CN101434582A - Phenyl (benzotriazolyl) benzoate compound - Google Patents
Phenyl (benzotriazolyl) benzoate compound Download PDFInfo
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- CN101434582A CN101434582A CNA200810203620XA CN200810203620A CN101434582A CN 101434582 A CN101434582 A CN 101434582A CN A200810203620X A CNA200810203620X A CN A200810203620XA CN 200810203620 A CN200810203620 A CN 200810203620A CN 101434582 A CN101434582 A CN 101434582A
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Abstract
The invention relates to a (methylbenzotriazole) phenol benzoate compound. The compound has a structure shown in the Formula I. The (methylbenzotriazole) phenol benzoate compound designed and synthesized has excellent ultraviolet absorption performance due to a relatively wide ultraviolet absorption wave band and a relatively large molar extinction coefficient. Besides, the (methylbenzotriazole) phenol benzoate compound designed and synthesized by the invention has relatively large molecular weight, thus being not easy to migrate and lose during the processing process of a high molecular polymer (served as an additive). In the Formula I, R1 is -OH, R2 and R3 are respectively selected from one of H or an electron-attracting group.
Description
Technical field
The present invention relates to a kind of phenylformic acid (benzotriazole base) benester compound.
Background technology
UV light stabilizing agent is a consumption and demand growth class additive faster in the present all kinds of polymeric material feed additives, has a wide range of applications in the industry of a large amount of weather resistant polymer materials of need such as agricultural, building, automobile, furniture consumption.
A main standard judging UV light stabilizing agent performance quality is: whether it has broad uv-absorbing wave band and bigger molar extinction coefficient.In addition, the cost of UV light stabilizing agent and " adaptability " (condition that satisfies harsh processing and use) also are comparatively main judging criterions.
No matter existing UV light stabilizing agent is aspect molar extinction coefficient: as the maximum molar extinction coefficient of existing benzotriazole category UV light stabilizing agent be 27,800 (East China University of Science's journal 1997,23,3:321-326); Still in the leeway that improvement is all arranged and improve aspect cost and " adaptability " (particularly adapting to the processing of high molecular polymer).
Summary of the invention
The present invention is from Molecular Structure Design, designed and synthesized phenylformic acid (benzotriazole base) benester compound, they possess excellent uv absorption property---and ((maximum molar extinction coefficient can reach 59,000 for 275nm～uv-absorbing wave band 400nm) and bigger molar extinction coefficient to have broad.In addition, because the present invention is designed and synthetic phenylformic acid (benzotriazole base) benester compound has bigger molecular weight, it is not easy to take place migration and runs off in the high molecular polymer course of processing (as additive).
The said phenylformic acid of the present invention (benzotriazole base) benester compound, it has structure shown in the formula I:
Among the formula I: R
1For-OH, R
2And R
3Independently be selected from H or the electron-withdrawing group a kind of respectively.
In optimal technical scheme of the present invention, R
2And R
3Independently be selected from respectively H, halogen (F, Cl, Br or I) ,-CN or-NO
2In a kind of.
In another optimal technical scheme of the present invention, R
2And R
3Independently be selected from respectively H, halogen (F, Cl, Br or I) ,-CN or-NO
2In a kind of, and R
2And R
3Identical.
Embodiment
A kind of method of preparation phenylformic acid of the present invention (benzotriazole base) benester compound, its key step is:
At first be raw material, after diazotization reaction, azo reaction and reduction reaction, get 2 benzotriazole base-5-hydroxyl phenol successively with the o-Nitraniline; Be raw material with substituted benzoic acid (compound shown in the formula A) then, after carboxylic acid halidesization, get corresponding substituted benzene carboxylic acid halides (compound shown in the formula B); At last compound shown in the formula B and 2 benzotriazole base-5-hydroxyl phenol are reacted target compound (compound shown in the formula I).Synthetic route is as follows:
Wherein: X is halogen (F, Cl, Br or I), R
1, R
2And R
3Described identical with preamble.
The present invention is further elaborated below by embodiment, and its purpose only is better to understand content of the present invention.Therefore, the cited case does not limit protection scope of the present invention:
Embodiment 1
2 hydroxybenzoic acid-(3 '-hydroxyl-4 '-the benzotriazole base) phenyl ester synthetic
(1) preparation of o-Nitraniline diazonium salt:
Have thermometer, in the 250ml there-necked flask of stirring rod, adding o-Nitraniline 4.14g, the dense HCl of 10.3ml and 5ml water, stirring fast, under cryosel bath condition, making reaction mixture be cooled to 0 ℃～5 ℃, adding 2.1g NaNO
2With the aqueous solution that 4ml water is made into, keep 0 ℃～5 ℃ reactions 30 minutes, add a small amount of urea element, in order to remove excessive nitrous acid.Stir, light blue up to the starch potassium iodide demonstration, remove by filter insolubles, it is standby to place cryosel to bathe diazonium salt solution.
(2) 2-nitro-2 ', the preparation of 4 '-dihydroxyl nitrogen benzide:
In having the 250ml there-necked flask of thermometer, stirring rod, add Resorcinol 3.63g (0.033mol) and 40ml water.Bathe controlled temperature at 0 ℃～5 ℃ with cryosel, the o-Nitraniline diazonium salt solution is added drop-wise in the Resorcinol solution.Dropwise, continue to stir 1 hour.Suction filtration, with the filter cake washing, filter cake is dry under infrared lamp behind the suction filtration, gets crude product.Make solvent recrystallization with ethanol, get red crystals 2-nitro-2 ', 4 '-dihydroxyl nitrogen benzide 6.76g, yield 87.1%, m.p.189 ℃～191 ℃.
(3) preparation of 2 benzotriazole base-5-hydroxyl phenol:
In being housed, the 250ml there-necked flask of reflux condensing tube, stirring rod adds 3.9g 2-nitro-2 ', 4 '-dihydroxyl nitrogen benzide, 60ml 95% ethanol, the NaOH solution of 50ml 15%.Reflux adds the sulfur-bearing reductive agent in batches, reacts stopped reaction 1.5 hours.While hot reaction mixture is poured in the frozen water, be neutralized to pH value 5～6 with 5% hydrochloric acid.Leave standstill, filter, washing, drying gets white solid 2 benzotriazole base-5-hydroxyl phenol 2.8g, yield 82%, M.p.198 ℃～200 ℃.
(4) preparation of bigcatkin willow acyl chlorides:
In the 50ml there-necked flask of reflux condensing tube is housed, add the 1.38g Whitfield's ointment, add 30ml sherwood oil (boiling range is 55 ℃～60 ℃), the pyridine of catalytic amount, the prolong top connects the tail gas absorption tube, fills the 10% NaOH aqueous solution in the tail gas absorption bottle.Stir extremely backflow of heat temperature raising down, with the solution that constant pressure funnel dropping 1.5ml sulfur oxychloride and 10ml sherwood oil are made into, the control rate of addition dropwised in about about 30 minutes, continued back flow reaction 8 hours.Stopped reaction, steaming desolventizes and a small amount of unreacted sulfur oxychloride and pyridine, gets the pale yellow oily liquid body, and is standby with the methylene dichloride 50ml dissolving through no water treatment.
(5) preparation of target compound:
2 benzotriazole base-5-the hydroxyl phenol that in the single port flask of 500ml, adds 2.27g, the 200ml methylene dichloride, the 5ml pyridine, stir down and slowly to be added drop-wise in reaction system by the dichloromethane solution of the bigcatkin willow acyl chlorides of step (4) preparation 50ml, keeping temperature of reaction is 10 ℃～30 ℃, reacted stopped reaction 6 hours～8 hours.Reaction mixture is transferred in the 500ml separating funnel water, 5% aqueous sodium carbonate and water washing respectively.Use anhydrous magnesium sulfate drying, use activated carbon decolorizing, steaming desolventizes, and gets faint yellow solid target compound 2.95g, and yield 85% is a solvent recrystallization with ethyl acetate and normal hexane, gets white solid 2.35g, yield 68%, M.p.177 ℃～179 ℃.
Uv-absorption maximum wavelength (the λ of target compound
Max) be 354, its absorption bands is 295nm～400nm, molar extinction coefficient (ε) is 4.7 * 10
4
1H-NMR：δ(H
a)＝7.03～7.05(d，1H)，δ(H
b)＝7.06～7.08(d，1H)，δ(Hc
+d)＝7.92～7.95(m，2H)，δ(H
e+f)＝7.48～7.50(m，2H)，δ(H
g)＝10.40(s，1H)，δ(H
h)＝6.95(s，1H)，δ(H
i)＝10.90(s，1H)，δ(H
j)＝6.96～6.99，(d，1H)δ(H
k)＝8.06～8.08(m，1H)，δ(H
l)＝7.53～7.57(m，1H)，δ(H
m)＝8.46～8.48(d，1H)。
Embodiment 2
2-hydroxyl-3, the 5-dibromobenzoic acid-(3 '-hydroxyl-4 '-the benzotriazole base) phenyl ester synthetic
(1) 3,5-dibromosalicylic acid
Add Whitfield's ointment 13.8g in the 250ml there-necked flask of stirring rod is housed, the 100ml Glacial acetic acid slowly drips the solution that is made into by 12.8ml liquid bromine and 50ml Glacial acetic acid, dropwises, and control reaction temperature continues reaction 1 hour below 25 ℃.Stir the downhill reaction mixture and add the 80ml frozen water, make reaction mixture be cooled to 10 ℃～15 ℃.Leave standstill, filter.Use dilute acetic acid, water washing more respectively, drying gets white solid 3,5-dibromosalicylic acid 28g, yield 95%, m.p218 ℃～220 ℃.
(2) 3,5-dibromo bigcatkin willow acyl chlorides
Add 2.96 grams 3 in the 50ml there-necked flask of reflux condensing tube is housed, the 5-dibromosalicylic acid adds the 20ml glycol dimethyl ether, the pyridine of catalytic amount, and the prolong top connects the tail gas absorption tube, fills the 10% NaOH aqueous solution in the tail gas absorption bottle.Stir down heat temperature raising to 60 ℃, drip the solution that is made into by 1.5ml sulfur oxychloride and 5ml glycol dimethyl ether, dropwise, continue reaction 1 hour with constant pressure funnel.Be warming up to backflow, continue reaction 6 hours.Stopped reaction, steaming desolventizes and a small amount of unreacted sulfur oxychloride and pyridine, gets oily liquids, and is standby with the methylene dichloride 40ml dissolving through no water treatment.
(3) preparation of target compound:
The methylene dichloride and the 5ml pyridine that in the there-necked flask of 500ml, add 2.27 gram 2 benzotriazole base-5-hydroxyl phenols, the no water treatment of 200ml process.Stir down with 40ml by step (2) make 3, the dichloromethane solution of 5-dibromo bigcatkin willow acyl chlorides slowly is added drop-wise in the reactor, temperature of reaction remains on 10 ℃～30 ℃.Dropwise, continued stirring reaction 6 hours～8 hours.Stopped reaction is transferred to reaction mixture in the separating funnel, respectively water, 5% aqueous sodium carbonate, water washing.Use anhydrous magnesium sulfate drying, use activated carbon decolorizing, steaming desolventizes, and gets target compound crude product 4.1g, and yield 81% with the ethyl acetate solvent recrystallization, gets pale solid (target compound) 3.6g, yield 71%.M.p.159.9℃～160.2℃。
Uv-absorption maximum wavelength (the λ of target compound
Max) be 310, its absorption bands is 290nm～400nm, molar extinction coefficient (ε) is 5.9 * 10
4
1H-NMR：δ(H
a)＝7.03～7.05(d，1H)，δ(H
b)＝7.59(d，1H)，δ(H
C+d)＝7.95～8.10(m，2H)，δ(H
e+f)＝7.46～7.51(m，2H)，δ(H
g)＝10.44(s，1H)，δ(H
h)＝6.42～6.45(s，1H)，δ(H
i)＝11.94(s，1H)，δ(H
j)＝7.74，(s，1H)，δ(H
k)＝7.623(s，1H)。
Embodiment 3
2-hydroxyl-3,5-dinitrobenzoic acid-(3 ' hydroxyl-4 '-benzotriazole base) phenyl ester synthetic
The preparation of (1) 3,5-dinitrobenzene bigcatkin willow acyl chlorides:
In being housed, the 50ml there-necked flask of reflux condensing tube adds 2.28 grams 3, the pyridine of 5-dinitrosalicylic acid, 20ml glycol dimethyl ether and catalytic amount, and the prolong top connects the tail gas absorption tube, fills the 10% NaOH aqueous solution in the tail gas absorption bottle.Stir down heat temperature raising to 60 ℃, drip the solution that is made into by 1.5ml sulfur oxychloride and 5ml glycol dimethyl ether with constant pressure funnel, the control rate of addition dropwised in about 30 minutes, and holding temperature continues reaction 1 hour.Be warming up to backflow, continue reaction 6 hours.Stopped reaction, steaming desolventizes and a small amount of unreacted sulfur oxychloride and pyridine, gets the pale yellow oily liquid body, and is standby with the 45ml methylene dichloride dissolving through no water treatment.
(2) preparation of target compound
The methylene dichloride and the 5ml pyridine that in the there-necked flask of 500ml, add 2.27 gram 2 benzotriazole base-5-hydroxyl phenols, the no water treatment of 200ml process.Stir down 45ml by 3 of step (1) preparation, 5-dinitrobenzene bigcatkin willow acyl chlorides dichloromethane solution slowly is added drop-wise in the reactor.The control rate of addition dropwised in 3 hours～4 hours, at room temperature continued reaction 6 hours.Stopped reaction is transferred to reaction mixture in the separating funnel, respectively water, 5% aqueous sodium carbonate, water washing.Use anhydrous magnesium sulfate drying, use activated carbon decolorizing, steaming desolventizes, and gets yellow solid, is solvent recrystallization with the ethyl acetate, gets faint yellow solid 3.1g (target compound), yield 73%, M.p.151.6 ℃～151.8 ℃.
Uv-absorption maximum wavelength (the λ of target compound
Max) be 366, its absorption bands is 290nm～390nm, molar extinction coefficient (ε) is 4.0 * 10
4
1H-NMR is as follows: δ (H
a)=8.41～8.45 (d, 1H), δ (Hb)=8.55～8.60 (d, 1H), δ (H
C+d)=8.63～8.67 (m, 2H), δ (H
E+f)=8.03～8.07 (m, 2H), δ (H
g)=10.46～10.47 (s, 1H), δ (H
h)=6.42～6.45 (s, 1H), δ (H
i)=12.40～12.43 (s, 1H), δ (H
j)=9.11～9.12, (s, 1H), δ (H
k)=8.96～8.99 (s, 1H).
Claims (4)
1, a kind of phenylformic acid (benzotriazole base) benester compound is characterized in that said compound has structure shown in the formula I:
Among the formula I: R
1For-OH, R
2And R
3Independently be selected from H or the electron-withdrawing group a kind of respectively.
2, compound as claimed in claim 1 is characterized in that, wherein R
2And R
3Independently be selected from respectively H, F, Cl, Br ,-CN or-NO
2In a kind of.
3, compound as claimed in claim 1 or 2 is characterized in that, wherein R
2And R
3Independently be selected from respectively H, F, Cl, Br ,-CN or-NO
2In a kind of, and R
2And R
3Identical.
4, compound as claimed in claim 3, it is characterized in that, described compound be 2 hydroxybenzoic acid-(3 '-hydroxyl-4 '-the benzotriazole base) phenyl ester, 2-hydroxyl-3, the 5-dibromobenzoic acid-(3 '-hydroxyl-4'-benzotriazole base) phenyl ester or 2-hydroxyl-3, the 5-dinitrobenzoic acid-(3'-hydroxyl-4 '-the benzotriazole base) phenyl ester.
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| CNA200810203620XA CN101434582A (en) | 2008-11-28 | 2008-11-28 | Phenyl (benzotriazolyl) benzoate compound |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050823A (en) * | 2010-10-27 | 2011-05-11 | 华东理工大学 | Synthesis and representation of guanine analogue as novel light stabilizer |
| WO2019091450A1 (en) * | 2017-11-10 | 2019-05-16 | 江苏恒瑞医药股份有限公司 | Method for preparing benzofuran derivative |
| CN109824614A (en) * | 2017-11-23 | 2019-05-31 | 苏州兆海纺织科技有限公司 | A kind of reactive ultraviolet absorber of the base containing benzotriazole and its preparation method and application |
-
2008
- 2008-11-28 CN CNA200810203620XA patent/CN101434582A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050823A (en) * | 2010-10-27 | 2011-05-11 | 华东理工大学 | Synthesis and representation of guanine analogue as novel light stabilizer |
| WO2019091450A1 (en) * | 2017-11-10 | 2019-05-16 | 江苏恒瑞医药股份有限公司 | Method for preparing benzofuran derivative |
| CN111094279A (en) * | 2017-11-10 | 2020-05-01 | 江苏恒瑞医药股份有限公司 | Preparation method of benzofuran derivative |
| US11390614B2 (en) | 2017-11-10 | 2022-07-19 | Jiangsu Hengrui Medicine Co., Ltd. | Method for preparing benzofuran derivative |
| CN111094279B (en) * | 2017-11-10 | 2023-06-16 | 江苏恒瑞医药股份有限公司 | Preparation method of benzofuran derivative |
| CN109824614A (en) * | 2017-11-23 | 2019-05-31 | 苏州兆海纺织科技有限公司 | A kind of reactive ultraviolet absorber of the base containing benzotriazole and its preparation method and application |
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Open date: 20090520 |