CN104529715A - Preparation method of 3,3',5,5'-tetraalkyl-4,4'-biphenol - Google Patents
Preparation method of 3,3',5,5'-tetraalkyl-4,4'-biphenol Download PDFInfo
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- CN104529715A CN104529715A CN201410798506.1A CN201410798506A CN104529715A CN 104529715 A CN104529715 A CN 104529715A CN 201410798506 A CN201410798506 A CN 201410798506A CN 104529715 A CN104529715 A CN 104529715A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
- C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
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Abstract
The invention discloses a preparation method of 3,3',5,5'-tetraalkyl-4,4'-biphenol. The preparation method comprises the following steps: with 2,6-dialkyl phenol as a raw material, carrying out oxidation coupling in the presence of an oxidant high haloid acid to generate 3,3',5,5'-tetraalkyl-4,4'-diphenoquinone, and then reducing the 3,3',5,5'-tetraalkyl-4,4'-diphenoquinone by a cheap and efficient organic reductant to prepare the 3,3',5,5'-tetraalkyl-4,4'-biphenol. The preparation method is simple in process, short in period, small in amount of by-product, high in yield, simple in equipment and small in investment, has no need for charging oxygen or pressurizing and has industrial application prospect.
Description
Technical field
The invention belongs to Chemicals preparing technical field, be specifically related to a kind of 3,3 ', 5, the preparation method of 5 '-tetraalkyl-4,4 '-'-biphenyl diphenol.
Background technology
3, 3 ', 5, 5 '-tetraalkyl-4, in 4 '-'-biphenyl diphenol representative 3, 3 ', 5, 5 '-tetramethyl--4, 4 '-'-biphenyl diphenol is a kind of yellowish solid, fusing point 223-225 DEG C, 3, 3 ', 5, 5 '-tetraalkyl-4, 4 '-'-biphenyl diphenol is 3, 3 ', 5, 5 '-tetraalkyl-4, the initial reactant of 4 '-biphenyldiglycid ether, 3, 3 ', 5, 5 '-tetraalkyl-4, 4 '-biphenyldiglycid ether can be used as semiconductor packages, it has low melt viscosity, good preservation stability and processing characteristics, its cured article has good cracking resistance line weldability, caking agent can be widely used in, powder coating, epoxy molding plastic etc., especially have a good application prospect in high performance Electronic Packaging field.
3,3 ', 5,5 '-tetramethyl--4,4 '-'-biphenyl diphenol, the preparation of the reaction about it of report at present can adopt single stage method and two-step approach.In single stage method, severe reaction conditions, stir speed (S.S.) 8000-10000r/min, also will blast oxygen or pressurization simultaneously, and the inevitable polyphenylene oxide producing diphenoquinone and differing molecular quality in reaction product.In two-step approach, the first step reaction first generates quinone, and then reduction obtains phenol, but, in the prior art 3,3 ', 5, the preparation method of 5 '-tetramethyl--4,4 '-'-biphenyl diphenol, by product is more, and experimental implementation is more loaded down with trivial details.
Summary of the invention
For solving the shortcoming and defect part of prior art, the object of the present invention is to provide a kind of 3,3 ', 5, the preparation method of 5 '-tetraalkyl-4,4 '-'-biphenyl diphenol, the method synthesis technique is simple, and the cycle is short, and productive rate is high, and by product is few, efficient.
For achieving the above object, the present invention adopts following technical scheme:
A kind of as shown in general formula (1) 3,3 ', 5, the preparation method of 5 '-tetraalkyl-4,4 '-'-biphenyl diphenol,
formula (1), wherein R1, R2 are the straight or branched type alkyl of carbon atom quantity 1 to 10, and R1 and R2 is identical or different, comprises the following steps:
(1) by 2,6-dialkyl group phenol as shown in general formula (2),
formula (2), wherein R3, R4 is the straight or branched type alkyl of carbon atom quantity 1 to 10, R3 and R4 is identical or different, be dissolved in appropriate N, in dinethylformamide (DMF), be warmed up to 70-90 DEG C, then the high hydracid aqueous solution of (dripping off in 5-10min) massfraction 30-40% is slowly dripped, produce when there being bubble in system and precipitate when generating (being generally after starting to drip high hydracid aqueous solution 10min), remove thermal source, continue the product that stirring reaction obtains, 3 shown in general formula (3) are obtained through purifying, 3 ', 5, 5 '-tetraalkyl-4, 4 '-biphenyl diquinone,
formula (3), wherein R5, R6 are the straight or branched type alkyl of carbon atom quantity 1 to 10, and R5 and R6 is identical or different;
(2) 3 shown in the general formula (3) step (1) obtained, 3 ', 5,5 '-tetraalkyl-4,4 '-biphenyl diquinone is dissolved in the industrial spirit of 70-80 DEG C, then inorganic reducing agent and water reaction is added, finally product separation is purified and obtain 3,3 ', 5 shown in general formula (1), 5 '-tetraalkyl-4,4 '-'-biphenyl diphenol.
Preferably, it is 1 part by molfraction 2,6-dialkyl group phenol in step (1); High hydracid in the high hydracid aqueous solution is 0.5-1 part; DMF (DMF) is 5-10 part.
Preferred, described high hydracid is at least one in perchloric acid, Periodic acid and hyperbromic acid.
Preferably, the described system of step (1) produces the time of continuing stirring reaction after bubble removes thermal source with precipitation is 0.5-1h.
Preferably, the method for purification described in step (1) is that water washing and precipitating removes impurity, then uses the NaOH solution washing of 40-50 DEG C, suction filtration, 50 DEG C of vacuum-dryings.
Preferably, by molfraction 3 in step (2), 3 ', 5,5 '-tetraalkyl-4,4 '-biphenyl diquinone is 1 part, and inorganic reducing agent is 5-20 part, industrial spirit 50-100 part, water 10-20 part.
Preferred, described inorganic reducing agent is Na
2sO
3, NaHSO
3, Na
2s
2o
4and Na
2s
2o
3in at least one.
Preferred, described water is deionized water.
Preferably, the described reaction times 1-2h of step (2).
Preferably, the described product separation of step (2) is purified as adding 100-200 molar part frozen water cooling precipitation, filters, 50 DEG C of vacuum-dryings.
Principle of the present invention is: utilize 2,6-dialkyl group phenol to be raw material, generates 3,3 ' by oxygenant height hydracid oxidation coupling, 5,5 '-tetraalkyl-4,4 '-biphenyl diquinone, then obtain 3 by the inorganic reducing agent reduction of Cheap highly effective, 3 ', 5,5 '-tetraalkyl-4,4 '-'-biphenyl diphenol.
Compared with prior art, the present invention has the following advantages and beneficial effect:
The single stage method that contrast is reported at present and two-step approach prepare 3,3 ', 5,5 '-tetraalkyl-4,4 '-'-biphenyl diphenol, the high-efficient oxidant height hydracid that the present invention selects makes combined coefficient greatly improve, productive rate is all more than 90%, especially in substituent R 1, when R2 is different or substituting group is larger, this aspect achieves breakthrough, and single stage method in the past and saline oxidizing agent oxidation two-step approach Patents are when R1, R2 are different or when substituting group is larger, reactive behavior meeting step-down, productive rate can decline a lot (productive rate <60%); In addition, preparation method's synthesis technique of the present invention is simple, and the cycle is extremely short, and by product is few, and efficiently, do not need to blast oxygen or pressurization, the simple less investment of equipment, has the prospect of industrial applications.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of as shown in general formula (1) 3,3 ', 5, the preparation method of 5 '-tetraalkyl-4,4 '-'-biphenyl diphenol, comprises the following steps:
(1) raw material is 2 shown in general formula (2), 6-xylenol 30g is dissolved in 50g N, in dinethylformamide (DMF), be warmed up to 70 DEG C, slowly drip the high chloro acid solution 140g of (5min drips off) massfraction 30%, producing when there being a large amount of bubble in system, when precipitation generates, remove thermal source, continue to stir 1h, the product water washing and precipitating of reaction removes impurity, use 40 DEG C of NaOH solution washings again, suction filtration, 50 DEG C of vacuum-dryings, obtain 3,3 ', 5,5 '-tetramethyl--4,4 '-biphenyl diquinone; Productive rate 90%
(2) by above-mentioned 3,3 ', 5,5 '-tetramethyl--4,4 '-biphenyl diquinone 20g is dissolved in the 100mL industrial spirit of 70 DEG C, add inorganic reducing agent S-WAT 30g and 20mL water, reaction times 1h, product separation is purified as adding 1.5L frozen water cooling precipitation, filter, 50 DEG C of vacuum-dryings, obtain final product, productive rate 95%.
Final product obtained by step (2)
1h-NMR test result is as follows:
1H-NMR(CDCl3,in ppm)：7.15–7.25(d,4H,aromatic)，4.75(2H,OH)，2.25–2.30(s,12H,CH
3)。
Embodiment 2
A kind of as shown in general formula (1) 3,3 ', 5, the preparation method of 5 '-tetraalkyl-4,4 '-'-biphenyl diphenol, comprises the following steps:
(1) raw material is 2 shown in general formula (2), 6-DI-tert-butylphenol compounds 30g is dissolved in 60gN, in dinethylformamide (DMF), be warmed up to 80 DEG C, slowly drip the Periodic acid aqueous solution 70g of (7min drips off) massfraction 30%, producing when there being a large amount of bubble in system, when precipitation generates, remove thermal source, continue to stir 0.5h, the product water washing and precipitating of reaction removes impurity, use 45 DEG C of NaOH solution washings again, suction filtration, 50 DEG C of vacuum-dryings, obtain 3,3 ', 5,5 '-tetra-tert-4,4 '-biphenyl diquinone; Productive rate 90%.
(2) by above-mentioned 3,3 ', 5,5 '-tetra-tert-4,4 '-biphenyl diquinone 20g is dissolved in the 100mL industrial spirit of 75 DEG C, adds inorganic reducing agent V-Brite B (Na
2s
2o
4) 20g and 20mL water, reaction times 1.5h, product separation is purified as adding 2L frozen water cooling precipitation, and filter, 50 DEG C of vacuum-dryings, obtain final product, productive rate 93%.
Final product obtained by step (2)
1h-NMR test result is as follows:
1H-NMR(CDCl3,in ppm)：7.15–7.25(d,4H,aromatic)，5.1(s,2H,OH)，1.41-1.45(s,36H,CH
3)。
Embodiment 3
A kind of as shown in general formula (1) 3,3 ', 5, the preparation method of 5 '-tetraalkyl-4,4 '-'-biphenyl diphenol, comprises the following steps:
(1) raw material is dissolved in 40gN for the 6-tert-butyl o cresylol 30g shown in general formula (2), in dinethylformamide (DMF), be warmed up to 90 DEG C, the Periodic acid aqueous solution 50g of slow dropping (10min drips off) massfraction 40%, produce when there being a large amount of bubble in system, when precipitation generates, remove thermal source, continue to stir 0.5h, the product water washing and precipitating of reaction removes impurity, use 50 DEG C of NaOH solution washings again, suction filtration, 50 DEG C of vacuum-dryings, obtain 3,5 '-di-t-butyl-5,3 '-dimethyl diphenyl diquinone; Productive rate 90%
(2) by above-mentioned 3,5 '-di-t-butyl-5,3 '-dimethyl diphenyl diquinone 20g is dissolved in the 100mL industrial spirit of 80 DEG C, adds inorganic reducing agent V-Brite B (Na
2s
2o
4) 15g and 20mL water, reaction times 2h, product separation is purified as adding 1L frozen water cooling precipitation, and filter, 50 DEG C of vacuum-dryings, obtain final product.
Final product obtained by step (2)
1h-NMR test result is as follows:
1H-NMR(CDCl3,in ppm)：7.15–7.25(d,4H,aromatic)，4.75(s,2H,OH)，2.25–2.30(s,6H,CH
3)，1.41-1.45(s,18H,CH
3)。
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. one kind as shown in general formula (1) 3,3 ', 5, the preparation method of 5 '-tetraalkyl-4,4 '-'-biphenyl diphenol,
formula (1), wherein R1, R2 are the straight or branched type alkyl of carbon atom quantity 1 to 10, and R1 and R2 is identical or different, it is characterized in that, described preparation method comprises the following steps:
(1) by 2,6-dialkyl group phenol as shown in general formula (2),
formula (2), wherein R3, R4 are the straight or branched type alkyl of carbon atom quantity 1 to 10, R3 and R4 is identical or different, is dissolved in DMF, be warmed up to 70-90 DEG C, then in 5-10min, drip the high hydracid aqueous solution of massfraction 30-40%, when producing when there being bubble in system and precipitate generation, removing thermal source, continue the product that stirring reaction obtains, obtaining 3 shown in general formula (3) through purifying, 3 ', 5,5 '-tetraalkyl-4,4 '-biphenyl diquinone
formula (3), wherein R5, R6 are the straight or branched type alkyl of carbon atom quantity 1 to 10, and R5 and R6 is identical or different;
(2) 3 shown in the general formula (3) step (1) obtained, 3 ', 5,5 '-tetraalkyl-4,4 '-biphenyl diquinone is dissolved in the industrial spirit of 70-80 DEG C, then inorganic reducing agent and water reaction is added, finally product separation is purified and obtain 3,3 ', 5 shown in general formula (1), 5 '-tetraalkyl-4,4 '-'-biphenyl diphenol.
2. preparation method according to claim 1, is characterized in that, pressing molar basis 2,6-dialkyl group phenol in step (1) is 1 part; High hydracid in the high hydracid aqueous solution is 0.5-1 part; DMF is 5-10 part.
3. preparation method according to claim 2, is characterized in that, described high hydracid is at least one in perchloric acid, Periodic acid and hyperbromic acid.
4. preparation method according to claim 1, is characterized in that, it is 0.5-1h that the described system of step (1) produces the time of continuing stirring reaction after bubble removes thermal source with precipitation.
5. preparation method according to claim 1, is characterized in that, the method for purification described in step (1) is that water washing and precipitating removes impurity, then uses the NaOH solution washing of 40-50 DEG C, suction filtration, 50 DEG C of vacuum-dryings.
6. preparation method according to claim 1, is characterized in that, in step (2) by mol 3,3 ', 5,5 '-tetraalkyl-4,4 '-biphenyl diquinone is 1 part, and inorganic reducing agent is 5-20 part, industrial spirit 50-100 part, water 10-20 part.
7. preparation method according to claim 6, is characterized in that, described inorganic reducing agent is Na
2sO
3, NaHSO
3, Na
2s
2o
4and Na
2s
2o
3in at least one.
8. preparation method according to claim 6, is characterized in that, described water is deionized water.
9. preparation method according to claim 1, is characterized in that, the described reaction times 1-2h of step (2).
10. preparation method according to claim 1, is characterized in that, the described product separation of step (2) is purified as adding 100-200 molar part frozen water cooling precipitation, filters, 50 DEG C of vacuum-dryings.
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| CN201410798506.1A CN104529715A (en) | 2014-12-18 | 2014-12-18 | Preparation method of 3,3',5,5'-tetraalkyl-4,4'-biphenol |
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| CN201410798506.1A CN104529715A (en) | 2014-12-18 | 2014-12-18 | Preparation method of 3,3',5,5'-tetraalkyl-4,4'-biphenol |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107304164A (en) * | 2017-03-20 | 2017-10-31 | 哈尔滨工业大学（威海） | A kind of green synthesis method of biphenyl quinones |
| CN111960927A (en) * | 2020-08-28 | 2020-11-20 | 湖南长岭石化科技开发有限公司 | Method for preparing 3,3',5,5' -tetraalkyl-4, 4' -biphenol by catalytic hydrogenation |
| CN113683486A (en) * | 2021-09-10 | 2021-11-23 | 江苏越科新材料有限公司 | Preparation method of 2,2 ', 6,6 ' -tetramethyl-4, 4 ' -biphenol |
| CN114292176A (en) * | 2021-12-08 | 2022-04-08 | 广东省科学院化工研究所 | Preparation method of biphenyl diquinone derivative |
| CN115677455A (en) * | 2022-11-15 | 2023-02-03 | 广东省科学院化工研究所 | Preparation method of tetraalkyl diphenol |
Citations (2)
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|---|---|---|---|---|
| US3631208A (en) * | 1966-06-10 | 1971-12-28 | Gen Electric | Coupling of phenols with diphenoquinones |
| CN1706782A (en) * | 2005-04-30 | 2005-12-14 | 中国科学院广州化学研究所 | Prepn process of 3,3',5,5'-tetraalkyl-4,4'-diphenol |
-
2014
- 2014-12-18 CN CN201410798506.1A patent/CN104529715A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3631208A (en) * | 1966-06-10 | 1971-12-28 | Gen Electric | Coupling of phenols with diphenoquinones |
| CN1706782A (en) * | 2005-04-30 | 2005-12-14 | 中国科学院广州化学研究所 | Prepn process of 3,3',5,5'-tetraalkyl-4,4'-diphenol |
Non-Patent Citations (1)
| Title |
|---|
| 贾志梅: "以联苯二醌衍生物为ETM的单层多组份有机光导体的研究", 《中国优秀硕士学位论文全文数据库(电子期刊)》, no. 08, 15 August 2006 (2006-08-15), pages 135 - 8 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107304164A (en) * | 2017-03-20 | 2017-10-31 | 哈尔滨工业大学（威海） | A kind of green synthesis method of biphenyl quinones |
| CN111960927A (en) * | 2020-08-28 | 2020-11-20 | 湖南长岭石化科技开发有限公司 | Method for preparing 3,3',5,5' -tetraalkyl-4, 4' -biphenol by catalytic hydrogenation |
| CN113683486A (en) * | 2021-09-10 | 2021-11-23 | 江苏越科新材料有限公司 | Preparation method of 2,2 ', 6,6 ' -tetramethyl-4, 4 ' -biphenol |
| CN114292176A (en) * | 2021-12-08 | 2022-04-08 | 广东省科学院化工研究所 | Preparation method of biphenyl diquinone derivative |
| CN114292176B (en) * | 2021-12-08 | 2023-07-18 | 广东省科学院化工研究所 | Preparation method of biphenyl diquinone derivative |
| CN115677455A (en) * | 2022-11-15 | 2023-02-03 | 广东省科学院化工研究所 | Preparation method of tetraalkyl diphenol |
| CN115677455B (en) * | 2022-11-15 | 2023-12-05 | 广东省科学院化工研究所 | Preparation method of tetraalkyl diphenol |
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