JPH0364492B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the following formula () 2-ethylidene-5 (or 6)-formylbicyclo[2.2.1]heptane (hereinafter referred to as "EFBH")
(abbreviated as )). EFBH and its derivatives obtained by the method of the present invention are useful compounds as perfumes, raw materials for perfumes, organic synthesis reagents, and raw materials for polymeric compounds (Japanese Patent Application Laid-Open No. 1983-1989-1).
No. 142937, Patent Application No. 57-94460). Conventionally, the method of manufacturing EFBH was
57-142937 discloses the following two methods. However, method A requires four steps from 2-ethylidenebicyclo[2.2.1]heptene (hereinafter abbreviated as "EBH"), the yield in each step is not necessarily good, and the reaction is problematic as an industrial method. There was a problem in terms of practicality because it included Further, although method B is extremely simple and is a preferred method, it has a problem in that it uses a large amount of expensive metal catalyst. That is, according to the description in JP-A-57-142937, rhodium compounds give the highest yield among various catalysts, but the yield is still only about 65% at most, and in this case, 0.1 mol of EBH ( 12
g) against rhodium compound [RhH(CO)
(PPh ₃ ) ₃ ] is used in a large amount of 0.003 mol (2.7 g). Therefore, it is considered that this rhodium compound is extremely expensive. The production cost of EFBH became extremely high, and it was not a satisfactory industrial method. In order to overcome the problems of Method B, it is necessary to reduce the amount of expensive rhodium compound used, but reducing the amount used causes a decrease in the reaction rate and yield. A major cause of this decrease in yield is the production of high-boiling byproducts, and a large amount of byproducts also poses a major obstacle to reusing or regenerating the catalyst. In the olefin oxo reaction using such a rhodium compound as a catalyst, a method is known in which phosphine is added in excess. For example, JP 57-59826, JP 56-16482, JP 55-28970
No. 55-28969 and No. 55-27165, the amount is 1×10 ³ times the rhodium compound, preferably 10 to 3 times the mole.
100 times the molar amount of tertiary phosphine, and
No. 73628 and No. 55-89238 report a method in which tertiary phosphine is added in an amount of 20 to 200 times the molar amount of the rhodium compound. However, although such tertiary phosphine has a cocatalytic effect of increasing the selectivity, it also has the effect of reducing the reaction rate. It was thought that a range of about 10 to 100 times the molar amount would be good. However, especially in the oxo reaction of EBH,
When a rhodium compound was reacted in the presence of a catalyst containing a conventionally preferred amount of tertiary phosphine (1 to 100 times the mole), the selectivity (yield) was about 70% at most. (Special application 1987-
No. 94460). Therefore, as a result of further investigation of the conditions for the oxo reaction of EBH, the present inventor found that, surprisingly, if a much larger amount of tertiary phosphine was added than normally thought, the yield of EFBH could be increased. 90% at once
The present invention has been completed based on the discovery that the rhodium compound can be used in an extremely small amount. That is, the present invention provides a method for producing EFBH ( ) by subjecting EBH ( ) to an oxo reaction in the presence of a catalyst consisting of a rhodium compound and a tertiary phosphine, in which the rhodium compound is
Use 0.1 to 100 ppm of EBH and 1,000 to 10,000 times the mole of tertiary phosphine to the rhodium compound.
This is a method for producing EFBH. Rhodium compounds used in the present invention include rhodium phosphine complexes, such as RhH(CO).
(PR ₁ R ₂ R ₃ ) ₃ , RhCl (CO) (PR ₁ R ₂ R ₃ ) ₂ , RhCl
(PR ₁ R ₂ R ₃ ) ₃ (in the formula, R ₁ , R ₂ and R ₃ represent an aryl group), and the like. The usage amount of this rhodium compound is calculated as rhodium metal equivalent to EBH.
0.1 to 100 ppm is sufficient, especially low concentrations of 1 to 10 ppm give very good yields. For tertiary phosphine, the following formula () (In the formula, R ₁ , R ₂ and R ₃ are the same as above) are used, and specific examples include:
Examples include triphenylphosphine, ditolylphenylphosphine, methoxyphenyldiphenylphosphine, trismethoxyphenylphosphine, tritolylphosphine, and triphenylmosphine is particularly preferred. These tertiary phosphines are used in an amount of 1,000 to 10,000 mol based on the rhodium compound. If the amount of tertiary phosphine is less than this, high-boiling by-products will be produced and the yield will decrease, which is not preferable. The reaction can be carried out in a solvent, but as shown in the examples, a sufficiently high yield can be obtained without a solvent, so a solvent is not necessarily required. The reaction temperature changes depending on the amount of catalyst, so if the amount of catalyst is small, the reaction rate should be increased, and if the amount of catalyst is relatively large, the reaction temperature needs to be lowered to avoid heat generation due to rapid reaction. . A preferred temperature range is 80-180°C, particularly preferably 100-150°C. The reaction pressure ranges from 20 to 250 atmospheres. The mixing ratio of carbon monoxide and hydrogen used is in the range of 0.5 to 2.0, preferably 0.8 to 1.2. As described above, the method of the present invention has the following advantages. In other words, a very small amount of rhodium catalyst
EFBH can be obtained with a high yield of over 90%. The side reaction of EBH, which is a diolefin, to form a dialdehyde is suppressed in the presence of an excess of tertiary phosphine, and the reaction is substantially stopped when only one side of EBH (the double bond at the 5-position) reacts. Therefore, control of the reaction becomes extremely easy. After the side reaction products are reduced and the EFBH is recovered by distillation, the residue containing the catalyst layer can be reused and subjected to the oxo reaction. In this way, by decreasing the amount of catalyst while keeping the amount of tertiary phosphine added constant, the selectivity (yield) increases.
This is surprising, and therefore, the method of the present invention is extremely superior to the conventional method. The present invention will be explained in detail below with reference to Examples. Example 1 EBH 120g (1 mol), [RhH(CO)(PPh ₃ ) ₃ ]
Add 10 mg (1.09 x 10 ^-5 mol) and 2.86 g (1.09 x 10 ^-2 mol) of triphenylphosphine into the autoclave. After replacing the air in the autoclave with nitrogen, the autoclave is pressurized with a partial pressure of 20 atm of CO and 20 atm of _H2 (40 atm in total), and then the autoclave is heated to 110°C. After reaching the given temperature, the equal partial pressure
Further pressurize with CO and H ₂ to bring the initial pressure to 100 atm.
If the gauge pressure is below 40 atm, the equal partial pressures will be
Pressurize CO and _H2 to 100 atmospheres. The reaction ends when gas absorption stops. This took about 3.5 hours. After the autoclave is cooled to room temperature and returned to normal pressure, the contents are taken out. By distilling this under reduced pressure, the desired 2-ethylidene-5 (or 6) is obtained.
-Formylbicyclo[2.2.1]heptane (EFBH)
get. Boiling point: 94-97℃/16mmHg Yield: 141.8g (yield 94.4%), residue 6.6g Elemental analysis (as C ₁₀ H ₁₄ O) Calculated value (%): C, 79.96: H, 9.39 Actual value (%) :C, 79.81:H, 9.50 IR (liquid film, cm ^-1 ): 3050, 2810, 2710, 1720,
1690 H-NMR (CDCl ₃ solvent, TMS internal standard, δ);
9.48 (1H, -C H O) 5.25 (Complex multiplet, 1H, =C H -CH ₃ ) 3.3-1.2 (Complex multiplet, 12H) MS (Relative intensity): This compound has at least four types of Although isomers exist, capillary columns [Shimadzu Corporation's
The results of gas mass measurement using Thermon 600T, column length 40 m are shown below. Peak 1 (9%): 150 (M ⁺ , 13), 122 (7), 121 (10),
16(6), 94(28), 93(100), 91(25), 79(26), 77
(22), 55(5) Peak 2 (35%): 150 (M ⁺ , 12), 122(8), 121(9),
106(6), 94(29), 93(100), 91(25), 79(24), 7
7
(22), 55(7) Peak 3 (50%): 150 (M ⁺ , 53), 121 (45), 106
(20), 94 (29), 93 (100), 92 (16), 91 (50), 7
9
(54), 77 (36), 55 (15) Peak 4 (6%): 150 (M ⁺ , 33), 121 (20), 106
(20), 94 (56), 93 (100), 92 (14), 91 (52), 7
9
(56), 77 (44), 67 (13) Example 2 6.6 g of the residue obtained in Example 1 and 120 g (1 mole) of EBH were charged into an autoclave and reacted in the same manner as in Example 1 to yield 140.6 g of EFBH. (yield
93.6%). In this way, the method of the present invention shows a high yield as shown in Example 1, so the production of by-products is small, and even if the residual catalyst is reused, a high yield can be obtained.
EFBH can be generated. Examples 3 to 4 Example 1 shows the yield and selectivity of EFBH when the amount of rhodium compound and the amount of tertiary phosphine added are changed.
Table 1 shows the results in comparison with the comparative example.

[Table] Example 5 The amount of triphenylphosphine was 0.572g (2.18×
121.7 g (yield: 81%) of EFBH was obtained in exactly the same manner as in Example 1, except that the amount of EFBH was reduced to 10 ^-3 mol). In addition,
The amount of triphenylphosphine in this example is 200 times the mole of the rhodium compound.

Claims (1)

[Claims] Linear formula () 2-ethylidene-bicyclo [2.2.1]
By subjecting heptene to an oxo reaction in the presence of a catalyst consisting of a rhodium compound and a tertiary phosphine, the following formula () In the method for producing 2-ethylidene-5 (or 6)-formylbicyclo[2.2.1]heptane represented by 100ppm, following formula () _{2 -} ethylidene- ₅ (or 6) - Method for producing formylbicyclo[2.2.1]heptane. 2 The rhodium compound is RhH(CO)
(PR ₁ R ₂ R ₃ ) ₃ , RhCl (CO) (PR ₁ R ₂ R ₃ ) ₂ or RhCl
(CO)(PR ₁ R ₂ R ₃ ) ₃ (wherein R ₁ , R ₂ and R ₃ represent an aryl group). 3. The production method according to claim 1, wherein the tertiary phosphine is triphenylphosphine. 4. The production method according to any one of claims 1 to 3, in which the oxo reaction is carried out without a solvent.