Moisture Absorption Reaction and Fluorescence Property of Highly Active Michael System Based on Arylidenemalononitrile

doi:10.7503/cjcu20210690

Abstract

Abstract:

The phenols and alcohols as nucleophiles are common in oxa-Michael reaction， while H₂O normally cannot react with Michael system 2，2'-｛［5-（tert-butyl）-2-hydroxy-1，3-phenylene］bis（methaneylylidene）｝dimalononitrile（1） was reported， which could rapidly absorb water in the air to afford a stable 2-［5-（tert-butyl）-3-（2，2- dicyano-1-hydroxyethyl）-2-hydroxybenzyli-dene］malononitrile（2） via oxa-Michael addition. The high activity of compound 1 resulted from the synergistic effect among the two dicyanovinyl groups and the one hydroxyl group. In dimethyl sulfoxide（DMSO）， compound 2 could quickly dehydrate to give compound 1 in the presence of various alkaline catalysts. In PBS buffer（pH=10）， compound 2 immediately converted to compound 1， and then converted back to compound 2 slowly. When heat the silica gel plate loading compound 2， the fluorescence conversion from blue to red were observed. Hence， compound 2 adsorbed on silica gel might be developed into a thermosensitive fluorescent material. In addition， compound 2 adsorbed on silica gel showed fluorescence responses to some organic vapors.

Key words: Oxa-Michael reaction, Arylidenemalononitrile, Moisture absorption reaction, Fluorescence property

CLC Number:

O622.6

TrendMD:

LI Qiao, ZHAO Yang, WANG Enju. Moisture Absorption Reaction and Fluorescence Property of Highly Active Michael System Based on Arylidenemalononitrile[J]. Chem. J. Chinese Universities, 2022, 43(3): 20210690.

Figures/Tables 8

Scheme 1 Structures of the target molecules

Fig.1 Color in natural light(A) and fluorescence under 365 nm(B) of compound 2 adsorbed on silica gel at gradient temperatures of 30(A1, B1), 40(A2, B2), 50(A3, B3), 60(A4, B4), 70(A5, B5) and 80 ℃(A6, B6)

Table 1 Effect of various catalysts on the dehydration reaction of compound 2

Number	Solvent	Catalyst	Reaction（30 ℃）	Number	Solvent	Catalyst	Reaction（30 ℃）
1	DMSO	MeCOOH	No reaction	8	CH₃CN	MeCOOH	No reaction
2	DMSO	Pyridine	Reaction ^a	9	CH₃CN	Pyridine	No reaction
3	DMSO	Et₃N	Reaction ^b	10	CH₃CN	Et₃N	Reaction ^b
4	DMSO	Na₂CO₃	Reaction ^b	11	CH₃CN	Na₂CO₃	Reaction ^c
5	DMSO	K₂CO₃	Reaction ^b	12	CH₃CN	K₂CO₃	Reaction ^c
6	DMSO	CaO	Reaction ^b	13	CH₃CN	CaO	Reaction ^b
7	DMSO	Silica gel	Reaction ^b	14	CH₃CN	Silica gel	No reaction

Fig.2 Fluorescence spectra(A, C) and pictures(B, D) of compound 2(10 μmol/L) excited at 560 nm(A, C) and 365 nm(B, D) in DMSO(A, B) and CH3CN(C, D) upon addition of various catalysts

Scheme 2 Proposed plausible mechanism for hydroxyl group promoting reaction

Fig.3 Response of compound 2 adsorbed on silica gel to organic vapors(degrease cotton soaked with organic solvents)(A—D) Natural light; (A′—D′) 365 nm. (A) Free; (B) ethyl acetate; (C) THF; (D) acetone.

Fig.4 Time?dependent fluorescence spectra excited at 470 nm(A) and pictures in natural light and under 365 nm(B) of compound 2(10 μmol/L) in PBS buffer solution(pH=10)Time?dependent fluorescence spectra were recorded every 3 min for about 1 h.

Fig.5 Fluorescence emission spectra of compound 2(10 μmol/L) in PBS buffer at different pH values when excited at 360 nmInset： pictures at pH=4 and pH=10 in ultraviolet analyzer under 365 nm.

References 20

1	Hong Y. M.， Shen Z. L.， Mo W. M.， Hu X. Q.， Chin. J. Org. Chem.， 2009， 29（10）， 1544—1554（洪一鸣，沈振陆，莫卫民，胡信全. 有机化学， 2009， 29（10）， 1544—1554）
2	Wu W. B.， Liu B.， Chem. J. Chinese Universities， 2020， 41（2）， 191—203 （武文博，刘斌. 高等学校化学学报， 2020， 41（2）， 191—203）
3	Singh A.， Lim C. K.， Lee Y. D.， Maeng J. H.， Lee S.， Koh J.， Kim S.， ACS Appl. Mater. Inter.， 2013， 5（18）， 8881—8888
4	Li H.， Peng W.， Feng W.， Wang Y.， Chen G.， Wang S.， Li S.， Li H.， Wang K.， Zhang J.， Chem. Commun.， 2016， 52（25）， 4628—4631
5	Guo Z. Q.， Yan C. X.， Zhu W. H.， Angew. Chem. Int. Edit.， 2020， 59（25）， 9812—9825
6	Shao A. D.， Guo Z. Q.， Zhu S. J.， Zhu S. Q.， Shi P.， Tian H.， Zhu W. H.， Chem. Sci.， 2014， 5（4）， 1383—1389
7	Guo Z. Q.， Shao A. D.， Zhu W. H.， J. Mater. Chem. C， 2016， 4（14）， 2640—2646
8	Yao S.， Shao A. D.， Zhao W. R.， Zhu S. J.， Shi P.， Guo Z. Q.， Zhu W. H.， Shi J. L.， RSC Adv.， 2014， 4（103）， 58976—58981
9	Dou W. T.， Zhang J. J.， Li Q.， Guo Z. Q.， Zhu W. H.， Chen G. R.， Zhang H. Y.， He X. P.， ChemBioChem， 2019， 20（14）， 1856—1860
10	Shi C. X.， Guo Z. Q.， Yan Y. L.， Zhu S. Q.， Xie Y. S.， Zhao Y. S.， Zhu W. H.， Tian H.， ACS Appl. Mater. Interfaces， 2013， 5（1）， 192—198
11	Sohn S.， Koh B. H.， Baek J. Y.， Byun H. C.， Lee J. H.， Shin D. S.， Ahn H.， Lee H. K.， Hwang J.， Jung S.， Kim Y. H.， Dyes Pigments， 2017， 140， 14—21
12	Luo T. Y.， Lin Z. S.， Li Z. Y.， Wang Y.， Xu W. H.， Zhao C. X.， Wang H.， Luan X. J.， Organic Electronics， 2021， 88， 106003
13	Lakshmi P. R.， Kumar P. S.， Elango K. P.， Spectrochim. Acta Part A， 2020， 229， 117974
14	Gong S. H.， Zhang X.， Li N.， Tang B.， Chem. J. Chinese Universities， 2020， 41（9）， 1933-1944 （公少华，张霞，李娜，唐波. 高等学校化学学报， 2020， 41（9）， 1933-1944）
15	Gilanizadeh M.， Zeynizadeh B.， New J. Chem.， 2018， 42（11）， 8553—8566
16	Gong K.， Zhang D. Q.， Wang Y. Y.， Li C. H.， Zhang H. M.， Li H. R.， Feng H. R.， Mol. Catal.， 2021， 509， 111663
17	Jadhav S. N.， Patil S. P.， Sahoo D. P.， Rath D.， Parida K， Rode C. V.， Catal. Lett.， 2020， 150（8）， 2331—2351
18	Muhammad S.， Javed M. N.， Ali F. I.， Bari A.， Hashmi I. A.， J. Mol. Liq.， 2020， 300， 112372
19	Feghhi A.， Malakooti R.， Malakooti S.， Hooshmand N.， Chemistry Select， 2019， 4（9）， 2551—2561
20	Yadav S.， Srivastava M.， Rai P.， Singh J.， Tiwari K. P.， Singh J.， New J. Chem.， 2015， 39（6）， 4556—4561

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