CN106008381A - Method for preparing benzotriazole-alkylene bisphenol compound - Google Patents
Method for preparing benzotriazole-alkylene bisphenol compound Download PDFInfo
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- CN106008381A CN106008381A CN201610387787.0A CN201610387787A CN106008381A CN 106008381 A CN106008381 A CN 106008381A CN 201610387787 A CN201610387787 A CN 201610387787A CN 106008381 A CN106008381 A CN 106008381A
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- benzotriazole base
- alkylidene bisphenols
- bisphenols compound
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- 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
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Abstract
The invention discloses a method for preparing a benzotriazole-alkylene bisphenol compound, and is characterized in that the method comprises the following steps: step 1, dissolving a first part of UV-P, dialkyl amine and paraformaldehyde in an alcohol solvent, and carrying out a stirring reaction at the temperature of 95-105 DEG C; step 2, after stirring for 24 h, drying the alcohol solvent by distillation in vacuum, to obtain an intermediate; step 3, dissolving the intermediate and a second part of UV-P in an aromatic hydrocarbon or alkane solvent, adding sodium methylate, heating the solution to 140-150 DEG C, and carrying out a reflux reaction for 10 h; step 4, after the reaction is finished, steaming out a part of the aromatic hydrocarbon or alkane solvent, and cooling and crystallizing to obtain a crude product; and step 5, recrystallizing the crude product to obtain a white solid, wherein the UV-P has the structural formula represented by the formula I, the white solid has the structural formula represented by the formula II. The preparation method has the beneficial effect of good yield.
Description
Technical field
The present invention relates to the preparation method field of bisphenol compound, particularly to a kind of benzotriazole base-alkylidene bisphenols compound
Preparation method.
Background technology
Benzotriazole base-alkylidene bisphenols compound both the most also can also can have as antioxidant as light stabilizer
There are highly lipophilic and excellent volatility resistance.When using benzotriazole base-alkylidene bisphenols in the organic materials such as synthetic resin
After compound, also can effectively be protected even if organic material is exposed in air and light continuously for a long time.
The Chinese patent of Publication No. 1188110 discloses a kind of benzotriazole base-alkylidene bisphenols compound, its preparation method,
And the stable organic material containing them.This patent is by 2-hydroxy phenyl benzotriazole and 2, and the substituted phenol of 4-and aldehyde are at alkali
React to obtain benzotriazole base-alkylidene bisphenols compound in the presence of property catalyst and organic amine.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of benzotriazole base-alkylidene bisphenols compound.This preparation method has
Good yield.
The above-mentioned technical purpose of the present invention has the technical scheme that
The preparation method of a kind of benzotriazole base-alkylidene bisphenols compound, comprises the steps:
Step 1: first part of UV-P, dialkylamine, paraformaldehyde are dissolved in alcohols solvent, stirring reaction at 95-105 DEG C；
Step 2: after stirring 24h, be evaporated alcohols solvent under vacuo, obtain intermediate；
Step 3: intermediate and second part of UV-P are dissolved in aromatic hydrocarbons or alkane solvents, adds Feldalat NM, is heated to by solution
140-150 DEG C, back flow reaction 10h；
Step 4: after reaction terminates, steaming part aromatic hydrocarbons or alkane solvents, crystallisation by cooling obtains crude product；
Step 5: crude product obtains white solid after carrying out recrystallization；
UV-P structural formula is shown in formula I:
White solid structural formula is as shown in Formula II:
As preferably, according to mol ratio, described first part of UV-P: dialkylamine=1: 1.2-1.5.
As preferably, according to mass ratio, described first part of UV-P: paraformaldehyde=4-5:1.
As preferably, described dialkylamine selects the one in diethylamine, di-n-propylamine and dibutyl amine.
As preferably, described alcohols solvent selects the one in amylalcohol, isobutanol, isoamyl alcohol and butanol, described first part of UV-P
It is 0.375g/ml with the mass volume ratio of alcohols solvent.
As preferably, according to mol ratio, described intermediate: second part UV-P=1: 1.
As preferably, described Feldalat NM adds as a solution, contains the methanol of 28%wt, press in described sodium methoxide solution
According to mol ratio, described intermediate: Feldalat NM=2.5: 1.
As preferably, described aromatic hydrocarbons or alkane solvents select the one in nonane, 1，2，4-trimethylbenzene, o-Dimethylbenzene, institute
The mass volume ratio stating intermediate and aromatic hydrocarbons or alkane solvents is 0.23g/ml.
As preferably, described recrystallization use normal hexane as solvent.
As preferably, after part aromatic hydrocarbons or alkane solvents steam, crude product solution reaches saturated.
In sum, the method have the advantages that
1, preparation process being undertaken in two steps, first part of UV-P and paraformaldehyde are reacted in the presence of organic amine and obtain centre by the first step
Body, intermediate and second part of UV-P in sodium methoxide catalyzed lower reaction, thus can be reduced the reaction temperature of first step reaction by second step
Degree, reduces the generation of side reaction, improves yield.
2, water is had to generate in first step course of reaction, although first step reaction end carries out evaporated in vacuo, but due to water
Boiling point is higher, causes water to be often difficult to eliminate, and uses anti-as catalyst intermediate and second part of UV-P of Feldalat NM
Should, then Feldalat NM can react generation methanol and sodium hydroxide with the water not eliminated.
Detailed description of the invention
This specific embodiment is only explanation of the invention, and it is not limitation of the present invention, and those skilled in the art exist
As required the present embodiment can be made after reading this specification and there is no the amendment of creative contribution, but as long as the present invention's
All protected by Patent Law in right.
If no special instructions, the reagent used in the embodiment of the present invention is purchased from Aladdin.
The production code member of the paraformaldehyde in embodiment is C104190.
UV-P structural formula is shown in formula I:
White solid structural formula is as shown in Formula II:
The Feldalat NM that embodiment 1-5 uses adds the most in the form of a solution, contains the methanol of 28%wt in sodium methoxide solution.
Embodiment 1
The preparation method of a kind of benzotriazole base-alkylidene bisphenols compound, comprises the steps:
Step 1: UV-P 225g, diethylamine 88g, paraformaldehyde 56g are dissolved in 600mL amylalcohol solvent, at 95-105 DEG C
Lower stirring reaction；
Step 2: after stirring 24h, being evaporated amylalcohol under vacuo, obtain intermediate 298.84g, yield is 96.4%；
Step 3: be dissolved in o-Dimethylbenzene 196mL solvent by intermediate 33.8g and UV-P 22.5g, adds 3g sodium methoxide solution,
Solution is heated to 140-150 DEG C, back flow reaction 10h；
Step 4: after reaction terminates, steaming part o-Dimethylbenzene and make solution reach saturated, crystallisation by cooling obtains crude product 42.27g, and yield is
91.5%:
Step 5: crude product normal hexane obtains white solid 40.98g after carrying out recrystallization, and yield is 88.7%.
The result of elementary analysis C, H, N and O of white solid approximates with value of calculation, as shown in the table.
| Element | Value of calculation (%) | Actual value (%) |
| Carbon | 70.12 | 70.15 |
| Hydrogen | 4.79 | 4.76 |
| Nitrogen | 18.17 | 18.16 |
| Oxygen | 6.92 | 6.93 |
Embodiment 2
The preparation method of a kind of benzotriazole base-alkylidene bisphenols compound, comprises the steps:
Step 1: UV-P 225g, dibutyl amine 168g, paraformaldehyde 45g are dissolved in 600mL iso-butanol solvent, at 95-105 DEG C
Lower stirring reaction；
Step 2: after stirring 24h, being evaporated isobutanol under vacuo, obtain intermediate 354.65g, yield is 96.9%；
Step 3: be dissolved in 1，2，4-trimethylbenzene 196mL solvent by intermediate 33.8g and UV-P 22.5g, adds 3g Feldalat NM
Solution, is heated to 140-150 DEG C, back flow reaction 10h by solution；
Step 4: after reaction terminates, steaming part 1，2，4-trimethylbenzene and make solution reach saturated, crystallisation by cooling obtains crude product 42.6g, receives
Rate is 92.2%；
Step 5: crude product normal hexane obtains white solid 41.16g after carrying out recrystallization, and yield is 89.1%.
The result of elementary analysis C, H, N and O of white solid approximates with value of calculation, as shown in the table.
| Element | Value of calculation (%) | Actual value (%) |
| Carbon | 70.12 | 70.07 |
| Hydrogen | 4.79 | 4.83 |
| Nitrogen | 18.17 | 18.14 |
| Oxygen | 6.92 | 6.96 |
Embodiment 3
The preparation method of a kind of benzotriazole base-alkylidene bisphenols compound, comprises the steps:
Step 1: UV-P 225g, di-n-propylamine 141g, paraformaldehyde 56g are dissolved in 600mL isoamyl alcohol solvent, at 95-105 DEG C
Lower stirring reaction；
Step 2: after stirring 24h, being evaporated isoamyl alcohol under vacuo, obtain intermediate 331.92g, yield is 98.2%；
Step 3: be dissolved in nonane 196mL solvent by intermediate 33.8g and UV-P 22.5g, adds 3g sodium methoxide solution, by molten
Liquid is heated to 140-150 DEG C, back flow reaction 10h；
Step 4: after reaction terminates, steam part nonane and make solution reach saturated, crystallisation by cooling obtains crude product 42.83g, and 92.7%；
Step 5: crude product normal hexane obtains white solid 41.26g, yield 89.3% after carrying out recrystallization.
The result of elementary analysis C, H, N and O of white solid approximates with value of calculation, as shown in the table.
| Element | Value of calculation (%) | Actual value (%) |
| Carbon | 70.12 | 70.13 |
| Hydrogen | 4.79 | 4.82 |
| Nitrogen | 18.17 | 18.15 |
| Oxygen | 6.92 | 6.90 |
Embodiment 4
The preparation method of a kind of benzotriazole base-alkylidene bisphenols compound, comprises the steps:
Step 1: UV-P 225g, di-n-propylamine 152g, paraformaldehyde 45g are dissolved in 600mL butanol solvent, at 95-105 DEG C
Lower stirring reaction；
Step 2: after stirring 24h, be evaporated butanol under vacuo, obtain intermediate 332.93g, yield 98.5%；
Step 3: be dissolved in 1，2，4-trimethylbenzene 196mL solvent by intermediate 33.8g and UV-P 22.5g, adds 3g Feldalat NM
Solution, is heated to 140-150 DEG C, back flow reaction 10h by solution；
Step 4: after reaction terminates, steaming part 1，2，4-trimethylbenzene and make solution reach saturated, crystallisation by cooling obtains crude product 42.92g, receives
Rate is 92.9%；
Step 5: crude product normal hexane obtains white solid 41.53g after carrying out recrystallization, and yield is 89.9%.
The result of elementary analysis C, H, N and O of white solid approximates with value of calculation, as shown in the table.
| Element | Value of calculation (%) | Actual value (%) |
| Carbon | 70.12 | 70.08 |
| Hydrogen | 4.79 | 4.83 |
| Nitrogen | 18.17 | 18.16 |
| Oxygen | 6.92 | 6.93 |
Embodiment 5
The preparation method of a kind of benzotriazole base-alkylidene bisphenols compound, comprises the steps:
Step 1: UV-P 225g, diethylamine 110g, paraformaldehyde 51.8g are dissolved in 600mL butanol solvent, at 95-105 DEG C
Lower stirring reaction；
Step 2: after stirring 24h, being evaporated butanol under vacuo, obtain intermediate 307.21g, yield is 99.1%；
Step 3: be dissolved in o-Dimethylbenzene 196mL solvent by intermediate 33.8g and UV-P 22.5g, adds 3g sodium methoxide solution,
Solution is heated to 140-150 DEG C, back flow reaction 10h；
Step 4: after reaction terminates, steaming part o-Dimethylbenzene and make solution reach saturated, crystallisation by cooling obtains crude product 43.15g, and yield is
93.4%:
Step 5: crude product normal hexane obtains white solid 41.76g after carrying out recrystallization, and yield is 90.4%.
The result of elementary analysis C, H, N and O of white solid approximates with value of calculation, as shown in the table.
| Element | Value of calculation (%) | Actual value (%) |
| Carbon | 70.12 | 70.11 |
| Hydrogen | 4.79 | 4.74 |
| Nitrogen | 18.17 | 18.15 |
| Oxygen | 6.92 | 7.00 |
Claims (10)
1. a preparation method for benzotriazole base-alkylidene bisphenols compound, is characterized in that: comprise the steps:
Step 1: first part of UV-P, dialkylamine, paraformaldehyde are dissolved in alcohols solvent, stirring reaction at 95-105 DEG C；
Step 2: after stirring 24h, be evaporated alcohols solvent under vacuo, obtain intermediate；
Step 3: intermediate and second part of UV-P are dissolved in aromatic hydrocarbons or alkane solvents, adds Feldalat NM, is heated to by solution
140-150 DEG C, back flow reaction 10h；
Step 4: after reaction terminates, steaming part aromatic hydrocarbons or alkane solvents, crystallisation by cooling obtains crude product；
Step 5: crude product obtains white solid after carrying out recrystallization；
UV-P structural formula is shown in formula I:
White solid structural formula is as shown in Formula II:
The preparation method of benzotriazole base-alkylidene bisphenols compound the most according to claim 1, is characterized in that: according to mol ratio,
Described first part of UV-P: dialkylamine=1: 1.2-1.5.
The preparation method of benzotriazole base-alkylidene bisphenols compound the most according to claim 1, is characterized in that: according to mass ratio,
Described first part of UV-P: paraformaldehyde=4-5: 1.
The preparation method of benzotriazole base-alkylidene bisphenols compound the most according to claim 1, is characterized in that: described dialkyl group
Amine selects the one in diethylamine, di-n-propylamine and dibutyl amine.
The preparation method of benzotriazole base-alkylidene bisphenols compound the most according to claim 1, is characterized in that: described alcohols is molten
The one in amylalcohol, isobutanol, isoamyl alcohol and butanol, described first part of UV-P and the mass volume ratio of alcohols solvent are selected in agent
For 0.375g/ml.
The preparation method of benzotriazole base-alkylidene bisphenols compound the most according to claim 1, is characterized in that: according to mol ratio,
Described intermediate: second part UV-P=1: 1.
The preparation method of benzotriazole base-alkylidene bisphenols compound the most according to claim 1, is characterized in that: described Feldalat NM
Add as a solution, described sodium methoxide solution contains the methanol of 28%wt, according to mol ratio, described intermediate: methanol
Sodium=2.5: 1.
The preparation method of described benzotriazole base-alkylidene bisphenols compound the most according to claim 1, is characterized in that: described
Aromatic hydrocarbons or alkane solvents select the one in nonane, 1，2，4-trimethylbenzene, o-Dimethylbenzene, described intermediate and aromatic hydrocarbons or alkane
The mass volume ratio of kind solvent is 0.23g/ml.
The preparation method of described benzotriazole base-alkylidene bisphenols compound the most according to claim 1, is characterized in that: described
Recrystallization use normal hexane as solvent.
The preparation method of described benzotriazole base-alkylidene bisphenols compound the most according to claim 1, is characterized in that: when
After part aromatic hydrocarbons or alkane solvents steam, crude product solution reaches saturated.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4681905A (en) * | 1984-11-07 | 1987-07-21 | Adeka Argus Chemical Co., Ltd. | Stabilizer compositions for synthetic resins imparting improved light stability |
| US4937348A (en) * | 1984-11-09 | 1990-06-26 | Adeka Argus Chemical Co., Ltd. | Process for preparing 2,2'-methylene-bis-(4-hydrocarbyl-6-benzotriazolylphenols) |
| JPH0339326A (en) * | 1989-07-06 | 1991-02-20 | Mitsubishi Gas Chem Co Inc | Copolycarbonate resin and production thereof |
| US5237071A (en) * | 1991-01-22 | 1993-08-17 | Fairmount Chemical Company, Inc. | Process for preparing 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-hydrocarbyl phenols) |
| JPH05310713A (en) * | 1992-05-13 | 1993-11-22 | Asahi Denka Kogyo Kk | Treatment of benzotriazole compound |
| US5360692A (en) * | 1992-06-04 | 1994-11-01 | Fuji Photo Film Co., Ltd. | Positive type 1,2-naphthoquinonediazide photoresist composition containing benzotriazole light absorbing agent |
| US5808086A (en) * | 1996-07-31 | 1998-09-15 | Johoku Chemical Co., Ltd. | Process for preparing bis (2-hydroxyphenyl-3-benztriazole) methanes |
-
2016
- 2016-06-01 CN CN201610387787.0A patent/CN106008381A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4681905A (en) * | 1984-11-07 | 1987-07-21 | Adeka Argus Chemical Co., Ltd. | Stabilizer compositions for synthetic resins imparting improved light stability |
| US4937348A (en) * | 1984-11-09 | 1990-06-26 | Adeka Argus Chemical Co., Ltd. | Process for preparing 2,2'-methylene-bis-(4-hydrocarbyl-6-benzotriazolylphenols) |
| JPH0339326A (en) * | 1989-07-06 | 1991-02-20 | Mitsubishi Gas Chem Co Inc | Copolycarbonate resin and production thereof |
| US5237071A (en) * | 1991-01-22 | 1993-08-17 | Fairmount Chemical Company, Inc. | Process for preparing 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-hydrocarbyl phenols) |
| JPH05310713A (en) * | 1992-05-13 | 1993-11-22 | Asahi Denka Kogyo Kk | Treatment of benzotriazole compound |
| US5360692A (en) * | 1992-06-04 | 1994-11-01 | Fuji Photo Film Co., Ltd. | Positive type 1,2-naphthoquinonediazide photoresist composition containing benzotriazole light absorbing agent |
| US5808086A (en) * | 1996-07-31 | 1998-09-15 | Johoku Chemical Co., Ltd. | Process for preparing bis (2-hydroxyphenyl-3-benztriazole) methanes |
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Application publication date: 20161012 |