CN101967111A - 5-(4-hydroxyphenyl azo)-1,3-phthaloyl glycine and preparation method thereof - Google Patents

Abstract

The invention provides a compound of 5-(4-hydroxyphenyl azo)-1,3-phthaloyl glycine and a preparation method thereof. The preparation method comprises the following steps of: carrying out nitration, acylation, reduction and diazotization coupling reaction on isophthalic acid used as a raw material, to synthesize the 5-(4-hydroxyphenyl azo)-1,3-phthaloyl glycine; and carrying out structure representation through an IR (infrared) spectrum and 1HNMR (1 Hydrogen Nuclear Magnetic Resonance). The invention is an important raw material which is chemically synthesized by modern organic macromolecules.

Description

5-(4-hydroxy phenyl azo)-1,3-phenyl-diformyl glycine and preparation method

Technical field

The invention belongs to organic chemistry filed, be specifically related to 5-(4-hydroxy phenyl azo)-1,3-phenyl-diformyl glycine and synthetic method thereof.

Background technology

Along with the continuous development of science and technology, thermotolerance, stability requirement in leading-edge fields such as space flight, military affairs to material are more and more higher, and m-phthalic acid is exactly the intermediate of this material of preparation, and it has stronger thermotolerance, hydrolytic resistance and erosion resistance.Can carry out reactions such as salify, dehydration, hydrogenation, halogenation, be mainly used in and produce coating, special fibre, hotmelt, printing-ink, poly-vinegar fiber dyeability modifier and resin plasticizer etc.

High purity m-phthaloyl chloride quality meets the polymerization-grade requirement, can be used as the monomer of polymeric amide, polyester, polyarylester, polyaramide, liquid crystal polymer, aramid fiber etc., can be used as the properties-correcting agent of superpolymer simultaneously, the intermediate of agricultural chemicals and medicine industry.

Along with going deep into of macromolecular material research, hyperbranched polymer has become one of focus of polymer research field because of its particular structure and performance.The end group of its good solubility, low-viscosity and numerous modifications makes hyperbranched polymer be applied in fields such as coating, photic materials, demonstrates application prospects in fields such as medicament slow release, functional film material, polymer processing aid, photoelectric functional materials.

The design of functional high molecule material and acquisition are one of main challenges, and the molecular material that particularly has light, electricity, magnetic property more and more is subjected to scientist's attention.Nitrogen benzide chromophore have photic anti--along isomerization characteristic and photoinduction orientation, become one of photoelectric field indispensable material.Therefore, preparing small molecules and polymkeric substance with multiple functional group, novel structure and character excellence provide more wide space must for the application of this class material.

Summary of the invention

The present invention designs and has synthesized 5-(4-hydroxy phenyl azo)-1,3-phenyl-diformyl glycine, and it combines the character of m-phthaloyl chloride and glycine, is the necessary monomer of synthetic azo hyper-branched polyester.

The present invention synthesizes the 5-nitroisophthalic acid with m-phthalic acid; and then acidylate obtains 5-nitro m-phthaloyl chloride; then with the synthetic 5-nitro isophthaloyl glycine of glycine reactant; obtain the amino isophthaloyl glycine of 5-with hydrogen reducing then; carry out the diazonium coupling reaction at last and make final product 5-(4-hydroxy phenyl azo)-1,3-phenyl-diformyl glycine.

5-(4-hydroxy phenyl azo)-1,3-phenyl-diformyl glycine is its chemical name, structural formula is

Be golden yellow solid, fusing point is 251.8～253.4 ℃.

Concrete synthesis step of the present invention is as follows:

The first step, 5-nitroisophthalic acid synthetic, m-phthalic acid and H ₂SO ₄, electronic stirring slowly dripped nitric acid after 10 minutes under 60 ℃ of waters bath with thermostatic control, after dropwising, was warmed up to 100 ℃, continued reaction after 1 hour, reaction solution is poured in the trash ice, and suction filtration, the product recrystallization obtains crystal;

Synthesizing of second step, 5-nitro m-phthaloyl chloride, add excessive SOCl to the 5-nitroisophthalic acid ₂, after the backflow, steam SOCl ₂, get light yellow crystal;

Synthesizing of the 3rd step, 5-nitro isophthaloyl glycine, at room temperature, glycine and NaOH are dissolved in the suitable quantity of water, under agitation slowly add 5-nitro m-phthaloyl chloride, stir and to make in the reaction solution solid all after the dissolving, acidifying, suction filtration is used ethyl alcohol recrystallization, gets white solid;

Synthesizing of the 4th step, 5-amino isophthaloyl glycine, 5-nitro isophthaloyl glycine, palladium-carbon catalyst and ethanol are mixed, stir, after hydrogen reducing was intact, the suction filtration drying got faint yellow solid;

The 5th step, 5-(4-hydroxy phenyl azo)-1, synthesizing of 3-phenyl-diformyl glycine under ice-water bath stirs, mixes the amino isophthaloyl glycine of 5-, water and concentrated hydrochloric acid, and the cold NaNO that will prepare ₂Solution slowly is added drop-wise in the mixed solution, keeps 0～5 ℃ of reaction 15min, obtains clarifying diazonium salt solution; Under ice-water bath stirs, phenol, sodium hydroxide and water are mixed, and use saturated Na ₂CO ₃Solution is transferred PH=8～9, obtains sodium phenylate solution; Above-mentioned diazonium salt solution is added drop-wise in the sodium phenylate solution, behind the stirring reaction 40min, uses the dilute hydrochloric acid acidifying, suction filtration is used ethyl alcohol recrystallization, gets golden yellow solid, and yield is 50%～73%;

The chemical equation that relates in synthetic is seen Fig. 1.

Intermediate product in the building-up process and final product are carried out IR and HNMR detection, and IR characteristic absorbance frequency data see Table 1.

Final product 5-of the present invention (4-hydroxy phenyl azo)-1,3-phenyl-diformyl glycine, it combines the character of m-phthaloyl chloride and glycine, is the necessary monomer of synthetic azo hyper-branched polyester.

The IR characteristic absorbance frequency data of table 1, three kinds of materials

Description of drawings

Chemical equation in Fig. 1, the building-up process, wherein 1 is the 5-nitroisophthalic acid, 2 is 5-nitro m-phthaloyl chloride, 3 is 5-nitro isophthaloyl glycine, 4 is the amino isophthaloyl glycine of 5-, and 5 is 5-(4-hydroxy phenyl azo)-1,3-phenyl-diformyl glycine.

The IR spectrogram of Fig. 2,5-nitro isophthaloyl glycine, wherein 3380cm ^-1Be acid amides ν _-NHAbsorption peak; 3300-2500cm ^-1Be carboxylic acid ν _-OHAbsorption peak; 2960cm ^-1Be alkyl ν _-CH2Absorption peak; 1710cm ^-1ν c=o absorption peak for carboxylic acid; 1653cm ^-1Be acid amides ν c=o absorption peak; 1597cm ^-1, 1450cm ^-1Be phenyl ring skeletal vibration absorption peak; 1352cm ^-1Be nitro symmetrical stretching vibration absorption peak; 1238cm ^-1Be carboxylic acid ν _-OHThe formation vibration absorption peak; 823cm ^-1, 729cm ^-1Be 1,3 of phenyl ring, 5-three replaces absorption peak.

The IR spectrogram of the amino isophthaloyl glycine of Fig. 3,5-, wherein 3402cm ^-1Be acid amides and amino ν _-NHAbsorption peak; 3300-2500cm ^-1Be carboxylic acid ν _-OHAbsorption peak; 2912cm ^-1Be alkyl ν _-CH2Absorption peak; 1718cm ^-1ν c=o absorption peak for carboxylic acid; 1647cm ^-1Be acid amides ν c=o absorption peak; 1597cm ^-1, 1465cm ^-1Be phenyl ring skeletal vibration absorption peak; 1213cm ^-1Be carboxylic acid ν _-OHThe formation vibration absorption peak; 824cm ^-1, 754cm ^-1Be 1,3 of phenyl ring, 5-three replaces absorption peak.

Fig. 4,5-(4-hydroxy phenyl azo)-1, the IR spectrogram of 3-phenyl-diformyl glycine, 3300-2500cm ^-1Be carboxylic acid ν _-OHAbsorption peak; 3077cm ^-1Be the unsaturated C-H stretching vibration of phenyl ring absorption peak; 2940cm ^-1Be alkyl ν _-CH2Absorption peak; 1710cm ^-1ν c=o absorption peak for carboxylic acid; 1641cm ^-1Be acid amides ν c=o absorption peak; 1591cm ^-1, 1476cm ^-1Be phenyl ring skeletal vibration absorption peak; 1229cm ^-1Be carboxylic acid ν _-OHThe formation vibration absorption peak; 835cm ^-1, 758cm ^-1Be 1,3 of phenyl ring, 5-three replaces absorption peak.

Fig. 5,5-(4-hydroxy phenyl azo)-1,3-phenyl-diformyl glycine ¹The HNMR spectrogram, 3.98～4.00ppm is the proton signal peak of methylene radical, 6.97～7.01ppm and 7.87～7.90ppm are the proton signal peak that has the phenyl ring of hydroxyl, 8.45ppm and 8.49ppm is the trisubstituted proton signal of phenyl ring peak, 9.17～9.19ppm is the proton signal peak of acid amides N-H, 10.46ppm be the proton signal peak of phenolic hydroxyl group, 12.65ppm is the proton signal peak of carboxyl.

Embodiment

Synthesizing of the first step, 5-nitroisophthalic acid:

In being furnished with the 100mL there-necked flask of reflux condensing tube, add the 16.6g m-phthalic acid, slowly add 32mL H while stirring ₂SO ₄, behind the electronic stirring 10min, slowly drip 22mL nitric acid under 60 ℃ of waters bath with thermostatic control with constant pressure funnel, after dropwising, be warmed up to 100 ℃, after continuing to react 1h, reaction solution is poured in the trash ice into suction filtration.The product recrystallization obtains crystal.Yield: 89.7%.

Synthesizing of second step, 5-nitro m-phthaloyl chloride:

In the 100mL round-bottomed flask, add the 10.55g5-nitroisophthalic acid, add excessive SOCl ₂, after the backflow, steam SOCl ₂, get light yellow crystal.Yield: 97.12%.

Synthesizing of the 3rd step, 5-nitro isophthaloyl glycine:

At room temperature, 7.5g glycine, 4.5gNaOH are dissolved in the suitable quantity of water, under agitation slowly add 10.4g 5-nitro m-phthaloyl chloride.After solid all dissolves in the solution of stirring back, acidifying, suction filtration is used ethyl alcohol recrystallization, gets white solid.Yield: 90.6%.

Synthesizing of the 4th step, the amino isophthaloyl glycine of 5-:

Add 6.5g 5-nitro isophthaloyl glycine in the 250mL Erlenmeyer flask, add catalyzer, 80mL ethanol, stir, after hydrogen reducing was intact, the suction filtration drying got faint yellow solid.Yield: 73.5%.

The 5th step, 5-(4-hydroxy phenyl azo)-1,3-phenyl-diformyl glycine synthetic

Under agitation, the amino isophthaloyl glycine of 2.95g5-, 30mL water, the dense HCl of 3mL are added in the 100mL Erlenmeyer flask, and with the NaNO for preparing ₂Drips of solution is added in the Erlenmeyer flask, keeps reaction 15min, obtains diazonium salt solution.Stir down, in the 500mL beaker, add 100mL water, 0.78g phenol, stir, transfer pH.Above-mentioned diazonium salt solution is added drop-wise in the phenol solution, and behind the stirring reaction, suction filtration gets golden yellow solid.Yield: 66.1%.

Intermediate product in the building-up process and final product are carried out IR and HNMR detection, and each IR spectrogram and HNMR spectrogram are seen Fig. 2～Fig. 5.

Claims (7)

1. compound 5-(4-hydroxy phenyl azo)-1,3-phenyl-diformyl glycine is characterized in that its chemical name is 5-(4-hydroxy phenyl azo)-1,3-phenyl-diformyl glycine, structural formula is

Be golden yellow solid, fusing point is 251.8～253.4 ℃.

2. the described compound 5-of claim 1 (4-hydroxy phenyl azo)-1, the preparation method of 3-phenyl-diformyl glycine is characterized in that concrete steps are as follows:

The first step, 5-nitroisophthalic acid synthetic, m-phthalic acid and H ₂SO ₄, electronic stirring slowly dripped nitric acid after 10 minutes under 60 ℃ of waters bath with thermostatic control, after dropwising, was warmed up to 100 ℃, continued reaction after 1 hour, reaction solution is poured in the trash ice, and suction filtration, the product recrystallization obtains crystal;

Synthesizing of second step, 5-nitro m-phthaloyl chloride, add excessive SOCl to the 5-nitroisophthalic acid ₂, after the backflow, steam SOCl ₂, get light yellow crystal;

Synthesizing of the 3rd step, 5-nitro isophthaloyl glycine, at room temperature, glycine and NaOH are dissolved in the suitable quantity of water, under agitation slowly add 5-nitro m-phthaloyl chloride, stir and to make in the reaction solution solid all after the dissolving, acidifying, suction filtration is used ethyl alcohol recrystallization, gets white solid;

Synthesizing of the 4th step, 5-amino isophthaloyl glycine, 5-nitro isophthaloyl glycine, palladium-carbon catalyst and ethanol are mixed, stir, after hydrogen reducing was intact, the suction filtration drying got faint yellow solid;

The 5th step, 5-(4-hydroxy phenyl azo)-1, synthesizing of 3-phenyl-diformyl glycine under ice-water bath stirs, mixes the amino isophthaloyl glycine of 5-, water and concentrated hydrochloric acid, and the cold NaNO that will prepare ₂Solution slowly is added drop-wise in the mixed solution, keeps 0～5 ℃ of reaction 15min, obtains clarifying diazonium salt solution; Under ice-water bath stirs, phenol, sodium hydroxide and water are mixed, and use saturated Na ₂CO ₃Solution is transferred PH=8～9, obtains sodium phenylate solution; Above-mentioned diazonium salt solution is added drop-wise in the sodium phenylate solution, behind the stirring reaction 40min, uses the dilute hydrochloric acid acidifying, suction filtration is used ethyl alcohol recrystallization, gets golden yellow solid, and yield is 50%～73%;

Wherein, the mol ratio of the used amino isophthaloyl glycine of 5-, phenol and sodium hydroxide is 1: 1: 1 in the preparation process.

3. compound 5-according to claim 2 (4-hydroxy phenyl azo)-1, the preparation method of 3-phenyl-diformyl glycine is characterized in that the cold NaNO that the first step is used ₂Strength of solution is 16.6%, and preparation is placed on 0～5 ℃ of preservation.

4. compound 5-according to claim 2 (4-hydroxy phenyl azo)-1, the preparation method of 3-phenyl-diformyl glycine is characterized in that the chemical structural formula of intermediate product 5-nitro isophthaloyl glycine is

5. the preparation method of intermediate product 5-nitro isophthaloyl glycine according to claim 4 is characterized in that the concrete operations step is as follows:

The first step, 5-nitroisophthalic acid synthetic, m-phthalic acid and H ₂SO ₄, electronic stirring slowly dripped nitric acid after 10 minutes under 60 ℃ of waters bath with thermostatic control, after dropwising, was warmed up to 100 ℃, continued reaction after 1 hour, reaction solution is poured in the trash ice, and suction filtration, the product recrystallization obtains crystal;

Synthesizing of second step, 5-nitro m-phthaloyl chloride, add excessive SOCl to the 5-nitroisophthalic acid ₂, after the backflow, steam SOCl ₂, get light yellow crystal;

Synthesizing of the 3rd step, 5-nitro isophthaloyl glycine, at room temperature, glycine and NaOH are dissolved in the suitable quantity of water, under agitation slowly add 5-nitro m-phthaloyl chloride, stir and to make in the reaction solution solid all after the dissolving, acidifying, suction filtration, use ethyl alcohol recrystallization, get white solid, yield is 90～90.7%.

6. the preparation method of compound according to claim 2 is characterized in that the chemical structural formula of the amino isophthaloyl glycine of intermediate product 5-is

7. the preparation method of the amino isophthaloyl glycine of intermediate product 5-according to claim 6 is characterized in that the concrete operations step is as follows:

The first step, 5-nitroisophthalic acid synthetic, m-phthalic acid and H ₂SO ₄, electronic stirring slowly dripped nitric acid after 10 minutes under 60 ℃ of waters bath with thermostatic control, after dropwising, was warmed up to 100 ℃, continued reaction after 1 hour, reaction solution is poured in the trash ice, and suction filtration, the product recrystallization obtains crystal;

Synthesizing of second step, 5-nitro m-phthaloyl chloride, add excessive SOCl to the 5-nitroisophthalic acid ₂, after the backflow, steam SOCl ₂, get light yellow crystal;

Synthesizing of the 3rd step, 5-nitro isophthaloyl glycine, at room temperature, glycine and NaOH are dissolved in the suitable quantity of water, under agitation slowly add 5-nitro m-phthaloyl chloride, stir and to make in the reaction solution solid all after the dissolving, acidifying, suction filtration is used ethyl alcohol recrystallization, gets white solid;

Synthesizing of the 4th step, 5-amino isophthaloyl glycine, 5-nitro isophthaloyl glycine, catalyzer and ethanol are mixed, stir, after hydrogen reducing was intact, the suction filtration drying got faint yellow solid, and yield is 68%～75%.

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