JPS61171463A - Acrylic acid ester compound containing azo bond - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R<1> is H or methyl; R<2> is CmH2m+1 (m is 1-4) or OCmH2m+1]. USE:Useful for the stationary phase of preparative gas chromatography. It has the property of liquid crystal. PREPARATION:The compound of formula I can be produced by the dehydro chlorination reaction of the acid chloride compound of formula II having acryloyl group with the azo compound of formula III in the presence of a hydro gen chloride scavenger such as triethylamine. The reaction is carried out prefer ably by using about 1mol of the compound of formula III per 1mol of the com pound of formula II. Since the compound of formula I has a polymerizable unsaturated bond in the molecular formula, it can be polymerized easily by a radical polymerization initiator for the polymerization of ordinary vinyl com pound. A novel polymer of formula IV (n is polymerization degree) can be produced by the polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an azo bond-containing acrylic acid ester compound which is a new substance. This azo bond-containing acrylic acid ester compound and the polymer obtained by polymerizing it are said to be particularly useful as separation stationary phases in gas chromatography, and are also excellent liquid crystals (prior art). Many types of phases are already known, such as various phthalate esters and liquid paraffin. However, no substance has yet been developed for the stationary phase that exhibits satisfactory performance in mutually separating specific compounds with relatively large molecular weights and isomers of pheromone substances that have close boiling points.

(Structure of the Invention) The present inventors have repeatedly conducted synthetic research regarding the above technical problem,
As a result of detailed analysis and testing, we succeeded in developing a new azo bond-containing acrylic ester compound represented by the general formula % () below.

R1 in general formula (I) represents a hydrogen atom or a methyl group. Also, R2 is the formula C@H2fi+□ or oC餉H2
, Ya.

8 (t; L m is 1 to 4) -h, a lower group selected from methyl group, ethyl group, propyl group, butyl group and methoxy group, ethoxy group, propoxy group, butoxy group is an alkyl group or an alkoxy group.

The azo bond-containing acrylic ester compound represented by the above general formula (I) provided by the present invention is composed of an acid chloride compound having an acryloyl group represented by the linear formula % () and the following general formula (R', R2 is as described above) It is synthesized by dehydrochlorinating an azo compound represented by the following formula in the presence of a hydrogen chloride scavenger such as triethylamine. In the reaction, it is desirable to use approximately the same mole of the azo compound of general formula (III) per mole of the acid chloride compound of formula (II). Note that the product is purified by washing and recrystallization. The acid chloride compound having an acryloyl group of formula (II) above can be produced from thionyl chloride using p-hydroxybenzoic acid, 2-chloroethanol and acrylic acid as raw materials. Namely.

After adding potassium hydroxide and potassium iodide to 4-hydroxybenzoic acid in an ethanol-water system, it is reacted with 2-chloroethanol to obtain 4-(2-hydroxyethoxy)benzoic acid, which is then reacted with p-hydroxyquinoline and p-hydroxybenzoic acid. - 4-(2-propenoyloxyethoxy)benzoic acid is produced by reacting with acrylic acid in a benzene solvent to which toluenesulfonic acid and boric acid are added. Next, this product is reacted with thionyl chloride in the presence of dimethylacetamide and 2,6-di-t-butyl-p-methylphenol to obtain the acid chloride compound of formula (1).

Moreover, the azo compound of the general formula (HI) can be produced from p- and phenol or m-cresol. That is, after treating p-substituted aniline with hydrochloric acid,
The azo compound of general formula (TII) is obtained by reaction with a phenol sodium salt buffer or m-cresol sodium salt buffer in the presence of sodium nitrite.

The azo bond-containing acrylic ester compound obtained by the present invention is normally a crystalline solid.

As mentioned above, it has properties as a liquid crystal, and is a substance that is particularly useful as a stationary phase in gas chromatography.

In addition, since this compound has a polymerizable unsaturated bond (acryloyl group) in its molecular formula, it can be easily polymerized using a radical polymerization initiator used for the polymerization of general vinyl compounds. A useful new polymer is obtained.

R' and R'' in the formula are the same as above, and n indicates the degree of polymerization, but this polymer generally has a weight average molecular weight in terms of polystyrene determined by GPC method of 1,000 to 100,00.
It is obtained as having 0.

-M KtA-1++ -Hq 71 my k)
! -'y i / 1-kl-)X Demonstrates high separation ability as a stationary phase. In addition, it has a wide range of liquid crystal properties and has a long life when used repeatedly during heating and cooling, making it extremely effective in practical applications.

Next, reference examples, examples, and polymerization examples will be given and explained.

Reference example 1 4-hydroxybenzoic acid 6 into 175 ml of ethanol
Add 9g (0.5mol) and add 75ml of water while cooling.
75 g of potassium hydroxide dissolved in No. 2 was added. After adding a small amount of potassium iodide, the mixture was refluxed with stirring and 44 g (0.55 mol) of 2-chloroethanol was added using a dropping funnel over a period of 3 hours. After refluxing for 20 hours, the ethanol was distilled off and the reaction mixture was diluted with 500IIIQ water. After washing with ether, adjust pl+ to 4 with hydrochloric acid, filter, and dry to obtain 4-(2-hydroxyethoxy).
70 g (yield: 76.9%) of a white solid, which is benzoic acid, was obtained. It was further recrystallized from ethanol. The melting point of this material was 181°C.

4-(2-hydroxyethoxy)benzoic acid 36.4g
(0.2 mol), 8 g of p-hydroquinoline, 8 g of P-toluenesulfonic acid and 200 μl of boric acid were added to 12 mol of benzene.
It was added to a mixed solution of 0 mQ and 120 mn of acrylic acid. Then, the mixture was refluxed for 15 hours, cooled to room temperature, and 4 times the amount of ether was added, followed by extraction with warm water. After dehydrating the ether layer with sulfur salt,
The ether was recovered by distillation.

Next, 38g of white solid, which is 4-(2-propenoyloxyethoxy)benzoic acid, was recrystallized with 2-propanol.
(yield 80.5%). The melting point of this substance is 141℃
Met.

Reference example 2 12.3g of p-methoxyaniline (0,1
mol) into 40 mQ of distilled water, add dilute hydrochloric acid (concentrated hydrochloric acid 30 mQ)
g diluted with distilled water to 100a+I2) was added dropwise.

The mixture was cooled to 5° C., and 4 g (0.1 mol) of sodium nitrite dissolved in 16 mΩ of distilled water was added dropwise. After stirring for 1 hour while maintaining the temperature at 5°C, m-cresol sodium salt buffer (m-cresol 10.8 g (0.1 mol), sodium hydroxide 4 g (0.1 mol) and sodium carbonate 12 g was distilled. The above solution was added dropwise to the solution (dissolved in 170 mA of water) while stirring. After neutralization with hydrochloric acid, the solid content obtained by filtration was redissolved in ether. Nythyl was distilled off and dried. Dissolve in ethanol again.

Recrystallization was performed by adding hexane to obtain p-(p'-methoxyphenylazo)m-cresol in a yield of 66%.

The melting point of this material was 136°C.

Reference Example 3 Using 14.9 g (0.1 mol) of p-butylaniline as a raw material and operating in the same manner as in Reference Example 2, using hexane as a recrystallization solvent, p-(p'-n-butylphenyl Azo) m-cresol was obtained in a yield of 78%.

The melting point of this material was 66°C.

Reference example 4 13.7 g of p-ethoxyaniline (0,
1 mol) was operated in the same manner as in Reference Example 2, and recrystallization was performed by dissolving it in benzene and adding hexane to obtain p-(p'-ethoxyphenylazo)m-cresol in a yield of 78%. The melting point of this substance was 121'C.
1 Reference Example 5 12.1 g of p-ethylaniline (0,1
p-(p'-ethylphenylazo)m-cresol was obtained in a yield of 71% by operating in the same manner as in Reference Example 2 using hexane as the recrystallization solvent. The melting point of this material was 98°C.

Reference Example 6 In Reference Example 2, the m-cresol sodium salt buffer was replaced with a phenol sodium salt buffer (phenol 9.
4 g (0.1 mol) and 4 g (0.1 mol) of sodium hydroxide (
0.1 mol) and 12 g of sodium carbonate in distilled water 17
p-(p'-methoxyphenylazo)phenol was obtained in a yield of 70% using benzene as the recrystallization solvent. The melting point of this substance is 146℃
Met.

Reference Example 7 13.7g of p-ethoxyaniline (0,1
mol) and operated in the same manner as in Reference Example 6, recrystallization was performed by adding hexane after dissolving in ethanol, p
-(p'-ethoxyphenylazo)phenol in yield of 8
Obtained at 0%. The melting point of this material was 127°C.

Reference Example 8 14.9 g of p-m-butylaniline (0-
By using hexane as the dry crystal solvent, p-(p'-n-butylphenylazo)m-cresol was obtained with a yield of 90%. .

Example 1 4-(2-propenoyloxyethoxy)benzoic acid7.
08 g (0.03 mol), 2 drops of dimethylacetamide, 2,6-di-t-butyl-p-methylphenol and 20 mQ of thionyl chloride were stirred at 45°C for 30 minutes.
heated to. Thionyl chloride was removed by vacuum distillation, and the remaining acid chloride was dissolved in 50 mfi of dehydrated ether. A solution of 5 mfi of triethylamine and 100 mQ of tetrahydrofuran in which 7.26 g (0.03 mol) of intermediate material p-(p'-methoxyphenylazo)m-cresol was dissolved was cooled to 5°C and added dropwise over 30 minutes. After 3 hours reaction.

The mixture was filtered and the filtrate was removed. The solid residue was dissolved in chloroform, washed with water, and dehydrated with boron sulfate.

Thereafter, it was recrystallized with ethanol to obtain 10.19 g of pure solid content.

When we measured the infrared absorption spectrum of this substance, we found that the absorption due to the ester group was at 1730 ci'' and the absorption due to the phenyl group (1610, 1589, 1513, 1
425, 1263, 1228 cm-'') were observed, and absorption of 2855cn-1 due to the me-1-oxy group also appeared.Next, when the mass spectrum was measured using the direct introduction method, a molecular weight peak of 460 was detected. Then, when the NMR spectrum was measured, the methyl group bonded to the phenyl group was 2.80 ppm, the methoxy group bonded to the phenyl group was 4.01 ppm, the two methylenes sandwiched between the ether bonds were 4.59 ppm, and acrylic acid. Vinyl group of ester is 6.12pp+n, 6.45ρpn+
, 6.68 ppm, and phenyl groups from 7 to 9 ppm
It was discovered that this substance was a new substance, acrylic acid ester monomer [M□], which was complicatedly cursed by m.

...[M] Furthermore, this substance was added to a polarizing microscope with a heating stage lol.
As I observed, as the temperature was increased to the crystal, a fibrous texture characteristic of nematic liquid crystals was observed at temperatures above 99°C.

Thereafter, when the temperature was further increased to 168° C. or higher, no tissue image was observed, indicating that the liquid crystal had a nematic range of 69°.

The transition temperature was also confirmed by DSC and was consistent with the above temperature.

Example 2 The same procedure as in Example 1 was performed using 8.04 g (0.03 mol) of p-(p'-n-butylphenylazo)m-cresol as the intermediate raw material, and the pure solid content was 8.46.
I got g.

When this infrared absorption spectrum was measured, absorption due to the ester group was observed at 1732 cxr 1, and absorption due to a series of phenyl groups was observed, and 2950 a based on methylene was observed.
114 and 2880 am'' also appeared strongly.Next, when the mass spectrum was measured using the direct introduction method, a molecular weight peak of 486 appeared.Then, when the NMR spectrum was measured, compared to Example 1, the methoxy group bonded to the phenyl group was detected. disappears, and instead the butyl group bonded to the phenyl group becomes CH,: 1.000pp
m, -CH2Cl, -; 1.50 ppm, -(I>C
H2-: Appeared at 2.70 ppm, and was found to be an acrylic acid ester monomer [M2], which is a new substance.

...[M2] Furthermore, when this substance was observed with a polarizing microscope, 75
It was found to be a nematic liquid crystal over the range 456°C to 120°C. The transition temperature was also confirmed by DSC and was found to match the above temperature.

Example 3 When the same procedure as in Example 1 was carried out using 7.68 g (0.03 mol) of p-(p'-ethoxyphenylazo)m-cresol as the intermediate raw material, the pure solid content was 12.05 g.
I got it.

When this infrared absorption spectrum was measured, absorption due to a series of phenyl groups including 1728an-1 due to an ester group was observed. Next, when a mass spectrum was measured using a direct introduction method, a molecular weight peak of 474 appeared. Then, when the NMR spectrum was measured, Example 1
The methoxy group bonded to the phenyl group disappears compared to
Instead, each ethoxy group bonded to a phenyl group is C
H3; 1.15ppm.

-nOCII--: 4-22onm L, -taiq
h νh, 4< It was found that the monomer [M3] was an acrylic acid ester monomer having a similar property to IC.

Furthermore, this substance was examined using a polarizing microscope. As a result, it was found to be a nematic liquid crystal with a temperature range of 68'' from 108° C. to 176° C. When the transition temperature was also confirmed by DSC, it matched with the above temperature.

Example 4 In Example 1, 7.20 g (0.03 mol) of p-(p'-ethylphenylazo)m-cresol was added to the intermediate raw material.
When the same operation was performed using the same method, 9.76 g of pure solid content was obtained.

When this infrared absorption spectrum was measured, absorption due to ester groups was observed at 1725 il, and a series of absorptions due to phenyl groups were observed. Then, when the NMR spectrum was measured, compared to Example 1, the methoxy group bonded to the phenyl group disappeared, and instead, the ethyl group bonded to the phenyl group was an acrylic ester monomer, which is a substance with CH□; 1° order. It turned out to be [M4].

...[M4] Furthermore, when this substance was observed using a polarizing microscope, it was found that 81
It was found to be a nematic liquid crystal with a temperature range of 40° from 121°C. The transition temperature was also confirmed by DSC and was found to match the above temperature.

Example 5 The same procedure as in Example 1 was carried out using 6.84 g (0.03 mol) of p-(p'-methoxyphenylazo)phenol as the intermediate raw material to obtain 11.96 g of pure solid content.

When this infrared absorption spectrum was measured, absorption by the ester group at 1740G-1 and a series of phenyl groups appeared, and absorption by the methoxy group also appeared at 2855cm-1.
appeared in '. Next, when a mass spectrum was measured using the direct introduction method, the molecular weight peak of 446 was cursed. Furthermore, when the NMR spectrum was measured, the methyl group bonded to the phenyl group disappeared compared to Example 1, and the other things were the same. Therefore, it was found that this is an acrylic acid ester monomer [M,] which is a new substance.

...[M5] Further observation of this substance with a polarizing microscope shows the following 11
It was found that the liquid crystal was a nematic liquid crystal with a temperature range of 126 seconds from 4°C to 240°C. The transition temperature was also confirmed by DSC and was found to match the above temperature.

Example 6 The same procedure as in Example 1 was carried out using 7.26 g (0.03 mol) of p-(p'-nitoxyphenylazo)phenol as the intermediate raw material, and a pure solid content of 7.49 g was obtained.

When this infrared absorption spectrum was measured, absorption due to ester group appeared at 1740 cxr-'', and
(A series of absorptions due to enyl groups also appeared.

Next, when a mass spectrum was measured using a direct introduction method, a molecular weight peak of 460 was detected. Furthermore, when an NMR spectrum was measured, it was found that, compared to Example 3, the methyl group bonded to the phenyl group disappeared, but the rest was the same. Therefore, this was found to be an acrylic acid ester monomer [M6], which is a new substance.

...(M,) Furthermore, when this substance was observed using a polarizing microscope, 10
It was found to be a nematic liquid crystal over the range 133' from 0°C to 233°C. The transition temperature was also confirmed by DSC and was found to match the above temperature.

Example 7 In Example 1, 7.56 g (0.03 mol) of p-(p'-n-butylphenylazo)phenol was added to the intermediate raw material.
When the same operation was performed using , 7.38 g of pure solid content was obtained.

When this infrared absorption spectrum was measured, absorption due to the ester group appeared at 1740 txtr-'', and a series of absorptions due to the phenyl group were also cursed.Furthermore, when the NMR spectrum was measured, compared to Example 2, it was found that the absorption due to the ester group appeared at 1740 txtr-''. The bonded methoxy group disappeared and the rest remained the same.Therefore, this was found to be an acrylic acid ester monomer [M7], which is a new substance.

...[M7] Further, when this substance was observed with a polarizing microscope, 10
It was found to be a nematic liquid crystal over the range 796 from 2°C to 181°C. The transition temperature was also confirmed by DSC and was found to match the above temperature.

Polymerization Example 1 2 g of acrylic acid ester monomer [M-technique] was dissolved in 20 ml of tetrahydrofuran, and azobisisobutyronitrile was added as a polymerization initiator in an amount of 1 mol % based on 7 mer, and the reaction was carried out at 60°C for 8 hours under a nitrogen atmosphere. did. The produced polymer was transferred into ether cooled to 5°C and precipitated. The precipitate was redissolved in chloroform, precipitated in the same solvent, filtered and dried to obtain a solid content of 0.30 g.

When this NMR spectrum was measured, it was found that C
11□=absorption of C11- disappears and 10) 12-C11-
It turned out that it became. Then, when it was dissolved in tetrahydrofuran and the weight average molecular weight in terms of polystyrene was determined by GPC method, it was found to be 5,734. Therefore, this substance was found to be a new polymer [P-product].

...[P Engineering] Furthermore, when this substance was observed using a polarizing microscope, it was found that 88
It was found to be a nematic liquid crystal with a temperature range of 163 degrees from .degree. C. to 245.degree. The transition temperature was also confirmed by DSC and was found to match the above temperature.

Polymerization Example 2 Polymerization Example 1 using acrylic acid ester monomer (MJ2g)
A solid content of 0.15 g was obtained in the same manner as above.

When the NMR spectrum was measured, compared to the acrylic acid ester monomer [M2], <C
It was found that the absorption of 1+, =CH- disappeared and became =CH, -CH-. When the weight average molecular weight was determined by GPC method, it was found to be 20,250, indicating that it was a novel polymer [P2].

+ CH2-CH+rl ... [P2] Furthermore, when this substance was observed using a polarizing microscope, it was shown that 80
It was found to be a nematic liquid crystal over the range 163a from .degree. C. to 243.degree. The transition temperature was also confirmed by DSC and was found to match the above temperature.

Polymerization Example 3 Using acrylic acid ester monomer (32 g of Mg), the same procedure as in Polymerization Example 1 was carried out to obtain a solid content of 0.52 g.

When the NMR spectrum was measured, it was found that <CH,
It was found that the absorption of =CH- disappeared and became =CH2-CH-. As determined by GPC method, the weight average is 9□, 78°, 77°, 0. □,. toast'Ah, I found out one thing.

-(-CH2-CH+n...[P,] Furthermore, when this substance was observed with a polarizing microscope, 95
It was found that it was a nematic liquid crystal with a temperature range of 160'' from 255°C to 255°C.The transition temperature was also confirmed by DSC and was found to match the above temperature.

Polymerization Example 4 Using 32 g of acrylic acid ester monomer CM, the same procedure as in Polymerization Example 1 was carried out to obtain a solid content of 0.56 g.

When the NMR spectrum was measured, compared to acrylic acid ester monomer [M4], <CH□
It was found that the absorption of =CH- disappeared and became -CIl□-CH-. When the weight average molecular weight was determined by GPC method, it was found to be 8702, indicating that it was a novel polymer [P4].

...[P4] Furthermore, when this substance was observed using a polarizing microscope, it was found that 81
It was found that the liquid crystal was a nematic liquid crystal with a temperature ranging from 142'' to 223°C.The transition temperature was also confirmed by DSC and was found to match the above temperature.

Polymerization Example 5 Using acrylic acid ester monomer (32 g of Mg), the same procedure as in Polymerization Example 1 was carried out to obtain a solid content of 0.84 g.

When the NMR spectrum was measured, C11 based on acrylic acid was compared to the acrylic acid ester monomer [M,].
It was found that the absorption of □=CH- disappeared and became =CH, -CH-. When the weight average molecular weight was determined by GPC method, it was found to be 11,760, indicating that it was a novel polymer [Ps].

...[P,] Furthermore, when this substance was observed using a polarizing microscope, 1
It was found to be a nematic liquid crystal with a temperature range of 175° from 10°C to 285°C. The transition temperature was also confirmed by DSC and was found to match the above temperature.

Polymerization Example 6 Using 2 g of acrylic acid ester monomer (Ms), the same procedure as in Polymerization Example 1 was carried out to obtain a solid content of 0.44 g.

When the NMR spectrum was measured, compared to acrylic acid ester monomer [M6], <C
It was found that the absorption of H2=CHl- disappeared and became -C11, -CH-. When the weight average molecular weight was determined by GPC method, it was found to be 6019, indicating that it was a novel polymer [P6].

...[P6] Furthermore, when this substance was observed using a polarizing microscope, it was found that 9
It was found to be a nematic liquid crystal over the range 160' from 5°C to 255°C. The transition temperature was also confirmed by DSC and was found to match the above temperature.

Polymerization Example 7 Using an acrylic acid ester monomer (Mt: 12 g), the same procedure as in Polymerization Example 1 was carried out to obtain a solid content of 0.66 g.

When the NMR spectrum was measured, it was found that acrylic acid-based (CH2
The absorption of =CH- disappeared and became =CH, -CH-. When the weight average molecular weight was determined by GPC method, it was found to be 13,790, indicating that it was a novel polymer [P,].

1,000 CH2-CM +n ... [P7] Furthermore, when this substance was observed using a polarizing microscope, it was shown that 10
It was found to be a nematic liquid crystal with a temperature range of 173° from 2°C to 275°C. The transition temperature was also confirmed by DSC and was found to match the above temperature.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 is a hydrogen atom or a methyl group, R^2 is C
_mH_2_m_+_1 or OC_mH_2_m_+
An azo bond-containing acrylic ester compound represented by a group represented by _1, where m is an integer of 1 to 4.