JPH0648980A - New acid chloride - Google Patents

Abstract

PURPOSE:To obtain a new acid chloride useful as a raw material for producing polymers such as cross-linking agents, esterification agents, amidation agents, etc. CONSTITUTION:Bicyclo[2,2,2]octo-citric(2alpha,3beta,5alpha,6beta)-tetr acarbonyl-chloride (C12H8 O4Cl4) of formula I. The compound of formula I is obtained by hydrolying, e.g. a compound of formula II to afford a carboxylic acid salt or carboxylic acid and reacting the acid salt or the acid with a chlorinating agent in the presence of a catalyst such as dimethylformamide at -70-+250 deg.C for 10min to 18hr.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel acid chloride, the object of which is to exhibit excellent performance as a raw material for producing a polymer such as a crosslinking agent, an esterifying agent, an amidating agent, an acylating agent. Acid chloride, bicyclo [2,2,2] oct-
It is intended to provide 7-ene- (2α, 3β, 5α, 6β) -tetracarbonyl chloride.

[0002]

2. Description of the Related Art Aromatic or alicyclic polyvalent acid chlorides are widely used as raw materials for producing polymers such as crosslinking agents and condensing agents. Aromatic polyvalent acid chlorides generally form rigid condensates, but have problems such as poor reactivity. On the other hand, although the alicyclic polyvalent acid chloride has good reactivity, the flexibility of the condensate has been a problem depending on its use. Therefore, from the viewpoint of forming a rigid condensate while maintaining good reactivity of the alicyclic polyvalent acid chloride, a polyvalent acid chloride composed of a bicyclo ring has been noted.

However, like the alicyclic polyvalent acid chloride, the polyvalent acid chloride comprising the bicyclo ring is stable and has a risk in production (synthesis) and in the production (synthesis) process. There were problems such as complexity, yield, and difficulty in obtaining raw materials, and the production thereof was hardly performed. Further, unlike the aromatic ones, these polyvalent acid chlorides have various isomers mixed, and due to the variation in reactivity between the isomers,
There is also a problem that a stable condensate cannot be obtained when the ratio of isomers is different.

[0004]

However, in recent years, regarding the polyvalent acid chloride comprising a bicyclo ring, which is considered to have the advantages of both the aromatic polyvalent acid chloride and the alicyclic polyvalent acid chloride, As a result of the progress of the research on the above, the interest as a raw material for producing a polymer such as a crosslinking agent, a condensing agent, an esterifying agent, an amidating agent and an acylating agent has been increasing. Therefore, in the industry, it has been desired to create an excellent new acid chloride that can be used safely and widely as a raw material for polymer production.

[0005]

In the present invention, a novel acid chloride having a single isomeric structure, bicyclo [2,2,2], is used.
2] The above-mentioned conventional problems are solved by providing octo-7 ene- (2α, 3β, 5α, 6β) -tetracarbonyl chloride.

[0006]

The structure of the novel acid chloride according to the present invention will be described below. The novel acid chloride of the present invention is bicyclo [2,2,2] oct-7ene- (2α, 3β, 5α, 6β) -tetracarbonyl chloride represented by the general formula 2 [Chemical Formula 2].

[0007]

[Chemical 2]

This novel acid chloride, bicyclo [2,2,2]
2] Oct-7-ene- (2α, 3β, 5α, 6β) -tetracarbonyl chloride is white to dark brown crystals, and its melting point is 96 ° C.

The absorption wave number (cm ^-1 ) of the infrared absorption spectrum of this new acid chloride was 1790 (s) as measured by Nujol method (see FIG. 1).

Further, the proton magnetic resonance spectrum ( ¹ H-
Σ value of NMR) is 3.44 to 3.52 (2H, m), 3.58 to 3.64 (2H, m),
The values were 3.96 to 4.04 (2H, m) and 6.44 to 6.52 (2H, m) (see FIG. 2). In addition, carbon magnetic resonance spectrum ( ¹³ C-NMR)
Σ values of 35.81, 52.32, 55.80, 132.93, 173.03,
It was 173.09 (see Figure 3).

Bicyclo [2,2,2] oct-7
As a result of gas chromatography (GC) analysis under the following conditions, ene- (2α, 3β, 5α, 6β) -tetracarbonyl chloride was methyl esterified with methanol, and a single peak was observed at a retention time of 9.1 min. The purity was 100% (see FIG. 4).・ Column DB-1, 0.025mmφ × 29m, df = 0.25μm ・ Column pressure 1.5 kg / cm ²・ Inlet temperature 250 ℃ ・ Column temperature 150 to 280 ℃, 10 ℃ / min ・ Detector temperature 250 ℃ ・ Carrier gas He, 40ml / min

The results of elemental analysis are C: 40.10%,
It was H: 2.21% (theoretical value, C: 40.22%, H: 2.23%).

From the above results, the obtained compound is bicyclo [2,2,2] oct-7ene- (2α, 3β, 5
It was identified as α, 6β) -tetracarbonyl chloride.

Such a novel acid chloride is a bicyclo [2,2,2] compound represented by the general formula 3
2] Oct-7ene-2,3,5,6-tetracarboxylic dianhydride (Aldrich) can be easily prepared as a starting material.

[0015]

[Chemical 3]

The starting material bicyclo [2,2,2]
2] Octo-7ene-2,3,5,6-tetracarboxylic dianhydride is hydrolyzed to a carboxylic acid salt or carboxylic acid by a conventional method, and reacted with a chlorinating agent to give various isomers. Bicyclo [2,2,2] oct-7ene-2,3,5,6-tetracarbonyl chloride with mixed bodies is obtained. Further, by recrystallizing the obtained compound, the bicyclo [2,2,2]
2] Oct-7ene- (2α, 3β, 5α, 6β) -tetracarbonyl chloride.

The above chlorination reaction is carried out without solvent or in an aprotic solvent. Examples of the aprotic solvent used include hexane, heptane, octane, benzene, toluene, tetrahydroxyfuran (T
HF), dioxane and the like can be preferably used, and heptane is particularly preferably used.

As the chlorinating agent, thionyl chloride,
Phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, oxalyl chloride, phosgene, etc. are preferably exemplified, but are not particularly limited. The amount of the chlorinating agent added is the amount of bicyclo [2,2,2] oct-7ene-2,3,5,5 used.
1 to 5 with respect to the carboxylic acid group of 6-tetracarboxylic acid
The equivalent, preferably 1.2 to 2.0 equivalents,
It is preferable because it has the highest yield.

Furthermore, a catalyst for promoting the reaction with the chlorinating agent can be used. As the catalyst, dimethylformamide, pyridine, zinc chloride, hexamethylphosphoric triamide (HMPA) and the like can be preferably used.

The reaction is -70 in the presence of a solvent.
C. to 250.degree. C., more preferably from room temperature to the reflux temperature of the solvent, for 10 minutes to 18 hours.

After completion of the reaction, the resulting acid chloride solution is
If there is a residue, it is washed by decantation or filtration, and the solution layer obtained after washing is concentrated under reduced pressure.
By recrystallizing the concentrated residue using a recrystallization solvent,
The novel acid chloride of the present invention can be obtained. As the recrystallization solvent, heptane or benzene / hexane system is preferably used, but it is not particularly limited.

Bicyclo [2,2,2] oct-7 obtained by hydrolyzing bicyclo [2,2,2] oct-7 ene-2,3,5,6-tetracarboxylic dianhydride This novel acid chloride, bicyclo [2,2,2] oct, is obtained by treating ene-2,3,5,6-tetracarboxylic acid with an appropriate chlorinating agent and then recrystallizing the same. -7 en- (2α, 3β,
5α, 6β) -Tetracarbonyl chloride can be obtained.

[0023]

INDUSTRIAL APPLICABILITY The novel acid chloride as described above has a high degree of purity as an acid chloride and is extremely versatile as a polymer manufacturing material such as a crosslinking agent, an esterifying agent, an amidating agent and an acylating agent. It is a substance with great utility.

[0024]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Example 1 Bicyclo [2,2,2] oct-7ene-2,3,5
6-tetracarboxylic dianhydride 10g (4
0.3 mmol) and 12.9 g (193.5 mmol) of KOH in 80% ethanol
The mixture was heated under reflux in ml for 2 hours and then cooled. After the reaction, ethanol was distilled off, the mixture was extracted with acidified ether and dehydrated with magnesium sulfide. The obtained ether layer was concentrated under reduced pressure, and bicyclo [2,2,2] oct-7ene-
7.2 g of 2,3,5,6-tetracarboxylic acid (yield 63
%) Was obtained.

The resulting bicyclo [2,2,2] oct-
7 ene-2,3,5,6-tetracarboxylic acid 0.82 g (2.9
mmol) and 2.76 g (23.2 mmol) of thionyl chloride and 1 drop of DMF were suspended in 3 ml of heptane and heated at 60 ° C. for 4 hours.
After cooling, the acid chloride solution was decanted, and the resulting solution layer was distilled off under reduced pressure. By recrystallizing the obtained reaction residue in a mixed solvent of benzene and hexane, white crystals of bicyclo [2,2,2] oct-7ene-
0.75 g (yield 73%) of (2α, 3β, 5α, 6β) -tetracarbonyl chloride was obtained.

The resulting bicyclo [2,2,2] oct-
7-ene- (2α, 3β, 5α, 6β) -tetracarbonyl chloride has an absorption wavenumber (c
m ⁻¹ ) was 1790 (s) (see FIG. 1), and the σ value of the proton magnetic resonance spectrum ( ¹ H-NMR) (400 MHz, CDCl ₃ ) was 3.44 to 3.52 (2H, m), 3.58. ~ 3.64 (2H, m), 3.96 ~ 4.04
(2H, m), 6.44 to 6.52 (2H, m) (see FIG. 2),
The σ value of the carbon magnetic resonance spectrum ( ¹³ C-NMR) is 35.8.
1, 52.32, 55.80, 132.93, 173.03, 173.09 (see FIG. 3), and further obtained bicyclo [2,2,2].
2] Oct-7-ene- (2α, 3β, 5α, 6β) -tetracarbonyl chloride was methyl-esterified with methanol and analyzed by gas chromatography (GC). As a result, a single peak (retention time 9.1 min) was obtained. There was (Fig. 4
Also, as a result of elemental analysis, C: 40.10%,
Since it was H: 2.21% (theoretical value, C: 40.22%, H: 2.23%), bicyclo [2,2,2] oct-7ene- (2α, 3β, 5α, 6β) -tetracarbonyl chloride was obtained. Was identified as

[Brief description of drawings]

FIG. 1 is a novel acid chloride of the present invention, bicyclo [2,2].
2,2] Oct-7ene- (2α, 3β, 5α, 6β)
-Infrared absorption spectrum (Nujol method) chart of tetracarbonyl chloride.

FIG. 2 is a proton magnetic resonance spectrum ( ¹ H-NMR) chart of the above.

FIG. 3: Carbon magnetic resonance spectrum ( ¹³ C-NMR) of the same as above.
It is a chart.

FIG. 4 is a gas chromatography (GC) chart of the above.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Mitsuru Shimizu 1-2 1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Denko Corporation (72) Inventor Masahiko Hirose 1-2 1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Denko Corporation (72) Inventor Yasuo Kihara 1-2-2 Shimohozumi, Ibaraki-shi, Osaka Nitto Electric Works Ltd. (72) Masatoshi Maeda 1-2-1 Shihohozumi, Ibaraki-shi, Osaka Nitto Denko Co., Ltd. (72) Inventor Ei Igabata 1-2-2 Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation (72) Inventor Kenji Matsumoto 1-21-2 Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation Within

Claims (1)

[Claims] 1. A novel acid chloride represented by the general formula 1 [Chemical formula 1], bicyclo [2,2,2] oct-7ene-
(2α, 3β, 5α, 6β) -Tetracarbonyl chloride (C ₁₂ H ₈ O ₄ Cl ₄ ). [Chemical 1]