CN113831277A - Preparation method of hindered amine quaternary ammonium salt - Google Patents
Preparation method of hindered amine quaternary ammonium salt Download PDFInfo
- Publication number
- CN113831277A CN113831277A CN202111082310.9A CN202111082310A CN113831277A CN 113831277 A CN113831277 A CN 113831277A CN 202111082310 A CN202111082310 A CN 202111082310A CN 113831277 A CN113831277 A CN 113831277A
- Authority
- CN
- China
- Prior art keywords
- quaternary ammonium
- tetramethylpiperidine
- hindered amine
- reaction
- ammonium salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 amine quaternary ammonium salt Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 33
- XWKOFHVPNLKHOK-UHFFFAOYSA-N 4-chloro-2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CC(Cl)CC(C)(C)N1 XWKOFHVPNLKHOK-UHFFFAOYSA-N 0.000 claims abstract description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 12
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000006073 displacement reaction Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 74
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 27
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 7
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 238000005649 metathesis reaction Methods 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 6
- 150000001412 amines Chemical class 0.000 abstract description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011149 active material Substances 0.000 abstract description 3
- 150000001408 amides Chemical class 0.000 abstract description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 239000003899 bactericide agent Substances 0.000 abstract description 3
- 239000004009 herbicide Substances 0.000 abstract description 3
- 239000002265 redox agent Substances 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 150000003512 tertiary amines Chemical class 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- LRAJIZNKBMCWJE-UHFFFAOYSA-N n,n,2,2,6,6-hexamethylpiperidin-4-amine Chemical compound CN(C)C1CC(C)(C)NC(C)(C)C1 LRAJIZNKBMCWJE-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
- C07D211/94—Oxygen atom, e.g. piperidine N-oxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
The invention relates to the technical field of redox active materials of flow batteries, and particularly provides a preparation method of hindered amine quaternary ammonium salt, which comprises the following steps: carrying out a displacement reaction on 4-hydroxy-2, 2,6, 6-tetramethylpiperidine and phosphorus oxychloride to obtain 4-chloro-2, 2,6, 6-tetramethylpiperidine which undergoes a nucleophilic substitution reaction with amine to obtain 2,2,6, 6-tetramethylpiperidine-4-ammonium chloride; then, in the presence of a catalyst, carrying out oxidation reaction on 2,2,6, 6-tetramethylpiperidine-4-ammonium chloride and hydrogen peroxide to obtain 2,2,6, 6-tetramethylpiperidyloxy-4-ammonium chloride; in addition, the intermediate (formula III) prepared by the invention can react with tertiary amine, amide, nitrogen-containing aromatic ring, nitrogen-containing heterocycle and the like to provide a great variety of hindered amine-containing quaternary ammonium salts; the quaternary ammonium salt can be used as main components or raw materials of bactericides, herbicides, surfactants, redox agents and the like, has wide application and extremely high economic value.
Description
Technical Field
The invention belongs to the technical field of redox active materials of flow batteries, and particularly relates to a preparation method of hindered amine quaternary ammonium salt.
Background
Clean renewable energy sources such as wind energy, water energy and solar energy have fluctuation and discontinuity, the renewable energy sources can not be used in a large-scale energy storage system, and the energy storage system can adjust the supply and demand balance of a power system, so that large-scale renewable energy power generation facilities can be smoothly merged into a power grid.
The flow battery is a large-scale energy storage technology, realizes the storage and release of energy mainly by the redox reaction of electrolyte, and can be used for storing the electric quantity generated by renewable energy sources such as wind energy, water energy, solar energy and the like.
The traditional flow battery mainly takes transition metals such as vanadium, chromium and the like as electroactive materials and has the defects of limited metal reserves, strong corrosivity of electrolyte, serious transmembrane permeation, slow kinetics and the like. The water system organic flow battery adopts water-soluble organic electroactive molecules as electrolyte, has the advantages of rich raw material sources and adjustable performance height,
the electrolyte is used as an energy storage medium of the flow battery, and the active substance is the core of the electrolyte and determines the performance of the battery. The N, N, N,2,2,6, 6-heptamethylpiperidyloxy-4-ammonium chloride is reported to be used as an organic redox active material of the aqueous organic flow battery, has good water solubility, and is superior to the traditional organic flow battery in performances such as electrolytic voltage, stored energy, current density and the like, and meanwhile, the aqueous organic flow battery system keeps pH neutrality, so that the corrosivity of battery materials is greatly reduced, and the maintenance cost of the battery is reduced. Even under the high-temperature condition, the aqueous organic flow battery containing N, N, N,2,2,6, 6-heptamethylpiperidyloxy-4-ammonium chloride still has good charge and discharge performance and wider application prospect. Therefore, the method has great significance for the synthesis research of N, N, N,2,2,6, 6-heptamethylpiperidinyloxy-4-ammonium chloride.
However, at present, few reports on the synthesis of N, N, N,2,2,6, 6-heptamethylpiperidinyloxy-4-ammonium chloride at home and abroad are available. In 2017, patent CN109803955A discloses that triacetonamine and dimethylamine are subjected to hydrogenation reduction in an organic solvent, after solvent removal, an intermediate obtained by reduction and methyl chloride generate ammonium salt in a mixed solvent of acetonitrile and toluene, and finally oxidation is performed to obtain TEMPO-4-ammonium chloride. In patent CN108140864A, triacetonamine is sequentially oxidized by hydrogen peroxide, reduced by equivalent reducing agent, reacted with methyl iodide to form salt and subjected to anion exchange to obtain TEMPO-4-ammonium chloride. U.S. Pat. No. 4, 20180072669, 1 discloses the use of 2,2,6, 6-tetramethylpiperidin-4-amine with formaldehyde in the presence of formic acid to form N, N,2,2,6, 6-hexamethylpiperidin-4-amine.
Compared with the prior art, the method has the advantages of wide raw material source, low cost, simple overall operation steps, safe and reliable reaction and high product purity. In addition, the intermediate (formula III) prepared by the invention can react with tertiary amine, amide, nitrogen-containing aromatic ring, nitrogen-containing heterocycle and the like to provide a great variety of hindered amine-containing quaternary ammonium salts. The quaternary ammonium salt can be used as main components or raw materials of bactericides, herbicides, surfactants, redox agents and the like, has wide application and extremely high economic value.
Disclosure of Invention
In order to solve the problems, the invention discloses a preparation method of hindered amine quaternary ammonium salt with low raw material cost, simple operation steps and high product purity.
In order to achieve the purpose, the invention provides the following specific technical scheme:
the invention provides a hindered amine quaternary ammonium salt, which has a structural formula shown as a formula (I):
a preparation method of hindered amine quaternary ammonium salt comprises the following steps:
s1: adding 4-hydroxy-2, 2,6, 6-tetramethylpiperidine shown in a formula II and phosphorus oxychloride into a solvent, and carrying out a displacement reaction to obtain 4-chloro-2, 2,6, 6-tetramethylpiperidine shown in a formula III;
s2: adding 4-chloro-2, 2,6, 6-tetramethylpiperidine and trimethylamine into a solvent, and carrying out nucleophilic substitution reaction to obtain N, N, N,2,2,6, 6-heptamethylpiperidine-4-ammonium chloride shown in a formula IV;
s3, adding N, N, N,2,2,6, 6-heptamethylpiperidine-4-ammonium chloride and hydrogen peroxide into a solvent, and carrying out oxidation reaction under the action of a catalyst to obtain N, N, N,2,2,6, 6-heptamethylpiperidinyloxy-4-ammonium chloride shown in the formula I;
further, in the step S1, the molar ratio of the 4-hydroxy-2, 2,6, 6-tetramethylpiperidine to the phosphorus oxychloride to the solvent is 1: 0.3-1.5: 0.5-30.
Preferably, the molar ratio of the 4-hydroxy-2, 2,6, 6-tetramethylpiperidine to the phosphorus oxychloride to the solvent in the step S1 is 1: 0.4-0.7: 2-20.
Further, the solvent for the displacement reaction in the step S1 is one or more of acetonitrile, cyclohexane, benzene, toluene, and xylene; the temperature of the replacement reaction is 30-140 ℃, and the time of the replacement reaction is 0.5-6 h.
Preferably, the solvent for the displacement reaction in the step S1 is toluene, the temperature for the displacement reaction is 90-120 ℃, and the time for the displacement reaction is 0.5-2 h.
Further, in the step S2, the molar ratio of the 4-chloro-2, 2,6, 6-tetramethylpiperidine to the trimethylamine to the solvent is 1: 0.5-10: 0.5-40.
Preferably, the molar ratio of 4-chloro-2, 2,6, 6-tetramethylpiperidine to trimethylamine to solvent in step S2 is 1: 1-5: 2-30.
Further, the solvent for nucleophilic substitution reaction in step S2 is one or more of acetonitrile, 1, 2-dichloroethane, benzene, toluene, and xylene.
Preferably, the solvent for the nucleophilic substitution reaction in step S2 is one or both of acetonitrile and toluene.
Further, the temperature of the nucleophilic substitution reaction in the step S2 is 30-140 ℃, and the time of the nucleophilic substitution reaction is 4-48 h.
Preferably, the temperature of the nucleophilic substitution reaction in the step S2 is 50-110 ℃, and the time of the nucleophilic substitution reaction is 8-24 h.
Further, the molar ratio of the N,2,2,6, 6-heptamethylpiperidine-4-ammonium chloride, hydrogen peroxide, solvent and catalyst in the oxidation reaction in step S3 is 1: 1.5-8: 0.5-100: 0.003-0.1.
Preferably, in the step S3, the molar ratio of N,2,2,6, 6-heptamethylpiperidine-4-ammonium chloride to hydrogen peroxide to solvent to catalyst is 1: 1.5-5: 2-40: 0.005-0.08.
Further, the solvent for the oxidation reaction in the step S3 is water; the catalyst is one or more of magnesium hydroxide and magnesium sulfate.
Further, the temperature of the oxidation reaction in the step S3 is 20-100 ℃, and the time of the oxidation reaction is 4-24 h.
Preferably, the temperature of the oxidation reaction in the step S3 is 55-90 ℃, and the time of the oxidation reaction is 6-18 h.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention has wide source of raw materials and low cost, and is suitable for industrial production.
2. The invention has simple overall operation steps, safe and reliable reaction and high product purity.
3. The intermediate (formula III) prepared by the invention can react with tertiary amine, amide, nitrogen-containing aromatic ring, nitrogen-containing heterocycle and the like, and provides a great variety of easily water-soluble hindered amine-containing quaternary ammonium salts. The quaternary ammonium salt can be used as main components or raw materials of bactericides, herbicides, surfactants, redox agents and the like, has wide application and extremely high economic value.
Drawings
FIG. 1 is a HNMR map of a target product prepared in step S1 of example 1 of the present invention;
FIG. 2 is a HNMR map of the target product prepared in step S2 of example 1 of the present invention;
fig. 3 is a HNMR map of the target product prepared in step S3 of example 1 of the present invention.
Detailed Description
The present invention is described in detail below with reference to the drawings and examples, but the present invention is not limited thereto.
Example 1
1) Synthesis of 4-chloro-2, 2,6, 6-tetramethylpiperidine (III):
dissolving 157g of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine in 500g of toluene, cooling the temperature to 5 ℃, and dropwise adding 76.5g of phosphorus oxychloride into the reaction solution, wherein the temperature is controlled not to exceed 10 ℃ in the dropwise adding process; then slowly heating to 110 ℃, keeping the temperature for reaction for 2h, cooling to 30 ℃, adding 200g of water, stirring vigorously for 1h, then adjusting the pH value to 10, extracting with dichloromethane, drying with anhydrous magnesium sulfate, and performing rotary evaporation on the solvent to obtain 172g of colorless liquid with 98% GC content, namely 4-chloro-2, 2,6, 6-tetramethylpiperidine, which is directly used in the next stage.
1H NMR (400MHz, D2O) δ = 4.35(m, 1H), 2.17(d, 2H), 1.79(br, 1H), 1.42(t, 2H), 1.24(s, 6H), 1.19(s, 6H)。
2) Synthesis of N,2,2,6, 6-heptamethylpiperidine-4-ammonium chloride (IV):
adding 172g of 4-chloro-2, 2,6, 6-tetramethylpiperidine obtained in the previous stage into a 2L high-pressure reaction kettle, adding 500g of mixed solution of acetonitrile and toluene in a mass ratio of 1:1, carrying out nitrogen substitution, introducing 132g of trimethylamine, heating to 70 ℃, reacting for 8 hours, observing the pressure, cooling, decompressing and carrying out suction filtration to obtain 221g of white solid N, N, N,2,2,6, 6-heptamethylpiperidine-4-ammonium chloride, wherein the purity is 99.8% by HPLC (high performance liquid chromatography).
1H NMR (400MHz, D2O) δ = 3.88(t, 1H), 3.18(s, 9H),2.25(d, 2H), 1.52(t, 2H), 1.33(s, 6H), 1.32(s, 6H)。
3) Synthesis of N, N, N,2,2,6, 6-heptamethylpiperidinyloxy-4-ammonium chloride (I):
221g of N, N, N,2,6, 6-heptamethylpiperidine-4-ammonium chloride obtained in the last stage, 100g of water and 0.3g of magnesium hydroxide are put into a 2L four-neck round-bottom flask, 253g of 30% hydrogen peroxide is dropwise added after the temperature is raised to 55 ℃, the temperature is reduced and the filtration is carried out after the dropwise addition is finished and the reaction is carried out for 16 hours, the temperature is reduced and the filtration is carried out, the water is removed by reduced pressure distillation, 229g of orange solid N, N, N,2,2,6, 6-heptamethylpiperidinyloxy-4-ammonium chloride is obtained, and the purity is 99.3% by HPLC detection.
1H NMR (400MHz, D2O) δ = 3.79(t, 1H), 3.17(s, 9H), 2.26(d, 2H), 1.80(t, 2H), 1.30(s, 6H), 1.27(s, 6H)。
Example 2
1) Synthesis of 4-chloro-2, 2,6, 6-tetramethylpiperidine (III):
dissolving 1000g of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine in 3000g of toluene, cooling the temperature to 5 ℃, and dropwise adding 682g of phosphorus oxychloride into the reaction solution, wherein the temperature is controlled not to exceed 10 ℃ in the dropwise adding process; then slowly heating to 105 ℃, carrying out heat preservation reaction for 2h, cooling to 30 ℃, adding 2000g of water, stirring vigorously for 1h, adjusting the pH value to about 10, extracting with dichloromethane, drying with anhydrous magnesium sulfate, and carrying out rotary evaporation on the solvent to obtain 1076g of yellow liquid with the GC content of 97%, namely 4-chloro-2, 2,6, 6-tetramethylpiperidine, which is directly used in the next stage.
2) Synthesis of N, N, N,2,2,6, 6-heptamethylpiperidine-4-ammonium chloride (I):
adding 1076g of 4-chloro-2, 2,6, 6-tetramethylpiperidine obtained in the previous stage into a high-pressure reaction kettle, adding 1500g of acetonitrile and toluene in a mass ratio of 1:1, performing nitrogen replacement, introducing 670g of trimethylamine, heating to 80 ℃, reacting for 12 hours, observing the pressure, reducing the temperature, decompressing and filtering to obtain 1148g of white solid N, N, N,2,2,6, 6-heptamethylpiperidine-4-ammonium chloride, wherein the purity is 99.7% by HPLC (high performance liquid chromatography).
3) Synthesis of N, N, N,2,2,6, 6-heptamethylpiperidinyloxy-4-ammonium chloride (IV):
1148g of N, N, N,2,6, 6-heptamethylpiperidine-4-ammonium chloride, 1500g of water and 14g of magnesium hydroxide obtained in the previous stage are put into a four-neck round-bottom flask, 1400g of 30% hydrogen peroxide is dropwise added after the temperature is raised to 60 ℃, the temperature is kept for 18 hours after the dropwise addition reaction, the temperature is reduced, the filtration is carried out, the water is removed by reduced pressure distillation, and an orange solid N, N,2,2,6, 6-heptamethylpiperidinyloxy-4-ammonium chloride 1219g is obtained, and the purity is 99.6% by HPLC detection.
Example 3
1) Synthesis of 4-chloro-2, 2,6, 6-tetramethylpiperidine (III):
dissolving 800g of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine in 1200g of toluene, cooling the temperature to 5 ℃, and dropwise adding 540g of phosphorus oxychloride into the reaction solution, wherein the temperature is controlled not to exceed 10 ℃ in the dropwise adding process; then slowly heating to 100 ℃, keeping the temperature for reaction for 2h, cooling to 30 ℃, adding 600g of water, violently stirring for 1h, adjusting the pH value to about 10, extracting with dichloromethane, drying with anhydrous magnesium sulfate, and performing rotary evaporation on the solvent to obtain 861g of yellow liquid with the GC content of 97 percent, namely 4-chloro-2, 2,6, 6-tetramethylpiperidine, which is directly used in the next stage.
2) Synthesis of N, N, N,2,2,6, 6-heptamethylpiperidine-4-ammonium chloride (I):
adding 861g of 4-chloro-2, 2,6, 6-tetramethylpiperidine obtained in the previous stage into a high-pressure reaction kettle, adding 1200g of acetonitrile and toluene in a mass ratio of 1:1, performing nitrogen replacement, introducing 650g of trimethylamine, heating to 72 ℃, reacting for 10 hours, observing the pressure, reducing the temperature, relieving the pressure and performing suction filtration to obtain 910g of white solid N, N, N,2,2,6, 6-heptamethylpiperidine-4-ammonium chloride, wherein the purity is 99.3% by HPLC (high performance liquid chromatography).
3) Synthesis of N, N, N,2,2,6, 6-heptamethylpiperidinyloxy-4-ammonium chloride (IV):
861g of N, N, N,2,6, 6-heptamethylpiperidine-4-ammonium chloride obtained in the previous stage, 1200g of water and 10g of magnesium hydroxide are put into a four-neck round-bottom flask, the temperature is raised to 65 ℃, 1200g of 30% hydrogen peroxide is dropwise added, after the dropwise addition and the heat preservation reaction is finished for 17 hours, the temperature is reduced, the filtration is carried out, the water is removed by reduced pressure distillation, 910g of orange solid N, N, N,2,2,6, 6-heptamethylpiperidinyloxy-4-ammonium chloride is obtained, and the purity is 99.5% by HPLC.
The technical means disclosed in the invention scheme are not limited to the technical means disclosed in the above embodiments, but also include the technical scheme formed by any combination of the above technical features. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and such improvements and modifications are also considered to be within the scope of the present invention.
Claims (10)
1. A hindered amine quaternary ammonium salt is characterized in that the structural formula of the hindered amine quaternary ammonium salt is shown as the formula (I):
the preparation method of the hindered amine quaternary ammonium salt comprises the following steps:
s1: adding 4-hydroxy-2, 2,6, 6-tetramethylpiperidine shown in a formula II and phosphorus oxychloride into a solvent, and carrying out a displacement reaction to obtain 4-chloro-2, 2,6, 6-tetramethylpiperidine shown in a formula III;
s2: adding 4-chloro-2, 2,6, 6-tetramethylpiperidine and trimethylamine into a solvent, and carrying out nucleophilic substitution reaction to obtain N, N, N,2,2,6, 6-heptamethylpiperidine-4-ammonium chloride shown in a formula IV;
s3, adding N, N, N,2,2,6, 6-heptamethylpiperidine-4-ammonium chloride and hydrogen peroxide into a solvent, and carrying out oxidation reaction under the action of a catalyst to obtain N, N, N,2,2,6, 6-heptamethylpiperidinyloxy-4-ammonium chloride shown in the formula I;
2. the method for preparing hindered amine quaternary ammonium salt according to claim 1, wherein the molar ratio of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine to phosphorus oxychloride to solvent in step S1 is 1: 0.3-1.5: 0.5-30.
3. The method of claim 2, wherein the solvent for the displacement reaction in step S1 is one or more selected from acetonitrile, cyclohexane, benzene, toluene and xylene.
4. The method according to claim 1, wherein the temperature of the metathesis reaction in step S1 is 30-140 ℃, and the time of the metathesis reaction is 0.5-6 h.
5. The method for preparing the hindered amine quaternary ammonium salt according to claim 1, wherein the molar ratio of the 4-chloro-2, 2,6, 6-tetramethylpiperidine to the trimethylamine to the solvent in step S2 is 1: 0.5-10: 0.5-40.
6. The method for preparing the hindered amine quaternary ammonium salt according to claim 5, wherein the solvent for nucleophilic substitution reaction in the step S2 is one or more of acetonitrile, 1, 2-dichloroethane, benzene, toluene and xylene.
7. The method for preparing a hindered amine quaternary ammonium salt according to claim 1, wherein the temperature of the nucleophilic substitution reaction in step S2 is 30-140 ℃, and the time of the nucleophilic substitution reaction is 4-48 h.
8. The method for preparing a hindered amine quaternary ammonium salt according to claim 1, wherein the molar ratio of N,2,2,6, 6-heptamethylpiperidine-4-ammonium chloride, hydrogen peroxide, solvent and catalyst in the oxidation reaction in step S3 is 1: 1.5-8: 0.5-100: 0.003-0.1.
9. The method according to claim 8, wherein the solvent for the oxidation reaction of step S3 is water; the catalyst is one or more of magnesium hydroxide and magnesium sulfate.
10. The method for preparing the hindered amine quaternary ammonium salt according to claim 1, wherein the temperature of the oxidation reaction in the step S3 is 20-100 ℃, and the time of the oxidation reaction is 4-24 h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111082310.9A CN113831277A (en) | 2021-09-15 | 2021-09-15 | Preparation method of hindered amine quaternary ammonium salt |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111082310.9A CN113831277A (en) | 2021-09-15 | 2021-09-15 | Preparation method of hindered amine quaternary ammonium salt |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113831277A true CN113831277A (en) | 2021-12-24 |
Family
ID=78959610
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111082310.9A Pending CN113831277A (en) | 2021-09-15 | 2021-09-15 | Preparation method of hindered amine quaternary ammonium salt |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113831277A (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1281850A (en) * | 2000-06-30 | 2001-01-31 | 上海高桥石油化工公司精细化工厂 | Preparation method of 4-chloro-2,2,6,6-tetramethyl piperidine |
CN107721862A (en) * | 2017-10-17 | 2018-02-23 | 浙江工业大学 | The synthetic method of the adamantyl ammonium halide of N, N, N trimethyl 1 |
CN109803955A (en) * | 2016-08-12 | 2019-05-24 | 耶拿电池有限公司 | The method for being used to prepare 4- ammonium -2,2,6,6- tetraalkyl piperidine base salt |
CN111099941A (en) * | 2018-10-26 | 2020-05-05 | 中国科学院上海有机化学研究所 | Preparation method of alkyl nitrile compound |
-
2021
- 2021-09-15 CN CN202111082310.9A patent/CN113831277A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1281850A (en) * | 2000-06-30 | 2001-01-31 | 上海高桥石油化工公司精细化工厂 | Preparation method of 4-chloro-2,2,6,6-tetramethyl piperidine |
CN109803955A (en) * | 2016-08-12 | 2019-05-24 | 耶拿电池有限公司 | The method for being used to prepare 4- ammonium -2,2,6,6- tetraalkyl piperidine base salt |
CN107721862A (en) * | 2017-10-17 | 2018-02-23 | 浙江工业大学 | The synthetic method of the adamantyl ammonium halide of N, N, N trimethyl 1 |
CN111099941A (en) * | 2018-10-26 | 2020-05-05 | 中国科学院上海有机化学研究所 | Preparation method of alkyl nitrile compound |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Grice et al. | Chemical properties of metallocarboxylic acids of transition metals | |
KR101846111B1 (en) | Preparation Method of 1, 3, 6-Hexanetricarbonitrile | |
CN103930405A (en) | Method for preparing pentacyclic anion salt | |
CN112795943B (en) | Electrochemical synthesis method of 3, 4-dibromomaleimide | |
JP2017522265A (en) | Porphyrin molecular catalyst for selective electrochemical reduction of CO2 to CO | |
US20100256384A1 (en) | Method for producing purified ammonium salt of fluorinated bis-sulfonylimide | |
CN111041516B (en) | New preparation method of telmisartan intermediate of antihypertensive drug | |
CN104119243B (en) | A kind of energy-saving clean production method of iminodiethanoic acid | |
CN102190592B (en) | Synthetic method of methanamide compound | |
US20230312448A1 (en) | Formate production method, formic acid production method, and antifreezing agent production method | |
CN113831277A (en) | Preparation method of hindered amine quaternary ammonium salt | |
CN113501771B (en) | Preparation method of N- (2-aminoethyl) glycine derivative | |
KR20130102422A (en) | Novel visible light active graphene-based photocatalyst, method for regeneration of oxidoreductase cofactor and method for enzymatic production of formic acid from carbon dioxide using the same | |
CN109776540B (en) | Preparation method of sapropterin hydrochloride | |
JPH0782207A (en) | Production of fluorenone and oxidation catalyst used therein | |
CN101240425B (en) | Technique for preparing 2,2-dihydroxymethylpropionic acid by electrochemistry method | |
CN110002403A (en) | A kind of boron hydronitrogen sodium salt Na [BH3NH2BH3] synthetic method | |
CN115414965B (en) | Preparation method and application of terpyridyl supermolecular photocatalyst | |
CN111826679B (en) | Preparation method and electrocatalysis application of chitosan/ordered mesoporous carbon electrode material | |
CN114195704A (en) | Preparation method of TEMPO-quaternary ammonium salt for water-based flow battery | |
Burton et al. | Designer Ligands. Part 5.1 Synthesis of Polydentate Biphenyl Ligands | |
CN113735761B (en) | Preparation method of viologen compound for aqueous-phase organic flow battery | |
CN110452139B (en) | Preparation method of 2-methyl-3-bromo-6-methylsulfonyl benzonitrile | |
CN113666864A (en) | Preparation method of TEMPO-4-ammonium chloride | |
JPS62294191A (en) | Production of alkoxy acetate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20211224 |
|
WD01 | Invention patent application deemed withdrawn after publication |