CN103044342A - Azobenzene liquid crystal compound and click chemistry preparation method thereof - Google Patents
Azobenzene liquid crystal compound and click chemistry preparation method thereof Download PDFInfo
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- CN103044342A CN103044342A CN 201310006543 CN201310006543A CN103044342A CN 103044342 A CN103044342 A CN 103044342A CN 201310006543 CN201310006543 CN 201310006543 CN 201310006543 A CN201310006543 A CN 201310006543A CN 103044342 A CN103044342 A CN 103044342A
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Abstract
The invention relates to an azobenzene liquid crystal compound and a click chemistry preparation method thereof. The azobenzene liquid crystal compound is prepared by taking azide and a terminal alkyne compound as raw reaction materials and through click chemistry reaction. According to the azobenzene liquid crystal compound and the click chemistry preparation method, the raw materials are easy to obtain; a synthetic method is simple; reaction conditions are mild; a product is easy to purify; aftertreatment is simple; and the product yield is high.
Description
Technical field
The invention belongs to liquid crystalline cpd the field of chemical synthesis, be specifically related to a kind of liquid crystalline azo compounds and click chemistry preparation method thereof.
Background technology
Click chemistry is a kind of novel method of synthesizing fast a large amount of compounds that the Americanized scholar Sharpless of calendar year 2001 Nobel chemistry Prize winner proposes, and is the another synthetic technology of bringing significant innovation to traditional Synthetic Organic Chemistry after combinatorial chemistry.At present, this technology has been penetrated into the fields such as foundation, new drug development and synthetic polymer in lead compound storehouse.Click chemistry essence refers to select the raw material that is easy to get, by reliable, efficient and tool optionally chemical reaction realize that the carbon heteroatoms connects, the powerful and practical synthetic method of covers low-cost, fast synthetic a large amount of new compounds.Its core is to utilize a series of reliable, modular reactions to generate to contain heteroatomic compound.These reactions have following feature usually: raw materials used being easy to get; Operation is simple, and mild condition is insensitive to oxygen, water; Product yield is high, selectivity good; The easy purifying of product, aftertreatment are simple.
Summary of the invention
The object of the invention provides a kind of liquid crystalline azo compounds and click chemistry preparation method thereof.
For achieving the above object, the structure of liquid crystalline azo compounds of the present invention is shown in general formula (1):
Wherein the structure of R1 is: carbonatoms is a kind of in the alkyl of 1-12; The structure of R2 is: carbonatoms is a kind of in a kind of or fluorine-based, the trifluoromethyl, cyano group, nitro, isothiocyano, fluorophenyl, trifluoromethyl, cyano-phenyl, nitrophenyl, isothiocyano phenyl in the alkyl of 1-12.
The structural formula of R1 is in the described compound:
R
1=-C
nH
2n+1, wherein n is 1-12.
R in the described compound
2Structural formula be:
R
2=-F；
-CF
3；
-CN；
-NO
2；
-NCS；
Preparation method of the present invention may further comprise the steps:
Steps A: the preparation of intermediate m1
R
1-N
3?m1
With haloalkane R
1After X adds reaction vessel, in reaction vessel, add reaction solvent 3 and sodiumazide, under the condition of reflux, after stirring reaction 3-5 hour, remove reaction solvent 3, get intermediate m1; R wherein
1The mol ratio of X and sodiumazide is: 1:1.5 ~ 1:3; R1 is that carbonatoms is a kind of in the alkyl of 1-12, and reaction solvent 3 is one or more in tetrahydrofuran (THF), dioxane, DMF, the triethylamine;
Step B: the preparation of intermediate m2
With R
2The phenylazo halobenzene is dissolved in the solvent 1, place the logical nitrogen of reactor or protection of inert gas, then add trimethylsilyl acetylene, temperature of reaction is 30-80 ℃, the catalyzer 1 that adds reaction raw materials total mass 2%-5%, reaction is after 12-16 hour under the protection of inert gas, and desolventizing 1 is dissolved in products therefrom in the solvent 2, add catalyzer 2 after placing reactor, stirred 3-8 hour under the room temperature, then desolventizing 2, get intermediate m2;
Wherein, solvent 1 is one or more in tetrahydrofuran (THF), dioxane, triethylamine, DMF, the dimethyl propylamine; Catalyzer 1 is one or more in cuprous iodide, palladium metal, two (triphenylphosphine) palladium chloride, the triphenylphosphine; Solvent 2 is one or more in methyl alcohol, ethanol, Virahol, tetrahydrofuran (THF), dioxane, the DMF; Catalyzer 2 is mineral alkali; The mol ratio of R2 phenylazo halobenzene and trimethylsilyl acetylene is 1:1.5 ~ 1:3; The add-on of catalyzer 2 is 2 ~ 4 times of R2 phenylazo halobenzene mole number; Wherein R2 is that carbonatoms is a kind of in a kind of or fluorine-based, the trifluoromethyl, cyano group, nitro, isothiocyano, fluorophenyl, trifluoromethyl, cyano-phenyl, nitrophenyl, isothiocyano phenyl in the alkyl of 1-12, and the structure of R2 phenylazo halobenzene is shown in general formula (2):
Step C: click chemistry reaction preparation liquid crystalline azo compounds
In reaction vessel, add intermediate m1, intermediate m2 and reaction solvent 3, add the catalyzer 3 of reaction raw materials total mass 1 ~ 3%, after stirring reaction 3-6 under the condition of 60-120 ° of C hour, remove reaction solvent 3, get liquid crystalline azo compounds;
Wherein, catalyzer 3 is one or more in triethylamine, dimethyl propylamine, cuprous iodide, the cuprous chloride, and the mol ratio of intermediate m1 and intermediate m2 is 1:1.
R1X is alkyl chloride, bromoalkane or idoalkane in the described steps A.
X among the described step B in the R2 phenylazo halobenzene comprises chloro thing, bromo-derivative and iodo thing.
Mineral alkali is one or more in sodium hydroxide, potassium hydroxide, yellow soda ash, the salt of wormwood among the described step B.
The intermediate m2 of intermediate m1, the step B of described steps A and the azo liquid crystalline cpd of step C all adopt the method purifying of column chromatography, and the column chromatography developping agent is one or more in methylene dichloride, hexanaphthene, ethyl acetate, the sherwood oil.
Solvent 3 and R in the described steps A
1The ratio of X is: 1mol R
1X adds solvent 3300-600mL; 1mol R among the step B
2The phenylazo halobenzene is dissolved in the 1000-1200mL solvent 1,1mol R
2The amount that the phenylazo halobenzene adds solvent 2 is 1200-2000mL.
Rare gas element among the described step B is argon gas.
With respect to prior art, the present invention has following technique effect: generate trinitride with haloalkane and reaction of sodium azide, again take trinitride and terminal alkyne compound as reaction raw materials, react by click chemistry and to prepare liquid crystalline azo compounds, synthetic method of the present invention is simple, mild condition; The easy purifying of product, aftertreatment are simple, and product yield is high.
Description of drawings
Fig. 1 is example 1 target compound Fourier transform infrared collection of illustrative plates of the present invention.
Fig. 2 is example 2 target compound Fourier transform infrared collection of illustrative plates of the present invention.
Fig. 3 is example 3 target compound Fourier transform infrared collection of illustrative plates of the present invention.
Embodiment
Below by specific embodiment the present invention is described in further detail.
The present invention adopts the method for click chemistry to prepare liquid crystalline azo compounds, take trinitride and terminal alkyne compound as reaction raw materials, contain the method for the liquid crystalline cpd of azobenzene group in the molecule that occurs to click chemical reaction and prepare, reaction scheme of the present invention is as follows:
Example 1
Steps A: the preparation of intermediate m1
1-bromo pentane 15.1g is added in the reaction vessel, add 50mL tetrahydrofuran (THF) and 13.0g sodiumazide, under the condition of reflux, stirring reaction 3 hours.Reaction is removed reaction solvent after finishing, and thick product adopts the method purifying of column chromatography, and developping agent is methylene dichloride, makes intermediate m1, yield 96.4%.
Step B: the preparation of intermediate m2
Raw material (4-bromophenyl)-(4 '-amyl group phenyl)-diazene 33.1g is dissolved in the 100mL triethylamine; place reactor to lead to argon shield; then add the 19.6g trimethylsilyl acetylene; temperature of reaction is 80 ℃; add 0.7g triphenylphosphine palladium chloride and 0.7g cuprous iodide as catalyzer, argon shield reaction 12 hours.Behind the stopped reaction, be dissolved in after the desolventizing in the 200mL methyl alcohol, place the rear 27.6g of adding of reactor salt of wormwood, stirred 3 hours under the room temperature, then desolventizing, thick product adopts the method purifying of column chromatography, developping agent is hexanaphthene, obtains intermediate m2, yield 93.2%.
Step C: click chemistry reaction preparation liquid crystalline azo compounds
Add 11.3g intermediate m1,27.6g intermediate m2 and 120mL tetrahydrofuran (THF) in reaction vessel, add the 0.4g triethylamine as catalyzer, stirring reaction is 6 hours under the condition of 80 ° of C.After reaction is finished, remove reaction solvent, thick product adopts the method purifying of column chromatography, and developping agent is sherwood oil, obtains liquid crystalline azo compounds, yield 95.2%.As seen from Figure 1, the product of the present embodiment preparation is target compound.
Example 2
Steps A: the preparation of intermediate m1
The 12.3g1-n-propyl bromide is added in the reaction vessel, add 36mL DMF and 13.0g sodiumazide, under the condition of reflux, stirring reaction 3 hours.Reaction is removed reaction solvent after finishing, and thick product adopts the method purifying of column chromatography, and developping agent is methylene dichloride, makes intermediate m1, yield 93.1%.
Step B: the preparation of intermediate m2
Raw material 37.6g (4-iodophenyl)-(4 '-trifluoromethyl)-diazene is dissolved in the 120mL dimethyl propylamine; place reactor to lead to argon shield; then add the 19.6g trimethylsilyl acetylene; temperature of reaction is 30 ℃; add 0.7g palladium metal, 0.7g cuprous iodide and 0.7g triphenylphosphine as catalyzer, argon shield reaction 16 hours.Behind the stopped reaction, be dissolved in after the desolventizing in 80mL dioxane and the 40mL alcohol mixed solvent, add 40g yellow soda ash after placing reactor, stirred 8 hours under the room temperature, desolventizing, thick product adopts the method purifying of column chromatography, and developping agent is that volume ratio is methylene dichloride and the hexanaphthene of 1:4, make intermediate m2, yield 95.8%.
Step C: click chemistry reaction preparation liquid crystalline azo compounds
Add 8.5g intermediate m1,27.4g intermediate m2 and 100mL dioxane in reaction vessel, add the 0.4g triethylamine, stirring reaction is 5 hours under the condition of 100 ° of C.After reaction is finished, remove reaction solvent, thick product adopts the method purifying of column chromatography, and developping agent is that volume ratio is the methylene dichloride of 1:2: sherwood oil, make liquid crystalline azo compounds, and yield is 96.4%.As seen from Figure 2, the product of the present embodiment preparation is target compound.
Example 3
Steps A: the preparation of intermediate m1
The 19.3g sec-Octyl Bromide is added in the reaction vessel, add the 60mL dioxane, and the 13.0g sodiumazide, under the condition of reflux, stirring reaction 4 hours.Reaction is removed reaction solvent after finishing, and thick product adopts the method purifying of column chromatography, and developping agent is methylene dichloride, makes intermediate m1, and yield is 96.8%.
Step B: the preparation of intermediate m2
Raw material 37.6g (4-iodophenyl)-(4 '-trifluoromethyl)-diazene is dissolved in the mixed solvent of 60mL triethylamine and 60mL tetrahydrofuran (THF); place reactor to lead to nitrogen protection; then add the 19.6g trimethylsilyl acetylene; temperature of reaction is 50 ℃; add 0.7g two (triphenylphosphine) palladium chloride and 0.7g cuprous iodide as catalyzer, nitrogen protection reaction 15 hours.Behind the stopped reaction, be dissolved in after the desolventizing in the 120mL ethanol, add 8g sodium hydroxide after placing reactor, stirred 4 hours under the room temperature, desolventizing, thick product adopts the method purifying of column chromatography, and developping agent is that volume ratio is methylene dichloride and the hexanaphthene of 1:4, make intermediate m2, yield is 93.6%.
Step C: click chemistry reaction preparation liquid crystalline azo compounds
Add 15.5g intermediate m1,27.4g intermediate m2 and 120mL triethylamine (namely having as catalyzer as solvent) in reaction vessel, stirring reaction is 6 hours under the condition of 80 ° of C.After reaction is finished, remove reaction solvent, thick product adopts the method purifying of column chromatography, and developping agent is methylene dichloride and the sherwood oil of volume ratio 1:2, makes liquid crystalline azo compounds, and yield is 95.9%.As seen from Figure 3, the product of the present embodiment preparation is target compound.
Claims (9)
1. a liquid crystalline azo compounds is characterized in that, the structure of this compounds is shown in general formula (1):
Wherein the structure of R1 is: carbonatoms is a kind of in the alkyl of 1-12; The structure of R2 is: carbonatoms is a kind of in a kind of or fluorine-based, the trifluoromethyl, cyano group, nitro, isothiocyano, fluorophenyl, trifluoromethyl, cyano-phenyl, nitrophenyl, isothiocyano phenyl in the alkyl of 1-12.
2. a kind of liquid crystalline azo compounds according to claim 1 is characterized in that, the structural formula of R1 is in the described compound:
R
1=-C
nH
2n+1, wherein n is 1-12.
3. the chemistry of a liquid crystalline azo compounds is clicked the preparation method, it is characterized in that, may further comprise the steps:
Steps A: the preparation of intermediate m1
R
1-N
3m1
With haloalkane R
1After X adds reaction vessel, in reaction vessel, add reaction solvent 3 and sodiumazide, under the condition of reflux, after stirring reaction 3-5 hour, remove reaction solvent 3, get intermediate m1; R wherein
1The mol ratio of X and sodiumazide is: 1:1.5 ~ 1:3; R
1Be a kind of in the alkyl of 1-12 for carbonatoms, reaction solvent 3 is one or more in tetrahydrofuran (THF), dioxane, DMF, the triethylamine;
Step B: the preparation of intermediate m2
With R
2The phenylazo halobenzene is dissolved in the solvent 1, place the logical nitrogen of reactor or protection of inert gas, then add trimethylsilyl acetylene, temperature of reaction is 30-80 ℃, the catalyzer 1 that adds reaction raw materials total mass 2%-5%, reaction is after 12-16 hour under the protection of inert gas, and desolventizing 1 is dissolved in products therefrom in the solvent 2, add catalyzer 2 after placing reactor, stirred 3-8 hour under the room temperature, then desolventizing 2, get intermediate m2;
Wherein, solvent 1 is one or more in tetrahydrofuran (THF), dioxane, triethylamine, DMF, the dimethyl propylamine; Catalyzer 1 is one or more in cuprous iodide, palladium metal, two (triphenylphosphine) palladium chloride, the triphenylphosphine; Solvent 2 is one or more in methyl alcohol, ethanol, Virahol, tetrahydrofuran (THF), dioxane, the DMF; Catalyzer 2 is mineral alkali; The mol ratio of R2 phenylazo halobenzene and trimethylsilyl acetylene is 1:1.5 ~ 1:3; The add-on of catalyzer 2 is 2 ~ 4 times of R2 phenylazo halobenzene mole number; Wherein R2 is that carbonatoms is a kind of in a kind of or fluorine-based, the trifluoromethyl, cyano group, nitro, isothiocyano, fluorophenyl, trifluoromethyl, cyano-phenyl, nitrophenyl, isothiocyano phenyl in the alkyl of 1-12, and the structure of R2 phenylazo halobenzene is shown in general formula (2):
Step C: click chemistry reaction preparation liquid crystalline azo compounds
In reaction vessel, add intermediate m1, intermediate m2 and reaction solvent 3, add the catalyzer 3 of reaction raw materials total mass 1 ~ 3%, after stirring reaction 3-6 under the condition of 60-120 ° of C hour, remove reaction solvent 3, get liquid crystalline azo compounds;
Wherein, catalyzer 3 is one or more in triethylamine, dimethyl propylamine, cuprous iodide, the cuprous chloride, and the mol ratio of intermediate m1 and intermediate m2 is 1:1.
4. the chemistry of a kind of liquid crystalline azo compounds according to claim 3 is clicked the preparation method, it is characterized in that R in the described steps A
1X is alkyl chloride, bromoalkane or idoalkane.
5. the chemistry of a kind of liquid crystalline azo compounds according to claim 3 is clicked the preparation method, it is characterized in that R among the described step B
2X in the phenylazo halobenzene comprises chloro thing, bromo-derivative and iodo thing.
6. the chemistry of a kind of liquid crystalline azo compounds according to claim 3 is clicked the preparation method, it is characterized in that, mineral alkali is one or more in sodium hydroxide, potassium hydroxide, yellow soda ash, the salt of wormwood among the described step B.
7. the chemistry of a kind of liquid crystalline azo compounds according to claim 3 is clicked the preparation method, it is characterized in that, the intermediate m2 of intermediate m1, the step B of described steps A and the azo liquid crystalline cpd of step C all adopt the method purifying of column chromatography, and the column chromatography developping agent is one or more in methylene dichloride, hexanaphthene, ethyl acetate, the sherwood oil.
8. the chemistry of a kind of liquid crystalline azo compounds according to claim 3 is clicked the preparation method, it is characterized in that solvent 3 and R in the described steps A
1The ratio of X is: 1mol R
1X adds solvent 3300-600mL; 1mol R among the step B
2The phenylazo halobenzene is dissolved in the 1000-1200mL solvent 1,1molR
2The amount that the phenylazo halobenzene adds solvent 2 is 1200-2000mL.
9. the chemistry of a kind of liquid crystalline azo compounds according to claim 3 is clicked the preparation method, it is characterized in that, the rare gas element among the described step B is argon gas.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108277020A (en) * | 2018-01-25 | 2018-07-13 | 西京学院 | Utilize the multiaxis liquid crystal refrigerating material and preparation method of the synthesis of click chemistry method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108277020A (en) * | 2018-01-25 | 2018-07-13 | 西京学院 | Utilize the multiaxis liquid crystal refrigerating material and preparation method of the synthesis of click chemistry method |
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Application publication date: 20130417 |