CN102276560B - Method for treating aroma of gamma-lactone - Google Patents
Method for treating aroma of gamma-lactone Download PDFInfo
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Abstract
The invention provides a method for treating the aroma of gamma-lactone. The method specifically comprises the following steps of: slowly adding 2 to 10 weight percent of aqueous solution of diluted alkali into crude gamma-lactone which is required to be treated at the temperature of between 0 and 5 DEG C, stirring for 3 to 5 hours at the temperature, standing, separating, removing an aqueous phase, washing an organic phase by using water, and performing vacuum drying to obtain refined gamma-lactone with high-quality aroma.
Description
Technical field
The present invention relates to the perfume processing method of gamma lactone.Relate in particular to and adopt dilute alkaline aqueous solution to handle the perfume processing method of gamma lactone.
Background technology
At present, about synthesizing gamma-lactone shown in the following general formula (1), known for example have acrylate and primary alconol, carries out reacting by heating and make the method for γ-alkyl-gamma-butyrolactone (with reference to Japanese kokai publication sho 51-95058 communique) in the presence of ditertiary butyl peroxide and phosphoric acid salt and/or vitriol; Acrylate and primary alconol are reacted the method (with reference to Japanese kokai publication sho 55-133371 communique) of making γ-alkyl-gamma-butyrolactone in the presence of organo-peroxide and mineral acid and/or organic acid.
In the general formula (1), R
1Expression C
3～C
10Alkyl; R
2Expression hydrogen atom, methyl or ethyl; R
3Expression hydrogen atom or C
1～C
6Alkyl; R
4And R
5Can be identical or different, represent hydrogen atom or methyl separately; R
6Expression H, methyl or ethyl.
But above-mentioned method is owing to be to react in the presence of phosphoric acid salt, vitriol, mineral acid, organic acid, thus the by product of the reaction yield that can exert an influence, and also the processing after the reaction end is also numerous and diverse, so remain to be further improved.
For this reason, the someone has proposed to make pure and mild 2-olefin(e) acid ester to carry out reacting by heating in the presence of organo-peroxide and nitrogenous compound and has made the method for gamma lactone shown in the above-mentioned general formula (1) (with reference to Japanese kokai publication hei 4-275282); And make pure and mild 2-olefin(e) acid ester 1, carry out reacting by heating under the existence of 1-cyclohexane di-tert-butyl peroxide and make the method for gamma lactone shown in the above-mentioned general formula (1) (with reference to Japanese kokai publication hei 4-275282).
But aforesaid method is to carry out in autoclave, causes reaction complicated, and the cost height.Moreover the gamma lactone that aforesaid method obtains has tangible plastics smell or tart flavour, has influenced its quality.
Therefore, the inventor carried out research at the problems referred to above, and submitted to denomination of invention to be " synthesizing gamma-lactone and perfume processing method thereof " on December 24th, 2009 to Patent Office of the People's Republic of China, application number is 200910243871.5 application for a patent for invention.
Be specially, use peroxidized t-butyl perbenzoate, 2-olefin(e) acid shown in the pure and mild following general formula (3) shown in the following general formula (2) or its ester are reacted, under normal pressure, obtained gamma lactone shown in the general formula (1) with high yield and low cost as initiator.
In the general formula (2), R
1Expression C
3～C
10Alkyl; R
2Expression hydrogen atom, methyl or ethyl.
In the general formula (3), R
3Expression hydrogen atom or C
1～C
6Alkyl; R
4And R
5Can be identical or different, represent hydrogen atom or methyl separately; R
6Expression H, methyl or ethyl.
And then the inventor adopts carbonate, supercarbonate, gac, molecular sieve, sodium hydroxide, potassium hydroxide, diatomite etc. that the gamma lactone that aforesaid method obtains is carried out aftertreatment, has obtained removing the high-quality gamma lactone of plastics smell and tart flavour.
Summary of the invention
But the inventor is further finding in the work, because above-mentioned fragrance treatment process need filter out solid processing agent, so be unfavorable in the big industrial application of output.And, when adopting above-mentioned solid processing agent that gamma lactone is carried out the fragrance processing,, influenced yield because a part of gamma lactone is attracted on the solid processing agent.
Therefore, the purpose of this invention is to provide a kind of perfume processing method of gamma lactone, this method is to adopt dilute alkaline aqueous solution to replace solid processing agent.
That is, the invention provides a kind of perfume processing method of gamma lactone, it is characterized in that, comprise the steps:
Mixed processes: under 0～5 ℃, in thick gamma lactone, add dilute alkaline aqueous solution, keep this temperature and stirred 3～5 hours;
Separation circuit: mixed solution is separated into water and organic phase, removes water;
Washing procedure: organic phase is washed with water;
Drying process: the organic phase behind the described washing procedure is carried out drying.
In the fragrance of above-mentioned gamma lactone was handled, described alkali was preferably and is selected from the group of being made up of sodium hydroxide, potassium hydroxide, hydrated barta, calcium hydroxide one or more.
In the fragrance of above-mentioned gamma lactone was handled, the concentration of described dilute alkaline aqueous solution was preferably 2～10wt%.The lower limit of concentration is 3wt% more preferably, and more preferably 4wt% is preferably 5wt% especially, and the upper limit of concentration is preferably 9wt%, and more preferably 8wt% is preferably 7wt% especially, especially is preferably 6wt%.
In above-mentioned mixed processes, with respect to the thick gamma lactone of 100 mass parts, dilute alkaline aqueous solution is preferably 1～3 mass parts in solid content.Especially be preferably about 2 mass parts.
The preferred method that adopts standing separation in above-mentioned separation circuit.
The vacuum drying method of preferred employing in above-mentioned drying process.
By perfume processing method method of the present invention, can and obtain to have removed the high-quality gamma lactone of plastics smell and tart flavour with higher yield with easier method.Be particularly advantageous in industrial big output and make the situation of gamma lactone.
Embodiment
Embodiment
Below, enumerate embodiment and further describe the present invention, but the present invention is not limited to these embodiment.In addition, the present invention is that application number recited above is the continuity of 2009102438715 invention.Therefore, in order to save length, for identical part, for example measuring method etc. is not done duplicate explanation.
About the evaluation of fragrance is to form the first and second the third 3 people's groups, carries out the fragrance evaluation by the mode that nose is heard.Benchmark is as follows.
Zero: do not have plastics smell or tart flavour fully
△: a little plastics smell or tart flavour are arranged
*: plastics smell or tart flavour are heavier
Embodiment 1
Synthesis example 1
Synthesizing of＜γ-propyl group-gamma-butyrolactone 〉
Take into account in the reactor of Dropping feeder in equipment agitator, prolong, temperature, add butanols 444 grams (6.0 moles), be heated backflow, under the condition that keeps this temperature, while stirring with the mixed solution that dripped butanols 148 grams (2.0 moles), methyl acrylate 172g (2.0 moles) and peroxidized t-butyl perbenzoate 116 grams (0.6 mole) in 7 hours, dropwising the back continues to react 3 hours under this temperature, be cooled to room temperature then, reclaim excessive butanols, carry out rectification under vacuum then, obtain thick γ-propyl group-gamma-butyrolactone 150 grams.
＜fragrance is handled example 1 〉
Under 0～5 ℃, take out thick γ-propyl group-gamma-butyrolactone 50 grams that obtain in the above-mentioned synthesis example 1, to wherein slowly adding the sodium hydroxide 5wt% aqueous solution 20 grams, under this temperature, stirred 4 hours, leave standstill then, separate, remove water, organic phase is washed with water vacuum-drying, as a result, fine γ-propyl group-gamma-butyrolactone 49.8 grams of plastics smell and tart flavour have been obtained removing.Carry out the fragrance evaluation, be shown in following table 1.
＜fragrance is handled Comparative Examples 1 〉
Thick γ-the propyl group that obtains in the above-mentioned synthesis example 1 with another part-gamma-butyrolactone 50 grams and solid sodium hydroxide 1.0 restrain 25 ℃ mix 1 hour after, filter out sodium hydroxide.As a result, fine γ-propyl group-gamma-butyrolactone 47 grams of plastics smell and tart flavour have been obtained removing.Carry out the fragrance evaluation, be shown in following table 1.
Table 1
| First | Second | Third | |
| Fragrance is handled example 1 | ○ | ○ | ○ |
| Fragrance is handled Comparative Examples 1 | ○ | ○ | ○ |
Embodiment 2
Synthesis example 2
Synthesizing of＜γ-hexyl-gamma-butyrolactone 〉
Take into account in the reactor of Dropping feeder in equipment agitator, prolong, temperature, add enanthol 348 grams (3.0 moles), be heated 160 ℃, under the condition that keeps this temperature, while stirring with the mixed solution that dripped enanthol 116 grams (1.0 moles), methyl acrylate 86g (1.0 moles) and peroxidized t-butyl perbenzoate 39 grams (0.2 mole) in 7 hours, dropwising the back continues to react 3 hours under this temperature, be cooled to room temperature then, reclaim excessive enanthol, carry out rectification under vacuum then, obtain thick γ-hexyl-gamma-butyrolactone 153 grams.
＜fragrance is handled example 2 〉
Under 0～5 ℃, take out thick γ-hexyl-gamma-butyrolactone 50 grams that obtain in the above-mentioned synthesis example 2, to wherein slowly adding the potassium hydroxide 2wt% aqueous solution 50 grams, under this temperature, stirred 5 hours, leave standstill then, separate, remove water, organic phase is washed with water vacuum-drying, as a result, fine γ-hexyl-gamma-butyrolactone 49.6 grams of plastics smell and tart flavour have been obtained removing.Carry out the fragrance evaluation, be shown in following table 2.
＜fragrance is handled Comparative Examples 2 〉
Thick γ-the hexyl that obtains in the above-mentioned synthesis example 2 with another part-gamma-butyrolactone 50 grams and solid potassium hydroxide 1.0 restrain 25 ℃ mix 1 hour after, filter out potassium hydroxide.As a result, fine γ-hexyl-gamma-butyrolactone 47.4 grams of plastics smell and tart flavour have been obtained removing.Carry out the fragrance evaluation, be shown in following table 2.
Table 2
| First | Second | Third | |
| Fragrance is handled example 1 | ○ | ○ | ○ |
| Fragrance is handled Comparative Examples 1 | ○ | ○ | ○ |
Embodiment 3
Synthesis example 3
Synthesizing of＜γ-amyl group-gamma-butyrolactone 〉
Take into account in the reactor of Dropping feeder in equipment agitator, prolong, temperature, add hexanol 306 grams (3.0 moles), be heated 150 ℃, under the condition that keeps this temperature, while stirring with the mixed solution that dripped hexanol 102 grams (1.0 moles), vinylformic acid 72g (1.0 moles) and peroxidized t-butyl perbenzoate 39 grams (0.2 mole) in 7 hours, dropwising the back continues to react 3 hours under this temperature, be cooled to room temperature then, reclaim excessive enanthol, carry out rectification under vacuum then, obtain thick γ-amyl group-gamma-butyrolactone 140 grams.
＜fragrance is handled example 3 〉
Under 0～5 ℃, take out thick γ-amyl group-gamma-butyrolactone 50 grams that obtain in the above-mentioned synthesis example 3, to wherein slowly adding the hydrated barta 10wt% aqueous solution 10 grams, under this temperature, stirred 3 hours, leave standstill then, separate, remove water, organic phase is washed with water vacuum-drying, as a result, fine γ-amyl group-gamma-butyrolactone 49.3 grams of plastics smell and tart flavour have been obtained removing.Carry out the fragrance evaluation, be shown in following table 3.
＜fragrance is handled Comparative Examples 3 〉
Thick γ-the amyl group that obtains in the above-mentioned synthesis example 3 with another part-gamma-butyrolactone 50 grams and solid hydrogen barium oxide 1.0 restrain 25 ℃ mix 1 hour after, filter out hydrated barta.As a result, fine γ-amyl group-gamma-butyrolactone 47.8 grams of plastics smell and tart flavour have been obtained removing.Carry out the fragrance evaluation, be shown in following table 3.
Table 3
| First | Second | Third | |
| Fragrance is handled example 1 | ○ | ○ | ○ |
| Fragrance is handled Comparative Examples 1 | ○ | ○ | ○ |
Embodiment 4
Synthesis example 4
Synthesizing of＜γ-heptyl-gamma-butyrolactone 〉
Take into account in the reactor of Dropping feeder in equipment agitator, prolong, temperature, add octanol 390 grams (3.0 moles), be heated 160 ℃, under the condition that keeps this temperature, while stirring with the mixed solution that dripped octanol 130 grams (1.0 moles), ethyl propenoate 100g (1.0 moles) and peroxidized t-butyl perbenzoate 39 grams (0.2 mole) in 7 hours, dropwising the back continues to react 3 hours under this temperature, be cooled to room temperature then, reclaim excessive enanthol, carry out rectification under vacuum then, obtain thick γ-heptyl-gamma-butyrolactone 160 grams.
＜fragrance is handled example 4 〉
Under 0～5 ℃, take out thick γ-heptyl-gamma-butyrolactone 50 grams that obtain in the above-mentioned synthesis example, to wherein slowly adding the calcium hydroxide 7wt% aqueous solution 15 grams, under this temperature, stirred 4 hours, leave standstill then, separate, remove water, organic phase is washed with water vacuum-drying, as a result, fine γ-heptyl-gamma-butyrolactone 49.2 grams of plastics smell and tart flavour have been obtained removing.Carry out the fragrance evaluation, be shown in following table 4.
＜fragrance is handled Comparative Examples 4 〉
Thick γ-the heptyl that obtains in the above-mentioned synthesis example 4 with another part-gamma-butyrolactone 50 grams and solid hydrogen calcium oxide 1.0 restrain 25 ℃ mix 1 hour after, filter out calcium hydroxide.As a result, fine γ-heptyl-gamma-butyrolactone 46.8 grams of plastics smell and tart flavour have been obtained removing.Carry out the fragrance evaluation, be shown in following table 4.
Table 4
| First | Second | Third | |
| Fragrance is handled example 1 | ○ | ○ | ○ |
| Fragrance is handled Comparative Examples 1 | ○ | ○ | ○ |
From above table 1～4 as can be seen, when handling gamma lactone with dilute alkaline aqueous solution, compare with situation about handling with corresponding solid alkali, under the situation of guaranteeing high-quality fragrance, yield is higher, and operation is easier.
Industrial applicibility
According to the perfume processing method of gamma lactone of the present invention, can and obtain to have removed the high-quality gamma lactone of plastics smell and tart flavour with higher yield with easier method.The situation that is particularly useful for the big industrial manufacturing high-quality gamma lactone of output.
Claims (4)
1. the perfume processing method of gamma lactone shown in the general formula (1) is characterized in that,
Described gamma lactone is by using peroxidized t-butyl perbenzoate as initiator, 2-olefin(e) acid ester shown in the pure and mild following general formula (3) shown in the following general formula (2) is reacted under normal pressure obtain,
In the general formula (1), R
1Expression C
3～C
10Alkyl; R
2Expression hydrogen atom, methyl or ethyl; R
3Expression hydrogen atom or C
1～C
6Alkyl; R
4And R
5Can be identical or different, represent hydrogen atom or methyl separately,
In the general formula (2), R
1Expression C
3～C
10Alkyl; R
2Expression hydrogen atom, methyl or ethyl,
In the general formula (3), R
3Expression hydrogen atom or C
1～C
6Alkyl; R
4And R
5Can be identical or different, represent hydrogen atom or methyl separately; R
6Expression methyl or ethyl,
Described perfume processing method comprises the steps:
Mixed processes: under 0～5 ℃, in thick gamma lactone, add dilute alkaline aqueous solution, keep this temperature and stirred 3～5 hours;
Separation circuit: mixed solution is separated into water and organic phase, removes water;
Washing procedure: organic phase is washed with water;
Drying process: the organic phase behind the described washing procedure is carried out drying,
Described alkali is to be selected from the group of being made up of sodium hydroxide, potassium hydroxide, hydrated barta, calcium hydroxide one or more,
The concentration of described dilute alkaline aqueous solution is 2～10wt%,
In the described mixed processes, with respect to the thick gamma lactone of 100 mass parts, dilute alkaline aqueous solution is counted 1～3 mass parts with solid content.
2. the perfume processing method of gamma lactone as claimed in claim 1 is characterized in that, in the described mixed processes, with respect to the thick gamma lactone of 100 mass parts, dilute alkaline aqueous solution is counted 2 mass parts with solid content.
3. the perfume processing method of gamma lactone as claimed in claim 1 is characterized in that, adopts the method for standing separation in the described separation circuit.
4. the perfume processing method of gamma lactone as claimed in claim 1 is characterized in that, adopts vacuum drying method in the described drying process.
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