CN118164832B - Preparation method of 1, 6-hexanedialdehyde - Google Patents
Preparation method of 1, 6-hexanedialdehyde Download PDFInfo
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- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 50
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 78
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 67
- 239000000203 mixture Substances 0.000 claims description 63
- 239000000047 product Substances 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 32
- 239000000706 filtrate Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 150000007529 inorganic bases Chemical class 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract description 8
- 239000007800 oxidant agent Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000004896 high resolution mass spectrometry Methods 0.000 description 14
- 229940015043 glyoxal Drugs 0.000 description 6
- 238000005457 optimization Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- -1 manganate radical Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of organic synthesis, and discloses a preparation method of 1, 6-hexanedialdehyde. According to the method, cyclohexene and inorganic base are used as raw materials, and the preparation of 1, 6-hexanedial is realized by using potassium permanganate through condition regulation and control. Solves the problems of more byproducts, strong corrosiveness, difficult acquisition of oxidant and the like in the existing process of preparing the 1, 6-hexanedial by taking cyclohexene as a raw material, and realizes the convenient and economic synthesis of the 1, 6-hexanedial.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for preparing 1, 6-hexanedialdehyde. The method realizes the synthesis of the 1, 6-glyoxal with high yield and high selectivity through an effective catalytic system and reaction conditions, and has the advantages of simple process, low cost, easily obtained raw materials and the like.
Background
1, 6-Hexanedialdehyde is an important organic compound and is widely applied to the chemical industry, the medicine field and the like. The preparation methods of 1, 6-hexanedial which have been reported at present mainly use different types of oxidizing agents. For example, sodium periodate/silica gel oxidation systems (Journal of Organic Chemistry,1997, 62 (8): 2622.) formed using sodium periodate supported on silica gel, conventional synthesis methods using hydrogen peroxide (Journal ofOrganic Chemistry,1997, 62 (8): 2622.) utilize, ozone (Tetrahedron, 1997, 53 (14): 5217,Tetrahedron Letters,1966, 36:4273, CN102746127 a) or transition metal compounds (Organometallics 2015, 34, 4102.) to oxidize cyclohexene or the like (Industrial catalysts.2019, 27 (3): 75, sun Limin, zhou Cairong, jiang Denggao, et al.1, 2 cyclohexanediol and derivatives thereof synthesis and use of the same.Henan chemical, 2005,22 (3): 1-4. Wu Xiaojian, li Qiong, chen Mengran, et al.1, 6-hexanedialdehyde synthesis process research.perfume and essence cosmetics, 2006, 6:17-20). The preparation and storage of the oxidizing agent relied on in the processes are complex, so that the reaction conditions are harsh and the yield is low. Therefore, there is a need to develop a more efficient, economical, and environmentally friendly preparation method.
Disclosure of Invention
In order to solve the problems, the invention provides a novel preparation method of 1, 6-hexanedialdehyde. The method uses cyclohexene as a raw material, and can solve the problems of more byproducts, long reaction time, difficult preparation, separation and storage of oxidants and the like in the existing means by using potassium permanganate.
The technical scheme adopted for solving the technical problems is as follows: the preparation method of the 1, 6-glyoxal comprises the following steps:
s1, preparing raw materials: preparing cyclohexene, potassium permanganate and inorganic base;
S2, dissolving a catalyst: adding cyclohexene and inorganic base in the step S1 into a mixed solvent of water and acetonitrile, and stirring to uniformly disperse the raw materials;
S3, heating: slowly adding potassium permanganate into the system in batches at the temperature of 40-70 ℃, and stirring for 30-600min at the temperature of 40-70 ℃ after the material addition is completed;
S4, cooling the reaction solution: cooling the mixed reaction solution in the step S3 to room temperature, wherein solids are separated out in the cooling process;
S5, filtering: filtering the reaction liquid cooled in the step S4;
s6, recovering the solvent under reduced pressure: performing reduced pressure distillation on the filtrate obtained in the step S5, maintaining the pressure at 0.2-0.5KPa and the temperature at 20-40 ℃, and distilling until no liquid is distilled out;
s7.1, collection of 6-hexanedial: and (3) carrying out reduced pressure distillation on the solution remained in the system after the reduced pressure distillation in the step (S6), maintaining the pressure at 0.2-0.5KPa and the temperature at 60-90 ℃, and distilling until no liquid is distilled out, wherein the distilled liquid is 1, 6-glyoxal.
As an optimization, the inorganic base includes: one of sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH 4 OH), calcium hydroxide (Ca (OH) 2).
As optimization, the dosage of the potassium permanganate is 0.2-2:1 of the molar ratio of the potassium permanganate to cyclohexene;
as optimization, the dosage of the inorganic base is 0.2-1:1 of the mole ratio of the inorganic base to cyclohexene;
as optimization, the volume ratio of water to acetonitrile is 0.05-0.2:1;
The mixed solvent composed of water and acetonitrile is used for optimization, and the dosage of the mixed solvent is 10-50 times of the mass of cyclohexene.
As optimization, in the step S3, the adding time of the potassium permanganate is 10-20 g according to the using amount of the potassium permanganate in every 10 minutes.
The scheme relates to a preparation method of 1, 6-glyoxal, which has the following beneficial effects:
the potassium permanganate is adopted as the oxidant, and the preparation of the 1, 6-hexanedial is performed through ingenious design, so that compared with the existing preparation method depending on ozone, the corrosion of the oxidant to a preparation container is avoided, the convenience in the reaction operation process is improved, meanwhile, the low yield in use caused by the fact that the oxidant is too unstable is improved, and the higher preparation yield is ensured;
Under conventional conditions, potassium permanganate is easy to directly oxidize a reaction substrate into acid, for example, in 'experimental improvement of preparing adipic acid by oxidizing potassium permanganate' published by Xu Xiangyu, it is pointed out that 'potassium permanganate can oxidize cyclohexanone into adipic acid under acidic, neutral and alkaline conditions', while potassium permanganate has oxidizing property under acidic, neutral and alkaline conditions, the reactivity of potassium permanganate is greatly influenced by pH, and meanwhile, the solvent condition also greatly influences the reaction. According to the invention, through ingenious design, on one hand, the oxidizing property of potassium permanganate is reduced by means of the alkaline condition created by inorganic alkali, and on the other hand, the potassium permanganate dissolved in the solution is limited by means of a mixed solvent system consisting of acetonitrile and water, so that the intensity of the reaction is reduced. The double tubes are aligned, so that the potassium permanganate can stop cyclohexene oxidation at the stage of 1, 6-glyoxal. The chemical reaction equation involved in the reaction is completely different from the traditional preparation method of 1, 6-glyoxal, and specifically comprises the following steps:
Reaction equation for oxidizing cyclohexene by potassium permanganate in mixed solvent of acetonitrile and water under alkaline condition
The reaction mechanism of the reaction is shown as follows, potassium permanganate releases permanganate radical under alkaline condition, cyclohexene is attacked to generate an unstable intermediate, and then bond breaking is carried out to generate 1, 6-hexanedial and manganate radical. The manganate is combined with potassium ions which are released from the system to generate potassium manganate.
Schematic of the reaction mechanism
The core raw materials adopted by the invention are potassium permanganate and conventional inorganic base, the materials are cheap and easy to obtain, the preparation is convenient, and the requirements of convenience in the actual production process can be met. The invention makes the preparation process of 1, 6-hexanedialdehyde more economical and efficient by means of the combined application of potassium permanganate.
Detailed Description
In order that the manner in which the above-recited embodiments of the present invention can be readily understood, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which, however, are not intended to be limiting, any changes and modifications which, however, are believed to be within the scope of the invention, are deemed to be apparent and intended to be within the meaning and scope of the invention.
Example 1
100 G cyclohexene and 9.7 g sodium hydroxide are added into a single-port reaction bottle, the mixture is added into 1000 mL solvent (8 mL water+992 mL acetonitrile), the mixture is stirred to be uniform, 38 g potassium permanganate (the adding time is 38 minutes) is slowly added after the temperature is raised to 40 ℃, the reaction is carried out for 0.5 hour at the temperature of 40 ℃ after the feeding is finished, the mixture is still layered, insoluble matters are filtered and removed, and the mixture is distilled under reduced pressure (0.2 Kpa,20 ℃) until no liquid is distilled out. The filtrate was again distilled under reduced pressure (0.2 kpa,60 ℃) and the fractions were collected, after which the molecular weight of the resulting product was determined by high resolution mass spectrometry and found to be 115.0748, which was close to the theoretical molecular weight of 1, 6-hexanedial (m+h) + 115.0754), indicating that the resulting fraction was 1, 6-hexanedial. The total yield was 115 g% and 83%.
Example 2
100 G cyclohexene and 9.7 g sodium hydroxide are added into a single-port reaction bottle, the mixture is added into 1000 mL solvent (33 mL water+967 mL acetonitrile), the mixture is stirred to be uniform, 38 g potassium permanganate (the adding time is 38 minutes) is slowly added after the temperature is raised to 40 ℃, the reaction is carried out for 0.5 hour at the temperature of 40 ℃ after the feeding is finished, the mixture is still layered, insoluble matters are filtered and removed, and the mixture is distilled under reduced pressure (0.2 Kpa,20 ℃) until no liquid is distilled out. The filtrate was again distilled under reduced pressure (0.2 kpa,60 ℃) and the fractions were collected, after which the molecular weight of the resulting product was determined by high resolution mass spectrometry and found to be 115.0750, which was close to the theoretical molecular weight of 1, 6-hexanedial (m+h) + 115.0754), indicating that the resulting fraction was 1, 6-hexanedial. The total yield of the product 110 g was 79%.
Example 3
100 G cyclohexene and 9.7 g sodium hydroxide are added into a single-port reaction bottle, the mixture is added into 5000 mL solvent (40 mL water+4960 mL acetonitrile), the mixture is stirred to be uniform, 38 g potassium permanganate (the adding time is 38 minutes) is slowly added after the temperature is raised to 40 ℃, the reaction is carried out for 0.5 hour at 40 ℃ after the feeding is finished, the mixture is still layered, insoluble matters are filtered and removed, and the mixture is distilled under reduced pressure (0.2 Kpa,20 ℃) until no liquid is distilled out. The filtrate was again distilled under reduced pressure (0.2 kpa,60 ℃) and the fractions were collected, after which the molecular weight of the resulting product was determined by high resolution mass spectrometry and found to be 115.0749, which was close to the theoretical molecular weight of 1, 6-hexanedial (m+h) + 115.0754), indicating that the resulting fraction was 1, 6-hexanedial. The total yield of the product 112 g was 81%.
Example 4
100 G cyclohexene and 48 g sodium hydroxide are added into a single-port reaction bottle, 1000 mL solvent (8 mL water+992 mL acetonitrile) is added, stirring is carried out to ensure that the system is uniform, 38 g potassium permanganate (the adding time is 38 minutes) is slowly added after the temperature is raised to 40 ℃, the reaction is carried out for 0.5 hour at 40 ℃ after the feeding is finished, standing and layering are carried out, insoluble substances are removed by filtration, and reduced pressure distillation (0.2 Kpa,20 ℃) is carried out until no liquid is distilled out. The filtrate was again distilled under reduced pressure (0.2 kpa,60 ℃) and the fractions were collected, after which the molecular weight of the resulting product was determined by high resolution mass spectrometry and found to be 115.0747, which was close to the theoretical molecular weight of 1, 6-hexanedial (m+h) + 115.0754), indicating that the resulting fraction was 1, 6-hexanedial. The total yield of the product 112 g was 81%.
Example 5
100 G cyclohexene and 9.7 g sodium hydroxide are added into a single-port reaction bottle, the mixture is added into 1000 mL solvent (8 mL water+992 mL acetonitrile), the mixture is stirred to be uniform, 38 g potassium permanganate (the adding time is 38 minutes) is slowly added after the temperature is increased to 60 ℃, the reaction is carried out for 0.5 hour at 60 ℃ after the feeding is finished, the mixture is still layered, insoluble matters are filtered and removed, and the mixture is distilled under reduced pressure (0.2 Kpa,20 ℃) until no liquid is distilled out. The filtrate was again distilled under reduced pressure (0.2 kpa,60 ℃) and the fractions were collected, after which the molecular weight of the resulting product was determined by high resolution mass spectrometry and found to be 115.0751, which was close to the theoretical molecular weight of 1, 6-hexanedial (m+h) + 115.0754), indicating that the resulting fraction was 1, 6-hexanedial. The total yield of the product 114 g is 82%.
Example 6
100 G cyclohexene and 9.7 g sodium hydroxide are added into a single-port reaction bottle, the mixture is added into 1000 mL solvent (8 mL water+992 mL acetonitrile), the mixture is stirred to be uniform, 234 g potassium permanganate (the addition time is 230 minutes) is slowly added after the temperature is raised to 40 ℃, the reaction is carried out for 0.5 hour at the temperature of 40 ℃ after the material feeding is finished, the mixture is still layered, insoluble matters are filtered and removed, and the mixture is distilled under reduced pressure (0.2 Kpa,20 ℃) until no liquid is distilled out. The filtrate was again distilled under reduced pressure (0.2 kpa,60 ℃) and the fractions were collected, after which the molecular weight of the resulting product was determined by high resolution mass spectrometry and found to be 115.0753, which was close to the theoretical molecular weight of 1, 6-hexanedial (m+h) + 115.0754), indicating that the resulting fraction was 1, 6-hexanedial. The total yield was found to be 84% as 117 g.
Example 7
100 G cyclohexene and 9.7 g sodium hydroxide are added into a single-port reaction bottle, the mixture is added into 1000 mL solvent (8 mL water+992 mL acetonitrile), stirring is carried out to make the system uniform, 38 g potassium permanganate (the adding time is 38 minutes) is slowly added after the temperature is raised to 40 ℃, the reaction is carried out for 10 hours at 40 ℃ after the feeding is finished, the mixture is still layered, insoluble substances are removed by filtration, and the mixture is distilled under reduced pressure (0.2 Kpa,20 ℃) until no liquid is distilled out. The filtrate was again distilled under reduced pressure (0.2 kpa,60 ℃) and the fractions were collected, after which the molecular weight of the resulting product was determined by high resolution mass spectrometry and found to be 115.0748, which was close to the theoretical molecular weight of 1, 6-hexanedial (m+h) + 115.0754), indicating that the resulting fraction was 1, 6-hexanedial. The total obtained product 118 g was obtained in 85% yield.
Example 8
100 G cyclohexene and 9.7 g sodium hydroxide are added into a single-port reaction bottle, the mixture is added into 1000 mL solvent (8 mL water+992 mL acetonitrile), the mixture is stirred to be uniform, 38 g potassium permanganate (the adding time is 38 minutes) is slowly added after the temperature is raised to 40 ℃, the reaction is carried out for 0.5 hour at the temperature of 40 ℃ after the feeding is finished, the mixture is still layered, insoluble matters are filtered and removed, and the mixture is distilled under reduced pressure (0.2 Kpa,40 ℃) until no liquid is distilled out. The filtrate was again distilled under reduced pressure (0.2 kpa,60 ℃) and the fractions were collected, after which the molecular weight of the resulting product was determined by high resolution mass spectrometry and found to be 115.0751, which was close to the theoretical molecular weight of 1, 6-hexanedial (m+h) + 115.0754), indicating that the resulting fraction was 1, 6-hexanedial. The total yield of the product 112 g was 81%.
Example 9
100 G cyclohexene and 9.7 g sodium hydroxide are added into a single-port reaction bottle, the mixture is added into 1000 mL solvent (8 mL water+992 mL acetonitrile), the mixture is stirred to be uniform, 38 g potassium permanganate (the adding time is 38 minutes) is slowly added after the temperature is raised to 40 ℃, the reaction is carried out for 0.5 hour at the temperature of 40 ℃ after the feeding is finished, the mixture is still layered, insoluble matters are filtered and removed, and the mixture is distilled under reduced pressure (0.2 Kpa,20 ℃) until no liquid is distilled out. The filtrate was again distilled under reduced pressure (0.2 kpa,90 ℃) and the fractions were collected, after which the molecular weight of the resulting product was determined by high resolution mass spectrometry and found to be 115.0752, which was close to the theoretical molecular weight of 1, 6-hexanedial (m+h) + 115.0754), indicating that the resulting fraction was 1, 6-hexanedial. The total yield was 115 g% and 83%.
Example 10
100 G cyclohexene and 13.6 g potassium hydroxide are added into a single-port reaction bottle, the mixture is added into 1000 mL solvent (8 mL water+992 mL acetonitrile), the mixture is stirred to be uniform, 38 g potassium permanganate (the adding time is 38 minutes) is slowly added after the temperature is raised to 40 ℃, the reaction is carried out for 0.5 hour at the temperature of 40 ℃ after the feeding is finished, the mixture is still layered, insoluble matters are filtered and removed, and the mixture is distilled under reduced pressure (0.2 Kpa,20 ℃) until no liquid is distilled out. The filtrate was again distilled under reduced pressure (0.2 kpa,60 ℃) and the fractions were collected, after which the molecular weight of the resulting product was determined by high resolution mass spectrometry and found to be 115.0750, which was close to the theoretical molecular weight of 1, 6-hexanedial (m+h) + 115.0754), indicating that the resulting fraction was 1, 6-hexanedial. The total yield of the product 112 g was 81%.
Example 11
100 G cyclohexene and 8.5 g ammonium hydroxide are added into a single-port reaction bottle, the mixture is added into 1000 mL solvent (8 mL water+992 mL acetonitrile), the mixture is stirred to be uniform, 38 g potassium permanganate (the addition time is 38 minutes) is slowly added after the temperature is raised to 40 ℃, the reaction is maintained at 40 ℃ for 0.5 hour after the feeding is finished, the mixture is subjected to static layering, insoluble matters are removed by filtration, and the mixture is distilled under reduced pressure (0.2 Kpa,20 ℃) until no liquid is distilled out. The filtrate was again distilled under reduced pressure (0.2 kpa,60 ℃) and the fractions were collected, after which the molecular weight of the resulting product was determined by high resolution mass spectrometry and found to be 115.0750, which was close to the theoretical molecular weight of 1, 6-hexanedial (m+h) + 115.0752), indicating that the resulting fraction was 1, 6-hexanedial. The total yield was found to be 84% as 117 g.
Example 12
100 G cyclohexene and 18 g calcium hydroxide are added into a single-port reaction bottle, 1000 mL solvent (8 mL water+992 mL acetonitrile) is added, stirring is carried out to ensure that the system is uniform, 38 g potassium permanganate (the adding time is 38 minutes) is slowly added after the temperature is raised to 40 ℃, the reaction is carried out for 0.5 hour at 40 ℃ after the feeding is finished, standing and layering are carried out, insoluble substances are removed by filtration, and reduced pressure distillation (0.2 Kpa,20 ℃) is carried out until no liquid is distilled out. The filtrate was again distilled under reduced pressure (0.2 kpa,60 ℃) and the fractions were collected, after which the molecular weight of the resulting product was determined by high resolution mass spectrometry and found to be 115.0751, which was close to the theoretical molecular weight of 1, 6-hexanedial (m+h) + 115.0754), indicating that the resulting fraction was 1, 6-hexanedial. The total yield of product 111 g was 80%.
Comparative example 1
100 G cyclohexene is added into a single-port reaction bottle, 1000 mL solvent (8 mL water+992 mL acetonitrile) is added, the system is stirred uniformly, 38 g potassium permanganate is slowly added after the temperature is raised to 40 ℃, the addition time is 38 minutes, the reaction is carried out for 0.5 hour at 40 ℃ after the material addition is finished, the mixture is still layered, insoluble matters are removed by filtration, and the mixture is distilled under reduced pressure (0.2 Kpa,20 ℃) until no liquid is distilled out. The filtrate was again distilled under reduced pressure (0.2 kpa,60 ℃) and fractions were collected, and then the molecular weight of the obtained product was determined by high resolution mass spectrometry, resulting in no product of close molecular weight.
Comparative example 2
100 G cyclohexene and 9.7 g sodium hydroxide are added into a single-port reaction bottle, the mixture is added into 1000 mL solvent (acetonitrile only), the system is stirred uniformly, 38 g potassium permanganate is slowly added after the temperature is raised to 40 ℃, the addition time is 38 minutes, the reaction is carried out for 0.5 hour at 40 ℃ after the material addition is finished, the mixture is still layered, insoluble substances are removed by filtration, and the mixture is distilled under reduced pressure (0.2 Kpa,20 ℃) until no liquid is distilled out. The filtrate was again distilled under reduced pressure (0.2 kpa,60 ℃) and the fractions were collected, after which the molecular weight of the resulting product was determined by high resolution mass spectrometry and found to be 115.0751, which was close to the theoretical molecular weight of 1, 6-hexanedial (m+h) + 115.0754), indicating that the resulting fraction was 1, 6-hexanedial. The total yield was 25 g% and 18%.
Comparative example 3
100 G cyclohexene and 9.7 g sodium hydroxide are added into a single-port reaction bottle, the mixture is added into 1000 mL solvent (8 mL water+992 mL acetonitrile), the mixture is stirred to make the system uniform, after the temperature is raised to 40 ℃, the reaction is maintained at 40 ℃ for 0.5 hour, the mixture is kept still for layering, insoluble substances are removed by filtration, and the mixture is distilled under reduced pressure (0.2 Kpa,20 ℃) until no liquid is distilled out. The filtrate was again distilled under reduced pressure (0.2 kpa,60 ℃ C.) to give no target product.
Comparative example 4
100 G cyclohexene and 9.7 g sodium hydroxide are added into a single-port reaction bottle, the mixture is added into 1000 mL solvent (8 mL water+992 mL acetonitrile), the mixture is stirred to be uniform, 38 g potassium permanganate (the adding time is 38 minutes) is slowly added after the temperature is raised to 40 ℃, the reaction is carried out for 0.5 hour at the temperature of 40 ℃ after the feeding is finished, the mixture is still layered, insoluble matters are filtered and removed, and the mixture is distilled under reduced pressure (0.2 Kpa,70 ℃) until no liquid is distilled out. The filtrate was again distilled under reduced pressure (0.2 kpa,60 ℃) and the fractions were collected as the product 1, 6-hexanedial. No target product was obtained.
Comparative example 5
100 G cyclohexene and 9.7 g sodium hydroxide are added into a single-port reaction bottle, the mixture is added into 1000 mL solvent (8 mL water+992 mL acetonitrile), the mixture is stirred to be uniform, 38 g potassium permanganate (the adding time is 38 minutes) is slowly added after the temperature is raised to 40 ℃, the reaction is carried out for 0.5 hour at the temperature of 40 ℃ after the feeding is finished, the mixture is still layered, insoluble matters are filtered and removed, and the mixture is distilled under reduced pressure (0.2 Kpa,20 ℃) until no liquid is distilled out. The filtrate was again distilled under reduced pressure (0.2 kpa,30 ℃) and the fractions were collected as the product 1, 6-hexanedial. No target product was obtained.
It can also be seen from the examples described above that a higher 1, 6-hexanedial production efficiency can be achieved only when potassium permanganate is combined with an inorganic base. The reasonable choice of solvent conditions and conditions for subsequent reduced pressure distillation also has a great influence on the experiment. Of course, the above description is not limited to the above examples, and the technical features of the present invention that are not described may be implemented by or by using the prior art, which is not described herein again; the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the present invention, and those skilled in the art should not depart from the spirit of the present invention and should also fall within the scope of the appended claims.
Claims (12)
1. A preparation method of 1, 6-hexanedial is characterized in that: adding 100g cyclohexene and 9.7 g sodium hydroxide into a single-port reaction bottle, stirring to make the system uniform, heating to 40 ℃, slowly adding 38 g potassium permanganate within 38 minutes, maintaining the temperature at 40 ℃ for 0.5 hour after the material is added, standing for layering, filtering to remove insoluble substances, distilling under reduced pressure at 20 ℃ until no liquid is distilled out, distilling the filtrate under reduced pressure at 0.2 Kpa and 60 ℃ again, and collecting fractions to obtain the product.
2. A preparation method of 1, 6-hexanedial is characterized in that: adding 100 g cyclohexene and 9.7 g sodium hydroxide into a single-port reaction bottle, stirring to make the system uniform, heating to 40 ℃, slowly adding 38 g potassium permanganate within 38 minutes, maintaining the temperature at 40 ℃ for 0.5 hour after the addition, standing for layering, filtering to remove insoluble substances, distilling under reduced pressure at 0.2 Kpa and 20 ℃ until no liquid is distilled out, distilling the filtrate under reduced pressure again at 0.2 Kpa and 60 ℃, and collecting fractions to obtain the product.
3. A preparation method of 1, 6-hexanedial is characterized in that: adding 100 g cyclohexene and 9.7 g sodium hydroxide into a single-port reaction bottle, stirring to make the system uniform, heating to 40 ℃, slowly adding 38 g potassium permanganate within 38 minutes, maintaining the temperature at 40 ℃ for 0.5 hour after the addition, standing for layering, filtering to remove insoluble substances, distilling under reduced pressure at 0.2 Kpa and 20 ℃ until no liquid is distilled out, distilling the filtrate under reduced pressure again at 0.2 Kpa and 60 ℃, and collecting fractions to obtain the product.
4. A preparation method of 1, 6-hexanedial is characterized in that: adding 100g cyclohexene and 48 g sodium hydroxide into a single-port reaction bottle, stirring to make the system uniform, heating to 40 ℃, slowly adding 38 g potassium permanganate within 38 minutes, maintaining the temperature at 40 ℃ for reaction for 0.5 hour after the material is added, standing for layering, filtering to remove insoluble substances, distilling under reduced pressure at 0.2 Kpa and 20 ℃ until no liquid is distilled out, distilling the filtrate again under reduced pressure at 0.2 Kpa and 60 ℃, and collecting fractions to obtain the product.
5. A preparation method of 1, 6-hexanedial is characterized in that: 100 g cyclohexene and 9.7 g sodium hydroxide are added into a single-port reaction bottle, the solvent is 8 mL water and 992 mL acetonitrile, the system is stirred to be uniform, 38 g potassium permanganate is slowly added within 38 minutes after the temperature is raised to 60 ℃, the reaction is carried out for 0.5 hour at 60 ℃ after the material addition is finished, the mixture is still layered, insoluble substances are removed by filtration, the mixture is distilled under reduced pressure at 0.2 Kpa and 20 ℃ until no liquid is distilled, the filtrate is distilled under reduced pressure again at 0.2 Kpa and 60 ℃, and fractions are collected to obtain the product.
6. A preparation method of 1, 6-hexanedial is characterized in that: adding 100 g cyclohexene and 9.7 g sodium hydroxide into a single-port reaction bottle, stirring to make the system uniform, heating to 40 ℃, slowly adding 234 g potassium permanganate within 230 minutes, maintaining the temperature at 40 ℃ for 0.5 hour after the addition, standing for layering, filtering to remove insoluble substances, distilling under reduced pressure at 0.2 Kpa at 20 ℃ until no liquid is distilled out, distilling the filtrate under reduced pressure again at 0.2 Kpa at 60 ℃, and collecting fractions to obtain the product.
7. A preparation method of 1, 6-hexanedial is characterized in that: adding 100g cyclohexene and 9.7 g sodium hydroxide into a single-port reaction bottle, stirring to make the system uniform, heating to 40 ℃, slowly adding 38 g potassium permanganate within 38 minutes, maintaining the temperature at 40 ℃ for reaction for 10 hours after the material is added, standing for layering, filtering to remove insoluble substances, distilling under reduced pressure at 0.2 Kpa and 20 ℃ until no liquid is distilled out, distilling the filtrate under reduced pressure again at 0.2 Kpa and 60 ℃, and collecting fractions to obtain the product.
8. A preparation method of 1, 6-hexanedial is characterized in that: 100 g cyclohexene and 9.7 g sodium hydroxide are added into a single-port reaction bottle, the solvent is 8 mL water and 992 mL acetonitrile, the system is stirred to be uniform, 38 g potassium permanganate is slowly added within 38 minutes after the temperature is raised to 40 ℃, the reaction is carried out for 0.5 hour at the temperature of 40 ℃ after the material addition is finished, the mixture is still layered, insoluble substances are removed by filtration, reduced pressure distillation is carried out at 0.2 Kpa at 40 ℃ until no liquid is distilled out, the filtrate is subjected to reduced pressure distillation again at 0.2 Kpa at 60 ℃, and fractions are collected, thus obtaining the product.
9. A preparation method of 1, 6-hexanedial is characterized in that: 100 g cyclohexene and 9.7 g sodium hydroxide are added into a single-port reaction bottle, the solvent is 8 mL water and 992 mL acetonitrile, the system is stirred to be uniform, 38 g potassium permanganate is slowly added within 38 minutes after the temperature is raised to 40 ℃, the reaction is carried out for 0.5 hour at the temperature of 40 ℃ after the material addition is finished, the mixture is still layered, insoluble substances are removed by filtration, the mixture is distilled under reduced pressure at 0.2 Kpa and 20 ℃ until no liquid is distilled, the filtrate is distilled under reduced pressure again at 0.2 Kpa and 90 ℃, and fractions are collected to obtain the product.
10. A preparation method of 1, 6-hexanedial is characterized in that: adding 100 g cyclohexene and 13.6 g potassium hydroxide into a single-port reaction bottle, stirring to make the system uniform, heating to 40 ℃, slowly adding 38 g potassium permanganate within 38 minutes, maintaining the temperature at 40 ℃ for 0.5 hour after the addition, standing for layering, filtering to remove insoluble substances, distilling under reduced pressure at 0.2 Kpa and 20 ℃ until no liquid is distilled out, distilling the filtrate under reduced pressure again at 0.2 Kpa and 60 ℃, and collecting fractions to obtain the product.
11. A preparation method of 1, 6-hexanedial is characterized in that: 100 g cyclohexene and 8.5 g ammonium hydroxide are added into a single-port reaction bottle, the solvent is 8 mL water+992 mL acetonitrile, stirring is carried out to ensure that the system is uniform, 38 g potassium permanganate is slowly added within 38 minutes after the temperature is raised to 40 ℃, the reaction is carried out for 0.5 hour at the temperature of 40 ℃ after the material addition is finished, the mixture is still layered, insoluble substances are removed by filtration, the mixture is distilled under reduced pressure at 0.2 Kpa and 20 ℃ until no liquid is distilled, the filtrate is distilled under reduced pressure again at 0.2 Kpa and 60 ℃, and fractions are collected to obtain the product.
12. A preparation method of 1, 6-hexanedial is characterized in that: adding 100g cyclohexene and 18 g calcium hydroxide into a single-port reaction bottle, stirring to make the system uniform, heating to 40 ℃, slowly adding 38 g potassium permanganate within 38 minutes, maintaining the temperature at 40 ℃ for reaction for 0.5 hour after the material is added, standing for layering, filtering to remove insoluble substances, distilling under reduced pressure at 0.2 Kpa and 20 ℃ until no liquid is distilled out, distilling the filtrate again under reduced pressure at 0.2 Kpa and 60 ℃, and collecting fractions to obtain the product.
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| CN115991638A (en) * | 2021-10-20 | 2023-04-21 | 中国石油化工股份有限公司 | Method for preparing 1, 6-glyoxal, product obtained by method and reaction system |
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| CN115991638A (en) * | 2021-10-20 | 2023-04-21 | 中国石油化工股份有限公司 | Method for preparing 1, 6-glyoxal, product obtained by method and reaction system |
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