CN109232428B - Pyrazolyl azophenol compound and synthesis and derivation thereof - Google Patents

Pyrazolyl azophenol compound and synthesis and derivation thereof Download PDF

Info

Publication number
CN109232428B
CN109232428B CN201811257615.7A CN201811257615A CN109232428B CN 109232428 B CN109232428 B CN 109232428B CN 201811257615 A CN201811257615 A CN 201811257615A CN 109232428 B CN109232428 B CN 109232428B
Authority
CN
China
Prior art keywords
pyrazolyl
azophenol
methyl
diazenyl
synthesis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811257615.7A
Other languages
Chinese (zh)
Other versions
CN109232428A (en
Inventor
李涛
张召阳
贺逸昕
周颖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Jiaotong University
Original Assignee
Shanghai Jiaotong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Jiaotong University filed Critical Shanghai Jiaotong University
Priority to CN201811257615.7A priority Critical patent/CN109232428B/en
Priority to PCT/CN2019/070081 priority patent/WO2020082605A1/en
Publication of CN109232428A publication Critical patent/CN109232428A/en
Application granted granted Critical
Publication of CN109232428B publication Critical patent/CN109232428B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/38—Nitrogen atoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention relates to a pyrazolyl azophenol compound and synthesis and derivation thereof. In particular to 4- ((1-methyl-1H-pyrazol-4-yl) diazenyl) phenol, the structure of which is shown as follows:
Figure DDA0001843110330000011
the synthesis method of the 4- ((1-methyl-1H-pyrazol-4-yl) diazenyl) phenol is simple, and a plurality of azobenzene photoresponse functional molecules with long half-life Z isomers can be derived through phenolic hydroxyl. Compared with the prior art, the pyrazolyl azophenol compound provided by the invention has the advantages of easily available raw materials, simple synthesis process, high yield and easiness in mass production. The etherification and esterification reactions of the compound are classical organic reactions and have the advantages of mild conditions and high yield. In a word, the invention provides a convenient way for developing and utilizing the long half-life Z isomer azobenzene photoresponsive functional molecule.

Description

Pyrazolyl azophenol compound and synthesis and derivation thereof
Technical Field
The invention relates to an azobenzene compound and synthesis thereof, in particular to a pyrazolyl azophenol compound and synthesis and derivation thereof.
Background
Azobenzene is a classical photochromic molecule that converts from the E (trans) configuration to the Z (cis) configuration under uv light irradiation and reverts back to the E configuration from the Z configuration under visible light irradiation. Due to the reversible photoisomerization reaction, azobenzene compounds provide wide space for developing optically controlled functional materials and devices, and are paid attention to in various technical fields such as optical switches, optical driving, energy and information storage and the like.
For most applications, the stability of the isomer is of crucial importance. However, in general, the Z isomer of azobenzene compounds is less stable and will be rapidly thermally reverted to the E isomer. Although adjustable by substituents, azobenzenes with long half-life Z isomers are still quite rare. The document (J.Am.chem.Soc.2014,136,11878-11881) reports that the pyrazolyl azobenzene compound with an ultra-long half-life is 1-methyl- (phenyl diazenyl) -1H-pyrazole, the Z isomer of which has ultra-high stability and the half-life of which is up to 1000 days at room temperature (25 ℃). However, as the benzene ring of the molecule has no substituent, the molecule is not easy to derive, and the development and the application of the azobenzene molecule with the long half-life Z isomer are limited.
Disclosure of Invention
In order to overcome the defect that the existing long half-life azobenzene compound 1-methyl-4- (phenyl diazenyl) -1H-pyrazole is not easy to derive, the invention provides a pyrazolyl azophenol compound and a synthesis method and derivation thereof.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a pyrazolyl azophenol compound, in particular to 4- ((1-methyl-1H-pyrazol-4-yl) diazenyl) phenol, which has the following structure:
Figure BDA0001843110310000011
4- ((1-methyl-1H-pyrazol-4-yl) diazenyl) phenol, which can be regarded as a phenolic hydroxyl substituent of 1-methyl-4- (phenyldiazenyl) -1H-pyrazole.
The synthesis method of the 4- ((1-methyl-1H-pyrazol-4-yl) diazenyl) phenol is simple, and a plurality of azobenzene photoresponse functional molecules with long half-life Z isomers can be derived through phenolic hydroxyl.
The invention also provides a synthesis method of the pyrazolyl azophenol compound, which comprises the following steps:
diazotizing 4-amino-1-methylpyrazole, and then obtaining the target compound 4- ((1-methyl-1H-pyrazol-4-yl) diazenyl) phenol by utilizing the coupling reaction of aryl diazonium salt and phenol.
The synthetic route is as follows:
Figure BDA0001843110310000021
the invention also provides application of the pyrazolyl azo phenol compound, and ether or ester derivatives of pyrazolyl azo phenol are derived through etherification or esterification reaction of the phenolic hydroxyl of the 4- ((1-methyl-1H-pyrazol-4-yl) diazenyl) phenol.
The reaction formula is as follows:
Figure BDA0001843110310000022
the invention also provides an etherification reaction of pyrazolyl azophenol, wherein an etherification reagent is an organic reagent RCH with halogen substituent2X, where X ═ Cl, Br, I, R includes but is not limited to H, alkyl, aryl, or other possible organic groups,
the following product structure is obtained after the reaction:
Figure BDA0001843110310000023
in the above formula, R includes but is not limited to H, alkyl, aryl or other possible organic groups.
The invention also provides an esterification reaction of pyrazolyl azophenol, wherein an esterification reagent is an organic reagent with active acyl, and the following product structure is obtained after the reaction:
Figure BDA0001843110310000031
wherein R includes, but is not limited to, alkyl, aryl, or other possible organic groups.
The organic reagent with active acyl group includes carboxylic acid, acyl chloride and acid anhydride, etc.
The invention also provides an ether derivative of pyrazolyl azophenol, which has the following structure:
Figure BDA0001843110310000032
wherein R includes, but is not limited to, H, alkyl, aryl, or other possible organic groups.
The invention also provides an ester derivative of pyrazolyl azophenol, which has the following structure:
Figure BDA0001843110310000033
wherein R includes, but is not limited to, alkyl, aryl, or other possible organic groups.
The pyrazolyl azophenol compound provided by the invention has the parent structure of the ultra-long half-life azobenzene molecule 1-methyl-4- (phenyl diazenyl) -1H-pyrazole on one hand, and has phenolic hydroxyl group which is easy to be chemically derived on the other hand, so that the pyrazolyl azophenol compound can be used as a precursor to derive azobenzene photoresponsive functional molecules with long half-life Z isomers. Further, the invention prepares two series azobenzene molecules with long half-life Z isomers through simple etherification and esterification reactions.
The pyrazolyl azophenol compound provided by the invention has the advantages of easily obtained raw materials, simple synthesis process, high yield and easy mass production. The etherification and esterification reactions of the compound are classical organic reactions and have the advantages of mild conditions and high yield. In a word, the invention provides a convenient way for developing and utilizing the long half-life Z isomer azobenzene photoresponsive functional molecule.
Drawings
FIG. 1 is a nuclear magnetic spectrum of 4- ((1-methyl-1H-pyrazol-4-yl) diazenyl) phenol, a pyrazolyl azophenol compound obtained in examples 1 and 2;
FIG. 2 is a nuclear magnetic spectrum of the etherified derivative 4- ((4-methoxyphenyl) diazenyl) -1-methyl-1H-pyrazole obtained in example 3;
FIG. 3 is a nuclear magnetic spectrum of the etherified derivative 4- ((4- (allyloxy) phenyl) diazenyl) -1-methyl-1H-pyrazole obtained in example 4;
FIG. 4 is a nuclear magnetic spectrum of phenyl 4- ((1-methyl-1H-pyrazol-4-yl) diazenyl) acetate, an esterified derivative obtained in example 5.
Detailed Description
The invention is described in detail below with reference to specific figures and examples.
Example 1
Small batch Synthesis of Pyrazolylazophenol Compound 4- ((1-methyl-1H-pyrazol-4-yl) diazenyl) phenol (yield less than 0.73g)
The synthetic route is as follows:
Figure BDA0001843110310000041
4-amino-1-methylpyrazole (0.39g,4mmol,1eq.) was added to 10mL of deionized water, 2mL of concentrated hydrochloric acid (12.2mol/L,25mmol) was added, the temperature was reduced to 0 ℃ and 10mL of a cold aqueous solution of sodium nitrite (0.33g,4.8mmol,1.2eq.) was added dropwise, and the mixture was stirred for 15 min. 20mL of a mixed aqueous solution of cold phenol (0.45g,4.8mmol,1.2eq.) and sodium hydroxide (0.48g,12mmol) and sodium carbonate (1.3g,12mmol) was added dropwise thereto, and stirring was continued for 30 min. Then filtered, washed with water and dried to give the product as a yellow solid (0.73g, 90.4%).1H NMR(500MHz,CDCl3)δ7.98(s,1H),7.92(s,1H),6.91(d,J＝8.9Hz,2H),5.30(s,1H),3.97(s,3H)；UV-Vis(EA):λmax＝342.0nm；M.P.192.1-196.7℃。
EXAMPLE 2 Large Scale Synthesis of Pyrazolylazophenol Compound 4- ((1-methyl-1H-pyrazol-4-yl) diazenyl) phenol (yield 5.2g)
The synthetic route is as follows:
Figure BDA0001843110310000042
4-amino-1-methylpyrazole (2.91g,30mmol,1eq.) was added to 60mL of deionized water, 14mL of concentrated hydrochloric acid (12.2mol/L,170mmol) was added, the temperature was reduced to 0 ℃, 60mL of a cold aqueous solution of sodium nitrite (3.3g,48mmol,1.6eq.) was added dropwise, and stirring was carried out for 15 min. 120mL of cold benzene were then added dropwisePhenol (3.38g,36mmol,1.2eq.) and sodium hydroxide (3.2g,80mmol) were mixed with sodium carbonate (8.48g,80mmol) and the mixture was stirred for 30 min. Then filtered, washed with water and dried to give the product as a yellow solid (5.2g, 85.8%).1H NMR(500MHz,CDCl3)δ7.98(s,1H),7.92(s,1H),6.91(d,J＝8.9Hz,2H),5.30(s,1H),3.97(s,3H)；UV-Vis(EA):λmax＝342.0nm；M.P.192.1-196.7℃。
EXAMPLE 3 Synthesis of 4- ((4-methoxyphenyl) diazenyl) -1-methyl-1H-pyrazole, a pyrazolyl Azophenol etherified derivative
The synthetic route is as follows:
Figure BDA0001843110310000051
4- ((1-methyl-1H-pyrazol-4-yl) diazenyl) phenol (505mg,2.5mmol,1eq.), potassium tert-butoxide (365mg,3.25mmol,1.3eq.) and iodomethane (3.55g,25mmol,10eq.) were stirred at 40 ℃ in 10mL of N, N-dimethylformamide for 2H under reflux, and the progress of the reaction was monitored by TLC (PE: EA ═ 5: 1). After the reaction, water is added to separate out solid, and the solid is filtered and washed. The filter cake was dissolved in ethyl acetate, dried over anhydrous sodium sulfate, and separated by column chromatography (PE: EA ═ 5:1) to give yellow crystals (366mg, 68%).1H NMR(400MHz,CDCl3)δ7.98(s,1H),7.92(s,1H),7.78(d,J＝9.0Hz,2H),6.98(d,J＝9.0Hz,2H),3.96(s,3H),3.87(s,3H)；UV-Vis(CH3CN):λmax＝342.0nm；M.P.113.5-114.8℃。
EXAMPLE 4 Synthesis of the Pyrazolylazo-phenol etherified derivative 4- ((4- (allyloxy) phenyl) diazenyl) -1-methyl-1H-pyrazole
The synthetic route is as follows:
Figure BDA0001843110310000052
4- ((1-methyl-1H-pyrazol-4-yl) diazenyl) phenol (505mg,2.5mmol,1eq.), potassium tert-butoxide (365mg,3.25mmol,1.3eq.) and 3-bromo-1-propene (3.0g,25mmol,10eq.) were stirred at 65 ℃ in 10mL of N, N-dimethylformamide under reflux for 2H,the reaction progress was monitored by TLC (PE: EA ═ 5: 1). After the reaction is finished, the system is cooled to room temperature, water is added to separate out solid, and the solid is filtered and washed by water. The filter cake was dissolved in ethyl acetate, dried over anhydrous sodium sulfate, and separated by column chromatography (PE: EA ═ 5:1) to finally obtain yellow crystals (496mg, 82%).1H NMR(400MHz,CDCl3)δ7.98(s,1H),7.91(s,1H),7.77(d,J＝9.0Hz,2H),6.99(d,J＝9.0Hz,2H),6.07(ddd,J＝22.5,10.5,5.3Hz,1H),5.44(dd,J＝17.3,1.5Hz,1H),5.31(dd,J＝10.5,1.3Hz,1H),4.60(d,J＝5.3Hz,2H),3.95(s,3H)；UV-Vis(CH3CN):λmax＝342.5nm；M.P.102.4-103.7℃。
EXAMPLE 5 Synthesis of phenyl 4- ((1-methyl-1H-pyrazol-4-yl) diazenyl) acetate, a pyrazolyl azophenol esterified derivative
The synthetic route is as follows:
Figure BDA0001843110310000061
4- ((1-methyl-1H-pyrazol-4-yl) diazenyl) phenol (101mg,0.5mmol,1eq.) was dissolved in 5mL of tetrahydrofuran under nitrogen protection, triethylamine (83 μ L,0.6mmol,1.2eq.) was injected, acetyl chloride (177 μ L,2.5mmol,5eq.) was injected in an ice-water bath, and the mixture was stirred at room temperature for 48H, and the progress of the reaction was monitored by TLC (PE: EA ═ 5: 2). After the reaction was completed, a saturated ammonium chloride solution was added to quench the reaction, which was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and separated by column chromatography (PE: EA ═ 5:2), to finally obtain yellow crystals (98mg, 80.3%).1H NMR(400MHz,CDCl3)δ8.00(s,1H),7.96(s,1H),7.82(d,J＝8.9Hz,2H),7.21(d,J＝8.9Hz,2H),3.98(s,3H),2.33(s,3H)；UV-Vis(CH3CN):λmax＝331.5nm；M.P.107.2-110.0℃。
Example 6, method for half-life measurement of pyrazolyl azophenol derivatives, described below:
reference is made to the test methods for ultra-long half-lives (j.am. chem. soc.2014,136, 11878-11881). The specific method is that DMSO is used as a solvent, a UV-Vis absorption spectrum method is adopted to determine a rate constant k of Z → E reaction of the azobenzene derivative at 65, 75 and 85 ℃ (the first-order reaction kinetics is followed), an Arrhenius equation is used to calculate the rate constant k at 25 ℃, and then the half-life period of Z isomer at 25 ℃ is obtained. The results for the corresponding products of examples 3-5 are shown in the table below, with half-lives of several months to tens of months, exhibiting properties of ultra-long half-lives.
TABLE 1 Rate constants and half-lives of the Z isomers of the example derivatives at 25 deg.C
Figure BDA0001843110310000062
Figure BDA0001843110310000071
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (3)

1. An ether derivative of pyrazolyl azophenol, wherein the chemical formula of the ether derivative of pyrazolyl azophenol is as follows:
Figure DEST_PATH_IMAGE002
。
2. an ether derivative of pyrazolyl azophenol, wherein the chemical formula of the ether derivative of pyrazolyl azophenol is as follows:
Figure DEST_PATH_IMAGE004
。
3. an ester derivative of pyrazolyl azophenol, wherein the chemical formula of the ester derivative of pyrazolyl azophenol is as follows:
Figure DEST_PATH_IMAGE006
。
CN201811257615.7A 2018-10-26 2018-10-26 Pyrazolyl azophenol compound and synthesis and derivation thereof Active CN109232428B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201811257615.7A CN109232428B (en) 2018-10-26 2018-10-26 Pyrazolyl azophenol compound and synthesis and derivation thereof
PCT/CN2019/070081 WO2020082605A1 (en) 2018-10-26 2019-01-02 Pyrazolyl azophenol compound and synthesis and derivation thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811257615.7A CN109232428B (en) 2018-10-26 2018-10-26 Pyrazolyl azophenol compound and synthesis and derivation thereof

Publications (2)

Publication Number Publication Date
CN109232428A CN109232428A (en) 2019-01-18
CN109232428B true CN109232428B (en) 2022-02-15

Family

ID=65082360

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811257615.7A Active CN109232428B (en) 2018-10-26 2018-10-26 Pyrazolyl azophenol compound and synthesis and derivation thereof

Country Status (2)

Country Link
CN (1) CN109232428B (en)
WO (1) WO2020082605A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112831057B (en) * 2021-01-06 2022-02-15 北京科技大学 Visible light response aryl azo pyrazole polymer and synthesis method thereof
CN113912543B (en) * 2021-10-11 2022-12-23 上海交通大学 Pyrazolyl azoaniline-based light-operated small-molecule adhesive

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0419416D0 (en) * 2004-09-01 2004-10-06 Inst Of Ex Botany Ascr 4-Arylazo-3,5-Diamino-Pyrazole compounds and use thereof
JP4986159B2 (en) * 2007-11-09 2012-07-25 独立行政法人産業技術総合研究所 Light control technology for fluid flow rate
CN106008458A (en) * 2016-05-31 2016-10-12 上海交通大学 Azobenzene compound and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Arylazopyrazoles： azoheteroarene photoswitches offering quantitative isomerization and long termal half-lives;Claire E. Weston et al.;《J. Am. Chem. Soc.》;20140806;第136卷;第11878页Figure1; 第11879页Scheme1 *
Photoisomerization and Thermal Isomerization of Arylazoimidazoles;Joe Otsuki et al.;《J. Phys. Chem. A.》;20070207;第111卷;第1404页Chart1 和第1405页Table1 *
Photoswitchable Azoheterocycles via coupling of Lithiated Imidazoles with benzenediazonium salts;Thore Wendler et al.;《J. Org. Chem.》;20120308;第77卷;第3285页Scheme1 Table1 *
第11879页Scheme1. *

Also Published As

Publication number Publication date
WO2020082605A1 (en) 2020-04-30
CN109232428A (en) 2019-01-18

Similar Documents

Publication Publication Date Title
CN109232428B (en) Pyrazolyl azophenol compound and synthesis and derivation thereof
Khaligh Telescopic synthesis of azo compounds via stable arenediazonium bis (trifluoromethane) sulfonimide salts by using tert-butyl nitrite
CN113105357B (en) Synthesis method and application of novel p-aryl azophenol derivative
JP5541158B2 (en) Asymmetric azine compound and method for producing the same
CN110041223A (en) Using hydrazine class compound as the method for raw material oxidative synthesis azo compound
IT201800000667A1 (en) PROCEDURE FOR THE PREPARATION OF DISPLACED DIARYLOXYHETERODIAZOLIC COMPOUNDS
CN108276406B (en) Synthesis method of polycyclic 2-hydrogen pyrazole compound
CN109897033B (en) Method for synthesizing iodine-containing imidazo [1, 2a ] pyridine compound
CN107382910B (en) Difluoromethyl aldehyde hydrazone compound and preparation method thereof
CN112194608B (en) Synthesis method of visible light promoted 3-methyl-3-difluoroethyl-2-oxindole compound
Yu et al. A convenient approach to difluoromethylated all-carbon quaternary centers via Ni (II)-catalyzed enantioselective Michael addition
CN104945376B (en) A kind of synthetic method of 3 aroyl benzazolyl compounds
CN111269153B (en) Synthetic method of alpha, alpha-difluoro-beta-carbonyl sulfone compound
CN109265409B (en) Synthesis method of 2-substituted benzoxazole, 2-substituted benzothiazole and derivatives thereof
CN107382782B (en) Method for synthesizing polyaryl substituted naphthol derivative
CN107501234B (en) A kind of oil-source rock correlation and preparation method thereof
CN108440310B (en) Synthesis method of o-amino benzotrifluoride and derivatives thereof
CN106118688A (en) The synthetic method of benzophenanthrene decane epoxide bridging isobutyltrimethylmethane. phenyl porphyrin binary compound discotic mesogenic material
CN111233698A (en) Polymerizable asymmetric azobenzene and preparation method thereof
CN109879830A (en) A kind of oxaza heptane derivative and preparation method thereof containing exocyclic double bond
CN113683525B (en) Method for realizing N-H insertion reaction of ethyl phenyldiazoacetate and methylaniline by using micro-channel photoreaction technology
EP3401308A1 (en) Chiral compound, liquid crystal material, method for fabrication thereof, and display device
CN113861121B (en) Novel method for generating 2, 3-dihydroxyquinoxaline and derivatives thereof through direct oxidation
CN108822060B (en) 3-aryl substituted oxetane and preparation method thereof
JP7297066B2 (en) Fluorescent compound, its production method and its use

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information

Address after: 200030 Dongchuan Road, Minhang District, Minhang District, Shanghai

Applicant after: Shanghai Jiaotong University

Address before: 200030 Huashan Road, Shanghai, No. 1954, No.

Applicant before: Shanghai Jiaotong University

CB02 Change of applicant information
GR01 Patent grant
GR01 Patent grant