JPS59110643A - Production of 2-ethylidene-5(or 6)-formylbicyclo(2.2.1) heptane - Google Patents

Abstract

PURPOSE:The oxo reaction of 2-ethylidene-bicyclo[2.2.1]heptene is carried out in the presence of a rhodium compound and a much more amount of a tertiary phosphine than customarily used to enable high-yield production of the titled compound by use of a less amount of rhodium compound. CONSTITUTION:In the production of the objective compound of formula I in the presence of a catalyst composed of a rhodium compound and a tertiary (aromatic) phosphine, which may having formula II [R1-R3 are alkyl, cycloalkyl, aryl whicy may have substitutents such as 1-6C alkyl or alkoxy], the rhodium compound is used in an amount of 0.1-100ppm, preferably 1-10ppm as the metal, based on the compound of formula I and the tertiary phosphine is used in an amount of 200-10,000, preferably 1,000-10,000 times the moles of the rhodium compound and the reaction is effected at 80-180, preferably 100-150 deg.C under 20-250 atmospheric pressure.

Description

Detailed Description of the Invention The present invention is an improvement of 2-ethylidene-5(or 6)-formylbicyclo(2,2,1)hebutane (hereinafter abbreviated as "EFBHJ") represented by the following formula (l[). Regarding manufacturing methods.

EFB) and its derivatives obtained by the method of the present invention are useful compounds as fragrances, fragrance raw materials, organic synthesis reagents, and polymer compound raw materials (Japanese Patent Application Laid-open No. 142937/1983,
(Japanese Patent Application No. 57-94460).

Conventionally, as a method for manufacturing EFBH, Japanese Patent Application Laid-Open No. 1987-
Publication No. 142937 discloses the following two methods.

Method A: Method B: (1) (n) However, Method A requires four steps from 2-ethylidene bicyclo (2,2,13 heptene (hereinafter referred to as r'EBI (abbreviated as J)), and the yield of each step is The efficiency of this method is not necessarily good, and there are problems in terms of practicality because it involves reactions that are problematic as an industrial method.

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,
Among various catalysts, rhodium compounds give the highest yield, but the yield is still only about 65% at most, and in this case, the rhodium compound CRhH(CO)(PPh3) is 3: ]00.00
3 mol 2.7 de) is used frequently. Therefore, considering that this rhodium compound is extremely expensive, E
The production cost of FBH was extremely high and was not satisfactory as an 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 of the expensive rhodium compound causes a decrease in reaction rate and yield. This decrease in yield is largely due to the formation of high-boiling byproducts, but large amounts of byproducts also pose 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-A-57-59826
No. 56-16482, No. 55-28970, No. 55-28969, and No. 55-27165, the amount is 1 x 103 times the rhodium compound, preferably 10 to
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 said that a range of about 10 to 100 times the molar amount is good. However, especially in the oxo reaction of EBH, a rhodium compound is added to a previously preferred amount of tertiary phosphine (1 to 100 times the mole).
When the reaction was carried out in the presence of a catalyst containing
No. 4460).

Therefore, the present inventor further investigated the conditions for the oxo reaction of EBH and found that, surprisingly, if a much larger amount of tertiary bosphin is present than normally thought,
The present invention was completed based on the discovery that the yield of EFBH exceeds 90% at once, and that only a very small amount of rhodium compound is needed.

That is, the present invention provides a method for producing EFBI ((II)) by subjecting E B H'CI) 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 converted to EBH in terms of rhodium metal. 0.1
E
This is a method for producing B 1-I.

Rhodium compounds used in the present invention include rhodium phosphine complexes, such as RhH(CO)(PRI R2R
3) 3°RhCA (COXPRI R2R3)2,
RhCA(PRI R2R3)3 (wherein, R,, R
2 and R3 are the same or different and represent an alkyl group, a cycloalkyl group, an aryl group, or an aryl group substituted with an alkyl group or an alkoxy group having 1 to 6 carbon atoms. The amount of the rhodium compound to be used is 01 to 100 ppm based on 1 lnBH in terms of rhodium metal, and particularly a low concentration of 1 to 10 ppm provides an extremely good yield.

As the tertiary phosphine, those represented by the following formula (IIDR7 (in the formula, RI + R2 and R3 are the same as above) are used, and specific examples include triethylphosphine, tripropylphosphine, tributylphosphine, tricyclohexyl Examples include phosphine, dioctyl phenylphosphine, triphenylphosphine, ditolylphenylphosphine, methoxyphenyldiphenylphosphine, trismethoxyphenylphosphine, tritolylphosphine, and triphenylphosphine is particularly preferred.

These tertiary phosphines are 20
It is necessary to use 0 to ooo times the mole,
Among these, 1,000 to 10,000 times the mole is preferred.

If the amount of tertiary phosphine is less than this, high-boiling by-products will be produced and the yield will be reduced, 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.

Since the reaction rate varies depending on the amount of catalyst, it is necessary to increase the reaction rate when the amount of catalyst acid is small, and to lower the reaction temperature when the amount of catalyst is relatively large to avoid heat generation due to rapid reaction. The preferred temperature range is 80-180
℃, 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.

That is, (1) EFBi() can be obtained in a high yield of 90% or more using an extremely small amount of rhodium catalyst.

■The side reaction of EBH, which is a diolefin, to dialdehyde is suppressed in the presence of excess tertiary phosphine, and EBH
The reaction substantially stops when only one side (double bond at the 5th position) of f (double bond at position 5) has reacted. Therefore, the reaction is extremely easy to control. ■ Side reaction products are reduced, and EFB)I is After recovery by distillation, the residue containing the catalyst layer can be reused and subjected to the oxo reaction.

It is surprising that by decreasing the amount of catalyst while keeping the amount of tertiary phosphine added constant, the selectivity (yield) increases.
Therefore, the method of the present invention is much superior to the conventional method.

The present invention will be explained in detail below with reference to Examples.

Example I EBf(120i (1 mol), CRhH(CO)(P
Ph3)s]10~(1,09X10-''mol), triphenylphosphine2.86!i'(1,09X10
"mol" into the autoclave.After replacing the air in the autoclave with nitrogen, CO20 atmosphere, N220
(total of 40 atmospheres) and then heat the autoclave to 110°C. After reaching the predetermined temperature, the pressure is further increased using equal partial pressures of CO and N2, and the initial pressure is 1.
00 atmospheres. If the gauge pressure is below 40 atm, equal partial pressures of CO and N2 are added to the pressure to 100 atm. The point at which gas absorption stops is defined as the end of the reaction. During this time, it took about 3.5 hours.

After the autoclave is cooled to room temperature and returned to normal pressure, the contents are removed. By distilling this under reduced pressure, the desired 2-ethylidene-5 (or 6)-formy/rubicyclo[2,2,1]hebutane (EFBH) is obtained.

Boiling point: 96-97'C, /16 rhyme Hy-yield: 141.
8g- (yield 94.4φ), residue 6.6 elemental analysis (C+
o As H140) Calculated value (→: C, 79, 96: f (, 9, 39 actual measured value (correspondence): C, 79, 81: H, 9, 50 IR (liquid film, rm'): 3050. 2810. 27
101720, 1690' H-N1vlR (CDC right solvent, TMS internal standard,
δ); 9.48 (IH, -CHo) 5.25 (complex multiplet, l M, -=Cq-
C1 (3) 3.3-1.2 (complex multiplet, 12H) t
aS (relative intensity): There are at least four types of isomers in this compound;
The results of the gas mass measurement using 600 T and column length 40 tn are shown below. 1. Peak 1 (9th): 150 (M+, 13), '122
(7).

121(10), 106(6), 94(28)
.

93 (100), 91 (25), 79 (26)
.

77 (22), 55 (5) Beak 2 (35chi): 150 (M+, 12), 122
(8).

121(9), '106(6), 94(29).

93 (100), 91 (25), 79 (24)
.

77 (22), 55 (7) Beak 3 (50chi): 150 (M+, 53), 121
(45).

106 (20), 94 (29), 93 (100
).

92(16), 9i(50), 79(54).

77 (:36), 55 (15) Peak 4 (6ch): 150'(1', 7I+, 33
121(20).

106 (20), 94 (56), 93 (100).

92(14), 91(52), 79(56).

77(44), 67(13) Example 2 Residue 6.6f obtained in Example 1 and E B i-I 120
? E F B H1
40, f3? (Yield 93.6%) was obtained.

As shown in Example 1, the 4.1 color light method shows a high yield, so the generation of by-products is small, and even if the residue is used again, a high yield can be obtained. E F B H
can be generated.

Examples 3 to 4 Table 1 shows the yield and selectivity of EFBf (when the amount of O dium compound and the amount of tertiary phosphine added are changed in comparison with comparative examples including Example 1. .

Claims (1)

[Claims] 1. 2-ethylidene-bicyclo [2゜2.1] represented by the following formula (I)
A method for producing 2-ethylidene-5 (or 6)-formylbicyclo(z, 2.13) expressed by the following formula (II) by subjecting heptene to an oxo reaction in the presence of a catalyst consisting of a rhodium compound and a tertiary phosphine. In terms of rhodium metal, the rhodium compound is 0.1 to 2-ethylidene-bicyclo[2°2.1]heptene.
100 ppm. The following formula (If) (wherein al + R2 and R3 are the same or different, an alkyl group, a cycloalkyl group, an aryl group, or a carbon number 1
2-ethylidene-5 (or 6)-FormylbicycloC
2,2,11 Method for producing butane. 2. Tertiary phosphine is a rhodium compound i, oo
. The manufacturing method according to claim 1, wherein the amount is 10,000 times by mole. 3. The rhodium compound is RhH (COXPR, R2R
3) 3, RhCl (Co) (PR, R2R3
)2 or RhC-6(PRI R2R3)s (wherein,
R, , R, and R8 are the same or different and represent an alkyl group, a cycloalkyl group, an aryl group, or an aryl group substituted with an alkyl group or an alkoxy group having 1 to 6 carbon atoms) The manufacturing method described in paragraph 1. 4. The manufacturing method according to claim 1 or 2, wherein the tertiary phosphine is triphenylphosphine. 5. % correction of oxo reaction without solvent Claims 1 to 4
The manufacturing method described in any one of paragraphs.