CN110204555A - The preparation method and application of compound in triazine class with polyvinyl chloride light stabilization - Google Patents
The preparation method and application of compound in triazine class with polyvinyl chloride light stabilization Download PDFInfo
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- CN110204555A CN110204555A CN201910619822.0A CN201910619822A CN110204555A CN 110204555 A CN110204555 A CN 110204555A CN 201910619822 A CN201910619822 A CN 201910619822A CN 110204555 A CN110204555 A CN 110204555A
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- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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Abstract
The invention discloses a kind of preparation method and application of compound in triazine class with polyvinyl chloride light stabilization, belong to functional organic molecule synthesis technical field.Technical solution of the present invention main points are as follows: the compound in triazine class has structureThe present invention has obtained a kind of compound in triazine class of structure novel using cheap gavaculine as starting material, by a series of simple and effective synthesizing means；The compound in triazine class that the present invention obtains has good polyvinyl chloride light stabilization.
Description
Technical field
The invention belongs to functional organic molecule synthesis technical fields, and in particular to one kind has polyvinyl chloride light stabilization
Compound in triazine class preparation method and application.
Background technique
Compound in triazine class is a kind of nitrogen-containing heterocycle compound, is widely used in terms of chemical dyestuff, material, and is desinsection
Important composition structure in agent, herbicide.Recent study discovery, compound in triazine class can be also used for flame retardant area, such as
S-triazine cyclics not only play important role in the construction of Intumescent Retardant System (IFR), while can also make
It is introduced into epoxy resin for solidfied material and assigns its good flame retardant property and heat resistance.This substance flame retardant effect is significant,
It can assign by the excellent electrical property of ignition resistant substrate, mechanical property, splendid thermal stability, and there is low toxicity, it is cheap etc.
Advantage becomes the hot spot of recent domestic flame retardant area research.Simultaneously, it has been found that compound in triazine class can be applied
In field of polyvinyl chloride material, it is used as light stabilizer, such as chloro- 4, the 6- of such as 2- bis- (N- butyl -1- cyclohexyloxy -2,2,6,
6- tetramethyl -4- piperidines amido) -1,3,5-triazines, it is a kind of novel hindered amine light stabilizer, itself can be used as and be obstructed
Amine light stabilizer uses, and can also be used as the intermediate of uV-152, uV-116 light stabilizer.
Polyvinyl chloride (PVC) material is widely applied due to cheap price and excellent performance, but its maximum disadvantage
It is poor to the stability of light and heat.PVC material outdoors in use, due to by prolonged sunlight irradiate, material surface
Color can gradually deepen, while chain break can occur by PVC and cross-linking reaction releases a large amount of hydrogen chloride gas.Theoretically divide
It analyses, these three covalent bonds of C.C, C.H and C.CI is only existed on ideal PVC chain, in more than 190~220nm wave-length coverage
Ultraviolet light does not have absorption, but the photostability of PVC material is still poor, illustrates there is the knot for absorbing ultraviolet light in PVC material
Structure, we term it the defect sturcture of PVC, it be due to actual production and processing PVC during generate.This defect knot
Structure is the main reason for causing PVC material photostability poor, mainly includes allyl chloride, tertiary chlorine, tertiary hydrogen, carbon-carbon double bond, the end of the chain
Base, peroxide and oxygen containing functional group etc..Include 2 main reactions during PVC is photodegradative: first is dechlorination
Hydrogen reaction, this is similar to thermal degradation, and only initiation conditions are different；Second is oxidation reaction, forms peroxide, and cause
Chain crosslinking and chain fracture, thus make the mechanical properties decrease of PVC, lose use value.Light stabilizer be one kind be able to suppress or
Slow down the auxiliary agent for making high molecular material degrade due to photooxidation, its service life can be greatly prolonged.PVC light is stablized
Agent is to inhibit PVC material under the conditions of daylight or strong fluorescence, and photooxidation occurs and causes due to absorbing UV energy
Make a kind of plastic additive that PVC degrades.In recent years, demand rapid growth of the plastics industry to light stabilizer, is commonly applied to
Alkyd paint, PVC product etc.,
There is good polyvinyl chloride light stabilization in view of compound in triazine class, we are opened by chemical synthesis means
A kind of novel compound in triazine class is had issued, and has carried out polyvinyl chloride light stability test, it is desirable to which it can become potential
Polyvinyl chloride light stabilizer.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of compound in triazine class with polyvinyl chloride light stabilizer
Preparation method and application.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of with polyvinyl chloride light stabilization
Compound in triazine class, it is characterised in that have the following structure:
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of with polyvinyl chloride light stabilization
The preparation method of compound in triazine class, it is characterised in that specific steps are as follows:
A, a certain amount of gavaculine is added in n,N-Dimethylformamide under nitrogen protection, has been stirred at room temperature
N is added after fully dissolved, N'- carbonyl dimidazoles are to slowly warm up to certain temperature, and the temperature is kept to continue to stop after stirring a period of time
It only heats, the n,N-Dimethylformamide dissolved with adjacent chlorophenethylamine is added dropwise by dropping funel, after dripping at room temperature
It is stirred to react to raw material fully reacting, water is added into reaction solution, then adjusting reaction solution pH with dilute hydrochloric acid is 8~9, filtering reaction
Liquid, filtrate are extracted with dichloromethane repeatedly, merge organic phase, are concentrated to get 3- amino-N- (2 chlorine after anhydrous magnesium sulfate is dry
Phenethyl) benzamide；The gavaculine and N, the inventory molar ratio of N'- carbonyl dimidazoles and adjacent chlorophenethylamine
For 1:1~1.5:1；The reaction temperature is 60~80 DEG C；
B, a certain amount of 3- amino-N- (2 chlorobenzene ethyl) benzamide and sodium alkoxide and iodomethane are added in ethyl alcohol, are placed in
A period of time is reacted under the conditions of certain reaction temperature, distilled water is added into reaction solution, under vacuum conditions evaporating solvent under reduced pressure
Ethyl alcohol, then reaction solution is extracted with ethyl acetate respectively three times, merge organic phase, organic phase is by saturated sodium chloride solution washing two
It is secondary, organic phase is separated, obtained organic phase is dry with anhydrous magnesium sulfate, it is purified to obtain by silica gel column chromatography after concentration
Methoxyl group -3- amino-N- (2- chlorobenzene ethyl) benzimide；The sodium alkoxide is sodium methoxide, sodium ethoxide or sodium tert-butoxide；It is described
3- amino-N- (2 chlorobenzene ethyl) benzamide and the inventory molar ratio of sodium alkoxide and iodomethane be 1:1:3；The reaction
Temperature is -10 DEG C；
C, a certain amount of methoxyl group -3- amino-N- (2- chlorobenzene ethyl) benzimide is added in anhydrous tetrahydro furan,
The tetrahydrofuran solution dissolved with catalyst is added under nitrogen protection, molten after certain reaction temperature is stirred to react a period of time
There is the anhydrous tetrahydrofuran solution of hydroxy methyl acetate to be slowly added dropwise into reaction flask, after dripping under the conditions of the reaction temperature
The reaction was continued to raw material fully reacting, restores to room temperature, is extracted with ethyl acetate repeatedly respectively, merges organic phase, organic phase
It is concentrated under reduced pressure to give (2- (3- aminophenyl) -4- (2- chlorobenzyl) oxazole -5- base) methanol；The catalyst is hexamethyl two
Silicon substrate amido sodium or hexamethyldisilazide lithium；Methoxyl group -3- amino-N- (2- chlorobenzene ethyl) benzimide with urge
Agent and the inventory molar ratio of hydroxy methyl acetate are 1:2:2；The reaction temperature is -70 DEG C；
D, a certain amount of (2- (3- aminophenyl) -4- (2- chlorobenzyl) oxazole -5- base) methanol and cesium carbonate are added to
In n,N-Dimethylformamide, a certain amount of catalyst is added, is heated to certain reaction temperature after mixing evenly, reaction terminates
Reaction solution is poured into water afterwards, filtering reacting liquid, then to be extracted with ethyl acetate reaction solution multiple while hot, merges organic phase, concentration
By the isolated 3- of silica gel column chromatography (4,10- dihydrobenzo [6] dislikes English in heptan [4,3-d] oxazole -2- base)-aniline；Described
Catalyst is cuprous bromide；(2- (3- aminophenyl) -4- (2- chlorobenzyl) oxazole -5- base) methanol and cesium carbonate with urge
The inventory molar ratio of agent is 1:1:0.1~0.2；The reaction temperature is 80~100 DEG C；
E, under nitrogen protection a certain amount of 3- (4,10- dihydrobenzo [6] dislikes English in heptan [4,3-d] oxazole -2- base)-benzene
Amine is added in methylene chloride, and for reaction temperature as 0 DEG C or so, the methylene chloride being slowly added dropwise dissolved with the triphosgene of two times of equivalents is molten
Liquid after dripping under nitrogen atmosphere keeps 0 DEG C of environment, continues to be stirred to react to raw material fully reacting, under the conditions of 0 DEG C, to
The solution of potassium carbonate of saturation is added dropwise in reaction solution, the complete triphosgene of unreacted is quenched by alkaline solution, then separates organic phase,
Water phase is extracted with dichloromethane repeatedly, merges organic phase, and active carbon is added and stirs at room temperature a period of time, filtering reaction
Liquid obtains chloroformyl (3- (4,10- dihydrobenzos [6] dislike English in heptan [4,3-d] oxazole -2- base)) aniline after concentration；
F, a certain amount of chloroformyl (3- (4,10- dihydrobenzo [6] dislikes English in heptan [4,3-d] oxazole -2- base)) aniline
N,N-Dimethylformamide is added with N- amino-isopropyl alkane imines, stirring is completely dissolved under room temperature, hydrazine hydrate is added,
It is reacted to raw material fully reacting at room temperature, reaction solution is added to the water, at room temperature stirring a period of time,
Then it is multiple that reaction solution is extracted with ethyl acetate, merges organic phase, then is dry with anhydrous magnesium sulfate, is concentrated to give N- (3- (4,10-
Dihydrobenzo [6] dislikes English in heptan [4,3-d] oxazole -2- base)-aniline) -2- (propane -2- fork)-semicarbazides；The chloroformyl
(3- (4,10- dihydrobenzo [6] dislikes English in heptan [4,3-d] oxazole -2- base)) aniline rubs with N- amino-isopropyl alkane imines inventory
You are than being 1:2；
G, a certain amount of N- (3- (4,10- dihydrobenzo [6] dislikes English in heptan [4,3-d] oxazole -2- base)-aniline) -2- (third
Alkane -2- fork)-semicarbazides is added in anhydrous tetrahydro furan and stirs and be completely dissolved, and reaction temperature is placed in -60 DEG C, under nitrogen protection
The tetrahydrofuran solution dissolved with t-butyl hypochlorate is slowly added dropwise by syringe, a large amount of heat can be released during dropwise addition, leads to
It crosses syringe to be injected dropwise, control reaction temperature is no more than -40 DEG C, reacts one within the scope of -60~-40 DEG C after dripping
The section time, then it is slowly increased to 0 DEG C of condition, ice is added into reaction system to raw material fully reacting for reaction under the conditions of the temperature
Water quenching is gone out reaction solution, and solvents tetrahydrofurane is then evaporated off under vacuum conditions, then to be extracted with dichloromethane reaction solution multiple, is merged
Then organic phase is concentrated, most afterwards through the isolated 6- of silica gel column chromatography (4,10- dihydrobenzos [6] after anhydrous magnesium sulfate is dry
Dislike English in heptan [4,3-d] oxazole -2- base) -1,2- dihydrobenzo [e] [1,2,4] triazine -3 (4H) -one；N- (3- (the 4,10-
Dihydrobenzo [6] dislikes English in heptan [4,3-d] oxazole -2- base)-aniline) -2- (propane -2- fork)-semicarbazides and t-butyl hypochlorate
Inventory molar ratio is 1:3；
H, a certain amount of 6- (4,10- dihydrobenzo [6] dislikes English in heptan [4,3-d] oxazole -2- base) -1,2- dihydrobenzo
In the mixed solvent is added in [e] [1,2,4] (4H) -one of triazine -3 and 3,4- dimethoxy iodobenzene and potassium phosphate, stirs under room temperature
Catalyst is added under nitrogen protection after mixing uniformly, is added to water after being then slowly heated to certain temperature reaction a period of time
In, it stirs evenly at room temperature, filtering reacting liquid, filtrate is extracted with ethyl acetate three times, merge organic phase, passed through after concentration
The isolated target compound of silica gel column chromatography；(4,10- dihydrobenzo [6] dislikes English in heptan [4,3-d] oxazole -2- to the 6-
Base) -1,2- dihydrobenzo [e] [1,2,4] triazine -3 (4H) -one and 3,4- dimethoxy iodobenzene and potassium phosphate inventory mole
Than for 1:1.2:1；The mixed solvent is ethylene glycol and isopropanol；The catalyst is cuprous iodide and palladium carbon；It is described
Cuprous iodide and content be 5% the inventory mass ratio of palladium carbon be 1:2；(4,10- dihydrobenzo [6] dislikes heptan to the 6-
English [4,3-d] oxazole -2- base) -1,2- dihydrobenzo [e] [1,2,4] triazine -3 (4H) -one and cuprous iodide inventory mole
Than for 1:0.1；The reaction temperature is 80~100 DEG C.
Beneficial effects of the present invention: 1, the present invention passes through a system using cheap gavaculine as starting material
It arranges simple and effective synthesizing mean and has obtained a kind of compound in triazine class of structure novel；2, the triazines chemical combination that the present invention obtains
Object has good polyvinyl chloride light stabilization.
Detailed description of the invention
The nucleus magnetic hydrogen spectrum of Fig. 1 target compound
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
Under nitrogen protection, gavaculine 14g (0.1mol) and N, N- dimethyl formyl are added in 500mL four-hole bottle
Amine 200mL, is stirred at room temperature after being completely dissolved and N is added, N'- carbonyl dimidazoles 25g (0.15mol), it is seen that solution is muddy；Start to add
Heat is to slowly warm up to 60 DEG C, keeps the temperature to continue to stir 1.5h, stops heating, continue to stir；System is cooled to room temperature 25
DEG C, the n,N-Dimethylformamide 100mL dissolved with adjacent chlorophenethylamine 16g (0.1mol) is added dropwise by dropping funel, after dripping
It is stirred to react 5h at room temperature, TLC monitors raw material fully reacting, is added water 300mL into reaction solution, then with dilute hydrochloric acid tune
Saving reaction solution pH is 8~9, filtering reacting liquid, and filtrate is extracted repeatedly with methylene chloride 100mL, merges organic phase, through anhydrous slufuric acid
3- amino-N- (2 chlorobenzene ethyl) benzamide 25g is concentrated to get after magnesium is dry；MS(ESI)m/z:275.8[M+H]+。
Embodiment 2
Under nitrogen protection, gavaculine 14g (0.1mol) and N, N- dimethyl formyl are added in 500mL four-hole bottle
Amine 200mL, is stirred at room temperature after being completely dissolved and N is added, N'- carbonyl dimidazoles 16g (0.1mol), it is seen that solution is muddy；Start to add
Heat is to slowly warm up to 80 DEG C, keeps the temperature to continue to stir 3.5h, stops heating, continue to stir；System is cooled to room temperature 25
DEG C, the n,N-Dimethylformamide 100mL dissolved with adjacent chlorophenethylamine 16g (0.1mol) is added dropwise by dropping funel, after dripping
It is stirred to react 7h at room temperature, water 300mL is added into reaction solution, then adjusting reaction solution pH with dilute hydrochloric acid is 8~9, mistake
Reaction solution is filtered, filtrate is extracted repeatedly with methylene chloride 100mL, merges organic phase, through silicon after being concentrated after anhydrous magnesium sulfate is dry
Plastic column chromatography isolated 3- amino-N- (2 chlorobenzene ethyl) benzamide 20.8g；MS(ESI)m/z:275.8[M+H]+。
Embodiment 3
3- amino-N- (2 chlorobenzene ethyl) benzamide 27.5 (0.1mol), sodium ethoxide 7g are added in reaction flask
(0.1mol), iodomethane 43g (0.3mol) and ethyl alcohol 300mL, reaction temperature react 5h under the conditions of being placed in -10 DEG C, to reaction solution
Middle addition distilled water 200mL, under vacuum conditions evaporating solvent under reduced pressure ethyl alcohol 200mL, then extracted respectively with ethyl acetate 100mL
Reaction solution three times, merges organic phase, and organic phase is washed twice by saturated sodium-chloride 100mL solution, separates organic phase, will obtain
Organic phase it is dry with anhydrous magnesium sulfate, purified to obtain methoxyl group -3- amino-N- (2- by silica gel column chromatography after concentration
Chlorobenzene ethyl) benzimide 22.9g；MS(ESI)m/z:289.7[M+H]+。
Embodiment 4
3- amino-N- (2 chlorobenzene ethyl) benzamide 27.5 (0.1mol), sodium methoxide 11g are added in reaction flask
(0.2mol), iodomethane 43g (0.3mol) and ethyl alcohol 400mL, reaction temperature react 9h under the conditions of being placed in -10 DEG C, to reaction solution
Middle addition distilled water 200mL, under vacuum conditions evaporating solvent under reduced pressure ethyl alcohol 200mL, then extracted respectively with ethyl acetate 100mL
Reaction solution three times, merges organic phase, and organic phase is washed twice by saturated sodium-chloride 100mL solution, separates organic phase, will obtain
Organic phase it is dry with anhydrous magnesium sulfate, purified to obtain methoxyl group -3- amino-N- (2- by silica gel column chromatography after concentration
Chlorobenzene ethyl) benzimide 17.1g；MS(ESI)m/z:289.7[M+H]+。
Embodiment 5
3- amino-N- (2 chlorobenzene ethyl) benzamide 27.5 (0.1mol), potassium tert-butoxide 11g are added in reaction flask
(0.1mol), iodomethane 43g (0.3mol) and ethyl alcohol 400mL, reaction temperature react 6h under the conditions of being placed in -10 DEG C, to reaction solution
Middle addition distilled water 200mL, under vacuum conditions evaporating solvent under reduced pressure ethyl alcohol 200mL, then extracted respectively with ethyl acetate 100mL
Reaction solution three times, merges organic phase, and organic phase is washed twice by saturated sodium-chloride 100mL solution, separates organic phase, will obtain
Organic phase it is dry with anhydrous magnesium sulfate, purified to obtain methoxyl group -3- amino-N- (2- by silica gel column chromatography after concentration
Chlorobenzene ethyl) benzimide 24.3g；MS(ESI)m/z:289.7[M+H]+。
Embodiment 6
In the closed reaction flask for being placed on low-temperature reactor, methoxyl group -3- amino-N- (2- chlorobenzene ethyl) benzene
Azomethine 29g (0.1mol) is added in anhydrous tetrahydro furan 300mL, adds the hexamethyl that content is 20% under nitrogen protection
The tetrahydrofuran solution 200g (0.2mol) of two silicon substrate amido sodium is stirred to react 1h in -70 DEG C of reactions in low-temperature reactor,
Then the anhydrous tetrahydrofuran solution 50mL dissolved with hydroxy methyl acetate 18g (0.2mol) is slowly added dropwise into reaction flask, is dripped
The reaction was continued under the conditions of -70 DEG C after adding 6h restores to merge organic respectively three times with ethyl acetate 100mL extraction to room temperature
Phase, organic phase are concentrated under reduced pressure to give (2- (3- aminophenyl) -4- (2- chlorobenzyl) oxazole -5- base) methanol 22.7g；1H NMR
(400MHz,DMSO-d6): 7.96 (d, J=4.0Hz, 2H), 7.63-7.58 (m, 2H), 7.25 (t, J1=8.0Hz, J2=
8.0Hz,1H),7.05-6.98(m,3H),6.63(s,2H),4.74(s,2H),4.07(s,2H),3.69(m,1H)；MS(ESI)
m/z:315.5[M+H]+。
Embodiment 7
In the closed reaction flask for being placed on low-temperature reactor, methoxyl group -3- amino-N- (2- chlorobenzene ethyl) benzene
Azomethine 29g (0.1mol) is added in anhydrous tetrahydro furan 300mL, adds the hexamethyl that content is 20% under nitrogen protection
The tetrahydrofuran solution 200g (0.2mol) of two silicon substrate amido lithiums is stirred to react 1h in -70 DEG C of reactions in low-temperature reactor,
Then the anhydrous tetrahydrofuran solution 50mL dissolved with hydroxy methyl acetate 18g (0.2mol) is slowly added dropwise into reaction flask, is dripped
The reaction was continued under the conditions of -70 DEG C after adding, and 4h restores to room temperature after TLC monitoring raw material fully reacting, uses ethyl acetate respectively
100mL is extracted three times, merges organic phase, and organic phase is concentrated under reduced pressure to give (2- (3- aminophenyl) -4- (2- chlorobenzyl) oxazole -
5- yl) methanol 28.3g；1H NMR(400MHz,DMSO-d6): 7.96 (d, J=4.0Hz, 2H), 7.63-7.58 (m, 2H), 7.25
(t,J1=8.0Hz, J2=8.0Hz, 1H), 7.05-6.98 (m, 3H), 6.63 (s, 2H), 4.74 (s, 2H), 4.07 (s, 2H),
3.69(m,1H)；MS(ESI)m/z:315.5[M+H]+。
Embodiment 8
In reaction flask, (2- (3- aminophenyl) -4- (2- chlorobenzyl) oxazole -5- base) methanol 32g (0.1mol) and
Cesium carbonate 33g (0.1mol) is added in n,N-Dimethylformamide 200mL, is added cuprous bromide 1.5g (0.01mol), is stirred
100 DEG C are heated to after mixing uniformly, about reaction 10h, reaction solution are poured into water while hot, filtering reacting liquid, then use ethyl acetate
150mL extraction reaction solution is multiple, merges organic phase, through the isolated 3- of silica gel column chromatography (4,10- dihydrobenzos [6] after concentration
Dislike English in heptan [4,3-d] oxazole -2- base)-aniline 16.8g；1H NMR(400MHz,DMSO-d6):7.61-7.58(m,2H),7.37
(t,J1=8.0Hz, J2=8.0Hz, 2H), 7.17 (d, J=8.0Hz, 1H), 7.02-6.95 (m, 3H), 6.51 (s, 2H), 4.96
(s,2H),3.92(s,2H)；MS(ESI)m/z:279.3[M+H]+。
Embodiment 9
In reaction flask, (2- (3- aminophenyl) -4- (2- chlorobenzyl) oxazole -5- base) methanol 32g (0.1mol) and
Cesium carbonate 33g (0.1mol) is added in n,N-Dimethylformamide 200mL, is added cuprous bromide 3g (0.02mol), stirring
100 DEG C are heated to after uniformly, about reaction 10h, reaction solution are poured into water while hot, filtering reacting liquid, then use ethyl acetate
150mL extraction reaction solution is multiple, merges organic phase, through the isolated 3- of silica gel column chromatography (4,10- dihydrobenzos [6] after concentration
Dislike English in heptan [4,3-d] oxazole -2- base)-aniline 23.5g；1H NMR(400MHz,DMSO-d6):7.61-7.58(m,2H),7.37
(t,J1=8.0Hz, J2=8.0Hz, 2H), 7.17 (d, J=8.0Hz, 1H), 7.02-6.95 (m, 3H), 6.51 (s, 2H), 4.96
(s,2H),3.92(s,2H)；MS(ESI)m/z:279.3[M+H]+。
Embodiment 10
Under nitrogen protection, 3- (4,10- dihydrobenzos [6] evil English in heptan [4,3-d] oxazole -2- is added into four-hole bottle
Base)-aniline 28g (0.1mol) and methylene chloride 200mL, reaction temperature be slowly added dropwise as 0 DEG C or so dissolved with triphosgene 60g
The dichloromethane solution 500mL of (0.2mol) after dripping under nitrogen atmosphere keeps 0 DEG C of environment, continues to be stirred to react
The solution of potassium carbonate of saturation is added dropwise into reaction solution, passes through alkalinity under the conditions of 0 DEG C for 30min, TLC monitoring raw material fully reacting
The complete triphosgene of unreacted is quenched in solution, then separates organic phase, and water phase methylene chloride 100mL is extracted repeatedly, merged organic
Phase is added active carbon 20g, stirs 30min at room temperature, filtering reacting liquid obtains chloroformyl (3- (4,10- after concentration
Dihydrobenzo [6] dislikes English in heptan [4,3-d] oxazole -2- base)) aniline 29g；Elemental analysis calculated value [C18H13ClN2O3]:C,
63.44；H,3.85；N,8.22；Measured value: C, 63.71；H,3.92；N,8.16.
Embodiment 11
In confined reaction bottle, chloroformyl (3- (4,10- dihydrobenzos [6] dislike English in heptan [4,3-d] oxazole -2- base))
N, N- dimethyl formyl is added in aniline 34g (0.1mol) and N- amino-isopropyl alkane imines 15g (0.2mol, CAS:5281-20-9)
Amine 500mL, stirring is completely dissolved under room temperature, the hydrazine hydrate 200mL that content is 60% is added after being stirred to react 2h, in room
15h is reacted under the conditions of temperature reaction solution is added in water 1000mL, is stirred at room temperature after TLC monitors raw material fully reacting
30min is mixed, then with ethyl acetate 200mL extraction reaction 5 times, merges organic phase, active carbon 10g is added, at room temperature
Stir 50min, filtering reacting liquid, then dry with anhydrous magnesium sulfate, be concentrated to give N- (3- (and 4,10- dihydrobenzos [6] dislike English in heptan [4,
3-d] oxazole -2- base)-aniline) -2- (propane -2- fork)-semicarbazides 34.1g；MS(ESI)m/z:377.6[M+H]+。
Embodiment 12
In closed reaction flask, N- (3- (4,10- dihydrobenzos [6] dislike English in heptan [4,3-d] oxazole -2- base)-benzene
Amine) -2- (propane -2- fork)-semicarbazides 38g (0.1mol) is added stirring 20min in anhydrous tetrahydro furan 300mL and is completely dissolved,
Reaction temperature is placed in -60 DEG C, stirs 10min under nitrogen protection, is slowly added dropwise into reaction solution by syringe dissolved with secondary chlorine
The tetrahydrofuran solution 120mL of tert-butyl acrylate 33g (0.3mol), can release a large amount of heat during dropwise addition, by syringe by
Drop is injected, and control reaction temperature is no more than -40 DEG C, reacts 8h after dripping within the scope of -60~-40 DEG C, then slowly rise
To 0 DEG C of condition, 2h is reacted under the conditions of the temperature, TLC monitors raw material fully reacting, and ice water 300mL is added into reaction system
Then solvents tetrahydrofurane is evaporated off in quenching reaction liquid under vacuum conditions, then multiple with methylene chloride 100mL extraction reaction solution,
Merge organic phase, active carbon 15g is added, is heated to reflux stirring 10min, while hot filtering reacting liquid, it is then dry through anhydrous magnesium sulfate
Concentration after dry, most afterwards through the isolated 6- of silica gel column chromatography (4,10- dihydrobenzos [6] dislike English in heptan [4,3-d] oxazole -2- base) -
1,2- dihydrobenzo [e] [1,2,4] (4H) -one of triazine -3 29.5g；1H NMR(400MHz,DMSO-d6):8.68(s,1H),
8.32 (s, 1H), 8.05-8.02 (m, 1H), 7.59 (d, J=8.0Hz, 2H), 7.15 (d, J=4.0Hz, 1H), 6.96-6.89
(m,3H),6.09(s,1H),5.77(s,2H),3.93(s,2H)；Elemental analysis calculated value [C18H14N4O3]:C,64.66；H,
4.22；N,16.76；Measured value: C, 64.47；H,4.25；N,16.71.
Embodiment 13
In reaction flask, 6- (4,10- dihydrobenzos [6] dislike English in heptan [4,3-d] oxazole -2- base) -1,2- dihydrobenzo
[e] [1,2,4] (4H) -one 34g of triazine -3 (0.1mol) and 3,4- dimethoxy iodobenzene 32g (0.12mol) and potassium phosphate 43g
The in the mixed solvent of ethylene glycol 200mL and isopropanol 200mL is added in (0.2mol), under room temperature after mixing evenly, in nitrogen
The lower palladium carbon 3.8g for cuprous iodide 1.9g (0.01mol) being added and content is 5% of protection, is then slowly heated to 80 DEG C of reactions
After 3h, TLC monitor raw material fully reacting, reaction solution is added in water 500mL, stirs 30min at room temperature, filtering is anti-
Liquid is answered, three times with ethyl acetate 100mL extraction filtrate, merges organic phase, through the isolated targeted of silica gel column chromatography after concentration
Close object 41.3g；1H NMR(400MHz,DMSO-d6):8.82(s,1H),8.43(s,1H),8.15(s,1H),7.53-7.41(m,
3H), 7.20 (d, J=4.0Hz, 1H), 6.89-6.81 (m, 5H), 5.96 (s, 2H), 4.22 (s, 2H), 3.78-3.74 (m, 6H)
(" 3.78 (s, 3H), 3.74 (s, 3H) ") (the deuterated DMSO that this target compound uses carries out nuclear-magnetism detection, DMSO as solvent
Solvent peak in 2.4 and 3.3 positions, therefore at this, two peaks do not have to integral)；MS(ESI)m/z:471.5[M+H]+；Element point
Analyse calculated value [C26H22N4O5]:C,66.37；H,4.71；N,11.91；Measured value: C, 66.52；H,4.64；N,11.79.
Embodiment 14
In reaction flask, 6- (4,10- dihydrobenzos [6] dislike English in heptan [4,3-d] oxazole -2- base) -1,2- dihydrobenzo
[e] [1,2,4] (4H) -one 34g of triazine -3 (0.1mol) and 3,4- dimethoxy iodobenzene 32g (0.12mol) and potassium phosphate 22g
The in the mixed solvent of ethylene glycol 200mL and isopropanol 200mL is added in (0.1mol), under room temperature after mixing evenly, in nitrogen
The lower palladium carbon 3.8g for cuprous iodide 1.9g (0.01mol) being added and content is 5% of protection, is then slowly heated to 100 DEG C of reactions
After 5h, reaction solution is added in water 500mL, stirs 30min, filtering reacting liquid, with ethyl acetate 100mL at room temperature
It extracts filtrate three times, merges organic phase, through the isolated target compound 32.9g of silica gel column chromatography after concentration；1H NMR
(400MHz,DMSO-d6): 8.82 (s, 1H), 8.43 (s, 1H), 8.15 (s, 1H), 7.53-7.41 (m, 3H), 7.20 (d, J=
4.0Hz,1H),6.89-6.81(m,5H),5.96(s,2H),4.22(s,2H),3.78-3.74(m,6H)(“3.78(s,3H),
3.74 (s, 3H) ") (the deuterated DMSO that this target compound uses carries out nuclear-magnetism detection as solvent, and the solvent peak of DMSO is 2.4
With 3.3 positions, therefore two peaks do not have to integral at this)；MS(ESI)m/z:471.5[M+H]+；Elemental analysis calculated value
[C26H22N4O5]:C,66.37；H,4.71；N,11.91；Measured value: C, 66.52；H,4.64；N,11.79.
Embodiment 15
The test of polyvinyl chloride light stability
We carry out light using ultraviolet ageing method and stablize experiment, concrete operations are as follows: be first dissolved in polyvinyl chloride powder
In tetrahydrofuran organic solvent, the stabilizer of synthesis is then added thereto, makes the stabilizer being added under constant agitation
Be evenly dispersed in the tetrahydrofuran solvent of polyvinyl chloride, tetrahydrofuran solvent volatilize away as far as possible then, be made containing
The polychloroethylene film of stabilizer is dried in vacuo 12h at 45 DEG C, to ensure that the tetrahydrofuran solvent in polychloroethylene film is waved completely
It sends out；Polyvinyl chloride print is placed in ultraviolet ageing case, with ultraviolet lamp at a distance of 15cm, with ultraviolet lamp environmental test item
Part irradiates PVC sheets, every lh, tests the weight of polyvinyl chloride print.Polyvinyl chloride can take off under the irradiation of ultraviolet light
Hydrogen chloride generates conjugated double bond, and weight declines, after light stabilizer is added, the weight loss of polyvinyl chloride under same time ultraviolet lighting
Become smaller.Weight-loss ratio is smaller, and light stablizing effect is better.Light stablizing effect is characterized by weight loss.
W%=[(W1-W2)/W1]×100
W1The weight of polychloroethylene film, W before expression ultraviolet light2The weight of polychloroethylene film after expression ultraviolet light,
Specific experiment numerical value is as shown in the table:
As can be seen from the above table, with target compound in polyvinyl chloride additive amount increase, under ultraviolet light irradiation
Polychloroethylene film mass loss gradually decreases, it can be seen that, which can be used as polyvinyl chloride light stabilizer.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (10)
1. a kind of compound in triazine class with polyvinyl chloride light stabilization, it is characterised in that the molecule of the compound in triazine class
Structure are as follows:
2. the compound in triazine class according to claim 1 with polyvinyl chloride light stabilization, it is characterised in that this three
The specific preparation step of piperazine class compound are as follows:
A, a certain amount of gavaculine is added in n,N-Dimethylformamide under nitrogen protection, is stirred at room temperature completely molten
N is added after solution, N'- carbonyl dimidazoles are to slowly warm up to certain temperature, and the temperature is kept to continue to stop adding after stirring a period of time
Heat is added dropwise the n,N-Dimethylformamide dissolved with adjacent chlorophenethylamine by dropping funel, stirs at room temperature after dripping
Water is added into reaction solution to raw material fully reacting for reaction, then adjusting reaction solution pH with dilute hydrochloric acid is 8~9, filtering reacting liquid,
Filtrate is extracted with dichloromethane repeatedly, merges organic phase, is concentrated to get 3- amino-N- (2 chlorobenzene second after anhydrous magnesium sulfate is dry
Base) benzamide；
B, a certain amount of 3- amino-N- (2 chlorobenzene ethyl) benzamide and sodium alkoxide and iodomethane are added in ethyl alcohol, are placed in certain
A period of time is reacted under the conditions of reaction temperature, distilled water is added into reaction solution, under vacuum conditions evaporating solvent under reduced pressure ethyl alcohol,
Reaction solution is extracted with ethyl acetate respectively three times again, merges organic phase, organic phase is washed twice by saturated sodium chloride solution, point
It is from organic phase, obtained organic phase is dry with anhydrous magnesium sulfate, it is purified to obtain methoxy by silica gel column chromatography after concentration
Base -3- amino-N- (2- chlorobenzene ethyl) benzimide；
C, a certain amount of methoxyl group -3- amino-N- (2- chlorobenzene ethyl) benzimide is added in anhydrous tetrahydro furan, in nitrogen
The tetrahydrofuran solution dissolved with catalyst is added under protection, dissolved with hydroxyl after certain reaction temperature is stirred to react a period of time
The anhydrous tetrahydrofuran solution of acetic acid methyl ester is slowly added dropwise into reaction flask, continues under the conditions of the reaction temperature after dripping
After reaction to raw material fully reacting, restore to room temperature, be extracted with ethyl acetate respectively repeatedly, merges organic phase, organic phase decompression
It is concentrated to get (2- (3- aminophenyl) -4- (2- chlorobenzyl) oxazole -5- base) methanol；
D, a certain amount of (2- (3- aminophenyl) -4- (2- chlorobenzyl) oxazole -5- base) methanol and cesium carbonate are added to N, N-
In dimethylformamide, add a certain amount of catalyst, be heated to certain reaction temperature after mixing evenly, after reaction
Reaction solution is poured into water while hot, filtering reacting liquid, then to be extracted with ethyl acetate reaction solution multiple, is merged organic phase, is passed through after concentration
The isolated 3- of silica gel column chromatography (4,10- dihydrobenzo [6] dislikes English in heptan [4,3-d] oxazole -2- base)-aniline；
E, a certain amount of 3- (4,10- dihydrobenzo [6] dislikes English in heptan [4,3-d] oxazole -2- base)-aniline is added under nitrogen protection
Entering in methylene chloride, the dichloromethane solution of the triphosgene dissolved with two times of equivalents is slowly added dropwise as 0 DEG C or so in reaction temperature,
After dripping under nitrogen atmosphere, 0 DEG C of environment is kept, is continued to be stirred to react to raw material fully reacting, under the conditions of 0 DEG C, to anti-
The solution of potassium carbonate that saturation is added dropwise in liquid is answered, the complete triphosgene of unreacted is quenched by alkaline solution, then separates organic phase, water
It is mutually extracted with dichloromethane repeatedly, merges organic phase, active carbon is added and stirs at room temperature a period of time, filtering reaction
Liquid obtains chloroformyl (3- (4,10- dihydrobenzos [6] dislike English in heptan [4,3-d] oxazole -2- base)) aniline after concentration；
F, a certain amount of chloroformyl (3- (4,10- dihydrobenzo [6] dislikes English in heptan [4,3-d] oxazole -2- base)) aniline and N-
N,N-Dimethylformamide is added in amino-isopropyl alkane imines, and stirring is completely dissolved under room temperature, hydrazine hydrate is added, in room
Under the conditions of temperature after reaction to raw material fully reacting, reaction solution is added to the water, at room temperature stirring a period of time, then
It is multiple that reaction solution is extracted with ethyl acetate, merges organic phase, then is dry with anhydrous magnesium sulfate, is concentrated to give N- (3- (4,10- dihydros
Benzo [6] dislikes English in heptan [4,3-d] oxazole -2- base)-aniline) -2- (propane -2- fork)-semicarbazides；
G, a certain amount of N- (3- (4,10- dihydrobenzo [6] dislikes English in heptan [4,3-d] oxazole -2- base)-aniline) -2- (propane -
2- fork)-semicarbazides is added in anhydrous tetrahydro furan and stirs and be completely dissolved, and reaction temperature is placed in -60 DEG C, passes through under nitrogen protection
The tetrahydrofuran solution dissolved with t-butyl hypochlorate is slowly added dropwise in syringe, and a large amount of heat can be released during dropwise addition, passes through note
Emitter is injected dropwise, and control reaction temperature is no more than -40 DEG C, when reacting one section after dripping within the scope of -60~-40 DEG C
Between, then it is slowly increased to 0 DEG C of condition, reaction is added ice water into reaction system and quenches to raw material fully reacting under the conditions of the temperature
Go out reaction solution, and solvents tetrahydrofurane is then evaporated off under vacuum conditions, then to be extracted with dichloromethane reaction solution multiple, merges organic
Then phase is concentrated after anhydrous magnesium sulfate is dry, most through the isolated 6- of silica gel column chromatography, (4,10- dihydrobenzos [6] dislike heptan afterwards
English [4,3-d] oxazole -2- base) -1,2- dihydrobenzo [e] [1,2,4] triazine -3 (4H) -one；
H, a certain amount of 6- (4,10- dihydrobenzo [6] dislike English in heptan [4,3-d] oxazole -2- base) -1,2- dihydrobenzo [e] [1,
2,4] in the mixed solvent is added in (4H) -one of triazine -3 and 3,4- dimethoxy iodobenzene and potassium phosphate, stirs evenly under room temperature
Catalyst is added under nitrogen protection afterwards, is added to the water after being then slowly heated to certain temperature reaction a period of time, in room
It is stirred evenly under the conditions of temperature, filtering reacting liquid, filtrate is extracted with ethyl acetate three times, merge organic phase, through silicagel column after concentration
Chromatography obtains target compound.
3. the preparation method of the compound in triazine class according to claim 2 with polyvinyl chloride light stabilization, special
Sign is: gavaculine described in step A and N, and N'- carbonyl dimidazoles and the inventory molar ratio of adjacent chlorophenethylamine are
1:1~1.5:1；The reaction temperature is 60~80 DEG C.
4. the preparation method of the compound in triazine class according to claim 2 with polyvinyl chloride light stabilization, special
Sign is: sodium alkoxide described in step B is sodium methoxide, sodium ethoxide or sodium tert-butoxide；3- amino-the N- (2 chlorobenzene ethyl)
The inventory molar ratio of benzamide and sodium alkoxide and iodomethane is 1:1~2:3；The reaction temperature is -10 DEG C.
5. the preparation method of the compound in triazine class according to claim 2 with polyvinyl chloride light stabilization, special
Sign is: catalyst described in step C is sodium hexamethyldisilazide or hexamethyldisilazide lithium；The methoxy
The inventory molar ratio of base -3- amino-N- (2- chlorobenzene ethyl) benzimide and catalyst and hydroxy methyl acetate is 1:2:2；
The reaction temperature is -70 DEG C.
6. the preparation method of the compound in triazine class according to claim 2 with polyvinyl chloride light stabilization, special
Sign is: catalyst described in step D is cuprous bromide；Described (2- (3- aminophenyl) -4- (2- chlorobenzyl) oxazole -
5- yl) the inventory molar ratio of methanol and cesium carbonate and catalyst is 1:1:0.1~0.2；The reaction temperature is 80~100
℃。
7. the preparation method of the compound in triazine class according to claim 2 with polyvinyl chloride light stabilization, special
Sign is: chloroformyl described in step F (3- (4,10- dihydrobenzo [6] dislikes English in heptan [4,3-d] oxazole -2- base)) aniline
It is 1:2~2.1 with N- amino-isopropyl alkane imines inventory molar ratio.
8. the preparation method of the compound in triazine class according to claim 2 with polyvinyl chloride light stabilization, special
Sign is: N- described in step G (3- (4,10- dihydrobenzo [6] dislikes English in heptan [4,3-d] oxazole -2- base)-aniline) -2- (third
Alkane -2- fork) the inventory molar ratio of-semicarbazides and t-butyl hypochlorate is 1:3~3.1.
9. the preparation method of the compound in triazine class according to claim 2 with polyvinyl chloride light stabilization, special
Sign is: 6- described in step H (4,10- dihydrobenzo [6] dislikes English in heptan [4,3-d] oxazole -2- base) -1,2- dihydrobenzo
[e] [1,2,4] (4H) -one of triazine -3 and the inventory molar ratio of 3,4- dimethoxy iodobenzene and potassium phosphate are 1:1.2:1；It is described
Mixed solvent be ethylene glycol and isopropanol；The mixed solvent volume ratio is 1:1；The catalyst be cuprous iodide and
Palladium carbon；The inventory mass ratio for the palladium carbon that the cuprous iodide and content is 5% is 1:2；6- (the 4,10- dihydrobenzene
And [6] dislike English in heptan [4,3-d] oxazole -2- base) -1,2- dihydrobenzo [e] [1,2,4] (4H) -one of triazine -3 and cuprous iodide
Inventory molar ratio is 1:0.1；The reaction temperature is 80~100 DEG C.
10. the light stability test application of the compound in triazine class with polyvinyl chloride light stabilization as described in claim 1.
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