JP3482371B2 - Method for carbonylation of epoxide derivatives - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a carbonylation reaction conversion method for an epoxide derivative, which is excellent in reaction activity, selectivity and yield. Epoxide More specifically the present invention is to select the co-bar <br/> belt suitable solvent in the presence of a catalyst, by adjusting the reaction temperature and pressure within a proper range, having excellent product selectivity and yield Hydroesterification of derivatives (hy
The present invention relates to a reaction conversion method.

The present invention also relates to a method for producing a 1,3-alkanediol by carrying out a carbonylation reaction of an epoxide derivative. More specifically, the present invention relates to a method for preparing an epoxide derivative from a cobalt catalyst and a promoter. The present invention relates to a method of reacting with carbon monoxide and an alcohol to effectively convert it into a 3-hydroxyester, and subjecting the product to a hydrogenation reaction to convert it into a 1,3-alkanediol compound.

[0003]

2. Description of the Related Art Epoxide derivatives can be easily converted into difunctional compounds through a carbonylation reaction. Although such bifunctional compounds have been used as intermediates for useful organic compounds,
As a typical compound among them, an epoxide derivative is
There are 3-hydroxy ester derivatives synthesized by arsenide mud esterification reaction.

As a method for synthesizing a 3-hydroxyester derivative from an epoxide derivative, US Pat.
5,901 and 4,973,741 use methyl rhodium and ruthenium as catalysts in the presence of carbon monoxide and alcohols to convert methyl 3-hydroxypropionate from ethylene oxide to methyl 3-hydroxypropionate.
The description is for the synthesis of However, the above-mentioned U.S. Pat.
The yield of hydroxypropionate is as low as 60%,
There is a problem that other by-products are also produced in a considerable amount.

Other known methods for converting epoxides into 3-hydroxyesters by hydroesterification have yields of only 40 to 60% [(1) Dal.
canali, E .; Foa, M .; Synthesis
1986, 492. (2) Heck, R .; F. J. A
m. Chem. Soc. , 1963, 85, 1460.
(3) Eisemann, J .; L. ; Yamarti
no, R.N. L. Howard, Jr .; J. F. J. O
rg. Chem. 1961,2102. ]. It is considered that the reason for the low yield is that the isomerization reaction of the starting material easily occurs.

On the other hand, US Pat. Nos. 5,310,948 and 5,359,081 describe a process for carbonylation of epoxides in which epoxides and carbon monoxide are reacted in the presence of cobalt and a pyridine derivative. Announced that β-lactone was mainly produced as a reaction product and 3-hydroxyester was produced as a by-product.

[0007] I previously described urchin, 3-hydroxy ester derivatives effective to a method for economically synthesis is fact is not yet discovered.

Accordingly, the present inventors have found that the carbonylation conversion of an epoxide to provide an intermediate useful for the synthesis of organic compounds and alkanediols.
As sion) method, an epoxide derivative is reacted with carbon monoxide and an alcohol in the presence of a suitable equivalent solvent and cobalt catalysts, the 3-hydroxy ester derivatives by adjusting the reaction temperature and pressure within a proper range in a high yield Develop a synthetic hydroesterification method.

Since the 3-hydroxy ester derivative has two functional groups, it is known that it can be used as a solvent, a resin and a coating material, and it can be easily converted into another compound and used as a raw material for pharmaceuticals. It can also be used as an intermediate for synthesizing alkanediol as a raw material for polyester. On the other hand, alkanediol is a raw material for polyester synthesis.
It only not, is used a lot as well as an intermediate coating and organic synthesis. The synthesis route of the 1,3-diol is as follows: The hydrogenation reaction of the 3-hydroxyaldehyde derivative synthesized by the hydroformylation reaction of the epoxide derivative as shown in the following reaction formula.
It is general that the aldehyde group is converted to an alcohol group via n) to synthesize.

[Chemical 15] In synthesizing 1,3-alkanediols , 3
Even if the hydroxy ester is used as an intermediate, the yield and the expensive catalyst are problems during the synthesis of the 3-hydroxy ester. Thus the effective catalytic system of ethylene oxide
It is the actual situation that a method for obtaining a 1,3-alkanediol in a high yield by reacting this product with hydrogen to hydroesterify it to synthesize a 3-hydroxyester derivative by utilizing it has not been found yet. .

On the other hand, the present inventors synthesized a 3-hydroxyester intermediate by hydroesterifying an epoxide derivative according to the following reaction formula, and reacted the produced ester intermediate with hydrogen to obtain a high yield. Rate of 1,3
-Has developed a new process for obtaining alkanediols and a catalyst system for the hydroesterification reaction to obtain them.

[Chemical 16]

The purpose of the present invention is to solve the above-use a suitable solvent and a cobalt catalyst, by adjusting the reaction temperature and pressure within a proper range, in a high yield by hydroesterification reaction of the epoxide derivative It is to provide a method for synthesizing a 3-hydroxyester derivative.

Another object of the present invention is to react an epoxide derivative with carbon monoxide and an alcohol in the presence of a catalyst system consisting of a cobalt catalyst and a promoter to effectively convert the epoxide derivative into a 3-hydroxyester, thereby forming the above-mentioned product. 1,3-comprising the step of converting a product into a diol compound through a hydrogenation reaction
It is to provide a new method for producing alkanediol.

Another object of the present invention is a carbonylation reaction which reacts an epoxide derivative with carbon monoxide and an alcohol to effectively convert it into a 3-hydroxyester in the presence of a catalyst system comprising a cobalt catalyst and a promoter. At
It is to provide a new method for producing 1,3-alkanediol in high yield by developing a catalyst system having high activity and selectivity.

Another object of the present invention is to provide a new process for preparing a 1,3-alkanediol which can reduce the cost of the catalyst by using imidazole or its derivative as a promoter.

[0014]

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

[0015]

DETAILED DESCRIPTION OF THE INVENTION

A preferred embodiment of the present invention will be described below in detail.

The present embodiment relates to a carbonylation reaction conversion method of an epoxide derivative for synthesizing an intermediate 3 -hydroxyester derivative useful for the synthesis of organic compounds and alkanediols.

[0018] 3-hydroxy ester derivatives used as intermediates before Kia Le Kanji ol is synthesized through hydroesterification reaction of the epoxide derivative. The hydroesterification reaction is carried out by reacting an epoxide derivative with carbon monoxide and an alcohol in the presence of a suitable solvent using a cobalt catalyst. At this time, the reaction temperature is 3
It is preferable to carry out the reaction in the range of 0 to 130 ° C. and in the range of 40 to 110 ° C. CO pressure during the reaction is 100 to 3
000 psi (about 0.689 × 106 to 2.067 × 1
07 Pa) range, 200-1500 psi
It is preferably in the range of (about 1.378 × 10 6 to 1.033 × 10 7 Pa) .

Epoxide derivative used in the present embodiment
The body is represented by the following structural formula (E).

[Chemical 17] In the formula (E), R20 and R21 are each independently
To hydrogen; or a C1-C20 saturated straight-chain aliphatic carbon
Hydrogenated hydrocarbons, side chain aliphatic hydrocarbons, saturated cyclized hydrocarbons
Elementary, cyclic hydrocarbon containing ring, aliphatic carbonization containing aromatic ring
Hydrogen, in which at least one carbon chain hydrogen is F or C
Hydrocarbons substituted by l, aromatic carbons without substituents
Hydrogen, hydrogen of aromatic ring is at least one of F, Cl,
Substituted with a min group, nitrile group, or alkoxy group
Aromatic hydrocarbons.

As a preferred example of the epoxide derivative
Is ethylene oxide, propylene oxide, 1-butene
Oxide, 1-pentene oxide, 1-hexeneoxy
Side, 1-heptene oxide, 1-octene oxide,
1-nonene oxide, 1-decene oxide, 2-methyl
-Propylene oxide, 2-methyl-1-buteneoxy
2-methyl-1-pentene oxide, 2-methyl-
1-hexene oxide, 2-methyl-1-heptene oxy
Sid, 2-methyl-1-octene oxide, 2-methyl
-1-nonene oxide, 2-methyl-1-deceneoxy
De, 2-ethyl-1-butene oxide, 2-ethyl-1
-Pentene oxide, 2-ethyl-1-hexeneoxy
2-ethyl-1-heptene oxide, 2-ethyl-
1-octene oxide, 2-ethyl-1-noneneoxy
2-ethyl-1-decene oxide or this compound
At least one or more hydrogens in the intermediate carbons of
C5 carbon chain substituted compounds, arylben
Zen oxide, 2-methyl-arylbenzeneoxy
Or aromatic compounds such as styrene oxide
There are compounds containing rings.

[0021] wherein the alcohol is R "is table with OH, R"
Is C ₁ -C ₂₀ saturated or unsaturated linear hydrocarbon, side chain hydrocarbon, cyclic hydrocarbon or aromatic hydrocarbon or linear hydrocarbon containing aromatic group, preferably methyl, ethyl, isopropyl, Such as cyclohexyl, phenyl or benzyl.

A typical example of the cobalt catalyst is Co ₂
There is (CO) ₈ , and a promoter for promoting the reaction can also be used. At this time, the concentration of the product is adjusted to 1 to 50% by weight, preferably 5 to 40% by weight in the total solution.

As the solvent, an ether compound represented by the following formula (G-1), (G-2) or (G-3) or a compound represented by the following formula (G-4) may be used, the reactive with epoxide derivative R "OH Ru have use <br/> as direct solvent.

[Chemical 18]

[Chemical 19]

[Chemical 20]

[Chemical 21] Formula (G-1), (G-2), (G-3) or (G
In _{-4), R 22, R 23} , R 24, R 25 and _{R 26} are each independently _C 1 saturated straight chain aliphatic hydrocarbons _{-C 10,} side-chain aliphatic hydrocarbons, saturated A cyclized hydrocarbon, a chain hydrocarbon containing a ring, or an aliphatic hydrocarbon containing an aromatic ring ,

R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁
And R ₃₂ are each independently hydrogen; C _{1 to} C ₄ side chain or straight chain saturated hydrocarbon; F or Cl; or C ₁ to
An alkoxy group having carbon atoms of C _3, and,

P is a constant of 1 to 10, and q is a constant of 2 to 5.

(G-1), (G-2), (G-3)
Alternatively, when the solvent (G-4) is used, the 3-hydroxyester derivative is synthesized, and then the product 3-hydroxyester derivative is separated with water. When the solvent is alcohol, especially methyl, ethyl, isopropyl alcohol, the solvent is vacuum dried to separate the product,
When alcohol having more carbon atoms is used, it is separated by using water.

The 3-hydroxyester compound produced by the hydroesterification reaction of the epoxide derivative of the present embodiment is represented by the following formula (H-1) or (H-2) .

R ₂₀ , R ₂₁ and R ″ are as described above.

[Chemical formula 22]

[Chemical formula 23] At the time of the hydroesterification reaction of the present embodiment, the carbonyl compound [(H-1) or (H-
Besides the 2)], an isomer and by-products are produced respectively according to the type of the epoxide reactant.

Next, the epoxide derivative with hydroesterification synthesizing 3-hydroxy ester intermediate, the resulting ester intermediate is described how to obtain a 1,3-alkanediol by hydrogenation.

The method for hydroesterifying an epoxide derivative according to the present embodiment is as follows: (a) using a catalytic amount of a cobalt compound and an effective amount of a catalyst promoter, epoxide, carbon monoxide and an alcohol (R'OH). At a temperature of 30 to 150 ° C. and 50 to 3000 psi (about 0.344 × 10 6 to 2.067
X107 Pa), and the reaction is carried out under the pressure condition of 3-
2 to 95w of hydroxy ester and its derivatives
t% , (b) separating the product and solvent from the catalyst and promoter , and (c) separating the separated product and solvent in the presence of a hydrogenation catalyst at a temperature of 30 to 350 ° C. and 50 to 500
0 psi (about 0.344 × 106 to 3.445 × 107
It is reacted with hydrogen under a pressure of Pa), to produce a hydrogenation reaction mixture containing 1,3-alkanediol, and, separating and recovering; (d) 1,3-alkanediol from the product mixture It is characterized in that it consists of stages.
That is, the present embodiment is not limited to the use of an effective catalyst system.
In order to increase the yield of hydroxy ester and maximize the production of 1,3-alkanediol, the epoxide derivative is first hydroesterified.

As a catalyst system for the hydroesterification reaction, Co ₂ (CO) ₈ which is a cobalt type catalyst is used alone, or Co ₂ (CO) ₈ and imidazole, pyridine, pyrrole, pyrazine, pyrazole, pyrimidine as a promoter are used. (Pyrimidine), piperidine (piperi)
Dine) or a compound obtained by mixing these with an organic compound of a derivative is used, and a compound of the phosphine family is used without being bound. The ratio of cobalt compound to promoter is in the range of 1/0 to 1/100. In this embodiment, an imidazole derivative represented by the following chemical formula (1) is used. Imidazole and its derivatives are inexpensive and effective in reducing the cost of the catalyst.

[Chemical formula 24] In the above formula (1) , R ₁₄ , R ₁₅ , R ₁₆ and R
₁₇ independently represents hydrogen; C _1-10 side chain aliphatic hydrocarbon, straight chain aliphatic hydrocarbon, saturated cyclized hydrocarbon,
A chain hydrocarbon containing a ring or an aliphatic hydrocarbon containing an aromatic ring; F; Cl; an alkoxy group having a carbon number of C1 to ₃ ; OH; a side chain aliphatic carbon having a carbon number of _{1 to 10} containing OH Hydrogen; a straight chain aliphatic hydrocarbon containing OH; a saturated cyclized hydrocarbon containing OH; a chain hydrocarbon containing a ring containing OH; or an aliphatic hydrocarbon containing an aromatic ring containing OH is there.

The reaction conditions, at a temperature range of 30 to 0.99 ° C. while using a suitable solvent in the presence of an alcohol, preferably 40 to 120 ° C. and a pressure of CO is 50 to 3000 ps i (about 0.344 × 106A to HOB 2.067
× 107 Pa), preferably 100 to 1500 ps
i (about 0.689 × 106 to 1.033 × 107 Pa)
It is carried out in.

The above epoxide derivatives are represented by the following chemical formula (2) .

[Chemical 25] Prior Symbol formula (2), R ₁ and R ₂ are each independently hydrogen; C ₁ -C ₂₀ saturated straight-chain aliphatic hydrocarbon side chain aliphatic hydrocarbons, saturated cyclic hydrocarbons , A chain hydrocarbon containing a ring, or an aliphatic hydrocarbon containing an aromatic ring;
Alternatively, among the above hydrocarbons, at least one hydrogen in a carbon chain is substituted with F, Cl, or Br, an aromatic hydrocarbon having no substituent, or at least one hydrogen in an aromatic ring. It is an aromatic hydrocarbon substituted with F, Cl, an amine group, a nitrile group or an alkoxy group.

Preferred examples of the epoxide derivative are ethylene oxide, propylene oxide, 1-butene oxide, 1-pentene oxide, 1-heptene oxide, 1-octene oxide, 1-nonene oxide, 1
-Decene oxide, 2-methyl-propylene oxide,
Epifluorohydrin, epichlorohydrin, epibromohydrin, glycidol, methylglycidate,
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-1-nonene oxide, 2-methyl-1-decene 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, arylbenzene oxide, styrene oxide and the like.

[0035] The alcohol is table with R'OH, R '
_Are C _1-20 saturated or unsaturated linear hydrocarbons, side chain hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons, or linear hydrocarbons containing aromatics. Preferably R'is methyl, ethyl, isopropyl, cyclohexyl, phenyl, or benzyl.

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

The ether compound has a structural formula represented by the following chemical formula (3), (4) or (5) .

[Chemical formula 26]

[Chemical 27]

[Chemical 28] In the formula (3), (4) or (5) , R ₃ , R
₄ , R ₅ , R ₆ and R ₇ are each independently a C _1-10 saturated linear aliphatic hydrocarbon, a side chain aliphatic hydrocarbon, a saturated cyclized hydrocarbon, or a chain form containing a ring. A hydrocarbon or an aliphatic hydrocarbon containing an aromatic ring ,

M is a constant of 1 to 10, and n is a constant of 2 to 5.

[0039] The substituted aromatic compound has a structure represented by the following chemical formula (6).

[Chemical 29] In the formula (6) , R ₈ , R ₉ , R ₁₀ , R ₁₁ ,
R < ₁₂ > and R < ₁₃ > are each independently hydrogen, _C1-4 side chain saturated hydrocarbon, _C1-4 straight chain saturated hydrocarbon, F, C.
1 or an alkoxy group having _{1 to 3} carbon atoms.

3 produced by the hydroesterification reaction
-The concentration of hydroxy ester and its derivatives is 2-95 wt% in the total solution, preferably 5-90
wt%. The product ester compound is represented by the following chemical formula (7) or (8) .

[Chemical 30]

[Chemical 31] In the formula (7) or (8) , R ₁ , R ₂ and R ′ are as described above.

The compounds of the above formula (7) or (8) are
Since it is a compound containing a bifunctional group, it can be used as an intermediate for organic synthesis or as a coating material.

The product and the solvent are separated from the catalyst and the promoter by vacuum distillation or extraction with water, and the separation method depends on the kind of the solvent. When the solvent of the chemical formula (3) or (6) is used, the 3-hydroxy ester derivative produced by synthesizing the β-hydroxy ester derivative is separated using water. When the solvent is one of the chemical formulas (4) and (5) or an alcohol, particularly methyl, ethyl, and isopropyl alcohol, the solvent is vacuum distilled to separate the product, and an alcohol having more carbon atoms is used. If this is the case, separate with water as described above. At this time, the separation method using water is performed in the reaction mixture at 20 to 3000 psi (about 1.378 x 10).
5 to 2.067 × 107 Pa) in the presence of CO, 100
Water is added at a temperature of not higher than 0 ° C to extract 3-hydroxyester and its derivatives into the aqueous layer.

The separated product and solvent may or may not be separated and may be separated by a hydrogenation step.
ion) and the separated catalyst and promoter components are partially or wholly returned to the hydroesterification step for reaction.

Hydrogenation reaction (hydrogenatio)
n) is a Cu-Cr-based catalyst (copperc) as a catalyst.
romate) or Pd / C is preferable, 100-
250 ° C temperature range and 200-3000 psi (approx.
It is performed under a pressure condition of 1.378 × 10 6 to 2.067 × 10 7 Pa) .

The alkanediol produced through the hydrogenation reaction is separated and recovered to obtain the final product 1,3-alkanediol.

The invention according to this embodiment, Ru can more clearly understood me by the examples <br/> below. The example below
It is for illustrative purposes of the invention according to this embodiment, not be construed as constituting an attempt to limit the area of the invention.

[0047]

Examples <Epoxide Hydroesterification Reaction> (Examples 46 to 49: Ethylene Epoxide (EO)
Effect of temperature on the droesterification reaction)

85 mg (0.25 mmo) of catalyst Co ₂ (CO) ₈ was added to a 45 mL Parr high pressure reactor purged with nitrogen.
1) was added and dissolved in 10 mL of methanol (MeOH). The amount of the cobalt catalyst was tables in mmole units of metal atoms for quantitative comparison. 1.1 g (25 mmol) of ethylene oxide (EO) was added to the reactor. CO pressure in the reactor is 500 psi (approximately 3.445 ×
The pressure was increased to 106 Pa) and the temperature was raised to the reaction temperature while stirring. The temperature was allowed to proceed for 2 hours Mahan response lowered to room temperature, the remaining gas was removed. Then, the metal component was removed from the reaction mixture to obtain a product. The results of analysis by gas chromatography (GC) are shown in Table 1 below . As shown in Table 1, 50-100
As a result of changing to ℃, it can be seen that the higher the temperature, the higher the product yield. However, if the temperature is too high, the yield of by-products also increases. Therefore, 80 ° C was the most suitable reaction temperature.

[Table 1] a) MHP: methyl 3-hydroxypropionate (m
Ethyl3-hydropropionate)

B) MOE: 2-methoxyethanol (2
-Methyethanol [(HO (CH ₂ ) ₂
OMe])

C) acetaldecht
Hyde ) , oligomers , or unknown compounds ( Examples 50-53: propylene epoxide (PO))
Effect of temperature on hydroesterification reaction)

68 mg (0.20 mmol) of Co ₂ (CO) ₈ was added to a 45 mL Parr high pressure reactor purged with nitrogen.
Was dissolved in 10 mL of methanol (MeOH).
The amount of the cobalt catalyst was tables in mmole units of metal atoms for quantitative comparison. 0.58 g (10 mmol) of propylene oxide (PO) was added to the reactor. CO pressure to the reactor is 1000 psi (about 0.689
X107 Pa) and the temperature was raised to the reaction temperature while stirring. In the case of Example 52, 64 mg of K ₂ CO ₃ was added as a promoter in addition to the cobalt catalyst. 1
Was allowed to proceed for 5 hours Mahan response, the temperature is lowered to room temperature, the remaining gas was removed. Then, the metal component was removed from the reaction mixture to obtain a product. The results of analysis by gas chromatography are shown in Table 2 below . Shown in Table 2 below
Sea urchin, as in the case of ethylene oxide, the preferred reaction temperature is 80 ° C., in Example 52 and Example 51 was not used with promoters, all showed similar results.

[Table 2] a) MHB: methyl 3-hydroxybutyrate (met
hyl3-hydroxybutyrate [CH ₃ C
H (OH) CH ₂ CO ₂ CH ₃ ])

B) MOP: 1-methoxy-2-propanol (1-methoxy-2-propanol [C
_{H 3 CH (OH) CH 2} (OMe) ]) (Example 54 to 59: Effect of pressure on hydro esterification reaction)

The same procedure as in Examples 46 to 49 was performed except that the reaction temperature was set to 80 ° C. and the time and the carbon monoxide pressure were changed as shown in Table 3 below.
It was The results are shown in Table 3 . As shown in Table 3, the results of Examples 54 to 56, by the time increases, MHP product (methyl3-hydroxy
The amount of propionate) also Ri divided <br/> be gradually increased, mow yield changes of the product by pressure changes in the carbon monoxide partial in Example 57-59.

[Table 3] a) MHP: methyl 3-hydroxypropionate (m
Ethyl3-hydropropionate)

B) MOE: 2-methoxyethanol (2
-Methyethanol [HO (CH ₂ ) ₂ O
Me])

C) acetaldehyde
hyde), oligomers ( oligomers ), or unknown compounds (unknown compounds)

1 psi = 0.068948 bar = 0.
689 × 10 4 Pa ( Examples 60 to 64 and Comparative Example 11: Effect of solvent on hydroesterification reaction )

68 mg (0.20 mmol) Co ₂ (CO) ₈ was added to a 45 mL Parr high pressure reactor purged with nitrogen.
Was dissolved in 10 mL of solvent / MeOH (8/2 v / v). The amount of the cobalt catalyst was tables in mmole units of metal atoms for quantitative comparison. 0.58 g (10 mmol) of propylene oxide (PO) in the reactor
Was added. CO pressure of 1000 psi (approx.
0.689 × 10 7 Pa) and the temperature was raised to 80 ° C. with stirring. Was allowed to proceed for 15 hours Mahan response, the temperature is lowered to room temperature, the remaining gas was removed. Then, the metal component was removed from the reaction mixture to obtain a product. The results of analyzing this by gas chromatography are shown in Table 4.
It was shown to.

[Table 4] a) Used by mixing 2 mL of MeOH with 8 mL of each solvent

B) MHB: methyl 3-hydroxybutyrate (methyl3-hydroxybutyrate)
e [CH ₃ CH (OH) CH ₂ CO ₂ CH ₃ ])

C) MMHP: methyl 2-methyl-3 hydroxypropionate (methyl 2-methyl)
―3―hydropropionate [HOCH
_{2 CH (CH 3) CO 2} CH 3 ])

D) MOP: 1-methoxy-2-propanol (1-methoxy-2-propanol [C
H ₃ CH (OH) CH ₂ (OMe)])

In Example 60 using methanol, the PO conversion and MHB (m
Ethyl3-hydroxybutyrate) was excellent in selectivity. Example 61 with diethyl ether and Example 63 with methyl-t-butyl ether
The selectivity of the product was very good, but the reaction rate was slow.
In most of the solvent, but selectively was substituted poorly in PO (a position of the following reaction formula I) f CO insertion reaction occurs, under THF (Example 62), to excessive substituent ( The reaction also proceeds to the position b) in the following reaction formula I, and MMHP
(Methyl2-methyl-3-hydroxy
Propionate) was confirmed to be produced at about 5%. In Comparative Example 11 using dichloromethane, it was confirmed that the reaction hardly proceeded.

[Chemical 32] ( Examples 65 to 67: Hydroesterification reaction of various epoxide derivatives )

68 mg (0.20 mmol) Co ₂ (CO) ₈ was added to a 45 mL Parr high pressure reactor purged with nitrogen.
Was dissolved in 10 mL of methanol (MeOH).
The amount of the catalyst is expressed as mmo of metal atom for quantitative comparison.
Expressed in le units. Epoxide was added here as described in Table 9 below. CO pressure in reactor is 1000
It was filled to psi (about 0.689 × 10 7 Pa) , and the temperature was raised to 80 ° C. with stirring. 15:00
After completion of the reaction is allowed to proceed to Mahan response, the temperature is lowered to room temperature, to remove the remaining gas. Then, the metal component was removed from the reaction mixture to obtain a product. The results of analysis by gas chromatography are shown in Table 5 .

[Table 5] Each of a to epoxide) main product, b) by-products, and c) an isomer was shown in Table 6 below. Most of the by-products were produced by the direct attack of methanol on the substrate
Also than even the it was little by CO insertion reaction to those who are substrates substituents.

[Table 6] ( Examples 68 to 76: Co ₂ (C
O) ₈ catalyst for ethylene oxide hydroesterification )

The detailed content for this example is summarized in Table 7 below . A 450 mL Parr reactor was charged with a predetermined amount of solvent at room temperature and a nitrogen atmosphere, and then Co ₂ (CO) ₈ was charged. 5 COgas in the reactor
00ps i (about 3.445 × 106Pa) Mitsuru plus 80
℃ After 1 hour Ma攪拌were allowed to warm to, the gas is removed by lowering the temperature to room temperature, imidazole was added as the amount of accelerator was determined. Ethylene oxide was added to the reactor and CO at a predetermined pressure was charged into the reactor. Table 7
At the time of the reaction shown in Table 7 after heating to the temperature shown in
Mahan was allowed to respond. The reaction product was sampled by a tube during the reaction, 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.

[Table 7] Catalyst = 5 mmole, imidazole = 20 mmole,
Ethylene oxide = 500 mmole

1) 100 mL of methanol + tetraglyme

2) Imidazole 40 mmole

3) 1.4 mmole of ethylene oxide

4) Yield = selectivity × conversion rate

5) 3-HPM = methyl 3-hydroxypropionate or

3-Hydroxypropionic acid methyl ester

AA = acetaldehyde

DMA = acetaldehyde dimethyl acetal

ME = methoxyethanol

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

6) isolated dye (separated yield
( Percentage) ( Comparative Examples 12 to 13: Hydroesterification of ethylene oxide with Co ₂ (CO) ₈ catalyst )

In Comparative Example 12, 3-hydroxypyridine was used as a promoter instead of the above-mentioned imidazole,
Comparative Example 13 is than also using only Co 2 _{(CO) 8} without promoter as a catalyst, was analyzed in Example 68 and ethylene oxide hydroesterification to product synthesized in the same manner. The analysis results are shown in Table 8 below . Table 8
As shown in, when a pyridine derivative is used as an accelerator,
-HPM is produced in high yield, but a considerable amount of by-products including acetaldehyde are produced, and Co
It can be seen that the yield is very low when only ₂ (CO) ₈ is used as the catalyst.

[Table 8] 1) Catalyst = Co ₂ (CO) ₈ (1 mmole), 3-hydropyridine = 4 mmole, ethylene oxide = 200 mmole

2) Catalyst = Co ₂ (CO) ₈ (2.5 mm
ole), ethylene oxide = 650 mmole

3) Yield = selectivity × conversion rate

4) 3-HPM = methyl 3-hydroxypropionate or

3-Hydroxypropionic acid methyl ester

AA = acetaldehyde

DMA = acetaldehyde dimethyl acetal

ME = methoxyethanol

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

5) isolated dye (separated yield
Ratio) ( Examples 77 to 80: Hydroesterification reaction of other epoxide derivatives )

[0085] Example 77-80 is to exclude that the E varying the type of oxide instead of the ethylene oxide, to perform the experiment in the same manner as in Example 68 above, Table 9 below and the results Shown in .

[Table 9] Catalyst = 5 mmol, promoter = 10 mmol, epoxide = 500 mmol, temperature 80 ° C., pressure 34 bar, reaction time 4 hr, solvent = MeOH (200 mL).

1) isolated field (separated yield
Rate) ( Example 81: Hydrogenation reaction )

1 g of methyl 3-hydroxypropionate obtained from Examples 68 to 76 above was added to 10 m of MeOH.
After dissolving in L, add it to a 45 mL Parr reactor and add 0.5
g of copper chromate catalyst is added. 1500 psi (about 1.03 ) in the reactor at room temperature
3 × 10 7 Pa) hydrogen was added to increase the reactor temperature to 180
Heat to ℃ with stirring. After reacting for 15 hours, the reactor was cooled to room temperature, and then the reaction mixture was analyzed by GC. The conversion of methyl 3-hydroxypropionate is about 5%, and the selectivity of 1,3-propanediol is about 3%.
It was about%.

There is no simple modification of the invention according to the present embodiment.
Changes are easier for those with ordinary knowledge in this field.
And all such variations and modifications are within the scope of the invention.
Including.

[0089]

According to the onset light according to the present invention, in the presence of appropriate solvents and cobalt catalyst, the epoxide derivative under the conditions of CO pressure range of the reaction temperature and 100~3000psi of 30 to 130 ° C., and carbon monoxide It has an effect of the invention to provide a hydroesterification method for synthesizing a 3-hydroxyester derivative with high selectivity and yield by reacting with an alcohol. In addition, according to the method of the present invention, an epoxide derivative is reacted with carbon monoxide and an alcohol in a catalyst system composed of a cobalt catalyst and a promoter to effectively convert the epoxide derivative into a 3-hydroxy ester. , 3-alkanediol can be prepared, and by using a catalyst system having high activity and selectivity for the hydroesterification reaction, 3-hydroxy ester can be prepared in high yield, and imidazole or its derivative is used as a promoter. As a result, the cost of the catalyst can be reduced, and
It has the effect of inventing a new method for producing 3-alkanediols.

─────────────────────────────────────────────────── ───Continued from the front page (72) Inventor Yang Duk Joe Republic of Korea Daejeon Yousung-Ku Jong Min-Dong (no address) Expo part 404-502 (72) Inventor Byun Young Hung Tae Jeong Yousung of Korea Jung Min-Dong 462-5 Sejong Apart 110-203 (56) References JP-A-63-170338 (JP, A) JP-A-63-68544 (JP, A) JP-A-6-65223 (JP, A) JP-A-56-68644 (JP, A) Journal of the Chemical Society of Japan, 1979, No. 5, 635-640 (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 67/36-67/37 C07C 69/675 B01J 31/20

Claims (32)

(57) [Claims] 1. A catalyst system comprising an effective amount of a cobalt catalyst and an effective amount of a promoter selected from the group consisting of imidazole, pyrrole, pyrazine, pyrimidine, derivatives thereof, and mixtures thereof. , R "OH (wherein R" is Ru linear hydrocarbon der comprising linear hydrocarbons, saturated or unsaturated C ₁ -C _20, side chain hydrocarbon, a cyclic hydrocarbon or an aromatic hydrocarbon or aromatic) represented were charged to the reactor containing the alcohol and solvent in the reactor epoxide derivative was added to a pressure of CO is supplied such that the range of 100～3000Psi, and, 30 to the reaction temperature from room temperature method for synthesizing 3-hydroxy ester derivatives by hydroesterification reaction epoxide derivative, which comprises the steps of Ru was increased to a range of 130 ° C.. 2. The cobalt catalyst is Co ₂ (CO) ₈
The method for synthesizing a 3-hydroxyester derivative according to claim 1, wherein 3. The solvent has the following structural formula (G-1):
A compound represented by (G-2), (G-3) or (G-4) or an alcohol represented by R ″ OH (R ″ is the same as in claim 1 ) The method for synthesizing the 3-hydroxyester derivative according to claim 1 . [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] The structural formulas (G-1), (G-2), (G-3) or
In (G-4) , R ₂₂ , R ₂₃ , R ₂₄ , and R ₂₅
And R ₂₆ are each independently a C _{1 to} C ₁₀ saturated straight chain aliphatic hydrocarbon, a side chain aliphatic hydrocarbon, a saturated cyclized hydrocarbon, a chain hydrocarbon containing a ring, or an aromatic group. A ring-containing aliphatic hydrocarbon , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ and R
₃₂ are each independently _hydrogen; C 1 -C ₄ side chain or straight-chain saturated hydrocarbon; F or Cl; an alkoxy group having carbon or _C 1 -C _3, p is 1 to 10 it is a constant, and, q is a constant 2-5. Wherein said epoxide derivative according to claim 1, characterized by being represented by the following structural formula (E) 3-
Method for synthesizing hydroxy ester derivative . [Chemical 5] In the formula (E) , R ₂₀ and R ₂₁ are each independently hydrogen; or a C _{1 to} C ₂₀ saturated straight chain aliphatic hydrocarbon, a side chain aliphatic hydrocarbon, a saturated cyclized carbonization. Hydrogen, a chain type hydrocarbon containing a ring, an aliphatic hydrocarbon containing an aromatic ring, hydrogen of at least one or more carbon chains is F or C
a hydrocarbon substituted with l, an aromatic hydrocarbon having no substituent, an aromatic hydrocarbon in which hydrogen in the aromatic ring is substituted with at least one of F, Cl, an amine group, a nitrile group, or an alkoxy group. is there. 5. The CO pressure is 200 to 1500 p.
according to claim 1, characterized in that the range of si 3-
A method for synthesizing a hydroxy ester derivative. Wherein said reaction temperature, the method of synthesis according to claim 1, wherein the 3-hydroxy ester derivative which is a 40 to 110 ° C.. The concentration of 3-hydroxy ester derivatives of 7. The product at the hydroesterification reaction, 3-hydroxy ester derivative of claim 1, wherein 1 to 50 wt% in total solution Method of synthesis. The concentration of 3-hydroxy ester derivative 8. A product during the hydroesterification reaction, 3-hydroxy ester derivative according to claim 7, wherein 5 to 40% by weight total solution Method of synthesis. 9. A method of synthesizing 3-hydroxy ester derivative of claim 1, wherein said method further comprises the step of separating the 3-hydroxy ester derivative of the product. 10. The product separation step comprises the structural formula (G-1), (G-2), (G-3) or (G-4).
When using the solvent represented by
When the alcohol represented by OH is used, R ″ is C ₁ to
In the case of C ₃ hydrocarbons, the solvent is vacuum dried and separated,
The method for synthesizing a 3-hydroxy ester derivative according to claim 9, wherein when R ″ is a hydrocarbon having a C _{3 value} or more, separation is performed using water. 11. (a) An effective amount of a cobalt compound and imidazole, pyrrole, pyrazine, pyrimidine,
Using a catalyst system consisting of these derivatives, and an effective amount of a catalyst promoter selected from the group consisting of mixtures thereof, the epoxide is mixed with carbon monoxide and an alcohol (R'OH (R ' Is C1-20 saturated or unsaturated
Linear hydrocarbons, side chain hydrocarbons, cyclic hydrocarbons, aromatic carbons
Hydrogen, or 50 to a temperature of 0.99 ° C. to linear hydrocarbon is)) and 30 to containing aromatic 3000 ps i
To produce an intermediate 3-hydroxyester and its derivatives in an amount of 2 to 95 wt% , (b) separating the product and the solvent from the catalyst and the promoter , and (c) separating the mixture. 50-5000 at a temperature of 30-350 ° C. in the presence of a hydrogenation catalyst.
is reacted with hydrogen in ps i, produces a hydrogenation reaction mixture containing 1,3-alkanediol, and, a step that you separated and recovered from the product mixture; (d) 1,3-alkanediol A method for synthesizing a 1,3-alkanediol, comprising : 12. The 1,3-alkanediol according to claim 11, wherein the method of separating the product and the solvent in the step (b) from the catalyst and the promoter is vacuum distillation. Method. 13. The method for separating the product and the solvent in the step (b) from the catalyst and the promoter comprises adding water to the reaction mixture in the presence of CO at 20 to 3000 psi at a temperature of 100 ° C. or lower. The method for synthesizing a 1,3-alkanediol according to claim 11 , wherein the 3-hydroxyester of the intermediate product and its derivatives are extracted into an aqueous layer. 14. The method of claim 11, wherein the separated cobalt and promoter component, further comprising the step of reacting back to partially or totally step (a)
A method for synthesizing the described 1,3-alkanediol. 15. The method for synthesizing a 1,3-alkanediol according to claim 11, wherein the ratio of the cobalt compound to the accelerator is 1/0 to 1/100. 16. The method for synthesizing a 1,3-alkanediol according to claim 11 , wherein the accelerator is a derivative of imidazole represented by the following formula (1) . [Chemical 6] In the above formula (1) , R ₁₄ , R ₁₅ , R ₁₆ and R
₁₇ independently contains hydrogen; a C _1-10 side chain aliphatic hydrocarbon, a straight chain aliphatic hydrocarbon, a saturated cyclized hydrocarbon, a chain hydrocarbon containing a ring, or an aromatic ring. Aliphatic hydrocarbon; F; Cl; Alkoxy group having C _1-3 carbon atoms; OH; C _1-10 side chain aliphatic hydrocarbon containing OH; Linear aliphatic hydrocarbon containing OH; OH A saturated cyclized hydrocarbon containing; a chain hydrocarbon containing a ring containing OH; or an aliphatic hydrocarbon containing an aromatic ring containing OH. 17. The method of synthesizing a 1,3-alkanediol according to claim 15 , wherein the accelerator is imidazole. 18. The step (a) comprises 40 to 120.
The method for synthesizing a 1,3-alkanediol according to claim 11, which comprises a temperature range of ° C. 19. The step (a) comprises 100 to 15
A pressure range of 00 psi.
11. A method for synthesizing the 1,3-alkanediol according to 11 . 20. The method for synthesizing a 1,3-alkanediol according to claim 11 , wherein the epoxide is represented by the following formula (2) . [Chemical 7] In the formula (2) , R ₁ and R ₂ are each independently hydrogen; a C ₁ -C ₂₀ saturated straight chain aliphatic hydrocarbon,
A side chain aliphatic hydrocarbon, a saturated cyclized hydrocarbon, a chain hydrocarbon containing a ring, or an aliphatic hydrocarbon containing an aromatic ring; or among at least one or more carbon chains among the above hydrocarbons Hydrocarbons in which hydrogen is replaced by F, Cl or Br, aromatic hydrocarbons without substituents, or hydrogens in aromatic rings are replaced by at least one F, Cl, amine group, nitrile group, or alkoxy group. Are aromatic hydrocarbons. 21. The R'of the alcohol (R'OH)
Is a C _1-10 saturated straight chain aliphatic hydrocarbon, a side chain aliphatic hydrocarbon, a saturated cyclized hydrocarbon, a chain hydrocarbon containing a ring or an aliphatic hydrocarbon containing an aromatic ring. The method for synthesizing a 1,3-alkanediol according to claim 11, wherein 22. The solvent is represented by the following formulas (3), (4),
Alternatively, it is one of the ether compounds represented by (5) , and the method for synthesizing a 1,3-alkanediol according to claim 11 . [Chemical 8] [Chemical 9] [Chemical 10] In the formula (3), (4), or (5) , R ₃ , R
₄ , R ₅ , R ₆ and R ₇ are each independently a C _1-10 saturated straight chain aliphatic hydrocarbon, a side chain aliphatic hydrocarbon,
It is a saturated cyclized hydrocarbon, a chain hydrocarbon containing a ring, or an aliphatic hydrocarbon containing an aromatic ring; m is a constant of 1 to 10 and n is a constant of 2 to 5. 23. The method for synthesizing a 1,3-alkanediol according to claim 11, wherein the solvent is acetate. 24. The method for synthesizing a 1,3-alkanediol according to claim 11 , wherein the solvent is the alcohol (R′OH) according to claim 11 . 25. The method for synthesizing a 1,3-alkanediol according to claim 11 , wherein the solvent is represented by the following formula (6) . [Chemical 11>] In the formula (6) , R ₈ , R ₉ , R ₁₀ , R ₁₁ ,
R < ₁₂ > and R <_13> are each independently hydrogen, _C1-4 side chain saturated hydrocarbon, _C1-4 straight chain saturated hydrocarbon, F, C.
1 or an alkoxy group having _{1 to 3} carbon atoms. 26. The product is represented by the following formula (7) or
The method for synthesizing a 1,3-alkanediol according to claim 11 , which is an ester compound represented by (8) . [Chemical 12] [Chemical 13] In the formula (7) or (8), R ₁ and R ₂ are each independently hydrogen; C _{1 to} C ₂₀ saturated straight chain aliphatic hydrocarbon, side chain aliphatic hydrocarbon, and saturated. A cyclized hydrocarbon, a chain hydrocarbon containing a ring, or an aliphatic hydrocarbon containing an aromatic ring; or, in the hydrocarbons, at least one hydrogen of the carbon chain is replaced with F, Cl or Br. , A non-substituted aromatic hydrocarbon, or an aromatic ring in which hydrogen in the aromatic ring is replaced by at least one F, Cl, amine group, nitrile group or alkoxy group. 27. hydrogenation catalyst in the step (c) is, according to claim 11, characterized in that it is selected from the group consisting of compounds of Kron copper (copperchromate) and Pd / C system 1, 3 -A method for synthesizing alkanediols. 28. The hydrogen pressure in step (c) is 200.
The method for synthesizing a 1,3-alkanediol according to claim 11, which comprises a pressure range of 1 to 3000 psi. 29. The reaction temperature of step (c) is 100.
12. The method for synthesizing a 1,3-alkanediol according to claim 11 , characterized in that 30. Hydroesterification of an epoxide derivative
React to synthesize 3-hydroxy ester derivative
In the catalyst system for
A catalyst system comprising a promoter selected from the group consisting of pyrrole, pyrazine, pyrimidine, derivatives thereof, and mixtures thereof. 31. The cobalt catalyst is Co ₂ (C ₂ O 3 ).
The catalyst system of claim 30, wherein the _8. 32. The catalyst system according to claim 30 , wherein an imidazole derivative represented by the following formula (1) is used as the promoter . [Chemical 14] In the above formula (1) , R ₁₄ , R ₁₅ , R ₁₆ and R
₁₇ independently represents hydrogen; C _1-10 side chain aliphatic hydrocarbon, straight chain aliphatic hydrocarbon, saturated cyclized hydrocarbon,
A chain hydrocarbon containing a ring or an aliphatic hydrocarbon containing an aromatic ring; F; Cl; an alkoxy group having a carbon number of C1 to ₃ ; OH; a side chain aliphatic carbon having a carbon number of _{1 to 10} containing OH Hydrogen; a linear aliphatic hydrocarbon containing OH; a saturated cyclized hydrocarbon containing OH; a chain hydrocarbon containing a ring containing OH; or a C _1-10 aromatic ring containing OH Aliphatic hydrocarbons.