CN109369370A - The preparation method of 2,3,5- tricarboxylic cyclopentane acetic acid - Google Patents

The preparation method of 2,3,5- tricarboxylic cyclopentane acetic acid Download PDF

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Publication number
CN109369370A
CN109369370A CN201811219343.1A CN201811219343A CN109369370A CN 109369370 A CN109369370 A CN 109369370A CN 201811219343 A CN201811219343 A CN 201811219343A CN 109369370 A CN109369370 A CN 109369370A
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China
Prior art keywords
autoclave
acetic acid
dicyclopentadiene
hydrolysate
reaction
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Pending
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CN201811219343.1A
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Chinese (zh)
Inventor
樊彬
竺贝贝
陶明
廖祖态
吕雪皓
袁继新
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Jiangxi Yang Fan New Material Co Ltd
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Jiangxi Yang Fan New Material Co Ltd
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Priority to CN201811219343.1A priority Critical patent/CN109369370A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/27—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with oxides of nitrogen or nitrogen-containing mineral acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated

Abstract

The invention discloses one kind 2,3, the preparation method of 5- tricarboxylic cyclopentane acetic acid, the following steps are included: aqueous solution of nitric acid and catalyst are added in autoclave, being filled with oxygen to oxygen pressure is 0.5~3MPa, it is heated to pre-heating temperature recession and removes heat source, one hydrolysate of dicyclopentadiene is added into autoclave using pump, the temperature of reaction system in the flow control autoclave by adjusting pump；After one hydrolysate of dicyclopentadiene feeds, autoclave is heated, to make the reaction system in autoclave the reaction was continued under heat-retaining condition 1~2h, then cooled to room temperature；Reaction gains are subjected to separation and purification, obtain 2,3,5- tricarboxylic cyclopentane acetic acid.Under the conditions of this method is existing for the catalyst, by nitric acid, one hydrolysate of oxygen cooxidation dicyclopentadiene, has the function that reduce nitric acid dosage, reduces discharged nitrous oxides and reduce cost.

Description

The preparation method of 2,3,5- tricarboxylic cyclopentane acetic acid
Technical field
The present invention relates to a kind of preparation methods of organic compound 2,3,5- tricarboxylic cyclopentane acetic acid.
Background technique
Structural formula 2,3,5- tricarboxylic cyclopentane acetic acid as shown in Equation 1 are a kind of chemical synthesis intermediate, n-butanol Rouge can be used for lubricant, and dicarboxylic anhydride can be used for adhesive, while its dicarboxylic anhydride or a kind of important polyimides raw material, It can be used for the preparation of the liquid crystal orientation film of TFT LCD.
It is disclosed in document J.Chem.soc., 1936,142-153 a kind of by six carboxyl ester ring of 2,2,4,4,5,5- Amyl -1- malonic acid rouge flows back the method for obtaining 2,3,5- tricarboxylic basic ring vaiproic acids, but this side in the solution of potassium hydroxide Method raw material sources are not easy.Patent GB872355 describes a kind of ozone, dicyclopentadiene, hydrogen peroxide preparation tri- carboxyl of 2,3,5- The method of 2-Cyclopentylacetic acid, this method are difficult fully reacting, and product purity is not high, and ozone oxidation speed is slow, are difficult big Large-scale production.Patent CN104193612 is reported with sodium metaperiodate, osmium tetroxide, dicyclopentadiene, hydrogen peroxide preparation 2,3,5- The method of tricarboxylic cyclopentyl acetic acid, oxidizing agent sodium periodate economic cost used in this method is high, osmium tetroxide severe toxicity, volatility By force.Patent JP2011241161 provide a kind of dicyclopentadiene at 40-80 DEG C with the inorganic nitrogen oxides (HNO of oxidisability3、 HNO2、NO2And N2O4) contact the method for forming 2,3,5- tricarboxylic cyclopentyl acetic acid.But this method needs to consume a large amount of inorganic Nitrogen oxides (10~17 times of dicyclopentadiene mole), made crude yield (45~55%) and purity (50~58%) compared with Low, highly finished product yield is only 28%.
Referring to JP2011241161, attempt to be direct oxidation into target product by dicyclopentadiene, but can only actually examine It measures a small amount of required target product to generate, mainly generates object and be partial oxidation products 1 and aoxidize excessive product 2:
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of catalysis nitric acid oxygen of 2,3,5- tricarboxylic cyclopentyl acetic acid The synthetic method of cooxidation, i.e., existing for the catalyst under the conditions of, by nitric acid, one hydrolysate of oxygen cooxidation dicyclopentadiene, Have the function that reduce nitric acid dosage, reduce discharged nitrous oxides and reduce cost.
In order to solve the above technical problem, the present invention provides a kind of preparation method of 2,3,5- tricarboxylic cyclopentane acetic acid, Successively the following steps are included:
1) it, synthesizes:
Aqueous solution of nitric acid and catalyst are added in autoclave, being filled with oxygen to oxygen pressure is 0.5~3MPa (reaction process Middle maintenance oxygen pressure is stablized), it is heated to pre-heating temperature recession and removes heat source, one water of dicyclopentadiene is added into autoclave using pump Object is solved, the temperature of reaction system is pre-heating temperature ± 2 DEG C in the flow control autoclave by adjusting pump；Dicyclopentadiene one After hydrolysate feeds, autoclave is heated, to make the reaction system in autoclave in pre-heating temperature ± 2 DEG C The reaction was continued under heat-retaining condition 1~2h, then cooled to room temperature；
The molar ratio of nitric acid and one hydrolysate of dicyclopentadiene is 0.3~2:1, and catalyst amount is one water of dicyclopentadiene The 0.05~5% of object mole is solved, pre-heating temperature is 35~75 DEG C (preferably 45~50 DEG C)；
Remarks: therefore exothermic heat of reaction when one hydrolysate of dicyclopentadiene is added is not necessarily to heat source at this time；Pre-heating temperature etc. It is same as reaction temperature；
Closed after autoclave addition aqueous solution of nitric acid, catalyst, leak detection is oxygenated, and heating starts to react；
2), separation and purification:
The reaction gains (transparency liquid) of step 1) are subjected to separation and purification, obtain 2,3,5- tricarboxylic cyclopentane acetic acid.
The separation and purification can refer to patent JP2011241161.
The improvement of preparation method as of the invention 2,3,5- tricarboxylic cyclopentane acetic acid, the separation and purification of step 2) Are as follows:
The reaction gains (transparency liquid) of step 1) are concentrated under reduced pressure, it is cooling that solid, filtering, after filter cake is dried under reduced pressure is precipitated Obtain crude product；
After crude product is dissolved in dehydrated alcohol, adds crystal seed and recrystallized in 5 ± 1 DEG C；Gained crystal is washed, dry It is dry, obtain 2,3,5- tricarboxylic cyclopentane acetic acid (white powder product)；
Crude product: dehydrated alcohol=1:1.5~2.5 mass ratio；Crystal seed: the mass ratio of crude product=1%.
The further improvement of preparation method as 2,3,5- tricarboxylic cyclopentane acetic acid of the invention: the step 1) In, catalyst NH4VO3, the aqueous solution of nitric acid quality solubility is 10~70% (preferential 30~70%).
In step 1) of the invention, it is about 0.1~1ml/ that one hydrolysate of dicyclopentadiene, which is pumped into the flow velocity in autoclave, min。
Reaction equation of the invention is as follows:
The method of the present invention and the preparation method of existing 2,3,5- tricarboxylic cyclopentane acetic acid compare, and have the advantage that
1), method of the invention is low in cost, and catalyst amount is few.
2), in contrast to JP2011241161 nitric acid oxidation dicyclopentadiene at target product, the method for the present invention passes through nitric acid Higher one hydrolysate of dicyclopentadiene of co-oxidants oxidation activity of oxygen composition, reaction yield are higher.
3), in contrast to normal pressure system, the method for the present invention forms cooxidation with nitric acid by the oxygen of introducing certain pressure The dosage of nitric acid and the discharge amount of nitrogen oxides can be effectively reduced in agent, reduce cost of material.
4), the present invention is closed system, and compared with unlimited system, solving that flow of oxygen is big, the nitric acid rate of recovery is low etc. is lacked It falls into.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in This:
The preparation method of embodiment 1, one kind 2,3,5- tricarboxylic cyclopentyl acetic acid, with one hydrolysate of dicyclopentadiene, nitre Acid, oxygen are raw material, are successively followed the steps below:
1) it, synthesizes:
Aqueous solution of nitric acid (nitric acid 0.13mol), the 0.0480gNH of 27.8mL30% are added in 200mL autoclave4VO3 (0.00041mol) is filled with the oxygen (oxygen pressure is maintained to stablize in reaction process) of 1MPa, is preheating to 45 DEG C of recession and removes heat source, with pump One hydrolysate 40g (0.27mol) of dicyclopentadiene is added into kettle, by flow velocity (0.1~1ml/min) control volume for adjusting pump Be that temperature is constant all the time (for 45 ± 2 DEG C), one hydrolysate of dicyclopentadiene feed after using external heat source to autoclave into Row heating, to make the reaction system in autoclave the reaction was continued under 45 ± 2 DEG C of heat-retaining condition 2h；After reaction time arrives, Cooled to room temperature, pressure release.
That is, nitric acid: one hydrolysate of dicyclopentadiene=0.5:1 molar ratio, NH4VO3It rubs for one hydrolysate of dicyclopentadiene The 0.15% of that amount.
2), separation and purification (can refer to patent JP2011241161):
(pressure, 60 DEG C of the temperature of -0.95MPa) is concentrated under reduced pressure in the reaction gains (transparency liquid) of step 1) until It is the 80% of original volume, solid is precipitated after being cooled to room temperature, filter, filter cake is dried under reduced pressure (pressure of -0.95MPa, 60 DEG C of temperature Degree is lower 10 hours dry), crude product 46.1g, yield 66.5% are obtained, HPLC testing product content is 95.1%.
Dehydrated alcohol 90g is added in above-mentioned crude product to be dissolved, is added crystal seed (2,3,5- tricarboxylic cyclopentane acetic acid) 0.5g stands one week under the conditions of 5 DEG C.The crystallization being precipitated is filtered, is washed with glacial acetic acid (1ml), ethyl alcohol (4ml), be dried under reduced pressure (- 0.95MPa pressure is dried to constant weight at a temperature of 60 DEG C), obtain 2,3,5- tricarboxylic cyclopentane acetic acid (white powder) 30.0g, yield 43.3%, HPLC testing product content 99.5%.
Reaction condition in embodiment 2~3, change embodiment 1, that is, change the step the catalyst n H in 1)4VO3Dosage, Remaining is equal to embodiment 1, to obtain embodiment 2~3, gained total recovery and the comparison of embodiment 1 are as shown in table 1.
Table 1
Embodiment 4~9 changes reaction condition in embodiment 1, that is, changes the step nitric acid dosage in 1), concentration of nitric acid, Remaining is equal to embodiment 1, to obtain embodiment 4~9, gained total recovery and the comparison of embodiment 1 are as shown in table 2.
Table 2
Reaction condition in embodiment 10~15, change embodiment 1, that is, change the step reaction temperature, the oxygen pressure in 1) Power, remaining is equal to embodiment 1, to obtain embodiment 10~15, gained total recovery and the comparison of embodiment 1 are as shown in table 3.
Table 3
Comparative example 1, the use for cancelling catalyst in embodiment 1, that is, NH4VO3Dosage be changed to 0 by 0.0480g, remaining etc. It is same as embodiment 1.
Acquired results are as follows: yield 24.1%.
Oxygen is filled with into autoclave in comparative example 2, cancellation embodiment 1, that is, be changed to oxygen pressure by 1MPa 0MPa；Remaining is equal to embodiment 1.
Acquired results are as follows: yield 9.0%.
High pressure kettle device in embodiment 1 is changed to isometric three-necked flask (sealing, be unable to pressure-bearing) by comparative example 3；This When, oxygen pressure is normal pressure (about 0.1MPa), remaining is equal to embodiment 1.
Acquired results are as follows: yield 19.2%.
Reaction condition in comparative example 4~5, change embodiment 1, that is, change the step the reaction temperature in 1), remaining is equivalent In embodiment 1, to obtain comparative example 4~5, acquired results are shown in Table 4.
Table 4
Comparative example 4 5
Reaction temperature/DEG C 25 85
Yield/% 13.1 16.1
The time that the reaction was continued in 1 step 1) of embodiment is changed to 0.5h, 3h by 2h by comparative example 6 respectively；Remaining is equal to
Embodiment 1, acquired results are shown in Table 5.
Table 5
The time that the reaction was continued Yield/%
0.5h 15.6
3h 43.5
The above list is only a few specific embodiments of the present invention for finally, it should also be noted that.Obviously, this hair Bright to be not limited to above embodiments, acceptable there are many deformations.Those skilled in the art can be from present disclosure All deformations for directly exporting or associating, are considered as protection scope of the present invention.

Claims (3)

  1. The preparation method of 1.2,3,5- tricarboxylic cyclopentane acetic acid, it is characterized in that successively the following steps are included:
    1) it, synthesizes:
    Aqueous solution of nitric acid and catalyst are added in autoclave, being filled with oxygen to oxygen pressure is 0.5~3MPa, is heated to preheating Heat source is removed in temperature recession, and one hydrolysate of dicyclopentadiene is added into autoclave using pump, high by the flow control for adjusting pump The temperature for pressing reaction system in kettle is pre-heating temperature ± 2 DEG C；One hydrolysate of dicyclopentadiene feed after, to autoclave into Row heating, to make the reaction system in autoclave the reaction was continued under the heat-retaining condition of pre-heating temperature ± 2 DEG C 1~2h, so Cooled to room temperature afterwards；
    The molar ratio of nitric acid and one hydrolysate of dicyclopentadiene is 0.3~2:1, and catalyst amount is one hydrolysate of dicyclopentadiene The 0.05~5% of mole, pre-heating temperature are 35~75 DEG C；
    2), separation and purification:
    The reaction gains of step 1) are subjected to separation and purification, obtain 2,3,5- tricarboxylic cyclopentane acetic acid.
  2. 2. the preparation method of according to claim 12,3,5- tricarboxylic cyclopentane acetic acid, it is characterized in that the step 2) Separation and purification are as follows:
    The reaction gains of step 1) are concentrated under reduced pressure, it is cooling that solid is precipitated, it filters, filter cake obtains crude product after being dried under reduced pressure；
    After crude product is dissolved in dehydrated alcohol, adds crystal seed and recrystallized in 5 ± 1 DEG C；Gained crystal is washed, dry, Obtain 2,3,5- tricarboxylic cyclopentane acetic acid；
    Crude product: dehydrated alcohol=1:1.5~2.5 mass ratio；Crystal seed: the mass ratio of crude product=1%.
  3. 3. the preparation method of according to claim 1 or 22,3,5- tricarboxylic cyclopentane acetic acid, it is characterized in that the step 1) in: catalyst NH4VO3, the aqueous solution of nitric acid quality solubility is 10~70%.
CN201811219343.1A 2018-10-19 2018-10-19 The preparation method of 2,3,5- tricarboxylic cyclopentane acetic acid Pending CN109369370A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0231681B2 (en) * 1983-04-14 1990-07-16 Japan Synthetic Rubber Co Ltd TETORAKARUBON SANNOSEIZOHOHO
JP2004182658A (en) * 2002-12-04 2004-07-02 Nissan Chem Ind Ltd Method for manufacturing alicyclic tetracarboxylic acid
US7692041B2 (en) * 2006-08-07 2010-04-06 The University Of Montana Method of oxidation using nitric acid
CN104478701A (en) * 2014-11-24 2015-04-01 常州大学 Method for synthesizing adipic acid by oxidizing alcohol ketone (KA) oil with nitric acid in continuous flow microchannel reactor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0231681B2 (en) * 1983-04-14 1990-07-16 Japan Synthetic Rubber Co Ltd TETORAKARUBON SANNOSEIZOHOHO
JP2004182658A (en) * 2002-12-04 2004-07-02 Nissan Chem Ind Ltd Method for manufacturing alicyclic tetracarboxylic acid
US7692041B2 (en) * 2006-08-07 2010-04-06 The University Of Montana Method of oxidation using nitric acid
CN104478701A (en) * 2014-11-24 2015-04-01 常州大学 Method for synthesizing adipic acid by oxidizing alcohol ketone (KA) oil with nitric acid in continuous flow microchannel reactor

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