JP2000063297A - Production of bicyclo[2.2.1]heptane derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a bicyclo[2.2.1]heptane derivative having high traction coefficient at high temperature and excellent low-temperature viscosity characteristics by dimerizing a raw material compound at or below a specific temperature in the presence of an acid catalyst and hydrogenating the product in the presence of a hydrogenation catalyst at a temperature within a specific range. SOLUTION: The objective compound of the formula ((m) is 2 or 3; (n) is 1 or 2) can be produced by dimerizing a bicyclo[2.2.1]heptane ring compound substituted with methylene group and methyl group (e.g. 2-methylene-3- methylbicyclo[2.2.1]heptane or 3-methylene-2-methylbicyclo[2.1.1]heptane) and/or a bicyclo[2.2.l]heptene ring compound substituted with methyl group (e.g. 2,3- dimethylbicyclo[2.2.1]hept-2-ene) in the presence of an acid catalyst (e.g. a Lewis acid) at <=60 deg.C and hydrogenating the produced dimer in the presence of a hydrogenation catalyst (e.g. nickel-based catalyst) at 200-300 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a bicyclo [2.
2.1] A method for producing a heptane derivative, more specifically, a method for producing a bicyclo [2.2.1] heptane derivative which has a high traction coefficient at high temperature and excellent low temperature viscosity characteristics and is useful as a fluid for traction drive. Regarding

[0002]

2. Description of the Related Art A traction type CVT (continuously variable transmission) for automobiles has a large torque transmission capacity and severe operating conditions. Therefore, the traction coefficient of the traction oil used is the lowest value in the operating temperature range, that is, high temperature. (140
It is essential that the traction coefficient at (° C.) is sufficiently higher than the design value of CVT.

On the other hand, due to the low temperature startability in cold regions, the viscosity is low even at -40 ° C. (150,000 mPa · s or less).
Low temperature viscosity characteristics are required. Furthermore, since it is used even at high temperatures, it is required to prevent volatilization of the base oil at high temperatures and to retain sufficient oil film. Among the above performances, especially the traction coefficient at high temperature and low temperature viscosity are contradictory performances,
Although the development of traction oil that satisfies both requirements was desired, the development was extremely difficult. Against this background, the present inventors have conducted diligent research and found a group of compounds having an excellent high temperature traction coefficient (Japanese Patent Publication No. 7-103387), but the low temperature viscosity characteristics are still insufficient. It was

[0004]

The present invention has been made from the above viewpoint, and has a high traction coefficient at high temperatures,
Another object of the present invention is to provide a method for producing a bicyclo [2.2.1] heptane derivative which has excellent low temperature viscosity characteristics and is useful as a traction drive fluid.

[0005]

As a result of further intensive studies, the present inventors have found that the object of the above invention can be effectively achieved by combining a specific raw material and a specific reaction condition. The invention has been completed. That is, the gist of the present invention is as follows. (1) Methylene group- and methyl group-substituted bicyclo [2.2.
1] a heptane ring compound and / or a methyl group-substituted bicyclo [2.2.1] heptene ring compound in the presence of an acid catalyst 6
By dimerizing at 0 ° C. or lower and hydrogenating the resulting dimer at 200 to 300 ° C. in the presence of a hydrogenation catalyst, the following formula (I) is obtained.

[0006]

[Chemical 2]

(In the formula, m represents 2 or 3, and n represents 1 or 2.) A bicyclo [2.2.1] heptane derivative represented by the formula: bicyclo [2.2] ．
1] A method for producing a heptane derivative. (2) Methylene group- and methyl group-substituted bicyclo [2.2.
1] The bicyclo according to (1), wherein the heptane ring compound is 2-methylene-3-methylbicyclo [2.2.1] heptane and / or 3-methylene-2-methylbicyclo [2.2.1] heptane. [2.2.1] Method for producing heptane derivative. (3) The bicyclo according to (1) or (2), wherein the methyl group-substituted bicyclo [2.2.1] heptene ring compound is 2,3-dimethylbicyclo [2.2.1] hept-2-ene. [2.2.1] Method for producing heptane derivative. (4) The method for producing a bicyclo [2.2.1] heptane derivative according to any one of (1) to (3), wherein the acid catalyst is a Lewis acid. (5) The hydrogenation catalyst is a nickel-based catalyst (1) to
The method for producing a bicyclo [2.2.1] heptane derivative according to any one of (4).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. First, as the raw material olefin of the bicyclo [2.2.1] heptane derivative of the present invention, a methylene group- and methyl group-substituted bicyclo [2.2.1] heptane ring compound and / or
Alternatively, a methyl group-substituted bicyclo [2.2.1] heptene ring compound is used.

Specific examples of the methylene group- and methyl group-substituted bicyclo [2.2.1] heptane ring compound include 2-methylene-3-methylbicyclo [2.2.1].
Heptane, 3-methylene-2-methylbicyclo [2.
2.1] heptane, 2-methylene-7-methylbicyclo [2.2.1] heptane, 3-methylene-7-methylbicyclo [2.2.1] heptane, 2-methylene-5-methylbicyclo [2] 1.2.1] Heptane, 3-methylene-
5-methylbicyclo [2.2.1] heptane, 2-methylene-6-methylbicyclo [2.2.1] heptane, 3
-Methylene-6-methylbicyclo [2.2.1] heptane, 2-methylene-1-methylbicyclo [2.2.1]
Heptane, 3-methylene-1-methylbicyclo [2.
2.1] heptane, 2-methylene-4-methylbicyclo [2.2.1] heptane, 3-methylene-4-methylbicyclo [2.2.1] heptane, 2-methylene-3,7
-Dimethylbicyclo [2.2.1] heptane, 3-methylene-2,7-dimethylbicyclo [2.2.1] heptane, 2-methylene-3,6-dimethylbicyclo [2.
2.1] heptane, 3-methylene-2,6-dimethylbicyclo [2.2.1] heptane, 2-methylene-3,3
-Dimethylbicyclo [2.2.1] heptane, 3-methylene-2,2-dimethylbicyclo [2.2.1] heptane and the like can be mentioned. Among them, exo-3-
Methyl-2-methylenebicyclo [2.2.1] heptane and endo-3-methyl-2-methylenebicyclo [2.
2.1] heptane is present in 2-methylene-3-methylbicyclo [2.2.1] heptane, exo-2-methyl-3-methylenebicyclo [2.2.1] heptane and en
do-2-methyl-3-methylenebicyclo [2.2.
1-] 3-methylene-2-methylbicyclo [2.2.1] heptane in which heptane is present is preferred.

Specific examples of the methyl group-substituted bicyclo [2.2.1] heptene ring compound include 2,3-dimethylbicyclo [2.2.1] hept-2-ene and 2,7-dimethylbicyclo. [2.2.1] hept-2-ene, 2,
5-dimethylbicyclo [2.2.1] hept-2-ene, 2,6-dimethylbicyclo [2.2.1] hept-
2-ene, 1,2-dimethylbicyclo [2.2.1] hept-2-ene, 2,4-dimethylbicyclo [2.2.
1] hept-2-ene, 2,3,7-trimethylbicyclo [2.2.1] hept-2-ene, 2,3,6-trimethylbicyclo [2.2.1] hept-2-ene, etc. Can be mentioned. Of these, 2,3-dimethylbicyclo [2.2.1] hept-2-ene is preferable.

An acid catalyst is used as a catalyst for dimerizing the above-mentioned raw material olefin. As the acid catalyst, specifically, mineral acids such as hydrofluoric acid and polyphosphoric acid, organic acids such as triflic acid, aluminum chloride, ferric chloride, tin tetrachloride, titanium tetrachloride, boron trifluoride, Examples thereof include boron trifluoride complex, boron tribromide, aluminum bromide, Lewis acids such as gallium chloride and gallium bromide, and organic aluminum compounds such as triethylaluminum, diethylaluminum chloride and ethylaluminum dichloride.

Lewis acid catalysts such as boron trifluoride, boron trifluoride complex, tin tetrachloride, titanium tetrachloride, and aluminum chloride are preferable in that dimerization is preferably performed at a temperature as low as possible. Of these, boron trifluoride complexes such as boron trifluoride diethyl ether complex, boron trifluoride water complex, and boron trifluoride alcohol complex are more preferable.

The amount of these catalysts used is not particularly limited, but is usually in the range of 0.1 to 100% by weight, preferably 0.5 to 20% by weight, based on the raw material olefin. A solvent is not always necessary for this dimerization, but it can also be used for handling the starting olefin or catalyst during the reaction or for controlling the progress of the reaction. Examples of such a solvent include saturated hydrocarbons such as various pentanes, various hexanes, various octanes, various nonanes, and various decane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclosan, decalin, diethyl ether,
Examples thereof include ether compounds such as tetrahydrofuran, halogen-containing compounds such as methylene chloride and dichloroethane, and nitro compounds such as nitromethane and nitrobenzene.

The dimerization reaction is carried out in the presence of these catalysts and the like, but the reaction temperature must be 60 ° C. or lower. The temperature is preferably 40 ° C. or lower in order to suppress isomerization. The lower limit temperature is not particularly limited as long as the reaction proceeds, but economically, −70 ° C. or higher is preferable, and −30 ° C.
The above is more preferable. Appropriate conditions are set in the above temperature range depending on the type of catalyst and solvent, but the reaction pressure is usually normal pressure, and the reaction time is usually 0.5 to 10
A time range is preferred.

Next, the dimer of the starting olefin thus obtained is hydrogenated. This hydrogenation reaction is carried out in the presence of a hydrogenation catalyst, and the catalyst is diatomaceous earth,
A hydrogenation catalyst in which a metal such as nickel, ruthenium, palladium, platinum, rhodium, or iridium is supported on an inorganic oxide carrier such as alumina, silica alumina, or activated carbon is used. Among the above catalysts, nickel-based catalysts such as nickel / diatomaceous earth and nickel / silica-alumina are preferable from the viewpoint of physical properties of the hydride formed. If necessary, a solid acid such as zeolite, silica-alumina or activated clay may be used as a co-catalyst for the hydrogenation reaction.

The amount of the catalyst used is preferably 0.1 to 100% by weight, more preferably 1 to 20% by weight, based on the dimerization product. Also, this hydrogenation reaction proceeds in the same manner as the above-mentioned dimerization reaction in the absence of a solvent, but a solvent can also be used. In that case, as the solvent, various pentanes, various hexanes, various octanes, various nonanes, Examples thereof include saturated hydrocarbons such as various types of decane, and alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclosan, and decalin.

The reaction temperature is essential to be 200 to 300 ° C, preferably 220 to 280 ° C. If it is lower than 200 ° C, lowering of viscosity and increase in viscosity index due to isomerization do not sufficiently occur, and if it is higher than 300 ° C, yield is lowered due to decomposition reaction, which is not preferable. The reaction pressure is not particularly limited, but it is from normal pressure to 200 kg.
/ Cm ² G, preferably atmospheric pressure to 100 kg / cm ² G
Can be performed in the range of. 5 to 90 in terms of hydrogen pressure
kg / cm ² G, preferably 10-80 kg / cm ² G
Is. The reaction time is usually 1 to 10 hours.

By the above hydrogenation, the bicyclo [2.2.1] heptane derivative represented by the above formula (I) can be obtained. This bicyclo [2.2.1] heptane derivative is
It has a high traction coefficient at high temperatures and excellent low temperature viscosity characteristics, and can be used as a traction drive CVT oil all over the world from cold regions to high temperature regions.

Further, the bicyclo [2.
2.1] Among heptane derivatives, those having a high traction coefficient at high temperature and excellent low temperature viscosity characteristics,
As described later in detail in Examples, 2-methylene-3-methylbicyclo [2.2.1] heptane and 3-methylene-2-methylbicyclo [2.2.
1] Heptane and 2,3-dimethylbicyclo [2.2.
1] exo-2-methyl-exo-3 prepared using a mixture of hept-2-enes, using a boron trifluoride diethyl ether complex as a dimerization catalyst and a nickel / diatomaceous earth catalyst as a hydrogenation catalyst. -Methyl-endo-
2-[(endo-3-methylbicyclo [2.2.1]]
Hept-exo-2-yl) methyl] bicyclo [2.
2.1] Heptane and exo-2-methyl-exo-3-
Methyl-endo-2-[(endo-2-methylbicyclo [2.2.1] hept-exo-3-yl) methyl] bicyclo [2.2.1] heptane (component A), en
do-2-methyl-exo-3-methyl-exo-2-
[(Exo-3-methylbicyclo [2.2.1] hept-exo-2-yl) methyl] bicyclo [2.2.1]
Heptane and endo-2-methyl-exo-3-methyl-exo-2-[(exo-2-methylbicyclo [2.
2.1] hept-exo-3-yl) methyl] bicyclo [2.2.1] heptane (component B) and endo-2-
Methyl-exo-3-methyl-exo-2-[(end
o-3-methylbicyclo [2.2.1] hept-end
o-2-yl) methyl] bicyclo [2.2.1] heptane and endo-2-methyl-exo-3-methyl-ex
o-2-[(endo-2-methylbicyclo [2.2.
1] hept-endo-3-yl) methyl] bicyclo [2.2.1] heptane (component C) can be mentioned. Structural formulas of A, B, and C components are represented by the following formulas (II) and (II
It is shown by I) and (IV).

[0020]

[Chemical 3]

[0021]

[Chemical 4]

[0022]

[Chemical 5]

[0023]

[Example 1]

(Preparation of raw material olefin) Into a 2 liter stainless steel autoclave, 561 g (8 mol) of crotonaldehyde and 352 g (2.67 mol) of dicyclopentadiene were charged and reacted at 170 ° C. for 3 hours with stirring.
After cooling the reaction solution to room temperature, Raney nickel catalyst [M-300T, manufactured by Kawaken Fine Chemical Co., Ltd.] 18
g, hydrogen pressure 9 kg / cm ² G, reaction temperature 150 ° C.
And hydrogenated for 4 hours. After cooling, after filtering off the catalyst,
The filtrate was distilled under reduced pressure, and 105 ° C / 20 mmHg fraction 565
g was obtained. As a result of analyzing this fraction by mass spectrum and nuclear magnetic resonance spectrum, this fraction was found to be 2-hydroxymethyl-3-methylbicyclo [2.2.1] heptane and 3
-Hydroxymethyl-2-methylbicyclo [2.2.
1] It was confirmed to be heptane.

Then, 20 g of γ-alumina [N612N, manufactured by JGC Chemical Co., Ltd.] was placed in a quartz glass flow type atmospheric pressure reaction tube having an outer diameter of 20 mm and a length of 500 mm, and the reaction temperature was 2
The dehydration reaction was carried out at 85 ° C. and weight hourly space velocity (WHSV) of 1.1 hr ⁻¹ to give 2-methylene-3-methylbicyclo [2.
2.1] Heptane and 3-methylene-2-methylbicyclo [2.2.1] heptane 55% by weight and 2,3-dimethylbicyclo [2.2.1] hept-2-ene 30% by weight
2-hydroxymethyl-3-methylbicyclo [2.2.1] heptane and 3-hydroxymethyl-2-containing
490 g of a dehydration reaction product of methylbicyclo [2.2.1] heptane was obtained.

(Preparation of dimer hydride) Boron trifluoride diethyl ether complex 8 was placed in a 1-liter four-necked flask.
g, and 400 g of the olefin compound obtained above are added,
The dimerization reaction was carried out at 20 ° C. for 4 hours while stirring using a mechanical stirrer. The reaction mixture was diluted with dilute NaO.
After washing with an aqueous solution of H and a saturated saline solution, 12 g of a nickel / diatomaceous earth catalyst for hydrogenation (manufactured by JGC Chemical Co., Ltd., N-113) was added to a 1-liter autoclave, and a hydrogen pressure was 30 k.
The hydrogenation reaction was carried out under the conditions of g / cm ² G, reaction temperature of 250 ° C. and reaction time of 6 hours. After the reaction was completed, the catalyst was removed by filtration, and the filtrate was distilled under reduced pressure to obtain 240 g of the target dimer hydride. Table 1 shows the general properties and measurement results of the traction coefficient of this dimer hydride.

This dimer hydride was subjected to precision distillation separation twice by a rotary band type distillation apparatus having 120 theoretical plates to obtain 1 g of 149.2 ° C./5 mmHg component (A component).
Got When the component A was analyzed, e with a purity of 98% by weight
xo-2-methyl-exo-3-methyl-endo-2
-[(Endo-3-methylbicyclo [2.2.1] hept-exo-2-yl) methyl] bicyclo [2.2.
1] Heptane and exo-2-methyl-exo-3-methyl-endo-2-[(endo-2-methylbicyclo [2.2.1] hept-exo-3-yl) methyl] bicyclo [2.2] .1] was found to be heptane.
The structural formula of the component A is as shown in the above formula (II). Mass chromatogram, ¹ H-N used in this structural analysis
MR, ¹³ C-NMR, ¹³ C- ¹³ C-NMR, ¹ H- ¹³ C
Each NMR spectrogram is shown in FIGS.

By precision distillation separation in the same manner as above, 13.6 g of 133.6 ° C./2 mmHg component (B component)
Got Analysis of the B component revealed that e with a purity of 99% by weight
ndo-2-methyl-exo-3-methyl-exo-2
-[(Exo-3-methylbicyclo [2.2.1] hept-exo-2-yl) methyl] bicyclo [2.2.
1] Heptane and endo-2-methyl-exo-3-methyl-exo-2-[(exo-2-methylbicyclo [2.2.1] hept-exo-3-yl) methyl] bicyclo [2.2] .1] was found to be heptane.
The structural formula of the B component is as shown in the above formula (III). Mass chromatogram, ¹ H-N used in this structural analysis
MR, ¹³ C-NMR, ¹³ C- ¹³ C-NMR, ¹ H- ¹³ C
Each NMR spectrogram is shown in FIGS. The dimer hydride prepared in Example 1 was analyzed by gas chromatography and as a result, it contained 20% by weight of A component and 60% by weight of B component.

Example 2 Table 1 shows the measurement results of general properties and traction coefficient of the fraction containing 65% by weight of A component and 25% by weight of B component obtained by the precision distillation of Example 1. [Example 3] In Example 1, the hydrogenation reaction was carried out at 250
240 g of a dimer hydride was obtained in the same manner except that the treatment was carried out at 200 ° C. for 2 hours instead of at 6 ° C. for 6 hours. This dimer hydride was subjected to precision distillation separation twice with a rotary band distillation apparatus having 120 theoretical plates to obtain 1 g of the above-mentioned B component. Moreover, 18.6 g of 138.6 ° C./2 mmHg component (C component) was obtained by precision distillation separation in the same manner as above. When the component C was analyzed, it was found that endo-2-methyl-exo-3-having a purity of 100% by weight.
Methyl-exo-2-[(endo-3-methylbicyclo [2.2.1] hept-endo-2-yl) methyl] bicyclo [2.2.1] heptane and endo-2-
Methyl-exo-3-methyl-exo-2-[(end
o-2-methylbicyclo [2.2.1] hept-end
It was found to be o-3-yl) methyl] bicyclo [2.2.1] heptane. The structural formula of the C component is the above formula (I
V). Mass chromatogram, ¹ H-NMR, ¹³ C-NMR, ¹³ C used in this structural analysis
- shows a ¹³ each spectrogram of ^{C-NMR, 1 H- 13 C} -NMR in 11-15. The dimer hydride prepared in Example 3 was analyzed by gas chromatography and as a result, it contained 45% by weight of the B component and 45% by weight of the C component.

Example 4 Table 1 shows the measurement results of general properties and traction coefficient of the fraction containing 88% by weight of B component and 10% by weight of C component obtained by the precision distillation of Example 3. . [Example 5] In Example 1, the catalyst for the dimerization reaction was
Instead of 8 g of boron trifluoride diethyl ether complex,
140 g of a dimer hydride was obtained in the same manner except that 32 g of tin tetrachloride was used. As a result of analyzing this dimer hydride by gas chromatography, it contained 20% by weight of the component A and 60% by weight of the component B. The general properties and the measurement results of the traction coefficient are shown in Table 1.

Example 6 In Example 1, the catalyst for the dimerization reaction was 8 g of boron trifluoride diethyl ether complex.
Instead of, use 20 g of 116% polyphosphoric acid at 50 ° C.
Dimer hydride 2 in the same manner except that the reaction was performed in
80 g was obtained. Mass spectrum of this dimer hydride,
As a result of analysis by a nuclear magnetic resonance spectrum, it was found to be a bicyclo [2.2.1] heptane derivative represented by the above formula (I). Table 1 shows the general properties and the measurement results of the traction coefficient. Example 7 The same as Example 1 except that the dimerization catalyst was reacted at 10 ° C. using 8 g of boron trifluoride 1.5 water complex instead of 8 g of boron trifluoride diethyl ether complex. As a result, 200 g of a dimer hydride was obtained. As a result of mass spectrum analysis and nuclear magnetic resonance spectrum analysis of this dimer hydride, it was found to be a bicyclo [2.2.1] heptane derivative represented by the above formula (I). Table 1 shows the general properties and the measurement results of the traction coefficient.

Comparative Example 1 Instead of carrying out the hydrogenation reaction at 250 ° C. for 6 hours in Example 1, 160 ° C. and 4
240 g of a dimer hydride was obtained in the same manner except that it was carried out for a time. Mass spectrum of this dimer hydride,
As a result of analysis by a nuclear magnetic resonance spectrum, it was found to be a bicyclo [2.2.1] heptane derivative represented by the above formula (I). Table 1 shows the general properties and the measurement results of the traction coefficient. Comparative Example 2 350.5 g (5 mol) of crotonaldehyde and 198.3 g (1.5 mol) of dicyclopentadiene were charged into a 1-liter stainless steel autoclave and stirred at 170 ° C. for 2 hours for reaction. After cooling the reaction solution to room temperature, 22 g of 5% ruthenium-carbon catalyst [manufactured by NE Chemcat Co., Ltd.] was added, and the hydrogen pressure was adjusted to 7
Hydrogenation was carried out at 0 kg / cm ² G and a reaction temperature of 180 ° C. for 4 hours. After cooling, the catalyst was filtered off, and the filtrate was distilled under reduced pressure to obtain 242 g of 70 ° C./0.9 mmHg fraction. As a result of analyzing this fraction by mass spectrum and nuclear magnetic resonance spectrum, this fraction was found to be 2-hydroxymethyl-3-methylbicyclo [2.2.1] heptane and 3-hydroxymethyl-2-methylbicyclo [2. 2.1] It was confirmed to be heptane.

Then, γ-alumina (Norton Alumina SA-6273, manufactured by Nikka Seiko Co., Ltd.) 15 was added to a flow-type atmospheric pressure reaction tube made of quartz glass having an outer diameter of 20 mm and a length of 500 mm.
g, the reaction temperature is 270 ° C., the weight hourly space velocity (WHS
V) The dehydration reaction was performed at 1.07 hr ⁻¹ , and 2-methylene-
3-Methylbicyclo [2.2.1] heptane and 3-methylene-2-methylbicyclo [2.2.1] heptane 65
2-hydroxymethyl-3-methylbicyclo [2.2.1] heptane containing 3% by weight and 28% by weight 2,3-dimethylbicyclo [2.2.1] hept-2-ene and 3
-Hydroxymethyl-2-methylbicyclo [2.2.
1] 196 g of a dehydration reaction product of heptane was obtained.

(Preparation of dimer hydride) 9.5 g of activated clay (Galleon Earth NS manufactured by Mizusawa Chemical Co., Ltd.) and 190 g of the olefin compound obtained above were placed in a 500 ml four-necked flask at 145 ° C. The mixture was stirred for 3 hours to carry out a dimerization reaction. After filtering the activated clay from this reaction mixture, it was placed in a 1 liter autoclave for hydrogenation nickel /
Diatomaceous earth catalyst [N-113, manufactured by JGC Chemical Co., Ltd.] 6 g
, Hydrogen pressure 40 kg / cm ² G, reaction temperature 160
The hydrogenation reaction was carried out under conditions of ° C and a reaction time of 4 hours. After completion of the reaction, the catalyst was removed by filtration, and the filtrate was distilled under reduced pressure to obtain 116 g of dimer hydride having a boiling point of 126 to 128 ° C./0.2 mmHg fraction. The dimer hydride was analyzed by mass spectrum and nuclear magnetic resonance spectrum, and as a result, bicyclo [2.2.1] represented by the above formula (I) was obtained.
It was found to be a heptane derivative. Table 1 shows the general properties and the measurement results of the traction coefficient.

Comparative Example 3 280 g of a dimer hydride was obtained in the same manner as in Example 6, except that the dimerization reaction was carried out at 100 ° C. instead of at 50 ° C.
As a result of mass spectrum analysis and nuclear magnetic resonance spectrum analysis of this dimer hydride, it was found to be a bicyclo [2.2.1] heptane derivative represented by the above formula (I). Table 1 shows the general properties and the measurement results of the traction coefficient. In addition, the measurement of the traction coefficient in the above Examples and Comparative Examples was carried out by a two-cylinder friction tester. That is, a cylinder of the same size (diameter 52
mm, thickness 6 mm, the driven side has a radius of curvature of 10 mm, and the driving side has a flat type without crowning). One of them is continuously changed at a constant speed, and the other rotation speed is changed continuously. With a weight of 98.0N,
The tangential force generated between the two cylinders, that is, the traction force was measured to obtain the traction coefficient. This cylinder is bearing steel SU
Made of J-2 mirror finish, average peripheral speed 6.8m /
s, the maximum Hertzian contact pressure was 1.23 Gpa. When measuring the traction coefficient at a fluid temperature (oil temperature) of 140 ° C., the oil temperature is raised from 40 ° C. to 140 ° C. by heating the oil tank with a heater,
The traction coefficient at a slip rate of 5% was calculated.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

INDUSTRIAL APPLICABILITY The bicyclo [2.2.1] heptane derivative produced by the method of the present invention has a high traction coefficient at high temperature and an excellent low temperature viscosity property, and is excellent in all regions from cold regions to high temperature regions. Traction drive type C in the world
It can be used as VT oil.

[Brief description of drawings]

Figure 1: Mass chromatogram of component A

FIG. 2: ¹ H-NMR spectrogram of component A

FIG. 3: ¹³ C-NMR spectrogram of component A

FIG. 4: ¹³ C- ¹³ C two-dimensional NMR spectrogram of component A

FIG. 5: ¹ H- ¹³ C two-dimensional NMR spectrogram of component A

FIG. 6: Mass chromatogram of B component

FIG. 7: ¹ H-NMR spectrogram of component B

FIG. 8: ¹³ C-NMR spectrogram of component B

FIG. 9: ¹³ C- ¹³ C two-dimensional NMR spectrogram of component B

FIG. 10: ¹ H- ¹³ C two-dimensional NMR spectrogram of component B

FIG. 11: Mass chromatogram of C component

FIG. 12: ¹ H-NMR spectrogram of C component

FIG. 13: ¹³ C-NMR spectrogram of C component

FIG. 14: ¹³ C- ¹³ C two-dimensional NMR spectrogram of C component

FIG. 15: ¹ H- ¹³ C two-dimensional NMR spectrogram of C component

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C07B 61/00 300 B01J 23/74 321X (72) Inventor Kazushi Hata 24 Anezaki coast, Ichihara city, Chiba prefecture 4F term (reference) 4H006 AA02 AB60 AC10 AC11 AC23 AD11 BA09 BA10 BA11 BA18 BA35 BA37 BA66 BA70 BC10 BC11 BE20 BE56 BJ20 FC34 4H039 CA10 CA29 CB10 CL11

Claims (5)

[Claims] 1. A methylene group- and methyl group-substituted bicyclo [2.2.1] heptane ring compound and / or a methyl group-substituted bicyclo [2.2.1] heptene ring compound at 60 ° C. or lower in the presence of an acid catalyst. By dimerizing and dimerizing the resulting dimer at 200 to 300 ° C. in the presence of a hydrogenation catalyst, the following formula (I): (In the formula, m represents 2 or 3, and n represents 1 or 2.)
A method for producing a bicyclo [2.2.1] heptane derivative, which comprises obtaining the bicyclo [2.2.1] heptane derivative represented by: 2. A methylene group- and methyl group-substituted bicyclo [2.2.1] heptane ring compound is 2-methylene-3.
-Methylbicyclo [2.2.1] heptane and / or 3
The method for producing a bicyclo [2.2.1] heptane derivative according to claim 1, which is -methylene-2-methylbicyclo [2.2.1] heptane. 3. A methyl group-substituted bicyclo [2.2.1] heptene ring compound is 2,3-dimethylbicyclo [2.
2.1] hept-2-ene, The method for producing a bicyclo [2.2.1] heptane derivative according to claim 1 or 2. 4. The acid catalyst is a Lewis acid.
5. The method for producing the bicyclo [2.2.1] heptane derivative according to any one of 1. 5. The bicyclo [2.2.1] according to any one of claims 1 to 4, wherein the hydrogenation catalyst is a nickel-based catalyst.
Method for producing heptane derivative.