CN108863841A - A kind of ortho position fluoro azobenzene derivatives and preparation method thereof - Google Patents
A kind of ortho position fluoro azobenzene derivatives and preparation method thereof Download PDFInfo
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- CN108863841A CN108863841A CN201710318976.7A CN201710318976A CN108863841A CN 108863841 A CN108863841 A CN 108863841A CN 201710318976 A CN201710318976 A CN 201710318976A CN 108863841 A CN108863841 A CN 108863841A
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- ortho position
- fluorine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/20—Diazonium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
Abstract
The present invention discloses a kind of ortho position fluoro azobenzene derivatives and preparation method thereof, the fluorine-substituted azobenzene derivatives in ortho position are prepared for using the method for diazonium coupling, by introducing two fluorine atoms in azobenzene ortho-position, effectively reduce the cloud density of nitrogen nitrogen double bond, the red shift of azobenzene molecule absorption spectrum is realized, cis-configuration stability greatly improves.It is simple and efficient using diazo coupling reaction synthesis ortho position fluoro azobenzene, yield is higher, and material obtained has excellent optical property, is expected to be applied in fields such as optical drive, luminous energy storage, Supramolecular Assemblings.
Description
Technical field
The present invention relates to a kind of preparations of ortho position fluoro azobenzene, have in solar energy storage, optical drive field extensive
Application prospect.
Background technique
It is to regulate and control the effective means of azobenzene Photophysics, therefore design and synthesize different functional groups and take that functional group, which replaces,
The azobenzene molecule in generation is basis and the key in the field.In past research, a large amount of azobenzene molecule is synthesized.Needle
To different azobenzene molecule structures, a large amount of synthetic method is developed and is furtherd investigate, and has gradually formed more perfect idol
Pyridine blending theory.Different synthetic methods has its advantage, and there is also limitations.Such as diazo coupling reaction is the most frequently used
Synthesis azobenzene molecule method.Mainly passing through level-one arylamine diazotising forms electrophilic diazonium salt, Jin Eryu for the reaction
The aromatic reagent of nucleophilic is coupled, to generate azobenzene molecule.In general, the time of diazo coupling reaction is relatively short,
Yield is higher, and required reaction condition is also relatively simple, therefore is also widely used in idol by favor in azobenzene synthesis field
In the commercial synthesis of pyridine molecule.But the diazonium salt formed in the reaction process is often unstable, is easy during the reaction
It decomposes and generates danger.Meanwhile also will affect the yield and purity of product by the positioning performance of the nucleopilic reagent of attack, such as
The polarization of fruit nucleopilic reagent is not strong, then is likely to reaction and generates isomer similar in property, this is just to product
Separation causes difficulty
Using the synthetic method reported before, many novel azobenzene molecules are synthesized, and have been shown excellent
Photophysical Behaviors are expected to apply in frontiers such as visible optical drive, luminous energy storage, light-operated drug releases.General azobenzene molecule
Photo-isomerisation process be by ultraviolet optical drive, and ultraviolet light is larger to the pollution of environment, and which limits azobenzenes
Application range.Such as in situ in molecular switch, ultraviolet light is easy scattering, is difficult to permeate from tissue or cell, in addition, ultraviolet
Light will also result in injury to organism itself.Therefore, we have designed and synthesized a kind of fluorine-substituted azobenzene in novel ortho position
Molecule, by regulating and controlling the energy level of remy hair isomery, to obtain, visible absorption, isomerisation degree are high, cis-configuration is stable
Azobenzene molecule.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of ortho position fluoro azobenzene derivatives and its systems
Preparation Method has designed and synthesized a kind of fluorine-substituted azobenzene molecule in novel ortho position, by regulating and controlling the energy level of cis-trans isomerism, from
And obtain the azobenzene molecule that visible absorption, isomerisation degree are high, cis-configuration is stable.
Technical purpose of the invention is achieved by following technical proposals：
A kind of fluorine-substituted azobenzene derivatives in ortho position, shown in following chemical formula
The fluorine-substituted azobenzene derivatives AZO-1 in ortho position：X and Y1It is F, Y2For H.
The synthesis process of the design molecule of the above-mentioned fluorine-substituted azobenzene derivatives AZO-1 in ortho position, preparation process are as follows：
Shown in the following chemical formula of the synthetic route of AZO-1
It carries out as steps described below：
Step 1, the preparation of diazonium salt：It weighs 4- amino -3- fluobenzoic acid to be dissolved in the aqueous solution of NaOH, is denoted as A；Claim
Take NaNO2Dissolution in deionized water, forms NaNO2Aqueous solution, by NaNO under the conditions of ice bath stirring2Aqueous solution is added drop-wise to A
In；After being completely dissolved dispersion, solution is added drop-wise in HCL aqueous solution, keeping temperature is 0~5 DEG C, is stirred to react 30-
60min, obtains diazonium salt solution, and ice bath saves；NaNO2Molar ratio with 4- amino-3- fluobenzoic acid is (1-1.2)：1；
The molar ratio of HCl and 4- amino -3- fluobenzoic acid is 1:3.5~1:4；
In step 1, NaNO2Molar ratio with 4- amino-3- fluobenzoic acid is (1-1.1)：1.
In step 1, the molar ratio of HCl and 4- amino -3- fluobenzoic acid is 1：(3.6—3.8).
In step 1, by NaNO under the conditions of ice bath stirring2Aqueous solution is added drop-wise in A, and rate of addition is per minute 1-
5ml。
In step 1, after being completely dissolved dispersion, solution is added drop-wise in HCL aqueous solution, rate of addition is per minute
1—5ml。
In step 1, keeping temperature is 0~2 DEG C, is stirred to react 40-50min.
Step 2, coupling reaction：It takes the dissolution of 3- fluoroaniline to be dispersed in HCL aqueous solution, is denoted as B；And prepare step 1
Diazonium salt solution is added dropwise in B and stirs；Diazonium salt prepared by 3- fluoroaniline and step 1 is equimolar ratio；
In step 2, diazonium salt solution prepared by step 1 is added dropwise in B and is stirred, rate of addition is 1-5ml per minute.
The concentration of HCL aqueous solution is consistent with HCL aqueous solution concentration in step 1 in step 2.
Step 3, pH is adjusted：By NaHCO3Saturated aqueous solution is added dropwise to the tune that pH is carried out in the mixed solution of step 2 preparation
PH is adjusted to 5~7, is continued stirring 5-10 hours under condition of ice bath, the fluorine-substituted azo benzenesulfonamide derivative in ortho position can be obtained by section
Object.
In step 3, after being stirred to react under condition of ice bath, give it is static, it is static after decompression filter is precipitated；Distilled water
Washing is precipitated to neutrality, and 60 DEG C of vacuum drying obtain crude product；By crude product carry out column chromatography for separation purification (silica gel is stationary phase,
CH2Cl2/ ethyl acetate is eluent), crude product is purified, decompression filters, and 60 DEG C of vacuum drying obtain smart product.
It is characterized with azobenzene derivatives of infrared, the ultraviolet and DSC to preparation, as shown in attached drawing 1-3.By in Fu
Leaf infrared spectroscopy characterizes functional group's type of fluoro azobenzene, 1442cm-1,1411cm-1The absorption peak at place belongs to N=N's
Characteristic absorption peak.1107cm-1The absorption peak at place is the characteristic absorption of C-F key.It is conjugated additionally, due to carbonyl and phenyl ring, makes to exist originally
1750cm-1The carboxyl characteristic peak at place thinks that lower wave number direction is moved to 1697cm-1, and in 1610cm-1Place divides out a new suction
Receive peak, i.e. the ring vibration absorption peak of phenyl ring.763cm-1Place's absorption peak is attributed to the bending vibration of phenyl ring.Due to the introducing of fluorine atom,
π-π * the transition absorption of azo unit is mobile to visible light region.Therefore there is a spy at 420nm in the azobenzene derivatives
Levy absorption peak.The heat release feelings of the fluoro azobenzene material after energy is filled in 420nm illumination are measured by differential scanning calorimetry
There is an obvious and wider exothermic peak in 40~130 DEG C of sections of first time heating, it was demonstrated that heating is released for the first time in condition
Heat be energy by being discharged when azo molecules are changed into transconfiguration by cis-structure.
The present invention is prepared for facing the fluorine-substituted azobenzene derivatives in position using the method for diazonium coupling, by azobenzene
Ortho position different location introduces two fluorine atoms, effectively reduces the cloud density of nitrogen nitrogen double bond, realizes azobenzene molecule suction
The red shift of spectrum is received, cis-configuration stability greatly improves.Utilize diazo coupling reaction synthesis ortho position fluoro azobenzene letter
Single efficient, yield is higher, and the azobenzene derivatives of acquisition contain strong electron-withdrawing group at ortho position, is able to extend azobenzene cis-structure
Reply half-life period；Meanwhile the introducing of fluorine atom will reduce the cloud density in nitrogen nitrogen double bond, so that absorption spectrum is to visible
Light region is mobile.Material obtained has excellent optical property, is expected in optical drive, luminous energy storage, Supramolecular Assembling etc.
It is applied in field.
Detailed description of the invention
Fig. 1 is the Fourier infrared absorption spectrogram of azobenzene derivatives of the invention.
Fig. 2 is the uv-visible absorption spectroscopy figure of azobenzene derivatives of the invention.
Fig. 3 is the differential scanning calorimetric curve figure of azobenzene derivatives of the invention.
Specific embodiment
Technical scheme is described further combined with specific embodiments below.
Embodiment 1
1) preparation of diazonium salt：Weigh 1.55g 4- amino -3- fluobenzoic acid (10mmol) and 0.4g NaOH
(10mmol), is dissolved in the deionized water of 30mL, is denoted as A.Weigh 0.76g NaNO2(11mmol) is dissolved in 10mL deionization
In water, by 10mL NaNO under the conditions of ice bath stirring2It is slowly dropped in A.Until completely dissolved, solution is added drop-wise to dropwise
40mL HCl(1mol L-1) in, keeping temperature is 0~5 DEG C, is stirred to react 60min, obtains diazonium salt solution, and ice bath saves.
2) coupling reaction：Weighing 1.11g 3- fluoroaniline (10mmol) (is 1 with diazonium salt molar ratio:1) and it is dissolved in HCl
(1mol L-1) in, it is denoted as B；And above-mentioned diazonium salt solution is slowly added dropwise in B and is stirred.
3) pH is adjusted：Prepare NaHCO3Saturated aqueous solution；The aqueous solution is added dropwise in above-mentioned mixed solution and carries out PH
Adjusting, pH is adjusted to 5~7；Continue stirring 5 hours under condition of ice bath, depressurizes to filter after static and be precipitated；Distillation washing
It washs and is precipitated to neutrality, 60 DEG C of vacuum drying obtain crude product.
4) it purifies：Crude product is carried out column chromatography for separation purification, and (silica gel is stationary phase, CH2Cl2/ ethyl acetate is elution
Agent), crude product is purified, decompression filters, and 60 DEG C of vacuum drying obtain smart product.
Embodiment 2
1) preparation of diazonium salt：3.1g 4- amino -3- fluobenzoic acid (20mmol) and 0.8g NaOH (20mmol) are weighed,
It is dissolved in the deionized water of 100mL, is denoted as A.Weigh 1.52g NaNO2(22mmol) is dissolved in 20mL deionized water,
By 20mL NaNO under the conditions of ice bath stirring2It is slowly dropped in A.Until completely dissolved, solution is added drop-wise to 80mL HCl dropwise
(1mol L-1) in, keeping temperature is 0~5 DEG C, is stirred to react 60min, obtains diazonium salt solution, and ice bath saves.
2) coupling reaction：Weighing 2.22g 3- fluoroaniline (20mmol) (is 1 with diazonium salt molar ratio:1) and it is dissolved in HCl
In, it is denoted as B；And above-mentioned diazonium salt solution is slowly added dropwise in B and is stirred.
3) pH is adjusted：Prepare NaHCO3Saturated aqueous solution；The aqueous solution is added dropwise in above-mentioned mixed solution and carries out PH
Adjusting, pH is adjusted to 5~7；Continue stirring 8 hours under condition of ice bath, depressurizes to filter after static and be precipitated；Distillation washing
It washs and is precipitated to neutrality, 60 DEG C of vacuum drying obtain crude product.
4) it purifies：Crude product is carried out column chromatography for separation purification, and (silica gel is stationary phase, CH2Cl2/ ethyl acetate is elution
Agent), crude product is purified, decompression filters, and 60 DEG C of vacuum drying obtain smart product.
It is adjusted according to the technological parameter of the content of present invention, two kinds of fluorine-substituted azos in ortho position in the present invention can be achieved
The preparation of benzene derivative AZO-1 shows almost the same performance.Illustrative description is done to the present invention above, it should say
It is bright, in the case where not departing from core of the invention, any simple deformation, modification or other skilled in the art
The equivalent replacement of creative work can not be spent to each fall within protection scope of the present invention.
Claims (9)
1. a kind of fluorine-substituted azobenzene derivatives in ortho position, which is characterized in that the fluorine-substituted azobenzene derivatives in ortho position are changed as follows
Shown in formula,：
Wherein, the fluorine-substituted azobenzene derivatives AZO-1 in ortho position：X and Y1It is F, Y2For H.
2. a kind of preparation method of the fluorine-substituted azobenzene derivatives in ortho position, which is characterized in that carry out as steps described below：
Step 1, the preparation of diazonium salt：It weighs 4- amino -3- fluobenzoic acid to be dissolved in the aqueous solution of NaOH, is denoted as A；It weighs
NaNO2Dissolution in deionized water, forms NaNO2Aqueous solution, by NaNO under the conditions of ice bath stirring2Aqueous solution is added drop-wise in A；
After being completely dissolved dispersion, solution is added drop-wise in HCL aqueous solution, keeping temperature is 0~5 DEG C, is stirred to react 30-60min, obtains
To diazonium salt solution, ice bath is saved；NaNO2Molar ratio with 4- amino-3- fluobenzoic acid is (1-1.2)：1；HCl and 4- ammonia
The molar ratio of base -3- fluobenzoic acid is 1:3.5~1:4；
Step 2, coupling reaction：It takes the dissolution of 3- fluoroaniline to be dispersed in HCL aqueous solution, is denoted as B；And the diazonium for preparing step 1
Salting liquid is added dropwise in B and stirs；Diazonium salt prepared by 3- fluoroaniline and step 1 is equimolar ratio；
Step 3, pH is adjusted：By NaHCO3Saturated aqueous solution is added dropwise to the adjusting that pH is carried out in the mixed solution of step 2 preparation, will
PH is adjusted to 5~7, continues stirring 5-10 hours under condition of ice bath, the fluorine-substituted azobenzene derivatives in ortho position can be obtained.
3. the preparation method of the fluorine-substituted azobenzene derivatives in ortho position according to claim 2, which is characterized in that in step
In 1, NaNO2Molar ratio with 4- amino-3- fluobenzoic acid is (1-1.1)：1；Mole of HCl and 4- amino -3- fluobenzoic acid
Than being 1：(3.6—3.8).
4. the preparation method of the fluorine-substituted azobenzene derivatives in ortho position according to claim 2, which is characterized in that in step
In 1, by NaNO under the conditions of ice bath stirring2Aqueous solution is added drop-wise in A, and rate of addition is 1-5ml per minute；Wait be completely dissolved
After dispersion, solution is added drop-wise in HCL aqueous solution, rate of addition is 1-5ml per minute.
5. the preparation method of the fluorine-substituted azobenzene derivatives in ortho position according to claim 2, which is characterized in that in step
In 1, keeping temperature is 0~2 DEG C, is stirred to react 40-50min.
6. the preparation method of the fluorine-substituted azobenzene derivatives in ortho position according to claim 2, which is characterized in that in step
In 2, diazonium salt solution prepared by step 1 is added dropwise in B and is stirred, rate of addition is 1-5ml per minute.
7. the preparation method of the fluorine-substituted azobenzene derivatives in ortho position according to claim 2, which is characterized in that in step
In 3, after being stirred to react under condition of ice bath, give it is static, it is static after decompression filter is precipitated；During distillation water washing is precipitated to
Property, 60 DEG C of vacuum drying obtain crude product；Crude product is subjected to column chromatography for separation purification, silica gel is stationary phase, CH2Cl2/ acetic acid second
Ester is eluent, is purified to crude product, and decompression filters, and 60 DEG C of vacuum drying obtain smart product.
8. a kind of fluorine-substituted azobenzene derivatives in ortho position as described in claim 1, which is characterized in that the introducing of fluorine atom will
The cloud density in nitrogen nitrogen double bond is reduced, so that absorption spectrum is mobile to visible light region, is able to extend the cis- knot of azobenzene
The reply half-life period of structure.
9. a kind of fluorine-substituted azobenzene derivatives in ortho position as described in claim 1 are in optical drive, luminous energy storage, oversubscription subgroup
Application in dress field.
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Cited By (3)
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| CN111196774A (en) * | 2020-02-15 | 2020-05-26 | 桂林理工大学 | Asymmetric azobenzene capable of solid-liquid conversion and preparation method thereof |
| CN113173865A (en) * | 2021-03-12 | 2021-07-27 | 山西大同大学 | Graphene synergistic heat storage composite material driven by visible light and preparation method and application thereof |
| CN113173864B (en) * | 2020-10-30 | 2023-06-30 | 山西大同大学 | Graphene synergistic photo-thermal energy storage composite material and preparation method and application thereof |
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Cited By (4)
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| CN111196774A (en) * | 2020-02-15 | 2020-05-26 | 桂林理工大学 | Asymmetric azobenzene capable of solid-liquid conversion and preparation method thereof |
| CN113173864B (en) * | 2020-10-30 | 2023-06-30 | 山西大同大学 | Graphene synergistic photo-thermal energy storage composite material and preparation method and application thereof |
| CN113173865A (en) * | 2021-03-12 | 2021-07-27 | 山西大同大学 | Graphene synergistic heat storage composite material driven by visible light and preparation method and application thereof |
| CN113173865B (en) * | 2021-03-12 | 2023-03-28 | 山西大同大学 | Graphene synergistic heat storage composite material driven by visible light and preparation method and application thereof |
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