CN103922923B - A kind of 2-(4-methoxyphenoxy) industrialized preparing process of Sodium Propionate - Google Patents
A kind of 2-(4-methoxyphenoxy) industrialized preparing process of Sodium Propionate Download PDFInfo
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- C07C51/41—Preparation of salts of carboxylic acids
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- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
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Abstract
The present invention relates to preparation method's technical field of compound, particularly relate to a kind of sweetness inhibitor 2-(4-methoxyphenoxy) industrialized preparing process of Sodium Propionate, with p methoxy phenol and 2-methyl chloropropionate for raw material, under sodium hydroxide and catalyst action, take water as solvent, react 6 ~ 24 hours at 60 ~ 90 DEG C, obtain product 2-(4-methoxyphenoxy) propionic acid; After by 2-(4-methoxyphenoxy) propionic acid and sodium hydroxide puts in ethanol, namely reacting by heating obtains 2-(4-methoxyphenoxy) Sodium Propionate.The present invention take water as solvent, effectively can remove the impurity generated in product, and synthesis, purification process technique are simple, and product purity is high, is applicable to suitability for industrialized production 2-(4-methoxyphenoxy) Sodium Propionate.
Description
Technical field
The present invention relates to the preparing technical field of compound, particularly relate to a kind of 2-(4-methoxyphenoxy) industrialized preparing process of Sodium Propionate.
Background technology
Sugar has very important effect in field of food, it not only can be used as sweeting agent, can also be used as anticorrosion, fresh-keeping, expand, hyperchromic, flavouring, dispersion, loose, bonding sizing etc., have the mouthfeel characteristic of exquisiteness, lubrication, be a kind of indispensable basic raw material in food-processing.When some food lacks sugar, its matter structure is deteriorated, and the quality guaranteed period shortens greatly; But when sugar degree is higher, then had again sweet excessively greasy sensation, and affected the mouthfeel of food, and the appearance of sweetness inhibitor solves the problem of " crossing sweet excessively greasy " just.
2-(4-methoxyphenoxy) Sodium Propionate is one in sweetness inhibitor, be a kind of crude substance be present in coffee berry, its sterling is white crystalline powder shape, tasteless; Be heated and baking in process, even if also very stable under low pH value condition, in shelf life of products, it suppresses the property retention of sugariness constant.1987, U.S.'s seasonings and association of production of flavor manufacturer were to 2-(4-methoxyphenoxy) application of Sodium Propionate in dessert, candy, preserved fruit and frosting assess, and result is shown to be " generally recognized as safe material ".But natural 2-(4-methoxyphenoxy) Sodium Propionate purifying technique complexity, and purification cost of material is higher, the domestic and international chemical preparation process to this material is studied for this reason, US Patent No. 4,544,565 preparation methods devising this kind of material, but the method productive rate is low, and the product purity obtained is low, be difficult to reach the standard used as foodstuff additive; Chinese patent CN200910273148.1 sweetness inhibitor 2-(4-methoxyphenoxy) synthetic method of Sodium Propionate, with p methoxy phenol and 2-chloropropionate for raw material, adopt dehydrated alcohol to make solvent to synthesize, the method purification step is complicated, energy consumption is high, and production cost is high, be unfavorable for suitability for industrialized production.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the object of the present invention is to provide that a kind of reaction conditions is gentle, synthesis and purifying process is simple, cost is low and applicable scale operation 2-(4-methoxyphenoxy) industrial method of Sodium Propionate.
To achieve these goals, technical scheme of the present invention is as follows:
2-(4-methoxyphenoxy) industrialized preparing process of Sodium Propionate, it comprises the steps:
(1) by p methoxy phenol, sodium hydroxide, catalyzer, water be 1:(1 ~ 3 in mass ratio): (0.01 ~ 0.03): the ratio mix and blend of (3 ~ 20), after heating makes the temperature of mixture be increased to 60 DEG C ~ 70 DEG C, drip the 2-methyl chloropropionate relative to quality 1 ~ 2 times amount of p methoxy phenol, namely reaction obtains product 2-(4-methoxyphenoxy) propionic acid;
(2) by 2-(4-methoxyphenoxy) propionic acid, sodium hydroxide is 1:(1 ~ 1.1 according to mol ratio) put in organic solvent, heating for dissolving makes it reaction, obtains 2-(4-methoxyphenoxy) Sodium Propionate.
Preferably, described organic solvent is the one in methyl alcohol, ethanol, acetone or the trimethyl carbinol.
Preferably, the consumption of described organic solvent is 2-(4-methoxyphenoxy) 5 ~ 10 times of propionic acid quality.
Preferably, also comprising after described step (1) described product 2-(4-methoxyphenoxy) propionic acid carries out purification processes, be specially: reacted mixed solution sulphuric acid soln furnishing is acid, cooling, centrifugal, obtain purer 2-(4-methoxyphenoxy) propionic acid; After the reaction taking water as solvent, directly to reaction product adjust ph, to reach the object of purified reaction product, this process operation is simple, and cost is lower.
Preferably, the mass concentration of described sulphuric acid soln is 30% ~ 50%.
Preferably, also comprise described 2-(4-methoxyphenoxy after described step (2)) purification of Sodium Propionate, its concrete technology is recrystallization.
Preferably, described catalyzer is potassiumiodide or sodium iodide.
Preferably, the temperature of the described reaction in described step 1 is 60 DEG C ~ 90 DEG C, and the time of described reaction is 6 ~ 24 hours.
Preferably, the temperature of the described heating for dissolving in described step (2) is 70 DEG C ~ 80 DEG C.
Product 2-(4-methoxyphenoxy of the present invention) structural formula of compound following (I) of Sodium Propionate:
It is by p methoxy phenol (II) and 2-methyl propionate (III) under catalyst action, synthesize in aqueous phase; Recrystallization obtains in organic solvent in the basic conditions subsequently.
Its reaction formula is as follows:
The present invention adopts water to make solvent, reacts in aqueous phase, does not use any organic solvent in this reaction, has saved cost, is also conducive to the purification processes of product simultaneously, and this reaction conditions is gentle, and technique is simple; At end reaction after product directly crystallisation by cooling in organic solvent, eliminate product extraction, the technique such as concentrated, and product purity is high, can reach the standard used as foodstuff additive; This invention simplifies production process in a word, reduce energy consumption, be applicable to large-scale industrial production 2-(4-methoxyphenoxy) Sodium Propionate.
Accompanying drawing explanation
Fig. 1 .2-(4-methoxyphenoxy) Sodium Propionate standard substance HPLC figure;
Fig. 2. the present invention synthesis 2-(4-methoxyphenoxy) Sodium Propionate HPLC figure.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Embodiment 1
A kind of sweetness inhibitor 2-(4-methoxyphenoxy) industrialized preparing process of Sodium Propionate, concrete procedure of processing comprises:
(1) following raw material is got: p methoxy phenol 10kg, sodium hydroxide 10kg, potassiumiodide 0.12kg, water 100kg, join in reaction vessel, stir 30 minutes at normal temperatures, mix and rear this reaction vessel to be heated, above mixed raw material is made to be warming up to 60 DEG C, and make its temperature remain on 60 DEG C ~ 70 DEG C, drip the 2-methyl chloropropionate of 11.85kg wherein, under the effect of catalyzer potassiumiodide, p methoxy phenol and 2-methyl chloropropionate react, keep temperature during reaction at 60 DEG C ~ 90 DEG C, sodium hydroxide acid that is continuous and that produce in reacting simultaneously neutralizes, reaction is carried out towards the direction of positive reaction always, terminate after 12h is carried out in reaction,
(2) product is cooled to normal temperature, the sulphuric acid soln of massfraction 30% is dripped in reacted mixed solution, when to drop to pH of mixed be 2.0, stop dripping, subsequently mixeding liquid temperature is reduced to less than 45 DEG C, centrifugal to mixed solution, namely obtain white solid 2-(4-methoxyphenoxy) propionic acid 14.28kg;
(3) subsequently by the 2-(4-methoxyphenoxy of gained) propionic acid and 3.05kg sodium hydroxide puts in 75kg ethanol; be heated to 75 DEG C subsequently; making 2-(4-methoxyphenoxy) propionic acid and sodium hydroxide dissolves completely; leave standstill subsequently; crystallisation by cooling; centrifugal removing ethanol; obtain white or faint yellow solid; by this white or faint yellow solid in the vacuum drying oven of 60 DEG C ~ 90 DEG C dry 2 hours; obtain white 2-(4-methoxyphenoxy) Sodium Propionate solid 12.52kg, yield is 71.2%;
(4) Product checking: the 2-(4-methoxyphenoxy getting obtained white) Sodium Propionate solid 0.2259g pure water dissolves and is settled to 100mL, upper machine testing after filtering; Wherein
Detecting instrument: Shimadzu SPD-M10AVP detector;
Chromatographic column: Yi Lite post HypersilODS25 μm of 4.6mm*250mm;
Chromatographic condition: moving phase: Yi Jing ︰ pure water (with phosphoric acid adjust pH 4-5)=30 ︰ 70;
Flow velocity: 1.0mL/min;
Sample size: 2 μ L;
As shown in Figure 2, wherein external standard concentration (ESTDconcentration) is 2237.276 μ g/mL to detected result, according to following formula:
Obtaining product purity is thus 99.03%, meets the use standard of foodstuff additive.
Embodiment 2
A kind of sweetness inhibitor 2-(4-methoxyphenoxy) industrialized preparing process of Sodium Propionate, concrete procedure of processing comprises:
(1) p methoxy phenol 10kg, sodium hydroxide 10kg, sodium iodide 0.12kg, water 100kg are added in reaction vessel, stir 30 minutes at normal temperatures, raw material is mixed rear to reaction vessel heating, make mixed raw material thing be warming up to 60 DEG C, and keep mixed material temperature to be 60 DEG C ~ 70 DEG C, add 2-methyl chloropropionate 11.85kg wherein, limit edged stirs, and after having added 2-methyl chloropropionate, continues heating, make temperature of reaction remain on 90 DEG C, terminate after reaction times 12h;
(2) product is cooled to normal temperature, the sulphuric acid soln that massfraction is 50% is dripped in reacted mixed solution, when to drop to pH of mixed be 2.0, stop dripping, centrifugal when subsequently mixeding liquid temperature being brought down below 45 DEG C, namely obtain white solid 2-(4-methoxyphenoxy) propionic acid 13.2kg;
(3) by the 2-(4-methoxyphenoxy of gained) propionic acid and 2.82kg sodium hydroxide puts in 75kg alcoholic solution, the optional methyl alcohol of alcoholic solution herein, ethanol, one in acetone or the trimethyl carbinol, be heated to 70 DEG C ~ 80 DEG C, making 2-(4-methoxyphenoxy) propionic acid and sodium hydroxide dissolves, leave standstill subsequently, crystallisation by cooling, centrifugally slough alcoholic solution, obtain white or faint yellow solid, by this white or faint yellow solid in the vacuum drying oven of 60 DEG C ~ 90 DEG C dry 2 hours, obtain white or flaxen 2-(4-methoxyphenoxy) Sodium Propionate, its quality is 12kg, total recovery is 68%,
(4) Product checking is with embodiment 1, its detected result: product purity >=99.00%, meets the use standard of foodstuff additive.
Comparative example
A kind of sweetness inhibitor 2-(4-methoxyphenoxy) Industrialized synthesis method of Sodium Propionate, specifically comprise the following steps:
First p methoxy phenol 10kg, 2-chloropropionate 12.5kg, salt of wormwood 13kg, catalyzer potassiumiodide or sodium iodide 0.16kg, dehydrated alcohol 65L are added in reaction vessel and mixed, heating reflux reaction is about 6h, cold filtration, filtrate Distillation recovery ethanol;
Ethyl acetate 80L and deionized water 10L is added subsequently in the much filtrate of above-mentioned filtration gained, static layering removes unreacted raw material, collect water layer and water layer food grade hydrochloric acid is adjusted pH to 2.0, a large amount of white solid to be generated, gradation adds the solid in ether dissolution water layer, each 65L, extracts three times altogether, then washed twice to remove residual potassium ion with deionized water 32L again by the ether layer of collection, distillation removing solvent ether obtains white solid 2-(4-methoxyphenoxy) propionic acid;
Then by gained 2-(4-methoxyphenoxy) propionic acid dissolution of solid is in equimolar aqueous sodium hydroxide solution, then under 80 DEG C of conditions vacuum distilling except anhydrating, obtain 2-(4-methoxyphenoxy) Sodium Propionate, its total mass is 10.75kg, productive rate 61.37%, and Product checking to obtain product purity on the low side, be only 95.10%, do not meet the use standard of foodstuff additive.
By the known beneficial effect of the present invention of above Experimental comparison:
(1) adopt water to make solvent, react, do not use any organic solvent in this reaction, saved cost in aqueous phase, be also conducive to the purification processes of product simultaneously, and this reaction conditions is gentle, technique is simple;
(2) in the reaction product taking water as solvent, directly to reaction product adjust ph, can reach the object of purified reaction product, this process operation is simple, and cost is lower;
(3) at end reaction after product directly crystallisation by cooling in organic solvent, eliminate product extraction, the technique such as concentrated, and product purity is high, can reach the standard used as foodstuff additive;
This invention simplifies production process in a word, reduce energy consumption, productive rate is high and product purity is high, is applicable to large-scale industrial production sweetness inhibitor 2-(4-methoxyphenoxy) Sodium Propionate.
Above-described embodiment, just preferred embodiment of the present invention, is not used for limiting the scope of the present invention, therefore all equivalences done with the structure described in the claims in the present invention, feature and principle change or modify, and all should be included within the claims in the present invention scope.
Claims (1)
1. an industrialized preparing process for 2-(4-methoxyphenoxy) Sodium Propionate, is characterized in that, comprise the steps:
(1) by p methoxy phenol 10kg, sodium hydroxide 10kg, potassiumiodide 0.12kg, water 100kg mixes, stir 30 minutes at normal temperatures, heating makes the temperature of mixture be increased to 60 DEG C, and make its temperature remain on 60 DEG C ~ 70 DEG C, drip the 2-methyl chloropropionate of 11.85kg wherein, under the effect of catalyzer potassiumiodide, p methoxy phenol and 2-methyl chloropropionate react, keep temperature during reaction at 60 DEG C ~ 90 DEG C, sodium hydroxide acid that is continuous and that produce in reacting simultaneously neutralizes, reaction is carried out towards the direction of positive reaction always, terminate after 12h is carried out in reaction,
(2) product is cooled to normal temperature, the sulphuric acid soln of massfraction 30% is dripped in reacted mixed solution, when to drop to pH of mixed be 2.0, stop dripping, subsequently mixeding liquid temperature is reduced to less than 45 DEG C, centrifugal to mixed solution, namely obtain white solid 2-(4-methoxyphenoxy) propionic acid;
(3) subsequently 2-(4-methoxyphenoxy) propionic acid of gained and 3.05kg sodium hydroxide are put in 75kg ethanol, be heated to 75 DEG C subsequently, 2-(4-methoxyphenoxy) propionic acid and sodium hydroxide are dissolved completely, leave standstill subsequently, crystallisation by cooling, centrifugal removing ethanol, obtain white or faint yellow solid, by this white or faint yellow solid in the vacuum drying oven of 60 DEG C ~ 90 DEG C dry 2 hours, obtain white 2-(4-methoxyphenoxy) Sodium Propionate solid, product purity is 99.03%.
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| CN104725219B (en) * | 2015-02-11 | 2017-08-08 | 华中农业大学 | The preparation method of S 2 (4 methoxyphenoxy) sodium propionate |
| CN109111355A (en) * | 2018-08-31 | 2019-01-01 | 浙江工业大学 | A kind of chemical synthesis process of (R) -2- phenoxy propionic acid |
| CN113788749A (en) * | 2021-10-26 | 2021-12-14 | 武汉罗化科技有限公司 | Industrial preparation method and application of sweet inhibitor sodium 2- (4-methoxyphenyl) propionate |
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| CN101492359A (en) * | 2009-02-27 | 2009-07-29 | 黄贤明 | Process for producing phenoxy alkane acid derivative |
| CN101735037A (en) * | 2009-12-11 | 2010-06-16 | 华中农业大学 | Synthesis method of sweet taste inhibitor 2-(4- methoxyphenyl) sodium propionate |
| CN102010326A (en) * | 2010-10-28 | 2011-04-13 | 华南理工大学 | Industrial method for synthesizing 2-(4-methoxyphenoxy)-propionic acid through phase transfer |
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| CN101492359A (en) * | 2009-02-27 | 2009-07-29 | 黄贤明 | Process for producing phenoxy alkane acid derivative |
| CN101735037A (en) * | 2009-12-11 | 2010-06-16 | 华中农业大学 | Synthesis method of sweet taste inhibitor 2-(4- methoxyphenyl) sodium propionate |
| CN102010326A (en) * | 2010-10-28 | 2011-04-13 | 华南理工大学 | Industrial method for synthesizing 2-(4-methoxyphenoxy)-propionic acid through phase transfer |
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