The present invention relates to a process for carbonylation of epoxide derivatives, in which the reactivity, selectivity and the yield are superior. More specifically, the present invention relates to a process for hydroformylation of an epoxide derivative in which there is utilized a transition metal catalyst having a cyclopentadienyl radical, thereby improving the reactivity and selectivity. Further, the present invention relates to a process for hydroesterification of an epoxide derivative, in which a proper catalyst is selected, and the reaction temperature and pressure are adjusted within proper ranges in the presence of a cobalt catalyst, thereby improving the product selectivity and the yield.
The epoxide derivatives can be easily converted into difunctional compounds through a carbonylation reaction. These difunctional compounds are used as an intermediate of useful organic compounds. Among them, the typical compounds are the 3-hydroxyaldehyde derivatives and the 3-hydroxyester derivatives, the former being synthesized by a hydroformylation of epoxide derivatives, and the latter being synthesized by a hydroesterification of an epoxide derivative. In the 3-hydroxyaldehyde derivatives which are synthesized by the hydroformylation, aldehyde group is converted into an alcohol radical through a hydrogenation, thereby obtaining alkanediol. Among the alkanediol derivatives, 1,3-propanediol is known to be an intermediate for synthesizing the polyester which is used for making fibers and films. Further, it is also used as an intermediate for coating materials and for organic synthesis. Meanwhile the 3-hydroxyester derivatives which are obtained by the hydroesterification of the epoxide derivatives have two active radicals, respectively. Therefore, they are known to be useful as solvents, resins and coating materials. Further, they can be converted into other compounds, so that they can be used in the medical field. Further, they are also used as an intermediate for synthesizing the alkanediols. In a known process for synthesizing the 3-hydroxyaldehyde showing a high selectivity under a low temperature and a low pressure, there are used a cobalt catalyst and phosphine oxide ligand as a promoter. However, when phosphine oxide ligand is used as a promoter, the recovery and regeneration of the catalyst become complicated.
U.S. Pat. Nos. 5,770,776, 5,723,389 and 5,731,478 disclose processes in which ethylene oxide is hydroformylated, and a hydrogenation of aldehyde group is adopted. In these processes, a cobalt catalyst is used, and another metal compound or ligand is used as the promoter instead of the phosphine oxide ligand, thereby improving the activity and the selectivity of the cobalt catalyst.
U.S. Pat. Nos. 5,135,901 and 4,973,741 disclose another process for obtaining the 3-hydroxyester derivative from the epoxide derivatives. In this process, there is synthesized methyl 3-hydroxypropionate from ethylene oxide by using rhodium and ruthenium as catalysts in the presence of carbon monoxide and alcohol. However, in this process, in spite of the use of expensive catalysts, the yield of the 3-hydroxypropionate is as low as 60%, and by-products are produced in considerable amounts. Further, there is another known process for obtaining a 3-hydroxyester by hydroesterification of the epoxide. In this process also, the yield is as low as 40-60%. [(1) Dalcanali, E.; Foa, M. Synthesis 1986, 492. (2) Heck, R. F., J. Am. Chem. Soc., 1963, 85, 1460. (3) Eismann, J. L.; Yamartino, R. L.; Howard, Jr. J. F., J. Org. Chem. 1961, 2102.]. The reason why the yield is so low is that the isomerization reaction of the starting material readily occurs.
Meanwhile, U.S. Pat. Nos. 5,310,948 and 5,359,081 relate to a carbonylation of the epoxide, in which the epoxide and carbon monoxide are reacted in the presence of cobalt and pyridine derivatives. The final product is mainly -lacton, and the by-product is the 3-hydroxyester.
As described above, there has not yet been found an effective process for synthesizing the 3-hydroxyester derivative, in which economy is ensured.
Therefore, the present inventors have conducted studies on the carbonylation of epoxides for obtaining an intermediate which is useful for synthesizing an organic compound and alkanediol. For this purpose, a transition metal compound in which a cyclopentadiene radical had been coupled to a 9th group transition metal was made to react with a compound having one or more active radicals. The compound thus obtained was used as a catalyst in the presence of a cobalt compound to obtain 3-hydroxyaldehyde derivatives with a high reactivity and selectivity, thereby establishing a process for hydroformylation. Further, an epoxide derivative was made to react with carbon monoxide and alcohol in the presence of a proper solvent and a cobalt catalyst, and the reaction temperature and pressure were adjusted to proper levels to obtain a 3-hydroxyester derivative with a high yield, thereby establishing a process for hydroesterification.
It is an object of the present invention to provide transition metal catalysts which show superior reactivity and selectivity in the hydroformylation of epoxide derivatives.
It is another object of the present invention to provide transition metal catalysts which show superior recovery and regeneration characteristics in the hydroformylation of epoxide derivatives.
It is still another object of the present invention to provide a process for hydroformylation of epoxide derivatives, in which a cobalt compound and a transition metal compound with superior reactivity and selectivity are used, thereby synthesizing a 3-hydroxyaldehyde derivative with high selectivity and yield.
It is still another object of the present invention to provide a process for hydroesterification of epoxide derivatives, in which a proper solvent and a cobalt catalyst are used, and the reaction temperature and pressure are adjusted to proper ranges, thereby synthesizing 3-hydroxyester derivatives with a high yield.
In the present invention, there is provided a process for carbonylation of epoxide derivatives for synthesizing 3-hydroxyaldehyde derivatives and 3-hydroxyester derivative which are the useful intermediates are used for synthesizing organic compounds and alkanediols.
In achieving the above objects, the present invention is characterized as follows. That is, the 3-hydroxyaldehyde derivatives are synthesized by a hydroformylation of epoxide derivatives. The hydroformylation reactions are carried out in the following manner. A cobalt compound and a transition metal compound having a cyclopentadienyl radical (which is separately synthesized) are dissolved in a non-aqueous solvent. Then, an epoxide derivative is added, then carbon monoxide and hydrogen (CO/H2) are introduced into the reactor, and then, the reactor is put into an oil bath which is maintained at a desired temperature. Alternatively, a transition metal compound having the above mentioned cyclopentadienyl radical is synthesized in a non-aqueous solvent, and then, the hydroformylation process is carried out without any separating step.
The mole ratios of the cobalt compound to the transition metal having the cyclopentadienyl radical are preferably 1000:1xcx9c1:5, and more preferably 100:1xcx9c1:2. The mole ratio of CO/H2 which are supplied for the hydroformylation is preferably 3/1xcx9c1/10, and more preferably 2/1xcx9c1/5. The total pressure is preferably 100xcx9c3000 psi, and more preferably 500xcx9c2000 psi. The temperature is raised from the normal temperature to 30 degrees C.xcx9c120 degrees C., and more preferably to 60xcx9c100 degrees C. in proceeding the hydroformylation.
Now the catalyst, the solvent and the epoxide derivatives which are used in the hydroformylation of the present invention will be described in detail.
The transition metal catalysts which are used in the hydroformylation are transition metal compounds which are prepared by bonding the 9th group transition metal to the cyclopentadienyl radical. Or it is one of those compounds which are synthesized by reacting the above mentioned transition metal compound with a compound having one or more active radicals. The transition metal compounds may be bonded with ligands other than the cyclopentadienyl radical, and this is expressed by at least one of the following formulas: 
The compounds belonging to (A-1) are neutral or cationic, M represents the 9th group transition metals such as cobalt, rhodium, and iridium, and the oxidation state of the metal is 1 or 3;
(a) is: a 1-valence anion of BF4xe2x80x94, PF6xe2x80x94, ClO4xe2x80x94, SO3CF3xe2x80x94 or BRxe2x80x24xe2x80x94 (Rxe2x80x2 representing: hydrogen; or an alkyl radical of saturated or unsaturated aliphatic chain type or ring type hydrocarbons or aromatic hydrocarbons having C1xcx9cC10); a halogen atom of F, Cl, Br or I; or a 2-valence anion of CO32xe2x88x92 or SO42xe2x88x92;
1 is an integer of 0-2 in case where (a) is a 1-valence anion or a halogen atom, and is 0-1 in case where (a) is a 2-valence anion;
R1xcx9cR5 are hydrogen; saturated or unsaturated aliphatic or aromatic hydrocarbons of C1xcx9cC20, or saturated or unsaturated aliphatic or aromatic hydrocarbons having nitrile radicals at the end or at the middle, or having amine radicals at the end or at the middle; or a halogen atom of F, Cl, Br or I;
a, b and c in Xa, Yb and Zc are integers of 0xcx9c3, with a+b+c=3;
Xa, Yb and Zc, respectively, are carbon monoxide; a halogen atom of F, Cl, Br or I; hydroxy radical; aliphatic or aromatic hydrocarbon having no branch at C1xcx9cC10; aliphatic or aromatic hydrocarbon having branches at C1xcx9cC10; hydroxy radical including aliphatic or aromatic hydrocarbons with branches at C1xcx9cC10; saturated or unsaturated aromatic hydrocarbon of C1xcx9cC10, or a nitrile including aliphatic hydrocarbons with saturated or unsaturated aliphatic chains; a ketone including aliphatic hydrocarbons or aliphatic chain type or ring type hydrocarbons of C1xcx9cC20; ether including aliphatic hydrocarbons or aliphatic chain type or ring type hydrocarbons of C1xcx9cC20; an amine expressed by N(R6)(R7)(R8) (here, R6, R7 and R8 respectively representing hydrogen or alkyl radicals including carbon chains of saturated or unsaturated aliphatic hydrocarbons or aliphatic chain type or ring type hydrocarbons of C1xcx9cC20); pyrrole, pyrazine, pyrazole, imidazole, pyrimidine, piperidine, pyridine or their derivatives, all of them having C3xcx9cC30; or compounds expressed by the following formulas, or their mixtures: 
wherein, Q1 represents N, P, As or Sb;
Q2 and Q3 are P, As or Sb;
Rc, Rd and Re are hydrogen or alkyl radicals including saturated or unsaturated aliphatic or aromatic chain type or ring type hydrocarbons of C1xcx9cC20, or aromatic hydrocarbons, or preferably hydrogen; aliphatic hydrocarbons (cyclohexyl or carbon chains of C1xcx9cC5); phenyl or benzyl; compounds including at least one or more of nitrile radicals, amine radicals of RfRgNxe2x80x94, aldehyde radicals or ketone radicals in the aliphatic hydrocarbon or in phenyl or in benzyl (Rf and Rg represent hydrogen; or alkyl radicals including saturated or unsaturated aliphatic or aromatic chain type or ring type hydrocarbons of C1xcx9cC20, or aliphatic hydrocarbons, or preferably carbon chains of C1xcx9cC10 having no branches, carbon chains having branches, ring type compounds, or aliphatic hydrocarbons; f and g being integers of 0xcx9c2, with f+g=2); a halogen atom of F, Cl, Br or I; phosphine radicals, arsine radicals or stibine radicals including saturated or unsaturated aliphatic or aromatic chain type or ring type hydrocarbons or aromatic hydrocarbons of C1xcx9cC30; and
in the Rc, Rd and Re, c, d, and e are integers of 0xcx9c3, with c+d+e=3.
In the formula (A-2), M, (a) and R1xcx9cR5 are the same as defined in (A-1);
m is an integer of 0, 2 or 4 in the case where (a) is a 1-valence anion or a halogen atom, or is an integer of 0, 1, or 2 in the case where (a) is a valence-2 anion;
Xaxe2x80x2 is a halogen atom of F, Cl, Br or I; a hydroxy radical; alkoxy including saturated or unsaturated aliphatic or aromatic hydrocarbons of C1xcx9cC10; a nitrile including saturated or unsaturated aliphatic or aromatic hydrocarbons of C1xcx9cC10; or a compound expressed by the above formulas (I), (II) or (III); and
Ybxe2x80x2 is a carbon monoxide; a halogen atom of F, Cl, Br or I; a hydroxy radical; or an alkoxy radical including saturated or unsaturated aliphatic or aromatic hydrocarbons of C1xcx9cC10, such a compound being one furnishing the electrons dually.
The transition metal compounds which are expressed by the formulas (A-1) and (A-2) can be used as a catalyst together with a cobalt compound during the hydroformylation. Or the compounds can be used as a catalyst when a new compound obtained by reacting with a compound having one or more active radicals is hydroformylated together with a cobalt compound. The transition metal compounds of the present invention and the synthesized compounds as described above can be used as a promoter together with the cobalt catalyst to improve the catalyst activity and the selectivity. The above mentioned compounds having one or more active radicals are expressed by the following formulas: 
wherein, Q4, Q5, Q6, and Q7 respectively are N, P, As or Sb;
R9, R9xe2x80x2, R9xe2x80x3, R9xe2x80x2xe2x80x3, R9xe2x80x3xe2x80x3 and R9xe2x80x2xe2x80x3xe2x80x3 are hydrogen; aliphatic hydrocarbons, aromatic hydrocarbons, or both of the aliphatic and aromatic hydrocarbons of C1xcx9cC20, or preferably hydrogen; aliphatic hydrocarbons (C1xcx9cC5 carbon chains or cyclohexyl); phenyl or benzyl; compounds including at least one or more of nitrile radicals, amine radicals of RfRgNxe2x80x94, aldehyde radicals or ketone radicals in the aliphatic hydrocarbon or in phenyl or in benzyl (Rf and Rg respectively represent hydrogen; or alkyl radicals including saturated or unsaturated aliphatic or aromatic chain type or ring type hydrocarbons of C1xcx9cC20, or aliphatic hydrocarbons, or preferably carbon chains of C1xcx9cC10 having no branches, carbon chains having branches, ring type compounds, or aliphatic hydrocarbons; and f and g being integers of 0xcx9c2, with f+g=2); a halogen atom of F, Cl, Br or I; phosphine radicals, arsine radicals or stibine radicals including aliphatic or aromatic chain type or ring type hydrocarbons or aromatic hydrocarbons of C1xcx9cC30; and
R10, R10xe2x80x2 and R10xe2x80x3 are alkyl radicals including carbon chains of saturated or unsaturated aliphatic chain type or ring type hydrocarbons or aromatic hydrocarbons having C1xcx9cC20, and preferably carbon chains of C1xcx9cC10 having no branches, carbon chains having branches, ring type compounds, or aromatic hydrocarbons.
The transition metal compounds of formulas (A-1) and (A-2) can be reacted with the compounds of the formulas (B-1), (B-2) and (B-3) having one or more active radicals, so that a transition metal catalyst can be obtained as expressed by formulas (C-1), (C-2), (C-3), (C-4) and (C-5) below. 
wherein, M1, M2, M3 and M4 are the 9th group transition metals such as cobalt, rhodium or iridium, their valence being 1 or 3;
(b) is 1-valence anions BF4xe2x80x94, PF6xe2x80x94, ClO4xe2x80x94, SO3CF3xe2x80x94 or BRxe2x80x24 (Rxe2x80x2 is hydrogen; or alkyl radical of saturated or unsaturated aliphatic chain or ring type hydrocarbons or aromatic hydrocarbons having C1xcx9cC10); a halogen atom of F, Cl, Br or I; or valence-2 anions of CO32xe2x88x92 or SO42xe2x88x92;
n is an integer of 0xcx9c8 in the case where (b) is 1- valence anion, and an integer of 0xcx9c4 in the case where (b) is a 2-valence anion;
R1xcx9cR5 are hydrogen; saturated or unsaturated aliphatic or aromatic hydrocarbons of C1xcx9cC20, or saturated or unsaturated aliphatic or aromatic hydrocarbons having nitrile radicals at the end or at the middle, or having amine radicals at the end or at the middle; or a halogen atom of F, Cl, Br or I;
Xa1, Xa2, Xa3, Xa4, Ya1, Ya2, Ya3, and Ya respectively are carbon monoxide; halogen atom of F, Cl, Br or I; hydroxy radicals; aliphatic or aromatic hydrocarbons having no branch at C1xcx9cC10; aliphatic or aromatic hydrocarbons having branches at C1xcx9cC10; alkoxy including aliphatic or aromatic hydrocarbons with branches at C1xcx9cC10; nitrile radicals including saturated or unsaturated aliphatic hydrocarbons of C1xcx9cC10, or nitrile radicals including aliphatic hydrocarbons with saturated or unsaturated aliphatic chains; ketone including aromatic hydrocarbons or aliphatic chain type or ring type hydrocarbons of C1xcx9cC20; ether including aromatic hydrocarbons or aliphatic chain type or ring type hydrocarbons of C1xcx9cC20; amine expressed by N(R6)(R7)(R8) (here, R6, R7 and R8 respectively represent hydrogen or alkyl radicals including carbon chains of saturated or unsaturated aromatic hydrocarbons or aliphatic chain type or ring type hydrocarbons of C1xcx9cC20); pyrrole, pyrazine, pyrazole, imidazole, pyrimidine, piperidine, pyridine or their derivatives, all of them having C3xcx9cC30; or compounds expressed by the formulas (I), (II) or (III), or their mixtures:
Q8, Q9, Q10, Q11, Q12 and Q13 respectively are N, P, As or Sb;
R11, R11xe2x80x2, R11xe2x80x3, R11xe2x80x2xe2x80x3, R13, R13xe2x80x2, R13xe2x80x3, R13xe2x80x2xe2x80x3, R15, R15xe2x80x2, R15xe2x80x3, R15xe2x80x2xe2x80x3, R17, R17xe2x80x2, R17xe2x80x3, R17xe2x80x2xe2x80x3, R17xe2x80x3xe2x80x3 and R17xe2x80x2xe2x80x3xe2x80x3 are hydrogen; alkyl radicals including saturated or unsaturated aliphatic or aromatic chain type or ring type hydrocarbons of C1xcx9cC20, or aromatic hydrocarbons, or preferably hydrogen; aromatic hydrocarbons (cyclohexyl or carbon chains of C1xcx9cC5); phenyl or benzyl; compounds including at least one or more of nitrile radicals, amine radicals of RfRgNxe2x80x94, aldehyde radicals or ketone radicals in the aromatic hydrocarbon or in phenyl or in benzyl (Rf and Rg respectively represent hydrogen; or alkyl radicals including saturated or unsaturated aliphatic or aromatic chain type or ring type hydrocarbons of C1xcx9cC20, or aromatic hydrocarbons, or preferably carbon chains of C1xcx9cC10 having no branches, carbon chains having branches, ring type compounds, or aromatic hydrocarbons; and f and g being integers of 0xcx9c2, with f+g=2); compounds including one or more aldehyde radicals or ketone radicals; a halogen atom of F, Cl, Br or I; phosphine radicals, arsine radicals or stibine radicals including saturated or unsaturated aliphatic or aromatic chain type or ring type hydrocarbons or aromatic hydrocarbons of C1xcx9cC30; and
R12, R14 and R16 are alkyl radicals of saturated or unsaturated aliphatic chain or ring type hydrocarbons or aromatic hydrocarbons having C1xcx9cC20, or preferably carbon chains of C1xcx9cC10 having no branches, carbon chains having branches, ring type compounds or aromatic hydrocarbons.
The typical example of the cobalt compound which is used together with the transition metal catalyst having a cyclopentadienyl radical is Co2(CO)8. This transition metal catalyst is used dissolved in an etherial non-aqueous solvent at a certain mole ratio relative to a cobalt compound as shown below:
R18xe2x80x94Oxe2x80x94R19xe2x80x83xe2x80x83(D)
wherein, R18 and R19 respectively are aliphatic hydrocarbons of C1xcx9cC20 having no branches, aliphatic hydrocarbons having branches, aromatic hydrocarbons, or hydrocarbons including both of the aliphatic and aromatic hydrocarbons.
Preferably the solvent is methyl-t-butyl ether (MTBE), and it is desirable to use it after saturating it with water.
The epoxide derivatives which are used in the present invention are expressed by the following formula (E): 
wherein, R20 and R21 are hydrogen; aliphatic hydrocarbons of C1xcx9cC20 having no branches; aliphatic hydrocarbons having branches; saturated ring type hydrocarbons; chain type hydrocarbons having a ring; aliphatic hydrocarbons having aromatic rings; hydrocarbons of one or more carbons with the hydrogen substituted by F or Cl; hydrocarbons with no substituted radicals; or aromatic hydrocarbons with the hydrogen of aromatic ring substituted by F, Cl, amine radical, nitrile radical, or alkoxy radical.
The desirable examples of the epoxide derivatives include aromatic compounds and compounds having aromatic rings such as ethylene oxide, propylene oxide, 1-butane oxide, 1-pentane oxide, 1-heptane oxide, 1-octane oxide, 1-nonane oxide, 1-decane oxide, 2-methyl-propylene oxide, 2-methyl-1-butane oxide, 2-methyl-1-octane oxide, 2-methyl-nonane oxide, 2-methyl-1-decane oxide, 2-methyl-1-butane oxide, 2-methyl-1-pentane oxide, 2-methyl-1-hexane oxide, 2-ethyl-1-heptane oxide, 2-ethyl-1-octane oxide, 2-ethyl-1-nonane oxide, 2-ethyl-1-decane oxide, a compound with one of its hydrogen substituted by carbons of C1xcx9cC5, aryl-benzene oxide, 2-methyl-aryl-benzene oxide, and styrene oxide.
The epoxide derivatives which are expressed by the formula (E) are hydroformylated to form a 3-hydroxyaldehyde derivative which is a kind of carbonyl compound. The 3-hydroxyaldehyde derivatives can be expressed by a formula (F) as shown below: 
wherein, R20 and R21 are the same as those of formula (E).
In the reaction mixture of the hydroformylation of the present invention, besides the carbonyl compound (F), there is formed a small amount of alkanediol in which hydrogenation has occurred to the carbonyl radical. Further, there are produced small amounts of acetic aldehyde, acetone, and methyl-ethyl-ketone through the isomerization reaction of the epoxide, in accordance with the kinds of the epoxide.
The 3-hydroxyester derivatives, which can be used as the precursor of the alkanediol like the 3-hydroxyaldehyde derivatives, are synthesized through the hydroesterification of the epoxide derivatives. The hydroesterification is proceeded in such a manner that the epoxide derivatives are reacted with carbon monoxide and alcohol in the presence of a proper solvent. Under these conditions, the reaction temperature is preferably 30xcx9c130 degrees C., and more preferably 40xcx9c110 degrees C. During the reaction, the CO pressure is preferably 100xcx9c3000 psi, and more preferably 200xcx9c1500 psi.
The above epoxide derivatives are the same as those of the compound (E) which is used in the hydroformylation reaction.
The alcohol is expressed by Rxe2x80x3OH. Here, Rxe2x80x3 is a saturated or unsaturated linear hydrocarbon of C1xcx9cC20, a hydrocarbon having branches, a ring type hydrocarbon, an aromatic hydrocarbon, or a linear hydrocarbon including an aliphatic, or preferably methyl, ethyl, isopropyl, cyclohexyl, phenyl or benzyl.
The typical example of the cobalt catalyst is Co2(CO)8, and a promoter may be used in order to enhance the reaction. Under this condition, the concentration of the formed product is adjusted to 1xcx9c50 wt % of the total solution, and preferably to 5xcx9c40 wt %.
The solvent may be an etherial compound expressed by any one of the following formulas (G-1), (G-2) and (G-3), or may be a compound expressed by the following formula (G-4). Or Rxe2x80x3OH which is reactable with the epoxide derivative, may be directly used as a solvent. 
In the formulas (G-1), (G-2), (G-3) and (G-4), R22, R23, R24, R25, and R26 are saturated aliphatic hydrocarbons of C1xcx9cC10 having no branches; aliphatic hydrocarbons having branches; saturated ring type hydrocarbons; chain type hydrocarbons having rings; or aliphatic hydrocarbons having aromatic rings;
R27, R28, R29, R30, R31 and R32 are hydrogen; saturated hydrocarbons of C1xcx9cC4 having branches or no branches; F or Cl; alkoxy radical having C1xcx9cC3; and
p is an integer of 1xcx9c10, and q is an integer of 2xcx9c5.
In the case where a solvent of one of the formulas (G-1) to (G-4) is used, first a 3-hydroxyester derivative is synthesized, and this product is separated by using water. In the case where the solvent is an alcohol, particularly in the case where the solvent is methyl, ethyl, or isopropyl alcohol, the product is separated by evaporation of the solvent. If the solvent is an alcohol having more than four carbon atoms, the separation is carried out using water.
The 3-hydroxyesters which are obtained through the hydroesterification of the epoxide derivatives, according to the present invention is expressed by the following formula (H-1) or (H-2): 
wherein, R20, R21 and Rxe2x80x3 are as described above.
During the hydroesterification of the present invention, besides the carbonyl compound [(H-1) or (H-2)], there are formed isomers and auxiliary products depending on the kinds of the epoxide derivatives.
The present invention will be more thoroughly understood by the below described actual examples. These examples are not intended to limit the scope of the present invention, but are just for specifically presenting the present invention to help understanding the present invention.
* All the rhodium analogues were prepared in the same manner as described below.
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