JP2005254048A - Hydroformylation catalyst comprising dendrimer type phosphine-rhodium complex, and hydroformylation method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydroformylation catalyst having a dendrimer type phosphine or phosphite ligand, a hydroformylation method using the same, and a novel dendrimer type phosphine compound useful as a catalyst or a ligand of the catalyst Alternatively, a phosphite compound thereof is provided.
SOLUTION: The present invention is for hydroformylation comprising a rhodium complex having a dendrimer type phosphine or phosphite as a ligand obtained by growing a monodentate or bidentate type arylphosphine or an aryl moiety of a phosphite into a dendrimer type. And a method for producing a carbonyl compound by a hydroformylation reaction using the catalyst, and a dendrimer-type monodentate phosphine or phosphite, or a rhodium complex thereof.
[Selection figure] None

Description

  The present invention relates to a catalyst for hydroformylation comprising a rhodium complex having a dendrimer type phosphine or phosphite as a ligand obtained by growing a monodentate or bidentate type arylphosphine or an aryl moiety of a phosphite into a dendrimer type, and The present invention relates to a method for producing a carbonyl compound by a hydroformylation reaction using benzene, a dendrimer type monodentate phosphine or phosphite, or a rhodium complex thereof.

A dendrimer is a macromolecule having a spherical structure in which molecular species are polymerized in a spherical shape around a molecule of a polyfunctional group such as an amine that is the core of a central part (Patent Document 1, and Non-Patent Documents 1 to 3), a molecule that has a function of encapsulation from a specific structure that is dense on the outside and sparse on the inside, and has attracted attention in the fields of host-guest chemistry and nanochemistry It is a seed.
Also in catalytic chemistry, attention is paid to its unique structure, and it is expected to construct an effective reaction field. As an extremely useful substituent, a catalyst having a dendrimer site has been studied so far. There are two orientations: a metal atom serving as a catalyst center is arranged in the center of the dendrimer (see Non-Patent Documents 4 to 6 etc.) and a surface portion of the dendrimer (see Non-Patent Documents 7 to 9 etc.). Has been shown. In the latter method of arranging metal atoms on the surface portion, a large number of metal atoms could be arranged on the spherical surface of the dendrimer. Further, in the former method in which a metal atom is arranged in the central portion, it is difficult to obtain a preferable result because the metal atom is covered with a dendrimer molecule.
As described above, various forms using a specific shape called a dendrimer have been studied, but so far, no specific effect due to the dendrimer site has been recognized in most catalysts.

Various catalytic reactions such as hydrogenation and hydroformylation using transition metal phosphine complexes are known. Known phosphine ligands include monodentate coordination such as triphenylphosphine (TPP) and bidentate coordination such as 1,2-bis (diphenylphosphino) ethane (DPPE). ing.
The inventors of the present invention have produced a dendrimerized phosphine ligand and have studied the ability to form a complex with platinum (see Non-Patent Document 10). These phosphine ligands form complexes with platinum relatively stably and are soluble in benzene, THF, and dichloromethane, and some platinum complexes have the ability to form oxidative adducts with iodides. Was.

US Pat. No. 4,189,872 (1981) Buhleier, E., et al., (1978) Synthesis, 155. Tomalia, D. A., et al., (1985) Polym. J., 17, 117 Newkome, G. R., et al., (1985) J. Org. Chem., 50, 2003 Maraval, V., et al., (2000) Organometallics, 19, 4025 Kleij, A. W., et al., (2000) Angew. Chem. Int. Ed. Engl., 39, 176 Voegtle, F., et al., (1999) J. Am. Chem. Soc., 121, 6290 Feeder, N., et al., (2000) Angew. Chem. Int. Ed. Engl., 39, 1661 Eggeling, E. B., et al., (2000) J. Org. Chem., 65, 8857 Beletskaya, I. P., et al., (2000) Tetrahedron Lett., 41, 1081 B. S. Balaji, Y. Obora, et al., (2001) Organometallics, 20, 5342

  The present invention relates to a catalyst having a dendrimer type phosphine or phosphite ligand, in particular, a hydroformylation catalyst, a hydroformylation method using the same, and a novel dendrimer type phosphine compound useful as a catalyst or a ligand of the catalyst. Alternatively, a phosphite compound thereof is provided.

The inventors of the present invention designed and synthesized a novel dendrimer complex catalyst that can express a specific action of a dendrimer by directly incorporating a dendrimer site into the ligand structure. As a ligand that can be expected, a bidentate phosphine ligand having a dendrimer moiety and a platinum complex thereof have been reported (see Non-Patent Document 10). In the process of examining these catalytic capacities, new monodentate phosphine ligands were synthesized as ligands that can construct reaction fields more effectively, and these rhodium complexes have extremely active hydroformylation catalytic capabilities. I found out.
That is, the present invention relates to a catalyst comprising a rhodium complex having a dendrimer-type phosphine or phosphite as a ligand obtained by growing a monodentate or bidentate arylphosphine or phosphite aryl moiety into a dendrimer type, preferably hydroformyl. The present invention relates to a catalyst for chemical conversion. More specifically, the present invention relates to a dendrimer phosphine or phosphite obtained by growing a monodentate or bidentate aryl phosphine or phosphite aryl moiety into a dendrimer form, which has the following general formula (I):

_{(DAr) 2 P - (-} Y-P (dAr) -) k -dAr (I)

Wherein Y represents a C _1-10 alkylene group, k represents 0 or 1, and dAr represents the following formula (II),

-Ar-X-(-Ar'-X-) _m- R (II)

(In the formula, Ar represents an aryl group or an aryloxy group, X represents each independently —O—, —NH—, —COO—, or —CONH—, and Ar ′ represents a C _7-20 aralkyl group. the illustrated, R represents cycloalkyl of _C alkyl group having _{1 to 20,} an aralkyl group of _{C 7 to 20,} cycloalkyl group of _{C 3 to 20,} or a _{C 4 to 20} - represents an alkyl group, m is from 1 to 5 Indicates an integer.)
The group represented by these is shown. )
A catalyst comprising a rhodium complex having a dendrimer-type phosphine or phosphite as a ligand obtained by growing a monodentate or bidentate type arylphosphine represented by the above formula or an aryl moiety of a phosphite into a dendrimer type, preferably for hydroformylation Relates to the catalyst. More specifically, the present invention relates to a dendrimer-type phosphine or phosphite obtained by growing a monodentate or bidentate arylphosphine or phosphite aryl moiety into a dendrimer type having the following general formula (III) or Formula (IV)

(In the formula, [Gn] represents the following formula (V),

In the formula, R represents a C _1-20 alkyl group, a C _7-20 aralkyl group, a C _3-20 cycloalkyl group, or a C _4-20 cycloalkyl-alkyl group,
n shows the integer of 1-5. )
It is related with the catalyst which consists of rhodium complex which makes the dendrimer type phosphine represented by these, or its phosphite a ligand, Preferably, it is a catalyst for hydroformylation.
The present invention also relates to a method for producing a corresponding carbonyl compound by a hydroformylation reaction by reacting an organic unsaturated compound, carbon monoxide, and hydrogen in the presence of the catalyst of the present invention described above.
Furthermore, the present invention provides the following general formula (III),

（式中、［Ｇｎ］は、次式（Ｖ）、

(In the formula, [Gn] represents the following formula (V),

In the formula, R represents a C _1-20 alkyl group, a C _7-20 aralkyl group, a C _3-20 cycloalkyl group, or a C _4-20 cycloalkyl-alkyl group,
n shows the integer of 1-5. )
The dendrimer type phosphine represented by these, its phosphite, or its rhodium complex.

The phosphine represented by the general formula (I) in the present invention is an aryl phosphine or a phosphite, and a phosphorus atom such as a triphenylphosphine moiety or a triphenylphosphite moiety, or a bis (diphenylphosphino) ethane moiety. The aryl group portion is of a dendrimer type with the portion as the core, and is the portion represented by the symbol (dAr) in the general formula (I).
The phosphorus atom portion that is the central nucleus in the phosphine represented by the general formula (I) of the present invention may be for monodentate coordination (when k in the general formula (I) is 0) or bidentate. It may be used for coordination (when k in the general formula (I) is 1). However, from the viewpoint of ease of production and use as a catalyst, it is for monodentate coordination (k in the general formula (I) is 0). Case). Examples of the alkylene group for bidentate coordination include linear or branched alkylene groups having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Preferred alkylene groups include methylene group, ethylene group, propylene group, butylene group, 2-methylpropylene group and the like.
The structural portion represented by (dAr) forming the dendrimer type in the phosphine represented by the general formula (I) of the present invention is not particularly limited as long as it is a dendrimer type containing an aryl group. What has the structure shown by (II) is preferable.
In addition, “the phosphite” in the present invention means that two or three P—C bonds in the phosphine compound of the present invention are P—O—C bonds.

As the aryl group in the present invention, a monocyclic, polycyclic, or condensed cyclic carbocyclic aromatic group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, or a heterocyclic group. An aromatic group is mentioned. In the case of a heterocyclic ring, a ring having 1 to 3 hetero atoms each independently selected from a nitrogen atom, an oxygen atom, or a sulfur atom is included. Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, and a pyridyl group, and a preferable aryl group includes a phenyl group.
The aryloxy group in the present invention is a group in which an oxygen atom is bonded to the above-described aryl group, and examples thereof include a phenoxy group and a naphthyloxy group.
The Ar group in the general formula (II) of the present invention is the above-described aryl group or aryloxy group, one of which is bonded to a phosphorus atom and the other is substituted with one or more X groups. If there is one X group, the dendrimer will extend linearly, and if there are two or more X groups, it will extend in a branched manner. In consideration of the three-dimensional congestion of the dendrimer to be formed, the number is preferably about 1 or 2.
The X groups in the general formula (II) of the present invention are each independently -O- group (ether group), -NH- (amino group), -COO- (carboxyl group), and -CONH- (amide group). A group selected from the group consisting of The nitrogen atom in the amino group or amide is exemplified by monosubstitution, but may be disubstitution. In the case of 2-substitution, the dendrimer extends from this part in a branched manner. In the case of a carboxyl group or an amide group, the X group may be bonded from any direction.

As an alkyl group in this invention, C1-C20, Preferably it is 1-15, or a C1-C10 linear or branched alkyl group is mentioned. Preferred alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, n-hexyl and n-octyl. Examples include groups.
Examples of the cycloalkyl group in the present invention include a monocyclic, polycyclic, condensed cyclic, or bridged cyclic alkyl group having 3 to 20, preferably 5 to 15 or 5 to 10 carbon atoms. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a bicyclo [2,2,1] heptyl group.
As the cycloalkyl-alkyl group in the present invention, the total number of carbon atoms is 4 to 20, preferably 6 to 15, or the number of carbon atoms is 6 to 10, and the above-described alkyl group is bonded to the above-described cycloalkyl group. Groups. For example, a cyclopentyl-methyl group, a cyclopentyl-ethyl group, a cyclohexyl-methyl group, a cyclohexyl-ethyl group, a bicyclo [2,2,1] heptyl-methyl group and the like can be mentioned.
The aralkyl group in the present invention is a straight-chain or branched aralkyl group having 7 to 20, preferably 7 to 15 or 7 to 10 carbon atoms, and includes the above-described alkyl group of the present invention. The above aryl group is bonded. Examples of the aralkyl group include a benzyl group, a phenethyl group, an α-naphthylmethyl group, and a β-naphthylmethyl group.
Various substituents that do not inhibit the catalytic activity of the present invention may be bonded to the alkyl group, aryl group, cycloalkyl group, cycloalkyl-alkyl group, and aralkyl group described above of the present invention. Examples of such a substituent include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen such as chlorine and bromine, an amino group substituted with an alkyl group having 1 to 20 carbon atoms, and nitro. Group, cyano group and the like.

The Ar ′ group in the general formula (II) of the present invention is one in which one is bonded to one X group bonded to the Ar group and the other is bonded to one or more X groups.
The repeating unit portion represented by the formula (—Ar′—X—) _m in the general formula (II) of the present invention is a portion that determines the spread and shape of the dendrimer, and the number of repetitions m is usually 1-5. The degree is preferable, but not limited thereto. As the number of repetitions increases, the distance between the outer surface portion of the dendrimer and the portion of the phosphorus atom serving as the central nucleus increases, and at the same time, the periphery of the phosphorus atom becomes three-dimensionally congested. Moreover, since a dendrimer cannot be formed if there is no repetition number, the repetition number m is usually preferably about 1 to 5. More preferably, it is about 1-3 or 1-2.

Preferred examples of the dendrimer-type phosphine or phosphite obtained by growing the aryl moiety of the monodentate or bidentate arylphosphine or phosphite represented by the general formula (I) of the present invention into a dendrimer type include those represented by the general formula ( III) or a phosphine represented by the general formula (IV) or a phosphite thereof.
The dendrimer type phosphine represented by the general formula (III) of the present invention or a phosphite thereof and a rhodium complex thereof are novel compounds not described in any literature.

The dendrimer-type phosphine compound of the present invention can be produced by polymerizing a polyfunctional raw material that generates a structure represented by a repeating unit portion (-Ar'-X-) _m. Since it is difficult to control the number of repetitions, a method of manufacturing in stages is preferable. As a preferable production method, first, Z ₁ —Ar—X—Z ₂ (wherein Ar and X represent the groups described above, and Z ₁ and Z ₂ represent a reactive leaving group). Then, Z ₃ —Ar′—X—Z ₄ (wherein Ar ′ and X are the above-mentioned groups, and Z ₃ and Z ₄ are reactive leaving groups). And this reaction is performed until the required number of repetitions is reached, and finally Z ₅ -Ar′-X—R (wherein Ar ′, X, and R represent the groups described above, Z ₅ represents a reactive leaving group.) Is reacted to produce a dendrimer moiety with the terminal reactive functional group as a less reactive group. The reverse synthetic route can also be selected for the dendrimer moiety. This can then be activated by reacting with a strong base such as an alkyl metal compound and reacted with phosphorus halide to produce the dendrimer phosphine of the present invention. The phosphite compound of the present invention can be produced by reacting an aryloxy compound having a terminal hydroxyl group with a phosphorus halide.
More specifically, the production of the dendrimer type phosphine of the present invention is exemplified by the case where k in the general formula (I) is 0, Ar is a phenyl group, X is an ether group, and Ar ′ is a benzyl group. I will explain.
First, a production example of a dendrimer unit (hereinafter also referred to as G1 unit) when the number of repetitions is 1 (m = 1) is shown in the following scheme 1.

3,6-dihydroxybenzoic acid ester is reacted with benzyl bromide to give 3,6-dibenzyloxybenzoic acid ester, then the ester moiety is reduced to a hydroxymethyl form, and then the hydroxyl group is halogenated to give 3, 6-Dibenzyloxy-benzyl bromide (G1-Br) is prepared.
Next, a production example of a dendrimer unit (hereinafter also referred to as G2 unit) when the number of repetitions is 2 (m = 2) is shown in the following scheme 2.

By reacting 2 mol of 3,6-dibenzyloxy-benzyl bromide (G1-Br) obtained in Scheme 1 with 1 mol of 3,6-dihydroxybenzyl alcohol, 3,6-bis (3 6-Dibenzyloxy-benzyloxy) benzyl alcohol (G2-OH) is halogenated in the same manner as described above to produce the bromide (G2-Br).
Next, according to the following scheme 3 respectively, it reacts with 4-bromophenol to produce a moiety having a dendrimer unit G1 or G2.

The dendrimer units G1 and G2 thus produced can be activated with, for example, n-butyllithium and then reacted with phosphorus trichloride to produce the desired dendrimer phosphine. In the case of bidentate phosphine, phosphorus halide such as 1,2-bis (dichlorophosphino) ethane may be used instead of phosphorus trichloride.
A dendrimer type phosphine having a dendrimer unit (G1) when the number of repetitions that can be produced in this way is 1 (m = 1) is hereinafter referred to as (G1) ₃ P, and the number of repetitions is 2 (m = 2). The dendrimer type phosphine having the dendrimer unit (G2) in the case is hereinafter referred to as (G2) ₃ P.

  Among the dendrimer-type phosphines or phosphites that can be produced in this way, the dendrimer-type phosphine represented by the following general formula (III) or a phosphite thereof and a rhodium complex thereof are novel compounds not described in any literature.

(In the formula, [Gn] represents the following formula (V),

In the formula, R represents a C _1-20 alkyl group, a C _7-20 aralkyl group, a C _3-20 cycloalkyl group, or a C _4-20 cycloalkyl-alkyl group,
n shows the integer of 1-5. )
Or a phosphite thereof.

  The alkyl group, aralkyl group, cycloalkyl group, and cycloalkyl-alkyl group in the general formula (III) are the same as those described above. Preferable R group of the compound represented by the general formula (III) of the present invention includes benzyl group, phenethyl group, ethyl group and the like, and benzyl group is more preferable. Preferred values of n include 1 or 2.

A rhodium complex can be obtained by reacting the dendrimer-type phosphine thus produced with a rhodium compound (MP Andersen, et al, Inorg. Chem. 20, 4101 (1981), etc.). As the rhodium compound used in this reaction, a zero-valent rhodium compound, a divalent rhodium compound, or the like can be used. Examples include (cyclooctadiene (COD)) ₂ Rh, [RhCl (COD)] ₂ , and Rh ₆ (CO) ₁₆ , but are not limited thereto.
Also, the dendrimer type phosphine of the general formula (III) of the present invention described above can be similarly converted to a rhodium complex.
Further, the catalyst comprising a rhodium complex in the present invention is not necessarily required to perform such a complex formation reaction, and can be used as it is in a state where the dendrimer type phosphine and the rhodium compound described above are mixed. Such use in a mixed state is also included in the scope of the rhodium complex in the present invention.
The amount of phosphorus in the phosphine and the amount of rhodium in the rhodium complex of the present invention is 0.1 to 20 mol, preferably 1 to 20 mol, 1 to 10 mol, 3 to 3 mol of rhodium with respect to 1 mol of rhodium. It is selected in the range of 20 mol or 3 to 10 mol.

Next, the present inventors examined the catalytic ability of the present invention by taking a hydroformylation reaction of dihydrofuran as an example in the presence of a rhodium complex catalyst having a dendrimer type phosphine as a ligand.
Table 1 shows the results of experiments conducted at low pressure (0.5 MPa) and high pressure (4 MPa or 6 MPa). As a result, in the conventional hydroformylation using 2,3-dihydrofuran when triphenylphosphine is used as a ligand, 2- and 3-formyltetrahydrofuran are 13% at low pressure and 35% at high pressure. When DPPE was used as the ligand, the yield was 29% at high pressure, whereas the bidentate dendrimer first generation ligand (general formula (I) The target product was obtained in a high yield of 61% for k = 1) and 86% for the second-generation dendrimer ligand of the single conformation (k = 0 in the general formula (I)). From these results, it was shown that the phosphine ligand having a dendrimer moiety is extremely useful for the catalytic hydroformylation reaction.
In particular, a monoconformation type phosphine represented by the general formula (III) in which k is 0 in the general formula (I) of the present invention is excellent in yield at low pressure, It can be seen that the catalyst enables a high-performance hydroformylation reaction at low pressure.

The hydroformylation reaction in the present invention can be carried out in the same manner as in the conventional method by using the catalyst of the present invention as a catalyst. The raw material compound in the hydroformylation reaction of the present invention is an organic unsaturated compound, an organic compound having at least one ethylenic double bond, and having no substituent that inhibits the hydroformylation reaction. There is no particular limitation, and various ethylenically unsaturated compounds such as dihydrofuran, styrene, cyclohexene, propylene, and pentene can be used.
Carbon monoxide and hydrogen gas may be prepared separately, but water gas can be used. As the solvent, various inert solvents such as benzene and THF can be used. The reaction temperature can be selected from room temperature to the boiling point of the solvent. The pressure can be selected in a wide range of 0.1 to 30 MPa, preferably 0.1 to 10 MPa, preferably 0.1 to 5 MPa in terms of gauge pressure.

  The present invention has found a catalytic effect having a nano-controlled space in the center of the dendrimer by using a dendrimer-type phosphine as a ligand and further arranging the phosphorus atom of the phosphine in the center of the dendrimer. Particularly in hydroformylation, the present invention provides a catalyst having an excellent catalytic activity in which a target substance can be produced in a very high yield despite a low pressure. Such a high catalytic activity in the nano-controlled space in the center of the dendrimer has been achieved for the first time by the present invention, and provides an innovative catalyst in the development of a homogeneous catalyst and a method of using the dendrimer.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited at all by these Examples.

Production of (G1) ₃ P (2-a) (G1) ₃ P was produced according to the reaction formula shown below.

1-[(4-Bromophenoxy) methyl] -3,5-bis (phenylmethoxy) benzene ((G1) -OPhBr) (1.50 g, 3.16 mmol) in a 50 mL two-necked eggplant flask under an argon atmosphere Was dissolved in 17 mL of tetrahydrofuran and stirred at -78 ° C. An n-butyllithium / hexane solution (2.1 mL, 1.58 M) was added dropwise to the solution over 10 minutes, and the mixture was stirred at −78 ° C. for 60 minutes. Then, a phosphorus trichloride / toluene solution (0.92 mL, 1.15 M) was added dropwise over 10 minutes and stirred at -78 ° C. After 90 minutes, the mixture was returned to room temperature and stirred overnight. Distilled water (5 mL) was added to the reaction mixture, and the mixture was stirred for 30 minutes. The organic phase was transferred to a dried eggplant flask containing magnesium sulfate and dehydrated. Thereafter, the mixture was filtered through Celite under an argon atmosphere, and the filtrate was concentrated to obtain a white solid. The obtained solid was dissolved in 3 mL of dichloromethane, and 6.5 mL of methanol was added little by little and allowed to stand overnight. Except for the supernatant, the remaining solvent was removed to obtain 0.94 g of the desired product in 73%.
Mass spectrometry (FD-MS): m / z 1217 (M ^<+> ).
¹ H NMR (CDCl ₃ ): δ
5.01 (s, 6H, OCH ₂ Ar), 5.03 (s, 12H, OCH ₂ Ar),
6.56-6.58 (m, 3H, ArH),
6.64-6.58 (m, 6H, ArH),
6.98 (dd, 6H, J = 8 Hz, ⁴ J _HP = 8 Hz, ArH),
7.30-7.43 (m, 36H).
¹³ C NMR (CDCl ₃ ): δ
70.27 (OCH ₂ Ar), 70.54 (OCH ₂ Ar), 102.02
106.38, 115.49 (d, ³ J _CP = 7.3 Hz), 117.13,
127.96, 128.44, 129.01,
135.42 (d, ² J _CP = 20 Hz), 137.12, 139.67,
159.70, 160.60;
³¹ P NMR (CDCl ₃ ): δ
-8.85.
As Analysis Calculated _{C 81 H 69 O 9 P:} C, 79.91; H, 5.71.
Found: C, 80.04; H, 5.87.

Production of (G2) ₃ P (2-b) (G2) ₃ P was produced according to the reaction formula shown below.

1,3-bis [[3,5-bis (phenylmethoxy) phenyl] methoxy] -5-[(4-bromophenoxy) methyl] benzene ((G2) — in a 30 mL two-necked eggplant flask under an argon atmosphere OPhBr) (1.04 g, 1.16 mmol) was added, dissolved in 6 mL of tetrahydrofuran, and stirred at -78 ° C. An n-butyllithium / hexane solution (0.75 mL, 1.58 M) was added dropwise to the solution over 10 minutes, and the mixture was stirred at −78 ° C. for 60 minutes. Next, a phosphorus trichloride / toluene solution (0.33 mL, 1.15 M) was added dropwise over 10 minutes and stirred at -78 ° C. After 90 minutes, the mixture was returned to room temperature and stirred overnight. 3 mL of distilled water was added to the reaction mixture and stirred for 30 minutes, and the organic phase was transferred to a dried two-necked eggplant flask containing magnesium sulfate for dehydration. Thereafter, the mixture was filtered through Celite under an argon atmosphere, and the filtrate was concentrated to obtain a white solid. The obtained solid was dissolved in 3 mL of dichloromethane, and 3 mL of methanol was added little by little and allowed to stand overnight. Except for the supernatant, the remaining solvent was removed to obtain 0.63 g of the desired product at 67%.
Mass spectrometry (ESI-MS): m / z 2490 (M ^<+> ).
¹ H NMR (CDCl ₃ ): δ
4.97 (m, 18H, OCH ₂ Ar), 5.03 (m, 24H, OCH ₂ Ar), 6.55 (m, 3H, ArH), 6.58 (m, 6H, ArH),
6.66 (d, 6H, J = 2 Hz, ArH), 6.69 (m, 12H, ArH), 6.94 (d, 6H, J = 8 Hz, ArH), 7.30-7.42 (m , 66H). ¹³ C NMR (CDCl ₃ ): δ
70.41 (OCH ₂ Ar), 70.52 (OCH ₂ Ar), 101.00,
106.82, 115.51, 127.98, 128.43, 129.00,
129.91, 132.70, 135.47 (d, ² J _CP = 18 Hz),
137.17, 139.59, 160.49, 160.59;
³¹ P NMR (CDCl ₃ ): δ
-8.80.
Elemental Analysis Calculated _{C 165 H 141 O 21 P:} C, 79.56; H, 5.71.
Actual measurement value: C.I. 79.78; H, 5.83

Production of (3,5-dibenzyloxy-benzyloxy) ₃ P (4-a) (3,5-dibenzyloxy-benzyloxy) ₃ P was produced according to the following reaction formula.

Under an argon atmosphere, 3,5-bis (benzyloxy) benzyl alcohol (3-a ((G1) -OH) in Scheme 1) (1.78 g, 5.6 mmol) was placed in a 50 mL two-necked eggplant flask, and 10 mL of tetrahydrofuran was added. And 1.0 mL of triethylamine were added. Subsequently, it cooled to -78 degreeC and the phosphorus trichloride / toluene solution (2.1 mL, 1.15M) and the tetrahydrofuran 12mL mixed solution were dripped. Then, it returned to room temperature and stirred overnight. The reaction mixture was filtered through silica gel under an argon atmosphere and washed with 30 mL of tetrahydrofuran. The solvent was distilled off and the residue was purified by silica gel column chromatography using diethyl ether / hexane / triethylamine (40: 50: 1). The isolation yield was not determined.
Mass spectrometry (FD-MS): m / z 989 (M ^<+> ).
¹ H NMR (CDCl ₃ ): δ
4.82 (d, 6H, ³ J _HP = 8 Hz, OCH ₂ Ar),
4.93 (s, 12H, OCH ₂ Ar),
6.51 (t, 3H, J = 2 Hz ArH),
6.10 (d, 6H, J = 2 Hz, ArH),
7.27-7.38 (m, 30H).
¹³ C NMR (CDCl ₃ ): δ
64.82 (d, ² J _CP = 11 Hz, OCH ₂ Ar),
70.40 (OCH ₂ Ar), 101.92, 106.68, 127.94,
128.35, 128.94, 137.21,
140.92 (d, ³ J _CP = 6 Hz), 160.44;
³¹ P NMR (CDCl ₃ ): δ
140.93.

Production of (G1-O) ₃ P (6-a) (G1-O) ₃ P was produced according to the following reaction formula.

1-[(4-Hydroxyphenoxy) methyl] -3,5-bis (phenylmethoxy) benzene (5-a ((G1) -hydroxy compound of OPhBr)) (1) in a 30 mL two-necked eggplant flask under an argon atmosphere 0.0 g, 2.4 mmol) was added, and tetrahydrofuran (4.5 mL) and triethylamine (0.45 mL) were added. Subsequently, it cooled to -78 degreeC and the phosphorus trichloride / toluene solution (0.7 mL, 1.15M) and the tetrahydrofuran mixed solution 5.5mL were dripped. Then, it returned to room temperature and stirred overnight. The reaction mixture was filtered through silica gel under an argon atmosphere and washed with 40 mL of tetrahydrofuran. The target product was obtained in an amount of 0.48 g, 47% by distilling off the solvent and performing reprecipitation with dichloromethane / hexane.
¹ H NMR (CDCl ₃ ): δ
5.05 (s, 6H, OCH ₂ Ar), 5.12 (s, 12H, OCH ₂ Ar),
6.72 (s, 3H, ArH), 6.81 (s, 6H, ArH),
7.01 (d, 6H, J = 9 Hz, ArH),
7.20 (d, 6H, J = 9 Hz, ArH), 7.43-7.54 (m, 30H).
¹³ C NMR (CDCl ₃ ): δ
70.56 (OCH ₂ Ar), 70.87 (OCH ₂ Ar), 102.16
106.90, 116.37, 122.25 (d, ³ J _CP = 6 Hz),
128.12, 128.58, 129.15, 137.05, 140.03
145.88 (d, ² J _CP = 3 Hz), 155.87, 160.74.
³¹ P NMR (CDCl ₃ ): δ
129.96.

Hydroformylation reaction with rhodium complex catalyst using triphenylphosphine ligand (Comparative example)
[Rh (COD) ₂ ] BF ₄ (3.9 mg, 0.0096 mmol), triphenylphosphine (10.0 mg, 0.038 mmol), and bibenzyl (as an internal standard) were placed in an argon-substituted glass liner and added to 2 mL of benzene. After dissolving and stirring, 2,3-dihydrofuran (0.072 mL, 0.95 mmol) was added and stirred for 15 minutes. The glass liner was placed in an autoclave and a hydrogen / carbon monoxide (1: 1) mixed gas was added (0.5 MPa). After 16 hours, the mixture in the reaction vessel was taken out and the yield was measured by gas chromatography. 2- and 3-formyltetrahydrofuran were obtained in 13% yield.

Hydroformylation reaction using (G1) ₃ P (2-a) of the present invention [Rh (COD) ₂ ] BF ₄ (3.9 mg, 0.0096 mmol) on a glass liner substituted with argon, prepared in Example 1 (G1) ₃ P (2-a) (46.3 mg, 0.038 mmol) and bibenzyl (as an internal standard) were added, dissolved in 2 mL of benzene and stirred, and after 1 hour, 2,3-dihydrofuran (0.072 mL) 0.95 mmol) and stirred for 15 minutes. The glass liner was placed in an autoclave and a hydrogen / carbon monoxide (1: 1) mixed gas was added (0.5 MPa). After 16 hours, the mixture in the reaction vessel was taken out and the yield was measured by gas chromatography. 2- and 3-formyltetrahydrofuran were obtained in 85% yield.

Hydroformylation reaction using (G2) ₃ P (2-b) of the present invention [Rh (COD) ₂ ] BF ₄ (3.9 mg, 0.0096 mmol) on a glass liner substituted with argon, prepared in Example 2 (G2) ₃ P (2-b) (94.7 mg, 0.038 mmol) and bibenzyl (as an internal standard) were added, dissolved in 2 mL of benzene and stirred, and after 1 hour, 2,3-dihydrofuran (0.072 mL) 0.95 mmol) and stirred for 15 minutes. The glass liner was placed in an autoclave and a hydrogen / carbon monoxide (1: 1) mixed gas was added (0.5 MPa). After 16 hours, the mixture in the reaction vessel was taken out and the yield was measured by gas chromatography. 2- and 3-formyltetrahydrofuran were obtained in 86% yield.
The results of these hydroformylation reactions are summarized in Table 1 below.

From the left side of Table 1, the experiment number, the type of phosphine used, the phosphorus / rhodium ratio (P / Rh), the pressure of hydrogen gas and carbon monoxide gas (MPa), the yield (%), 2-formyltetrahydrofuran and The production ratio (2/3) of 3-formyltetrahydrofuran is shown respectively.
As a result, it can be seen that the catalyst of the present invention is extremely high in activity, which can achieve a yield more than twice that of conventional triphenylphosphine. In particular, it is highly active at low pressure and is an industrially advantageous catalyst.

  The present invention provides an extremely high activity catalyst utilizing a nano-controlled space by dendrimer, particularly a catalyst for hydroformylation. By using the catalyst of the present invention, aldehydes that are various industrial raw materials, The production of various alcohols from the raw material can be carried out easily and in high yield, and is extremely useful industrially. The compound represented by the general formula (III) of the present invention is It is extremely useful industrially as the catalyst of the invention or the phosphine therefor.

Claims (12)

  A catalyst for hydroformylation comprising a rhodium complex having a dendrimer type phosphine or phosphite as a ligand obtained by growing a monodentate or bidentate type arylphosphine or an aryl moiety of a phosphite into a dendrimer type. A dendrimer-type phosphine or phosphite obtained by growing a monodentate or bidentate arylphosphine or phosphite aryl moiety into a dendrimer type has the following general formula (I):
_{(DAr) 2 P - (-} Y-P (dAr) -) k -dAr (I)
Wherein Y represents a C _1-10 alkylene group, k represents 0 or 1, and dAr represents the following formula (II),
-Ar-X-(-Ar'-X-) _m- R (II)
(In the formula, Ar represents an aryl group or an aryloxy group, X represents each independently —O—, —NH—, —COO—, or —CONH—, and Ar ′ represents a C _7-20 aralkyl group. the illustrated, R represents cycloalkyl of _C alkyl group having _{1 to 20,} an aralkyl group of _{C 7 to 20,} cycloalkyl group of _{C 3 to 20,} or a _{C 4 to 20} - represents an alkyl group, m is from 1 to 5 Indicates an integer.)
The group represented by these is shown. )
The catalyst according to claim 1, which is a dendrimer-type phosphine or phosphite obtained by growing a monodentate or bidentate arylphosphine represented by the formula:   The catalyst according to claim 2, wherein the aryl group of the aryl phosphine or phosphite is a phenyl group or a phenoxy group.   The catalyst according to claim 2 or 3, wherein the aralkyl group of arylphosphine or phosphite is a benzyl group. A dendrimer-type phosphine or phosphite obtained by growing a monodentate or bidentate arylphosphine or phosphite aryl moiety into a dendrimer type has the following general formula (III) or general formula (IV):

(In the formula, [Gn] represents the following formula (V),

In the formula, R represents a C _1-20 alkyl group, a C _7-20 aralkyl group, a C _3-20 cycloalkyl group, or a C _4-20 cycloalkyl-alkyl group,
n shows the integer of 1-5. )
The catalyst according to any one of claims 2 to 4, which is a dendrimer type phosphine represented by the formula (1) or a phosphite thereof.   The catalyst according to claim 5, wherein the dendrimer-type phosphine ligand is a phosphine or phosphite represented by the general formula (III).   The catalyst according to claim 5 or 6, wherein R in the formula (IV) is a benzyl group.   The catalyst according to any one of claims 2 to 7, wherein the raw compound for hydroformylation is dihydrofuran.   A method for producing a corresponding carbonyl compound by a hydroformylation reaction by reacting an organic unsaturated compound, carbon monoxide, and hydrogen in the presence of the catalyst according to any one of claims 1 to 8.   The method according to claim 9, wherein the organic unsaturated compound is dihydrofuran. The following general formula (III),

(In the formula, [Gn] represents the following formula (V),

In the formula, R represents a C _1-20 alkyl group, a C _7-20 aralkyl group, a C _3-20 cycloalkyl group, or a C _4-20 cycloalkyl-alkyl group,
n shows the integer of 1-5. )
The dendrimer type phosphine represented by these, its phosphite, or its rhodium complex. R in formula (III) is a benzyl group, The phosphine or its phosphite of Claim 11, or its rhodium complex.