CN113698338B - Preparation method of styrene double oxidation product - Google Patents
Preparation method of styrene double oxidation product Download PDFInfo
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- CN113698338B CN113698338B CN202111149978.0A CN202111149978A CN113698338B CN 113698338 B CN113698338 B CN 113698338B CN 202111149978 A CN202111149978 A CN 202111149978A CN 113698338 B CN113698338 B CN 113698338B
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
Abstract
The invention discloses a preparation method of a styrene double oxidation product, which comprises the following steps: uniformly mixing a cobalt catalyst, a styrene compound, N-hydroxyphthalimide and an organic solvent, stirring for reaction under an oxygen condition, and separating and purifying after the reaction is finished to obtain a styrene double-oxidation product; the cobalt catalyst is at least one of cobalt chloride or cobalt chloride hexahydrate. The method takes the styrene compound and the N-hydroxyphthalimide as raw materials, and realizes the double oxidation of the styrene under the catalysis of the transition metal cobalt, and the method has the advantages of simple process, mild reaction condition, high selectivity, high yield, low catalyst cost, environment friendliness, cost reduction and economic benefit improvement; the product of the invention is an important synthesis intermediate, can be used for preparing products such as phenyl glycol, alpha-oxo acetophenone and the like, and is further applied to the fields of perfume, pharmaceutical synthesis, pesticide chemistry, paint dye synthesis and the like.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of a styrene double oxidation product.
Background
Olefins are a class of inexpensive, readily available and versatile building blocks that can be converted into a variety of multifunctional compounds. Among them, the double oxidation of olefins has been the focus of research since it can provide different oxygen-containing molecules such as 1, 2-diols, alpha-hydroxyketones and 1, 2-dicarbonyl compounds, which have a wide range of uses in synthetic chemistry. For example: 1, 2-dihydroxy compounds are important synthetic intermediates which are widely used in the fields of pesticides, medicine, fragrances and fine chemicals. 2-phenoxy-1-phenyl ethanol is often used for lignin selective catalytic conversion to prepare common medical intermediate aniline and the like.
Conventional olefin double oxidation processes such as: pre vost-Woodward reaction, sharpless dihydroxylation reaction, etc. are widely used in organic synthesis. However, the process often uses expensive heavy metals and stoichiometric oxidants, which are very harmful to the environment, which also limits its further use. Therefore, it is very necessary to develop a new method for the double oxidation of olefins which is simple, efficient, environmentally friendly and suitable for industrial production. Cobalt metal is an inexpensive and environmentally friendly catalyst, but it is very lacking in reports of double oxidation reactions of olefins. Oxygen is a sustainable natural resource, has the advantages of large reserve, low cost, green environmental protection and the like, and the molecular oxygen selective alkylene oxide reaction accords with the concept of green chemistry, thus being a very significant clean production technology. The product of styrene double oxidation prepared by the method is a synthetic intermediate with wide application. The method can simply and efficiently synthesize the alpha-oxo acetophenone compound in one step. The method can also be used for synthesizing the phenyl glycol compound widely applied to the fields of liquid crystal materials, spices, medicine synthesis and the like, and provides a novel efficient green and clean synthesis method for the industrial preparation of the phenyl glycol compound.
Disclosure of Invention
In view of the foregoing, it is necessary to provide a preparation method of a styrene double oxidation product, so as to solve the technical problems of high cost and complex preparation process of a catalyst used for preparing the styrene double oxidation product in the prior art.
The invention provides a preparation method of a styrene double oxidation product, which comprises the following steps:
uniformly mixing a cobalt catalyst, a styrene compound, N-hydroxyphthalimide and an organic solvent, stirring for reaction under an oxygen condition, and separating and purifying after the reaction is finished to obtain a styrene double-oxidation product; the catalyst is at least one of cobalt chloride or cobalt chloride hexahydrate.
Compared with the prior art, the invention has the beneficial effects that:
the method takes the styrene compound and the N-hydroxyphthalimide as raw materials, and realizes the double oxidation of the styrene under the catalysis of the transition metal cobalt, and the method has the advantages of simple process, mild reaction condition, high selectivity, high yield, low catalyst cost, environment friendliness, cost reduction and economic benefit improvement;
the product of the invention is an important synthesis intermediate, can be used for preparing products such as phenyl glycol, alpha-oxo acetophenone and the like, and is further applied to the fields of perfume, pharmaceutical synthesis, pesticide chemistry, paint dye synthesis and the like.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a preparation method of a styrene double oxidation product, which comprises the following steps:
and (3) uniformly mixing a cobalt catalyst, a styrene compound, N-hydroxyphthalimide and an organic solvent, stirring for reaction under an oxygen condition, and separating and purifying after the reaction is finished to obtain a styrene double-oxidation product.
In the present invention, the cobalt catalyst is at least one of cobalt chloride or cobalt chloride hexahydrate, preferably cobalt chloride hexahydrate. According to the invention, the styrene compound and N-hydroxyphthalimide (NHPI) are reacted under the combined action of the cobalt chloride catalyst and oxygen to generate the product of the styrene double-oxidation alcohol, the product cannot further react with the cobalt chloride catalyst, and the final styrene double-oxidation product has good selectivity and high yield.
In the present invention, the styrene compound has the following structural formula:
wherein R is 1 Is H, alkyl or halogen, R 2 Is H, alkyl or phenyl, R 3 Is H or alkyl.
In some embodiments of the invention, R 1 Is H or C 1 ～C 3 Alkyl of R 2 Is H, R 3 Is H or methyl.
In some embodiments of the present invention, the styrenic compound is at least one of styrene (A-a), 4-methylstyrene (A-b), alpha-methylstyrene (A-c), 3-methylstyrene (A-d), 2, 5-dimethylstyrene (A-e).
In the invention, the molar ratio of the styrene compound to the N-hydroxyphthalimide is 1: (0.1 to 10), further 1: (0.3 to 2), and further 1:0.5.
in the invention, the molar ratio of the styrene compound to the catalyst is 1: (0.01 to 0.3), further 1: (0.025 to 0.1), and further 1:0.05.
in the present invention, the organic solvent is at least one of 1, 2-dichloroethane, acetonitrile, dichloromethane, and acetone, and preferably 1, 2-dichloroethane. In the present invention, the inventors found that the highest yield of the product was obtained when 1, 2-dichloroethane was used as the organic solvent of choice during the experiment.
In the invention, the dosage ratio of the styrene compound to the organic solvent is (10-100) mg:1mL, further (20-50) mg:1mL.
In the invention, the temperature of the stirring reaction is 20-60 ℃, preferably 40 ℃; the stirring reaction time is 8 to 12 hours, preferably 12 hours.
In the invention, the steps of separation and purification are specifically as follows: after the stirring reaction is finished, pouring the reaction liquid into a separating funnel, adding water, extracting with ethyl acetate, performing reduced pressure distillation on an organic phase to obtain a crude product, and performing column chromatography separation and purification to obtain a styrene double-oxidation product.
The reaction general formula of the invention is:
in some embodiments of the present invention, a process for the preparation of a styrene bis-oxidation product comprises the steps of:
adding a cobalt catalyst, a styrene compound, N-hydroxyphthalimide and an organic solvent into a reactor, then introducing oxygen, introducing condensate water into a condensing tube from bottom to top, and then placing the reactor into an oil bath pot at 20-60 ℃ for heating reaction for 8-12 h; pouring the reaction liquid into a separating funnel, adding distilled water, extracting with ethyl acetate, distilling the organic phase under reduced pressure to obtain a crude product, and separating and purifying by column chromatography to obtain a styrene double-oxidation product.
Example 1
In this example, styrene and N-hydroxyphthalimide are used as raw materials to prepare 2- (2-hydroxy-2-phenethyl) isoindole-1, 3-dione (C-aa), and the influence of factors such as catalyst types, catalyst amounts, reaction raw material amounts, reaction temperatures, reaction time, solvents and the like on the reaction is examined, and specific reaction conditions and yields are shown in Table 1.
Wherein, the structural formula of the styrene double oxidation product is as follows:
the preparation method comprises the following steps:
a cobalt catalyst, styrene, N-hydroxyphthalimide, 2mL of an organic solvent, and one of the magnons No. 5 were added to the reactor. Then 1atm oxygen was introduced. And (3) introducing condensed water into the condensing pipe from bottom to top, and then placing the reactor in an oil bath for heating reaction. After the reaction, pouring the reaction solution into a separating funnel, adding 15mL of distilled water, extracting 3 times with 10mL of ethyl acetate, performing reduced pressure distillation on an organic phase to obtain a crude product, and performing column chromatography separation and purification to obtain a styrene double-oxidation product 2- (2-hydroxy-2-phenethyl) isoindole-1, 3-dione (C-aa) as a white solid.
TABLE 1
The nuclear magnetic resonance hydrogen and carbon spectra of the product 2- (2-hydroxy-2-phenethyl) isoindole-1, 3-dione (C-aa) of this example were determined to have the following structures: 1 H NMR(400MHz,CDCl 3 ):δ9.55(s,1H),7.88-7.81(m,2H),7.80-7.74(m,2H),7.41-7.32(m,5H),5.43–5.40(m,1H),4.55–5.45(m,2H)； 13 C NMR(100MHz,CDCl 3 ):δ163.8,135.7,134.8,128.9,128.8,128.7,127.1,123.9,85.5,79.0。
example 2
In this example, 2- (2-hydroxy-2-p-tolylethoxy) isoindole-1, 3-dione (C-ba) was prepared starting from 4-methylstyrene and N-hydroxyphthalimide and had the following structural formula:
the preparation method comprises the following steps:
to the reactor was added 0.02mmol of cobalt chloride hexahydrate, 0.4mmol of 4-methylstyrene, 0.2mmol of N-hydroxyphthalimide, 2mL of 1, 2-dichloroethane and one of the # 5 magnetons. Then 1atm oxygen was introduced. The condensation pipe is filled with condensed water from bottom to top, and then the reactor is placed in an oil bath pot with the temperature of 40 ℃ for heating reaction for 12 hours. The reaction solution was poured into a separating funnel, 15mL of distilled water was added, extraction was performed 3 times with 10mL of ethyl acetate, and the organic phase was distilled under reduced pressure to obtain a crude product, and the crude product was separated and purified by column chromatography to obtain 50.8mg of styrene bis-oxidation product 2- (2-hydroxy-2-p-tolylethoxy) isoindole-1, 3-dione (C-ba) as a white solid with a yield of 85%.
The product was structured via nmr hydrogen and carbon spectra: 1 H NMR(400MHz,CDCl 3 ):δ9.54(s,1H),7.86-7.80(m,2H),7.77-7.74(m,2H),7.29-7.26(m,2H),7.16(d,J＝7.96Hz,2H),5.40-5.40(m,1H),4.49(d,J＝5.76Hz,2H),2.32(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ162.8,137.7,133.7,131.7,128.4,127.7,126.1,122.8,84.2,77.9,20.1。
example 3
In this example, 2- (2-hydroxy-2-phenylpropoxy) isoindole-1, 3-dione (C-ca) was prepared from α -methylstyrene and N-hydroxyphthalimide, and had the following structural formula:
the preparation method comprises the following steps:
to the reactor was added 0.02mmol of cobalt chloride hexahydrate, 0.4mmol of α -methylstyrene, 0.2mmol of N-hydroxyphthalimide, 2mL of 1, 2-dichloroethane and one of the number 5 magnetons. Then 1atm oxygen was introduced. The condensation pipe is filled with condensed water from bottom to top, and then the reactor is placed in an oil bath pot with the temperature of 40 ℃ for heating reaction for 12 hours. The reaction solution was poured into a separating funnel, 15mL of distilled water was added, extraction was performed 3 times with 10mL of ethyl acetate, and the organic phase was distilled under reduced pressure to obtain a crude product, and the crude product was separated and purified by column chromatography to obtain 48.9mg of styrene bis-oxidation product 2- (2-hydroxy-2-phenylpropyloxy) isoindole-1, 3-dione (C-ca) as a white solid with a yield of 83%.
The product was structured via nmr hydrogen and carbon spectra: 1 H NMR(400MHz,CDCl 3 ):δ9.80(s,1H),7.89-7.82(m,2H),7.81–7.74(m,2H),7.633-7.48(m,2H),7.41-7.35(m,2H),7.33-7.27(m,1H),4.73-4.62(m,2H),1.66(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ163.8,140.8,134.9,128.7,128.6,127.9,125.4,123.9,84.4,79.8,22.9。
example 4
In this example, 2- (2-hydroxy-2- (m-tolyl) ethoxy) isoindole-1, 3-dione (C-da) was prepared starting from 3-methylstyrene and N-hydroxyphthalimide, and had the following structural formula:
the preparation method comprises the following steps:
to the reactor was added 0.02mmol of cobalt chloride hexahydrate, 0.4mmol of 3-methylstyrene, 0.2mmol of N-hydroxyphthalimide, 2mL of 1, 2-dichloroethane and one of the number 5 magnetons. Then 1atm oxygen was introduced. The condensation pipe is filled with condensed water from bottom to top, and then the reactor is placed in an oil bath pot with the temperature of 40 ℃ for heating reaction for 12 hours. The reaction solution was poured into a separating funnel, 15mL of distilled water was added, extraction was performed 3 times with 10mL of ethyl acetate, and the organic phase was distilled under reduced pressure to obtain a crude product, and the crude product was separated and purified by column chromatography to obtain 47.8mg of styrene bis-oxidation product 2- (2-hydroxy-2- (m-tolyl) ethoxy) isoindole-1, 3-dione (C-da) as a white solid with a yield of 81%.
The product was structured via nmr hydrogen and carbon spectra: 1 H NMR(400MHz,CDCl 3 ):δ9.54(s,1H),7.88-7.83(m,2H),7.80–7.73(m,2H),7.27-7.12(m,4H),5.41-5.37(m,1H),4.53-4.44(m,2H),2.34(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ163.8,138.5,135.7,134.8,129.6,128.7,128.6,127.8,124.1,123.8,85.6,79.1,21.4。
example 5
In this example, 2- (2, 5-dimethylphenyl) -2-hydroxyethoxy) isoindole-1, 3-dione (C-ea) was prepared from 2, 5-dimethylstyrene and N-hydroxyphthalimide, and had the following structural formula:
the preparation method comprises the following steps:
to the reactor was charged 0.02mmol of cobalt chloride hexahydrate, 0.4mmol of 2, 5-dimethylstyrene, 0.2mmol of N-hydroxyphthalimide, 2mL of 1, 2-dichloroethane and one of the # 5 magnetons. Then 1atm oxygen was introduced. The condensation pipe is filled with condensed water from bottom to top, and then the reactor is placed in an oil bath pot with the temperature of 40 ℃ for heating reaction for 12 hours. The reaction solution was poured into a separating funnel, 15mL of distilled water was added, extraction was performed 3 times with 10mL of ethyl acetate, and the organic phase was distilled under reduced pressure to obtain a crude product, and the crude product was separated and purified by column chromatography to obtain 51.4mg of styrene bis-oxidation product 2- (2, 5-dimethylphenyl) -2-hydroxyethoxy) isoindole-1, 3-dione (C-ea) as a white solid with a yield of 82%.
The product was structured via nmr hydrogen and carbon spectra: 1 H NMR(400MHz,CDCl 3 ):δ9.64(s,1H),7.88–7.84(m,2H),7.81–7.76(m,2H),7.18(s,1H),7.08–7.01(m,2H),5.67–5.63(m,2H),4.49–4.39(m,2H),2.36(s,3H),2.28(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ162.8,134.8,133.8,132.4,131.7,129.7,128.4,127.6,125.9,122.8,81.7,78.0,20.0,17.6。
the present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (9)
1. A method for preparing a styrene double oxidation product, which is characterized by comprising the following steps:
uniformly mixing a cobalt catalyst, a styrene compound, N-hydroxyphthalimide and an organic solvent, stirring for reaction under an oxygen condition, and separating and purifying after the reaction is finished to obtain a styrene double-oxidation product; the cobalt catalyst is at least one of cobalt chloride or cobalt chloride hexahydrate; the reaction general formula is as follows:
wherein R is 1 Is H, alkyl or halogen, R 2 Is H, alkyl or phenyl, R 3 Is H or alkyl.
2. The method for producing a styrene double oxidation product according to claim 1, wherein said R 1 Is H or C 1 ~C 3 Alkyl of R 2 Is H, R 3 Is H or methyl.
3. The method for producing a styrene double oxidation product according to claim 1, wherein the styrene compound is at least one of styrene, 4-methylstyrene, α -methylstyrene, 3-methylstyrene, and 2, 5-dimethylstyrene.
4. The method for producing a styrene double oxidation product according to claim 1, wherein the molar ratio of the styrene compound to the N-hydroxyphthalimide is 1: (0.1-10), wherein the molar ratio of the styrene compound to the catalyst is 1: (0.01 to 0.3).
5. The method for producing a styrene double oxidation product according to claim 4, wherein the molar ratio of the styrene compound to N-hydroxyphthalimide is 1: (0.3-2), wherein the molar ratio of the styrene compound to the catalyst is 1: (0.025 to 0.1).
6. The method for producing a styrene double oxidation product according to claim 1, wherein the organic solvent is at least one of 1, 2-dichloroethane, acetonitrile, dichloromethane, and acetone.
7. The method for producing a styrene double oxidation product according to claim 6, wherein the ratio of the styrene compound to the organic solvent is (10-100) mg:1mL.
8. The method for preparing a styrene double oxidation product according to claim 1, wherein the temperature of the stirring reaction is 20-60 ℃, and the stirring reaction time is 8-12 hours.
9. The method for preparing a styrene double oxidation product according to claim 1, wherein the steps of separating and purifying specifically include: after the stirring reaction is finished, pouring the reaction liquid into a separating funnel, adding water, extracting with ethyl acetate, performing reduced pressure distillation on an organic phase to obtain a crude product, and performing column chromatography separation and purification to obtain a styrene double-oxidation product.
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