CN117924055A - Synthesis method of 5-benzoyl amyl alcohol - Google Patents
Synthesis method of 5-benzoyl amyl alcohol Download PDFInfo
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- CN117924055A CN117924055A CN202211319703.1A CN202211319703A CN117924055A CN 117924055 A CN117924055 A CN 117924055A CN 202211319703 A CN202211319703 A CN 202211319703A CN 117924055 A CN117924055 A CN 117924055A
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- cation exchange
- exchange resin
- sodium ion
- cyclohexylbenzene
- hydrogen
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- -1 5-benzoyl amyl Chemical group 0.000 title claims abstract description 23
- 238000001308 synthesis method Methods 0.000 title claims abstract description 11
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 28
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 19
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002798 polar solvent Substances 0.000 claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000005342 ion exchange Methods 0.000 claims description 14
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 7
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- KHLCHQITTKZTBX-UHFFFAOYSA-N 2-(hydroxycarbamoyl)benzoic acid Chemical group ONC(=O)C1=CC=CC=C1C(O)=O KHLCHQITTKZTBX-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- LYGJENNIWJXYER-BJUDXGSMSA-N nitromethane Chemical group [11CH3][N+]([O-])=O LYGJENNIWJXYER-BJUDXGSMSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 3
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 13
- 238000004448 titration Methods 0.000 description 11
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 8
- PUATWLVUUBATLK-UHFFFAOYSA-N 6-hydroxy-1-phenylhexan-1-one Chemical compound OCCCCCC(=O)C1=CC=CC=C1 PUATWLVUUBATLK-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QQKAZZAULUMMKR-UHFFFAOYSA-N 2-n-hydroxybenzene-1,2-dicarboxamide Chemical compound NC(=O)C1=CC=CC=C1C(=O)NO QQKAZZAULUMMKR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940023913 cation exchange resins Drugs 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YQPMGZGFPCXDGW-UHFFFAOYSA-N 1-(2-hydroxyphenyl)hexan-2-one Chemical compound CCCCC(=O)CC1=CC=CC=C1O YQPMGZGFPCXDGW-UHFFFAOYSA-N 0.000 description 1
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 1
- 239000008037 PVC plasticizer Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- OECMNLAWCROQEE-UHFFFAOYSA-N cyclohexylbenzene;hydrogen peroxide Chemical compound OO.C1CCCCC1C1=CC=CC=C1 OECMNLAWCROQEE-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for synthesizing 5-benzoyl amyl alcohol, which comprises the following steps: cyclohexylbenzene-1-hydroperoxide is contacted with a sodium ion exchanged hydrogen cation exchange resin and a polar solvent. Compared with the prior art, the synthesis method of the invention not only greatly improves the selectivity of the 5-benzoyl amyl alcohol, but also has relatively mild reaction and good application prospect for amplified production.
Description
Technical Field
The invention relates to a method for synthesizing 5-benzoyl amyl alcohol.
Background
5-Benzoyl amyl alcohol (or 6-hydroxy-phenylhexanone) is a precursor of non-phthalate plasticizer, and the plasticizer is mainly used for producing flexible polyvinyl chloride (PVC) products, and has wide application in the fields of medical supplies, toys, food packaging and the like. In recent years, since the toxic effect of traditional phthalates on human endocrine is gradually confirmed in the field of PVC plasticizers, PVC using such plasticizers has been banned by a large number of countries to produce plastic products in close contact with human body. Therefore, a number of phthalate substitutes have been developed.
Some of the recently disclosed technologies show the possibility of a new process route for the synthesis of 5-benzoylpentanol, whereas 5-benzoylpentanol is generally present as a by-product of acidolysis in such processes. The concrete description is as follows: starting from cyclohexylbenzene, phenol+cyclohexanone is obtained by molecular oxidation to cyclohexylbenzene-1-hydroperoxide, followed by decomposition with an acidic catalyst. Such as w.c.e. ends, academic papers published by Tetrahedron using N-hydroxyphthalamide (NHPI) as an oxidation catalyst, and U.S. patent nos. 9029612, 61382749, etc., respectively. Furthermore, U.S. patent No. 2950320 discloses for the first time a process for the co-production of 5-benzoylpentanol by acidolysis of cyclohexylbenzene peroxide under acidic montmorillonite conditions, CN103154111 discloses information that acidolysis of cyclohexylbenzene peroxide in a polar solvent contributes to the formation of 5-benzoylpentanol, which all provide a reference and direction for the synthesis of 5-benzoylpentanol from cyclohexylbenzene hydroperoxide.
Disclosure of Invention
Compared with the prior art, the synthesis method can greatly improve the selectivity of the 5-benzoyl amyl alcohol, has relatively mild reaction and has good application prospect for amplified production.
In order to achieve the above object, the present invention provides a method for synthesizing 5-benzoylpentanol, comprising: cyclohexylbenzene-1-hydroperoxide is contacted with a sodium ion exchanged hydrogen cation exchange resin and a polar solvent.
Compared with the prior art, the synthesis method of the invention not only greatly improves the selectivity of the 5-benzoyl amyl alcohol, but also has relatively mild reaction and good application prospect for amplified production.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a method for synthesizing 5-benzoyl amyl alcohol, which comprises the following steps: cyclohexylbenzene-1-hydroperoxide is contacted with a sodium ion exchanged hydrogen cation exchange resin and a polar solvent. The method can greatly improve the selectivity of the 5-benzoyl amyl alcohol, has relatively mild reaction and has good application prospect for amplified production.
According to a preferred embodiment of the present invention, the sodium ion-exchanged hydrogen cation exchange resin has a sodium ion exchange rate of 10% to 70%.
According to a preferred embodiment of the present invention, the sodium ion exchanged hydrogen form of the cation exchange resin has a sodium ion exchange rate of 10% to 30%, for example 10%, 12%, 14%, 15%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, etc., including but not limited to this range. Whereby the selectivity of 5-benzoylpentanol can be further improved.
According to a preferred embodiment of the present invention, the method for preparing a sodium ion-exchanged hydrogen type cation exchange resin comprises: and placing the hydrogen type cation exchange resin in a sodium salt aqueous solution, and performing ion exchange under the condition of stirring to exchange part of hydrogen ions so as to obtain the sodium ion exchanged hydrogen type cation exchange resin.
According to a preferred embodiment of the invention, the ion exchange time is between 0.5 and 24 hours.
According to a preferred embodiment of the present invention, the hydrogen form cation exchange resin is selected from one or more of the group consisting of DL-1H hydrogen form cation exchange resins, 122 hydrogen form cation exchange resins, and Amberlyst 15 hydrogen form cation exchange resins.
According to a preferred embodiment of the present invention, the mass ratio of sodium ion exchanged hydrogen cation exchange resin to cyclohexylbenzene-1-hydroperoxide is from 0.1 to 1:1, preferably from 0.1 to 0.4:1, for example 0.1:1,0.2:1, 0.3:1, 0.4:1, etc., including but not limited to this range.
In the present invention, the object of the present invention can be achieved by a polar solvent which is conventional in the art, preferably, the polar solvent is selected from one or more of methyl isobutyl ketone, acetone, nitromethane, acetonitrile, dimethylformamide, methanol, preferably nitromethane or acetonitrile. By adopting the technical scheme, the selectivity of the 5-benzoyl amyl alcohol can be greatly improved, the reaction is relatively mild, and the method has good application prospect for amplified production.
In the present invention, preferably, the polar solvent is preferably nitromethane and acetonitrile, more preferably the volume ratio of the two is 2 to 6:1, for example, 2:1, 3:1, 4:1, 5:1, 6:1, etc., including but not limited to this range.
According to a preferred embodiment of the invention, the mass ratio of cyclohexylbenzene-1-hydroperoxide to polar solvent is from 0.15 to 0.3:1, for example, 0.15:1,0.2:1, 0.25:1, 0.3:1, etc., including but not limited to this range.
The present invention has no particular requirement on the source of cyclohexylbenzene-1-hydroperoxide, which is commercially available or synthesized, and according to a preferred embodiment of the present invention, the conditions under which cyclohexylbenzene-1-hydroperoxide is contacted with sodium ion-exchanged hydrogen type cation exchange resin and polar solvent include: the temperature is 40-60 ℃, such as 40 ℃, 45 ℃, 50 ℃,55 ℃, 60 ℃ and the contact time is determined according to the requirements, the invention has no special requirement on the contact time, and the general time is 0.5-2h.
According to a preferred embodiment of the present invention, the method for producing cyclohexylbenzene-1-hydroperoxide comprises: cyclohexylbenzene is oxidized in the presence of molecular oxygen in the presence of an oxidation catalyst.
According to a preferred embodiment of the invention, the source of molecular oxygen is oxygen or air; the oxidation catalyst is N-hydroxy phthalic acid amide, and the oxidation temperature is controlled between 80 ℃ and 120 ℃, preferably 93 ℃ to 98 ℃.
In the invention, the resin needs to be subjected to general pretreatment of the ionic resin before exchange, including but not limited to acid washing, water washing and the like, and the process has a great deal of disclosure in the field and is not repeated herein.
In the present invention, in the examples, the exchange was completed by adding NaCl solution of a determined mass and concentration to the pretreated resin, collecting the liquid after the reaction and titrating the Na ion exchange amount with a NaOH standard solution of a known concentration, and in addition, the maximum exchange capacity was measured by using the same method and controlling the excess NaCl solution. The sodium ion exchange rate (E) can be calculated from the following formula:
wherein,
V is the volume of NaOH consumed by titration after partial exchange, and the unit is mL;
vmax is the volume of NaOH consumed by titration after full exchange, and the unit is mL;
in the invention, the product composition is measured by GC, and the main product is quantified by an external standard method. The end point of the reaction is defined as the iodometric titration of peroxide concentrations below 0.5% or little change over time.
The present invention will be described in detail by examples.
Preparation example 1
Preparation of cyclohexylbenzene-1-hydroperoxide:
Into a 500mL three-neck flask, 194g of Cyclohexylbenzene (CHB), 6g of cyclohexylbenzene-1-hydrogen peroxide (1-CHBHP) and 0.5g of N-hydroxyphthalimide (NHPI) are added, 800mL/min of air is introduced through a bubbling pipe, and a cyclohexylbenzene oxidation solution containing 15-30% of 1-CHBHP is obtained after reaction for several hours at 95 ℃;
The catalyst was filtered off from the cooled cyclohexylbenzene oxidation solution, and the separated solution was washed with 3% na 2CO3 solution and water, respectively, and the residual trace water was distilled off. Then adding a small amount of pure 1-CHBHP seed crystal into the mixture, standing the mixture at 10 ℃ for 48 hours, filtering out pure 1-CHBHP crystals, washing the crystals with n-hexane for several times, and drying the crystals for later use, wherein the purity of the crystals is higher than 99% when detected by HPLC.
Example 1
Preparation of sodium ion exchanged hydrogen cation exchange resin:
5.85g of sodium chloride is dissolved in 67.3g of water to prepare an ion exchange solution, 1g of Amberlyst 15 after pretreatment is added into the solution, the solution is stirred for 2 hours at room temperature, and the Amberlyst 15 resin after treatment is obtained after filtration and drying, wherein the sodium ion exchange rate is 15%.
2.5G of 1-CHBHP crystals were dissolved in 10g of nitromethane for later use. Into a three-necked flask, 1g of the Amberlyst 15 resin after the treatment and 2.5g of nitromethane were charged. And slowly adding the prepared 1-CHBHP nitromethane solution through a constant pressure dropping funnel under the condition of N 2 atmosphere and 50 ℃, controlling the end point by an iodometric titration method, and detecting that the 1-CHBHP conversion rate is 100% and the 5-benzoyl amyl alcohol selectivity is 27.76% after the reaction is finished.
Example 2
The procedure of example 1 was followed except that Amberlyst 15 resin was replaced with DL-1H hydrogen type cation exchange resin, wherein the sodium ion exchange rate was 10%, and the other conditions were the same as in example 1. The end point is controlled by an iodometric titration method, and after the reaction is finished, the GC detects that the conversion rate of 1-CHBHP is 99.98 percent and the selectivity of 5-benzoyl amyl alcohol is 30.34 percent.
Example 3
The procedure of example 1 was followed except that the solvent was acetone, and the other conditions were the same as in example 1. The end point is controlled by an iodometric titration method, and after the reaction is finished, the GC detects that the conversion rate of 1-CHBHP is 100 percent and the selectivity of 5-benzoyl amyl alcohol is 7.9 percent.
Example 4
The procedure of example 1 was followed except that the solvent was replaced with a mixture of nitromethane and acetonitrile in a volume ratio of 5:1. the end point is controlled by an iodometric titration method, and after the reaction is finished, the GC detects that the conversion rate of 1-CHBHP is 100 percent and the selectivity of 5-benzoyl amyl alcohol is 35.10 percent.
Example 5
The procedure of example 1 was followed except that Amberlyst 15 resin had a sodium ion exchange rate of 50% and the remaining conditions were the same. The end point is controlled by an iodometric titration method, and after the reaction is finished, the GC detects that the conversion rate of 1-CHBHP is 93 percent and the selectivity of 5-benzoyl amyl alcohol is 8.85 percent.
Example 6
The procedure of example 1 was followed except that 0.1g of Amberlyst 15 resin was added, with the remaining conditions being the same. The end point is controlled by an iodometric titration method, and after the reaction is finished, the GC detects that the conversion rate of 1-CHBHP is 97 percent, and the selectivity of 5-benzoyl amyl alcohol is 20.88 percent.
Comparative example 1
The difference from example 1 is that 1g of Amberlyst 15 resin after treatment is replaced by 0.055g of 98% sulfuric acid, the other conditions are the same as in example 1, the end point is controlled by iodometric titration, 0.875g of 10% Na 2CO3 solution is added for neutralization after the reaction, after the reaction is finished, the conversion rate of 1-CHBHP is 99.98% and the selectivity of 5-benzoyl amyl alcohol is 18.55% through GC detection.
Comparative example 2
The difference from example 1 is that the solvent was replaced with acetone, 1g of the treated Amberlyst15 resin was replaced with 0.055g of 98% sulfuric acid, the other conditions were the same as in example 1, the end point was controlled by iodometric titration, 0.875g of 10% Na 2CO3 solution was added to neutralize after the reaction, and the conversion of 1-CHBHP was 100% and the selectivity of 5-benzoylpentanol was 2.10% as detected by GC.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method for synthesizing 5-benzoyl amyl alcohol, which is characterized by comprising the following steps: cyclohexylbenzene-1-hydroperoxide is contacted with a sodium ion exchanged hydrogen cation exchange resin and a polar solvent.
2. The synthesis method according to claim 1, wherein the sodium ion-exchanged hydrogen cation exchange resin has a sodium ion exchange rate of 10% to 70%.
3. The synthesis method according to claim 1, wherein the sodium ion-exchanged hydrogen cation exchange resin has a sodium ion exchange rate of 10% to 30%.
4. A synthesis method according to any one of claims 1 to 3, wherein the preparation method of the sodium ion-exchanged hydrogen cation exchange resin comprises: and placing the hydrogen type cation exchange resin in a sodium salt aqueous solution, and performing ion exchange under the condition of stirring to exchange part of hydrogen ions so as to obtain the sodium ion exchanged hydrogen type cation exchange resin.
5. The synthesis method according to claim 4, wherein the ion exchange time is 0.5 to 24 hours.
6. The synthetic method of any one of claims 1-5, wherein the hydrogen cation exchange resin is selected from one or more of DL-1H hydrogen cation exchange resin, 122 hydrogen cation exchange resin, and Amberlyst 15 hydrogen cation exchange resin.
7. The synthesis method according to any one of claims 1 to 6, wherein,
The mass ratio of the sodium ion-exchanged hydrogen type cation exchange resin to the cyclohexylbenzene-1-hydroperoxide is 0.1-1:1, preferably 0.1-0.4:1; and/or
The mass ratio of the cyclohexylbenzene-1-hydroperoxide to the polar solvent is 0.15-0.3:1, a step of; and/or
The conditions under which cyclohexylbenzene-1-hydroperoxide is contacted with the sodium ion exchanged hydrogen cation exchange resin and the polar solvent include: the temperature is 40-60 ℃.
8. The synthesis method according to any one of claims 1 to 7, wherein,
The polar solvent is selected from one or more of methyl isobutyl ketone, acetone, nitromethane, acetonitrile, dimethylformamide and methanol;
preferably, the polar solvent is nitromethane or acetonitrile.
9. The synthetic method according to any one of claims 1 to 8, wherein the preparation method of cyclohexylbenzene-1-hydroperoxide comprises: cyclohexylbenzene is oxidized in the presence of molecular oxygen in the presence of an oxidation catalyst.
10. The synthetic method of claim 9, wherein the source of molecular oxygen is oxygen or air; the oxidation catalyst is N-hydroxy phthalic acid amide, the oxidation temperature is 80-120 ℃, and the preferential temperature is 93-98 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211319703.1A CN117924055A (en) | 2022-10-26 | 2022-10-26 | Synthesis method of 5-benzoyl amyl alcohol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211319703.1A CN117924055A (en) | 2022-10-26 | 2022-10-26 | Synthesis method of 5-benzoyl amyl alcohol |
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| Publication Number | Publication Date |
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|---|---|---|---|
| CN202211319703.1A Pending CN117924055A (en) | 2022-10-26 | 2022-10-26 | Synthesis method of 5-benzoyl amyl alcohol |
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| Country | Link |
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