methylene dichloride 600ml extraction in reaction solution, then to organic layer wash, concentrate, underpressure distillation, obtain target product 87g, in target product 3,3-dimethyl butyrate aldehyde is 98.6%, yield is 87%.
Embodiment 4
In 2000ml four-hole boiling flask, add 3,3-dimethyl butyrate alcohol 153g(1.5mol) and the composite salt 9.8g(0.05mol of 2,2,6,6-tetramethyl--piperidino oxyradical and Potassium Bromide), be cooled to-10 ℃, start to drip mass percent and be 10% NaClO
2aqueous solution 1357ml(is containing 1.5mol NaClO
2), in dropping process, temperature remains between 0～-5 ℃, drips and finishes rear continuation stirring, is slowly warming up to 30 ℃ and carries out oxidizing reaction, and while detecting 3,3-dimethyl butyrate alcohol content≤1% to GC, reaction finishes; After reaction finishes, to adding methylene dichloride 300ml extraction in reaction solution, then to organic layer wash, concentrate, underpressure distillation, obtain target product 120g, in target product 3,3-dimethyl butyrate aldehyde is 98%, yield is 78.4%.
Embodiment 5
In 5000ml four-hole boiling flask, add 3,3-dimethyl butyrate alcohol 30.6g(0.3mol), THF500ml and 2,2,6, the composite salt 19.6g(0.1mol of 6-tetramethyl--piperidino oxyradical and Potassium Bromide), be cooled to-10 ℃, start to drip mass percent and be 10% NaClO
2aqueous solution 2714ml(is containing 3molNaClO
2), in dropping process, temperature remains between 0～-5 ℃, drips and finishes rear continuation stirring, carries out oxidizing reaction, and while detecting 3,3-dimethyl butyrate alcohol content≤1% to GC, reaction finishes; After reaction finishes, to adding methylene dichloride 600ml extraction in reaction solution, then to organic layer wash, concentrate, underpressure distillation, obtain target product 26g, in target product 3,3-dimethyl butyrate aldehyde is 98%, yield is 85%.
Embodiment 6
In 5000ml four-hole boiling flask, add 3,3-dimethyl butyrate alcohol 102g(1.0mol), 2,2,6, the composite salt 19.6g(0.1mol of 6-tetramethyl--piperidino oxyradical and Potassium Bromide) and butyl brometo de amonio 10g, be cooled to-10 ℃, start to drip mass percent and be 10% NaClO
2aqueous solution 2714ml(is containing 3molNaClO
2), in dropping process, temperature remains between 0～-5 ℃, drips and finishes rear continuation stirring, is slowly warming up to 20 ℃ and carries out oxidizing reaction, and while detecting 3,3-dimethyl butyrate alcohol content≤1% to GC, reaction finishes; After reaction finishes, to adding methylene dichloride 600ml extraction in reaction solution, then to organic layer wash, concentrate, underpressure distillation, obtain target product 85g, in target product 3,3-dimethyl butyrate aldehyde is 99%, yield is 84%.
Applicant statement, the present invention illustrates technical scheme of the present invention by above-described embodiment, but the present invention is not limited to above-described embodiment, does not mean that the technical qualification that the present invention must rely on above-described embodiment could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of the selected raw material of the present invention and ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. one kind 3, the preparation method of 3-dimethyl butyraldehyde, is characterized in that, under the existence of catalyzer, and 3,3-dimethyl butyrate alcohol and Textone generation oxidizing reaction and obtain;
Described catalyzer comprises 2,2,6,6-tetramethyl--piperidino oxyradical or its salt.
2. preparation method according to claim 1, is characterized in that, described 3, and the mol ratio of 3-dimethyl butyrate alcohol and Textone is (0.1～1): 1, be preferably (0.3～1): and 1, more preferably (0.5～1): 1.
3. preparation method according to claim 1 and 2, is characterized in that, described 2,2,6,6-tetramethyl--piperidino oxyradical or its salt and 3, the mol ratio of 3-dimethyl butyrate alcohol is (0.5～10): 100, be preferably (1～10): and 100, more preferably (3～10): 100.
4. according to the preparation method described in claim 1-3 any one, it is characterized in that, described catalyzer comprises the composite salt of 2,2,6,6-tetramethyl--piperidino oxyradical and Potassium Bromide.
5. according to the preparation method described in claim 1-4 any one, it is characterized in that, described oxidizing reaction is carried out in organic solvent;
Preferably, described organic solvent is any one or a few the mixture in heptane, toluene, ethyl acetate or methylene dichloride.
6. according to the preparation method described in claim 1-5 any one, it is characterized in that, the temperature of described oxidizing reaction is-20～30 ℃, is preferably 0～30 ℃, more preferably 10～30 ℃.
7. according to the preparation method described in claim 1-6 any one, it is characterized in that, the time of described oxidizing reaction is 1～100h, is preferably 2～48h, more preferably 5～24h.
8. according to the preparation method described in claim 1-7 any one, it is characterized in that, described catalyzer also comprises phase-transfer catalyst;
Preferably, described phase-transfer catalyst is butyl brometo de amonio.
9. according to the preparation method described in claim 1-8 any one, it is characterized in that, comprise the steps:
(1), by 3,3-dimethyl butyrate alcohol and catalyst mix, be cooled to-15～0 ℃, be preferably-10 ℃; Described catalyzer comprises the composite salt of 2,2,6,6-tetramethyl--piperidino oxyradical and Potassium Bromide, and optionally comprises butyl brometo de amonio;
Preferably, described mixing also comprises the mixing with organic solvent;
(2) in the described mixed solution of step (1), drip NaClO
2the aqueous solution, preferred mass per-cent are 8%～12%, more preferably 10% NaClO
2the aqueous solution, in dropping process, envrionment temperature remains between 0～-5 ℃;
(3) drip and to finish rear continuation and stir, and make temperature remain on-20～30 ℃, be preferably 0～30 ℃, more preferably 10～30 ℃, make 3,3-dimethyl butyrate alcohol and NaClO
2carry out oxidizing reaction, while detecting 3,3-dimethyl butyrate alcohol content≤1% to GC, reaction finishes.
10. according to preparation method described in claim 1-9 any one, it is characterized in that, described method also comprise reaction finish after with an organic solvent preferably methylene dichloride extract, then to organic layer wash, concentrate, the step of underpressure distillation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716305A (en) * | 2022-05-18 | 2022-07-08 | 江苏豪森药业集团有限公司 | Preparation method of alkyl formaldehyde structural compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716305A (en) * | 2022-05-18 | 2022-07-08 | 江苏豪森药业集团有限公司 | Preparation method of alkyl formaldehyde structural compound |
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