CN1156427C - Preparation method of malonic acid and its ester - Google Patents
Preparation method of malonic acid and its ester Download PDFInfo
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- CN1156427C CN1156427C CNB011414057A CN01141405A CN1156427C CN 1156427 C CN1156427 C CN 1156427C CN B011414057 A CNB011414057 A CN B011414057A CN 01141405 A CN01141405 A CN 01141405A CN 1156427 C CN1156427 C CN 1156427C
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- propanedioic
- propanedioic acid
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Abstract
The present invention relates to a simple industrialization method for obtaining malonic acid and ester with high yield and high purity by cyanide radical calcium acetate. The method comprises the steps as follows: I) the cyanide radical calcium acetate is carried out with alkaline hydrolysis by the calcium hydroxide of a water solution to obtain a malonate calcium solution; II) the obtained malonic acid calcium solution is acidized and hydrolyzed by strong inorganic acid to generate malonic acid; III) optionally, in the existence of a protonic acid catalyst, separated malonic acid adopts alcohol to esterify to obtain malonic ester.
Description
Invention field
The present invention relates to via cyanoacetic acid calcium, high yield, high purity ground obtains the simpler industrial method of propanedioic acid and ester thereof.
Background of invention
Propanedioic acid and ester thereof are the industrial raw material that is widely used in medicine, agricultural chemicals and makeup.
Propanedioic acid can become sodium malonate with the sodium hydroxide alkaline hydrolysis by cyanoacetic acid sodium, the hydrolysis and preparing in the presence of strong acid such as sulfuric acid of the product of gained.Malonic ester then can become cyanoacetic acid with hcl acidifying by cyanoacetic acid sodium, the latter prepare producing acid hydrolysis in the presence of the alcohol of required ester (referring to, " industrial organic synthesis basis ", the 412nd page, Yang Jinzong, Sinopec press, in December, 1998).In addition, also can obtain by this conventional route of the esterification that relates to propanedioic acid.
In addition, WO99/08988, JP-A-59-7135, JP-A-59-7136, JP-B-55-41227, US-A-2337858 also disclose by the hydrolysis in the presence of strong acid such as sulfuric acid, hydrochloric acid of cyanoacetic acid or its salt such as sodium salt, produce the method for propanedioic acid or its ester.
JP-B-53-127411 discloses malonamide nitrile calcium hydroxide basic hydrolysis, prepares the method for propanedioic acid afterwards with sulfuric acid acidation.
(A.H.Blatt compiles " organic synthesis collected works " [Organic Syntheses Collective]-second volume, John Wiley, New York, nineteen forty-three) discloses by the cyanoacetic acid alkaline hydrolysis in the 376th page, obtain malonate, and, generate propanedioic acid calcium this salt and calcium chloride reaction.Afterwards, this calcium salt is also used organic solvent extraction by the mode of acidolysis, provide free salt.
Yet disclosed method is still needing to improve aspect yield, product purity, acid consumption and the aftertreatment in these documents.Therefore, still need a kind of better, the industrial method of simpler preparation propanedioic acid and ester thereof.
At the deficiencies in the prior art, the present inventor has carried out research with great concentration to the method for producing propanedioic acid and ester thereof, found that, employing is via cyanoacetic acid calcium, can high yield, high purity ground obtains propanedioic acid and ester thereof, and very is fit to suitability for industrialized production, finished the present invention thus.
Summary of the invention
The novel method that the purpose of this invention is to provide preparation propanedioic acid and malonic ester.
Specifically, the invention provides a kind ofly, obtain the method for propanedioic acid and ester thereof via cyanoacetic acid calcium.
The invention provides prepare propanedioic acid and ester thereof method a), this method comprises the steps:
I), obtain the propanedioic acid calcium solution with cyanoacetic acid calcium calcium hydroxide aqueous solution alkaline hydrolysis;
II), produce propanedioic acid with the propanedioic acid calcium solution acidification hydrolization in the presence of strong inorganic acid (as sulfuric acid, hydrochloric acid) that obtains;
III) choose wantonly, in the presence of bronsted acid catalyst, adopt alcohol to carry out esterification isolated propanedioic acid, provide malonic ester.
Wherein, cyanoacetic acid calcium can prepare in order to the below method,
A) with Monochloro Acetic Acid calcium and calcyanide or sodium cyanide reaction, generate cyanoacetic acid calcium.
Perhaps can prepare in order to the below method,
A ') cyanoacetic acid and calcium hydroxide reaction make cyanoacetic acid calcium.
Detailed Description Of The Invention
Specifically, to prepare the specific embodiments of method of propanedioic acid or its ester as follows in the present invention:
Step I), under preferred 80-110 ℃, cyanoacetic acid calcium and calcium oxide or calcium hydroxide are lower than 1: 1 by being generally at 50-130 ℃, be preferably 1: the molar ratio reaction of 0.6-0.95, emit up to no tangible ammonia, be cooled to below 50 ℃, centrifugation goes out solids propanedioic acid calcium.
The difference of the temperature that is adopted during according to reaction etc. changes, and the reaction times was generally 1 to 20 hour.
Used temperature of reaction is with cyanoacetic acid calcium and calcium oxide or the mol ratio of calcium hydroxide is relevant and the time span of decision reaction.Therefore, under lower temperature, for example under 50 ℃, the reaction times can be longer, perhaps adopts the consumption of calcium oxide or calcium hydroxide little big with respect to the mol ratio of cyanoacetic acid calcium.On the contrary, for higher temperature of reaction, may use less calcium oxide or calcium hydroxide and short reaction times.
Step II) with step I) in the propanedioic acid calcium that obtains make the aqueous solution, stirring slightly under the cooling conditions and the strong inorganic acid aqueous solution, for example dilute sulphuric acid or concentrated hydrochloric acid aqueous solution reaction produces propanedioic acid and by product mineral acid calcium salt, calcium salt is leached or centrifugal removal, obtain the desired product propanedioic acid.
During reaction, add the strong acid of q.s, preferred excessive a little sulfuric acid makes the calcium ion in reaction vessel all generate the mineral acid calcium salt with inorganic acid reaction.
The difference of the temperature that is adopted during according to reaction etc. changes, and the reaction times was generally 1 to 10 hour.
The calcium ion that exists in used temperature of reaction and the reaction vessel is relevant with the mol ratio of strong inorganic acid and determines the time of reaction.
If desired, the propanedioic acid that obtains Step II) can carry out following steps III) obtain malonic ester.
Step II I): at bronsted acid catalyst, for example, chloro sulfonic acid, methylsulfonic acid, tosic acid, hydrochloric acid, sulfuric acid and other protonic acid preferably in the presence of sulfuric acid, under heating, adopt alcohol to carry out esterification isolated propanedioic acid, provide malonic ester.Step II I) operational condition can be referring to the propanedioic acid esterification method among the WO99/8988.
The alcohol that esterification is in the methods of the invention used is uncle or the secondary alcohol of C1-C10, for example methyl alcohol, ethanol, Virahol, particularly ethanol.
The starting raw material cyanoacetic acid calcium that adopts in the above-mentioned reaction can prepare with following step,
A) with Monochloro Acetic Acid calcium and calcyanide reaction, generate cyanoacetic acid calcium.
Step a) is at 30-120 ℃, under preferred 50-110 ℃, calcium chloroacetate and calcyanide by being generally at least 1: 1 mole, is preferably 1: 1.0-3.0 most preferably is the excessive a little (molar ratio reaction of (for example 1.01-1.50) for example.
The difference of the temperature that is adopted during according to reaction etc. changes, and the reaction times was generally 1 to 10 hour.
Used temperature of reaction is relevant with the calcium chloroacetate and the mol ratio of calcyanide and determines the time of reaction.Therefore, under lower temperature, for example under 40 ℃, the reaction times can be longer, perhaps adopts the consumption of calcyanide excessive a little greatly a bit with respect to calcium chloroacetate.On the contrary, for higher temperature of reaction, may use less calcyanide and short reaction times.
Perhaps can prepare with following step,
A ') cyanoacetic acid and calcium hydroxide reaction make cyanoacetic acid calcium.
The starting raw material Monochloro Acetic Acid calcium that is adopted in the step a) of the present invention is known substances, perhaps can prepare with known method itself, and for example, Monochloro Acetic Acid calcium adopts Monochloro Acetic Acid and calcium hydroxide reaction to prepare.
The another kind of starting raw material calcyanide that is adopted in the step a) of the present invention also is a known substances, perhaps can prepare with known method itself, and for example, calcyanide adopts prussic acid and calcium hydroxide reaction to prepare.
When considering to adopt more basic chemical feedstocks Monochloro Acetic Acid or prussic acid to carry out the inventive method, in the inventive method, also can be before step a), increase the step for preparing Monochloro Acetic Acid calcium or calcyanide (sodium) with more basic chemical feedstocks Monochloro Acetic Acid or prussic acid and calcium hydroxide (or sodium).
Step a ' of the present invention) the starting raw material cyanoacetic acid that is adopted in is a known substances in the organic synthesis, perhaps can prepare with known method itself.
In addition, when considering to adopt more basic chemical feedstocks Monochloro Acetic Acid or prussic acid to carry out the inventive method, the present invention can also adopt by Monochloro Acetic Acid, prussic acid and calcium oxide or calcium hydroxide direct in-situ and prepare propanedioic acid calcium.
Therefore, the method for preparing propanedioic acid or its ester of the present invention as follows (method b) carry out:
I ') in a reaction vessel, controlled temperature is lower than under 50 ℃, preferably is lower than under 40 ℃, slowly adds Monochloro Acetic Acid in calcium hydroxide aqueous solution, produces Monochloro Acetic Acid calcium; Feed prussic acid gas subsequently, no longer react to prussic acid, drop into calcium oxide or calcium hydroxide alkaline hydrolysis again, temperature of reaction is risen to more than 85 ℃, preferably between 90-120 ℃, reacted 2-20 hour, obtain the propanedioic acid calcium solution.
Then adopt the Step II of the inventive method) and III) prepare propanedioic acid or its ester.
The reaction process of the inventive method is normally carried out under normal pressure, but also can adopt the mode-for example of pressurization or decompression to carry out under the 0.1-10 crust.
The propanedioic acid that the inventive method is prepared or the aftertreatment of malonic ester can adopt conventional method to carry out, and for example adopt washing, decolouring, recrystallization, chromatogram, underpressure distillation etc.
Employing of the present invention via the method for cyanoacetic acid calcium with at present extensively the method for preparing propanedioic acid and ester thereof via cyanoacetic acid sodium of industrial applications compare, the former possesses following advantage:
One, because Ca
2+Electric field is better than Na
+, from the reaction mechanism angle, the former is easier to reaction, and the calcium hydroxide solubleness of generation is little, and the calcium hydroxide of trace has reduced the alkaline hydrolysis reaction, introduces calcium ion, uses sulfuric acid precipitation, can reach good separating effect.Therefore, adopt calcium hydroxide to replace sodium hydroxide in the reaction process, during aftertreatment, be easy to calcium ion is removed.
Two, the reaction of preparation cyanoacetic acid calcium, with respect to the reaction of preparation cyanoacetic acid sodium, the former reacts milder and decomposition of little.
Three, adopt cyano-containing lime acetate and calcium hydroxide to replace cyanoacetic acid sodium and sodium hydroxide, production cost is cheaper.
Four, for producing propanedioic acid, avoid with an organic solvent, environmental pollution when reducing aftertreatment, and method is simple, and solid-liquid separation significantly improves, thereby increases product purity.
Five, reaction conditions gentleness, the total recovery height of technological process.
Though should be appreciated that the present invention only to the preparation of propanedioic acid and ester thereof as detailed description, same principle also can be suitable for preparing other alkane dicarboxylic acid, for example, Succinic Acid or pentanedioic acid and commercial useful ester thereof.
Embodiment
Hereinafter, the present invention will make more detailed non-limiting description by the mode of embodiment.
Embodiment 1
In reactor, drop into Mono Chloro Acetic Acid 97.4g (1mol), add water 150ml dissolving, add 40g calcium hydroxide (95%) under 35 ℃ to be neutralized to pH=7, add and contain CN
-The calcyanide solution 236ml of 110g/L, be heated to 50 ℃, make its natural reaction, when being warming up to 100 ℃, being cooled to 50 ℃ and adding calcium hydroxide 56g (9 5%) again, be warming up to 102 ℃, back flow reaction 8 hours, do not have obvious ammonia and overflow, be cooled to 50 ℃, filtration, washing make propanedioic acid calcium 185.0g (Ca
2+24.00%).
Propanedioic acid calcium is dropped in the reactor, add water 400ml, pulled an oar 30 minutes, drip 30%H down in 60 ℃
2SO
4375g, 3 hours time, filtration, washing, decolouring, concentrated, sulfate radical, the reconcentration crystallization gets propanedioic acid 85.6g (99%), yield 81.48%.
The propanedioic acid that obtains is dropped into reactor, directly add 95% ethanol 47.2g, stirring is warming up to 75 ℃, drips 96% sulfuric acid 20.5 g under 75 ℃ ± 2 ℃, drips off the back and reacts 3 hours down in 85 ℃ ± 2 ℃.Be cooled to 60 ℃ after reaction is finished, add water 100ml under stirring, put only.Tell upper strata liquid, be neutralized to neutrality with 20% yellow soda ash, underpressure distillation gets diethyl malonate 119.3g (98.5%), yield 90% (is benchmark with the propanedioic acid).
Embodiment 2
Drop into Mono Chloro Acetic Acid 97.4g (1mol) in reactor, add water 150ml dissolving, 35 ℃ add 40g calcium hydroxide (95%) down and are neutralized to pH=7, add and contain CN
-The calcyanide solution 236ml of 110g/L is heated to 50 ℃, makes its spontaneous reaction, when being warming up to 105 ℃, be cooled to 50 ℃, add calcium hydroxide 56g (95%) again, be warming up to 105 ℃, back flow reaction 8 hours, do not have obvious ammonia and overflow, be cooled to 50 ℃, filter, wash propanedioic acid calcium 185.5g (Ca
2+24.30%).
Propanedioic acid calcium is dropped in the reactor, add water 200ml and make soup compound, under 60 ℃, drip 30%HCl 270g acidifying and make propanedioic acid solution then, again extracting solution is concentrated with ether extraction, filter, drying obtains propanedioic acid 79.5g (99%), yield 75.5%, obtain to such an extent that propanedioic acid gets esterification process by embodiment 1, can get malonic ester.
Comparative examples 1
The solution 356.7g that drops into cyano-containing sodium acetate 107g in reactor adds sodium hydroxide 41.0g in 95 ℃ of insulations 3 hours, make sodium malonate, in sodium malonate solution, add 1.05mol HCl acidifying, extract repeatedly through ether, remove ether and get propanedioic acid 80.1g (99.5%), yield 76.62%.
Claims (6)
1. method for preparing propanedioic acid and ester thereof, this method comprises:
I), obtain the propanedioic acid calcium solution with cyanoacetic acid calcium calcium hydroxide aqueous solution alkaline hydrolysis;
II), produce propanedioic acid with the propanedioic acid calcium solution acidification hydrolization in the presence of strong inorganic acid that obtains;
III) choose wantonly, in the presence of bronsted acid catalyst, adopt alcohol to carry out esterification isolated propanedioic acid, provide malonic ester.
2. according to the process of claim 1 wherein
I) at 50-130 ℃, with cyanoacetic acid calcium and calcium oxide or calcium hydroxide by 1: the molar ratio reaction of 0.6-0.95, emit up to no tangible ammonia, be cooled to below 50 ℃, centrifugation goes out solids propanedioic acid calcium;
II) with step I) in the propanedioic acid calcium that obtains make the aqueous solution, under stirring cooling conditions slightly, all react with the sulfuric acid amount of sulfuric acid reaction with being enough to make the calcium ion in the reaction vessel, produce propanedioic acid and by product calcium salt, calcium salt is leached or centrifugal removal, obtain propanedioic acid.
3. according to the method for claim 2, wherein
I) at 80-110 ℃, cyanoacetic acid calcium and calcium oxide or calcium hydroxide are by 1: the molar ratio reaction of 0.6-0.95, emit up to no tangible ammonia, and be cooled to below 50 ℃, centrifugation goes out solids propanedioic acid calcium;
II) with step I) in the propanedioic acid calcium that obtains make the aqueous solution, under stirring cooling conditions slightly, all react with the sulfuric acid amount of sulfuric acid reaction with being enough to make the calcium ion in the reaction vessel, produce propanedioic acid and byproduct calcium sulfate salt, calcium sulfate salt is leached or centrifugal removal, obtain propanedioic acid.
4, according to the process of claim 1 wherein that cyanoacetic acid calcium is to adopt the following steps preparation:
A) with Monochloro Acetic Acid calcium and calcyanide reaction, generate cyanoacetic acid calcium;
Perhaps
A ') with the reaction of cyanoacetic acid and calcium hydroxide, generates cyanoacetic acid calcium.
5, according to the method for claim 4, wherein step a) is following carrying out:
A) under 30-90 ℃, Monochloro Acetic Acid calcium and calcyanide are pressed 1: the 1.0-3.0 molar ratio reaction.
6, according to the method for claim 5, wherein step a) is following carrying out:
A) under 40-70 ℃, Monochloro Acetic Acid calcium and calcyanide are pressed 1: the 1.01-1.50 molar ratio reaction.
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| CNB011414057A CN1156427C (en) | 2001-09-24 | 2001-09-24 | Preparation method of malonic acid and its ester |
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| CNB011414057A CN1156427C (en) | 2001-09-24 | 2001-09-24 | Preparation method of malonic acid and its ester |
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| CN103159624B (en) * | 2011-12-08 | 2014-09-17 | 中国科学院大连化学物理研究所 | Method of preparing malonate diester by using malic acid as raw material |
| CN103408418B (en) * | 2013-08-22 | 2015-03-25 | 河北诚信有限责任公司 | Preparation and purification method of solid malonic acid |
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Owner name: CHONGQING SANXIA YINGLI CHEMICAL CO., LTD. Free format text: FORMER OWNER: QINGHUAZIGUANG YINGLI CHEMICAL TECHNOLOGY CO. LTD., BEIJING Effective date: 20070309 |
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Effective date of registration: 20070309 Address after: 631200, Chongqing Chongqing (longevity) chemical industry park, fine chemical two district Patentee after: Chongqing Sanxia Yingli Chemical Co., Ltd Address before: 100084 room 510, Thunis building, Beijing Patentee before: Beijing Tsinghua Unisplendour Insight Chemical Technology LLC |
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