KR100408806B1 - Process for Preparing 3-Hydroxy Propionic Acid and Salt from Exopide Derivative - Google Patents

Abstract

The present invention is to prepare a β-hydroxy ester by the carbonylation reaction of the epoxide derivative, the 3-hydroxy propionic acid by hydrolysis reaction of the β-hydroxy ester in the presence of an acid or a base (3-hydroxy propionic acid) Or a process for preparing 3-hydroxypropionic acid salts. The process for preparing β-hydroxyesters from epoxide derivatives comprises the steps of (a) using a catalytic amount of cobalt compound and an effective amount of promoter to bring epoxide, carbon monoxide and alcohol in a solvent at a temperature of 30 to 150 ° C. and 50 to 3000 psig. Reacting at a pressure of to produce β-hydroxyester as an intermediate and its derivative at 2 to 98 wt%; (b) separating the product and solvent from the catalyst and promoter. Hydrolyzing the β-hydroxyester to prepare 3-hydroxy propionic acid or 3-hydroxypropionic acid salt is (c) the separated product and the solvent in the presence of an acid or a base The reaction is carried out under to prepare 3-hydroxy propionic acid or a salt thereof. Acidic or alkaline resins may be used in place of the acids or bases.

Description

Process for preparing 3-Hydroxy Propionic Acid and Salt from Exopide Derivative

Field of invention

The present invention relates to a method for producing 3-hydroxypropionic acid or a salt thereof by carbonylating an epoxide derivative to produce β-hydroxyester and hydrolyzing the β-hydroxyester. More specifically, in the present invention, the epoxide derivative is reacted with carbon monoxide and alcohol in a catalyst system composed of a cobalt catalyst and an accelerator to effectively convert into a β-hydroxyester, and the β-hydroxyester is hydrolyzed in the presence of an acid or a base. To a 3-hydroxy propionic acid or a 3-hydroxypropionic acid salt.

Background of the Invention

Epoxide derivatives can be readily converted into difunctional compounds through carbonylation reactions and used as intermediates for preparing useful organic compounds. In particular, since 3-hydroxyester derivatives have two functional groups, they can be used as solvents, resins, and coating materials. They can be easily converted into other compounds, and can be used as pharmaceutical raw materials. It can also be used as an intermediate for synthesizing alkanediol. On the other hand, alkanediol is not only used as a raw material for polyester but also as a coating or an intermediate of organic synthesis. Synthetic pathways of 1,3-diol are generally hydrogenated of 3-hydroxyaldehyde derivatives synthesized by hydroformylation of epoxide derivatives (US Pat. Nos. 5,770,776, 5,723,389 and 5,731,478). However, the present inventors have synthesized a 3-hydroxyester intermediate by hydroesterifying an epoxide derivative and reacting the resulting ester intermediate with hydrogen to obtain a 1,3-alkanediol in high yield and a method for the same. A catalyst system for hydroesterification was developed and patented as Korean Patent Application No. 2000-5357 (February 3, 2000). As a result of repeated studies, it has been found that the hydrolysis reaction of β-hydroxyester in the presence of an acid or a base enables the synthesis of 3-hydroxypropionic acid or a salt thereof at a high yield and a low price. .

Not only can 3-hydroxypropionic acid or its salts be used as an important building block in organic synthesis, but these hydroxycarboxylic acids are very important as intermediates in plant and animal metabolic pathways. It is known to play a role.

Conventional synthesis methods of 3-hydroxypropionic acid or salts thereof can be summarized as in the following reaction scheme. As shown in Method 1, first, hydrogen cyanide is treated with epoxide and then hydrolysis is performed. The synthesis method is mentioned. This method requires the use of toxic hydrogen cyanide, which is difficult to trap and neutralize. In addition, Method 2 is a method using the synthesis method of Kolbe nitrile and can be obtained by hydrolysis after hypochlorous acid addition reaction to olefins [Ullmann encyclopedia, vol A13, p 507-517]. In addition, a method of synthesizing via selective oxidation of 1,3-propandiol in the presence of oxygen and a noble metal (US Pat. No. 5,321,156) and a method of synthesizing via α-halo-carboxylic acid ester, β Synthesis by hydrogenation of -ketoacids by hydrogen reduction method, hydration of acrylic acid (Ullmann encyclopedia, vol A13, p 507-517), and examples reported as by-products of carbonylation reaction (US patent 5,310,948). However, in the case of hydrolysis of nitrile groups such as these, there is a problem that a large amount of acid is required and a large amount of wastewater is generated in the process of neutralizing it again.

As described above, in synthesizing 3-hydroxypropionic acid or salt derivatives thereof, hydroesterification of ethylene oxide derivatives is used to synthesize β-hydroxyester intermediates, and the ester groups of the resulting ester intermediates are acid and base or their corresponding acidic or alkaline resins. A method of obtaining 3-hydroxypropionic acid or a salt derivative thereof by adding and hydrolyzing has not been suggested until now. In the present invention, a new method for synthesizing 3-hydroxypropionic acid or a salt derivative thereof is proposed.

An object of the present invention is to effectively convert an epoxide derivative into carbon monoxide and alcohol in the presence of a catalyst system consisting of a cobalt catalyst and an accelerator to effectively convert to β-hydroxyester, and hydrolyze the β-hydroxyester in the presence of an acid or base. Reaction to provide a method for producing 3-hydroxy propionic acid (3-hydroxy propionic acid) or 3-hydroxypropionic acid salt.

Another object of the present invention is to provide a catalyst system having a high activity and selectivity in a carbonylation reaction in which an epoxide derivative is reacted with carbon monoxide and alcohol in the presence of a catalyst system composed of a cobalt catalyst and an accelerator to effectively convert to a β-hydroxyester. The present invention aims to provide a method for preparing 3-hydroxy propionic acid or 3-hydroxypropionic acid salt in high yield.

The above and other objects of the present invention can be achieved by the present invention as described below.

1 is a schematic scheme for preparing 3-hydroxypropionic acid or salts thereof from an epoxide derivative in accordance with the present invention.

The present invention synthesizes β-hydroxyester intermediates by hydroesterifying epoxide derivatives and hydrolyzes the resulting ester intermediates in the presence of an acid or a base to form 3-hydroxypropionic acid or 3-hydroxypropionic acid. A method for preparing hydroxypropionic acid salts (see FIG. 1).

The present invention is to improve the yield of β-hydroxyester by using an effective catalyst system, first, in the hydroesterification of epoxide derivatives, Co2 (CO) 8, which is a cobalt catalyst, is used alone or Co2 ( As a promoter, a compound obtained by mixing an imidazole, pyridine, pyrrole, pyrazine, pyrazole, pyrimidine, piperidine, or a derivative thereof can be used. Uses that do not bind compounds of the pin system. The molar ratio of the cobalt compound and the accelerator is in the range of 1 / 0.01 to 1/100. In the present invention, a derivative of imidazole represented by the following formula (1) is used. Imidazole and its derivatives are inexpensive and have the effect of lowering the cost of the catalyst.

Wherein R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen; Aliphatic hydrocarbon group which is different of _{C 3~10 (branched aliphatic hydrocarbon having 3} to 10 carbon atoms), aliphatic hydrocarbon-free pieces of _{C 1 ~ 10 (linear aliphatic hydrocarbon} having 1 to 10 carbon atoms), a saturated C ₃ ~ ₁₀ the cyclized hydrocarbons (saturated cyclohydrocarbon having 3 to 10 carbon atoms), a chain-like hydrocarbon group comprising a ring of _{C 3 ~ 10 (cycloaliphatic hydrocarbon having} 3 to 10 carbon atoms), or an aliphatic containing aromatic ring of C ₇ ~ ₁₀ Hydrocarbons (aromatic aliphatic hydrocarbon having 7 to 10 carbon atoms); F; Cl; An alkoxy group having C ₁ to ₃ carbon; OH; Aliphatic hydrocarbons, C ₃ ~ _10, which is different, containing the OH (OH group-containing branched aliphatic hydrocarbon having 3 to 10 carbon atoms); Aliphatic hydrocarbons, C ₁ ~ ₁₀ does not have branches, containing the OH (OH group-containing linear aliphatic hydrocarbon having 1 to 10 carbon atoms); The cyclization of the hydrocarbon saturation C ₃ ~ ₁₀ containing OH (OH group-containing saturated cyclohydrocarbon having 3 to 10 carbon atoms); , Containing a chain-like hydrocarbon group OH of C ₃ ~ ₁₀ including a ring (OH group-containing cycloaliphatic hydrocarbon having 3 to 10 carbon atoms); Or an aliphatic hydrocarbon group (OH group-containing aromatic aliphatic hydrocarbon having 7 to 10 carbon atoms) of the C ₇ ~ ₁₀ containing aromatic ring, containing an OH.

The reaction conditions are carried out using an appropriate solvent in the presence of alcohol and at a temperature in the range of 30 to 150 ° C, preferably 40 to 120 ° C and a pressure of 50 to 3000 psig, preferably 100 to 1500 psig.

The epoxide derivatives are represented by the following general formula (2):

In Formula 2 R ₁ and R ₂ are each independently hydrogen; The C ₁ ~C of the aliphatic hydrocarbon group (linear aliphatic hydrocarbon having 1 to 20 carbon atoms), C 3 ~C 20 aliphatic hydrocarbon group of the (branched aliphatic hydrocarbon having 3 to 20 carbon atoms) in the not saturated up to _20, C ₃ ~C saturated cyclic hydrocarbon of up to _{20 (saturated cycloaliphatic hydrocarbon having 3 to} 20 carbon atoms), C 3 ~C chain hydrocarbon group containing a ring of up to _{20 (cycloaliphatic hydrocarbon having 3 to 20} carbon atoms), or C ₇ ~C aliphatic hydrocarbon group containing an aromatic ring of up to _{20 (aromatic aliphatic hydrocarbon having 7 to} 20 carbon atoms); Or is F, Cl or a hydrocarbon group which is substituted with a Br, C ₆ ~C aromatic hydrocarbons (aromatic hydrocarbon having 6 to 20 carbon atoms with no substituted group) do not have a substituent of up to ₂₀ hydrogen carbon chain of at least one or more from among the hydrocarbon , or the hydrogen of the aromatic ring at least one F, Cl, amine group, nitrile group, or an aromatic hydrocarbon to an alkoxy substituted with a C ₆ ~C _{20 (aromatic hydrocarbon having 6 to 20} carbon atoms in which a hydrogen on the aromatic ring is substituted with F, Cl, an amine group, a nitrile group or an alkoxy group).

Preferred examples of the epoxide derivatives are ethylene oxide, propylene oxide, 1-butene oxide, 1-pentene oxide, 1-heptene oxide, 1-octene oxide, 1-nonene oxide, 1-dicene oxide, 2-methyl-propylene oxide , Epifluorohydrin, epichlorohydrin, epibromohydrin, glycidol, methyl glycidate, ethyl glycidate, t -butyl glycidate, 2-methyl- 1-butene oxide, 2-methyl-1-pentene oxide, 2-methyl-1-hexene oxide, 2-methyl-1-heptene oxide, 2-methyl-1-octene oxide, 2-methyl-nonene oxide, 2- Methyl-1-dicene oxide, 2-ethyl-1-butene oxide, 2-ethyl-1 pentene oxide, 2-ethyl-1-hexene oxide, 2-ethyl-1-heptene oxide, 2-ethyl-1-octene oxide 2-ethyl-1-nonene oxide, 2-ethyl-1-decene oxide, allyl benzene oxide, styrene oxide and the like to be.

The alcohol is represented by R ₃ OH, wherein R ₃ is a C _1-20 saturated or unsaturated linear hydrocarbon, branched hydrocarbon, cyclic hydrocarbon, aromatic hydrocarbon, or linear hydrocarbon comprising aromatics. Preferably methyl, ethyl, isopropyl, cyclohexyl, phenyl, or benzyl alcohol.

As the solvent, an ether compound, a substituted aromatic compound, or an acetate compound may be further used, or the R ₃ OH may be directly used as a solvent.

The ether compound has the structural formula represented by the following formulas (3), (4), and 5:

Wherein _{R 9, R 10, R 11} , R 12 and R ₁₃ are independently C _1~10 of saturated aliphatic hydrocarbons (saturated aliphatic hydrocarbon having 1 to 10 carbon atoms having no branches) not between, C _3, respectively to ₁₀ branches with aliphatic hydrocarbons (branched aliphatic hydrocarbon having 3 to 10 carbon atoms), the saturated cyclic hydrocarbon of _{C 3 ~ 10 (saturated cyclohydrocarbon having} 3 to 10 carbon atoms) of the, including the ring of C ₃ - ₁₀ chain-like hydrocarbon (cycloaliphatic hydrocarbon having 3 to 10 carbon atoms) or, an aliphatic hydrocarbon (aromatic aliphatic hydrocarbon having 7 to 10 carbon atoms) containing an aromatic ring of C ₇ ~ _10; m is an integer from 1 to 10 and n is an integer from 2 to 5.

The product (B) of β-hydroxyesters synthesized from the epoxide derivative is represented by the following formula, wherein R ₁ and R ₂ in the formula are as defined in Formula 2, and R ₃ is C _1-20 saturated Or unsaturated linear hydrocarbons, branched hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons, or linear hydrocarbons comprising aromatics. Preferably R ₃ is methyl, ethyl, isopropyl, cyclohexyl, phenyl, or benzyl.

Further, in the present invention, the hydrolysis product using an acid and a base from the compound (B) can be represented by the following formulas (7) and (8). In the case of using a base here, it shows the structure of (D) which is a salt form of 3-hydroxypropionic acid. In (D) below, A + represents a cation such as potassium, calcium, barium, lead, lithium, rubidium, cesium or aluminum, including sodium salt.

In addition, the acids used herein include all strong acids and weak acids (sulfuric acid, hydrochloricacid, nitric acid, acetic acid, HF, H ₃ PO ₄ , perchloric acid, p- toluenesulfonic acid, trifluoromethylsulfonic acid, etc.) and have an equivalent acidity. Polymers (such as Amberlite IR-120, Dowex 50, Permutit RS, Permutite C 50D, Zeolit 225, CM-Sephadex C-25 or C-50), as well as Amberlite IRC-50, Permutit C, Permutite H or H-70 , Zeolit 236, strong acids such as SP-Sephadex C-25 or C-50). Similarly, in the case of bases, alkali bases (sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, calcium hydroxide, etc.) as well as weak bases such as pyridine and basic resins (Amberlite IR-4B or 45, Dowex 3, Permutit E) Weak bases such as Permutite A 240A, DEAE-Sephadex A-25 or A-50 and Amberlite IRA-400, Dowex 1, Permutit ESB, Permutite A 330D, Zeolit FF, QAE-Sephadex A-25 or A-50 Strong bases), and the use of these acids and bases with solid supports such as charcol and silica. In proceeding with the hydrolysis reaction, the reaction proceeded at a temperature in the range of 20 to 110 ° C. Preferably, the reaction proceeds in a nitrogen or argon atmosphere, but is possible in the air. In addition, the amounts of acid and base include both those used in excess from the amount of catalyst. In the case of hydrolysis, it is not recommended to increase the temperature excessively because the intramolecular elimination reaction proceeds to produce α, β-unsaturated carboxylic acid.

Since the derivatives synthesized in the present invention are compounds containing difunctional groups, they can be used as intermediates or building blocks for organic synthesis by themselves, and in the case of alkaline salts, the price is equivalent to $ 30-40 / kg. Its value is very high. When the β-hydroxyester intermediate is hydrogenated, 1,3-diol compounds can be economically obtained at low cost, and malonic acid derivatives / β-ketoester derivatives can be obtained as products produced by oxidizing the β-hydroxyester intermediates. In addition, various various compounds which are very usefully used industrially from the present invention can be obtained under the above reaction conditions.

The present invention can be more clearly understood by the following examples, which are only intended to illustrate the present invention and are not intended to limit the scope of the invention.

Example 1-10 Co in the presence of imidazole ₂ (CO) ₈ Hydroesterification of Ethylene Oxide by Catalyst

Details of this example are summarized in Table 1. In a nitrogen atmosphere at room temperature in a 450 mL Parr reactor, a predetermined amount of solvent was added and Co ₂ (CO) ₈ was added thereto. The reactor was filled with 500 psig of CO gas and heated to 80 ° C., stirred for 1 hour, lowered to room temperature, removed from gas, and imidazole was added as a defined amount of accelerator. Ethylene oxide was added to the reactor and carbon monoxide at a predetermined pressure was placed in the reactor. After raising the temperature by the temperature shown in the table was reacted for the reaction time shown in Table 1. During the reaction, the reaction product was sampled using a tube, and the product methyl 3-hydroxypropionate (3-HPM) was analyzed by GC. After the reaction, the temperature was lowered to room temperature, the catalyst was removed, and the product was separated and quantified.

Hydroesterification of Ethylene Oxide with Co ₂ (CO) ₈ Catalyst in the Presence of Imidazole Example catalyst Temperature (℃) Pressure (bar) Response time (hr) MeOH (mL) % Conversion Yield ⁴⁾ (%) Selection ⁵⁾ (mole%) 3-HPM 3-HPM AA DMA ME Dimer One Co ₂ (CO) ₈ 70 34 3 200 78.09 65.72 84.16 2.12 7.38 0.86 2.08 2 Co ₂ (CO) ₈ 70 50 3 200 68.23 60.53 88.70 5.38 0.14 1.65 1.5 3 Co ₂ (CO) ₈ 70 80 3 200 65.66 57.43 87.50 2.89 0.38 1.59 2 4 Co ₂ (CO) ₈ 60 50 3 200 45.19 38.52 85.24 3.66 0.17 0.95 0 5 Co ₂ (CO) ₈ 75 50 3 200 78.62 66.0 84.0 0.02 8.63 1.51 2.44 6 Co ₂ (CO) ₈ 80 50 3 200 91.61 68.68 75.0 8.27 5.70 2.30 2.60 7 Co ₂ (CO) ₈ 80 34 2 100 ¹⁾ - 82.44 ⁶⁾ - - - 0.65 3.75 8 ²⁾ Co ₂ (CO) ₈ 80 34 4 250 - 70.1 ⁶⁾ - - - 4.75 1.78 9 ³⁾ Co ₂ (CO) ₈ 80 34 4 200 - 66.4 ⁶⁾ - - - 10 Co ₂ (CO) ₈ 75 60 3 150 95.27 88.90 93.31 1.78 0.32 0.98 3.61

Catalyst = 5mmole, Imidazole = 20mmole, Ethylene Oxide = 500mmole

1) Methanol 100mL + Tetraglyme

2) imidazole 40mmole

3) ethylene oxide 1.4mmole

4) Yield = Selectivity × Conversion Rate

5) 3-HPM = methyl 3-hydroxy propionate or 3-hydroxy propiate

On-acid methyl ester

AA = acetaldehyde

DMA = acetaldehyde dimethyl acetal

ME = methoxy ethanol

Dimer = HOCH ₂ CH ₂ C (O) OCH ₂ CH ₂ (O) OCH ₃

6) isolated yield

Examples 11-14 Hydroesterification of Other Epoxide Derivatives

Examples 11 to 14 were carried out in the same manner as in Example 1, except that the type of oxide was replaced with ethylene oxide, and the results are summarized in Table 2 below.

Example catalyst accelerant Epoxide product Yield ¹⁾ (%) 11 Co ₂ (CO) ₈ Imidazole Propylene oxide Methyl3-hydroxy Butanoate 60.56 12 Co ₂ (CO) ₈ Imidazole Butylene oxide Methyl 3-hydroxy pentanoate 53.70 13 Co ₂ (CO) ₈ Imidazole Epichlorohydrin Methyl3-hydroxy4-chlorobutanoate 66.17 14 Co ₂ (CO) ₈ Imidazole Glycidol 3-hydroxyγ-butyrolactone 62.50

Catalyst = 5mmole, accelerator = 10mmole, epoxide = 500mmole, temperature 80 ℃, pressure 34bar, reaction time 4hr, solvent = MeOH (200mL)

1) isolated yield

Example 15 Hydrolysis of Methyl-3-hydroxy Propionate

This example relates to the synthesis of 3-Hydroxypropionic acid in the presence of an acid. When 0.5 g of methyl-3-hydroxy propionate is reacted for 12 hours in aqueous acid solution (3.0 mL of conc. HCl, 30 mL of water), 3-Hydroxypropionic acid is produced. ^The results of analysis using ¹ H-NMR, ¹³ C-NMR and gas chromatography showed more than 95% conversion and yield, respectively.

Example 16 Hydrolysis of Methyl-3-hydroxy Propionate

This example relates to the synthesis of sodium salt of 3-Hydroxypropionic acid. Sodium salt of 3-Hydroxypropionic acid is produced when 0.5 g of methyl-3-hydroxy propionate is reacted under alkaline aqueous solution (1.0 g NaOH, 15 mL of water) for 12 hours. ^The results of analysis using ¹ H-NMR, ¹³ C-NMR and gas chromatography showed more than 95% conversion and yield, respectively.

In the present invention, an epoxide derivative is reacted with carbon monoxide and alcohol in the presence of a catalyst system consisting of a cobalt catalyst and an accelerator to effectively convert to a β-hydroxyester, and the β-hydroxyester is hydrolyzed in the presence of an acid or a base. Has the effect of the invention to prepare 3-hydroxy propionic acid or 3-hydroxypropionic acid salt in high yield.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (10)

(a) using a catalytic amount of cobalt compound and an accelerator selected from imidazole, pyrrole, pyrazine, pyrimidine and derivatives thereof, the temperature of 30-150 ° C. and pressure of 50-3000 psig in the solvent for epoxide, carbon monoxide and alcohol Reacting under conditions to produce the intermediate β-hydroxyester and its derivatives; (b) separating the product from the catalyst and promoter; And (c) reacting the separated product in the presence of an acid or a base; Step (a) is a solvent for preparing 3-hydroxypropionic acid or a salt thereof from the epoxide derivative, characterized in that selected from the group consisting of ether compound, substituted aromatic compound, acetate compound and alcohol. Way. The method for preparing 3-hydroxypropionic acid or a salt thereof according to claim 1, wherein the epoxide is represented by the following formula: Wherein R ₁ and R ₂ are each independently hydrogen; The C ₁ ~C of the aliphatic hydrocarbon group (linear aliphatic hydrocarbon having 1 to 20 carbon atoms), C 3 ~C 20 aliphatic hydrocarbon group of the (branched aliphatic hydrocarbon having 3 to 20 carbon atoms) in the not saturated up to _20, C ₃ ~C saturated cyclic hydrocarbon of up to _{20 (saturated cycloaliphatic hydrocarbon having 3 to} 20 carbon atoms), C 3 ~C chain hydrocarbon group containing a ring of up to _{20 (cycloaliphatic hydrocarbon having 3 to 20} carbon atoms), or C ₇ ~C aliphatic hydrocarbon group containing an aromatic ring of up to _{20 (aromatic aliphatic hydrocarbon having 7 to} 20 carbon atoms); Or is F, Cl or a hydrocarbon group which is substituted with a Br, C ₆ ~C aromatic hydrocarbons (aromatic hydrocarbon having 6 to 20 carbon atoms with no substituted group) do not have a substituent of up to ₂₀ hydrogen carbon chain of at least one or more from among the hydrocarbon , or the hydrogen of the aromatic ring at least one F, Cl, amine group, nitrile group, or an aromatic hydrocarbon to an alkoxy substituted with a C ₆ ~C _{20 (aromatic hydrocarbon having 6 to 20} carbon atoms in which a hydrogen on the aromatic ring is substituted with F, Cl, an amine group, a nitrile group or an alkoxy group). The method for preparing 3-hydroxypropionic acid or a salt thereof according to claim 1, wherein the promoter is a derivative of imidazole represented by the following formula: Wherein R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen; Aliphatic hydrocarbon group which is different of _{C 3~10 (branched aliphatic hydrocarbon having 3} to 10 carbon atoms), aliphatic hydrocarbon-free pieces of _{C 1 ~ 10 (linear aliphatic hydrocarbon} having 1 to 10 carbon atoms), a saturated C ₃ ~ ₁₀ the cyclized hydrocarbons (saturated cyclohydrocarbon having 3 to 10 carbon atoms), a chain-like hydrocarbon group comprising a ring of _{C 3 ~ 10 (cycloaliphatic hydrocarbon having} 3 to 10 carbon atoms), or an aliphatic containing aromatic ring of C ₇ ~ ₁₀ Hydrocarbons (aromatic aliphatic hydrocarbon having 7 to 10 carbon atoms); F; Cl; An alkoxy group having C ₁ to ₃ carbon; OH; Aliphatic hydrocarbons, C ₃ ~ _10, which is different, containing the OH (OH group-containing branched aliphatic hydrocarbon having 3 to 10 carbon atoms); Aliphatic hydrocarbons, C ₁ ~ ₁₀ does not have branches, containing the OH (OH group-containing linear aliphatic hydrocarbon having 1 to 10 carbon atoms); The cyclization of the hydrocarbon saturation C ₃ ~ ₁₀ containing OH (OH group-containing saturated cyclohydrocarbon having 3 to 10 carbon atoms); , Containing a chain-like hydrocarbon group OH of C ₃ ~ ₁₀ including a ring (OH group-containing cycloaliphatic hydrocarbon having 3 to 10 carbon atoms); Or being an aliphatic hydrocarbon group (OH group-containing aromatic aliphatic hydrocarbon having 7 to 10 carbon atoms) of the C ₇ ~ ₁₀ containing aromatic ring, containing an OH. The method for producing 3-hydroxypropionic acid or a salt thereof according to claim 1, wherein the molar ratio of the cobalt compound and the promoter is 1 / 0.01 to 1/100. According to claim 1, wherein R _{3 of} the alcohol (R ₃ OH) is C _{1 ~} C _{10 Is} a saturated aliphatic hydrocarbon (linear aliphatic hydrocarbon having 1 to 10 carbon atoms), C _{3 ~} C ₁₀ Branches aliphatic hydrocarbons (branched aliphatic hydrocarbon having 3 to 10 carbon atoms), C 3 ~C saturated cyclic hydrocarbon of up to _{10 (saturated cycloaliphatic hydrocarbon having 3 to} 10 carbon atoms) , which comprises a ring to the C ₃ ~C ₁₀ chain-like hydrocarbon (cycloaliphatic hydrocarbon having 3 to 10 carbon atoms), or C ₇ ~C from epoxide derivative that is characterized by an aliphatic hydrocarbon (aromatic aliphatic hydrocarbon having 7 to 10 carbon atoms) containing an aromatic ring of 3 to ₁₀ A method for producing hydroxypropionic acid or a salt thereof. The method for preparing 3-hydroxypropionic acid or a salt thereof according to claim 1, wherein the solvent is one of an ether compound represented by the following formula: Wherein _{R 9, R 10, R 11} , R 12 and R ₁₃ are independently C _1~10 of saturated aliphatic hydrocarbons (saturated aliphatic hydrocarbon having 1 to 10 carbon atoms having no branches) not between, C _3, respectively to ₁₀ branches with aliphatic hydrocarbons (branched aliphatic hydrocarbon having 3 to 10 carbon atoms), the saturated cyclic hydrocarbon of _{C 3 ~ 10 (saturated cyclohydrocarbon having} 3 to 10 carbon atoms) of the, including the ring of C ₃ - ₁₀ chain-like hydrocarbon (cycloaliphatic hydrocarbon having 3 to 10 carbon atoms) or, an aliphatic hydrocarbon (aromatic aliphatic hydrocarbon having 7 to 10 carbon atoms) containing an aromatic ring of C ₇ ~ _10; m is an integer from 1 to 10 and n is an integer from 2 to 5. The method of claim 1, wherein the acid is sulfuric acid, hydrochloric acid, nitric acid, acetic acid, HF, H ₃ PO ₄ , perchloric acid, p- toluene sulfonic acid, trifluoromethylsulfonic acid, Amberlite IR-120, Dowex 50, Permutit RS, Permutite C 50D, Zeolit 225, CM-Sephadex C-25, CM-Sephadex C-50, Amberlite IRC-50, Permutit C, Permutite H, Permutite H-70, Zeolit 236, SP-Sephadex C-25, SP-Sephadex A process for preparing malonate derivatives from epoxide derivatives, which is selected from the group consisting of C-50. According to claim 1, wherein the base is pyridine, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, calcium hydroxide, or a basic resin from the epoxide derivative, characterized in that the 3-hydroxypropionic acid or salt thereof How to manufacture. The method of claim 7 or 8, wherein the acid or base is supported on a solid support. According to claim 1, wherein the step (c) is carried out at a temperature range of 20 ~ 110 ℃, the reaction of the hydroxy derivative or hydroxy from epoxide derivatives, characterized in that the reaction proceeds under nitrogen, argon or air atmosphere Method for manufacturing.