JPS60215648A - 6,6'-(ethylenedioxy)-di-2-naphthoic acid, its derivative and preparation thereof - Google Patents

Abstract

NEW MATERIAL:6,6'-(Ethylenedioxy)-di-2-naphthoic acid of the formula (R is OR' or halogen; R' is H, lower alkyl, cycloalkyl or aryl) and a derivative thereof. EXAMPLE:Ethyl 6,6'-(ethylenedioxy)-di-2-naphthoate. USE:A raw material useful for preparing condensation polymers such as aromatic polyesters, aromatic polyamides, etc. PREPARATION:An alkali metal salt of a 2-hydroxy-6-naphthoic acid ester is reacted with a 1,2-dihalogenated ethane in the presence of a solvent, e.g. N,N- dimethylformamide, at 50-200 deg.C, preferably 60-180 deg.C under ordinary - higher pressure. The resultant 6,6'-(ethylenedioxy)-di-2-naphthoic acid ester is hydrolyzed to afford the aimed 6,6'-(ethylenedioxy)-di-2-naphthoic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel 6,6'-('brange8=1c)-di-2-naphthoic acid, its derivatives and a process for their production.

Prior Art Various aromatic dicarboxylic acids have been known and are widely used as raw materials for synthetic polymers such as polyester, polyamide, etc.11 For example, phthalic acid is converted into polyethylene derephthalate, Tetramethylene derephthalate-1 and -C are used industrially as raw materials for binding polyethylene terephthalamide and the like to polybalaf, and other isophthalic acids are also used as raw materials for polymers. In addition, polyethylene naphthalene 1, which is made from naphthalene dicarboxylic acid as a raw material, has polyethylene naphthalene 1.
It is also known that it has higher mechanical and thermal performance than ~.

OBJECT OF THE INVENTION The inventors have discovered that these poly]-ethylene derephthalates,
As a result of extensive research into new dicarboxylic acids that can be used as raw materials for polyesters with even higher performance than polyethylene naphcrate, the present invention was achieved.

An object of the present invention is to provide a novel 6,6'-(ethylenedioxy)-di-2-naphthoic acid and its derivatives. A further object of the present invention is to provide ``6'' useful in the production of synthetic polymers such as A perfume polynisder aromatic polyamides, etc.
．． An object of the present invention is to provide 6'-(ethylenedioxy)-di-2-naphthoic acid and its derivatives. The object of the present invention is to provide a novel 6,6'-(ethylenedioxy)-di-2-
An object of the present invention is to provide a method for producing naphthoic acid and its derivatives.

Structure of the Invention The basic feature of the present invention is that 6,6'-(ethylenedioxy)-di2 represented by the following formula
-Lift-1 acid and its derivatives.

In the above formula, R' that forms Nisdel and °C are:
C1-4 lower alkyl groups, 06-1o cycloalkyl groups, C6-1o aryl groups, etc. are preferred, and specific examples include methyl, del, propyl, cyclohexyl, phenyl,
Preferred examples include Triel and the like. Among these, methyl, 1-tyl, and phenyl are particularly preferred. In addition, in the above formula, when R is halogen, R is Cρ, Br,
l is exemplified, and particularly preferably 0 sentences.

As a specific example of the compound represented by the above formula, C is 6.6'
-(ethylenedioxy)-di-2-su71-■ acid,
6.6'-(ethylenedioxy)-di-2-buhthoic acid methyl ester, 6.6'-(ethylenedioxy)-di-2-naphthoic acid ethyl ester.

6.6'-(ethylenedioxy)-di-2-naphthoic acid furyl ester, 6.6'-(ethylenedioxy)-di-2-naphthoic acid chloride, G, 6'-(ethylenedioxy)-di Examples include cyclohexyl 2-naphthoate.

A preferred method for producing Nisder 6.6'-(ethylenedioxy)-di-2-naphthoic acid ester includes an alkali metal salt of 2-hydroxy-6-naphthoic acid ester and 1,2-
For example, a method of reacting dihalogenated ethane in the presence of a solvent is mentioned.As the dinoflukali metal, sodium and potassium are preferable, and as the 1,2-shiba [1-glycan ethane, 1,2-dichloroethane, 1,2 -dibromoethane is preferred. Further, as a solvent, amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ethers such as tetrahydrofuran, dioxin, etc.; methanol and ethanol.

Alcohols such as propatool; acetone.

Examples include ketones such as methyl isobutyl ketone.

The reaction temperature is preferably 50 to 200°C, particularly preferably 60 to 180°C, and the reaction can be carried out at normal pressure to increased pressure.

The obtained 6,6'-(ethylenedioxy)-di2-
The naphthoic acid ester is preferably purified by a purification method such as recrystallization. As a recrystallization solvent for ester, N, N
- Amides such as dimethylformamide, etc.; Ethers such as detrahydrofuran, dioxane, etc.; Al-1-ols, such as 1-tanol, propatool, etc.; Ketones and the like are preferred.

6,6'-(J-ethylenedioxy)- in the present invention
2-naph i-technical acid is obtained by the above-mentioned method.1. :6.6'-(ethylenedioxy)-di-2-puftoic acid ester can be easily obtained by hydrolysis. This hydrolysis is preferably carried out in the presence of an alkali or an acid, particularly an alkali such as sodium hydroxide, potassium hydroxide or the like.

It is also a preferable method to coexist a water-soluble organic solvent such as methanol, ethanol, diogysan, dimethylformamide, etc. in order to increase the affinity between the ester and water. The preferred reaction temperature is 50 to 250°C, and the reaction is usually carried out at normal pressure to increased pressure.

Furthermore, acid halides can be synthesized from the above-mentioned dicarboxylic acids according to conventionally known methods; for example, acid chlorides can be obtained by reacting dicarboxylic acids with butanyl chloride in the presence of pyridine.

Effects of the invention 6,6'-(]-]thilene di A-x-di 2 of the present invention
- Naphthoic acid and its derivatives are polyesters.

It is useful as a raw material for producing polyamide, etc. For example 6.
6'-(ethylenedioxy)-di-2-pouf] ~ A polyester containing engineering acid as the acid component and ethylene glycol as the glycol component has a melting point close to 295°C and a high V
It has the advantage of being able to produce molded products with a leg ratio by melt molding.

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

In addition, the infrared absorption spectrum (IR) was measured using Nujol, and the nuclear magnetic resonance spectrum (NMR) 4;
The measurement was carried out by using L-deuterated chloroform as a solvent and embedding tetramethylsilane as the mark t1.

Example 1: Synthesis of 6,6'-(ethylenedioxy)-di-2-nut"-acid 1-Nisfur Ethanol 4ρ
After adding 1z57q of metallic sodium to avoid the reaction, 2-
Hydroxy-6-naphthoic acid-[del-[Stool 54
07 and 247 g of 1,2-sibu[1-siconitane were added, and the reaction was heated in JV flow F for 7 hours. After completion of the reaction, the solid 4B produced was filtered, washed with water, and further recrystallized with diochirin C to obtain G,6'-(ethylenedioxy)-G.
2-Naf 1 to engineering acid-L del soil stell 157,89 to 1!
? Ta. The melting point of this 1 dernis del is 192-194°C
The IR and NMl dogs are as shown in Figures 1 and 2, respectively. Further, the results of elemental analysis of this ethyl ester are as follows.

Elemental analysis C (%): '73.3, To I (%):
5.7 Example 2: Synthesis of 6,6'-(ethylenedioxy)-di-2-naphthoic acid edyl ester Add 1.149 g of metal putrium to 100 cc of ethanol and cause a -C reaction. ] 10.8 g of 1,2-6-natidoacetic acid ester and 2.5247 g of 1,2-1]ruethane were added and heated to 150'C for 3 hours in a crepe to avoid reaction. The resulting solid was filtered, washed with water, and then recrystallized with N,N-dimethylbormamide to give 6.6'-(
2.6 g of ethylenedioxy)-di2-boot1~]-acid di[del ester were obtained. The melting point of this ethyl ester is 192°C to 194°C, and elemental analysis IR, N
MR was the same as in Example 1.

Example 3: 6.6'-(ethylenedioxy)-di2-
Synthesis of nano-1-technical acid phenyl ester 2-hydroxy-
6-naph 1-2 acid phenyl ester 47.77 and sodium methoxide 10.29 N.

In addition to 150 cc of N-dimethylformamide, 100°
It was heated to C. Next, 14.39 g of 1,2-dibromoethane was added to the reaction mixture, and the reaction mixture was heated at 100 DEG C. for 1'' 3M.The reaction mixture was concentrated and poured into 1 glass of water to collect a solid. This solid was collected by filtration, N,N
-GJi''' (ethylenedioxy)-2-lift-[acid 7L ester 7.8L, I to 111K.The melting point of this) engineered 2-yl ester is 276°C- , 278°C, and elemental analysis value C%: 77.9%, 1-1%;
It was 4.7%. IR of phenyl ester here
is shown in Figure-3.

Example 4: 6,6'-(ethylenediA21-)-
Synthesis of di-2-naphthoic acid 6,6'-(di-brendioxy)-di-2-nara 1 to ethyl engineering acid 1 ster 103 obtained in Example 1 was added to 103 ml of water.
The mixture was mixed with 100 cc of di-Δkin and 103 ml of hydroxide, and reacted at about 100° C. for 7:3 hours with stirring.

After reaction route J', it was cooled, filtered, and then treated at 100° for 2 hours in 200 cc of a 20% sulfuric acid aqueous solution I! J! 6゜6'-(ethylenedioxy)-cy 2-norftX1 acid white solid 8.4! l? I got it. This 6.6'
The melting point of -(ethylenedioxy)-di-2-pfl-IM is higher than 350°C and the elemental analysis value is 0%; 71
, 6%, 1-1%; 4.5%.

Furthermore, the IR of this product is shown in Figure 4.

Example 5: 6.6'-(ethylenedioxy)-di2-
Synthesis of J-phthotechnic acid [collide 6.6'-(ethylenedione di)-di-2-naph; - Distillation of 5.0', l, thionyl chloride and 5CC of pyridine into dianyl chloride After the reaction was allowed to proceed for 3 hours, the precipitated solid was filtered. By recrystallizing the obtained solid with xylene, 6.6'-(ethylenedioxy)-di-2-natyl chloride 5.07 was obtained. The melting point of this talolide is 242-245°C, and the elemental analysis results are as follows: ICQ elemental analysis 0%:6
1.1. 1%; 3.3C-1%; 15,3 The IR of this chloride is shown in Figure 5.

[Brief explanation of the drawing]

Figures 1, 3, 4 and 5 are infrared absorption spectra of compounds I obtained in Examples 1 and 3°4.5, respectively. Figure-
2 is the nuclear magnetic resonance spectrum I of the compound obtained in Example 1.
It is le. . Written amendment to this procedure (method) August 1980, Director General of the Japan Patent Office 1, Patent Application No. 1987-7+805 2 Name of the invention 6.6'-(ethylenedioxy)-di-2-nantoe t
R. Derivatives thereof and their manufacturing methods 3 Relationship with the case of the person making the amendment Patent applicant 1-11 Minamihonmachi, Higashi-ku, Osaka (300) Representative Okamoto Sashibe 5 of Teijin Limited Date of amendment order July 31, 1980 Drawings subject to the 67' correction Contents of the 77 correction are as attached.

Claims (1)

[Claims] 1. 6,6'-(ethylenedioxy)-di2 represented by the following formula
- Natto [acid and its derivatives. 6,t3'-(ethylenedioxy)-di-2-naphthoate characterized by reacting an alkali metal salt of 2.2-hydroxy-6-naphthoic acid Nisder with 1.2-dihalogenated ethane. manufacturing method.