CN111057019A - Method for producing 2- (2 '-hydroxy-5' -methoxyphenyl) benzotriazole - Google Patents
Method for producing 2- (2 '-hydroxy-5' -methoxyphenyl) benzotriazole Download PDFInfo
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- methoxyphenyl
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- PITPRNOGWXAZAW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-methoxyphenol Chemical compound COC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 PITPRNOGWXAZAW-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- -1 alkali metal nitrite Chemical class 0.000 claims abstract description 29
- 239000012954 diazonium Substances 0.000 claims abstract description 18
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012964 benzotriazole Substances 0.000 claims abstract description 13
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 239000004304 potassium nitrite Substances 0.000 claims description 4
- 235000010289 potassium nitrite Nutrition 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 claims description 3
- 229960003868 paraldehyde Drugs 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 abstract description 16
- 230000002745 absorbent Effects 0.000 abstract description 16
- 230000004888 barrier function Effects 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
- C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing benzotriazole ultraviolet absorbent, in particular to a method for preparing 2- (2 '-hydroxy 5' -methoxyphenyl) benzotriazole, which comprises the following steps: reacting o-nitroaniline with alkali metal nitrite under the conditions of inorganic strong acid and low temperature to synthesize diazonium salt; under the alkaline condition, p-methoxyphenol is dissolved in an aliphatic solvent and coupled with diazonium salt under the low-temperature condition to obtain an azo compound; the azo compound is used for producing a semi-reduction product under the action of a reducing agent under the alkaline condition; the semi-reduction product is put in organic solvent and under the action of metal reducing agent, so that the product is obtained. By adopting the preparation method, the preparation of the ultraviolet absorbent 2- (2 '-hydroxy 5' -methoxyphenyl) benzotriazole is simpler, and has high content, high yield, no pollution and high barrier rate.
Description
Technical Field
The invention relates to a method for preparing benzotriazole ultraviolet absorbent, in particular to a method for preparing 2- (2 '-hydroxy 5' -methoxyphenyl) benzotriazole.
Background
Ultraviolet absorbers, which are the main type of light stabilizers, are substances that selectively absorb ultraviolet light of a fixed wavelength and then undergo energy conversion to release or consume energy as thermal energy or harmless low radiation, and do not harm the human body. The existing ultraviolet absorbent mainly comprises benzophenone absorbent, carboxylic acid absorbent and benzotriazole absorbent. The benzophenone absorbent and the carboxylic acid absorbent have low ultraviolet absorptivity, low barrier rate, easy leaching and short service life of protected materials (such as plastics). The benzotriazole ultraviolet absorbent is a nitrogen-containing heterocyclic compound with excellent performance and capable of absorbing ultraviolet with specific wavelength, and plays an important role in industry, agriculture and manufacturing.
A new benzotriazole ultraviolet absorbent with high absorptivity, high barrier rate and difficult leaching is needed to adapt to industrial application.
Disclosure of Invention
The invention aims to provide a method for preparing 2- (2 '-hydroxy 5' -methoxyphenyl) benzotriazole, which has high absorption rate and high barrier rate and is difficult to leach out.
The technical scheme of the invention is as follows:
a method of making 2- (2 '-hydroxy 5' -methoxyphenyl) benzotriazole comprising the steps of:
a. reacting o-nitroaniline with alkali metal nitrite under the conditions of inorganic strong acid and low temperature to synthesize diazonium salt;
b. under the alkaline condition, p-methoxyphenol is dissolved in an aliphatic solvent and coupled with diazonium salt under the low-temperature condition to obtain an azo compound;
c. the azo compound is used for producing a semi-reduction product under the action of a reducing agent under the alkaline condition;
d. the semi-reduction product is put in organic solvent and under the action of metal reducing agent, so that the product is obtained.
The strong inorganic acid used is hydrochloric acid or sulfuric acid.
The reaction temperature in the a.b step is controlled below 5 ℃.
The alkali metal nitrite used includes sodium nitrite or potassium nitrite.
The alkaline conditions described are the addition of an amount of NaOH, KOH or Ca (OH) to the solvent2And (4) forming.
Aliphatic solvents mentioned include cyclohexane, octane, petroleum ether.
Reducing agents described include inorganic salts: na (Na)2S、NaHS、NH4HS、(NH4)2S and their mixture, the aldehydes include formaldehyde, acetaldehyde, paraformaldehyde, paraldehyde, reducing sugar, and hydrazine.
Metallic reducing agents are described as Zn, Sn, Al, Fe and mixtures thereof.
The organic solvents mentioned are xylene, toluene, benzene.
The molar ratio of the o-nitroaniline to the p-methoxyphenol is 1: 1; the mass ratio of the alkali metal nitrite to the o-nitroaniline is 5-6: 10.
the invention has the beneficial effects that:
1. therefore, the invention discloses a 2- (2 '-hydroxy 5' -methoxyphenyl) benzotriazole ultraviolet absorbent, which can effectively absorb ultraviolet light of 260-400nm and has higher barrier rate (barrier rate 90.1%) compared with other ultraviolet absorbents. The light stabilizer is widely applied to plastics, synthetic rubber, dyes, fibers and the like, and is a high-efficiency light stabilizer.
2. The ultraviolet absorbent has high ultraviolet absorptivity and high blocking rate, is not easy to leach, and has good effect.
Drawings
FIG. 1 is a diagram showing ultraviolet absorption of 2- (2 '-hydroxy-5' -methoxyphenyl) benzotriazole.
Detailed Description
A process for the manufacture of 2- (2 '-hydroxy 5' -methoxyphenyl) benzotriazole, comprising the steps of:
a. reacting o-nitroaniline with alkali metal nitrite under the conditions of inorganic strong acid and low temperature to synthesize diazonium salt;
b. under the alkaline condition, p-methoxyphenol is dissolved in an aliphatic solvent and coupled with diazonium salt under the low-temperature condition to obtain an azo compound;
c. the azo compound is used for producing a semi-reduction product under the action of a reducing agent under the alkaline condition;
d. the semi-reduction product is put in organic solvent and under the action of metal reducing agent, so that the product is obtained.
The strong inorganic acid used is hydrochloric acid or sulfuric acid. The reaction temperature in the a.b step was controlled to 5 ℃ or lower. The alkali metal nitrite used includes sodium nitrite or potassium nitrite. The alkaline conditions described are the addition of an amount of NaOH, KOH or Ca (OH) to the solvent2And (4) forming. Aliphatic solvents mentioned include cyclohexane, octane, petroleum ether. Reducing agents described include inorganic salts: na (Na)2S、NaHS、NH4HS、(NH4)2S and their mixture, the aldehydes include formaldehyde, acetaldehyde, paraformaldehyde, paraldehyde, reducing sugar, and hydrazine. Metallic reducing agents are described as Zn, Sn, Al, Fe and mixtures thereof. The organic solvents mentioned are xylene, toluene, benzene.
Examples
1. a, preparing diazonium salt: adding 10g of o-nitroaniline, 30g of deionized water and 28ml of hydrochloric acid (33%) into a 100ml three-necked bottle provided with a stirrer and a thermometer, stirring, heating to 45 ℃, keeping the temperature for 1 hour, cooling to 0 ℃, adding 5.5g of sodium nitrite, keeping the temperature and stirring for 3 hours to obtain diazonium salt for later use.
b preparation of azo Compound: 100ml of cyclohexane and 10g of p-methoxyphenol were added to a 500ml three-necked flask equipped with a stirrer and a thermometer, and after dissolution by stirring at room temperature, NaOH6g was added, stirring was continued for 1 hour, the temperature was lowered to 0 ℃ and the diazonium salt to be used was added to the three-necked flask within 0.5 hour. 21g of a red azo compound was obtained.
c, half reduction reaction: into a 1000ml three-necked flask equipped with a stirrer and a thermometer were charged the above azo compound, Ca (OH)28g，NH4HS16g, and deionized water 280 ml. Stirring, heating to 50 deg.C, reacting for 1 hr to obtain yellow semi-reduced product 19 g.
d, reduction reaction: 20g of half-reduced product, 280ml of benzene and 10g of Fe powder are respectively added into a 500ml three-necked bottle provided with a stirrer and a thermometer, stirred and heated to 60 ℃, and reacted for 1 hour to obtain 15g of white product with the content of 99.3 percent.
2. a, preparing diazonium salt: adding 10g of o-nitroaniline, 30g of deionized water and 6ml of sulfuric acid (93%) into a 100ml three-necked bottle provided with a stirrer and a thermometer, stirring, heating to 45 ℃, keeping the temperature for 1 hour, cooling to 0 ℃, adding 5g of potassium nitrite, keeping the temperature and stirring for 3 hours to obtain diazonium salt for later use.
b preparation of azo Compound: in a 500ml three-necked flask equipped with a stirrer and a thermometer, 100ml of cyclohexane and 10g of p-methoxyphenol were charged, and after dissolving the mixture by stirring at room temperature, Ca (OH) was added26g, stirring is continued for 1 hour, the temperature is reduced to 0 ℃, and the diazonium salt for standby is added into a three-necked bottle within 0.5 hour. 22.4g of a red azo compound was obtained.
c, half reduction reaction: into a 1000ml three-necked flask equipped with a stirrer and a thermometer were charged the above azo compound, Ca (OH)28g, 10g of paraformaldehyde and 270ml of deionized water. Stirring, heating to 50 deg.C, reacting for 1 hr to obtain yellow semi-reduced product 20.8 g.
d, reduction reaction: 21g of semi-reduction product, 300ml of benzene, 8g of Sn powder and 1.5g of hydrazine are respectively added into a 500ml three-necked bottle provided with a stirrer and a thermometer, and the mixture is stirred and heated to 60 ℃ to react for 1 hour to obtain 17g of white product with the content of 98.9 percent.
3. a, preparing diazonium salt: adding 10g of o-nitroaniline, 30g of deionized water and 6ml of hydrochloric acid (93%) into a 100ml three-necked bottle provided with a stirrer and a thermometer, stirring, heating to 45 ℃, keeping the temperature for 1 hour, cooling to 0 ℃, adding 6g of sodium nitrite, keeping the temperature and stirring for 3 hours to obtain diazonium salt for later use.
b preparation of azo Compound: 50ml of cyclohexane, 30ml of petroleum ether and 10g of p-methoxyphenol are added into a 500ml three-necked flask equipped with a stirrer and a thermometer, after stirring and dissolving at room temperature, 6g of KOH is added, stirring is continued for 1 hour, the temperature is reduced to 0 ℃, and the diazonium salt for standby is added into the three-necked flask within 0.5 hour. 23.4g of a red azo compound was obtained.
c, half reduction reaction: into a 1000ml three-necked flask equipped with a stirrer and a thermometer, the above azo compound, Ca (OH)28g of hydrazine, 18g of hydrazine,280ml of deionized water. Stirring, heating to 50 deg.C, reacting for 1 hr to obtain 21.6g of yellow semi-reduced product.
d, reduction reaction: 20g of half-reduced product, 300ml of benzene, 5.5g of Sn powder and 1.5g of Zn powder are respectively added into a 500ml three-necked bottle provided with a stirrer and a thermometer, and the mixture is stirred and heated to 60 ℃ to react for 1 hour to obtain 16.5g of white product with the content of 99.2 percent.
The absorption principle of benzotriazole ultraviolet absorber
The benzotriazole ultraviolet absorbent can selectively absorb ultraviolet with the wavelength of 290-400nm, and a hydrogen atom on an ortho-hydroxyl and a nitrogen atom on benzotriazole generate a resonance effect. Researches show that the benzotriazole ultraviolet absorbers exist in a phenolic structure, and the light resistance of the benzotriazole ultraviolet absorbers is because the benzotriazole ultraviolet absorbers can perform reversible tautomeric conversion through hydrogen bond chelating rings in molecules, and after ultraviolet light is absorbed, protons can be rapidly transferred to nitrogen atoms to form tautomers, so that excitation energy is effectively converted, and redundant energy is rapidly converted into heat energy to be released, so that the absorbed energy is consumed, and the ultraviolet absorbers return to the ground state. Thus, the ultraviolet energy is converted into heat to be discharged, and the damage of the ultraviolet to the plastic products is avoided.
The synthesis process of the invention is divided into three steps: firstly, synthesizing diazonium salt; secondly, synthesizing an azo compound; and thirdly, reducing the azo compound. Other benzotriazole reductions require two steps (semi-reduction, reduction), thus reducing the synthesis steps.
The absorption intensity peak is 200nm-52nm, the absorption intensity is above 75%, the ultraviolet absorbent synthesized by the patent has wide absorption range and large absorption intensity. The absorption range is 200nm-520nm, and the absorption intensity is more than 75%.
The product synthesis route is as follows:
Claims (10)
1. a method of making 2- (2 '-hydroxy 5' -methoxyphenyl) benzotriazole comprising the steps of:
a. reacting o-nitroaniline with alkali metal nitrite under the conditions of inorganic strong acid and low temperature to synthesize diazonium salt;
b. under the alkaline condition, p-methoxyphenol is dissolved in an aliphatic solvent and coupled with diazonium salt under the low-temperature condition to obtain an azo compound;
c. the azo compound is used for producing a semi-reduction product under the action of a reducing agent under the alkaline condition;
d. the semi-reduction product is put in organic solvent and under the action of metal reducing agent, so that the product is obtained.
2. The process for producing 2- (2 '-hydroxy-5' -methoxyphenyl) benzotriazole according to claim 1, wherein: the strong inorganic acid used is hydrochloric acid or sulfuric acid.
3. The process for producing 2- (2 '-hydroxy-5' -methoxyphenyl) benzotriazole according to claim 1, wherein: the reaction temperature in the a.b step is controlled below 5 ℃.
4. The process for producing 2- (2 '-hydroxy-5' -methoxyphenyl) benzotriazole according to claim 1, wherein: the alkali metal nitrite used includes sodium nitrite or potassium nitrite.
5. The process for producing 2- (2 '-hydroxy-5' -methoxyphenyl) benzotriazole according to claim 1, wherein: the alkaline conditions described are the addition of an amount of NaOH, KOH or Ca (OH) to the solvent2And (4) forming.
6. The process for producing 2- (2 '-hydroxy-5' -methoxyphenyl) benzotriazole according to claim 1, wherein: aliphatic solvents mentioned include cyclohexane, octane, petroleum ether.
7. A manufacture of 2- (2 'according to claim 1'-hydroxy 5' -methoxyphenyl) benzotriazole, characterized in that: reducing agents described include inorganic salts: na (Na)2S、NaHS、NH4HS、(NH4)2S and their mixture, the aldehydes include formaldehyde, acetaldehyde, paraformaldehyde, paraldehyde, reducing sugar, and hydrazine.
8. The process for producing 2- (2 '-hydroxy-5' -methoxyphenyl) benzotriazole according to claim 1, wherein: metallic reducing agents are described as Zn, Sn, Al, Fe and mixtures thereof.
9. The process for producing 2- (2 '-hydroxy-5' -methoxyphenyl) benzotriazole according to claim 1, wherein: the organic solvents mentioned are xylene, toluene, benzene.
10. The process for producing 2- (2 '-hydroxy-5' -methoxyphenyl) benzotriazole according to claim 1, wherein: the molar ratio of the o-nitroaniline to the p-methoxyphenol is 1: 1; the mass ratio of the alkali metal nitrite to the o-nitroaniline is 5-6: 10.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52113974A (en) * | 1976-03-19 | 1977-09-24 | Kawaken Fine Chem Co Ltd | Synthesis of benzotriazole derivatives |
| CN102295613A (en) * | 2010-06-25 | 2011-12-28 | 吉林师范大学 | Method for preparing 2-(2'-hydroxyl 5'-tert-octyl phenyl)benzotriazole |
| CN108026054A (en) * | 2015-07-07 | 2018-05-11 | 3M创新有限公司 | substituted benzotriazole phenol |
| CN109073781A (en) * | 2016-04-21 | 2018-12-21 | 依视路国际公司 | The optical material of benzotriazole UV absorbers comprising red shift |
-
2019
- 2019-12-20 CN CN201911333135.9A patent/CN111057019A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52113974A (en) * | 1976-03-19 | 1977-09-24 | Kawaken Fine Chem Co Ltd | Synthesis of benzotriazole derivatives |
| CN102295613A (en) * | 2010-06-25 | 2011-12-28 | 吉林师范大学 | Method for preparing 2-(2'-hydroxyl 5'-tert-octyl phenyl)benzotriazole |
| CN108026054A (en) * | 2015-07-07 | 2018-05-11 | 3M创新有限公司 | substituted benzotriazole phenol |
| CN109073781A (en) * | 2016-04-21 | 2018-12-21 | 依视路国际公司 | The optical material of benzotriazole UV absorbers comprising red shift |
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Application publication date: 20200424 |