CN104557752B - 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 - Google Patents
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 Download PDFInfo
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- CN104557752B CN104557752B CN201310467452.6A CN201310467452A CN104557752B CN 104557752 B CN104557752 B CN 104557752B CN 201310467452 A CN201310467452 A CN 201310467452A CN 104557752 B CN104557752 B CN 104557752B
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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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Abstract
The invention discloses 1,3, the 5 three (hydroxyl 2 of 4 tert-butyl group 3,6 dimethyl benzyls) 1,3,5 triazines 2,4,6 (1H, 3H, 5H) the synthetic method of 3 ketone, DMF and cyanuric acid and triethylamine are added in reactor, then heats to after 80 100 DEG C and instills the mixed liquor of the hydroxyl benzyl chloride of 42,6 dimethyl of the tert-butyl group 3 and DMF again, after reaction through filtering, being evaporated, methanol solution modeling, obtain synthetic product.This synthetic method is simple to operate, and the reaction time is short, and accessory substance is few, and product yield is high.
Description
Technical field
The present invention relates to a kind of production method of chemical products, more particularly to a kind of 1,3,5- tri- (the 4- tert-butyl group -3- hydroxyls
Base -2,6- dimethyl benzyl) -1,3,5-triazines -2,4, the technique synthesis of 6 (1H, 3H, 5H)-triketones (antioxidant TH-1790)
Method.
Background technology
1,3,5- tri- (the 4- tert-butyl group -3- hydroxyls -2,6- dimethyl benzyl) -1,3,5-triazines -2,4,6 (1H, 3H, 5H) -
Triketone, trade name is antioxidant TH-1790, and its traditional preparation method is：In reactor it is disposable add the 4- tert-butyl groups-
Mixed liquor, triethylamine and the cyanuric acid of 2,6- dimethyl -3- hydroxyls benzyl chlorides and DMF, stirring reaction 18 hours under 40 degree.This
The kind method reaction time is especially long, higher applied to industrial energy consumption, and the accessory substance of reaction is also more.
The content of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the invention provides a kind of new preparation 1,3,5- tri- (the 4- tert-butyl groups-
3- hydroxyls -2,6- dimethyl benzyl) -1,3,5-triazines -2,4, the synthetic method of 6 (1H, 3H, 5H) -3 ketones, this method
The reaction time is shortened, the energy consumption in commercial Application is reduced, improves reaction yield.
The present invention 1,3,5- tri- (the 4- tert-butyl group -3- hydroxyls -2,6- dimethyl benzyl) -1,3,5-triazines -2,4,6 (1H,
3H, 5H) -3 ketone synthetic method, comprise the following steps：
(1) the reaction intermediate 4- tert-butyl group -2,6- dimethyl -3- hydroxyl benzyl chlorides are prepared
(1) concentrated hydrochloric acid and 2- tert-butyl group -4,6 xylenols are added in reactor, stirring is lower to add paraformaldehyde, then
Heating, insulation reaction；
(2) phosphorus trichloride is added dropwise, 30-50 DEG C of kettle temperature, insulation reaction is controlled；
(3) add and saturated common salt water washing is used at toluene, 30 DEG C of organic phase, toluene to the greatest extent is steamed in decompression, obtains the tertiary fourths of the 4-
Base -2,6- dimethyl -3- hydroxyl benzyl chlorides.
(2) 1,3,5- tri- (the 4- tert-butyl group -3- hydroxyls -2,6- dimethyl benzyl) -1,3,5-triazines -2,4,6 (1H, 3H,
The synthesis of 5H) -3 ketone
Disposable in a kettle. to add DMF and cyanuric acid, stirring is lower to add triethylamine, then heats up.By step
(1) 4- tert-butyl group -2,6- dimethyl -3- hydroxyls benzyl chlorides well prepared in advance and DMF mixed liquor are instilled wherein, insulation reaction,
Filtering is desalted at room temperature, solvent evaporated, and product, i.e., described 1,3,5- tri- (the 4- tert-butyl group -3- hydroxyls are obtained after methanol solution modeling
Base -2,6- dimethyl benzyl) -1,3,5-triazines -2,4,6 (1H, 3H, 5H) -3 ketones.
1,3,5- tri- (the 4- tert-butyl group -3- hydroxyls -2,6- dimethyl benzyl) -1,3,5-triazines that present invention synthesis is obtained -
2,4,6 (1H, 3H, 5H) -3 ketones, its molecular formula C42H57N3O6, structural formula is as follows
In synthetic method of the present invention, in the step (1), 4- tert-butyl groups -2,6- dimethyl -3- hydroxyls in the step (1)
The preparation of base benzyl chloride, warming temperature is 30-50 DEG C, and soaking time is 3-5 hours.Preferably, above-mentioned warming temperature is 35-40
DEG C, soaking time is 3.5-4.5 hours.
In the step (1), warming temperature is 80-100 DEG C in the step (2).
In the step (1), holding temperature is 100-120 DEG C in the step (2), and soaking time is 5 hours.
In synthetic method of the present invention, in the step (2), 4- tert-butyl groups -2,6- dimethyl -3- hydroxyls benzyl chloride and
The time for adding of DMF mixed liquors is 1.5-2 hours, and the Precipitation Temperature added after methanol is 1-2 DEG C.
In synthetic reaction of the present invention, reactant molar ratio cyanuric acid：The 4- tert-butyl group -2,6- dimethyl -3- hydroxyl benzyl chlorides：
Triethylamine is 1：3~4：3~4.5.Preferably, reactant molar ratio cyanuric acid：The 4- tert-butyl group -2,6- dimethyl -3- hydroxyls
Benzyl chloride：Triethylamine is 1：3~3.5：3.2~4.
In synthetic reaction of the present invention, solvent that step uses is evaporated for DMF, can be recycled.
The reaction scheme of synthetic reaction of the present invention is as follows：
Compared with prior art, the reaction time of the invention is short, and industrial energy consumption is low, and the accessory substance that reaction is produced is few, product
Purity it is high, reaction yield is high.
Embodiment
With reference to specific examples below, the present invention is described in further detail, and of the invention protects content not limit to
In following examples.Under the spirit and scope without departing substantially from inventive concept, those skilled in the art it is conceivable that change and excellent
Point is all included in the present invention, and using appended claims as protection domain.Implement the present invention process, condition,
Reagent, experimental method etc., are the universal knowledege and common knowledge of this area, this hair in addition to the following content specially referred to
It is bright that content is not particularly limited.
The present invention 1,3,5- tri- (the 4- tert-butyl group -3- hydroxyls -2,6- dimethyl benzyl) -1,3,5-triazines -2,4,6 (1H,
3H, 5H) -3 ketone synthetic method：
Step (1), adds concentrated hydrochloric acid and 2- tert-butyl group -4,6 xylenols in a kettle., and stirring is lower to add poly
Formaldehyde, then heats up, and is incubated 2 hours at this temperature.After insulation terminates, start that phosphorus trichloride, control kettle temperature 30-50 is added dropwise
DEG C, drip off within about 1 hour, and insulation reaction at this temperature.Reaction adds at toluene, 30 DEG C of organic phase after terminating and uses saturated common salt
Water washing, decompression steams toluene to the greatest extent and produces 4- tert-butyl group -2,6- dimethyl -3- hydroxyl benzyl chlorides；
Step (2), disposable in a kettle. to add DMF and cyanuric acid, stirring is lower to add triethylamine, then heats up.
Step (1) 4- tert-butyl group -2,6- dimethyl -3- hydroxyls benzyl chlorides well prepared in advance and DMF mixed liquor are instilled wherein, protected
Temperature reaction, at room temperature filtering is desalted, and solvent evaporated obtains product, i.e., described 1,3,5- tri- (the tertiary fourths of 4- after methanol solution modeling
Base -3- hydroxyls -2,6- dimethyl benzyl) -1,3,5-triazines -2,4,6 (1H, 3H, 5H) -3 ketones.
Embodiment 11, the synthesis of 4- tert-butyl group -2,6- dimethyl -3- hydroxyl benzyl chlorides
Disposably added in reaction bulb：32% hydrochloric acid 49g and 2- tert-butyl group -4,6 xylenol 49g, stirring is lower to be added
Enter paraformaldehyde 13.1g, then heat to 37 DEG C, and be incubated 2 hours at this temperature, TLC tracking reactions terminate.Insulation terminates
Afterwards, start that phosphorus trichloride 17.3g is added dropwise, control 40 DEG C of kettle temperature, drip off within about 1 hour, and be incubated about 4 hours, TLC at this temperature
Tracking reaction terminates.
Reaction stands 20min after 50g toluene, stirring 15min are added after terminating, point sub-cloud aqueous phase, at 30 DEG C of organic phase
With saturated common salt water washing (20mlx2 times), toluene to the greatest extent is steamed in decompression.
It is cooled to 35-40 DEG C, and controls to instill DMF (having heat release) at such a temperature.10min is stirred for after dripping off.Reaction solution
It is directly used in next step reaction.
Embodiment 21,3,5- tri- (the 4- tert-butyl group -3- hydroxyls -2,6- dimethyl benzyl) -1,3,5-triazines -2,4,6 (1H,
3H, 5H)-triketone synthesis
Disposably added in reaction bulb：DMF39g and cyanuric acid 10.5g, stirring is lower to add triethylamine 40.5g, then
It is when being warming up to 90 DEG C, Isosorbide-5-Nitrae well prepared in advance-tert-butyl group -2,6- dimethyl -3- hydroxyl benzyl chlorides 62.3g and DMF32.7g is mixed
Drop is closed to enter wherein.During have tiny backflow, and kettle temperature can be raised slowly, it is desirable to no more than 102 DEG C, be dripped within about 11/2 hour
It is complete.Then in 100-120 DEG C of insulation reaction 5 hours or so, TLC tracking reactions terminate.
After reaction terminates, filtering at room temperature is desalted, a small amount of DMF elution, is filtered dry.Most solvent is recovered under reduced pressure, 115g first is added
60g is steamed under alcohol, atmospheric pressure reflux, 1-2 DEG C is down to and keeps filtering after 30min, a small amount of cold methanol elution is filtered dry, and obtains product 1,3,
5- tri- (the 4- tert-butyl group -3- hydroxyls -2,6- dimethyl benzyl) -1,3,5-triazines -2,4,6 (1H, 3H, 5H)-triketones, yield
85%, HPLC content 96.5%, 159-166 DEG C of fusing point, appearance white, 1H-NMR (D2O)6：1.34 (27, S), 2.35 (18,
S), 4.42 (6, S) 5.0 (3, S), 6.61 (3, S).
Claims (8)
1.1,3,5- tri- (the 4- tert-butyl group -3- hydroxyl -2,6- dimethyl benzyls) -1,3,5- triazines -2,4,6 (1H, 3H, 5H)-three
The synthetic method of assimilation compound, it is characterised in that comprise the following steps：
(1) synthesis of the 4- tert-butyl groups -2,6- dimethyl -3- hydroxyl benzyl chlorides：
(1) concentrated hydrochloric acid and 2- tert-butyl group -4,6 xylenols are added in reactor, stirring is lower to add paraformaldehyde, Ran Housheng
Temperature, insulation reaction；
(2) phosphorus trichloride is added dropwise, 30-50 DEG C of kettle temperature, insulation reaction is controlled；
(3) add and saturated common salt water washing used at toluene, 30 DEG C of organic phase, toluene to the greatest extent is steamed in decompression, obtains the 4- tert-butyl group -2,
6- dimethyl -3- hydroxyl benzyl chlorides；
(2) synthesis of product：
Disposable in reactor to add DMF and cyanuric acid, stirring is lower to add triethylamine, then heats up, be prepared by step (1)
Obtained 4- tert-butyl group -2,6- dimethyl -3- hydroxyls benzyl chlorides and DMF mixed liquors is instilled wherein, insulation reaction, crosses filter off at room temperature
Salt, solvent evaporated, obtained after methanol solution modeling described 1,3,5- tri- (the 4- tert-butyl group -3- hydroxyls -2,6- dimethyl benzyls) -
1,3,5- triazines -2,4,6 (1H, 3H, 5H) -3 ketone；
The time for adding of the 4- tert-butyl groups -2,6- dimethyl -3- hydroxyls benzyl chloride and DMF mixed liquors is 1.5-2 hours；
Holding temperature in the step (2) is 100-120 DEG C.
2. the warming temperature in synthetic method as claimed in claim 1, it is characterised in that in step (1), the step (1)
For 30-50 DEG C.
3. soaking time is in synthetic method as claimed in claim 1, it is characterised in that in step (1), the step (2)
3-5 hours.
4. 1,3,5- tri- (the 4- tert-butyl group -3- hydroxyl -2,6- dimethyl benzyls) -1,3,5- triazine -2 as claimed in claim 1,
The synthetic method of 4,6 (1H, 3H, 5H) -3 ketones, it is characterised in that in the step (2), the reactant melamine
Acid: the 4- tert-butyl group -2,6- dimethyl -3- hydroxyl benzyl chlorides: the mol ratio of triethylamine is 1: 3~4: 3~4.5.
5. 1,3,5- tri- (the 4- tert-butyl group -3- hydroxyl -2,6- dimethyl benzyls) -1,3,5- triazine -2 as claimed in claim 4,
The synthetic method of 4,6 (1H, 3H, 5H) -3 ketones, it is characterised in that in the step (2), the reactant melamine
Acid: the 4- tert-butyl group -2,6- dimethyl -3- hydroxyl benzyl chlorides: the mol ratio of triethylamine is 1: 3~3.5: 3.2~4.
6. synthetic method as claimed in claim 1, it is characterised in that the warming temperature in the step (2) is 80-100
℃。
7. synthetic method as claimed in claim 1, it is characterised in that the soaking time in the step (2) is 5 hours.
8. synthetic method as claimed in claim 1, it is characterised in that in the step (2), the precipitation temperature added after methanol
Spend for 1-2 DEG C.
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| CN201310467452.6A CN104557752B (en) | 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 |
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| CN201310467452.6A CN104557752B (en) | 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 |
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| CN104557752B true CN104557752B (en) | 2017-07-25 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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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| US3795700A (en) * | 1971-03-10 | 1974-03-05 | American Cyanamid Co | Esters of 4-alkyl-2,6-dimethyl-3-hydroxybenzyl alcohol |
| US3723427A (en) * | 1971-11-16 | 1973-03-27 | American Cyanamid Co | Hindered tris(meta-hydroxybenzyl)cyanurate antioxidants |
| US3862053A (en) * | 1971-11-16 | 1975-01-21 | American Cyanamid Co | Hindered tris (meta-hydroxybenzyl)cyanurate antioxidants |
| CN101684067A (en) * | 2008-09-26 | 2010-03-31 | 中钢集团鞍山热能研究院有限公司 | Antioxidant 1790 intermediate and clean production method thereof |
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