CN108586202B - Synthesis method of intermediate 4-phenylbutanol - Google Patents
Synthesis method of intermediate 4-phenylbutanol Download PDFInfo
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- CN108586202B CN108586202B CN201810733661.3A CN201810733661A CN108586202B CN 108586202 B CN108586202 B CN 108586202B CN 201810733661 A CN201810733661 A CN 201810733661A CN 108586202 B CN108586202 B CN 108586202B
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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Abstract
The invention discloses a synthetic method of an intermediate 4-phenylbutanol, ferrous sulfate and I2、NaBH4Fe-N/C, tetrapyridyl phenazine and 4-phenylbutyric acid are used as main raw materials, and the raw materials are mixed according to the following ratio: 4-Phenylbutyric acid, I2The mass ratio is 5: 4; Fe-N/C, NaBH4The mass ratio is 5: 8; the molar ratio of the tetrapyridylphenazine to the ferrous sulfate is 5: 7; the synthesis process of the invention adopts a sodium borohydride system of 4-phenylbutyric acid and iodine to carry out reduction reaction under the action of the catalyst Fe-N/C to obtain the 4-phenylbutyric alcohol, compared with the traditional synthesis method, the catalyst is easy to separate and recover, and the temperature, the using amount, the proportion and the process flow of the experiment are continuously optimized through a large number of experiments, so that the reaction operation is convenient, the time is short, and the yield and the purity of the product are greatly improved.
Description
Technical Field
The invention relates to a synthesis method of an intermediate 4-phenylbutanol, belonging to the field of chemical synthesis.
Background
4-Phenylbutanol (4-phenylbutanol) CAS: 3360-41-6 is an important chemical intermediate for synthesizing 4- (4-phenylbutoxy) benzoic acid, and is long-acting beta2An intermediate of salmeterol (salmeterol), a receptor agonist, and can also be used for synthesizing caffeic acid phenylbutazone and the like with antitumor activity. The synthesis method is more, and the better method comprises the following steps: subjecting benzene and succinic anhydride to Friedel-crafts reaction to obtain 4-oxo-4-phenylbutyric acid, reducing carbonyl by zinc-amalgam, and finally using LiAlH4Reducing carboxyl to obtain carboxyl; the latter process improvement, reduction by Wolff-Kishner, esterification and NaBH4Reducing to obtain; esterification of 4-phenylbutyric acid and NaBH4Reduced or biologically converted by aromatic reductase. Prepared by taking benzene and gamma-butyrolactone as raw materials through Friedel-crafts reaction in one stepDissolving aluminum chloride and the product in alkaline water, separating out a benzene layer, neutralizing with acid to separate out the product, and distilling under reduced pressure to obtain a pure product; the reaction conversion rate is low, the post-treatment steps are complex, the yield and purity of the product are not high, and the industrial application and development of the product are limited, so that the synthesis method which is simple in process steps and high in product yield and purity is urgently needed to be invented.
Disclosure of Invention
The invention aims to provide a synthesis method of an intermediate 4-phenylbutanol, which can catalyze the reduction reaction of 4-phenylbutanoic acid under optimized conditions and has higher product yield.
1. A synthetic method of an intermediate 4-phenylbutanol is characterized by comprising the following steps:
step 1, a 250m1 four-neck flask was charged with 0.5g Fe-N/C catalyst 0.8g NaBH4And 30ml of tetrahydrofuran, mechanically stirring, slowly heating to 60 ℃, and keeping the temperature for 15 min;
step 2, adding 3.0g of 4-phenylbutyric acid into the system, reacting for 15min at constant temperature, and dropwise adding 10ml of 2.4g I2The tetrahydrofuran solution is gradually milky white, generates a large amount of bubbles, and is subjected to heat preservation reaction for 5 hours;
step 3, after the reaction is completed, stopping the reaction by using 5m 13 mol/L HCl, stirring the yellow organic liquid on the upper layer and the white solid on the lower layer for 15min, pouring the residual reaction liquid into a single-neck flask, and performing rotary evaporation to remove tetrahydrofuran to obtain orange color;
and 4, adding 30ml of dichloromethane for dissolving, performing suction filtration to obtain a light yellow filtrate, washing the light yellow filtrate by using saturated saline and deionized water in sequence, removing water by using anhydrous calcium chloride and removing iodine by using a small amount of sodium thiosulfate under the condition of magnetic stirring to obtain a colorless transparent organic liquid, and performing rotary evaporation to remove a cooling solvent to obtain a light yellow transparent liquid, namely 4-phenylbutanol.
The preparation method of the Fe-N/C catalyst comprises the following steps:
step 1, ultrasonically dispersing 0.25mmol of tetrapyridylphenazine in 25ml of N, N-dimethylformamide solvent, and naming the solution A;
step 2, dissolving 0.35mmol of ferrous sulfate in 10m1N, N-dimethylformamide solvent to obtain solution B;
step 3, slowly dripping the solution B into the solution A under strong stirring, and forming a red mixed solution after 15min of dripping is finished;
step 4, stirring for 30min, transferring to an oven for reaction at 160 ℃ for 12h, then performing centrifugal separation, washing with dichloromethane for three times, and performing vacuum drying at 60 ℃ for 24h to obtain a red precursor powder sample;
step 5, placing the dried precursor powder in a tube furnace, calcining for 1h at 600 ℃, 650, 700 and 750 ℃ in hydrogen atmosphere respectively, and heating at a rate of 30 ℃/min;
and 6, treating the pyrolyzed sample for 24 hours at 45 ℃ by 6M hydrochloric acid, washing the sample to be neutral by distilled water, and carrying out vacuum drying at 60 ℃ overnight to obtain the Fe-N/C catalyst.
Has the advantages that: the invention provides a synthesis method of an intermediate 4-phenylbutanol, wherein a sodium borohydride system of 4-phenylbutanoic acid and iodine is subjected to reduction reaction under the action of a catalyst Fe-N/C to obtain the 4-phenylbutanol. The high-content stable bound nitrogen atom component in the tetrapyridylphenoxazine (tpphz) molecule can promote the formation of nitrogen functional groups and high-concentration Fe-N active sites in the high-temperature pyrolysis process; the single finely designed precursor Fe-tpphz has unique structural characteristics, and Fe-N coordination centers are regularly distributed, so that the aggregation of iron species in the subsequent carbonization process can be effectively prevented; the application of the Fe-tpphz complex as a self-doping catalyst precursor completely eliminates the use of an external carrier. Strong interaction can be constructed between the generated catalyst active ingredients, thereby enhancing the catalytic activity and durability of the catalyst. In addition, the abundance of nanopores can facilitate diffusion and transport of reactive species. Through a large number of experiments, the temperature, the dosage, the proportion and the process flow of the experiments are continuously optimized, so that the reaction is convenient to operate and short in time, and the yield and the purity of the product are greatly improved.
Detailed Description
Example 1
1. A synthetic method of an intermediate 4-phenylbutanol is characterized by comprising the following steps:
step 1, a 250m1 four-neck flask was charged with 0.5g Fe-N/C catalyst 0.8g NaBH4And 30ml of tetrahydrofuran, mechanically stirring, slowly heating to 60 ℃, and keeping the temperature for 15 min;
step 2, adding 3.0g of 4-phenylbutyric acid into the system, reacting for 15min at constant temperature, and dropwise adding 10ml of 2.4g I2The tetrahydrofuran solution is gradually milky white, generates a large amount of bubbles, and is subjected to heat preservation reaction for 5 hours;
step 3, after the reaction is completed, stopping the reaction by using 5m 13 mol/L HCl, stirring the yellow organic liquid on the upper layer and the white solid on the lower layer for 15min, pouring the residual reaction liquid into a single-neck flask, and performing rotary evaporation to remove tetrahydrofuran to obtain orange color;
and 4, adding 30ml of dichloromethane for dissolving, performing suction filtration to obtain a light yellow filtrate, washing the light yellow filtrate by using saturated saline and deionized water in sequence, removing water by using anhydrous calcium chloride and removing iodine by using a small amount of sodium thiosulfate under the condition of magnetic stirring to obtain a colorless transparent organic liquid, and performing rotary evaporation to remove a cooling solvent to obtain a light yellow transparent liquid, namely 4-phenylbutanol.
The preparation method of the Fe-N/C catalyst comprises the following steps:
step 1, ultrasonically dispersing 0.25mmol of tetrapyridylphenazine in 25ml of N, N-dimethylformamide solvent, and naming the solution A;
step 2, dissolving 0.35mmol of ferrous sulfate in 10m1N, N-dimethylformamide solvent to obtain solution B;
step 3, slowly dripping the solution B into the solution A under strong stirring, and forming a red mixed solution after 15min of dripping is finished;
step 4, stirring for 30min, transferring to an oven for reaction at 160 ℃ for 12h, then performing centrifugal separation, washing with dichloromethane for three times, and performing vacuum drying at 60 ℃ for 24h to obtain a red precursor powder sample;
step 5, placing the dried precursor powder in a tube furnace, calcining for 1h at 600 ℃, 650, 700 and 750 ℃ in hydrogen atmosphere respectively, and heating at a rate of 30 ℃/min;
and 6, treating the pyrolyzed sample for 24 hours at 45 ℃ by 6M hydrochloric acid, washing the sample to be neutral by distilled water, and carrying out vacuum drying at 60 ℃ overnight to obtain the Fe-N/C catalyst.
Example 2
Step 2, adding 2.0g of 4-phenylbutyric acid into the system, reacting for 15min at constant temperature, and dropwise adding 10ml of 2.4g I2The tetrahydrofuran solution is gradually milky white, generates a large amount of bubbles, and is subjected to heat preservation reaction for 5 hours; the rest of the procedure was the same as in example 1.
Example 3
Step 2, adding 1.0g of 4-phenylbutyric acid into the system, reacting for 15min at constant temperature, and dropwise adding 10ml of 2.4g I2The tetrahydrofuran solution is gradually milky white, generates a large amount of bubbles, and is subjected to heat preservation reaction for 5 hours; the rest of the procedure was the same as in example 1.
Example 4
Step 2, adding 4.0g of 4-phenylbutyric acid into the system, reacting for 15min at constant temperature, and dropwise adding 10ml of 2.4g I2The tetrahydrofuran solution is gradually milky white, generates a large amount of bubbles, and is subjected to heat preservation reaction for 5 hours; the rest of the procedure was the same as in example 1.
Example 5
Step 2, adding 5.0g of 4-phenylbutyric acid into the system, reacting for 15min at constant temperature, and dropwise adding 10ml of 2.4g I2The tetrahydrofuran solution is gradually milky white, generates a large amount of bubbles, and is subjected to heat preservation reaction for 5 hours; the rest of the procedure was the same as in example 1.
Example 6
Step 2, adding 6.0g of 4-phenylbutyric acid into the system, reacting for 15min at constant temperature, and dropwise adding 10ml of 2.4g I2The tetrahydrofuran solution is gradually milky white, generates a large amount of bubbles, and is subjected to heat preservation reaction for 5 hours; the rest of the procedure was the same as in example 1.
Example 7
Step 2, adding 7.0g of 4-phenylbutyric acid into the system, reacting for 15min at constant temperature, and dropwise adding 10ml of 2.4g I2The tetrahydrofuran solution is gradually milky white, generates a large amount of bubbles, and is subjected to heat preservation reaction for 5 hours; the rest of the procedure was the same as in example 1.
Example 8
Step 2, to the above-mentioned body8.0g of 4-phenylbutyric acid are added, the reaction is carried out at constant temperature for 15min, 10ml of 2.4g I are added dropwise2The tetrahydrofuran solution is gradually milky white, generates a large amount of bubbles, and is subjected to heat preservation reaction for 5 hours; the rest of the procedure was the same as in example 1.
Example 9
Step 2, adding 9.0g of 4-phenylbutyric acid into the system, reacting for 15min at constant temperature, and dropwise adding 10ml of 2.4g I2The tetrahydrofuran solution is gradually milky white, generates a large amount of bubbles, and is subjected to heat preservation reaction for 5 hours; the rest of the procedure was the same as in example 1.
Example 10
Step 2, adding 10.0g of 4-phenylbutyric acid into the system, reacting for 15min at constant temperature, and dropwise adding 10ml of 2.4g I2The tetrahydrofuran solution is gradually milky white, generates a large amount of bubbles, and is subjected to heat preservation reaction for 5 hours; the rest of the procedure was the same as in example 1.
Comparative example 1
The difference from embodiment 1 is that: synthesis of intermediates step 1, with equal amounts of Fe3O4The rest of the procedure was exactly the same as in example 1.
Comparative example 2
The difference from embodiment 1 is that: synthesis of intermediate in step 1, the catalyst Fe-N/C was not added, and the rest of the procedure was exactly the same as in example 1.
Comparative example 3
The difference from embodiment 1 is that: synthesis of the catalyst in step 1, no further tetrapyridophenazine was added, and the procedure was exactly the same as in example 1.
Comparative example 4
The difference from embodiment 1 is that: synthesis of the catalyst in step 1, the same amount of pyridine was used instead of the tetrapyridylphenoxazine, and the rest of the procedure was exactly the same as in example 1.
Comparative example 5
The difference from embodiment 1 is that: in the step 2 of synthesizing the catalyst, the molar ratio of the tetrapyridyl phenazine to the ferrous sulfate is 7: 5, the rest of the procedure was exactly the same as in example 1.
Comparative example 6
The difference from embodiment 1 is that: in the catalyst synthesis step 2, the molar ratio of the tetrapyridyl phenazine to the ferrous sulfate is 1: 1, the rest of the procedure is exactly the same as in example 1.
Comparative example 7
The difference from embodiment 1 is that: in the catalyst synthesis step 5, calcining is carried out in a carbon dioxide atmosphere; the rest of the procedure was exactly the same as in example 1.
Comparative example 8
The difference from embodiment 1 is that: in the catalyst synthesis step 5, calcining is carried out in a nitrogen atmosphere; the rest of the procedure was exactly the same as in example 1.
Comparative example 9
The difference from embodiment 1 is that: catalyst synthesis in step 6, the pyrolysis sample was not treated with hydrochloric acid again and the rest of the procedure was exactly the same as in example 1.
Comparative example 10
The difference from embodiment 1 is that: catalyst synthesis in step 6, the pyrolysis sample was treated with sodium hydroxide of equal concentration, and the rest of the procedure was exactly the same as in example 1.
The results of the reactions under different conditions in the examples and the comparative examples are shown in the table
| 4-Phenylbutanol yield/%) | |
| Example 1 | 99.0 |
| Example 2 | 75.1 |
| Example 3 | 69.1 |
| Example 4 | 76.6 |
| Example 5 | 80.0 |
| Example 6 | 64.5 |
| Example 7 | 56.3 |
| Example 8 | 64.0 |
| Example 9 | 59.6 |
| Example 10 | 60.7 |
| Comparative example 1 | 45.7 |
| Comparative example 2 | 39.4 |
| Comparative example 3 | 43.5 |
| Comparative example 4 | 51.2 |
| Comparative example 5 | 58.1 |
| Comparative example 6 | 60.6 |
| Comparative example 7 | 44.0 |
| Comparative example 8 | 40.1 |
| Comparative example 9 | 49.6 |
| Comparative example 10 | 53.5 |
The experimental result shows that the catalyst has good catalytic effect on the reduction reaction of the 4-phenylbutyric acid, and when the reaction condition is fixed, the higher the yield of the intermediate is, the better the catalytic performance is, and otherwise, the worse the catalytic performance is; 4-Phenylbutyric acid, I2The mass ratio is 5: 4, other ingredients are fixed, the synthesis effect is best, and the difference from the example 1 is that the main raw materials of 4-phenylbutyric acid and I are respectively changed from the example 2 to the example 102The dosage and the proportion of the components have certain effect, but the yield is not as high as that of the embodiment 1; comparative examples 1 to 2 No longer added catalyst Fe-N/C and used Fe3O4The other steps are completely the same, so that the product yield is obviously reduced, which indicates that the composite catalyst has great influence on the reaction product; comparative examples 3 to 4 no longer added the tetrabyridine phenazine and replaced with pyridine, the effect was still poor, which indicates that the tetrapyridine phenazine is an essential component in catalyst synthesis; the molar ratio of the tetrapyridylphenazine to the ferrous sulfate is changed from the comparative examples 5 to 6, so that the catalytic effect is obviously poor, and the influence of the proportion of the tetrapyridylphenazine to the ferrous sulfate on the catalytic performance is large; comparative examples 7 to 8 were calcined in nitrogen and carbon dioxide atmosphere, respectively, and the catalytic reaction effect became worse, indicating that the catalyst calcination effect in hydrogen atmosphere was better; comparative examples 9 to 10The acid treatment is not needed, and the sodium hydroxide is used for alkali treatment, so that the activity of the catalyst is changed, the reaction effect is obviously deteriorated, and the product yield is obviously reduced; therefore, the catalyst has excellent catalytic effect on the synthesis reaction of the intermediate 4-phenylbutanol.
Claims (1)
1. A method for synthesizing an intermediate 4-phenylbutanol is characterized by comprising the following steps:
step 1, a 250m1 four-neck flask was charged with 0.5g Fe-N/C catalyst 0.8g NaBH4And 30ml of tetrahydrofuran, mechanically stirring, slowly heating to 60 ℃, and keeping the temperature for 15 min;
step 2, adding 3.0g of 4-phenylbutyric acid into the system, reacting for 15min at constant temperature, and dropwise adding 10ml of 2.4g I2The tetrahydrofuran solution is gradually milky white, generates a large amount of bubbles, and is subjected to heat preservation reaction for 5 hours;
step 3, after the reaction is completed, stopping the reaction by using 5m 13 mol/L HCl, stirring the yellow organic liquid on the upper layer and the white solid on the lower layer for 15min, pouring the residual reaction liquid into a single-neck flask, and performing rotary evaporation to remove tetrahydrofuran to obtain orange color;
step 4, adding 30ml of dichloromethane for dissolution, performing suction filtration to obtain a light yellow filtrate, washing the light yellow filtrate with saturated saline water and deionized water in sequence, removing water with anhydrous calcium chloride and iodine with a small amount of sodium thiosulfate under the condition of magnetic stirring to obtain a colorless transparent organic liquid, and performing rotary evaporation to remove a cooling solvent to obtain a light yellow transparent liquid, namely 4-phenylbutanol;
the preparation method of the Fe-N/C catalyst comprises the following steps:
step 1, ultrasonically dispersing 0.25mmol of tetrapyridylphenazine in 25ml of N, N-dimethylformamide solvent, and naming the solution A;
step 2, dissolving 0.35mmol of ferrous sulfate in 10m1N, N-dimethylformamide solvent to obtain solution B;
step 3, slowly dripping the solution B into the solution A under strong stirring, and forming a red mixed solution after 15min of dripping is finished;
step 4, stirring for 30min, transferring to an oven for reaction at 160 ℃ for 12h, then performing centrifugal separation, washing with dichloromethane for three times, and performing vacuum drying at 60 ℃ for 24h to obtain a red precursor powder sample;
step 5, placing the dried precursor powder in a tube furnace, calcining for 1h at 600 ℃, 650, 700 and 750 ℃ in hydrogen atmosphere respectively, and heating at a rate of 30 ℃/min;
and 6, treating the pyrolyzed sample for 24 hours at 45 ℃ by 6M hydrochloric acid, washing the sample to be neutral by distilled water, and carrying out vacuum drying at 60 ℃ overnight to obtain the Fe-N/C catalyst.
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Non-Patent Citations (3)
| Title |
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| "4-苯基丁醇的制备";陈华奇等;《中国医药工业杂志》;20071031;第38卷(第10期);第692页右栏最后一段和639页左栏第一段 * |
| "Fe-N/C氧还原电催化剂的设计制备";杨正坤;《中国博士学位论文全文数据库，工程科技Ⅰ辑》;20171130;第85页倒数1-2段 * |
| Bettina Hölzer et al."Kumada-Corriu coupling of Grignard reagents,probed with a chiral Grignard reagent".《Chemical Communications (Cambridge, United Kingdom)》.2003,第6卷第732页Table-1. * |
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