CN104557752A - Synthetic method of 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione compound - Google Patents

Synthetic method of 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione compound Download PDF

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CN104557752A
CN104557752A CN201310467452.6A CN201310467452A CN104557752A CN 104557752 A CN104557752 A CN 104557752A CN 201310467452 A CN201310467452 A CN 201310467452A CN 104557752 A CN104557752 A CN 104557752A
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tertiary butyl
synthetic method
dimethyl
hydroxyl
described step
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CN104557752B (en
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陈达
洪镛裕
刘乃兴
苏云清
石婷婷
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East China Normal University
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East China Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C07D251/32—Cyanuric acid; Isocyanuric acid

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a synthetic method of a 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione compound, wherein the synthetic method comprises the steps of adding DMF, cyanuric acid and triethylamine into a reaction kettle, then heating up to 80-100 DEG C, next dropwise adding a mixed solution of 4-tert-butyl-2,6-dimethyl-3-hydroxy benzyl chloride and DMF, after reaction, filtering, evaporating to dryness, dissolving with methanol and precipitating, and thus obtaining the synthetic product. The synthetic method has the advantages of simple operation, short reaction time, few by-products, and high product yield.

Description

The synthetic method of 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-3 ketone
Technical field
The present invention relates to a kind of production method of Chemicals, particularly relate to a kind of 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4, the process synthetic method of 6 (1H, 3H, 5H)-triketones (antioxidant TH-1790).
Background technology
1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketones, trade name is antioxidant TH-1790, its traditional preparation method is: disposable mixed solution, triethylamine and the tricyanic acid adding the 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride and DMF in reactor, stirring reaction 18 hours under 40 degree.This kind of method reaction times is long especially, is applied to industrial energy consumption higher, and the by product of reaction is also more.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides a kind of preparation 1,3 newly, 5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6 (1H, 3H, the synthetic method of 5H)-3 ketone, the method shortens the reaction times, decreases the energy consumption in industrial application, improves reaction yield.
The synthetic method of the present invention 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-3 ketone, comprises the steps:
(1) the preparation feedback intermediate 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride
(1) add concentrated hydrochloric acid and the 2-tertiary butyl-4,6 xylenol in reactor, add paraformaldehyde under stirring, then heat up, insulation reaction;
(2) drip phosphorus trichloride, control still temperature 30-50 DEG C, insulation reaction;
(3) add toluene, use saturated common salt water washing at organic phase 30 DEG C, toluene is to the greatest extent steamed in decompression, obtains the described 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride.
The synthesis of (two) 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-3 ketone
Disposablely in a kettle. add DMF and tricyanic acid, add triethylamine under stirring, then heat up.The mixed solution of previously prepared for step () the good 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride and DMF is instilled wherein, insulation reaction, filtered at room temperature desalts, solvent evaporated, after dissolve with methanol is separated out, obtain product, i.e. described 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-3 ketones.
The present invention synthesizes 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6 (1H, 3H, the 5H)-3 ketone obtained, its molecular formula C 42h 57n 3o 6, structural formula is as follows
In synthetic method of the present invention, in described step (), the preparation of the 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride in described step (1), warming temperature is 30-50 DEG C, and soaking time is 3-5 hour.Preferably, above-mentioned warming temperature is 35-40 DEG C, and soaking time is 3.5-4.5 hour.
In described step (), in described step (2), warming temperature is 80-100 DEG C.
In described step (), in described step (2), holding temperature is 100-120 DEG C, and soaking time is 5 hours.
In synthetic method of the present invention, in described step (two), the time for adding of the described 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride and DMF mixed solution is 1.5-2 hour, and adding the Precipitation Temperature after methyl alcohol is 1-2 DEG C.
In building-up reactions of the present invention, reactant molar ratio tricyanic acid: the 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride: triethylamine is 1:3 ~ 4:3 ~ 4.5.Preferably, reactant molar ratio tricyanic acid: the 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride: triethylamine is 1:3 ~ 3.5:3.2 ~ 4.
In building-up reactions of the present invention, the solvent that evaporate to dryness step adopts is DMF, can recycle.
The reaction scheme of building-up reactions of the present invention is as follows:
Compared with prior art, the reaction times of the present invention is short, and industrial energy consumption is low, and the by product that reaction produces is few, and the purity of product is high, and reaction yield is high.
Embodiment
In conjunction with following specific embodiment, the present invention is described in further detail, and protection content of the present invention is not limited to following examples.Under the spirit and scope not deviating from inventive concept, the change that those skilled in the art can expect and advantage are all included in the present invention, and are protection domain with appending claims.Implement process of the present invention, condition, reagent, experimental technique etc., except the following content mentioned specially, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.
The synthetic method of the present invention 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-3 ketone:
Step (one), adds concentrated hydrochloric acid and the 2-tertiary butyl-4,6 xylenol in a kettle., adds paraformaldehyde, then heat up under stirring, and is incubated 2 hours at this temperature.After insulation terminates, start to drip phosphorus trichloride, control still temperature 30-50 DEG C, within about 1 hour, drip off, and insulation reaction at this temperature.Add toluene after reaction terminates, use saturated common salt water washing at organic phase 30 DEG C, decompression is steamed toluene to the greatest extent and is namely obtained the 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride;
Step (two), disposablely in a kettle. adds DMF and tricyanic acid, adds triethylamine, then heat up under stirring.The mixed solution of previously prepared for step () the good 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride and DMF is instilled wherein, insulation reaction, filtered at room temperature desalts, solvent evaporated, after dissolve with methanol is separated out, obtain product, i.e. described 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-3 ketones.
The synthesis of embodiment 11, the 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride
Disposablely in reaction flask to add: 32% hydrochloric acid 49g and the 2-tertiary butyl-4,6 xylenol 49g, adds paraformaldehyde 13.1g, be then warming up to 37 DEG C under stirring, and be incubated 2 hours at this temperature, TLC follows the tracks of reaction and terminates.After insulation terminates, start to drip phosphorus trichloride 17.3g, control still temperature 40 DEG C, within about 1 hour, drip off, and be incubated about 4 hours at this temperature, TLC follows the tracks of reaction and terminates.
Add 50g toluene after reaction terminates, leave standstill 20min, point sub-cloud aqueous phase after stirring 15min, with saturated common salt water washing (20mlx2 time) at organic phase 30 DEG C, toluene is to the greatest extent steamed in decompression.
Be chilled to 35-40 DEG C, and control to instill DMF (having heat release) at such a temperature.10min is stirred again after dripping off.Reaction solution is directly used in next step reaction.
The synthesis of embodiment 21,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketone
Disposablely in reaction flask to add: DMF39g and tricyanic acid 10.5g, triethylamine 40.5g is added, when being then warming up to 90 DEG C, by previously prepared good 1 under stirring, the 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride 62.3g and the instillation of DMF32.7g mixed solution are wherein.Have tiny backflow in process, and still temperature slowly can raise, require to be no more than 102 DEG C, within about 11/2 hour, drip off.Then at 100-120 DEG C of insulation reaction 5 hours, TLC follows the tracks of reaction and terminates.
After reaction terminates, filtered at room temperature desalts, and a small amount of DMF drip washing, is filtered dry.Reclaim under reduced pressure is solvent to the greatest extent, adds 115g methyl alcohol, steams 60g under atmospheric pressure reflux, be down to 1-2 DEG C and filter after keeping 30min, a small amount of cold methanol drip washing is filtered dry, and obtains product 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketone, yield 85%, HPLC content 96.5%, fusing point 159-166 DEG C, appearance white, 1H-NMR (D 2o) 6:1.34 (27, S), 2.35 (18, S), 4.42 (6, S) 5.0 (3, S), 6.61 (3, S).

Claims (9)

  1. The synthetic method of 1.3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-3 ketone, is characterized in that, comprise the following steps:
    (1) synthesis of the 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride:
    (1) add concentrated hydrochloric acid and the 2-tertiary butyl-4,6 xylenol in reactor, add paraformaldehyde under stirring, then heat up, insulation reaction;
    (2) drip phosphorus trichloride, control still temperature 30-50 DEG C, insulation reaction;
    (3) add toluene, use saturated common salt water washing at organic phase 30 DEG C, toluene is to the greatest extent steamed in decompression, obtains the described 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride;
    (2) synthesis of product:
    Disposablely in reactor add DMF and tricyanic acid, add triethylamine under stirring, then heat up, the 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride step () prepared and DMF mixed solution instill wherein, insulation reaction, filtered at room temperature desalts, solvent evaporated, after dissolve with methanol is separated out, obtain described 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-3 ketones.
  2. 2. synthetic method as claimed in claim 1, it is characterized in that, in step (), the warming temperature in described step (1) is 30-50 DEG C.
  3. 3. synthetic method as claimed in claim 1, is characterized in that, in step (), in described step (2), soaking time is 3-5 hour.
  4. 4. 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2 as claimed in claim 1,6-dimethyl benzyl)-1,3,5-triazines-2,4, the synthetic method of 6 (1H, 3H, 5H)-3 ketones, it is characterized in that, in described step (two), described reactant tricyanic acid: the 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride: the mol ratio of triethylamine is 1:3 ~ 4:3 ~ 4.5.
  5. 5. 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2 as claimed in claim 4,6-dimethyl benzyl)-1,3,5-triazines-2,4, the synthetic method of 6 (1H, 3H, 5H)-3 ketones, it is characterized in that, in described step (two), described reactant tricyanic acid: the 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride: the mol ratio of triethylamine is 1:3 ~ 3.5:3.2 ~ 4.
  6. 6. synthetic method as claimed in claim 1, it is characterized in that, in described step (two), the time for adding of the described 4-tertiary butyl-2,6-dimethyl-3-hydroxyl benzyl chloride and DMF mixed solution is 1.5-2 hour.
  7. 7. synthetic method as claimed in claim 1, it is characterized in that, the warming temperature in described step (two) is 80-100 DEG C.
  8. 8. synthetic method as claimed in claim 1, it is characterized in that, the holding temperature in described step (two) is 100-120 DEG C; Soaking time is 5 hours.
  9. 9. synthetic method as claimed in claim 1, it is characterized in that, in described step (two), adding the Precipitation Temperature after methyl alcohol is 1-2 DEG C.
CN201310467452.6A 2013-10-09 2013-10-09 The synthetic method of 1,3,5 3 (dimethyl benzyl of 4 tert-butyl group, 3 hydroxyl 2,6) 1,3,5 triazine 2,4,6 (1H, 3H, 5H) 3 ketone Expired - Fee Related CN104557752B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106699678A (en) * 2016-12-26 2017-05-24 兰州精细化工高新技术开发公司 Synthesis method of antioxidant 1790
CN109912524A (en) * 2019-04-05 2019-06-21 南通大学 A kind of preparation method of hindered phenol anti-oxidants
CN114409960A (en) * 2022-01-21 2022-04-29 深圳市那鸿科技有限公司 Flame-retardant/antioxidant synergistic additive, synthetic method thereof and application thereof in recycling PET

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3795700A (en) * 1971-03-10 1974-03-05 American Cyanamid Co Esters of 4-alkyl-2,6-dimethyl-3-hydroxybenzyl alcohol
US3862053A (en) * 1971-11-16 1975-01-21 American Cyanamid Co Hindered tris (meta-hydroxybenzyl)cyanurate antioxidants
BE791369A (en) * 1971-11-16 1973-05-14 American Cyanamid Co TRIS- (META-HYDROXYBENZYL) CYANURATES SUBJECT TO STERIC PREVENTION AND USE AS ANTI-OXIDANTS
CN101684067B (en) * 2008-09-26 2012-07-18 中钢集团鞍山热能研究院有限公司 Clean production method of antioxidant 1790 intermediate

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106699678A (en) * 2016-12-26 2017-05-24 兰州精细化工高新技术开发公司 Synthesis method of antioxidant 1790
CN109912524A (en) * 2019-04-05 2019-06-21 南通大学 A kind of preparation method of hindered phenol anti-oxidants
CN114409960A (en) * 2022-01-21 2022-04-29 深圳市那鸿科技有限公司 Flame-retardant/antioxidant synergistic additive, synthetic method thereof and application thereof in recycling PET
CN114409960B (en) * 2022-01-21 2023-05-09 深圳市那鸿科技有限公司 Flame-retardant/antioxidant synergistic auxiliary agent, synthesis method thereof and application thereof in PET recovery

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