JPH0782281A - Diphosphinite compound and hydroformylation of olefin using the same - Google Patents

Abstract

PURPOSE:To provide the subject new compound manifesting both highly excellent reactivity and reaction characteristics as a ligand, giving high branch/linear form ratio, and capable of producing an intermediate for medicines by hydroformylation using the same. CONSTITUTION:The objective compound having bicyclo[2,2,1]heptane skeleton of the formula (R<1>-R<4> are each l-8C alkyl, 6-18C aryl or 7-18C aralkyl, R<1> and R<2> and/or R<3> and R<4> are each alkyl, aryl or aralkyl which may also be linked to each other via a bond except for P atom), e.g. endo, endo-2,5- bis[(diphenylphosphinyl)oxy]bicyclo @{9146/2-8}2,2,1]heptane. It is recommended that the compound of the formula be obtained, for example, by a process wherein norbornadiene is reacted with formic acid to produce norbornadiene diformate which is then oxidized with chromic acid and then reduced by hydrogenated tri(t-butoxy)aluminumlithium followed by reaction of a chlorophosphine.

Description

Detailed Description of the Invention

[0001]

The present invention relates to the chemical formula (1) [Chemical formula 2]

[0002]

[Chemical 2] [Wherein R ¹ , R ² , R ³ and R ⁴ are a group consisting of an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms and an aralkyl group having 7 to 18 carbon atoms] At least one group selected from the following, which may be the same or different from each other, and R ¹ and R ² and / or R ³ and R ⁴ are linked by a bond other than a phosphorus atom. Represents an optionally substituted alkyl group, aryl group or aralkyl group. ] It is related with the diphosphinite compound which has a bicyclo [2.2.1] heptane skeleton represented by these, and the catalyst containing the said compound and the rhodium compound, It is related with the hydroformylation reaction method of olefin.

[0003]

2. Description of the Related Art Conventionally, a method using a cobalt catalyst such as dicobalt octacarbonyl has been well known as a method for olefin hydroformylation reaction. However, this catalyst has low activity and requires high temperature and high pressure. Was not suitable for. Therefore, as an industrial hydroformylation reaction catalyst that overcomes such drawbacks, a rhodium complex catalyst that can obtain high activity under relatively mild conditions has been actively developed.

This hydroformylation reaction not only allows the production of major industrial chemicals by converting various olefin compounds into carbonyl compounds, but also medicines, agricultural chemicals,
It is a basic and very important reaction that provides a synthetic intermediate for fine chemicals such as fragrances. Therefore, this reaction is an extremely valuable reaction for producing useful chemicals not only in simple olefins but also in hydroformylation of olefins having a functional group. However, in the hydroformylation reaction of an olefin having a functional group, bra is generally used.
Two types of products, an nch form and a linear form, are formed, and the selectivity thereof is important, but there is a problem that the selectivity of the desired isomer is generally low.

In addition, when the hydroformylation reaction of an olefin is carried out using a rhodium catalyst, it is common to use a phosphine compound such as triphenylphosphine as a ligand, but in order to prevent deactivation of the expensive rhodium catalyst. There is a problem that the reaction activity decreases due to the addition of a large amount of phosphine ligand, and there has been a demand for the development of a more active catalyst system and a hydroformylation reaction method.

[0006]

DISCLOSURE OF THE INVENTION The present invention has an extremely high reaction activity industrially suitable as a ligand and a high branch.
It is an object of the present invention to provide a novel diphosphinite compound that simultaneously provides a ch body / linear body ratio, and an olefin hydroformylation reaction method using a catalyst composed of the compound and a rhodium complex.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have found that an extremely high reaction activity industrially suitable as a ligand and a high bra
As a result of intensive studies to provide a novel diphosphinite compound that simultaneously provides an nch body / linear body ratio and a method for hydroformylation reaction of an olefin using a catalyst composed of the compound and a rhodium complex, as a result, an extremely excellent ligand was obtained. The present invention has been completed by finding a compound exhibiting the above-mentioned reaction activity and reaction characteristics, and a hydroformylation reaction method using the same. That is, the present invention provides the chemical formula (1) [Chemical Formula 3].

[0008]

[Chemical 3] [Wherein R ¹ , R ² , R ³ and R ⁴ are a group consisting of an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms and an aralkyl group having 7 to 18 carbon atoms] At least one group selected from the following, which may be the same or different from each other, and R ¹ and R ² and / or R ³ and R ⁴ are linked by a bond other than a phosphorus atom. Represents an optionally substituted alkyl group, aryl group or aralkyl group. ] The diphosphinite compound which has a bicyclo [2.2.1] heptane skeleton represented by these is provided.

The present invention also relates to the bicyclo [2.2.1].
A method for hydroformylation of olefins, which comprises using a catalyst containing a diphosphinite compound having a heptane skeleton and a rhodium compound. The present invention will be described in more detail. The diphosphinite compound of the present invention is based on a bicyclo [2.2.1] heptane skeleton and has two phosphinyloxy groups at the 2,5-positions e.
It is an extremely precisely designed ligand branched into ndo and endo. In addition, "R ³ and R ⁴ represent an alkyl group, an aryl group or an aralkyl group which may be linked by a bond other than a phosphorus atom" means the chemical formula (2) [Chemical Formula 4]

[0010]

[Chemical 4] [In the formula, Y is an atom such as oxygen, nitrogen, or metal, or C ₁ to C.
Represents an atomic group such as a carbon chain of ₃ . ], R ³ and R ⁴ are directly bonded via Y or directly. The method for producing the diphosphinite compound in the present invention can be carried out by combining reactions known in the literature. For example, the chemical formula (3) [Chemical formula 5]

[0011]

[Chemical 5] , The readily available norbornadiene is converted to the diformate by reaction with formic acid, which is oxidized with chromic acid to norbornane-2,5-dione to give lithium tri (tert-butoxy) aluminium hydride. Can be selectively reduced to produce endo, endo-2,5-norbornanediol, and chlorophosphine can be reacted with this to produce.

The substituents on the phosphorus atom, R ¹ , R ² , R ³ and R ⁴ in the diphosphinite compound of the present invention include an alkyl group such as methyl, ethyl, propyl, butyl, octyl or cyclohexyl, phenyl, Examples include an aryl group such as naphthyl, m-tolyl, o-tolyl or m-sulfophenyl, an aralkyl group such as benzyl or naphthylmethyl, or a substituent forming a ring with a phosphorus atom such as a diphenylene group. However, it is not limited to this. Further, R ¹ , R ² , R ³ and R ⁴ may be different substituents.

According to the present invention, by using the above-mentioned diphosphinite compound as a ligand and combining it with a rhodium compound, it can be used as a catalyst for a hydroformylation reaction of an olefin, which has extremely high activity and selectively. It is possible to produce a branched aldehyde compound. In the hydroformylation reaction method of the present invention, the diphosphinite compound and the rhodium compound can be used as an effective catalyst simply by mixing, but if necessary, a complex formed from the diphosphinite compound and the rhodium compound can be used. Can be used as a catalyst after isolation.

The rhodium compound is not particularly limited as long as it forms a complex with a diphosphinite compound, and examples thereof include rhodium trichloride, bis (chlorodicarbonylrhodium), bis [chloro (cyclooctadiene). Rhodium], bis [chloro (norbornadiene)
Rhodium], hydridocarbonyltris (triphenylphosphine) rhodium, dicarbonylacetylacetonato rhodium, and the like.

The olefin to be hydroformylated using the present invention is not particularly limited, but ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-
Linear α-olefins such as octene or 1-decene,
Linear internal olefins such as 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-octene or 3-octene, isobutylene, 2-methyl-1-butene, 2
-Methyl-1-pentene, 3-methyl-1-pentene,
Branched α-olefins such as 2-methyl-1-hexene, 3-methyl-1-hexene, 2-methyl-1-heptene, 3-methyl-1-heptene or 4-methyl-1-heptene, 2,3 -Dimethyl-1-butene, 2,3-dimethyl-1-pentene, 2,4-dimethyl-1-pentene, 2,3-dimethyl-1-hexene, 2,4-dimethyl-1-hexene, 2,5 Multi-branched α-olefins such as -dimethyl-1-hexene or 3,4-dimethyl-1-hexene, cyclic olefins such as cyclohexene, 2-norbornene or bicyclo [2.2.2] octene-2, and these Double bond isomers, aryl-substituted olefins such as styrene, p-methylstyrene, p-isobutylstyrene or 2-vinylnaphthalene; Ralalkyl-substituted olefins, carbonyloxy group-substituted olefins such as vinyl acetate, N-
Nitrogen group-substituted olefins such as ethylaminoethylene or N-methylpyrrolidone, unsaturated alcohols such as allyl alcohol, and unsaturated ethers such as acrolein acetal, methyl vinyl ether or phenyl vinyl ether.
Examples thereof include ters, unsaturated esters such as methyl acrylate and methyl oleate, and unsaturated carboxylic acids such as cinnamic acid, and preferably 1-octene, styrene, p-isobutylstyrene, 2- Methoxy-6-
Α-Olefins such as vinylnaphthalene, methyl acrylate or vinyl acetate are used.

In the olefin hydroformylation reaction method using a diphosphinite compound and a rhodium compound according to the present invention, the amount of the rhodium compound is usually 100 mol% or less, preferably 10% with respect to the olefin.
Used at mol% or less. If it is 100 mol% or more, it cannot be said to be a catalytic reaction, and the cost becomes high, which is not industrially preferable. Further, the amount of the diphosphinite compound is usually 10 molar equivalents or less, preferably 5 molar equivalents or less with respect to the rhodium compound. When it is 10 molar equivalents or more, the reaction activity of the rhodium compound is reduced, which is not preferable. As the reaction conditions in the method of the present invention, general hydroformylation reaction conditions can be used. That is, the reaction temperature is usually -50 to 200.
℃, preferably 0 to 100 ℃, the pressure is usually 1 to 3
00 kg / cm ² G., preferably 10 to 100 kg / cm ² G., and the reaction time is usually 0.1 to 100 hours. Also,
The hydrogen / carbon monoxide ratio (volume ratio) is usually in the range of 0.1 to 10. The reaction solvent does not usually have to be used, but if necessary, an organic solvent inert to the reaction such as benzene, toluene or xylene can also be used. If desired, a high boiling by-product or an aldehyde that is a product can be used as a solvent.

[0017]

The present invention will be described in more detail with reference to the following examples. Example 1 Synthesis of endo, endo-2,5-bis [(diphenylphosphinyl) oxy] bicyclo [2.2.1] heptane (1) In a flask, 69.6 g of norbornadiene (0.
76 mmol) and formic acid 280 ml (88%, 5.32 m)
mol) was added, and the mixture was heated to reflux for 4 hours with stirring. The reaction solution was cooled, excess formic acid was distilled off under reduced pressure, and then distilled under reduced pressure to obtain 121.6 g (87%) of a mixture of norbornane-2,5-diformate. The resulting norbornane-2,5-diformate mixture was added to acetone 360 m.
1000 ml of 8N chromium trioxide-sulfuric acid solution was added dropwise over 19 hours while ice-cooling. After treating the excess oxidizing agent by adding isopropyl alcohol, the solid matter was filtered off, and the acetone in the filtrate was distilled off under reduced pressure. The residue was continuously extracted with diethyl ether, and the extract was distilled under reduced pressure to give norbornane-2,5.
30.0 g (34%) of dione was obtained.

(2) The flask is charged with hydrogenated tert.
-Butoxy) Aluminum lithium 6.1 g (24 mm
ol) in 15 ml of dry tetrahydrofuran and cooled to −10 ° C., and norbornane-2,5 obtained in (1).
A solution of 298 mg (2.4 mmol) of dione in 50 ml of dry tetrahydrofuran was added. After returning to room temperature and stirring for 1 hour, water was added to quench and the insoluble matter was filtered off. The filtrate was depressurized to remove the solvent, and the residue was purified by silica gel column chromatography (developing solution: ethyl acetate) to obtain 229 mg (74%) of endo, endo-2,5-norbornanediol.

(3) The endo, endo- obtained in (2)
2,5-Norbornanediol 100 mg (0.78 m
mol) in 15 ml of dry dichloromethane, 0.16 ml (2.0 mmol) of pyridine was added, and the mixture was cooled to 0 ° C., where 0.31 ml of chlorodiphenylphosphine was added.
(1.7 mmol) was added. The mixture was stirred at room temperature for 6 hours, concentrated under reduced pressure, and the residue was diluted with diethyl ether 30.
It was put in ml and the insoluble matter was filtered off. The filtrate was concentrated and the residue was purified by alumina column chromatography to give 100 mg (26%) of the title compound.

¹ H NMR (270 MHz, CDCl ₃ ) δ7.2-7.6 (m, 20H, Ph), 4.41 (m, 2H), 2.33 (brs, 2H),
2.00 (d, J = 13.53 Hz, 2H), 1.75 (ddd, J = 4.61, 11.87,
13.53 Hz, 2H), 1.37 (brs, 2H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ130.4 (d, J = 23.1 Hz), 129.9 (d, J = 21.9 Hz), 128.9
(d, J = 18.3 Hz), 128.1 (d, J = 7.3 Hz), 80.7 (d, J = 18.4
Hz), 42.2 (d, J = 4.9 Hz), 35.3, 29.2 (d, J = 6.1Hz). IR (KBr) 3062, 2956, 2930, 2874, 1477, 1432, 1364, 1231, 11
79, 1115, 1094, 1044, 1013, 876 cm ^-1 .

Example 2 Hydroformylation reaction of styrene 104.6 mg of styrene was added to a 50 ml autoclave.
(1 mmol), benzene 5 ml, dicarbonylacetylacetonato rhodium 1.3 mg (5 × 10 ⁻³ mo)
1, 0.5 mol%), and endo, e as a ligand
ndo-2,5-bis [(diphenylphosphinyl) oxy] bicyclo [2.2.1] heptane 3.0 mg (6
(× 10 ⁻³ mol) was added and the mixture was replaced with a 1: 1 mixed gas of carbon monoxide and hydrogen three times, and then 40 atm of a 1: 1 mixed gas of carbon monoxide and hydrogen was charged. The autoclave was kept at 30 ° C. and stirred for 20 hours. After releasing the residual gas, the reaction solution was filtered, the solvent was distilled off, and then distilled to obtain 130 mg of phenylpropionaldehyde. Yield 97%. 2-
The production ratio of phenylpropionaldehyde and 1-phenylpropionaldehyde was 96: 4.

Example 3 Hydroformylation Reaction of Vinyl Acetate 86 mg of vinyl acetate (1 m) in a 50 ml autoclave.
mol), benzene 5 ml, dicarbonylacetylacetonato rhodium 1.3 mg (5 × 10 ⁻³ mol, 0.1.
5 mol%), and endo, endo- as a ligand
2,5-bis [(diphenylphosphinyl) oxy] bicyclo [2.2.1] heptane 3.0 mg (6 × 10 ⁻³
mol) was added and the mixture was replaced with a 1: 1 mixed gas of carbon monoxide and hydrogen three times, and then 40 atm of a 1: 1 mixed gas of carbon monoxide and hydrogen was charged. Keep autoclave at 40 ° C, 2
Stirred for 0 hours. After releasing the residual gas, the reaction solution is filtered,
After the solvent was distilled off, the residue was distilled to obtain 111 mg of 2-acetoxypropionaldehyde. Yield 96%. No 1-acetoxypropionaldehyde was detected in this reaction.

Comparative Examples 1 to 4 The ligands used in Example 2 were replaced with endo, endo-2,
5-bis [(diphenylphosphino) methyl] bicyclo [2.2.1] heptane, 1,2-bis (diphenylphosphino) ethane, 1,4-bis (diphenylphosphino) butane, or 1,6- The reaction was carried out in the same manner as in Example 2 except that bis (diphenylphosphino) hexane was used and the stirring time was changed to 30 hours. The result
It is shown in Table 1 together with Example 2.

[0024]

[Table 1] From this result, as a ligand, endo, en of the present invention
With do-2,5-bis [(diphenylphosphinyl) oxy] bicyclo [2.2.1] heptane, the reaction is very high as compared with other ligands while maintaining high branch selectivity. It can be seen that activity is obtained.

Comparative Examples 5 and 6 The ligands used in Example 3 were replaced with endo, endo-2,
The reaction was carried out in the same manner as in Example 3 except that 5-bis [(diphenylphosphino) methyl] bicyclo [2.2.1] heptane or 1,2-bis (diphenylphosphino) ethane was used. It was The results are shown in Table 2 together with Example 3.

[0026]

[Table 2] From this result, as a ligand, endo, en of the present invention
With do-2,5-bis [(diphenylphosphinyl) oxy] bicyclo [2.2.1] heptane, the reaction is very high as compared with other ligands while maintaining high branch selectivity. It can be seen that activity is obtained.

[0027]

Industrial Applicability According to the present invention, a diphosphinite compound exhibiting extremely excellent reaction activity and reaction characteristics as a ligand can be obtained, and an extremely high activity can be obtained by a hydroformylation reaction of an olefin using the compound and a rhodium compound. Thus, an aldehyde compound can be selectively produced by branching.

Claims (2)

[Claims] 1. A chemical formula (1) [Chemical Formula 1] [Wherein R ¹ , R ² , R ³ and R ⁴ are a group consisting of an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms and an aralkyl group having 7 to 18 carbon atoms] At least one group selected from the following, which may be the same or different from each other, and R ¹ and R ² and / or R ³ and R ⁴ are linked by a bond other than a phosphorus atom. Represents an optionally substituted alkyl group, aryl group or aralkyl group. ] The diphosphinite compound which has a bicyclo [2.2.1] heptane skeleton represented by these. 2. A catalyst containing the diphosphinite compound according to claim 1 and a rhodium compound is used.
Method for hydroformylation reaction of olefin.