付秀芳，石崇慧，陳冠凡

(湖南科技大學(xué) 化學(xué)化工學(xué)院，湖南 湘潭，411201)

氮苯丙烯叉基苯胺衍生物紫外光譜中的取代基效應(yīng)

付秀芳，石崇慧，陳冠凡

(湖南科技大學(xué) 化學(xué)化工學(xué)院，湖南 湘潭，411201)

氮苯丙烯叉基苯胺；紫外吸收光譜； 激發(fā)態(tài)參數(shù)；取代基效應(yīng)

在有機(jī)共軛分子中，分子的前線軌道(HOMO/LUMO)之間的能級(jí)差受到其結(jié)構(gòu)的影響。改變有機(jī)共軛分子中的取代基可以精細(xì)地調(diào)節(jié)其前線軌道能級(jí)[1]，從而有效地改善有機(jī)共軛光電發(fā)光材料的光學(xué)性能。紫外吸收光譜作為反映分子的前線軌道之間能級(jí)差的常用光譜分析方法，其與分子結(jié)構(gòu)之間的定量關(guān)系備受化學(xué)研究者關(guān)注[2-5]，研究者們?cè)噲D找出兩者之間的定量關(guān)系，從而為有機(jī)共軛光電發(fā)光材料的設(shè)計(jì)合成提供理論依據(jù)。

著名的Hammett參數(shù)(σ參數(shù))[6]，曾是最早用于紫外吸收光譜定量研究的取代基參數(shù)。盡管其能夠廣泛應(yīng)用于多數(shù)有機(jī)共軛分子光譜中的取代基效應(yīng)定量研究，然而，其用于化合物激發(fā)態(tài)的性能研究的合理性仍受到某些研究者質(zhì)疑[7]。上世紀(jì)90年代，蔣錫夔和計(jì)國(guó)楨提出了自旋-離域效應(yīng)參數(shù)σJJ·[8]，建立了的單參數(shù)方程(自由基取代參數(shù)σ·)和雙參數(shù)方程(極性取代基參數(shù)σx和自由基取代參數(shù)σ·)，并成功的應(yīng)用于取代苯乙烯，取代苯乙炔等不同芳香化合物紫外吸收光譜的取代基效應(yīng)研究。

υmax=ρ·σ·+ C，

(1)

υmax=ρ·σ·+ρxσx+ C。

(2)

1 數(shù)據(jù)集

1.1 模型化合物的合成

氮苯丙烯叉基苯胺衍生物(N-(3-phenylallylidene)benzenamine，簡(jiǎn)稱PBA)均采用無(wú)溶劑縮合反應(yīng)制備得到(如圖1所示)[12]，其具體操作為：稱取10mmol取代肉桂醛和10mmol取代苯胺置于瑪瑙研缽中，兩者混合研磨，TCL檢測(cè)反應(yīng)終點(diǎn)，粗產(chǎn)物經(jīng)乙醇重結(jié)晶，得到相應(yīng)的產(chǎn)物，且產(chǎn)物結(jié)構(gòu)經(jīng)1H NMR 確證。

圖1 氮苯丙烯叉基苯胺衍生物的合成路線Fig.1 Synthetic route of the N-(3-phenylallylidene)benzenamine derivatives

p-Me2NPBAOMe-p(1),1H NMR(CDCl3,TMS,500MHz): 8.24(d,J=8.9Hz,1H),7.42(d,J=8.7Hz,2H),7.18(d,J=8.8Hz,2H),7.04(d,J=15.8Hz,1H),6.93(q,3H),6.69(d,J=8.7Hz,2H),3.82(s,3H),3.01(s,6H)。

p-Me2NPBAMe-p(2),1H NMR(CDCl3,TMS,500MHz): 8.24(d,J=9.0Hz,1H),7.43(d,J=8.8Hz,2H),7.17(d,J=8.1Hz,2H),7.07(q,3H),6.94(q,1H),6.70(d,J=8.7Hz 2H),3.02(s,6H),2.36(s,3H)。

p-Me2NPBAH(3),1H NMR(CDCl3,TMS,500MHz): 8.23(d,J=9.0Hz,1H),7.44(d,J=8.7Hz,2H),7.37(t,2H),7.19(t,3H),7.09(d,J=15.8Hz,1H),6.95(q,1H),6.70(d,J=8.8Hz 2H),3.02(s,6H)。

p-Me2NPBAF-p(4),1H NMR(CDCl3,TMS,500MHz): 8.20(d,J=9.0Hz,1H),7.43(d,J=8.8Hz,2H),7.10(m,5H),6.92(q,1H),6.69(d,J=8.8Hz 2H),3.02(s,6H)。

p-Me2NPBACl-p(5),1H NMR(CDCl3,TMS,500MHz): 8.19(d,J=9.0Hz,1H),7.43(d,J=8.9Hz,2H),7.32(d,J=8.6Hz,2H),7.09(t,3H),6.92(q,1H),6.69(d,J=8.7Hz 2H),3.02(s,6H)。

p-MeOPBAOMe-p(6),1H NMR(CDCl3,TMS,500MHz): 8.27(d,J=8.6Hz,1H),7.8(d,J=8.6Hz,2H),7.19(d,J=9.0Hz,2H),7.03(m,2H),6.92(q,4H),3.84(d,J=8.0Hz,6H)。

p-MeOPBAMe-p(7),1H NMR(CDCl3,TMS,500MHz): 8.26(d,J=8.7Hz,1H),7.48(d,J=8.7Hz,2H),7.18(d,J=8.1Hz,2H),7.09(q,3H),7.00(q,1H),6.92(d,J=8.8Hz,2H),3.84(s,3H),2.36(s,3H)。

p-MeOPBAPhH(8),1H NMR(CDCl3,TMS,500MHz): 8.24(d,J=8.8Hz,1H),7.49(d,J=8.8Hz,2H),7.37(d,J=7.5Hz,2H),7.15(m,4H),7.00(q,1H),6.92(d,J=8.8Hz,2H),3.84(s,3H)。

p-MeOPBAF-p(9),1H NMR(CDCl3,TMS,500MHz): 8.21(d,J=8.8Hz,1H),7.49(d,J=8.8Hz,2H),7.16(q,2H),7.08(m,3H),6.96(m,3H),3.84(s,3H)。

p-MeOPBACl-p(10),1H NMR(CDCl3,TMS,500MHz): 8.20(d,J=8.8Hz,1H),7.49(d,J=8.7Hz,2H),7.33(d,J=8.7Hz,2H),7.12(t,3H),6.96(m,3H),3.84(s,3H)。

p-MePBAOMe-p(11),1H NMR(CDCl3,TMS,500MHz): 8.29(d,J=7.3Hz,1H),7.43(d,J=8.0Hz,2H),7.20(d,J=8.7Hz,4H),7.08(d,J=8.4Hz,2H),6.92(d,J=8.9Hz,2H),3.38(s,3H),2.38(s,3H)。

p-MePBAMe-p(12),1H NMR(CDCl3,TMS,500MHz): 8.25(d,J=7.8Hz,1H),7.43(d,J=8.0Hz,2H),7.20(t,4H),7.10(q,4H),2.38(s,3H),2.36(s,3H)。

p-MePBAH(13),1H NMR(CDCl3,TMS,500MHz): 8.25(d,J=8.2Hz,1H),7.44(d,J=8.0Hz,2H),7.38(t,2H),7.20(q,5H),7.08(m,2H),2.38(s,3H)。

p-MePBAF-p(14),1H NMR(CDCl3,TMS,500MHz): 8.22(d,J=8.4Hz,1H),7.43(d,J=8.1Hz,2H),7.20(d,J=7.9Hz,2H),7.16(q,2H),7.07(m,4H),2.38(s,3H)。

p-MePBACl-p(15),1H NMR(CDCl3,TMS,500MHz): 8.22(d,J=8.8Hz,1H),7.44(d,J=8.0Hz,2H),7.33(d,J=8.6Hz,2H),7.21(d,J=7.9Hz,2H),7.09(m,4H),2.38(s,3H)。

HPBAOMe-p(16),1H NMR(CDCl3,TMS,500MHz): 8.31(q,1H),7.55(t,2H),7.41(q,2H),7.36(t,1H),7.22(q,2H),7.13(t,2H),6.93(q,2H).3.84(s,3H)。

HPBAMe-p(17),1H NMR(CDCl3,TMS,500MHz): 8.29(d,J=8.0Hz,1H),7.54(d,J=7.2Hz,2H),7.37(m,3H),7.19(d,J=8.1Hz,2H),7.12(t,4H),2.36(s,3H)。

HPBAH(18),1H NMR(CDCl3,TMS,500MHz): 8.29(d,J=7.8Hz,1H),7.55(d,J=7.1Hz,2H),7.39(m,5H),7.22(m,3H),7.13(m,2H)。

HPBAF-p(19),1H NMR(CDCl3,TMS,500MHz): 8.25(d,J=8.4Hz,1H),7.55(d,J=7.0Hz,2H),7.39(m,3H),7.17(m,3H),7.09(m,3H)。

HPBACl-p(20),1H NMR(CDCl3,TMS,500MHz): 8.23(d,J=8.5Hz,1H),7.54(d,J=7.0Hz,2H),7.37(m,5H),7.12(m,4H)。

p-ClPBAOMe-p(21),1H NMR(CDCl3,TMS,500MHz): 8.29(d,J=7.4Hz,1H),7.46(d,J=8.5Hz,2H),7.36(d,J=8.5Hz,2H),7.21(d,J=8.9Hz,2H),7.07(d,J=5.4Hz,2H),6.93(d,J=8.9Hz,2H),3.83(s,3H)。

p-ClPBAMe-p(22),1H NMR(CDCl3,TMS,500MHz): 8.27(d,J=8.3Hz,1H),7.45(d,J=8.5Hz,2H),7.35(d,J=8.5Hz,2H),7.19(d,J=8.0Hz,2H),7.11(d,J=8.2Hz,2H),7.07(d,J=4.8Hz,2H),2.36(s,3H)。

p-CPBAH(23),1H NMR(CDCl3,TMS,500MHz): 8.26(d,J=8.2Hz,1H),7.46(d,J=8.5Hz,2H),7.39(q,4H),7.24(t,1H),7.19(d,J=7.4Hz,2H),7.09(d,J=6.3Hz,2H)。

p-ClPBAF-p(24),1H NMR(CDCl3,TMS,500MHz): 8.24(d,J=7.9Hz,1H),7.46(d,J=8.5Hz,2H),7.37(d,J=8.5Hz,2H),7.17(q,2H),7.06(m,4H)。

p-ClPBACl-p(25),1H NMR(CDCl3,TMS,500MHz): 8.23(d,J=8.3Hz,1H),7.47(d,J=8.4Hz,2H),7.36(q,4H),7.12(q,3H),7.06(q,1H)。

1.2 模型化合物紫外吸收光譜的測(cè)定

表1 氮苯丙烯叉基苯胺衍生物的最大吸收波長(zhǎng)λmax(nm)及最大吸收波數(shù)υmax (cm-1)

表2 所用的取代基參數(shù)數(shù)值

2 結(jié)果與討論

分析表1中數(shù)據(jù)，不同苯環(huán)上的相同取代基對(duì)于氮苯丙烯叉基苯胺衍生物的紫外吸收光譜影響明顯不同。如MePBAH的最大吸收波長(zhǎng)和波數(shù)分別為311.41nm和32112 cm-1，而HPBAMe的最大吸收波長(zhǎng)和波數(shù)分別為323.90nm和30873cm-1。該現(xiàn)象意味著氮苯丙烯叉基苯胺衍生物紫外吸收光譜中碳端苯環(huán)和氮端苯環(huán)取代基效應(yīng)可能呈現(xiàn)出不同規(guī)律。

2.1 氮端苯環(huán)取代基效應(yīng)對(duì)氮苯丙烯叉基苯胺衍生物紫外吸收光譜的影響

表3 單參數(shù)方程對(duì)不同系列模型化合物最大吸收波數(shù)中氮端苯環(huán)取代基變化的回歸結(jié)果

表4 雙參數(shù)方程對(duì)不同系列模型化合物最大吸收波數(shù)中氮端苯環(huán)取代基變化的回歸結(jié)果

2.2 碳端苯環(huán)取代基效應(yīng)對(duì)氮苯丙烯叉基苯胺衍生物紫外吸收光譜的影響

根據(jù)先前的取代trans-二苯乙烯和取代氮芐叉基苯胺等的紫外光譜中取代基效應(yīng)的研究結(jié)果，我們發(fā)現(xiàn)，氮端苯環(huán)的取代基效應(yīng)適合用雙參數(shù)方程關(guān)聯(lián)，與先前取代氮芐叉基苯胺的紫外吸收光譜中取代基效應(yīng)類似；而碳端苯環(huán)的取代基效應(yīng)可用單參數(shù)方程關(guān)聯(lián)，與先前trans-二苯乙烯的紫外光譜中取代基效應(yīng)近似。

表5 單參數(shù)方程對(duì)不同系列模型化合物最大吸收波數(shù)中碳端苯環(huán)取代基變化的回歸結(jié)果

表6 雙參數(shù)方程對(duì)不同系列模型化合物最大吸收波數(shù)中碳端苯環(huán)取代基變化的回歸結(jié)果

3 結(jié)論

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[3]G.Vastag,S.Apostolov,B.Matijevi,et al.Structure-interaction relationship study of N-(4-phenylsubstituted) cyanoacetamides by multivariate methods[J].Journal of Chemometrics.2016,30(04): 210-216.

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[6]L.P.Hammett.The Effect of Structure upon the Reactions of Organic Compounds.Benzene Derivatives[J].Journal of American Chemistry Society,1937,59(01):96-103.

[7]高振衡,趙愛華,王明真.5-苯基-2-(2’-苯基(噁) 唑基-5’)1,3,4-(噁)二唑及其5-對(duì)位取代苯基衍生物的研究[J].有機(jī)化學(xué),1988,8,18-23.

[8]X.K.Jiang.Establishment and Successful Application of the σJJScale of Spin-Delocalization Substituent Constants[J].Accounts of Chemical Research,1997,30(07)：283-289.

[10]G.F.Chen,C.Z.Cao.Substituent effect on the UV spectra of p-disubstituted compounds XPh(CH=CHPh)nY (n=0,1,2) [J].Journal of Physical Organic Chemistry,2010,23(01): 776-782.

[11]G.F.Chen,C.Z.Cao,B.T.Lu,et al.The substituent effect on the UV energy of 4,4′-disubstituted benzylideneanilines[J].Journal of Physical Organic Chemistry,2012,25(08): 327-333.

[12]G.F.Chen,C.Z.Cao,B.Sheng,et al.Substituent effect study on δc values of the bridge group carbons in disubstituted cinnamyl aniline series[J].Journal of Physical Organic Chemistry,2012,25(02): 828-834.

[13]C.Hansch,A.Leo,R.W.A survey of Hammett substituent constants and resonance and field parameters[J].Chemical Reviews,1991,91 (02): 165-195.

The effect of substituent on the UV-Vis spectroscopy of substituted N-(3-phenylallylidene)benzenamine

FU Xiufang,SHI Conghui,CHEN Guanfan

(SchoolofChemistryandChemicalEngineering，HunanUniversityofScienceandTechnology，Xiangtan411201，China)

25 sorts of para-substituted N-(3-phenylallylidene)benzenamine were synthesized and their UV-Vis spectra were measured in ethanol.In the study on the UV energy of the titled compounds,for the effect of substituent X that is close to carbon in the bridge bond on the UV wavenumbers,its UV data can be correlated with a single-parameter equation,which is similar to the substituent effect of trans-stilbene on their UV wavenumbers.However,for the effect of substituent Y that is close to nitrogen in the bridge bond on the UV data,its UV energy can be correlated with a double-parameter equation,which resembles the substituent effect of benzylideneanilines on their UV wavenumbers.

N-(3-phenylallylidene)benzenamine; UV-Vis spectroscopy;excited-state substituent constant; substituent effect

1672-7010(2016)02-0108-07

2016-05-16

國(guó)家自然科學(xué)基金資助項(xiàng)目(21202043)

付秀芳(1992-),女,河南永城人,研究生,從事有機(jī)合成研究通信作者：陳冠凡(1978-),男，湖南韶山人，副教授,博士，從事有機(jī)合成研究；E-mail:gfchen@hnust.edu.cn

O621.4

A