CN100436432C - 2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑及其制备、应用 - Google Patents
2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑及其制备、应用 Download PDFInfo
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- CN100436432C CN100436432C CNB2006100523156A CN200610052315A CN100436432C CN 100436432 C CN100436432 C CN 100436432C CN B2006100523156 A CNB2006100523156 A CN B2006100523156A CN 200610052315 A CN200610052315 A CN 200610052315A CN 100436432 C CN100436432 C CN 100436432C
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- 238000002360 preparation method Methods 0.000 title abstract description 8
- QRXNXWBLXOJERO-UHFFFAOYSA-N 3-methyl-4-[(1,3,4-thiadiazol-2-yldiazenyl)methyl]phenol Chemical compound CC1=C(CN=NC=2SC=NN2)C=CC(=C1)O QRXNXWBLXOJERO-UHFFFAOYSA-N 0.000 title 1
- -1 2-[(2-methyl-4-hydroxyphenyl)azo]-1, 3, 4-thiadiazole compound Chemical class 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 16
- 230000003287 optical effect Effects 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 9
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004202 carbamide Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000012954 diazonium Substances 0.000 description 10
- 239000000523 sample Substances 0.000 description 8
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QUKGLNCXGVWCJX-UHFFFAOYSA-N 1,3,4-thiadiazol-2-amine Chemical class NC1=NN=CS1 QUKGLNCXGVWCJX-UHFFFAOYSA-N 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 150000001989 diazonium salts Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 210000003608 fece Anatomy 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000004867 thiadiazoles Chemical class 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明涉及一种新的化合物,2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑化合物,以及其制备和应用。化合物结构式如(I)所示,制备方法为噻二唑重氮盐和间甲基苯酚在尿素存在下,于-10~15℃在C1~C8的醇溶剂中发生偶合反应得到所述的2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑化合物,此合成方法原料易得,操作简单,反应条件温和,具有广泛的实施价值,合成的材料具有较高的三阶非线性极化率χ(3),较高的非线性折射率n2和较高的二阶超极化率γ以及超快的时间响应,是良好的有机三阶非线性材料。
Description
(一)技术领域
本发明涉及一种新的化合物,2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑化合物,以及其制备和应用。
(二)背景技术
非线性光学的目标之一是寻找在一定波长下同时具有强的非线性光学特性和超快时间响应的材料,以满足未来基于全光器件光计算的需要。众多的理论和实验已经证明,具有π电子共轭结构的有机分子材料是实现这一目标很有竞争力的材料。
偶氮类化合物是一类含有共轭大π电子体系的物质,已被发现具有较好的三阶非线性光学效应。它的这一效应与其在紫外或可见光波段存在的偶氮发色团π-π*强烈跃迁吸收带密切相关。接在偶氮发色团两端的基团的推-拉电子效应会显著地影响偶氮基团周围的共轭结构性质,从而导致上述π-π*吸收带的移动和展宽。实际上,偶氮基团π-π*跃迁在这类体系中的红移正暗示了体系电子的离域化程度增强,从而使得基态到激发态产生的跃迁偶极距增大,减少能隙,有利于提高材料的三阶非线性光学效应。
在这个研究过程中,发明人发现了一种新的化合物,2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑化合物,以及其制备方法,和作为有机三阶非线性光学材料的良好应用。
(三)发明内容
本发明的目的是提供一种作为良好的有机三阶非线性光学材料的新化合物,以及其制备方法。
所采用的技术方案如下:
一种2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑化合物,具有如式(I)所示的结构:
一种制备所述的2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑化合物的方法,式(II)所示的噻二唑重氮盐和间甲基苯酚在尿素存在下,于-10~15℃在C1~C8的醇溶剂中发生偶合反应得到所述的2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑化合物,
制备方法中,所述的噻二唑重氮盐与间甲基苯酚的物质的量比为1∶1~2,反应时间一般为1h到5h。
所述的醇溶剂的用量为间甲基苯酚质量的20~40倍。醇溶剂推荐选用甲醇、乙醇或异丙醇。
进一步,方法中所述的噻二唑重氮盐是由2-氨基-1,3,4-噻二唑与亚硝酰硫酸在-10~20℃的条件下于酸溶剂中发生重氮化反应得到,所述的2-氨基-1,3,4-噻二唑与亚硝酰硫酸的物质的量比为1∶1.2~1.5。
所述的酸溶剂推荐硫酸、乙酸或丙酸。酸溶剂的量为2-氨基-1,3,4-噻二唑质量的10~30倍。
由于原料2-氨基-1,3,4-噻二唑的碱性很弱,因此用强亲电性试剂亚硝酰硫酸对它进行重氮化,而且为了使反应完全,亚硝酰硫酸需过量20~50%,反应时间一般为30min到5h。
具体的,按照物质的量比,噻二唑重氮盐∶间甲基苯酚为1∶1.2,在尿素存在下,于-5~10℃在甲醇或乙醇中发生偶合反应1~5h,得到所述的2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑化合物。反应结束后,产物可析出,然后过滤,洗涤,用重结晶或柱层析法提纯。
2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑化合物可作为有机三阶非线性光学材料应用。2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑有机化合物具有π电子共轭结构。接于偶氮基团两边的噻二唑以及间甲基苯酚都是有效的供电子基团,从而使偶氮基团附近π电子的离域化程度增强,π-π*跃迁的能隙减小,跃迁偶极距增大。因此该材料具有较高的三阶非线性极化率χ(3),较高的非线性折射率n2和较高的二阶超极化率γ。对于非三阶非线性光学材料,是不存在三阶非线性极化率、非线性折射率和二级超极化率的。由于2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑不存在近共振或共振吸收,其三阶非线性光学效应主要来源于化合物的构型,且在共轭结构中的含硫杂环对二阶超极化率γ贡献显著。此外,该材料具有<110fs的超快时间响应。
本发明所述的2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑化合物的化学合成方法,原料易得,操作简单,反应条件温和,具有广泛的实施价值。
(四)附图说明
图1是用四波混频法测出的式(I)化合物的非线性光学响应对延迟时间图。其纵坐标表示四波混频共轭光强度,横坐标表示延迟时间。图中点为实验数据,实线为高斯拟合结果,拟合后响应峰的半高宽度为响应时间。
(五)具体实施方式:
以下以具体实施例来说明本发明的技术方案,但本发明的保护范围不限于此:
实施例1 2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑的合成
2.02g(0.020mol)2-氨基-1,3,4-噻二唑在搅拌下加入到30mL乙酸中,在15~20℃滴加过量30%的亚硝酰硫酸。然后搅拌3h得1,3,4-噻二唑重氮盐。
2.60g间甲基苯酚(0.024mol),0.8g尿素在搅拌下加入到100mL乙醇中,在-5~10℃滴加上述制得的重氮盐。然后搅拌3h,过滤,洗涤,得粗产物。用甲醇重结晶得到0.4g桔红色粉末状结晶产品,收率9.1%。m.p.224~226℃。IR,v/cm-1:3436(OH),1576(N=N),1234(C-N)。1HNMR,δ(ppm):10.94(s,1H,OH);9.57(s,1H,噻二唑环-H);7.80(d,1H,苯环-H);6.86(s,1H,苯环-H);6.80(d,1H,苯环-H)。元素分析(C9H8N4OS)实测值(计算值)(%):C48.69(49.08),H 3.64(3.66),N 25.06(25.44)。
实施例2 2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑的合成
2.02g(0.020mol)2-氨基-1,3,4-噻二唑在搅拌下加入到35mL丙酸中,在0~10℃滴加过量40%的亚硝酰硫酸。然后搅拌4h得1,3,4-噻二唑重氮盐。
2.81g间甲基苯酚(0.026mol),0.8g尿素在搅拌下加入到100mL甲醇中,在-5~10℃滴加上述制得的重氮盐。然后搅拌4h,过滤,洗涤,得粗产物。用甲醇重结晶得到0.8g桔红色粉末状结晶产品,收率18.2%。m.p.224~226℃。
实施例3 2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑的合成
2.02g(0.020mo l)2-氨基-1,3,4-噻二唑在搅拌下加入到30mL丙酸中,在-5~5℃滴加过量20%的亚硝酰硫酸。然后搅拌3h得1,3,4-噻二唑重氮盐。
2.60g间甲基苯酚(0.024mol),0.8g尿素在搅拌下加入到90mL乙醇中,在0~10℃滴加上述制得的重氮盐。然后搅拌4h,过滤,洗涤,得粗产物。用甲醇重结晶得到1.0g桔红色粉末状结晶产品,收率22.7%。m.p.224~226℃。
实施例4 作为有机三阶非线性材料的光学性能测试
本发明所述的2-[(2-甲基-4-羟基苯基)偶氮]-1,3,4-噻二唑有机材料的三阶非线性光学性能采用简并四波混频(DFWM)法测试。
实验中用Ti:Sapphire飞秒激光器作为光源,波长为800nm,脉宽为80fs,重复频率为1KHz,单脉冲能量约为0.05mJ。
样品的三阶非线性极化率χ(3)是通过相对测量法得到的,即在相同的条件下,用三阶非线性极化率已知的CS2介质作参考,通过比较它们信号的相对大小,求出样品的三阶非线性极化率。其三阶非线性极化率χ(3)的计算公式为:
式中下标s和r分别表示待测样品与参照样品CS2所对应的物理量。n为折射率,L为比色皿的厚度,α为线性吸收系数,Is和Ir分别是待测样品与参照样品的共轭光强度。参照样品CS2的χr (3)为6.7×10-14esu,nr为1.632。
由三阶光学非线性系数引起的非线性折射率为:
n2(esu)=12πx(3)/n2
样品溶质分子的二阶超极化率γ可由下式得到:
其中N为溶质的分子密度,N=6.02×1023c,c为样品溶液的摩尔浓度,式(I)化合物的c为5.40×10-4mol/L。f4为局域场修正因子,f4=[(n2+2)/3]4。
响应时间是由四波混频共轭光强度与延迟时间作图,再经高斯拟合后得到。
表1 测试材料的光学参数
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Derivatives of thiadiazolazo compounds asanalyticalreagents. V. Investigation of nickel(2+), cobalt(2+),iron(2+),copper(2+) and cadmium(2+) complexes with the azodyederivatives of 1,3,4-thiadiazole. Domagalina, Eugenia, Zareba, Stanislaw.Chem. Anal. (Warsaw),Vol.21 No.2. 1976 |
Derivatives of thiadiazolazo compounds asanalyticalreagents. V. Investigation of nickel(2+), cobalt(2+),iron(2+),copper(2+) and cadmium(2+) complexes with the azodyederivatives of 1,3,4-thiadiazole. Domagalina, Eugenia, Zareba, Stanislaw.Chem. Anal. (Warsaw),Vol.21 No.2. 1976 * |
Protonation Study and Mechanism of Hydrolysisof2-[(p-Methoxyphenylazo]-1,3,4-thiadiazole in AqueousSulfuricAcid at 60 °C.. Ogunjobi, Kayode Ade.J. Org. Chem.,Vol.59 No.12. 1994 |
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