CN113004110A - Synthesis method of 1, 4-dimethylnaphthalene - Google Patents
Synthesis method of 1, 4-dimethylnaphthalene Download PDFInfo
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- CN113004110A CN113004110A CN202110236431.8A CN202110236431A CN113004110A CN 113004110 A CN113004110 A CN 113004110A CN 202110236431 A CN202110236431 A CN 202110236431A CN 113004110 A CN113004110 A CN 113004110A
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
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Abstract
The invention discloses a method for synthesizing 1, 4-dimethylnaphthalene, belonging to the technical field of organic synthesis. The invention provides a method for synthesizing 1, 4-dimethylnaphthalene, which aims to reduce the production cost of the 1, 4-dimethylnaphthalene and realize industrial production, and comprises the following steps: reacting 4-bromomethylnaphthalene serving as a raw material with a methyl magnesium halide Grignard reagent in the presence of a nickel catalyst to obtain 1, 4-dimethylnaphthalene; the nickel catalyst is a nickel complex of nickel chloride and a ligand, and the ligand is selected from triethyl phosphite, bis (triphenylphosphine), bis (tricyclohexylphosphine) and 4,4，-dimethyl-2, 2，Bipyridine or 2-phenyl-4, 5-dihydro-1H-imidazole. The method can obtain high-purity 1, 4-dimethylnaphthalene with high yield under mild reaction conditions by optimizing reaction conditions, selecting a specific nickel catalyst and controlling the reaction temperature; the raw materials are cheap and easy to obtain, the production cost is obviously reduced, and the method is favorable for realizing industrial production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of 1, 4-dimethylnaphthalene.
Background
The 1, 4-dimethylnaphthalene is a fine chemical product with high added value, and is mainly used in the fields of plant production regulators and fluorescent whitening agents. The current synthetic routes mainly fall into two categories: the first one is prepared with naphthalene or naphthalene derivative as material and through methylation reaction, and the second one is prepared with benzene or benzene derivative as material and through addition and cyclization.
PL196901 reports that 1, 4-dimethylnaphthalene is catalytically synthesized by taking naphthalene and methanol as raw materials at 450 ℃ and under the pressure of 3 Mpa; CN109574781A reports that methyl naphthalene is used as a raw material and is subjected to methylation reaction with methanol under the catalysis of silicon-aluminum crystal zeolite to prepare 1, 4-dimethylnaphthalene, and the method of directly methylating methanol mostly obtains a plurality of dimethylnaphthalene isomer mixtures, so that the separation of target products is difficult, the yield is low, and the industrialization difficulty is high. Chemical Communications (2018),54(67),9313-9316 report the preparation of 1, 4-dimethylnaphthalene by Grignard reaction using 1, 4-dimethylthioether naphthalene as raw material, although the yield is high, the raw material is not easy to obtain; CN107266282A reports that 1, 4-dibromonaphthalene and methyl magnesium chloride are used as raw materials and are prepared through Grignard reaction, wherein the raw material 1, 4-dibromonaphthalene is difficult to prepare and is usually prepared through reaction of naphthalene and bromine, and the bromine is large in dosage, poor in reaction selectivity, harsh in conditions, low in yield and low in industrial value. In addition, JP2001278821A, Green Chemistry (2018),20(7),1448-145 reports that 1, 4-dimethylnaphthalene is synthesized by means of cyclic dehydrogenation and the like, but the method has the advantages of longer route, more expensive reagent, higher synthesis cost and lower economic value.
In view of the above, there is an urgent need to develop a method for preparing 1, 4-dimethylnaphthalene having a high industrial value.
Disclosure of Invention
The invention provides a method for synthesizing 1, 4-dimethylnaphthalene, which aims to reduce the production cost of the 1, 4-dimethylnaphthalene and facilitate the realization of industrial production, and comprises the following steps: reacting 4-bromomethylnaphthalene serving as a raw material with a methyl magnesium halide Grignard reagent in the presence of a nickel catalyst to obtain 1, 4-dimethylnaphthalene; the nickel catalyst is a nickel complex of nickel chloride and a ligand, wherein the ligand is selected from at least one of triethyl phosphite, bis (triphenylphosphine), bis (tricyclohexylphosphine), 4 '-dimethyl-2, 2' -bipyridine or 2-phenyl-4, 5-dihydro-1H-imidazole.
Wherein, in the synthesis method of the 1, 4-dimethylnaphthalene, the methyl magnesium halide Grignard reagent is methyl magnesium chloride.
In the method for synthesizing 1, 4-dimethylnaphthalene, the molar ratio of the 4-bromomethylnaphthalene to the methyl magnesium halide Grignard reagent is 1: 1 to 5.
Preferably, in the method for synthesizing 1, 4-dimethylnaphthalene, the molar ratio of the 4-bromomethylnaphthalene to the methyl magnesium halide grignard reagent is 1: 3.
in the method for synthesizing 1, 4-dimethylnaphthalene, the molar ratio of the 4-bromomethylnaphthalene to the nickel catalyst is 1: 1 to 15 percent.
Preferably, in the method for synthesizing 1, 4-dimethylnaphthalene, the molar ratio of the 4-bromomethylnaphthalene to the nickel catalyst is 1: 3 to 7 percent.
More preferably, in the method for synthesizing 1, 4-dimethylnaphthalene, the molar ratio of the 4-bromomethylnaphthalene to the nickel catalyst is 1: 5 percent.
Wherein, in the synthesis method of the 1, 4-dimethylnaphthalene, the reaction temperature is not lower than 50 ℃.
More preferably, in the method for synthesizing 1, 4-dimethylnaphthalene, the reaction temperature is 60 to 100 ℃.
Most preferably, in the method for synthesizing 1, 4-dimethylnaphthalene, the reaction temperature is 60 ℃.
In the method for synthesizing 1, 4-dimethylnaphthalene, the reaction is carried out in an organic solvent, and the organic solvent is at least one of hexane, heptane, cyclohexane, methylcyclohexane, petroleum ether, diethyl ether, tetrahydrofuran, methyltetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, xylene or trimethylbenzene.
The synthesis method of the 1, 4-dimethylnaphthalene comprises the following specific steps:
mixing 4-bromomethylnaphthalene, a nickel catalyst and an organic solvent, heating to a reaction temperature, dropwise adding a methyl magnesium halide Grignard reagent into the system, and performing post-treatment after the heat preservation reaction is finished to obtain 1, 4-dimethylnaphthalene;
or mixing the methyl magnesium halide Grignard reagent, the nickel catalyst and the organic solvent, heating to the reaction temperature, dropwise adding 4-bromomethylnaphthalene into the system, and performing post-treatment after the heat preservation reaction is finished to obtain the 1, 4-dimethylnaphthalene.
The invention has the beneficial effects that:
the method takes 4-bromomethylnaphthalene as a raw material, and makes the 4-bromomethylnaphthalene react with a methyl magnesium halide Grignard reagent to prepare the 1, 4-dimethylnaphthalene, and can obtain the high-purity 1, 4-dimethylnaphthalene with high yield under mild reaction conditions by optimizing reaction conditions, selecting a specific nickel catalyst and controlling the reaction temperature; and the raw material 4-bromomethylnaphthalene can be obtained by brominating 1-methylnaphthalene which is a byproduct in the coking industry, so that the cost is low, the production cost of the 1, 4-dimethylnaphthalene is obviously reduced, and the industrial production is favorably realized.
Detailed Description
Specifically, the synthesis method of the 1, 4-dimethylnaphthalene comprises the following steps: reacting 4-bromomethylnaphthalene serving as a raw material with a methyl magnesium halide Grignard reagent in the presence of a nickel catalyst to obtain 1, 4-dimethylnaphthalene; the nickel catalyst is a nickel complex of nickel chloride and a ligand, wherein the ligand is selected from at least one of triethyl phosphite, bis (triphenylphosphine), bis (tricyclohexylphosphine), 4 '-dimethyl-2, 2' -bipyridine or 2-phenyl-4, 5-dihydro-1H-imidazole.
In the invention, the methyl magnesium halide Grignard reagent adopts methyl magnesium chloride, which is relatively cheap and easily available in similar Grignard reagents, thereby being beneficial to reducing the production cost.
In order to ensure the product yield, the molar ratio of the 4-bromomethylnaphthalene to the methyl magnesium halide Grignard reagent in the invention is 1: 1-5; preferably, the molar ratio of the 4-bromomethylnaphthalene to the methyl magnesium halide Grignard reagent is controlled to be 1: 3.
in the invention, the mol ratio of the 4-bromomethylnaphthalene to the nickel catalyst is controlled to be 1: 1% -15%; preferably, the molar ratio of the 4-bromomethylnaphthalene to the nickel catalyst is controlled to be 1: 3% -7%; more preferably, the molar ratio of the 4-bromomethylnaphthalene to the nickel catalyst is controlled to be 1: 5 percent.
In the present invention, the addition mode of the nickel catalyst may be to add the ligand and the nickel dichloride separately (as in examples 1 and 2), or to add the nickel complex catalyst directly (as in example 3); when the ligand and the nickel dichloride are added separately, a nickel ligand catalyst (1 equivalent of nickel dichloride is complexed with 2 equivalents of ligand) is prepared according to the prior experience, and then reaction raw materials are added; when a nickel complex catalyst is used, the nickel complex catalyst, 4-bromomethylnaphthalene (or methyl magnesium halide grignard reagent) and a solvent may be directly mixed.
Tests show that the reaction temperature has great influence on the reaction effect, and in order to ensure the product yield, the reaction temperature is controlled to be not lower than 50 ℃; in order to stabilize the product yield to be more than 90%, the reaction temperature is preferably controlled to be 60-100 ℃; further considering that in industrial production, it is necessary to control relatively mild reaction conditions, the present invention most preferably controls the reaction temperature to 60 ℃ to obtain a high yield of the product under mild conditions.
In the present invention, the reaction is generally carried out in an organic solvent, which is at least one of hexane, heptane, cyclohexane, methylcyclohexane, petroleum ether, diethyl ether, tetrahydrofuran, methyltetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, xylene, or trimethylbenzene.
The invention also tests the influence of the dropping sequence of the 4-bromomethylnaphthalene and the methyl magnesium halide Grignard reagent on the reaction effect, and the result shows that the adding sequence of the 4-bromomethylnaphthalene and the methyl magnesium halide Grignard reagent basically has no influence on the reaction effect; therefore, the synthesis method comprises the following two specific steps:
mixing 4-bromomethylnaphthalene, a nickel catalyst and an organic solvent, heating to a reaction temperature, dropwise adding a methyl magnesium halide Grignard reagent into the system, and performing post-treatment after the heat preservation reaction is finished to obtain 1, 4-dimethylnaphthalene;
or mixing the methyl magnesium halide Grignard reagent, the nickel catalyst and the organic solvent, heating to the reaction temperature, dropwise adding 4-bromomethylnaphthalene into the system, and performing post-treatment after the heat preservation reaction is finished to obtain the 1, 4-dimethylnaphthalene.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
Taking 3.75g triethyl phosphite, 1.45g nickel chloride and 50mL tetrahydrofuran, stirring and heating to 60 ℃, reacting for 1h, and then adding 225mL 3M methyl magnesium chloride tetrahydrofuran solution. Adding 50mL of toluene into 50g of 4-bromomethylnaphthalene to prepare a solution, slowly dripping the solution into the Grignard reagent solution, preserving the temperature for reaction for 12 hours after dripping, then dripping the reaction solution into 5% dilute hydrochloric acid water for quenching, carrying out phase separation, carrying out decompression and desolventization by organic phase, and distilling the product at 80-100pa and 80-100 ℃ to obtain the product with the content of 98% and the yield of 93%.
Example 2
Taking 3.75g triethyl phosphite, 1.45g nickel chloride and 50mL tetrahydrofuran, stirring and heating to 60 ℃, reacting for 1h, then sequentially adding 50mL toluene and 50g 4-bromomethylnaphthalene, slowly dropwise adding 225mL 3M methyl magnesium chloride tetrahydrofuran solution after the temperature is raised to about 60 ℃, preserving heat and reacting for 12h after dropwise adding, then dropwise adding the reaction liquid into 5% dilute hydrochloric acid water for quenching, carrying out phase separation, carrying out decompression and desolventization by organic phase, and distilling the product at 80-100pa and 80-100 ℃, wherein the content is 95% and the yield is 91%.
Example 3
Taking 10g of 4-bromomethylnaphthalene, sequentially adding 10mL of tetrahydrofuran and 10mL of toluene, 1.5g of bis (triphenylphosphine) nickel dichloride, stirring and heating to 60 ℃, slowly dropwise adding 45mL of 3M methyl magnesium chloride tetrahydrofuran solution, preserving heat for reaction for 12h after dropwise adding, then dropwise adding reaction liquid into 5% dilute hydrochloric acid water for quenching, carrying out phase separation, carrying out pressure-relief desolventizing on organic phase, and distilling out a product at 80-100Pa, wherein the content is 93%, and the yield is 92%.
Examples 4 to 6: influence of temperature on the Effect of the reaction
The same operations as in example 1 were carried out except for the reaction temperature in examples 4 to 6, and the results are shown in Table 1.
TABLE 1
| Serial number | Temperature/. degree.C | Catalyst and process for preparing same | Content (wt.) | Yield of |
| 1 | 60 | Triethyl phosphite/nickel dichloride | 98％ | 93％ |
| 4 | 40 | Triethyl phosphite/nickel dichloride | 7％ | - |
| 5 | 80 | Triethyl phosphite/nickel dichloride | 91％ | 94.2％ |
| 6 | 100 | Triethyl phosphite/nickel dichloride | 85％ | 95％ |
As can be seen from Table 1, the reaction temperature has a great influence on the results, and when the temperature is lower, the product yield is greatly reduced; when the temperature is 60 ℃, the product yield can reach more than 90 percent, and the yield is slightly increased along with the temperature rise, so the reaction temperature is preferably controlled to be 60-100 ℃; however, considering that the industrial production requires the control of milder reaction conditions, it is most preferable to control the reaction temperature to 60 ℃ in the present invention to obtain a high yield of the product under mild conditions.
Examples 7 to 12: effect of the catalyst on the Effect of the reaction
In examples 7 to 9, the operations other than the catalyst were the same as those in example 3; the operations of examples 10 to 12 were the same as those of example 1 except for the catalyst, and the results are shown in Table 2.
TABLE 2
As can be seen from Table 2, the use of nickel dichloride significantly increases the product yield relative to other metals (or salts); meanwhile, a proper ligand also has great influence on the reaction result; tests prove that the nickel complex of nickel dichloride, bis (triphenylphosphine), bis (tricyclohexylphosphine), triethyl phosphite, 4 '-dimethyl-2, 2' -bipyridine or 2-phenyl-4, 5-dihydro-1H-imidazole is used as a catalyst, so that the product yield can be ensured to be stable to over 90%.
Claims (7)
1. A method for synthesizing 1, 4-dimethylnaphthalene is characterized in that: the method comprises the following steps: reacting 4-bromomethylnaphthalene serving as a raw material with a methyl magnesium halide Grignard reagent in the presence of a nickel catalyst to obtain 1, 4-dimethylnaphthalene; the nickel catalyst is a nickel complex of nickel chloride and a ligand, wherein the ligand is selected from triethyl phosphite, bis (triphenylphosphine), bis (tricyclohexylphosphine),4,4，-dimethyl-2, 2，At least one of bipyridine or 2-phenyl-4, 5-dihydro-1H-imidazole.
2. The method of synthesizing 1, 4-dimethylnaphthalene according to claim 1, characterized in that: the methyl magnesium halide Grignard reagent is methyl magnesium chloride.
3. The method of synthesizing 1, 4-dimethylnaphthalene according to claim 1, characterized in that: the molar ratio of the 4-bromomethylnaphthalene to the methyl magnesium halide Grignard reagent is 1: 1-5; preferably 1: 3.
4. the method of synthesizing 1, 4-dimethylnaphthalene according to claim 1, characterized in that: the mol ratio of the 4-bromomethylnaphthalene to the nickel catalyst is 1: 1% -15%; preferably 1: 3% -7%; more preferably 1: 5 percent.
5. The method of synthesizing 1, 4-dimethylnaphthalene according to claim 1, characterized in that: the reaction temperature is not lower than 50 ℃; preferably 60-100 ℃; more preferably 60 deg.c.
6. The method for synthesizing 1, 4-dimethylnaphthalene according to any one of claims 1 to 5, characterized in that: the reaction is carried out in an organic solvent, wherein the organic solvent is at least one of hexane, heptane, cyclohexane, methylcyclohexane, petroleum ether, diethyl ether, tetrahydrofuran, methyltetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, xylene or trimethylbenzene.
7. The method for synthesizing 1, 4-dimethylnaphthalene according to any one of claims 1 to 6, comprising: the method comprises the following specific steps:
mixing 4-bromomethylnaphthalene, a nickel catalyst and an organic solvent, heating to a reaction temperature, dropwise adding a methyl magnesium halide Grignard reagent into the system, and performing post-treatment after the heat preservation reaction is finished to obtain 1, 4-dimethylnaphthalene;
or mixing the methyl magnesium halide Grignard reagent, the nickel catalyst and the organic solvent, heating to the reaction temperature, dropwise adding 4-bromomethylnaphthalene into the system, and performing post-treatment after the heat preservation reaction is finished to obtain the 1, 4-dimethylnaphthalene.
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| CN107266282A (en) * | 2017-07-25 | 2017-10-20 | 利尔化学股份有限公司 | A kind of preparation method of 1,4 dimethylnaphthalene |
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| CN107266282A (en) * | 2017-07-25 | 2017-10-20 | 利尔化学股份有限公司 | A kind of preparation method of 1,4 dimethylnaphthalene |
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| BOYA FENG，等: "A methylation platform of unconventional inert aryl electrophiles: trimethylboroxine as a universal methylating reagent" * |
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