CN108658805B - Preparation method of asymmetric azobenzene - Google Patents

Preparation method of asymmetric azobenzene Download PDF

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CN108658805B
CN108658805B CN201810399239.9A CN201810399239A CN108658805B CN 108658805 B CN108658805 B CN 108658805B CN 201810399239 A CN201810399239 A CN 201810399239A CN 108658805 B CN108658805 B CN 108658805B
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hexane
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aromatic hydrazine
azobenzene
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龚跃法
姚瑞芳
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Huazhong University of Science and Technology
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
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Abstract

The invention discloses a method for preparing asymmetric azobenzene, belonging to the field of organic synthesis. The asymmetric azobenzene is obtained by the ring opening-oxidation reaction of 6-chloro-2-carbonyl bicyclo [3.1.0] hexane-6-formate compounds and aromatic hydrazine in a proper organic solvent. The reaction needs to be carried out at a specific temperature, and after the reaction is finished, the product can be separated by methods such as recrystallization, column chromatography and the like. The method has the characteristics of simple synthesis steps, simple and convenient operation, low cost and the like, and provides a new way for synthesizing the asymmetric azobenzene.

Description

Preparation method of asymmetric azobenzene
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of asymmetric azobenzene.
Background
The azobenzene compound is used as a ubiquitous basic structure skeleton and is widely applied to the fields of dyes, pigments, food additives, medicaments and the like. In addition, asymmetric azobenzenes have been extensively studied as a basic unit of photosensitive materials due to their robustness and their rapid and reversible conversion to cis and trans isomers under ultraviolet, visible light. Regarding the synthesis of asymmetric azobenzene, the main methods are: (1) coupling reaction of aromatic diazonium salt with phenol, aniline, etc.; (2) mills condensation reaction: firstly, phenol and nitroso form nitrosophenol in an acid medium, and then the nitrosophenol and arylamine are subjected to condensation reaction to prepare a series of asymmetric azobenzenes; (3) and dehydrogenating polysubstituted hydroazobenzene to obtain asymmetric azobenzene product. However, considering the above asymmetric azobenzene production method comprehensively, the following disadvantages are found: the method (1) needs the prior preparation of diazonium salt and aromatic hydrocarbon can only be phenol and aromatic amine compounds rich in electrons, so the variety of substituent groups on the synthesized asymmetric azobenzene is greatly limited; the preparation process of the method (2) is complex, and the intermediate product nitrosophenol is easy to oxidize in the air and decompose under the visible light; the method (3) needs to be carried out under acid catalysis, and is accompanied by the generation of a large amount of by-products such as benzidine, and the like, and the yield of the asymmetric azobenzene is low. Therefore, it is urgently needed to develop a simple and efficient method for synthesizing asymmetric azobenzene.
Disclosure of Invention
Aiming at the defects or the improvement requirements of the prior art, the invention provides a preparation method of asymmetric azobenzene, which is characterized in that 6-chloro-2-carbonyl bicyclo [3.1.0] hexane-6-formate compounds and aromatic hydrazine salt are subjected to ring-opening-oxidation reaction in a proper organic solvent at a certain reaction temperature to obtain the asymmetric azobenzene. Compared with the traditional asymmetric azobenzene synthesis method, the preparation method has the advantages of simple operation, various substituent groups contained in the asymmetric azobenzene product, high industrial application value and the like.
In order to achieve the purpose, the invention provides a preparation method of asymmetric azobenzene, which comprises the steps of dissolving a 6-chloro-2-carbonyl bicyclo [3.1.0] hexane-6-formate compound in an organic solvent, sequentially adding an aromatic hydrazine inorganic acid salt and an alkaline substance to perform a ring-opening reaction, and separating and purifying to obtain the asymmetric azobenzene.
Preferably, the structural formula of the 6-chloro-2-carbonyl bicyclo [3.1.0] hexane-6-formate compound is shown as the formula (1):
Figure BDA0001645308290000021
in the formula (1), R1And R2Each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aromatic group or a substituted aromatic group; wherein the aryl is selected from benzene, naphthalene, biphenyl, anthracene, phenanthrene, furan, thiophene, indole, thiazole and benzothiazole, the substituted aryl has 1-5 substituent groups, and the substituent groups are selected from halogen atoms, hydroxyl, sulfydryl, cyano, acylamino, sulfonamide and C1-C6Alkyl of (C)1-C6Alkyl alcohol of (1), C1-C6Alkyl amine of (C)1-C6Alkyl acid of (2), C1-C6Halogenoalkyl of, C2-C6Ester groups, halophenyl groups and halothienyl groups of (a);
r is alkyl selected from C1-C18Alkyl of (C)1-C18Halogenoalkyl of, C1-C18Alkyl alcohol of (1), C1-C18Alkyl amine of (C)2-C18Alkyl acid and C3-C18Alkyl esters of (a).
Preferably, the organic solvent is one or more of methanol, ethanol, isopropanol, butanol, acetonitrile, nitromethane, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, dichloromethane, chloroform, dichloroethane, tetrahydrofuran, diethyl ether, dibutyl ether, dioxane, ethylene glycol dimethyl ether, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, toluene, benzene, xylene, N-hexane, cyclohexane, chlorobenzene, dichlorobenzene, and water.
Preferably, the structural formula of the aromatic hydrazine is ArNHNH2Wherein Ar is selected from the group consisting of substituted phenyl, substituted naphthyl, substituted anthracyl, substituted phenanthryl, azaaryl, and thiaaryl.
Preferably, the aromatic hydrazine inorganic acid salt is aromatic hydrazine hydrochloride.
Preferably, the molar ratio of the 6-chloro-2-carbonyl bicyclo [3.1.0] hexane-6-formate compound to the aromatic hydrazine hydrochloride is 1: 1-1: 2; the concentration of the organic solvent is 0.1M-0.25M.
Preferably, the basic substance is at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, sodium carbonate, potassium phosphate, cesium carbonate, sodium hydride, sodium methoxide, sodium ethoxide, potassium tert-butoxide, triethylamine, pyridine, tetrahydropyrrole, and DBU.
In a further preferred embodiment of the present invention, the molar ratio of the basic substance to the aromatic hydrazine inorganic acid salt is 1:1 to 1: 5.
In a further preferred embodiment of the present invention, the reaction temperature is 40 to 250 ℃.
In a further preferred embodiment of the present invention, the reaction time is 2 to 48 hours.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) the method prepares the asymmetric azobenzene by one-step simple ring-opening reaction, has simple operation and is easy to commercialize.
(2) The 6-chloro-2-carbonyl bicyclo [3.1.0] hexane-6-formic acid ester compound is obtained by taking 2-cyclopentenone compounds and dichloroacetate as raw materials. The method has the advantages of easily available reaction raw materials, simple operation, mild reaction conditions and high yield, and is suitable for large-scale production.
(3) The invention selects aromatic hydrazine salt and 6-chlorine-2-carbonyl bicyclo [3.1.0] hexane-6-formic ether compound to carry out ring-opening reaction, the used reagent aromatic hydrazine salt is commercially available hydrochloride and sulfate, the price is low, and the production cost is saved.
(4) The reported synthesis method has limited kinds of aryl functional groups of the prepared asymmetric azobenzene and has great substrate limitation in synthesis. The asymmetric azobenzene synthesized by the method expands the structure type of the aromatic group. The reaction route innovatively designed by the invention provides a novel simple and convenient preparation method for synthesizing the azo compound.
Drawings
FIG. 1 is the NMR spectrum of the objective product obtained in example 1.
FIG. 2 is the NMR spectrum of the objective product obtained in example 7.
FIG. 3 is the NMR spectrum of the objective product obtained in example 8.
FIG. 4 is the NMR spectrum of the objective product obtained in example 9.
FIG. 5 is the NMR spectrum of the objective product obtained in example 10.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a preparation method of asymmetric azobenzene, which comprises the steps of dissolving a 6-chloro-2-carbonyl bicyclo [3.1.0] hexane-6-formate compound in an organic solvent, sequentially adding an aromatic hydrazine inorganic acid salt and an alkaline substance to carry out a ring-opening reaction, and separating and purifying to obtain the asymmetric azobenzene. The structural formula of the 6-chloro-2-carbonyl bicyclo [3.1.0] hexane-6-formate compound is shown as the formula (1):
Figure BDA0001645308290000041
in the formula (1), R1And R2Each independently selected from a hydrogen atom, a halogen atom, an alkyl group, an aromatic group or a substituted aromatic group; wherein the aryl is selected from benzene, naphthalene, biphenyl, anthracene, phenanthrene, furan, thiophene, indole, thiazole and benzothiazole, the substituted aryl has 1-5 substituent groups, and the substituent groups are selected from halogen atoms, hydroxyl, sulfydryl, cyano, acylamino, sulfonamide and C1-C6Alkyl of (C)1-C6Alkyl alcohol of (1), C1-C6Alkyl amine of (C)1-C6Alkyl acid of (2), C1-C6Halogenoalkyl of, C2-C6Ester groups, halophenyl groups and halothienyl groups of (a); r is alkyl selected from C1-C18Alkyl of (C)1-C18Halogenoalkyl of, C1-C18Alkyl alcohol of (1), C1-C18Alkyl amine of (C)2-C18Alkyl acid and C3-C18Alkyl esters of (a).
The structural formula of the aromatic hydrazine is ArNHNH2Wherein Ar can be substituted phenyl, substituted naphthyl, substituted anthryl, substituted phenanthryl, azaaryl and thiaaryl.
The asymmetric azobenzene has a chemical structural formula shown in a formula (3),
Figure BDA0001645308290000051
the chemical reaction formula of the preparation method is as follows:
Figure BDA0001645308290000052
the method specifically comprises the following steps: dissolving 1eq of the compound 1 in an organic solvent, sequentially adding 1 eq-2 eq of the compound 2 and an alkaline substance, carrying out ring opening-oxidation reaction at a certain temperature, and separating and purifying to obtain the asymmetric azobenzene 3.
The organic solvent of the preparation method can be polar aprotic solvents such as acetonitrile, nitromethane, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and the like, halogenated solvents such as dichloromethane, chloroform, dichloroethane and the like, ether solvents such as tetrahydrofuran, diethyl ether, butyl ether, dioxane and the like, aromatic hydrocarbons such as toluene, benzene, chlorobenzene, xylene and the like, and mixed solvents of the polar aprotic solvents, the halogenated solvents, the aromatic hydrocarbons or the ether solvents; in addition, water may also be used as a reaction solvent; the organic solvent is preferably toluene because the compound participating in the reaction has better reaction solubility in toluene, so that the yield of the asymmetric azobenzene under the same condition is improved.
The aromatic hydrazine inorganic acid salt is preferably aromatic hydrazine hydrochloride; the mol ratio of the chlorine-2-carbonyl bicyclo [3.1.0] hexane-6-formate compound to the aromatic hydrazine hydrochloride is 1: 1-1: 2, preferably 1: 1.2. The concentration of the organic solvent is 0.1M to 0.25M, preferably 0.2M.
The alkaline substance is at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, sodium carbonate, potassium phosphate, cesium carbonate, sodium hydride, sodium methoxide, sodium ethoxide, potassium tert-butoxide, triethylamine, pyridine, tetrahydropyrrole and DBU, preferably potassium carbonate.
The molar ratio of the alkaline substance to the aromatic hydrazine hydrochloride is 1: 1-1: 5, preferably 1:1.
The reaction can be smoothly carried out within 40-250 ℃, the reaction rate is higher when the temperature is high, and the yield of the obtained asymmetric azobenzene is higher. The reaction temperature is preferably 120 ℃ from the viewpoint of energy saving.
The reaction time is 2 to 48 hours, preferably 24 hours.
According to the preparation method of the asymmetric azobenzene, the reaction steps are controlled, and proper temperature and organic solvent are selected, so that the preparation method of the asymmetric azobenzene with cheap and easily-obtained raw materials and high yield is finally obtained. The asymmetric azobenzene is obtained by the ring opening-oxidation reaction of 6-chloro-2-carbonyl bicyclo [3.1.0] hexane-6-formate compounds and aromatic hydrazine in a proper organic solvent. The reaction needs to be carried out at a specific temperature, and after the reaction is finished, the product can be separated by methods such as recrystallization, column chromatography and the like. The method has the characteristics of simple synthesis steps, simple and convenient operation, low cost and the like, and provides a new way for synthesizing the asymmetric azobenzene.
The following are examples:
example 1
Step (1): 1642mg (20mmol) of 2-cyclopentenone and 2859mg (20mmol) of methyl dichloroacetate were dissolved in N, N-dimethylformamide (100ml), and 7820mg (24mmol) of cesium carbonate was added portionwise with stirring and reacted at room temperature for 48 hours. After the reaction, dichloromethane was extracted, the reaction mixture was washed with saturated brine to remove N, N-dimethylformamide, and the organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated by rotary evaporation under reduced pressure, and then separated by a silica gel column method to obtain 2.94g of methyl 6-chloro-2-carbonylbicyclo [3.1.0] hexane-6-carboxylate with a yield of 78%.
Figure BDA0001645308290000071
1H NMR(400MHz,CDCl3)δ(ppm)3.73(s,3H),2.73(t,J＝6.4Hz,1H),2.64(d,J＝6.4Hz,1H),2.48–2.36(m,1H),2.27–2.11(m,3H).
Step (2): putting the 6-chloro-2-carbonyl bicyclo [3.1.0] obtained in the step (1) into a reaction test tube with magnetic stirring]188mg (1mmol) of hexane-6-carboxylic acid methyl ester was dissolved in 5ml of toluene, and 174mg of phenylhydrazine hydrochloride (1.2mmol) and 166mg of potassium carbonate (1.2mmol) were added in this order; the mixed solution is stirred and reacted for 24 hours at the temperature of 120 ℃, after the reaction is finished, the mixed solution is washed by saturated saline solution, extracted by dichloromethane, combined with organic phases, dried by anhydrous sodium sulfate, filtered, decompressed, evaporated and concentrated, and then separated by a silica gel column method to obtain 151mg of trans-3-carbomethoxyazobenzene with the yield of 63 percent. (attached to FIG. 1 is1H NMR spectrum, which was indeed the structure of the compound by identification
Figure BDA0001645308290000072
1H NMR(400MHz,CDCl3)δ8.50–8.49(m,1H),8.08–8.06(m,1H),8.04–8.01(m,1H),7.88–7.86(m,2H),7.51(t,J＝8.0Hz,1H),7.47–7.41(m,3H),3.89(s,3H).
Example 2
Step (1) is the same as in example 1
Step (2): 188mg (1mmol) of methyl 6-chloro-2-carbonylbicyclo [3.1.0] hexane-6-carboxylate obtained in step (1) was put into a reaction tube equipped with magnetic stirring and dissolved in 5ml of N, N-dimethylformamide, and 174mg of phenylhydrazine hydrochloride (1.2mmol) and 166mg of potassium carbonate (1.2mmol) were sequentially added; the mixture was stirred at 120 ℃ for 24 hours, after the reaction was completed, the mixture was washed with saturated brine, extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and then separated by silica gel column chromatography to obtain 125mg of trans-3-carbomethoxyazobenzene with a yield of 52%.
Figure BDA0001645308290000081
Example 3
Step (1) is the same as in example 1
Step (2): 188mg (1mmol) of methyl 6-chloro-2-carbonylbicyclo [3.1.0] hexane-6-carboxylate obtained in step (1) was put into a reaction tube equipped with magnetic stirring and dissolved in 5ml of 1, 4-dioxane, and 174mg of phenylhydrazine hydrochloride (1.2mmol) and 166mg of potassium carbonate (1.2mmol) were sequentially added; the mixed solution is stirred and reacted for 24 hours at the temperature of 120 ℃, after the reaction is finished, the mixed solution is washed by saturated saline solution, extracted by dichloromethane, combined with organic phases, dried by anhydrous sodium sulfate, filtered, decompressed, evaporated and concentrated, and then separated by a silica gel column method to obtain 115mg of trans-3-carbomethoxyazobenzene with the yield of 48 percent.
Figure BDA0001645308290000082
In the above three examples, the effect of the solvent on the reaction was mainly reflected, and it can be seen that under the same conditions, the yield was significantly improved when toluene was used as the reaction solvent (example 1), while the yield was slightly inferior when N, N-dimethylformamide and 1, 4-dioxane were used as the reaction solvents.
Example 4
Step (1) is the same as in example 1
Step (2): 188mg (1mmol) of methyl 6-chloro-2-carbonylbicyclo [3.1.0] hexane-6-carboxylate obtained in step (1) was put into a reaction tube equipped with magnetic stirring and dissolved in 5ml of toluene, and 145mg of phenylhydrazine hydrochloride (1mmol) and 166mg of potassium carbonate (1.2mmol) were sequentially added; the mixed solution is stirred and reacted for 24 hours at the temperature of 120 ℃, after the reaction is finished, the mixed solution is washed by saturated saline, extracted by dichloromethane, combined with organic phases, dried by anhydrous sodium sulfate, filtered, decompressed, evaporated and concentrated, and then separated by a silica gel column method to obtain 142mg of trans-3-carbomethoxyazobenzene with the yield of 59 percent.
Figure BDA0001645308290000091
Example 5
Step (1) is the same as in example 1
Step (2): 188mg (1mmol) of methyl 6-chloro-2-carbonylbicyclo [3.1.0] hexane-6-carboxylate obtained in step (1) was put into a reaction tube equipped with magnetic stirring and dissolved in 5ml of toluene, and 174mg of phenylhydrazine hydrochloride (1.2mmol) and 48mg of sodium hydroxide (1.2mmol) were sequentially added; the mixed solution is stirred and reacted for 24 hours at the temperature of 120 ℃, after the reaction is finished, the mixed solution is washed by saturated saline, extracted by dichloromethane, combined with organic phases, dried by anhydrous sodium sulfate, filtered, decompressed, evaporated and concentrated, and then separated by a silica gel column method to obtain 122mg of trans-3-carbomethoxyazobenzene with the yield of 51 percent.
Figure BDA0001645308290000092
Example 6
Step (1) is the same as in example 1
Step (2): 188mg (1mmol) of methyl 6-chloro-2-carbonylbicyclo [3.1.0] hexane-6-carboxylate obtained in step (1) was put into a reaction tube equipped with magnetic stirring and dissolved in 5ml of toluene, and 174mg of phenylhydrazine hydrochloride (1.2mmol) and 166mg of potassium carbonate (1.2mmol) were sequentially added; the mixed solution is stirred and reacted for 24 hours at the temperature of 80 ℃, after the reaction is finished, the mixed solution is washed by saturated saline, extracted by dichloromethane, combined with organic phases, dried by anhydrous sodium sulfate, filtered, decompressed, evaporated and concentrated, and then separated by a silica gel column method to obtain 55mg of trans-3-carbomethoxyazobenzene with the yield of 23 percent.
Figure BDA0001645308290000093
Example 7
Step (1) is the same as in example 1
Step (2): putting the 6-chloro-2-carbonyl bicyclo [3.1.0] obtained in the step (1) into a reaction test tube with magnetic stirring]188mg (1mmol) of methyl hexane-6-carboxylate was dissolved in 5ml of toluene, and 210mg of p-methoxyphenylhydrazine hydrochloride (1.2mmol) and 166mg of potassium carbonate (1.2mmol) were added in this order; the mixed solution is stirred and reacted for 24 hours at the temperature of 120 ℃, after the reaction is finished, the mixed solution is washed by saturated saline, extracted by dichloromethane, combined with organic phases, dried by anhydrous sodium sulfate, filtered, decompressed, evaporated and concentrated, and then separated by a silica gel column method to obtain 130mg of trans-4' -methoxy-3-formic acid methyl ester azobenzene, wherein the yield is 48 percent. (FIG. 2 is a drawing thereof1HNMR spectrogram, which is actually the structure of the compound according to identification)
Figure BDA0001645308290000101
1H NMR(400MHz,CDCl3)δ8.47–8.46(m,1H),8.05–8.03(m,1H),8.01–7.99(m,1H),7.78–7.76(m,2H),7.49(t,J＝8.0Hz,1H),7.24(d,J＝8.0Hz,2H),3.88(s,3H),2.35(s,3H).
Example 8
Step (1) is the same as in example 1
Step (2): putting the 6-chloro-2-carbonyl bicyclo [3.1.0] obtained in the step (1) into a reaction test tube with magnetic stirring]188mg (1mmol) of hexane-6-carboxylic acid methyl ester was dissolved in 5ml of toluene, and 215mg of p-chlorophenylhydrazine hydrochloride (1.2mmol) and 166mg of potassium carbonate (1.2mmol) were added in this order; the mixed solution is stirred and reacted for 24 hours at the temperature of 120 ℃, after the reaction is finished, the mixed solution is washed by saturated saline, extracted by dichloromethane, combined with organic phases, dried by anhydrous sodium sulfate, filtered, decompressed, evaporated and concentrated, and then separated by a silica gel column method to obtain 145mg of trans-4' -chloro-3-carbomethoxyazobenzene with the yield of 53 percent. (FIG. 3 is the same as1HNMR spectrogram)
Figure BDA0001645308290000102
1H NMR(400MHz,CDCl3)δ8.49–8.48(m,1H),8.10–8.07(m,1H),8.03–8.00(m,1H),7.83–7.81(m,2H),7.52(t,J＝8.0Hz,1H),7.43–7.41(m,2H),3.90(s,3H).
Example 9
Step (1) and the same as example 1
Step (2): putting the 6-chloro-2-carbonyl bicyclo [3.1.0] obtained in the step (1) into a reaction test tube with magnetic stirring]188mg (1mmol) of methyl hexane-6-carboxylate was dissolved in 5ml of toluene, and 195mg of o-fluorophenylhydrazine hydrochloride (1.2mmol) and 166mg of potassium carbonate (1.2mmol) were added in this order; the mixture was stirred at 120 ℃ for 24 hours, after the reaction was completed, the mixture was washed with saturated brine, extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated by reduced pressure rotary evaporation, and then separated by a silica gel column method to obtain 173mg of trans-2' -fluoro-3-carbomethoxyazobenzene with a yield of 67%. (FIG. 4 is a drawing thereof1HNMR spectrogram, which is actually the structure of the compound according to identification)
Figure BDA0001645308290000111
1H NMR(400MHz,CDCl3)δ8.51–8.50(m,1H),8.09–8.06(m,1H),8.04–8.02(m,1H),7.71–7.66(m,1H),7.51(t,J＝8.0Hz,1H),7.42–7.36(m,1H),7.22–7.12(m,2H),3.88(s,3H).
Example 10
Step (1) and the same as example 1
Step (2): putting the 6-chloro-2-carbonyl bicyclo [3.1.0] obtained in the step (1) into a reaction test tube with magnetic stirring]188mg (1mmol) of methyl hexane-6-carboxylate was dissolved in 5ml of toluene, and 215mg of m-chlorophenylhydrazine hydrochloride (1.2mmol) and 166mg of potassium carbonate (1.2mmol) were added in this order; the mixed solution is stirred and reacted for 24 hours at the temperature of 120 ℃, after the reaction is finished, the mixed solution is washed by saturated saline, extracted by dichloromethane, combined with organic phases, dried by anhydrous sodium sulfate, filtered, decompressed, evaporated and concentrated, and then separated by a silica gel column method to obtain 132mg of trans-3' -chloro-3-carbomethoxyazobenzene with the yield of 48 percent. (FIG. 5 is a drawing thereof1HNMR spectrogram, which is actually the structure of the compound according to identification)
Figure BDA0001645308290000121
1H NMR(400MHz,CDCl3)δ8.49–8.48(m,1H),8.10(d,J＝8.0Hz,1H),8.04–8.01(m,1H),7.85–7.84(m,1H),7.80–7.77(m,1H),7.53(t,J＝8.0Hz,1H),7.40–7.39(m,2H),3.90(s,3H).
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (8)

1. A preparation method of asymmetric azobenzene is characterized in that 6-chloro-2-carbonyl bicyclo [3.1.0] hexane-6-formate compounds are dissolved in an organic solvent, aromatic hydrazine inorganic acid salt and alkaline substances are sequentially added to carry out ring opening reaction, and the asymmetric azobenzene is obtained after separation and purification; the structural formula of the 6-chloro-2-carbonyl bicyclo [3.1.0] hexane-6-formate compound is shown as the formula (1):
Figure FDA0002324579680000011
the asymmetric azobenzene has a chemical structural formula shown in a formula (3),
Figure FDA0002324579680000012
in the formula (1), R1And R2Is a hydrogen atom;
r is alkyl selected from C1-C18Alkyl groups of (a);
the structural formula of the aromatic hydrazine is ArNHNH2Wherein Ar is substituted phenyl.
2. The method according to claim 1, wherein the organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, dichloromethane, chloroform, dichloroethane, tetrahydrofuran, diethyl ether, butyl ether, dioxane, ethylene glycol dimethyl ether, toluene, benzene, xylene, chlorobenzene, dichlorobenzene, and water.
3. The method according to claim 1, wherein the aromatic hydrazine inorganic acid salt is an aromatic hydrazine hydrochloride.
4. The preparation method according to claim 3, wherein the molar ratio of the 6-chloro-2-carbonylbicyclo [3.1.0] hexane-6-carboxylate compound to the aromatic hydrazine hydrochloride is 1:1 to 1: 2; the concentration of the organic solvent is 0.1M-0.25M.
5. The method according to claim 1, wherein the basic substance is at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, potassium t-butoxide, triethylamine, pyridine, tetrahydropyrrole, and DBU.
6. The method according to claim 1, wherein the molar ratio of the basic substance to the aromatic hydrazine inorganic acid salt is 1:1 to 1: 5.
7. The method of claim 1, wherein the reaction temperature is 40 ℃ to 250 ℃.
8. The method according to claim 1, wherein the reaction time is 2 to 48 hours.
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