JP2000281695A - Method for carbonylation of epoxide derivatives - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a 3-hydroxylaldehyde derivative or a 3-hydroxy acid ester derivative and a 1,3-alkanediol derivative from an epoxide derivative with high reactivity and selectivity. SOLUTION: A hydroformylation reaction is carried out using a cobalt compound and a transition metal compound in which a group 1X metal and a cyclopentagenyl group are bonded or a derivative thereof, or a hydroester using CO and H ₂ in the presence of a cobalt catalyst. The resulting 3-hydroxy acid ester derivative is subjected to a hydrogenation reaction in the presence of a catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for converting a carbonyl derivative of an epoxide derivative which is excellent in reaction activity, selectivity and yield. More specifically, the present invention provides a method for converting a epoxide derivative into a hydroformylation using a transition metal catalyst containing a cyclopentadienyl group having excellent reaction activity and selectivity, and a method for preparing an appropriate solvent in the presence of a cobalt catalyst. The present invention relates to a method for hydroesterification of an epoxide derivative, which is excellent in product selectivity and yield by selecting and controlling the reaction temperature and pressure in appropriate ranges.

[0002] The present invention also relates to a method for producing a 1,3-alkanediol by a carbonylation reaction of an epoxide derivative. More specifically, the present invention relates to a method for converting an epoxide derivative from a cobalt catalyst and a promoter. The present invention relates to a method for reacting carbon monoxide and an alcohol with a catalyst system to effectively convert the product to a 3-hydroxyester, and subjecting the product to a hydrogenation reaction to convert the product to a 1,3-alkanediol compound.

[0003]

BACKGROUND OF THE INVENTION Epoxide derivatives can be easily converted to difunctional compounds through a carbonylation reaction. Although such bifunctional compounds have been used as intermediates of useful organic compounds,
A typical compound among them is a 3-hydroxyester derivative synthesized by a hydroesterification reaction with a 3-hydroxyaldehyde derivative synthesized by a hydroformylation reaction of an epoxide derivative.

In the 3-hydroxyaldehyde derivative synthesized by the hydroformylation reaction of the epoxide derivative, an alkanediol can be formed by changing an aldehyde group to an alcohol group through a hydrogenation reaction (hydrogenation). Among such alkanediol derivatives, 1,3-propanediol (1,3-propadiol)
Nediol is known as an intermediate for synthesizing polyester used for fibers, films and the like. It is also used as a coating material and an intermediate for organic synthesis. On the other hand, since the 3-hydroxyester derivative obtained by subjecting the epoxide derivative to a hydroesterification reaction has two functional groups, it is known that it can be used as a solvent, a resin, or a substance for coating. It can be easily converted and can be used as a raw material for medicine. It can also be used as an intermediate for synthesizing alkanediol.

High selectivity at low temperature and pressure 3-
As a method for synthesizing a hydroxyaldehyde derivative, a method using a phosphine oxide ligand as a cobalt catalyst and a promoter is known. However, the use of a phosphine oxide ligand as a promoter has the disadvantage that the recovery and regeneration of the catalyst are complicated.

Accordingly, US Pat. No. 5,770,776
No. 5,723,389 and 5,731,478
No. describes the activity and selectivity of cobalt catalysts by using a cobalt catalyst in the reaction of hydroformylating ethylene oxide and producing an alkanediol through a hydrogenation reaction, and using other metal compounds or ligands as promoters instead of phosphine oxide ligands. It describes the content that can be enhanced.

As a method for synthesizing a 3-hydroxyester derivative from an epoxide derivative, US Pat.
Nos. 5,901 and 4,973,741 disclose methyl 3-hydroxypropionate from ethylene oxide in the presence of carbon monoxide and alcohol using rhodium and ruthenium as catalysts.
Propionate).
However, the above-mentioned U.S. Pat.
There is a problem that the yield of -hydroxypropionate is as low as about 60%, and a considerable amount of other by-products are produced.

Further, other known methods for converting an epoxide into a 3-hydroxyester by hydroesterification reaction have a yield of only about 40 to 60% [(1) Dal
canali, E .; Foa, M .; Synthesis
1986, 492. (2) Heck, R.A. F. J. A
m. Chem. Soc. , 1963, 85, 1460.
(3) Eisenmann, J .; L. ; Yamamarti
no, R .; L. Howard, Jr .; J. F. J. O
rg. Chem. 1961, 102. ]. It is considered that the reason for such a 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 epoxide carbonylation method in which an epoxide and carbon monoxide are reacted in the presence of cobalt and a pyridine derivative. Reported that β-lactone was mainly produced as a reaction product and 3-hydroxyester was produced as a by-product.

As described above, the fact is that an effective and economical method for synthesizing a 3-hydroxyester derivative has not been found yet.

[0011] Accordingly, the present inventors have proposed carbonyl conversion of epoxides to provide intermediates useful in the synthesis of organic compounds and alkanediols.
and a compound formed by reacting a transition metal compound in which a cyclopentadienyl group is bonded to a transition metal of Group 9 or a compound having one or more functional groups together with a cobalt compound. A hydroformylation method for synthesizing 3-hydroxyaldehyde derivatives with high reaction activity and selectivity using as a catalyst, and reacting epoxide derivatives with carbon monoxide and alcohol in the presence of a suitable solvent and a cobalt catalyst, and reacting in an appropriate range By controlling the temperature and pressure, a hydroesterification method for synthesizing 3-hydroxyester derivatives in high yield has been developed.

Since 3-hydroxyester derivatives have two functional groups, it is known that they can be used as solvents, resins, and coating substances, and can be easily converted to other compounds and used as raw materials for medicine. It can also be used as an intermediate for synthesizing alkanediol as a raw material for polyester. Alkanediol, on the other hand, is used not only as a raw material for polyester synthesis but also as an intermediate in coating and organic synthesis. The synthesis route of such 1,3-diol is based on a hydrogenation reaction of a 3-hydroxyaldehyde derivative synthesized by a hydroformylation reaction of an epoxide derivative as shown in the following reaction formula.
After n), the aldehyde group is generally converted to an alcohol group for synthesis.

[0013]

[Chemical formula 29]

In the synthesis of 1,3-alkanediol, when the above-mentioned prior art 3-hydroxyaldehyde is used as an intermediate, oligomer formation due to instability of the aldehyde itself and degradation of polyester quality due to by-product acetal are caused. However, even if the 3-hydroxyester is used as an intermediate, the yield and the cost of the catalyst are problematic during the synthesis of the 3-hydroxyester. Thus, ethylene oxide is hydroesterified by utilizing an effective catalyst system to synthesize a 3-hydroxyester derivative, and this product is reacted with hydrogen to give 1,3 in a high yield.
The reality is that a method for obtaining 3-alkanediol has not yet been found.

On the other hand, the present inventors have synthesized a 3-hydroxyester intermediate by hydroesterifying an epoxide derivative according to the following reaction formula and reacting the produced ester intermediate with hydrogen to obtain a high yield. 1,3 at rate
-A new process for obtaining alkanediols and a catalyst system for said hydroesterification reaction to obtain them have been developed.

[0016]

[Chemical formula 30]

[0017]

An object of the present invention is to provide a transition metal catalyst having excellent reaction activity and selectivity in hydroformylation of an epoxide derivative.

Another object of the present invention is to provide a transition metal catalyst which can easily recover and regenerate the catalyst in the hydroformylation reaction of an epoxide derivative.

Still another object of the present invention is to provide a high-selectivity and high-yield 3-hydroxyaldehyde derivative by hydroformylation of an epoxide derivative using a transition metal compound and a cobalt compound having excellent reaction activity and selectivity as catalysts. To provide a method for synthesizing

Still another object of the present invention is to provide a high yield of 3-hydroxyester by hydroesterification of an epoxide derivative by adjusting the reaction temperature and pressure to an appropriate range using an appropriate solvent and a cobalt catalyst. It is to provide a method for synthesizing a derivative.

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

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

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

[0024]

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

Hereinafter, the contents of the present invention will be described in detail.

The present invention relates to a method for converting an epoxide derivative into a carbonylation reaction for synthesizing an intermediate 3-hydroxyaldehyde derivative and a 3-hydroxyester derivative useful for synthesizing an organic compound and an alkanediol. .

The 3-hydroxyaldehyde derivative is synthesized through a hydroformylation reaction of an epoxide derivative. In the hydroformylation reaction, a transition metal compound containing a cyclopentadienyl group and a cobalt compound separately synthesized as a catalyst are dissolved in a water-insoluble solvent at room temperature, an epoxide derivative is added, and carbon monoxide and hydrogen (C
O / H ₂ ) to raise the temperature to the reaction temperature. In addition, after the transition metal compound containing a cyclopentadienyl group is synthesized in a non-aqueous reaction solution, the hydroformylation reaction can be allowed to proceed in-situ without another separation process.

In the transition metal compound containing a cyclopentadienyl group, the transition metal: cobalt compound has a molar ratio of 1: 1000 to 5: 1, preferably 1: 100 to 5: 1.
Used in a 2: 1 molar ratio. The molar ratio of CO / H ₂ fed to the hydroformylation reaction is about 3 / 1-1 / 10, preferably 2 / 1-1 / 5. The total pressure is 100-3000 psi, preferably 500
~ 2000 psi. Temperature from normal temperature to 30 ℃ ～ 12
The temperature was raised to about 0 ° C. to allow the hydroformylation reaction to proceed.
It is preferably performed at 0 to 100 ° C.

Hereinafter, the catalyst, solvent and epoxide derivative used in the hydroformylation reaction of the present invention will be described in detail.

The transition metal catalyst used in the hydroformylation reaction has a transition metal compound produced by bonding a cyclopentadienyl group and a transition metal of Group 9 or has a transition metal compound and one or more functional groups. It is a compound synthesized by reacting with a compound. The transition metal compound,
In addition to the cyclopentadienyl group, it can be bonded to another ligand, and can be represented by the following structural formula (A-1) or (A-
Represented by 2):

[0031]

[Chemical formula 1]

[0032]

[Chemical formula 2]

The compound represented by the formula (A-1) is entirely neutral or cationic, and M is 9 in the periodic table.
A transition metal of the group cobalt, rhodium or iridium, wherein the oxidation number of the metal is monovalent or trivalent;
BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , SO ₃ CF ₃ ⁻ or BR ′ ₄ ⁻ (R ′ is hydrogen; or a C _{1 to} C ₁₀ saturated or unsaturated aliphatic chain or cyclic hydrocarbon; A monovalent anion of an alkyl group having a carbon chain containing an aromatic hydrocarbon); a halogen of F, Cl, Br, or I;
Or a divalent anion of CO ₃ ^2- or SO ₄ ^2- ;
l is a constant of 0 to 2 when (a) is a monovalent anion or a halogen, and is 0 or 1 when (a) is a divalent anion; R _{1 to} R ₅ are each Independently hydrogen; C ₁
~C saturated or unsaturated _C20 aliphatic or aromatic hydrocarbons, or contain a terminal or intermediate nitrile group-chain, saturated or unsaturated containing terminal or intermediate to an amine group of the chain aliphatic hydrocarbon Or an aromatic hydrocarbon; or a halogen of F, Cl, Br, or I; X _a , Y
_b , and _Zc , a, b and c are constants of 0 to 3, and a + b
X _a , Y _b and Z _c are each independently carbon monoxide; a halogen of F, Cl, Br or I; a hydroxy group; a C _{1 to} C ₁₀ linear aliphatic or aromatic side chain aliphatic or aromatic hydrocarbons C ₁ -C _10; hydrocarbons;
Alkoxy having a C ₁ -C ₁₀ side chain aliphatic or aromatic hydrocarbon; C ₁ -C ₁₀ saturated or unsaturated aliphatic hydrocarbon or an aromatic hydrocarbon having a saturated or unsaturated aliphatic chain; A nitrile comprising: a ketone comprising a C _{1 to} C ₂₀ aliphatic chain or a cyclic hydrocarbon or an aromatic hydrocarbon; C ₁
Ethers including aliphatic or cyclic hydrocarbons or aromatic hydrocarbons _{~C 20; N (R 6)} (R 7) R 6 amine (the represented by (R _8), R ₇ and R ₈ are Each independently hydrogen or an alkyl group having a C ₁ -C ₂₀ saturated or unsaturated aliphatic chain or a carbon chain containing a cyclic hydrocarbon or an aromatic hydrocarbon); a C ₃ -C ₃₀ pyrrole (py)
role), pyrazine, pyrazole, imidazole
zole), pyrimidine, piperidine, pyridine (pyr)
or a derivative thereof; or a compound represented by the following formula (I), (II) or (III) or a mixture thereof:

[0034]

[Chemical formula 3]

[0035]

[Chemical formula 4]

[0036]

[Chemical formula 5]

In the above formulas (I), (II) and (III), Q ₁ is each independently N, P, As or Sb; Q ₂ and Q ₃ are each independently P, As or R _c , R _d and R _e each independently represent hydrogen; or a carbon chain containing a C _{1 to} C ₂₀ saturated or unsaturated aliphatic or cyclic hydrocarbon or aromatic hydrocarbon. An alkyl group, preferably hydrogen; an aliphatic hydrocarbon (C
₁ -C ₅ carbon chain or cyclohexyl); phenyl or benzyl; wherein the aliphatic hydrocarbon or aromatic ring nitrile group of the phenyl or benzyl, R _f R _g N- represented by an amine group (wherein R _f and, R _g is each independently hydrogen; or an alkyl group having a C _{1 to} C ₂₀ saturated or unsaturated aliphatic chain or a carbon chain containing a cyclic hydrocarbon or an aromatic hydrocarbon, preferably C ₁ to C 20. linear shaped carbon chain of C _10, a side chain-type carbon chains, cyclic compounds, or an aromatic hydrocarbon; f and g in each 0-2 constants, f + g is 2
A) a compound containing at least one aldehyde group or ketone group; a halogen of F, Cl, Br or I; or a phosphine group containing a C _{1 to} C ₃₀ saturated or unsaturated aliphatic or aromatic carbon; Arsine (arsi
ne) groups or stibine groups;
And R _c , R _d , and R _e, where c, d, and e are each 0 to
A constant of 3 and c + d + e = 3.

In the formula (A-2), M, (a) and R _{1 to} R ₅ are as defined in the formula (A-1); Or 0 or 1 or 2 when (a) is a divalent anion; X _{a '} is carbon monoxide; F, Cl, Br, Or a halogen of I; a hydroxy group; an alkoxy having a C ₁ -C ₁₀ saturated or unsaturated aliphatic or aromatic hydrocarbon; a nitrile containing a C ₁ -C ₁₀ aliphatic or aromatic hydrocarbon; A compound represented by (I), (II) or (III); and Y _{b ′} is carbon monoxide; a halogen of F, Cl, Br, or I; a hydroxy group; or a C ₁ -C ₁₀ . Alkoxy groups with saturated or unsaturated aliphatic or aromatic hydrocarbons; It is a compound capable of donating electrons to the metal in duplicate.

The transition metal compound represented by (A-1) or (A-2) itself can be used as a catalyst together with a cobalt compound during the hydroformylation reaction, and each of them independently has one or more functional groups. The new compound synthesized by reacting with the containing compound can be used as a catalyst in the hydroformylation reaction together with the cobalt compound. The transition metal compound of the present invention and the synthesized compound serve as a promoter that increases the catalytic activity and selectivity when used with a cobalt catalyst. The compound having one or more functional groups is represented by the following formula (B-1):
Represented by (B-2) and (B-3):

[0040]

[Chemical formula 6]

[0041]

[Chemical formula 7]

[0042]

[Chemical formula 8]

The formulas (B-1), (B-2) and (B-
In 3), Q ₄ , Q ₅ , Q ₆ and Q ₇ are each independently N, P, As or Sb; R ₉ , R ₉ ′,
R ₉ ″, R ₉ ″ ″, R ₉ ″ ″ and R ₉ ″ ″ are each independently hydrogen; or a C _{1 to} C ₂₀ aliphatic hydrocarbon, aromatic hydrocarbon, Or a hydrocarbon containing two kinds of these aliphatic hydrocarbons and aromatic hydrocarbons at the same time, preferably hydrogen; aliphatic hydrocarbons (C ₁ -C ₅ carbon chain or cyclohexyl); phenyl or benzyl; Hydrogen or an amine group represented by R _f R _g N- on the aromatic ring of phenyl or benzyl (the above-mentioned R _f and R
_g is each independently hydrogen; or an alkyl group having a C _{1 to} C ₂₀ saturated or unsaturated aliphatic chain or a carbon chain containing a cyclic hydrocarbon or an aromatic hydrocarbon, preferably C _{1 to} C 20. ₁₀ linear carbon chains, side chain carbon chains, ring compounds, or aromatic hydrocarbons;
Where f + g is 2), a compound containing at least one aldehyde group or ketone group; F, Cl, B
halogen r or _I; C 1 _{-C 30} aliphatic or aromatic phosphine group containing carbon, be arsine group or stibine group; and R _10, R ₁₀ 'and R _10' 'is, C ₁ ~
An alkyl group having a carbon chain containing aliphatic or cyclic hydrocarbons or aromatic hydrocarbons, saturated or unsaturated C _20, preferably linear-shaped carbon chain of C ₁ -C _10, a side chain-type carbon chain , A ring compound or an aromatic hydrocarbon.

The transition metal compound represented by the formula (A-1) or (A-2) and one or more compounds represented by the formula (B-1), (B-2) or (B-3) When reacted with a compound having a functional group of the following formula (C-1), (C-2),
A transition metal catalyst represented by (C-3), (C-4) or (C-5) is produced:

[0045]

[Chemical formula 9]

[0046]

[Chemical formula 10]

[0047]

[Chemical formula 11]

[0048]

[Chemical formula 12]

[0049]

[Chemical formula 13]

The formulas (C-1), (C-2) and (C-
3) In (C-4) or (C-5), M ₁ , M
₂ , M ₃ and M ₄ are cobalt, rhodium or iridium of transition metals of Group 9 in the periodic table, and the oxidation number of the metal is monovalent or trivalent; (b) is BF ₄ ⁻ , PF ₆ ⁻ , C
^{_{lO 4 -, SO 3 CF 3}} - , or BR _'4 ^- (wherein R'
Is a hydrogen; or a C _{1 to} C ₁₀ saturated or unsaturated aliphatic chain or an alkyl group having a carbon chain containing a cyclic hydrocarbon or an aromatic hydrocarbon);
1, a halogen of l, Br or I; or a divalent anion of CO ₃ ²⁻ or SO ₄ ²⁻ ; n is a constant of 0 to 8 when (b) is a monovalent anion or halogen. ,
When (b) is a divalent anion, a constant of 0 to 4;
R _{1 to} R ₅ are each independently hydrogen; a C _{1 to} C ₂₀ saturated or unsaturated aliphatic or aromatic hydrocarbon, containing a nitrile group at the terminal or middle of the chain, Saturated or unsaturated aliphatic or aromatic hydrocarbons containing an intermediate amine group; or F, Cl, Br,
Or a halogen of I; X _a1 , X _a2 , X _a3 , X _a4 ,
Y _b1 , Y _b2 , Y _b3 and Y _b4 each independently represent carbon monoxide; a halogen of F, Cl, Br or I; a hydroxy group; a C _{1 to} C ₁₀ straight-chain aliphatic or aromatic hydrocarbon; C
Side chain aliphatic or aromatic hydrocarbons _{1 ~C 10;} C _{1 ~C}
An alkoxy having ₁₀ side chain aliphatic or aromatic hydrocarbons; a nitrile containing a C ₁ -C ₁₀ saturated or unsaturated aliphatic hydrocarbon or an aromatic hydrocarbon having a saturated or unsaturated aliphatic chain; C ether including C ₁ of -C ₂₀ aliphatic or cyclic hydrocarbons or aromatic hydrocarbons; ketones containing aliphatic or cyclic hydrocarbons or aromatic hydrocarbons _{1 ~C 20 N (R 6)} (R ₇ ) An amine represented by (R ₈ ) (wherein R ₆ , R ₇ and R ₈ are each independently hydrogen or a C ₁ -C ₂₀ saturated or unsaturated aliphatic chain or cyclic hydrocarbon or aromatic An alkyl group having a carbon chain containing a group hydrocarbon); C ₃ -C ₃₀ pyrrole (pyrr)
ole), pyrazine (pyrazine), pyrazole (pyrazole), imidazole (imidazo)
le), pyrimidine, piperidine, pyridine
ine) or a derivative thereof; or the formula (I),
(II) or (III) a compound or a mixture _{thereof; Q 8, Q 9, Q} 10 and Q ₁₁ are located at each independently N, P, As or Sb; R _11, R ₁₁ ', R
₁₁ ″, R ₁₁ ″, R ₁₃ , R ₁₃ ′, R ₁₃ ″, R ₁₃ ″, R
_{15, R 15 ', R 15} '', R 15''', R 17, R 17 ',
R ₁₇ ″, R ₁₇ ″ ″, R ₁₇ ″ ″ and R ₁₇ ″ ″ are each independently hydrogen; a C _{1 to} C ₂₀ aliphatic hydrocarbon, aromatic hydrocarbon, or These aliphatic hydrocarbons and aromatic hydrocarbons 2
A hydrocarbon containing at least one kind, preferably hydrogen; an aliphatic hydrocarbon (C ₁ -C ₅ carbon chain or cyclohexyl); phenyl or benzyl;
Or a nitrile group on the aromatic ring of phenyl or benzyl,
an amine group represented by _f R _g N- (the R _f and R _g are
Each independently represents hydrogen; or an alkyl group having a C _{1 to} C ₂₀ saturated or unsaturated aliphatic chain or a carbon chain containing a cyclic hydrocarbon or an aromatic hydrocarbon;
A straight-chain carbon chain, a side-chain carbon chain, a cyclic compound, or an aromatic hydrocarbon having ₁ to ₁₀ carbon atoms; f and g are each a constant of 0 to 2, and f + g is 2), an aldehyde group or compound a ketone group containing at least one; C ₁ -C ₃₀ aliphatic or aromatic phosphine group containing carbon, be arsine group or stibine group;; F, Cl, Br or I halogen, and R _12, R ₁₄ and R ₁₆ are each independently C _1-
An alkyl group having a carbon chain containing aliphatic or cyclic hydrocarbons or aromatic hydrocarbons, saturated or unsaturated C _20, preferably linear-shaped carbon chain of C ₁ -C _10, a side chain-type carbon chain , A ring compound or an aromatic hydrocarbon.

A typical example of the cobalt compound used together with the transition metal catalyst containing a cyclopentadienyl group is Co ₂ (CO) ₈ . The transition metal catalyst is used by dissolving it in a fixed molar ratio with a cobalt compound in a water-insoluble ether-based solvent represented by the following structural formula (D):

[0052]

[Chemical formula 14]

In the above formula, R ₁₈ and R ₁₉ each independently represent a C ₁ -C ₂₀ straight-chain aliphatic hydrocarbon, side-chain aliphatic hydrocarbon, aromatic hydrocarbon, or these aliphatic hydrocarbon and aromatic hydrocarbon. It is a hydrocarbon containing two group hydrocarbons at the same time. A preferred solvent is methyl-t-butyl ether (MTB
In E), it is effective to use water saturated.

The epoxide derivative used in the present invention is represented by the following structural formula (E):

[0055]

[Chemical formula 15]

In the above formula, R ₂₀ and R ₂₁ are each independently hydrogen; or a C ₁ -C ₂₀ saturated straight-chain aliphatic hydrocarbon, side-chain aliphatic hydrocarbon, saturated cyclized hydrocarbon. , A chain hydrocarbon containing a ring, an aliphatic hydrocarbon containing an aromatic ring, and hydrogen of at least one carbon chain is F or C
1 is a hydrocarbon, an aromatic hydrocarbon having no substituent, an aromatic hydrocarbon in which the hydrogen of the aromatic ring is substituted with at least one of F, Cl, an amine group, a nitrile group, and an alkoxy group. is there.

Preferred examples of the epoxide derivative include ethylene oxide, propylene oxide, 1-butene oxide, 1-pentene oxide, 1-hexene oxide, 1-heptene oxide, 1-octene oxide,
1-nonene oxide, 1-decene oxide, 2-methyl-propylene oxide, 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 or at least one hydrogen at an intermediate carbon of these compounds is C ₁ -C ₁ .
And compounds substituted in the carbon chain of C _5, aryl benzene oxide, 2-methyl - aryl benzene oxides are the aromatic compound or a compound containing an aromatic ring such as styrene oxide.

The epoxide derivative represented by the above formula (E) produces a kind of 3-hydroxyaldehyde derivative of a carbonyl compound by a hydroformylation reaction. The 3-hydroxyaldehyde derivative has the following structural formula (F)
Represented by:

[0059]

[Chemical formula 31]

R ₂₀ and R ₂₁ are as described in the above formula (E).

In the hydroformylation reaction of the present invention,
In the reaction mixture, a small amount of the carbonyl compound (F) and an alkanediol which has undergone a hydrogenation reaction with the carbonyl group are produced, and compounds such as acetaldehyde, acetone and methyl ethyl ketone which are produced by the isomerization reaction of the epoxide are converted to the epoxide. It is produced in small amounts depending on the type of each.

Like the above-mentioned 3-hydroxyaldehyde derivative, the 3-hydroxyaldehyde used as an intermediate of alkanediol
The hydroxy ester derivative is synthesized through a hydroesterification reaction of the epoxide derivative. The hydroesterification reaction proceeds 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 30 to 130.
It is preferable to carry out the reaction in the range of 40 to 110 ° C. The pressure of CO during the reaction is 100-3000ps
i, preferably in the range of 200 to 1500 psi.

As the epoxide derivative, the same epoxide derivative as the compound (E) used in the hydroformylation reaction is used.

The alcohol is represented by R ″ OH, and R ″ includes a C ₁ -C ₂₀ saturated or unsaturated linear hydrocarbon, side chain hydrocarbon, cyclic hydrocarbon or aromatic hydrocarbon or aromatic. It is a linear hydrocarbon, preferably methyl, ethyl, isopropyl, cyclohexyl, phenyl or benzyl.

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

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. R ″ OH that reacts with the epoxide derivative is used directly as a solvent:

[0067]

[Chemical formula 16]

[0068]

[Chemical formula 17]

[0069]

[Chemical formula 18]

[0070]

[Chemical formula 19]

The formulas (G-1), (G-2) and (G-
In 3) and (G-4), R ₂₂ , R ₂₃ , R ₂₄ , and R ₂₅
And R ₂₆ are each independently a C ₁ -C ₁₀ saturated linear aliphatic hydrocarbon, side chain aliphatic hydrocarbon, saturated cyclized hydrocarbon, chain-containing hydrocarbon containing a ring, or aromatic An aliphatic hydrocarbon containing a ring; R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁
And R ₃₂ are each independently hydrogen; a C ₁ -C ₄ side chain or linear saturated hydrocarbon; F or Cl; or C ₁ -C
P is an alkoxy group having ₃ carbons;
10 is a constant, and q is a constant of 2 to 5.

(G-1), (G-2), (G-3)
Alternatively, when the solvent of (G-4) is used, after synthesizing a 3-hydroxyester derivative, the product 3-hydroxyester derivative is separated with water. When the solvent is alcohol, particularly methyl, ethyl, and isopropyl alcohol, the product is separated by vacuum drying the solvent,
When an alcohol having a larger number of carbon atoms is used, separation is performed using water.

The 3-hydroxyester compound produced by the hydroesterification reaction of the epoxide derivative of the present invention is represented by the following formula (H-1) or (H-2):
R ₂₀ , R ₂₁ and R ″ are as described above.

[0074]

[Chemical formula 32]

[0075]

[Chemical formula 33]

In the hydroesterification reaction of the present invention, in addition to the carbonyl compound [(H-1) or (H-2)], isomers and by-products are added to the reaction mixture depending on the type of the epoxide reactant. Each is generated.

The present invention relates to a method for hydroesterifying an epoxide derivative to synthesize a 3-hydroxyester intermediate, and hydrogenating the resulting ester intermediate to obtain a 1,3-alkanediol.

The process for hydroesterification of epoxide derivatives according to the present invention comprises the steps of (a) using a catalytic amount of a cobalt compound and an effective amount of a catalyst promoter to convert epoxide, carbon monoxide and alcohol (R'OH) from 30 to 30; Reacting at a temperature of 150 ° C. and a pressure of 50 to 3000 psig to produce 2 to 95 wt% of the intermediate 3-hydroxyester and its derivatives; (b) converting the product and the solvent from a catalyst and a promoter. (C) separating the separated product and the solvent in the presence of a hydrogenation catalyst for 30 to 3 minutes;
Reacting with hydrogen at a temperature of 50 ° C. and a pressure of 50 to 5000 psig to produce a hydrogenation reaction mixture comprising 1,3-alkanediol; and (d) the 1,3
-Separating and recovering the alkanediol from the product mixture. That is, the present invention aims at maximizing the production of 1,3-alkanediol by increasing the yield of 3-hydroxyester by using an effective catalyst system. First, an epoxide derivative is subjected to a hydroesterification reaction. As the catalyst system for the hydroesterification reaction, a cobalt-based catalyst such as Co ₂ (CO) ₈ may be used alone, or Co ₂ (CO) ₈ and imidazole, pyridine, pyrrole, pyrazine, pyrazole, pyrimidine may be used as a promoter. , Piperidine (piperi
dine) or a compound obtained by mixing these derivatives with an organic compound, and a compound obtained by not binding a phosphine-based compound. The ratio between the cobalt compound and the accelerator is in the range of 1/0 to 1/100. In the present invention, an imidazole derivative represented by the following formula (1) is used. Imidazole and its derivatives are inexpensive and have the effect of reducing the cost of the catalyst.

[0079]

[Chemical formula 34]

In the above formula, R ₁₄ , R ₁₅ , R ₁₆ and R
₁₇ is each independently hydrogen; a C _1-10 side chain aliphatic hydrocarbon, a linear aliphatic hydrocarbon, a saturated cyclized hydrocarbon, a chain hydrocarbon containing a ring, or a fat containing an aromatic ring Group hydrocarbons; F; Cl; alkoxy groups having _{1 to 3} carbon atoms; OH; C1 to ₁₀ side chain aliphatic hydrocarbons containing OH; linear aliphatic hydrocarbons containing OH; A saturated cyclic hydrocarbon; a chain hydrocarbon containing a ring containing OH; or an aliphatic hydrocarbon containing an aromatic ring containing OH.

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

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

[0083]

[Chemical formula 35]

In the above formula 2, R ₁ and R ₂ are each independently hydrogen; C _{1 to} C ₂₀ saturated straight-chain aliphatic hydrocarbon, side-chain aliphatic hydrocarbon, saturated cyclized hydrocarbon ,
A chain hydrocarbon containing a ring, or an aliphatic hydrocarbon containing an aromatic ring; or a hydrocarbon in which hydrogen of at least one or more carbon chains in the hydrocarbons is substituted with F, Cl, or Br; An aromatic hydrocarbon having no substituent or an aromatic hydrocarbon in which hydrogen of an aromatic ring is substituted with at least one of F, Cl, an amine group, a nitrile group, and an alkoxy group.

Preferred examples of the epoxide derivative include ethylene oxide, propylene oxide, 1-butene oxide, 1-pentene oxide, 1-heptene oxide, 1-octene oxide, 1-nonene oxide,
-Decene oxide, 2-methyl-propylene oxide,
Epifluorohydrin, epichlorohydrin, epibromohydrin, glycidol, methyl glycidat (methyl glycidat)
e), 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.

[0086] The alcohol appears at R'OH, R 'is a linear hydrocarbon containing a saturated or unsaturated linear hydrocarbons C _{1 to 20,} the side chain hydrocarbon, cyclic hydrocarbon, aromatic hydrocarbon or aromatic and, It is. Preferably R 'is methyl, ethyl, isopropyl, cyclohexyl, phenyl, or benzyl.

As the solvent, an ether compound, a substituted aromatic compound, or an acetate compound is additionally used, or R′OH is directly used as the solvent.

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

[0089]

[Chemical formula 36]

[0090]

[Chemical formula 37]

[0091]

[Chemical formula 38]

In the above formula, R ₃ , R ₄ , R ₅ , R ₆
And R ₇ are each independently a C _1-10 saturated linear aliphatic hydrocarbon, side chain aliphatic hydrocarbon, saturated cyclized hydrocarbon, chain hydrocarbon containing a ring, or an aromatic ring. M is a constant of 1 to 10, and n is a constant of 2 to 5.

The substituted aromatic compound has a structural formula represented by the following chemical formula (6):

[0094]

[Chemical formula 39]

In the above formula, R ₈ , R ₉ , R ₁₀ ,
R ₁₁ , R ₁₂ and R ₁₃ are each independently hydrogen, C _1-4 side-chain saturated hydrocarbon, C _1-4 straight-chain saturated hydrocarbon, F, C
l or an alkoxy group having _{1 to 3} carbon atoms.

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

[0097]

[Chemical formula 40]

[0098]

[Chemical formula 41]

In the above formula, R ₁ , R ₂ and R ′ are as described above.

Since the compounds of the formulas 7 and 8 are compounds containing a bifunctional group, they themselves can be used as intermediates for organic synthesis or substances for coating.

The product and the solvent are separated from the catalyst and the promoter by vacuum distillation or extraction with water. The separation method depends on the type of the solvent. When the solvent represented by the chemical formula 3 or 6 is used, the 3-hydroxyester derivative generated by synthesizing the β-hydroxyester derivative is separated using water. The solvent is the above-mentioned chemical formula 4,
In the case of 5 or alcohol, especially in the case of methyl, ethyl and isopropyl alcohol, the product is separated by vacuum distillation of the solvent, and when an alcohol having a higher carbon number is used, water is added as described above. Separate using. At this time, in a separation method using water, water is added to the reaction mixture in the presence of 20 to 3000 psig of CO at a temperature of 100 ° C. or less to extract 3-hydroxyester and its derivatives into an aqueous layer.

The separated products and solvents can be separated or not separated and subjected to a hydrogenation step (hydrogenat).
and the separated catalyst and promoter components are partially or wholly returned to the hydroesterification step to react.

Hydrogenation reaction (hydrogenatio)
n) is a Cu—Cr-based catalyst (copper)
chromate) or Pd / C is preferred, 100
Performed in a temperature range of ~ 250 ° C and pressure conditions of 200-3000 psig.

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

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

[0106]

EXAMPLES Examples 1 to 13: Synthesis of transition metal catalysts 1 to 13 Example 1: Catalyst 1 (IrCp * Cl ₂ PPh ₂ CH ₂ C)
Synthesis of H ₂ CH ₂ CH ₂ PPh ₂ IrCp * Cl ₂ ) [IrC was added to a 100 mL branch flask equipped with a condenser.
p * Cl ₂ ] ₂ compound 0.5 g (0.628 mmol)
(Cp * = pentamethylcyclopentagenenyl (pen
tamylcyclopentadieny
l)) was dissolved in 50 mL of methylene chloride solvent. Here, PPh ₂ CH ₂ CH ₂ CH ₂ CH ₂ PPh ₂
After adding 0.27 g (0.63 mmol), the temperature was raised and refluxed for 3-5 hours, and then the solvent was reduced to about 10 mL under vacuum. 20 mL of diethyl ether was added thereto to separate an orange precipitate.
The product yield was 95-98%.

Example 2: Catalyst 2 (IrCp * Cl ₂ PP
h in _{2 CH 2 CH 2 CH 2 PPh} 2 IrCp * Cl 2) loaded 100mL branch with flask condenser [IRC
p * Cl ₂ ] ₂ compound 0.5 g (0.628 mmol)
(Cp * = pentamylcyclopentent
adienyl) was dissolved in 50 mL of methylene chloride solvent. Here, PPh ₂ CH ₂ CH ₂ CH ₂ PPh
₂ After adding 0.260 g (0.628 mmol), the temperature was raised to reflux for 3 to 5 hours, and the solvent was removed under vacuum for 1 hour.
The volume was reduced to about 0 mL. Here is diethyl ether 20
mL was added to separate the orange precipitate. The product yield was 95-96%.

Example 3 Catalyst 3 (IrCp * Cl ₂ PP
h in _{2 CH 2 CH 2 PPh 2 IrCp} * Cl 2) loaded 100mL branch with flask condenser [IRC
p * Cl ₂ ] ₂ compound 0.5 g (0.628 mmol)
(Cp * = pentamylcyclopentent
adienyl) was dissolved in 50 mL of methylene chloride solvent. Here, PPh ₂ CH ₂ CH ₂ PPh ₂₀ .
After adding 25 g (0.628 mmol), the temperature was raised to reflux for 3 to 5 hours, and the solvent was reduced to about 10 mL under vacuum. 20 mL of diethyl ether was added thereto to separate an orange precipitate. The product yield is 96
９８98%.

Example 4: Catalyst 4 (IrCp * Cl ₂ PP
Synthesis of h ₂ CH ₂ PPh ₂ IrCp * Cl ₂ ) [IrC was added to a 100 mL branched flask equipped with a condenser.
p * Cl ₂ ] ₂ compound 0.5 g (0.628 mmol
l) (Cp * = pentamylcyclope)
ntadienyl) was dissolved in 50 mL of methylene chloride solvent. Where PPh ₂ CH ₂ PPh ₂ 0.2
After adding 41 g (0.628 mmol), the temperature was raised to reflux for 3 to 5 hours, and the solvent was reduced to about 10 mL under vacuum. 20 mL of diethyl ether was added thereto to separate an orange precipitate. The product yield is 96
９７97%.

Example 5: Catalyst 5 (IrCp * Cl ₂ PC
Synthesis of y ₂ CH ₂ CH ₂ PCy ₂ IrCp * Cl ₂ ) [IrC was added to a 100 mL branched flask equipped with a condenser.
p * Cl ₂ ] ₂ compound 0.5 g (0.628 mmol)
(Cp * = pentamylcyclopentent
adienyl) was dissolved in 50 mL of methylene chloride solvent. Here, PCy ₂ CH ₂ CH ₂ PCy ₂ 0.
265 g (0.628 mmol) (Cy = cycloh
After adding exyl), the temperature was raised to reflux for 3 to 5 hours, and the solvent was reduced to about 10 mL under vacuum. 20 mL of diethyl ether was added thereto to separate an orange precipitate. The product yield was 95-97%.

Example 6: Catalyst 6 (IrCp * Cl ₂ (p
0.5 g (0.628 mmol) of [IrCp * Cl ₂ ] ₂ compound in a 100 mL branched flask (Cp * = pent)
Amylcyclopentadienyl) was dissolved in 50 mL of methylene chloride solvent. After 0.1 g (1.3 mmol) of pyridine was added thereto and stirred for 3 to 5 hours, the solvent was reduced to about 10 mL under vacuum. 20 mL of diethyl ether was added thereto, and a yellow precipitate was separated. The product yield was 93-95%.

Example 7: Catalyst 7 (IrCp * Cl ₂ P
Synthesis of (CH ₂ CH ₂ CN) ₃ ) 0.5 g (0.628 mmol) of [IrCp * Cl ₂ ] ₂ compound in a 100 mL branched flask (Cp * = pent)
Amylcyclopentadienyl) was dissolved in 50 mL of methylene chloride solvent. Here, 0.263 g of P (CH ₂ CH ₂ CN) ₃ (1.3 mmo)
l) and after stirring for 1-2 hours, the solvent is removed under vacuum
The volume was reduced to about 0 mL. Here is diethyl ether 20
mL was added to separate the orange precipitate. The product yield was 94-96%.

Example 8: Catalyst 8 (IrCp * Cl ₂ PP
Synthesis of h ₃ ) 0.5 g (0.628 mmol) of [IrCp * Cl ₂ ] ₂ compound in a 100 mL branched flask (Cp * = pent)
Amylcyclopentadienyl) was dissolved in 50 mL of methylene chloride solvent. 6 here added PPh ₃ 0.341g (1.3mmol)
After stirring for 7 hours, the solvent was reduced to about 10 mL under vacuum. 20 mL of diethyl ether was added thereto to separate an orange precipitate. 96-98% product yield
Met.

Example 9: Catalyst 9 (IrCp * Cl ₂ PC
Synthesis of y ₃ ) [IrCp * Cl ₂ ] ₂ compound 0.5 g (0.628 mmol) (Cp * = pent) in a 100 mL branched flask
Amylcyclopentadienyl) was dissolved in 50 mL of methylene chloride solvent. Here, 0.364 g (1.3 mmol) of PCy ₃ was added to add 2 to
After stirring for 3 hours, the solvent was reduced to about 10 mL under vacuum. 20 mL of diethyl ether was added thereto to separate an orange precipitate. 95-97% product yield
Met.

Example 10: Catalyst 10 (IrCp * Cl ₂₎
(IrCp * Cl ₂ ] ₂ compound 0.5 g (0.628 mmol) (Cp * = pent) in a 100 mL branched flask
Amylcyclopentadienyl) was dissolved in 50 mL of methylene chloride solvent. After stirring for 2 to 3 hours while adding 1 atm of CO thereto, the solvent was reduced to about 10 mL under vacuum. 20 mL of diethyl ether was added thereto, and a yellow precipitate was separated. The product yield was 90-94%.

Example 11: Catalyst 11 ([IrCp * (C
Synthesis of [H ₃ CN) ₃ ] (OTf) ₂ ) 0.5 g (0.628 mmol) of [IrCp * Cl ₂ ] ₂ compound in a 100 mL branched flask (Cp * = pent)
Amylcyclopentadienyl) was dissolved in acetonitrile (50 mL) solvent. Here A
gOTf 0.25 g (1.256 mmol) was added to give 1
After stirring for hours, the formed AgCl was filtered (f
lter) and the solvent was reduced to about 10 mL under vacuum. 20 mL of diethyl ether was added thereto to separate a pale yellow precipitate. The product yield is 90-
93%.

Example 12: Catalyst 12 ((Cp * Cl ₂ I
r) (Ph) P [CH ₂ CH ₂ PPh ₂ IrCp * Cl
₂ ] ₂ ) 0.5 g (0.628 mmol) of [IrCp * Cl ₂ ] ₂ compound in a 100 mL branched flask (Cp * = pent)
Amylcyclopentadienyl) was dissolved in a methylene chloride (50 mL) solvent. Here, PhP [CH ₂ CH ₂ PPh ₂ ] ₂ (TRIPHO
S) After adding 0.224 g (0.419 mmol) and stirring for 5 hours, the solvent was reduced to about 5 mL under vacuum. To this, 30 mL of diethyl ether was added to separate a pale yellow precipitate. The product yield was 80-85%.

Example 13: Catalyst 13 ((Cp * Cl ₂ I
r) P [CH ₂ CH ₂ PPh ₂ IrCp * Cl ₂ ] ₃ )
0.5 g (0.628 mmol) of [IrCp * Cl ₂ ] ₂ compound in a 100 mL branched flask (Cp * = pent)
Amylcyclopentadienyl) was dissolved in a methylene chloride (50 mL) solvent. Here, P [CH ₂ CH ₂ PPh ₂ ] ₃ (TETRAPHO
S) After adding 0.211 g (0.314 mmol) and stirring for 5 hours, the solvent was reduced to about 5 mL under vacuum. To this, 30 mL of diethyl ether was added to separate a pale orange precipitate. 80-85% product yield
Met.

(Epoxide Hydroformylation Reaction) Examples 14 to 15 and Comparative Examples 1 to 2 At room temperature, a 450 mL Parr reactor was charged with 100 mL of water-saturated methyl tert-butyl ether (methyl-t-butyl ether).
t-butyl ether; MTBE) and C
o ₂ (CO) ₈ (0.25 mmol) and the catalyst 2 synthesized according to Example 2 were added in the molar ratio described in Table 1. After mounting the reactor under nitrogen, CO / H ₂ (1 /
1) The mixture was replaced three times with a mixed gas. To this reactor was added 11 g of ethylene oxide (EO) and CO / H ₂ (450 /
1050 psi) was fed to the reactor. After increasing the temperature to 80 ° C., the reaction was allowed to proceed for the time shown in Table 1. During the reaction, the reaction product was sampled using a tube (sa
The product, 3-hydroxypropanal (HPA) was analyzed by GC. After the temperature was lowered to room temperature after the reaction, the catalyst was removed and the product was separated and quantified.

Comparative Examples 1 and 2 were the same as in Example 1 except that triphenylphosphine oxide (OPPh ₃ ) was used in place of the catalyst 2 in the molar ratio shown in Table 1 below.
The product synthesized by hydroformylation of ethylene oxide in the same manner as in Example 4 was analyzed. The analysis results
The HPA of the product is listed in Table 1 in small amounts.
-Contains propanediol (1,3-PD). Example 1 using the transition metal catalyst of the present invention and a cobalt compound
It can be seen that the catalytic activity and selectivity for HPA in 4 to 15 are higher than those in Comparative Examples 1 and 2.

[0121]

[Table 1]

A) P / M: transition metal catalyst (Promoter) / cobalt (Metal) b) AA: acetaldehyde c) TOF: turnover rate per hour (Turn Over F)
frequency (sub.mol / cat.mole)
/ Hr)) put saturated methyl -t- butyl ether water 10mL in Examples 16-20 and Comparative Examples 3-6 at ambient temperature for 45mLParr reactor _{(MTBE), Co 2 (CO} ) 8 (0.25mmol ) And Example 2
Was added in the molar ratio shown in Table 2 below. After installing the reactor under nitrogen, CO / H
₂ Replaced three times with (1/1) mixed gas. The reactor was charged with the amount of ethylene oxide (EO) shown in Table 2 below and charged with CO / H ₂ (450/1050 psi).
After increasing the temperature to 80 ° C., the reaction was allowed to proceed for the time described in Table 2. After the temperature was lowered to room temperature after the reaction, the product was separated and quantified after removing the catalyst. The results are shown in Table 2.

In Comparative Example 3, the catalyst 2 was omitted and only the cobalt compound was used as the catalyst. Comparative Examples 4 to 6
Instead of triphenylphosphine oxide (OPPh
₃ ) was used in the molar ratios shown in Table 2 below, and Comparative Example 4 was used.
Was synthesized by hydroformylation of ethylene oxide in the same manner as in Example 16, except that MTBE containing 10 ppm or less of water was used, and ethylene oxide was added in the amounts shown in Table 2 below. The product was analyzed. The analysis results are shown in Table 2 and the HPA of the product was a small amount of 1,3-propanediol (1,3-
PD). When the molar ratio of Ir to Co ([Ir] / [Co]) in the transition metal catalyst is about 1/15 (Examples 16 and 17), the catalytic activity of the reaction and the HPA It can be seen that the selectivity for is particularly excellent.

[0124]

[Table 2]

A) P / M: Transition metal catalyst (Promot
er) / Cobalt (Metal) Examples 21-38 The catalyst was changed and the hydroformylation reaction was allowed to proceed as described in Table 3 below. The reaction was performed in the same manner as in Example 14, except for the catalyst used and the reaction time. The results are reported in Table 3, where the product HPA contains a small amount of 1,3-propanediol (1,3-PD).
As can be seen from Table 3, when the catalyst synthesized according to the present invention is used, the reaction activity and the selectivity are high.

[0126]

[Table 3]

A) P / M: transition metal catalyst (Promoter) / cobalt (Metal) b) [IrCp ^* Cl ₂ ] ₂ : product of STREM c) RhCp * -p: RhCp * Cl ₂ (PPh ₂ CH)
₂ CH ₂ CH ₂ PPh ₂ ) RhCp * Cl ₂ (Rh = Rhodium, Cp * = pentameth)
ylcyclopentadienyl) d) oligomer Example 39 Instead of using catalyst 1 isolated after synthesis [IrCp * C
l ₂ ] ₂ compound in MTBE and then PPh ₂ CH ₂
CH ₂ CH ₂ CH ₂ PPh ₂ (diphenylphosphinobutan)
e)) and refluxed for 24 hours without separating the synthesized catalyst 1, except that Co ₂ (CO) ₈ was added to this solution to allow the catalytic reaction to proceed, except that the catalyst was allowed to proceed. It was carried out in. The results were also very similar to Example 22.

Example 40 Instead of using the catalyst 10 separated after the synthesis, [IrCp *
After placing the Cl ₂ ] ₂ compound in MTBE, the mixture was refluxed for 5 hours in a CO atmosphere without separating the synthesized catalyst 10, but Co ₂ (CO) ₈ was added to this solution to allow the catalytic reaction to proceed. The procedure was performed in the same manner as in Example 31 except for the above. The results were also very similar to Example 31.

Examples 41 to 43 and Comparative Examples 7 to 9 The hydroformylation reaction was carried out in the same manner as in Example 14 except that the type of the epoxide derivative as the reactant was changed. In Comparative Examples 7 to 9, hydroformylation of ethylene oxide was performed in the same manner as in Examples 41 to 43, except that triphenylphosphine oxide (OPPh ₃ ) was used as a catalyst in the molar ratio shown in Table 4 below. The synthesized product was analyzed. The product contains a trace amount of an isomeric ketone compound, and the yields shown in Table 4 below are based on the product from which the solvent, catalyst, by-products, and the like are removed and isolated. . The results are shown in Table 4 below, and show that when the catalyst 2 is used together with a cobalt compound, the catalyst activity is excellent.

[0130]

[Table 4]

Example 44 At room temperature, 150 mL of water-saturated methyl tert-butyl ether (MTBE) was charged into a 450 mL Parr reactor at room temperature, and cobalt (0.85 g) and catalyst 2 synthesized according to Example 2 (0. 22g). After mounting the reactor under nitrogen, it was replaced three times with CO / H ₂ (1/1) mixed gas. 11 g of ethylene oxide (EO) was added to this reactor.
Was added and CO / H ₂ (450/1050 psi) was added. After raising the temperature to 80 ° C., the reaction was allowed to proceed for 1.5 hours. After the temperature was lowered to room temperature after the reaction, the product was extracted with water under nitrogen, and the yield was measured. After the extraction, the MTBE solution containing the catalyst was put into the reactor again, and the catalytic reaction was performed in the same manner. At this time, the yield was 8
When reused twice as in Example 15 at 2.6%,
It was 82% after 1.5 hours, and when it was reused three, four and five times, it showed about 72%, 65% and 57% respectively after 2 hours reaction. From the results, it can be seen that the catalytic activity of the reaction and the selectivity for HPA are high even after reuse several times.

Example 45 At room temperature, 150 mL of water-saturated methyl tert-butyl ether was charged into a 450 mL Parr reactor at room temperature, and cobalt (0.85 g) and the catalyst 1 synthesized according to Example 10 were added.
0 (0.15 g). After mounting the reactor under nitrogen, it was replaced three times with CO / H ₂ (1/1) mixed gas. To this reactor was added 11 g of ethylene oxide to produce CO / H
₂ (450/1050 psi). 80 ℃
Then, the reaction was carried out for 1.5 hours. After the temperature was lowered to room temperature after the reaction, the product was extracted with water under nitrogen, and the yield was measured. MT containing catalyst after extraction
The BE solution was put into the reactor again, and the catalytic reaction was performed in the same manner. At this time, the yield was 81%, and the second time showed a higher yield of about 84% than that of Example 31 after the reaction for 2 hours. About 76%, 69% and 59% were represented. From this result, it can be seen that the catalyst activity of the reaction and the selectivity for HPA are high even if it is reused several times.

Comparative Example 10 A 450 mL Parr reactor at room temperature was charged with 150 mL of water-saturated methyl tert-butyl ether, and cobalt (0.87 g) and OPPh ₃ (0.40 g) were charged. After mounting the reactor under nitrogen, CO / H ₂ (1
/ 1) Replaced three times with the mixed gas. To this reactor was added 11 g of ethylene oxide (EO) and CO / H ₂ (450
/ 1050 psi). After raising the temperature to 80 ° C., the reaction was performed for 2 hours. After the reaction, the temperature was lowered to room temperature, and the product was extracted with water under nitrogen, and the yield was measured. After the extraction, the MTBE solution containing the catalyst was put into the reactor again to perform the catalytic reaction in the same manner. At this time, the yield was about 73% as in Comparative Example 2,
When reused three times, four times and five times, about 71%, 64%, 58% and about 51% were shown after the reaction for 2 hours, respectively.
Compared with Examples 44 and 45, the catalytic activity of the reaction and HP
The selectivity for A was low.

(Epoxide Hydroesterification Reaction) Examples 46 to 49: Effect of Temperature on Ethylene Epoxide (EO) Hydroesterification Reaction Catalyst C was added to a 45 mL Parr high-pressure reactor substituted with nitrogen.
85 mg (0.25 mmol) of o ₂ (CO) ₈ was added and dissolved in 10 mL of methanol (MeOH). The amount of the cobalt catalyst was calculated as mmo of the metal atom for quantitative comparison.
It was expressed in le units. 1.1 g (25 mmol) of ethylene oxide (EO) was added to the reactor. Fill the reactor with a CO pressure of 500 psi,
The temperature was raised to the reaction temperature while stirring. After the reaction was allowed to proceed for 2 hours, the temperature was lowered to room temperature, and the remaining gas was removed. Then, a metal component was removed from the reaction mixture to obtain a product. This was analyzed by gas chromatography (GC), and the result is shown in Table 5 below. As described in Table 5 below, as a result of changing from 50 to 100 ° C,
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.

[0135]

[Table 5]

A) MHP: Methyl 3-hydroxypropionate (m
ethyl 3-hydroxypropionat
e) b) MOE: 2-methoxyethanol (2-metho)
xyethanol) (HO (CH ₂ ) ₂ OMe) c) acetaldehyde,
Oligomers or unknown unknowns
own Compounds,) Example 50 to 53: Co ₂ to 45mLParr high pressure reactor which is substituted to the effect of nitrogen of temperature on hydroesterification reaction of propylene epoxide (PO)
68 mg (0.20 mmol) of (CO) ₈ was added and dissolved in 10 mL of methanol (MeOH). For quantitative comparison, the amount of the cobalt catalyst is the amount of mmole of metal atom.
It was expressed in units. 0.58 g (10 mmol) of propylene oxide (PO) was added to the reactor. The reactor was charged with a CO pressure of 1000 psi and the temperature was raised to the reaction temperature with stirring. In the case of Example 52, K ₂ CO ₃ was used as a promoter in addition to the cobalt catalyst.
4 mg was added. After the reaction was allowed to proceed for 15 hours, the temperature was lowered to room temperature, and the remaining gas was removed. Then, a metal component was removed from the reaction mixture to obtain a product. This was analyzed by gas chromatography, and the result is shown in Table 6 below. As in the case of ethylene oxide, the preferred reaction temperature was 80 ° C., and Examples 52 with and without the promoter all showed similar results.

[0137]

[Table 6]

A) MHB: Methyl 3-hydroxybutyrate (met
hyl 3-hydroxybutyrate) (CH
_{3 CH (OH) CH 2 CO} 2 CH 3) b) MOP: 1- methoxy-2-propanol (1-m
ethanol-2-propanol (CH ₃ CH (O
H) CH ₂ (OMe)) Examples 54-59: Effect of Pressure on Hydroesterification Reaction The reaction temperature was 80 ° C. and the time and carbon monoxide pressure were varied as described in Table 7 below. The results were described in Table 7 by the same method as in Examples 46 to 49, except for the above. From the results of Examples 54 to 56, the MHP (methyl 3-hy
It can be seen that the amount of hydroxypropionate also increases over time, and in Examples 57-59 the change in product yield due to the change in carbon monoxide pressure can be seen.

[0139]

[Table 7]

A) MHP: Methyl 3-hydroxypropionate (m
ethyl 3-hydroxypropionat
e) b) MOE: 2-methoxyethanol (2-metho)
xyethanol) (HO (CH ₂ ) ₂ OMe) c) acetaldehyde (acetaldehyd)
e), oligomers or unknowns (u
known compounds) (psi = 0.0
68948Bar) Examples 60 to 64 and Comparative Example 11: Co ₂ to 45mLParr high pressure reactor which is substituted to the effect of nitrogen of solvent to hydroesterification reaction
68 mg (0.20 mmol) of (CO) ₈ was added and dissolved in 10 mL of a solvent / MeOH (8/2 v / v). The amount of the cobalt catalyst was expressed in mmole of metal atom for quantitative comparison. 0.58 g (10 mmol) of propylene oxide (PO) was added to the reactor. The reactor was charged with a CO pressure of 1000 psi and the temperature was increased to 80 ° C. with stirring. After the reaction was allowed to proceed for 15 hours, the temperature was lowered to room temperature, and the remaining gas was removed. Then, a metal component was removed from the reaction mixture to obtain a product. This was analyzed by gas chromatography, and the results are shown in Table 8.

[0141]

[Table 8]

A) 8 mL of each solvent is used by mixing 2 mL of MeOH. B) MHB: Methyl 3-hydroxybutyrate (met)
hyl 3-hydroxybutyrate (CH _{3
CH (OH) CH 2 CO 2} CH 3) c) MMHP: Methyl 2-Methyl-3-hydroxy propionate (methyl 2-methyl-3- hy
hydroxypropionate (HOCH ₂ CH
(CH ₃ ) CO ₂ CH ₃ ) d) MOP: 1-methoxy-2-propanol (1-m
ethanol-2-propanol (CH ₃ CH (O
H) CH ₂ (OMe)) Example 60 using methanol showed a higher PO conversion ratio and a higher MHB (methyl)
The selectivity of 3-hydroxybutyrate) was excellent. Example 61 using diethyl ether and methyl-
In Example 63 using t-butyl ether, the selectivity of the product was very excellent, but the reaction rate was slow. In most of the solvents, the CO insertion reaction occurs when PO is insufficiently substituted selectively (position a in the reaction formula I). However, under THF (Example 62), the compound having a large number of substituents (the reaction formula The reaction also proceeds to MMHP (methyl 2-
methyl-3-hydroxypropiona
te) was confirmed to be produced at about 5%. In Comparative Example 11 using dichloromethane, it was confirmed that the reaction hardly proceeded.

[0143]

[Chemical formula 42]

[0144] Example 65 to 67: Co ₂ to 45mLParr high pressure reactor which is substituted in the hydroesterification reaction nitrogen various epoxide derivatives
68 mg (0.20 mmol) of (CO) ₈ was added and dissolved in 10 mL of methanol (MeOH). The amount of the catalyst is expressed in mmole of metal atom for quantitative comparison. The epoxide was added here as described in Table 9 below. The reactor was charged to a CO pressure of 1000 psi and the temperature was increased to 80 ° C. with stirring. When the reaction was allowed to proceed for 15 hours to complete the reaction, the temperature was lowered to room temperature, and the remaining gas was removed. Then, a metal component was removed from the reaction mixture to obtain a product. The results obtained by analyzing this by gas chromatography are shown in Table 9.

[0145]

[Table 9]

A) the main product for each epoxide;
Table 10 below shows b) by-products and c) isomers.
Most of the by-products were formed by direct attack of the methanol by the substrate, and were hardly due to the CO insertion reaction into the substrate substituent.

[0147]

[Table 10]

Examples 68 to 76: C in the presence of imidazole
o ₂ (CO) ₈ catalyzed hydroesterification of ethylene oxide The details for this example are summarized in Table 11. 450mL pearl (Par) at normal temperature and nitrogen atmosphere
r) After adding a predetermined amount of solvent to the reactor,
₂ (CO) ₈ was added. 500g COgas in the reactor
After sig was filled and the temperature was raised to 80 ° C., the mixture was stirred for 1 hour, then cooled to room temperature to remove gas, and a predetermined amount of imidazole was added as a promoter. Ethylene oxide was added to the reactor and CO at a predetermined pressure was introduced into the reactor. After raising the temperature to the temperature shown in the table, the reaction was carried out for the reaction time shown in Table 11. The reaction was sampled by 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.

Hydroesterification of ethylene oxide with Co ₂ (CO) ₈ catalyst in the presence of imidazole:

[0150]

[Table 11]

Catalyst = 5 mmole, imidazole = 20
mmole, ethylene oxide = 500 mmole 1) 100 mL of methanol + tetraglyme (Tetr
aglyme) 2) imidazole 40 mmole 3) ethylene oxide 1.4 mmole 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 Yield Comparative Examples 12 to 13: Hydroesterification of Ethylene Oxide with Co ₂ (CO) ₈ Catalyst Comparative Example 12 uses 3-
Comparative Example 13 uses only Co ₂ (CO) ₈ as a catalyst without a promoter, and uses hydroxypyridine as a promoter. The product synthesized by hydroesterifying ethylene oxide in the same manner as in Example 68 is used. The material was analyzed. The results of the analysis are set forth in Table 12 below. When a pyridine derivative is used as a promoter, 3-HPM is produced in a high yield, but considerable amounts of by-products including acetaldehyde are produced, and when only Co ₂ (CO) ₈ is used as a catalyst without a promoter, It can be seen that the yield is very low.

[0152]

[Table 12]

1) Catalyst = Co ₂ (CO) ₈ (1 mmol)
e), 3-hydropyridine = 4 mmole, ethylene oxide = 200 mmole 2) catalyst = Co ₂ (CO) ₈ (2.5 mmole), ethylene oxide = 650 mmole 3) Yield = selectivity × conversion 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 Yield Examples 77-80: Hydroesterification of Other Epoxide Derivatives Examples 77-80 are as described above except that the type of oxide was changed in place of the ethylene oxide. Experiments were performed in the same manner as in Example 68, and the results are summarized in Table 13 below.

[0154]

[Table 13]

Catalyst = 5 mmol, Promoter = 10 mmol
1, epoxide = 500 mmol, temperature 80 ° C, pressure 3
4 bar, reaction time 4 hr, solvent = MeOH (200 m
L) 1) Isolated Yield Example 81: Hydrogenation reaction After dissolving 1 g of methyl 3-hydroxypropionate obtained from the above Examples 68 to 76 in 10 mL of MeOH, put it in a 45 mL Parr reactor and 0.5 g of cron. Add copper chromate catalyst. At room temperature, 1500 psig of hydrogen is added to the reactor and the reactor is heated to 180 ° C. with stirring. Fifteen
After the reaction, the reactor was cooled to room temperature, and the reaction mixture was analyzed using GC. The conversion of methyl 3-hydroxypropionate was about 5%, and the selectivity for 1,3-propanediol was about 3%.

[0156]

The method for hydroformylation of an epoxide derivative according to the present invention can be carried out by using only a cobalt catalyst using a catalyst comprising a transition metal compound containing a cyclopentadienyl group and a cobalt compound, or by using cobalt and a known accelerator. The present invention has the effect of the invention of synthesizing a 3-hydroxyaldehyde derivative from an epoxide derivative with high catalytic activity and selectivity from the conventional technique used. The catalyst has an effect of the invention which is easy to recover and regenerate, unlike the existing catalyst to which a phosphine compound is bonded. Further, by reacting the epoxide derivative with carbon monoxide and an alcohol in the presence of a suitable solvent and a cobalt catalyst under the conditions of a reaction temperature range of 30 to 130 ° C. and a CO pressure range of 100 to 3000 psi, 3-hydroxy is obtained. The present invention has an effect of providing a hydroesterification method for synthesizing an ester derivative with high selectivity and yield. Further, according to the method of the present invention, an epoxide derivative is reacted with carbon monoxide and an alcohol in a catalyst system comprising a cobalt catalyst and a promoter to be effectively converted into a 3-hydroxyester, and this product is converted into a 1-hydroxyester through a hydrogenation reaction. , 3-Alkanediol, and 3-hydroxyester can be produced in high yield by using a catalyst system having high activity and selectivity for the hydroesterification reaction, and using imidazole or a derivative thereof 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-alkanediol.

Simple modifications and alterations of the present invention can be easily implemented by those having ordinary skill in the art, and all such modifications and alterations are included in the scope of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 45/58 C07C 45/58 47/19 47/19 67/26 67/26 69/675 69/675 / / C07B 61/00 300 C07B 61/00 300 (72) Inventor Jan Duk Joe Republic of Korea Daejeon Yu-Song Jeong Min-Dong (No Address) Expopart 404-502 (72) Inventor Byung Young Hung Republic of Korea Taejong Yousung-Jeongmin-Dong 462-5 Sejong Apart 110-203

Claims (42)

[Claims] 1. The following structural formula (A-1) or (A-2)
A transition metal compound containing a cyclopentadienyl group represented by the formula: or a compound synthesized by reacting the transition metal compound with a compound having one or more functional groups. Transition metal catalyst for use in hydroformylation reaction: [Chemical formula 2] In the above formula, M is a transition metal of Group 9 in the periodic table, cobalt, rhodium or iridium, and the oxidation number of the metal is 1
(A) is BF ₄ ⁻ , PF ₆ ⁻ ,
ClO ₄ ⁻ , SO ₃ CF ₃ ⁻ or BR ′ ₄ ⁻ (R ′ is hydrogen; or a C _{1 to} C ₁₀ saturated or unsaturated aliphatic chain or a carbon chain containing a cyclic hydrocarbon or an aromatic hydrocarbon. A monovalent anion having the formula:
A halogen of F, Cl, Br or I; or a divalent anion of CO ₃ ²⁻ or SO ₄ ²⁻ ;
In the case of a valent anion or a halogen, a constant of 0 to 2,
0 or 1 when (a) is a divalent anion; m
Is a constant of 0, 2 or 4 when (a) is a monovalent anion or a halogen, and is 0, 1 or 2 when (a) is a divalent anion; R _{1 to} R ₅ Is each independently hydrogen; a saturated or unsaturated aliphatic or aromatic hydrocarbon of C _{1 to} C ₂₀ , containing a nitrile group at the end or middle of the chain, or an amine group at the end or middle of the chain. Or a saturated or unsaturated aliphatic or aromatic hydrocarbon containing; or a halogen of F, Cl, Br, or I; _a , _b, and _c in X _a , Y _b, and Z c are from 0 to 3;
A + b + c = 3; X _a , Y _b and Z _c
Are each independently carbon monoxide; F, Cl, Br or I
A hydroxy group; a C _{1 to} C ₁₀ straight-chain aliphatic or aromatic hydrocarbon; a C _{1 to} C ₁₀ side-chain aliphatic or aromatic hydrocarbon; a C _{1 to} C ₁₀ side-chain aliphatic or An alkoxy having an aromatic hydrocarbon; a nitrile containing a C _{1 to} C ₁₀ saturated or unsaturated aliphatic hydrocarbon or an aromatic hydrocarbon having a saturated or unsaturated aliphatic chain; C
Ether including C ₁ of -C ₂₀ aliphatic or cyclic hydrocarbons or aromatic hydrocarbons; ketones containing the ₁ -C ₂₀ aliphatic or cyclic hydrocarbons or aromatic hydrocarbon N
The amine represented by (R ₆ ) (R ₇ ) (R ₈ )
₆ , R ₇ and R ₈ each independently represent hydrogen or C ₁ -C
An alkyl group having a carbon chain containing ₂₀ saturated or unsaturated aliphatic chains or cyclic hydrocarbons or aromatic hydrocarbons); a C ₃ -C ₃₀ pyrrole, a pyrazine, a pyrazole.
le), imidazole, pyrimidine, piperidine (pipe)
pyridine, pyridine or a derivative thereof; or a compound represented by the following formula (I), (II) or (III) or a mixture thereof: [Chemical formula 4] [Chemical formula 5] (In the above formulas (I), (II) and (III), Q ₁ is each independently N, P, As or Sb; Q ₂ and Q
₃ is each independently P, As or Sb; R _c ,
R _d and R _e are each independently hydrogen; or C ₁ -C ₂₀
An alkyl group having a carbon chain containing a saturated or unsaturated aliphatic chain or a cyclic hydrocarbon or an aromatic hydrocarbon, preferably hydrogen; an aliphatic hydrocarbon (a C ₁ -C ₅ carbon chain or cyclohexyl); Phenyl or benzyl; a nitrile group or an amine group _represented by R _f R _g N- on the aliphatic hydrocarbon or the aromatic ring of phenyl or benzyl (the R _f and R _g are each independently hydrogen;
₁ is an alkyl group having a carbon chain containing saturated or unsaturated aliphatic or cyclic hydrocarbons or aromatic hydrocarbons -C _20, linear-shaped carbon chain preferably C ₁ -C _10,
F and g are each a constant of 0 to 2 and f + g is 2), or a compound containing at least one aldehyde group; F, Cl , Br or I halogen; or C ₁
Saturated or unsaturated aliphatic or aromatic phosphine group containing carbon -C _30, arsine (Arsine) a group or stibine (stibine) group; and R _c, c in R _d and R _e, d and e Is a constant of 0 to 3 and c + d + e = 3); X _{a ′} is carbon monoxide;
A halogen of F, Cl, Br, or I; a hydroxy group;
An alkoxy having a C ₁ -C ₁₀ saturated or unsaturated aliphatic or aromatic hydrocarbon; a nitrile containing a C ₁ -C ₁₀ aliphatic or aromatic hydrocarbon; or the above formula (I), (II) or A compound represented by (III);
And Y _{b ′} is carbon monoxide; a halogen of F, Cl, Br, or I; a hydroxy group; or an alkoxy group having a C _{1 to} C ₁₀ saturated or unsaturated aliphatic or aromatic hydrocarbon. 2. The epoxide derivative according to claim 1, wherein the compound having one or more functional groups is represented by the following formula (B-1), (B-2) or (B-3). Transition metal catalyst for use in the hydroformylation reaction of [Chemical formula 7] [Chemical formula 8] In the above formula, Q ₄ , Q ₅ , Q ₆ and Q ₇ are each independently N, P, As or Sb; R ₉ , R ₉ ′,
R ₉ ″, R ₉ ″ ″, R ₉ ″ ″ and R ₉ ″ ″ are each independently hydrogen; or a C _{1 to} C ₂₀ aliphatic hydrocarbon, aromatic hydrocarbon, Or a hydrocarbon containing two kinds of these aliphatic hydrocarbons and aromatic hydrocarbons at the same time, preferably hydrogen; aliphatic hydrocarbons (C ₁ -C ₅ carbon chain or cyclohexyl); phenyl or benzyl; A nitrile group or an amino group _represented by R _f R _g N- on hydrogen or an aromatic ring of phenyl or benzyl (the above R _f and R _g
Is each independently hydrogen; or an alkyl group having a C _{1 to} C ₂₀ saturated or unsaturated aliphatic chain or a carbon chain containing a cyclic hydrocarbon or an aromatic hydrocarbon, preferably C _{1 to} C ₁₀ Is a straight-chain carbon chain, a side-chain carbon chain, a ring compound, or an aromatic hydrocarbon;
Where f + g is 2), a compound containing at least one aldehyde group or ketone group; F, Cl, B
halogen r or I; C ₁ -C ₃₀ aliphatic or aromatic phosphine group containing carbon, be arsine group or stibine group; and R _10, R ₁₀ 'and R _10' 'is, C ₁ ~
An alkyl group having a carbon chain containing aliphatic or cyclic hydrocarbons or aromatic hydrocarbons, saturated or unsaturated C _20, preferably linear-shaped carbon chain of C ₁ -C _10, a side chain-type carbon chain , A ring compound or an aromatic hydrocarbon. 3. A compound [(B) having at least one functional group with the transition metal compound [(A-1) or (A-2)].
-1), (B-2) or (B-3)] to give a compound synthesized by the following formula (C-1), (C-2),
A transition metal catalyst for use in a hydroformylation reaction of an epoxide derivative according to claim 2, which is represented by (C-3), (C-4) or (C-5): [Chemical formula 10] [Chemical formula 11] [Chemical formula 12] [Chemical formula 13] In the above formula, R _{1 to} R ₅ are as defined in claim 1; M ₁ , M ₂ , M ₃ and M ₄ are the same as M in claim 1; (b) (A) according to claim 1
X _a1 , X _a2 , X _a3 , X _a4 , Y _b1 , Y _b2 ,
2. The method according to claim 1, wherein Y _b3 and Y _b4 are each independently X _a.
And Y _b and be _{identical; Q 8, Q 9, Q} 10, Q 11, Q 12
And Q ₁₃ are as claimed in claim 2, wherein Q _4, Q _5, Q ₆ and Q ₇
R ₁₁ , R ₁₁ ′, R ₁₁ ″, R ₁₁ ″,
_{R 13, R 13 ', R} 13'', R 13''', R 15, R 15 ',
R ₁₅ ″, R ₁₅ ″, R ₁₇ , R ₁₇ ′, R ₁₇ ″, R ₁₇ ″,
R ₁₇ ″ ″ and R ₁₇ ″ ″ ″ represent R ₉ ,
R ₉ ', R _9' ', R _9' '', R ₉ 'be the same as'''and R _9' ''''; R _12, R ₁₄ and R ₁₆ are, according to claim 2, wherein R
Is the same as ₁₀ ; and n is a constant of 0-8 when (b) is a monovalent anion or a halogen, and is a constant of 0-4 when (b) is a divalent anion. . 4. The transition metal compound containing a cyclopentadienyl group according to claim 1 and a cobalt compound having a molar ratio of transition metal to cobalt of 1:
Charge into a reactor containing a water-insoluble solvent in a ratio of 1000 to 5: 1; add an epoxide derivative; and add carbon monoxide and hydrogen (CO / H ₂ ) at a molar ratio of 3/1 to 1/10. ,
A 3-hydroxyaldehyde derivative by a hydroformylation reaction from the epoxide derivative, characterized in that the total pressure is supplied to 100 to 3000 psi; and the reaction temperature is raised from room temperature to 30 ° C. to 120 ° C. How to synthesize. 5. The molar ratio of transition metal to cobalt in the transition metal compound containing a cyclopentadienyl group is 1:
The method for synthesizing a 3-hydroxyaldehyde derivative according to claim 4, wherein the ratio is 100 to 2: 1. 6. The CO / H ₂ molar ratio supplied to the reaction is 2/1 to 1/5.
The method for synthesizing the 3-hydroxyaldehyde derivative described in the above. 7. The total pressure of CO / H ₂ is from 500 to
The method for synthesizing a 3-hydroxyaldehyde derivative according to claim 4, wherein the pressure is 2000 psi. 8. The method for synthesizing a 3-hydroxyaldehyde derivative according to claim 4, wherein the reaction temperature is 60 to 100 ° C. 9. The water-insoluble solvent has the following structural formula (D)
The method for synthesizing a 3-hydroxyaldehyde derivative according to claim 4, wherein the method is represented by the following formula: In the above formula, R ₁₈ and R ₁₉ each independently represent C _1-
Linear aliphatic hydrocarbon C _20, side chain aliphatic hydrocarbons, aromatic hydrocarbons, or their aliphatic hydrocarbons and aromatic hydrocarbons two simultaneously containing hydrocarbons. 10. The method according to claim 9, wherein the water-insoluble solvent is methyl-t-butyl ether (MTBE) saturated with water. 11. The 3-epoxide derivative according to claim 4, wherein the epoxide derivative is represented by the following structural formula (E).
Method for synthesizing hydroxyaldehyde derivative: In the above formula, R ₂₀ and R ₂₁ are each independently hydrogen;
Or C _{1 to} C ₂₀ saturated linear aliphatic hydrocarbons, side chain aliphatic hydrocarbons, saturated cyclized hydrocarbons, chain-type hydrocarbons containing rings, aliphatic hydrocarbons containing aromatic rings ,
A hydrocarbon in which hydrogen of at least one or more carbon chains is substituted with F or Cl, an aromatic hydrocarbon having no substituent,
An aromatic hydrocarbon in which hydrogen of an aromatic ring is substituted with at least one of F, Cl, an amine group, a nitrile group, and an alkoxy group. 12. The structural formula (A-1) according to claim 1,
Or charging the transition metal compound represented by (A-2) into a reactor containing a water-insoluble solvent; the structural formula (B-1), (B-2) or (B-3) according to claim 2; The compound having at least one functional group represented by the formula (1) is charged into the reactor and refluxed; and the cobalt compound is converted to a transition metal compound having a molar ratio of transition metal to cobalt of 1: 1000 to 1,000.
Charge the reactor to 5: 1; add the epoxide derivative; add 3% carbon monoxide and hydrogen (CO / H ₂ ).
At a molar ratio of 1/1 to 1/10, the total pressure is 100 to 30.
A method of synthesizing a 3-hydroxyaldehyde derivative from an epoxide derivative by a hydroformylation reaction, wherein the reaction temperature is increased from room temperature to 30 ° C. to 120 ° C .; 13. The method according to claim 1, wherein the cobalt catalyst is R "OH (the R"
Is a C ₁ -C ₂₀ saturated or unsaturated linear hydrocarbon, a side chain hydrocarbon, a cyclic hydrocarbon or a linear hydrocarbon containing an aromatic hydrocarbon or aromatic, preferably methyl, ethyl and isopropyl, cyclohexyl , Phenyl, or benzyl) into a reactor containing an alcohol and a solvent; add the epoxide derivative to the reactor; supply CO at a pressure in the range of 100-3000 psi; Reaction temperature is from 30 to 13
The temperature is raised to the range of 0 ° C .;
-A method for synthesizing hydroxyester derivatives. 14. The method according to claim 1, wherein the cobalt catalyst is Co ₂ (CO)
_The method for synthesizing a 3-hydroxyester derivative according to claim 13, wherein 15. The solvent has the following structural formula (G-1):
It is a compound represented by (G-2), (G-3) or (G-4) or an alcohol represented by R "OH (R" is the same as in the above claim 13). 14. A method for synthesizing a 3-hydroxyester derivative according to claim 13: [Chemical formula 17] [Chemical formula 18] [Chemical formula 19] In the above formula, R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each independently a C ₁ -C ₁₀ saturated linear aliphatic hydrocarbon, side chain aliphatic hydrocarbon, saturated ring, R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R _31, and R are hydrogenated hydrocarbons, chain hydrocarbons containing rings, or aliphatic hydrocarbons containing aromatic rings.
₃₂ is each independently hydrogen; a C _{1 to} C ₄ side chain or linear saturated hydrocarbon; F or Cl; or an alkoxy group having a C _{1 to} C ₃ carbon; Is a constant; and q is a constant of 2-5. 16. The method according to claim 13, wherein the epoxide derivative is represented by the following structural formula (E).
Method for synthesizing -hydroxyester derivative: In the above formula, R ₂₀ and R ₂₁ are each independently hydrogen;
Or a C _{1 to} C ₂₀ saturated linear aliphatic hydrocarbon, a side chain aliphatic hydrocarbon, a saturated cyclized hydrocarbon, a chain hydrocarbon containing a ring, an aliphatic hydrocarbon containing an aromatic ring, A hydrocarbon in which hydrogen of at least one or more carbon chains is replaced by F or Cl, an aromatic hydrocarbon having no substituent, an aromatic ring having at least one hydrogen atom of F, Cl, an amine group, a nitrile group, or An aromatic hydrocarbon substituted with an alkoxy group. 17. The pressure of CO is 200 to 1500.
The method for synthesizing a 3-hydroxyester derivative according to claim 13, which is in the range of psi. 18. The method for synthesizing a 3-hydroxyester derivative according to claim 13, wherein the reaction temperature is 40 to 110 ° C. 19. The 3-hydroxyester derivative according to claim 13, wherein the concentration of the 3-hydroxyester derivative as a product in the hydroesterification reaction is 1 to 50% by weight in the whole solution. Synthesis method. 20. The 3-hydroxyester derivative according to claim 19, wherein the concentration of the 3-hydroxyester derivative as a product in the hydroesterification reaction is 5 to 40% by weight in the whole solution. Synthesis method. 21. The method of claim 13, wherein the method further comprises the step of separating the 3-hydroxyester derivative of the product. 22. The method according to claim 22, wherein the step of separating the product is performed by using the compound represented by the structural formula (G-1), (G-2), (G-3) or (G-4).
When using a solvent represented by the following formula:
When an alcohol represented by OH is used, R ″ is C _1-
In the case of C ₃ hydrocarbons, the solvent is vacuum dried and separated,
Synthesis process according to claim 21, wherein the 3-hydroxy ester derivatives, wherein R "are separated using water in the case of hydrocarbons in excess of C _3. 23. (a) Using a catalyst system comprising a catalytic amount of a cobalt compound and an effective amount of a catalyst promoter, convert epoxide in a solvent to carbon monoxide, an alcohol (R'OH) and
50 to 3000 psig at a temperature of 0 to 150 ° C
(B) separating the product and the solvent from the catalyst and the promoter; and (c) separating the product and the solvent from the catalyst and the promoter. The obtained product and the solvent are separated at a temperature of 30 to 350 ° C. in the presence of a hydrogenation catalyst at a temperature of 50 to 5000.
reacting with psig of hydrogen to produce a hydrogenation reaction mixture comprising the 1,3-alkanediol; and (d) separating and recovering the 1,3-alkanediol from the product mixture; Features 1,
A method for synthesizing 3-alkanediol. 24. The method of claim 23, wherein the method of separating the product and the solvent in step (b) from the catalyst and the promoter is vacuum distillation. Method. 25. A method of separating the product and the solvent of the step (b) from the catalyst and the promoter, wherein the reaction mixture produced is heated to 100 ° C. in the presence of 20 to 3000 psig of CO.
The method for synthesizing 1,3-alkanediol according to claim 23, wherein water is added at the following temperature to extract the 3-hydroxyester of the intermediate product and its derivatives into an aqueous layer. . 26. The method of claim 23, further comprising reacting the separated cobalt and the promoter component partially or completely to the step (a).
A method for synthesizing the described 1,3-alkanediol. 27. The method according to claim 27, wherein the cobalt compound is Co ₂ (C
O) ₈ alone or a compound obtained by mixing Co ₂ (CO) ₈ with an organic compound of imidazole, pyridine, pyrrole, pyrazine, pyrazole, pyrimidine, piperidine or a derivative thereof. A method for synthesizing a 1,3-alkanediol according to claim 23. 28. The method for synthesizing 1,3-alkanediol according to claim 23, wherein the ratio of the cobalt compound and the promoter is 1/0 to 1/100. 29. The method according to claim 23, wherein the accelerator is an imidazole derivative represented by the following formula.
For synthesizing the described 1,3-alkanediol: In the above formula, R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each independently hydrogen; a C _1-10 side chain aliphatic hydrocarbon, a linear aliphatic hydrocarbon, a saturated cyclized hydrocarbon, A chain hydrocarbon containing a ring, or an aliphatic hydrocarbon containing an aromatic ring; F; C
l; an alkoxy group having C _1-3 carbon atoms; OH; OH
Chain form hydrocarbon containing a ring while containing the OH;; saturated cyclic hydrocarbon containing OH; linear aliphatic hydrocarbon containing OH; side chain aliphatic hydrocarbons C _{1 to 10} while containing or OH And an aliphatic hydrocarbon containing an aromatic ring. 30. The method for synthesizing 1,3-alkanediol according to claim 28, wherein the accelerator is imidazole. 31. The method according to claim 31, wherein the step (a) is performed in the range of 40 to 120.
The method for synthesizing a 1,3-alkanediol according to claim 23, wherein the temperature is in a temperature range of ° C. 32. The method according to claim 30, wherein the step (a) is performed in the range of 100 to 15
The method for synthesizing a 1,3-alkanediol according to claim 23, wherein the method comprises a pressure range of 00 psig. 33. The method for synthesizing 1,3-alkanediol according to claim 23, wherein the epoxide is represented by the following formula: In the above formula, R ₁ and R ₂ are each independently hydrogen;
₁ -C ₂₀ saturated straight-chain aliphatic hydrocarbon side chain aliphatic hydrocarbons, saturated cyclic hydrocarbons, aliphatic comprising a chain-shaped hydrocarbon or an aromatic ring, including ring hydrocarbyl; or Among the hydrocarbons, hydrocarbons in which at least one or more carbon chains of hydrogen are substituted by F, Cl or Br, aromatic hydrocarbons having no substituent, or hydrogen of an aromatic ring having at least one F , Cl, an amine group, a nitrile group, or an alkoxy group. 34. R ′ of the alcohol (R′OH)
Is a saturated linear aliphatic hydrocarbon having _{1 to 10} carbon atoms, a side chain aliphatic hydrocarbon, a saturated cyclized hydrocarbon, a chain hydrocarbon containing a ring or an aliphatic hydrocarbon containing an aromatic ring. 24. The method for synthesizing a 1,3-alkanediol according to claim 23. 35. The method according to claim 23, wherein the solvent is one of ether compounds represented by the following formula.
For synthesizing the described 1,3-alkanediol: [Chemical formula 24] [Chemical formula 25] In the above formula, R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are
Each independently a C _1-10 saturated linear aliphatic hydrocarbon, side chain aliphatic hydrocarbon, saturated cyclized hydrocarbon, chain-shaped hydrocarbon containing a ring, or aliphatic containing an aromatic ring M is a constant from 1 to 10 and n is a constant from 2 to 5; 36. The method for synthesizing a 1,3-alkanediol according to claim 23, wherein the solvent is acetate. 37. The method for synthesizing 1,3-alkanediol according to claim 23, wherein the solvent is the alcohol (R′OH) according to claim 12. 38. The method for synthesizing a 1,3-alkanediol according to claim 23, wherein the solvent is represented by the following formula: In the above formula, R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R
₁₃ is each independently hydrogen, C _1-4 side chain saturated hydrocarbon, C _1-4 straight chain saturated hydrocarbon, F, Cl, or C
An alkoxy group having _{1 to 3} carbons. 39. The method for synthesizing a 1,3-alkanediol according to claim 23, wherein the product is an ester compound represented by the following formula: [Chemical formula 28] R ₁ and R ₂ are each independently hydrogen; C _{1 to} C ₂₀ saturated linear aliphatic hydrocarbons, side-chain aliphatic hydrocarbons, saturated cyclized hydrocarbons, and chain forms containing rings Hydrocarbons or aliphatic hydrocarbons containing an aromatic ring; or hydrocarbons in which at least one or more carbon chains of the hydrocarbons are substituted with F, Cl or Br, unsubstituted aromatics A group hydrocarbon or an aromatic hydrocarbon in which hydrogen of an aromatic ring is substituted with at least one of F, Cl, an amine group, a nitrile group, and an alkoxy group. 40. The method of claim 23, wherein the hydrogenation catalyst in step (c) is selected from the group consisting of copper chromate and compounds of the Pd / C family. A method for synthesizing 3-alkanediol. 41. The hydrogen pressure of the step (c) is 200
24. The method for synthesizing a 1,3-alkanediol according to claim 23, wherein the pressure is in a pressure range of from 3000 to 3000 psig. 42. The reaction temperature of the step (c) is 100
The method for synthesizing a 1,3-alkanediol according to claim 23, wherein the temperature is in the range of from 250 to 250 ° C.