JPH03123754A - Dicyclopentadiene derivative - Google Patents

Abstract

NEW MATERIAL:A dicyclopentadiene derivative expressed by formulas I and II. USE:An industrial and pharmaceutical raw materials. PREPARATION:Cyclopentadiene expressed by formula III is reacted with carbon dioxide in the presence of 1,5-diazabicyclo[5.4.0]undec-5-ene(DBU) to provide a compound expressed by formula IV, which is then suspended in water and treated to afford dicyclopentadienedicarboxylic acid expressed for formula V. The resultant compound expressed by formula V is subsequently reacted with the cyclopentadiene expressed by formula III to provide the compound expressed by formula I. Furthermore, the compound expressed by formula I is reacted with diazomethane to carry out esterification and 1,3-dipolar addition and afford the compound expressed by formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel dicyclopentadiene derivative useful as an industrial raw material and a pharmaceutical raw material.

[Conventional technology]

As is well known, dicyclopentadiene (Tricyelo[S, 2.1.O'''1deci
-3.8-dient) is the C of residual oil from naphtha pyrolysis.
It is produced at low cost by heating the S fraction to 80-120°C to double cyclopentadiene and separating it, and is used for the following purposes. That is, it is used as a diene component for crosslinking ethylene-propylene rubber, and in dicyclopentadiene-modified polyester. Furthermore, it is used as a raw material for adamancune, and as a raw material for organic synthesis such as polymer raw materials, pharmaceuticals, and agricultural chemicals by converting it into cyclopentadiene through thermal decomposition.

As described above, dicyclopentadiene is an important substance as an inexpensive industrial raw material, and synthetic reactions using this dicyclopentadiene have been actively carried out for a long time. In particular, much research has been conducted on norbornene derivatives as they are expected to have interesting properties.

[Problem to be solved by the invention]

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel dicyclopentadiene derivative useful as an industrial raw material or a pharmaceutical raw material.

[Means to solve the problem]

The inventors of the present invention have conducted extensive research to solve the above-mentioned problems.1. DBU (+, S-diazabicyclo[S,
When carbon dioxide and cyclopentadiene are reacted in the presence of 4.0] undec-5-ene), carboxylation proceeds efficiently under mild conditions to yield a carboxylic acid derivative of cyclopentadiene. This led to the discovery of the structures of these new derivatives.

The present invention was made based on the discovery of a highly reactive and useful new substance using inexpensive dicyclopentadiene as a starting material, and is represented by the following structural formula (I).
and (n) (I) (It) A dicyclopentadiene derivative represented by (It).

Next, the method for producing the dicyclopentadiene derivative of the present invention will be explained in more detail, but this is only an example.
It can also be produced by other similar chemical methods.

<Production> (1) (11) (iii) The production method involves reacting cyclopentadiene (i) with carbon dioxide in the presence of DBU to form a compound represented by the structural formula (i), which then produces dicyclopentadiene (i). dicarboxylic acid (m
1) is synthesized, and further, the compound represented by the structural formula (I) is obtained by reacting this dicyclopentadiene dicarboxylic acid (i) with cyclopentadiene (i). When the obtained compound (1) is reacted with diazomethane, a compound represented by structural formula (n) is obtained by esterification and 1,3-dipolar addition. The structures of these compounds have been determined through elemental analysis and NMR measurements, as will be described later.

The present invention will be explained in more detail below using Examples.

〔Example〕

*: In the above formula, DBLJ is 1. as described above.
It is a compound named 5-diazabicyclo[5,4,0]undec-5-ene.

Cyclopentadiene 4.0561 (61,5mmoQ
), DBUI 5.113g (99.4mmall)
20a+IL of DMF in a 50ml reaction tube.
(N,N-dimethylformamide). This reaction tube was placed in an autoclave, and the air inside was replaced with CO2 while cooling to 0°C. After replacement, CO240
kg/cm2 atmosphere for 30 minutes, and then CO□ was gradually removed. Then, the reaction tube was taken out, and after adding a small amount of ice water to the reaction solution, this solution was poured into a large amount of ice-hydrochloric acid, and a solid was precipitated. After extraction with ether, anhydrous magnesium sulfate was added to the ether layer, and the mixture was left overnight to dry. When the solvent is distilled off, cyclopentadiene tricarpone? t & 10 as an ocher solid
．． 103 g (51.0 mmall) was obtained. The yield was 83%.

This cyclopentadiene tricarboxylic acid 10゜102
g (51,0II1moQ) was suspended in 25 mQ of water and stirred at room temperature for 3 hours. After stirring, filter the reaction mixture,
When dried under reduced pressure in a vacuum desiccator for 3 days, cyclopentadiene dicarboxylic acid was dissolved as a flesh-colored solid at 5.153
g(33,5a+moit) was obtained.

The yield was 66%, and the melting point was 203-205°C.

Cyclopentadiene dicarboxylic acid and cyclopentadiene dicarboxylic acid 3.025 g (19,6 mmo
D and cyclopentadiene 8.663g (131+nm
The solution was dissolved in 25 ml of DMF and left at room temperature for 24 hours. At the beginning of the reaction, some of the dicarboxylic acids are DM
It did not dissolve in F and remained as a solid, but when stirring was continued, it gradually disappeared as the reaction progressed.

The reaction solution was poured into ice-hydrochloric acid and extracted with ether, and the ether layer was roughly extracted with an aqueous NaHCOs solution. After the aqueous layer was made acidic with hydrochloric acid, extraction was performed again with ether, and this ether layer was dried over anhydrous magnesium sulfate. When the solvent was distilled off, tricyclo[5,2.

1.02.6]deca-3,8-diene-1,8-dicarboxylic acid was obtained in an amount of 4.302 g with a yield of 99%. When this crude product is recrystallized from 2-butanone,
3.722 g of white solid [compound (I) above] was obtained. The recrystallization yield was 87%, and the melting point of the obtained crystals was 203-205°C.

In addition, the infrared absorption spectrum of this compound (I) was
It is shown in the figure, and the characteristic values of the spectrum are shown below.

I R(KB r) 2900 cm-' (methylene group).

1690 cm-' (carboxyl group) Also, from the elemental analysis values shown below for (I) of this compound, it is clear that it is a 1:1 adduct.

(Tricyclo [5,2,1,0"l'1 deca-3,
Elemental analysis value of 8-diene-1,8-dicarboxylic acid (iv)) CH Actual value (%) 65.73 5.5
0 theoretical value [CI2H12] (%) 65.44
5.49 Neaker of excess diazomethane produced by conventional method 3.8-diene-1,8-dicarboxylic acid (1)0
．． It was gradually added to 516 g (3.4 mmall) of an ether solution, and after the addition was complete, it was left for 30 minutes. Acetic acid was added to the reaction solution until the yellow color of the diazomethane disappeared to stop the reaction. When the solvent was distilled off, a product (a novel dicyclopentadiene derivative [the compound of (I) above]) was obtained. When this was recrystallized from hexane, pale yellow needle-shaped crystals were obtained. The yield was 85% and the melting point was 105.5-107°C. The infrared absorption spectrum of the obtained compound (I[) is shown in FIG. 2, and the characteristic values of the spectrum are shown below.

I R(KB r) 1725 cm-' (carboxyl group) Also, the elemental analysis values of this compound (n) are shown below.

(Elemental analysis value of novel dicyclopentadiene derivative (II)) CHN Actual value (%) 62.011 6.3
1 9.22-chill solution was added to the above tricyclo[5,2,1
,02・6]De theoretical value (C+sH+aO□)(%)
62.05 6.25 9.65 Compound (I), (
The structure of n) was determined by 270 MHz'HNMR measurement.

These NMR measurement values are shown below, as well as more detailed structural formulas of compounds (I) and (n).

(Compound (■)) 3.55 (IR, dd, 2-H).

5.60 (2tl, s, 3-■, 4-■).

6.66 (l [l, s, 9-■).

・Found: C, 65, 73; H, 5, 5
0% ;・ C11cd tar Ct2HIzo
4: C, 65,44; H, 5,49% (compound (■)) 1H NMR (D to ) δ - 1,71 (4■, ad, 1G-■).

1, H (1■, m, Sa -■).

2.23 (l[1, dd, 5β-H).

3.04 (lH, +m, 6-H).

3.22 (ill, dd, 7-■)l・'HNM
R (CDC et al.) δ − 1,04 & 1.6R (Ill, d, l [I, m, H-H
).

243 (2H, m, 5-It).

2.79 (+n, at, u-[1).

195 (In, m, 6-11).

3.22-345 (1■, d, lit, i+, 7-[
1j-[1).

3.74 & 3.77 (3H,s, 3H,s, CJ).

4.49 & 4.73 (1■, dd, lH, dd, II
−■).

5.64-5.74 (2H, m, 3-[1,4-11
).

・FoIIfid: C, 6108; H, 6, 31;
N, 9.22%1・Ca1cd for C+sH
+aO4N2'C, 62,05, H, 6,25; N,
9.65% [Effect of the Invention] As explained above, according to the present invention, a novel dicyclopentadiene derivative useful as an industrial raw material and a pharmaceutical raw material can be provided.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the infrared absorption spectrum of compound (I),
FIG. 2 is a diagram showing an infrared absorption spectrum of compound (I[).

Claims (2)

[Claims] (1) Structural formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) A dicyclopentadiene derivative represented by (2) Structural formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) A dicyclopentadiene derivative represented by