CN103342630B - Method for synthesizing diaryl ether compounds - Google Patents
Method for synthesizing diaryl ether compounds Download PDFInfo
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- CN103342630B CN103342630B CN201310325266.9A CN201310325266A CN103342630B CN 103342630 B CN103342630 B CN 103342630B CN 201310325266 A CN201310325266 A CN 201310325266A CN 103342630 B CN103342630 B CN 103342630B
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Abstract
The invention relates to a preparation method for synthesizing compounds, particularly a method for synthesizing diaryl ether compounds. The invention aims to solve the problem of difficulty in implementing industrialized production due to the defects of complex preparation technique, strict reaction conditions, uncontrollable operation, too many byproducts, and high oxidation tendency and difficulty in storage of the catalyst used in reaction in the existing preparation method for synthesizing diaryl ether compounds. The method comprises the following steps: 1. preparing a diaryl ether compound crude product; and 2. purifying to obtain the diaryl ether compounds. By using the cupric salt which is easy to store and introducing the cheap ligand, the invention saves the cost and is simple to operate; and the invention has the advantages of mild reaction conditions, low temperature and high yield. The invention is used for synthesizing diaryl ether compounds.
Description
Technical field
The present invention relates to the preparation method of synthetic compound.
Background technology
Diaryl ether and derivative thereof are compounds very important in organic chemistry, are widely used to produce high temperature resistant composite.In organic synthesis, some have the important intermediate that bioactive diphenyl ether compound has high-efficiency low-toxicity novel pyrethroid vinegar agricultural chemicals, also can be used as the raw material of the Chemicals such as pressure sensitive dye, high temperature resistant luboil, tobacco sterilant and allotment spiceleaf rose chrysanthemum perfume fragrance, nitrofen compares the product having research and development future at present.Because diaryl ether compound thing more and more receives in the remarkable function of each side such as medicine and material the concern that people get over, so the efficient and synthesis of diaryl ether compound of low cost of application novel method has now become the work problem of many researchers.
Liv Ullmann linked reaction is the important reaction of a class in modern organic reaction synthesis, and it has unique irreplaceable effect in organic synthesis history, and it mainly synthesizes the highly effective reaction of a class of C-C key, C-N key, C-O key, C-S key.This reaction can be prepared organic ENERGETIC MATERIALS, synthesized rare natural product and have bioactive compound, therefore, has important use value in organic synthesis.In recent years, because the widely using of nitrofen compounds in agricultural chemicals, the studied person of synthesis of C-O key paid close attention to.But this reaction not only needs reaction conditions gentle, and requirement has selectivity that is elevated chemical, three-dimensional and region, is more and more subject to people's attention in the research of organic synthesis.
Liv Ullmann linked reaction custom catalysts is copper complex, and copper belongs to d
10transition metal, copper complex easily occurs when catalyzed reaction to be oxidized addition-activation substrate, and catalytic cycle is eliminated-completed in reduction.So title complex is widely used in the formation of catalysis C-C key, C-N key, C-S key and C-O key etc., make over some with ordinary method be difficult to realize reaction be accomplished.But copper catalysis Liv Ullmann linked reaction needs to use cuprous salt to carry out catalysis Liv Ullmann linked reaction as copper source usually, but cuprous salt has the shortcomings such as oxidizable not easily preservation.Need high temperature, the measures such as pressurization, attracted operation thus wayward, by product is many.
In sum, there is complicated process of preparation in the method for existing synthesis of diaryl ether compound, temperature of reaction is about 200 DEG C, severe reaction conditions, operate wayward, and under high temperature, intermolecular activation energy improves, the selectivity of intermolecular reaction reduces, cause by product many, and reaction uses cuprous salt to carry out catalysis Liv Ullmann linked reaction as copper source, but cuprous salt has oxidizable shortcoming of not easily preserving, thus is difficult to the problem realizing suitability for industrialized production.
Liu Jianli 2010 University Of Suzhou's Master's thesis " the Ullmann linked reaction research of Cu (II) catalysis " discloses a kind of synthetic method of diaryl sulfide compound, carries out according to the following steps: by halogenated aryl hydrocarbon, thiophenol, Cu (OAc) H
2o, 2,2 ＇-bisglyoxaline, cesium carbonate and methyl-sulphoxide add in the reaction tubes with piston, N
2under protection, be heated to 80 DEG C and stir 3h; Reaction terminates rear cool to room temperature, adds water dilution, is extracted with ethyl acetate three times, merge organic phase, with anhydrous sodium sulfate drying, obtains crude product, with sherwood oil as carrying out agent, being further purified obtaining final product by column chromatography after concentrated.
Summary of the invention
There is complicated process of preparation in the method that the present invention will solve existing synthesis of diaryl ether compound, severe reaction conditions, operate wayward, by product is many, and the oxidizable shortcoming of not easily preserving of the catalyzer reacting used, thus be difficult to the problem realizing suitability for industrialized production, and a kind of method of synthesis of diaryl ether compound is provided.
A method for synthesis of diaryl ether compound, specifically carry out according to following steps:
One, diaryl ether crude compound is prepared: in trifluoroacetic acid copper, add pyridine carboxylic acid, cesium carbonate, sodium ascorbate, poly(oxyethylene glycol) 400 and dimethyl sulfoxide (DMSO) successively, and be uniformly mixed 10min ~ 20min, add phenols and aryl iodide more successively for thing, then it is 40 ~ 60 DEG C by room temperature to temperature under nitrogen protection, and be 40 ~ 60 DEG C of reaction 10h ~ 18h in temperature, obtain diaryl ether crude compound;
Described phenols and aryl iodide are 1:(1 ~ 1.5 for the mol ratio of thing); Described trifluoroacetic acid copper and the mol ratio of phenols are 1:(5 ~ 15); Described pyridine carboxylic acid and the mol ratio of phenols are 1:(3 ~ 8); Described cesium carbonate and the mol ratio of phenols are (1.5 ~ 2.5): 1; Described sodium ascorbate and the mol ratio of phenols are 1:(4 ~ 8); Described poly(oxyethylene glycol) 400 and the mol ratio of phenols are 1:5; The volume of described dimethyl sulfoxide (DMSO) is (7mL ~ 12mL): 1mmol with the ratio of the amount of substance of phenols;
Two, purification process: add distilled water in the diaryl ether crude compound first obtained to step one, obtain mixture, be that extraction agent extracts again with ether, extract 3 times, the usage quantity of single extraction ether is (5 ~ 15) mL/mL, merge 3 extraction liquids, obtain combining extraction liquid, utilize distilled water to be combined extraction liquid to wash, wash 2 times, the usage quantity of single washing distilled water is (10 ~ 25) mL/mL, obtain the combining extraction liquid after washing, then utilization is revolved steaming instrument and the combining extraction liquid after washing is revolved steam to former combining extraction liquid volume 2% ~ 13%, obtain revolving and steam rear extraction liquid, silica gel is added again in extraction liquid after revolving steaming, the add-on of silica gel is (0.01 ~ 0.03) g/mL, obtain the silica gel containing product, be leacheate again with sherwood oil, take silica gel as stationary phase, silica gel tiling containing product is carried out chromatography to stationary phase, obtain diaryl ether compound.
The invention has the beneficial effects as follows: one, reaction conditions is gentle, temperature low (50 DEG C), the selectivity of intermolecular reaction improves, therefore yield high (70% ~ 88.12%), solving temperature of reaction controls at 200 DEG C, severe reaction conditions, operate wayward, the shortcoming that by product is many; Two, use cupric salt, easily preserve, introduce cheap part, cost-saving, simple to operate, solve and use cuprous salt to carry out catalysis Liv Ullmann linked reaction as copper source, but cuprous salt there is oxidizable shortcoming of not easily preserving.
The present invention, for the synthesis of diaryl ether compound, is particularly useful for suitability for industrialized production diaryl ether.
Accompanying drawing explanation
Fig. 1 is the nmr spectrum of diphenyl ether compound prepared by embodiment one;
Fig. 2 is the partial enlarged drawing of the nmr spectrum of diphenyl ether compound prepared by embodiment one;
Fig. 3 is the nuclear-magnetism spectrum resonance figure of adjacent methyldiphenyl ether compound prepared by embodiment two;
Fig. 4 is the partial enlarged drawing of the nmr spectrum of adjacent methyldiphenyl ether compound prepared by embodiment two;
Fig. 5 is the nmr spectrum of m-phenoxy toluene compound prepared by embodiment three;
Fig. 6 is the partial enlarged drawing of the nmr spectrum of m-phenoxy toluene compound prepared by embodiment three;
Fig. 7 is the nmr spectrum to methyldiphenyl ether compound prepared by embodiment four;
Fig. 8 is the partial enlarged drawing of the nmr spectrum to methyldiphenyl ether compound prepared by embodiment four;
Fig. 9 is the nmr spectrum of methoxydiphenyl ether compound prepared by embodiment five;
Figure 10 is the partial enlarged drawing of the nmr spectrum of methoxydiphenyl ether compound prepared by embodiment five;
Figure 11 is the nmr spectrum of meta-methoxy diphenyl ether compound prepared by embodiment six;
Figure 12 is the partial enlarged drawing of the nmr spectrum of meta-methoxy diphenyl ether compound prepared by embodiment six;
Figure 13 is the nmr spectrum to methoxyl group diphenyl ether compound prepared by embodiment seven;
Figure 14 is the partial enlarged drawing of the nmr spectrum to methoxyl group diphenyl ether compound prepared by embodiment seven;
Figure 15 is the nmr spectrum of m-chloro diphenyl ether compound prepared by embodiment eight;
Figure 16 is the partial enlarged drawing of the nmr spectrum of m-chloro diphenyl ether compound prepared by embodiment eight;
Figure 17 is the nmr spectrum of p-dichlorobenzene ether compound prepared by embodiment nine;
Figure 18 is the partial enlarged drawing of the nmr spectrum of p-dichlorobenzene ether compound prepared by embodiment nine;
Figure 19 is the nmr spectrum to dibromodiphenyl ether compound prepared by embodiment ten;
Figure 20 is the partial enlarged drawing of the nmr spectrum to dibromodiphenyl ether compound prepared by embodiment ten.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the method for a kind of synthesis of diaryl ether compound described in present embodiment, specifically carry out according to following steps:
One, diaryl ether crude compound is prepared: in trifluoroacetic acid copper, add pyridine carboxylic acid, cesium carbonate, sodium ascorbate, poly(oxyethylene glycol) 400 and dimethyl sulfoxide (DMSO) successively, and be uniformly mixed 10min ~ 20min, add phenols and aryl iodide more successively for thing, then it is 40 ~ 60 DEG C by room temperature to temperature under nitrogen protection, and be 40 ~ 60 DEG C of reaction 10h ~ 18h in temperature, obtain diaryl ether crude compound;
Described phenols and aryl iodide are 1:(1 ~ 1.5 for the mol ratio of thing); Described trifluoroacetic acid copper and the mol ratio of phenols are 1:(5 ~ 15); Described pyridine carboxylic acid and the mol ratio of phenols are 1:(3 ~ 8); Described cesium carbonate and the mol ratio of phenols are (1.5 ~ 2.5): 1; Described sodium ascorbate and the mol ratio of phenols are 1:(4 ~ 8); Described poly(oxyethylene glycol) 400 and the mol ratio of phenols are 1:5; The volume of described dimethyl sulfoxide (DMSO) is (7mL ~ 12mL): 1mmol with the ratio of the amount of substance of phenols;
Two, purification process: add distilled water in the diaryl ether crude compound first obtained to step one, obtain mixture, be that extraction agent extracts again with ether, extract 3 times, the usage quantity of single extraction ether is (5 ~ 15) mL/mL, merge 3 extraction liquids, obtain combining extraction liquid, utilize distilled water to be combined extraction liquid to wash, wash 2 times, the usage quantity of single washing distilled water is (10 ~ 25) mL/mL, obtain the combining extraction liquid after washing, then utilization is revolved steaming instrument and the combining extraction liquid after washing is revolved steam to former combining extraction liquid volume 2% ~ 13%, obtain revolving and steam rear extraction liquid, silica gel is added again in extraction liquid after revolving steaming, the add-on of silica gel is (0.01 ~ 0.03) g/mL, obtain the silica gel containing product, be leacheate again with sherwood oil, take silica gel as stationary phase, silica gel tiling containing product is carried out chromatography to stationary phase, obtain diaryl ether compound.
The reaction expression of step one is:
Wherein R
1for hydrogen, 3-chlorine, 4-chlorine or 4-bromine; R
2for hydrogen, 2-methyl, 3-methyl, 4-methyl, 2-methoxyl group, 3-methoxyl group or 4-methoxyl group.
All all have impact to speed of reaction and yield by the consumption of present embodiment known poly(oxyethylene glycol) 400, trifluoroacetic acid copper, part and additive in reaction process, wherein the add-on of poly(oxyethylene glycol) 400 has the greatest impact to reaction.When the mol ratio of poly(oxyethylene glycol) 400 and phenols is less than 1:5, speed of response is very slow, and yield does not increase; When the mol ratio of poly(oxyethylene glycol) 400 and phenols is 1:5, the reaction times shortens rapidly, and yield increases; When the mol ratio of poly(oxyethylene glycol) 400 and phenols is greater than 1:5, speed of reaction and yield do not have considerable change, therefore, only reach optimal effectiveness when the mol ratio of poly(oxyethylene glycol) 400 and phenols is 1:5.
The beneficial effect of present embodiment is: one, reaction conditions is gentle, temperature low (50 DEG C), the selectivity of intermolecular reaction improves, therefore yield high (70% ~ 88.12%), solving temperature of reaction controls at 200 DEG C, severe reaction conditions, operate wayward, the shortcoming that by product is many; Two, use cupric salt, easily preserve, introduce cheap part, cost-saving, simple to operate, solve and use cuprous salt to carry out catalysis Liv Ullmann linked reaction as copper source, but cuprous salt there is oxidizable shortcoming of not easily preserving.
Embodiment two: present embodiment and embodiment one unlike: the phenols described in step one is phenol, ortho-methyl phenol, m-methyl phenol, p-methyl phenol, hydroxyanisole, meta-methoxy phenol or p methoxy phenol.Other is identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two unlike: the aryl iodide described in step one for thing be iodobenzene, a chloroiodobenzone, to chloroiodobenzone or to bromo-iodobenzene.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one, two or three unlike: in step one, mixture is uniformly mixed 15min; add phenols and aryl iodide more successively for thing; then be 50 DEG C by room temperature to temperature under nitrogen protection, and be 50 DEG C of reaction 11h ~ 15h in temperature.Other with embodiment one, two or three identical.
Embodiment five: one of present embodiment and embodiment one, two, three or four are 1:1.2 unlike: the phenols described in step one and aryl iodide for the mol ratio of thing; Described trifluoroacetic acid copper and the mol ratio of phenols are 1:10; Described pyridine carboxylic acid and the mol ratio of phenols are 1:5; Described cesium carbonate and the mol ratio of phenols are 2:1; Described sodium ascorbate and the mol ratio of phenols are 1:5; The volume of described dimethyl sulfoxide (DMSO) is 10mL:1mmol with the ratio of the amount of substance of phenols.Other with embodiment one, two, three or four identical.
Embodiment six: present embodiment and embodiment one, two, three, one of four or five unlike: add distilled water in the diaryl ether crude compound first obtained to step one in step 2, obtain mixture, be that extraction agent extracts again with ether, extract 3 times, the usage quantity of single extraction ether is 10mL/mL, merge 3 extraction liquids, obtain combining extraction liquid, utilize distilled water to be combined extraction liquid to wash, wash 2 times, the usage quantity of single washing distilled water is 20mL/mL, obtain the combining extraction liquid after washing, then utilization is revolved steaming instrument and the combining extraction liquid after washing is revolved steam to former combining extraction liquid volume 5% ~ 12%, obtain revolving and steam rear extraction liquid, silica gel is added again in extraction liquid after revolving steaming, the add-on of silica gel is 0.02g/mL, obtain the silica gel containing product, be leacheate again with sherwood oil, take silica gel as stationary phase, silica gel tiling containing product is carried out chromatography to stationary phase, obtain diaryl ether compound.Other with embodiment one, two, three, four or five identical.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment one:
A kind of method of synthesizing diphenyl ether compound described in the present embodiment, specifically carry out according to following steps:
One, diphenyl ether compound crude product is prepared: in 0.0134g trifluoroacetic acid copper, add 0.0098g pyridine carboxylic acid, 0.2607g cesium carbonate, 0.0158g sodium ascorbate, 0.016g poly(oxyethylene glycol) 400 and 4ml dimethyl sulfoxide (DMSO) successively, and be uniformly mixed 15min, add 0.0367g phenol and 0.0538g iodobenzene more successively, then it is 50 DEG C by room temperature to temperature under nitrogen protection, and be 50 DEG C of reaction 12h in temperature, obtain diphenyl ether compound crude product;
Two, purification process: add 100mL distilled water in the diphenyl ether compound crude product first obtained to step one, obtain mixture, be that extraction agent extracts again with ether, extract 3 times, the usage quantity of single extraction ether is 50mL, merge 3 extraction liquids, obtain combining extraction liquid, utilize distilled water to be combined extraction liquid to wash, wash 2 times, the usage quantity of single washing distilled water is 100mL, obtain the combining extraction liquid after washing, then utilization is revolved steaming instrument and the combining extraction liquid after washing is revolved steaming to 1.5mL, obtain revolving and steam rear extraction liquid, silica gel is added again in extraction liquid after revolving steaming, the add-on of silica gel is 0.1g, obtain the silica gel containing product, be leacheate again with sherwood oil, take silica gel as stationary phase, silica gel tiling containing product is carried out chromatography to stationary phase, namely the method for synthesis diphenyl ether compound is completed.
The diphenyl ether compound crude product that step one obtains can reach 92% by Liquid Detection productive rate.
The diphenyl ether compound sterling that step 2 obtains can reach 0.050g by weighing, and yield is 75.00% as calculated.
The nmr spectrum of diphenyl ether compound prepared by the present embodiment as the partial enlarged drawing of the nmr spectrum of the diphenyl ether compound of Fig. 1 and preparation as shown in Figure 2, obtain
1h NMR (400MHz, CDCl
3) δ 7.33 (t, J=7.7Hz, 4H), 7.09 (t, J=7.1Hz, 2H), 7.01 (d, J=8.4Hz, 4H), the diphenyl ether compound structural formula that therefore prepared by the present embodiment is
Embodiment two:
A kind of method of synthesizing adjacent methyldiphenyl ether compound described in the present embodiment, specifically carry out according to following steps:
One, adjacent methyl diphenyl ether crude compound is prepared: in 0.0134g trifluoroacetic acid copper, add 0.0098g pyridine carboxylic acid, 0.2607g cesium carbonate, 0.0158g sodium ascorbate, 0.016g poly(oxyethylene glycol) 400 and 4ml dimethyl sulfoxide (DMSO) successively, and be uniformly mixed 15min, add 0.0433g ortho-methyl phenol and 0.0538g iodobenzene more successively, then it is 50 DEG C by room temperature to temperature under nitrogen protection, and be 50 DEG C of reaction 12h in temperature, obtain adjacent methyl diphenyl ether crude compound;
Two, purification process: add 100mL distilled water in the adjacent methyl diphenyl ether crude compound first obtained to step one, obtain mixture, be that extraction agent extracts again with ether, extract 3 times, the usage quantity of single extraction ether is 50mL, merge 3 extraction liquids, obtain combining extraction liquid, utilize distilled water to be combined extraction liquid to wash, wash 2 times, the usage quantity of single washing distilled water is 100mL, obtain the combining extraction liquid after washing, then utilization is revolved steaming instrument and the combining extraction liquid after washing is revolved steaming to 1.5mL, obtain revolving and steam rear extraction liquid, silica gel is added again in extraction liquid after revolving steaming, the add-on of silica gel is 0.1g, obtain the silica gel containing product, be leacheate again with sherwood oil, take silica gel as stationary phase, silica gel tiling containing product is carried out chromatography to stationary phase, namely the method for synthesizing adjacent methyldiphenyl ether compound is completed.
The adjacent methyl diphenyl ether crude compound that step one obtains can reach 98% by Liquid Detection productive rate.
The adjacent methyl diphenyl ether pure compounds that step 2 obtains can reach 0.062g by weighing, and yield is 84.05% as calculated.
The nmr spectrum of adjacent methyldiphenyl ether compound prepared by the present embodiment as the partial enlarged drawing of the nmr spectrum of the adjacent methyldiphenyl ether compound of Fig. 3 and preparation as shown in Figure 4, obtain
1h NMR (400MHz, CDCl
3) δ 7.31-7.22 (m, 3H), 7.15 (td, J=7.8,1.3Hz, 1H), 7.08-7.00 (m, 2H), 6.94-6.86 (m, 3H), 2.24 (s, 3H), the adjacent methyl diphenyl ether structural formula of compound that therefore prepared by the present embodiment is
Embodiment three:
A kind of method of synthesizing m-phenoxy toluene compound described in the present embodiment, specifically carry out according to following steps:
One, m-phenoxy toluene crude compound is prepared: in 0.0134g trifluoroacetic acid copper, add 0.0098g pyridine carboxylic acid, 0.2607g cesium carbonate, 0.0158g sodium ascorbate, 0.016g poly(oxyethylene glycol) 400 and 4ml dimethyl sulfoxide (DMSO) successively, and be uniformly mixed 15min, add 0.0433g m-methyl phenol and 0.0538g iodobenzene more successively, then it is 50 DEG C by room temperature to temperature under nitrogen protection, and be 50 DEG C of reaction 12h in temperature, obtain m-phenoxy toluene crude compound;
Two, purification process: add 100mL distilled water in the m-phenoxy toluene crude compound first obtained to step one, obtain mixture, be that extraction agent extracts again with ether, extract 3 times, the usage quantity of single extraction ether is 50mL, merge 3 extraction liquids, obtain combining extraction liquid, utilize distilled water to be combined extraction liquid to wash, wash 2 times, the usage quantity of single washing distilled water is 100mL, obtain the combining extraction liquid after washing, then utilization is revolved steaming instrument and the combining extraction liquid after washing is revolved steaming to 1.5mL, obtain revolving and steam rear extraction liquid, silica gel is added again in extraction liquid after revolving steaming, the add-on of silica gel is 0.1g, obtain the silica gel containing product, be leacheate again with sherwood oil, take silica gel as stationary phase, silica gel tiling containing product is carried out chromatography to stationary phase, namely the method for synthesis m-phenoxy toluene compound is completed.
The m-phenoxy toluene crude compound that step one obtains can reach 96% by Liquid Detection productive rate.
The m-phenoxy toluene pure compounds that step 2 obtains can reach 0.059g by weighing, and yield is 80.00% as calculated.
The nmr spectrum of m-phenoxy toluene compound prepared by the present embodiment as the partial enlarged drawing of the nmr spectrum of the m-phenoxy toluene compound of Fig. 5 and preparation as shown in Figure 6, obtain
1h NMR (400MHz, CDCl
3) δ 7.32 (dd, J=8.4,7.6Hz, 2H), 7.21 (dd, J=12.9,5.1Hz, 1H), 7.08 (t, J=7.4Hz, 1H), 7.03-6.97 (m, 2H), 6.91 (d, J=7.5Hz, 1H), 6.84-6.78 (m, 2H), 2.32 (s, 3H), the m-phenoxy toluene structural formula of compound that therefore prepared by the present embodiment is
Embodiment four:
The method of a kind of synthesis to methyldiphenyl ether compound described in the present embodiment, specifically carry out according to following steps:
One, prepare methyl diphenyl ether crude compound: in 0.0134g trifluoroacetic acid copper, add 0.0098g pyridine carboxylic acid, 0.2607g cesium carbonate, 0.0158g sodium ascorbate, 0.016g poly(oxyethylene glycol) 400 and 4ml dimethyl sulfoxide (DMSO) successively, and be uniformly mixed 15min, add 0.0433g p-methyl phenol and 0.0538g iodobenzene more successively, then it is 50 DEG C by room temperature to temperature under nitrogen protection, and be 50 DEG C of reaction 12h in temperature, obtain methyl diphenyl ether crude compound;
Two, purification process: what first obtain to step one adds 100mL distilled water in methyl diphenyl ether crude compound, obtain mixture, be that extraction agent extracts again with ether, extract 3 times, the usage quantity of single extraction ether is 50mL, merge 3 extraction liquids, obtain combining extraction liquid, utilize distilled water to be combined extraction liquid to wash, wash 2 times, the usage quantity of single washing distilled water is 100mL, obtain the combining extraction liquid after washing, then utilization is revolved steaming instrument and the combining extraction liquid after washing is revolved steaming to 1.5mL, obtain revolving and steam rear extraction liquid, silica gel is added again in extraction liquid after revolving steaming, the add-on of silica gel is 0.1g, obtain the silica gel containing product, be leacheate again with sherwood oil, take silica gel as stationary phase, silica gel tiling containing product is carried out chromatography to stationary phase, namely the method for synthesis to methyldiphenyl ether compound is completed.
What step one obtained can reach 99% to methyl diphenyl ether crude compound by Liquid Detection productive rate.
What step 2 obtained can reach 0.064g to methyl diphenyl ether pure compounds by weighing, and yield is 86.76% as calculated.
The present embodiment prepare to the nmr spectrum of methyldiphenyl ether compound as the partial enlarged drawing of the nmr spectrum to methyldiphenyl ether compound of Fig. 7 and preparation as shown in Figure 8, obtain
1h NMR (400MHz, CDCl
3) δ 7.31 (dd, J=8.5,7.5Hz, 2H), 7.13 (d, J=8.2Hz, 2H), 7.06 (t, J=7.4Hz, 1H), 6.98 (dd, J=8.6,0.9Hz, 2H), 6.92 (d, J=8.5Hz, 2H), 2.33 (s, 3H), what therefore prepared by the present embodiment to methyl diphenyl ether structural formula of compound is
Embodiment five:
A kind of method of synthesizing methoxydiphenyl ether compound described in the present embodiment, specifically carry out according to following steps:
One, methoxydiphenyl ether crude compound is prepared: in 0.0134g trifluoroacetic acid copper, add 0.0098g pyridine carboxylic acid, 0.2607g cesium carbonate, 0.0158g sodium ascorbate, 0.016g poly(oxyethylene glycol) 400 and 4ml dimethyl sulfoxide (DMSO) successively, and be uniformly mixed 15min, add 0.0497g hydroxyanisole and 0.0538g iodobenzene more successively, then it is 50 DEG C by room temperature to temperature under nitrogen protection, and be 50 DEG C of reaction 12h in temperature, obtain methoxydiphenyl ether crude compound;
Two, purification process: add 100mL distilled water in the methoxydiphenyl ether crude compound first obtained to step one, obtain mixture, be that extraction agent extracts again with ether, extract 3 times, the usage quantity of single extraction ether is 50mL, merge 3 extraction liquids, obtain combining extraction liquid, utilize distilled water to be combined extraction liquid to wash, wash 2 times, the usage quantity of single washing distilled water is 100mL, obtain the combining extraction liquid after washing, then utilization is revolved steaming instrument and the combining extraction liquid after washing is revolved steaming to 1.5mL, obtain revolving and steam rear extraction liquid, silica gel is added again in extraction liquid after revolving steaming, the add-on of silica gel is 0.1g, obtain the silica gel containing product, be leacheate again with sherwood oil, take silica gel as stationary phase, silica gel tiling containing product is carried out chromatography to stationary phase, namely the method for synthesis methoxydiphenyl ether compound is completed.
The methoxydiphenyl ether crude compound that step one obtains can reach 98% by Liquid Detection productive rate.
The methoxydiphenyl ether pure compounds that step 2 obtains can reach 0.063g by weighing, and yield is 85.41% as calculated.
The nmr spectrum of methoxydiphenyl ether compound prepared by the present embodiment as the partial enlarged drawing of the nmr spectrum of the methoxydiphenyl ether compound of Fig. 9 and preparation as shown in Figure 10, obtain
1h NMR (400MHz, CDCl
3) δ 7.36-7.29 (m, 2H), 7.16 (ddd, J=8.2,7.3,1.8Hz, 1H), 7.10-6.93 (m, 6H), 3.87 (s, 3H), the methoxydiphenyl ether structural formula of compound that therefore prepared by the present embodiment is
Embodiment six:
A kind of method of synthesizing meta-methoxy diphenyl ether compound described in the present embodiment, specifically carry out according to following steps:
One, meta-methoxy diphenyl ether compound crude product is prepared: in 0.0134g trifluoroacetic acid copper, add 0.0098g pyridine carboxylic acid, 0.2607g cesium carbonate, 0.0158g sodium ascorbate, 0.016g poly(oxyethylene glycol) 400 and 4ml dimethyl sulfoxide (DMSO) successively, and be uniformly mixed 15min, add 0.0497g meta-methoxy phenol and 0.0538g iodobenzene more successively, then it is 50 DEG C by room temperature to temperature under nitrogen protection, and be 50 DEG C of reaction 12h in temperature, obtain meta-methoxy diphenyl ether compound crude product;
Two, purification process: add 100mL distilled water in the meta-methoxy diphenyl ether compound crude product first obtained to step one, obtain mixture, be that extraction agent extracts again with ether, extract 3 times, the usage quantity of single extraction ether is 50mL, merge 3 extraction liquids, obtain combining extraction liquid, utilize distilled water to be combined extraction liquid to wash, wash 2 times, the usage quantity of single washing distilled water is 100mL, obtain the combining extraction liquid after washing, then utilization is revolved steaming instrument and the combining extraction liquid after washing is revolved steaming to 1.5mL, obtain revolving and steam rear extraction liquid, silica gel is added again in extraction liquid after revolving steaming, the add-on of silica gel is 0.1g, obtain the silica gel containing product, be leacheate again with sherwood oil, take silica gel as stationary phase, silica gel tiling containing product is carried out chromatography to stationary phase, namely the method for synthesis meta-methoxy diphenyl ether compound is completed.
The meta-methoxy diphenyl ether compound crude product that step one obtains can reach 96% by Liquid Detection productive rate.
The meta-methoxy diphenyl ether compound sterling that step 2 obtains can reach 0.060g by weighing, and yield is 81.34% as calculated.
The nmr spectrum of meta-methoxy diphenyl ether compound prepared by the present embodiment as the partial enlarged drawing of the nmr spectrum of the meta-methoxy diphenyl ether compound of Figure 11 and preparation as shown in figure 12, obtain
1h NMR (400MHz, CDCl
3) δ 7.33 (dd, J=8.3,7.6Hz, 2H), 7.22 (t, J=8.5Hz, 1H), 7.10 (t, J=7.4Hz, 1H), 7.06-7.00 (m, 2H), 6.67-6.63 (m, 1H), 6.59 (dd, J=5.0,2.6Hz, 2H), 3.77 (s, 3H), the meta-methoxy diphenyl ether compound structural formula that therefore prepared by the present embodiment is
Embodiment seven:
The method of a kind of synthesis to methoxyl group diphenyl ether compound described in the present embodiment, specifically carry out according to following steps:
One, prepare methoxyl group diphenyl ether compound crude product: in 0.0134g trifluoroacetic acid copper, add 0.0098g pyridine carboxylic acid, 0.2607g cesium carbonate, 0.0158g sodium ascorbate, 0.016g poly(oxyethylene glycol) 400 and 4ml dimethyl sulfoxide (DMSO) successively, and be uniformly mixed 15min, add 0.0497g p methoxy phenol and 0.0538g iodobenzene more successively, then it is 50 DEG C by room temperature to temperature under nitrogen protection, and be 50 DEG C of reaction 12h in temperature, obtain methoxyl group diphenyl ether compound crude product;
Two, purification process: what first obtain to step one adds 100mL distilled water in methoxyl group diphenyl ether compound crude product, obtain mixture, be that extraction agent extracts again with ether, extract 3 times, the usage quantity of single extraction ether is 50mL, merge 3 extraction liquids, obtain combining extraction liquid, utilize distilled water to be combined extraction liquid to wash, wash 2 times, the usage quantity of single washing distilled water is 100mL, obtain the combining extraction liquid after washing, then utilization is revolved steaming instrument and the combining extraction liquid after washing is revolved steaming to 1.5mL, obtain revolving and steam rear extraction liquid, silica gel is added again in extraction liquid after revolving steaming, the add-on of silica gel is 0.1g, obtain the silica gel containing product, be leacheate again with sherwood oil, take silica gel as stationary phase, silica gel tiling containing product is carried out chromatography to stationary phase, namely the method for synthesis to methoxyl group diphenyl ether compound is completed.
What step one obtained can reach 99% to methoxyl group diphenyl ether compound crude product by Liquid Detection productive rate.
What step 2 obtained can reach 0.065g to methoxyl group diphenyl ether compound sterling by weighing, and yield is 88.12% as calculated.
The present embodiment prepare to the nmr spectrum of methoxyl group diphenyl ether compound as the partial enlarged drawing of the nmr spectrum to methoxyl group diphenyl ether compound of Figure 13 and preparation as shown in figure 14, obtain
1h NMR (400MHz, CDCl
3) δ 7.27 (dd, J=11.4,4.6Hz, 2H), 7.02 (dd, J=10.7,4.0Hz, 1H), 7.00-6.91 (m, 4H), 6.90-6.83 (m, 2H), 3.78 (s, 3H), therefore the present embodiment prepare to methoxyl group diphenyl ether compound structural formula be
Embodiment eight:
A kind of method of synthesizing m-chloro diphenyl ether compound described in the present embodiment, specifically carry out according to following steps:
One, m-chloro diphenyl ether compound crude product is prepared: in 0.0134g trifluoroacetic acid copper, add 0.0098g pyridine carboxylic acid, 0.2607g cesium carbonate, 0.0158g sodium ascorbate, 0.016g poly(oxyethylene glycol) 400 and 4ml dimethyl sulfoxide (DMSO) successively, and be uniformly mixed 15min, add chloroiodobenzone between 0.0367g phenol and 0.1116g successively again, then it is 50 DEG C by room temperature to temperature under nitrogen protection, and be 50 DEG C of reaction 14h in temperature, obtain m-chloro diphenyl ether compound crude product;
Two, purification process: add 100mL distilled water in the m-chloro diphenyl ether compound crude product first obtained to step one, obtain mixture, be that extraction agent extracts again with ether, extract 3 times, the usage quantity of single extraction ether is 50mL, merge 3 extraction liquids, obtain combining extraction liquid, utilize distilled water to be combined extraction liquid to wash, wash 2 times, the usage quantity of single washing distilled water is 100mL, obtain the combining extraction liquid after washing, then utilization is revolved steaming instrument and the combining extraction liquid after washing is revolved steaming to 1.5mL, obtain revolving and steam rear extraction liquid, silica gel is added again in extraction liquid after revolving steaming, the add-on of silica gel is 0.1g, obtain the silica gel containing product, be leacheate again with sherwood oil, take silica gel as stationary phase, silica gel tiling containing product is carried out chromatography to stationary phase, namely the method for synthesis m-chloro diphenyl ether compound is completed.
The m-chloro diphenyl ether compound crude product that step one obtains can reach 93% by Liquid Detection productive rate.
The m-chloro diphenyl ether compound sterling that step 2 obtains can reach 0.064g by weighing, and yield is 80.19% as calculated.
The nmr spectrum of m-chloro diphenyl ether compound prepared by the present embodiment as the partial enlarged drawing of the nmr spectrum of the m-chloro diphenyl ether compound of Figure 15 and preparation as shown in figure 16, obtain
1h NMR (400MHz, CDCl
3) δ 7.40-7.32 (m, 2H), 7.28-7.22 (m, 1H), 7.15 (t, J=7.4Hz, 1H), 7.10-6.96 (m, 4H), 6.92-6.85 (m, 1H), the m-chloro diphenyl ether compound structural formula that therefore prepared by the present embodiment is
Embodiment nine:
A kind of method of synthesizing p-dichlorobenzene ether compound described in the present embodiment, specifically carry out according to following steps:
One, p-dichlorobenzene ether compound crude product is prepared: in 0.0134g trifluoroacetic acid copper, add 0.0098g pyridine carboxylic acid, 0.2607g cesium carbonate, 0.0158g sodium ascorbate, 0.016g poly(oxyethylene glycol) 400 and 4ml dimethyl sulfoxide (DMSO) successively, and be uniformly mixed 15min, add 0.0367g phenol and 0.1116g more successively to chloroiodobenzone, then it is 50 DEG C by room temperature to temperature under nitrogen protection, and be 50 DEG C of reaction 14h in temperature, obtain p-dichlorobenzene ether compound crude product;
Two, purification process: add 100mL distilled water in the p-dichlorobenzene ether compound crude product first obtained to step one, obtain mixture, be that extraction agent extracts again with ether, extract 3 times, the usage quantity of single extraction ether is 50mL, merge 3 extraction liquids, obtain combining extraction liquid, utilize distilled water to be combined extraction liquid to wash, wash 2 times, the usage quantity of single washing distilled water is 100mL, obtain the combining extraction liquid after washing, then utilization is revolved steaming instrument and the combining extraction liquid after washing is revolved steaming to 1.5mL, obtain revolving and steam rear extraction liquid, silica gel is added again in extraction liquid after revolving steaming, the add-on of silica gel is 0.1g, obtain the silica gel containing product, be leacheate again with sherwood oil, take silica gel as stationary phase, silica gel tiling containing product is carried out chromatography to stationary phase, namely the method for synthesis p-dichlorobenzene ether compound is completed.
The p-dichlorobenzene ether compound crude product that step one obtains can reach 96% by Liquid Detection productive rate.
The p-dichlorobenzene ether compound sterling that step 2 obtains can reach 0.065g by weighing, and yield is 81.45% as calculated.
The nmr spectrum of p-dichlorobenzene ether compound prepared by the present embodiment as the partial enlarged drawing of the nmr spectrum of the p-dichlorobenzene ether compound of Figure 17 and preparation as shown in figure 18, obtain
1h NMR (400MHz, CDCl
3) δ 7.47-7.39 (m, 2H), 7.34 (dd, J=8.5,7.5Hz, 2H), 7.12 (t, J=7.4Hz, 1H), 7.00 (dd, J=8.6,1.0Hz, 2H), 6.93-6.85 (m, 2H), the p-dichlorobenzene ether compound structural formula that therefore prepared by the present embodiment is
Embodiment ten:
The method of a kind of synthesis to dibromodiphenyl ether compound described in the present embodiment, specifically carry out according to following steps:
One, prepare dibromodiphenyl ether crude compound: in 0.0134g trifluoroacetic acid copper, add 0.0098g pyridine carboxylic acid, 0.2607g cesium carbonate, 0.0158g sodium ascorbate, 0.016g poly(oxyethylene glycol) 400 and 4ml dimethyl sulfoxide (DMSO) successively, and be uniformly mixed 15min, add 0.0367g phenol and 0.1324g more successively to bromo-iodobenzene, then it is 50 DEG C by room temperature to temperature under nitrogen protection, and be 50 DEG C of reaction 14h in temperature, obtain dibromodiphenyl ether crude compound;
Two, purification process: what first obtain to step one adds 100mL distilled water in dibromodiphenyl ether crude compound, obtain mixture, be that extraction agent extracts again with ether, extract 3 times, the usage quantity of single extraction ether is 50mL, merge 3 extraction liquids, obtain combining extraction liquid, utilize distilled water to be combined extraction liquid to wash, wash 2 times, the usage quantity of single washing distilled water is 100mL, obtain the combining extraction liquid after washing, then utilization is revolved steaming instrument and the combining extraction liquid after washing is revolved steaming to 1.5mL, obtain revolving and steam rear extraction liquid, silica gel is added again in extraction liquid after revolving steaming, the add-on of silica gel is 0.1g, obtain the silica gel containing product, be leacheate again with sherwood oil, take silica gel as stationary phase, silica gel tiling containing product is carried out chromatography to stationary phase, namely the method for synthesis to dibromodiphenyl ether compound is completed.
What step one obtained can reach 96% to dibromodiphenyl ether crude compound by Liquid Detection productive rate.
What step 2 obtained can reach 0.068g to dibromodiphenyl ether pure compounds by weighing, and yield is 70.00% as calculated.
The present embodiment prepare to the nmr spectrum of dibromodiphenyl ether compound as the partial enlarged drawing of the nmr spectrum to dibromodiphenyl ether compound of Figure 19 and preparation as shown in figure 20, obtain
1h NMR (400MHz, CDCl
3) δ 7.47-7.39 (m, 2H), 7.34 (dd, J=8.5,7.5Hz, 2H), 7.12 (t, J=7.4Hz, 1H), 7.00 (dd, J=8.6,1.0Hz, 2H), 6.93-6.85 (m, 2H), what therefore prepared by the present embodiment to dibromodiphenyl ether structural formula of compound is
Claims (6)
1. a method for synthesis of diaryl ether compound, is characterized in that a kind of method of synthesis of diaryl ether compound, specifically carries out according to following steps:
One, diaryl ether crude compound is prepared: in trifluoroacetic acid copper, add pyridine carboxylic acid, cesium carbonate, sodium ascorbate, poly(oxyethylene glycol) 400 and dimethyl sulfoxide (DMSO) successively, and be uniformly mixed 10min ~ 20min, add phenols and aryl iodide more successively for thing, then it is 40 ~ 60 DEG C by room temperature to temperature under nitrogen protection, and be 40 ~ 60 DEG C of reaction 10h ~ 18h in temperature, obtain diaryl ether crude compound;
Described phenols and aryl iodide are 1:(1 ~ 1.5 for the mol ratio of thing); Described trifluoroacetic acid copper and the mol ratio of phenols are 1:(5 ~ 15); Described pyridine carboxylic acid and the mol ratio of phenols are 1:(3 ~ 8); Described cesium carbonate and the mol ratio of phenols are (1.5 ~ 2.5): 1; Described sodium ascorbate and the mol ratio of phenols are 1:(4 ~ 8); Described poly(oxyethylene glycol) 400 and the mol ratio of phenols are 1:5; The volume of described dimethyl sulfoxide (DMSO) is (7mL ~ 12mL): 1mmol with the ratio of the amount of substance of phenols;
Two, purification process: add distilled water in the diaryl ether crude compound first obtained to step one, obtain mixture, be that extraction agent extracts again with ether, extract 3 times, the usage quantity of single extraction ether is (5 ~ 15) mL/mL, merge 3 extraction liquids, obtain combining extraction liquid, utilize distilled water to be combined extraction liquid to wash, wash 2 times, the usage quantity of single washing distilled water is (10 ~ 25) mL/mL, obtain the combining extraction liquid after washing, then utilization is revolved steaming instrument and the combining extraction liquid after washing is revolved steam to former combining extraction liquid volume 2% ~ 13%, obtain revolving and steam rear extraction liquid, silica gel is added again in extraction liquid after revolving steaming, the add-on of silica gel is (0.01 ~ 0.03) g/mL, obtain the silica gel containing product, be leacheate again with sherwood oil, take silica gel as stationary phase, silica gel tiling containing product is carried out chromatography to stationary phase, obtain diaryl ether compound.
2. the method for a kind of synthesis of diaryl ether compound according to claim 1, is characterized in that the phenols described in step one is phenol, ortho-methyl phenol, m-methyl phenol, p-methyl phenol, hydroxyanisole, meta-methoxy phenol or p methoxy phenol.
3. the method for a kind of synthesis of diaryl ether compound according to claim 1, it is characterized in that the aryl iodide described in step one for thing be iodobenzene, a chloroiodobenzone, to chloroiodobenzone or to bromo-iodobenzene.
4. the method for a kind of synthesis of diaryl ether compound according to claim 1; it is characterized in that in step one, mixture is uniformly mixed 15min; add phenols and aryl iodide more successively for thing; then be 50 DEG C by room temperature to temperature under nitrogen protection, and be 50 DEG C of reaction 11h ~ 15h in temperature.
5. the method for a kind of synthesis of diaryl ether compound according to claim 1, is characterized in that the phenols described in step one and aryl iodide are 1:1.2 for the mol ratio of thing; Described trifluoroacetic acid copper and the mol ratio of phenols are 1:10; Described pyridine carboxylic acid and the mol ratio of phenols are 1:5; Described cesium carbonate and the mol ratio of phenols are 2:1; Described sodium ascorbate and the mol ratio of phenols are 1:5; The volume of described dimethyl sulfoxide (DMSO) is 10mL:1mmol with the ratio of the amount of substance of phenols.
6. the method for a kind of synthesis of diaryl ether compound according to claim 1, to it is characterized in that in step 2 adding distilled water in the diaryl ether crude compound first obtained to step one, obtain mixture, be that extraction agent extracts again with ether, extract 3 times, the usage quantity of single extraction ether is 10mL/mL, merge 3 extraction liquids, obtain combining extraction liquid, utilize distilled water to be combined extraction liquid to wash, wash 2 times, the usage quantity of single washing distilled water is 20mL/mL, obtain the combining extraction liquid after washing, then utilization is revolved steaming instrument and the combining extraction liquid after washing is revolved steam to former combining extraction liquid volume 5% ~ 12%, obtain revolving and steam rear extraction liquid, silica gel is added again in extraction liquid after revolving steaming, the add-on of silica gel is 0.02g/mL, obtain the silica gel containing product, be leacheate again with sherwood oil, take silica gel as stationary phase, silica gel tiling containing product is carried out chromatography to stationary phase, obtain diaryl ether compound.
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| US4288386A (en) * | 1979-05-18 | 1981-09-08 | Rhone-Poulenc Industries | Ullmann reaction for the synthesis of diaryl ethers |
| CN1656894A (en) * | 2004-02-19 | 2005-08-24 | 黑龙江大学 | Diphenyl ether herbicide and its preparation method |
| CN101423460A (en) * | 2008-11-25 | 2009-05-06 | 安徽立兴化工有限公司 | Method for preparing chlorinated diphenyl ether |
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| US4288386A (en) * | 1979-05-18 | 1981-09-08 | Rhone-Poulenc Industries | Ullmann reaction for the synthesis of diaryl ethers |
| CN1656894A (en) * | 2004-02-19 | 2005-08-24 | 黑龙江大学 | Diphenyl ether herbicide and its preparation method |
| CN101423460A (en) * | 2008-11-25 | 2009-05-06 | 安徽立兴化工有限公司 | Method for preparing chlorinated diphenyl ether |
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