CN113603626A - Preparation method of free radical initiator and application of free radical initiator in oxidation reaction - Google Patents
Preparation method of free radical initiator and application of free radical initiator in oxidation reaction Download PDFInfo
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- CN113603626A CN113603626A CN202111004416.7A CN202111004416A CN113603626A CN 113603626 A CN113603626 A CN 113603626A CN 202111004416 A CN202111004416 A CN 202111004416A CN 113603626 A CN113603626 A CN 113603626A
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- radical initiator
- hydroxylamine
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- tetrachlorophthalimide
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- 239000003999 initiator Substances 0.000 title claims abstract description 40
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 32
- 150000003254 radicals Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 19
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- UTRBHXSKVVPTLY-UHFFFAOYSA-N 4,5,6,7-tetrachloro-2-hydroxyisoindole-1,3-dione Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C2=C1C(=O)N(O)C2=O UTRBHXSKVVPTLY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012046 mixed solvent Substances 0.000 claims abstract description 10
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 7
- -1 N-hydroxy tetrachlorophthalimide radical Chemical class 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000012043 crude product Substances 0.000 claims abstract description 3
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 38
- 239000003054 catalyst Substances 0.000 claims description 26
- YHIYSPGAOWANSA-UHFFFAOYSA-N 2-chloro-1-methyl-4-methylsulfonylbenzene Chemical compound CC1=CC=C(S(C)(=O)=O)C=C1Cl YHIYSPGAOWANSA-UHFFFAOYSA-N 0.000 claims description 23
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 16
- 229910001882 dioxygen Inorganic materials 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 14
- CTTWSFIIFMWHLQ-UHFFFAOYSA-N 2-chloro-4-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=C(C(O)=O)C(Cl)=C1 CTTWSFIIFMWHLQ-UHFFFAOYSA-N 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 claims description 8
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005750 Copper hydroxide Substances 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 2
- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
- 239000013460 polyoxometalate Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 21
- 239000000203 mixture Substances 0.000 description 21
- 229960000583 acetic acid Drugs 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 17
- 239000000706 filtrate Substances 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000012362 glacial acetic acid Substances 0.000 description 16
- 238000004064 recycling Methods 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 239000005457 ice water Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- NZSLSTXKPQAVHL-UHFFFAOYSA-N 2-$l^{1}-oxidanylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N([O])C(=O)C2=C1 NZSLSTXKPQAVHL-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 239000011572 manganese Chemical class 0.000 description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 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 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- WSKSHHDHKIAMKX-UHFFFAOYSA-N 4,5,6-trichloro-2-benzofuran-1,3-dione Chemical compound ClC1=C(Cl)C(Cl)=CC2=C1C(=O)OC2=O WSKSHHDHKIAMKX-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002740 effect on eyes Effects 0.000 description 1
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- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
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- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
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- 230000000638 stimulation Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
- C07B61/02—Generation of organic free radicals; Organic free radicals per se
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of a free radical initiator, which comprises the steps of feeding hydroxylamine raw material, inorganic base and water according to a proportion, carrying out acid-base neutralization reaction at 0-25 ℃, and dissociating hydroxylamine; adding tetrachlorophthalic anhydride, stirring at room temperature for reaction for 0.5-2h, then reacting at 60-95 ℃ for 4-12h, washing with water, and drying at 60-80 ℃ for 10-24h to obtain a crude product of N-hydroxy tetrachlorophthalimide; recrystallizing the crude N-hydroxy tetrachlorophthalimide in a mixed solvent of toluene and ethanol, filtering, and drying at 60-80 ℃ to obtain the N-hydroxy tetrachlorophthalimide radical initiator. The method has the advantages of simple adopted raw materials, easily controlled conditions, green and environment-friendly preparation process and good preparation repeatability, and the free radical initiator is used in the oxidation reaction to obtain products with high purity and high yield, and the products obtained after being recycled for multiple times still have high separation yield and purity.
Description
Technical Field
The invention relates to the technical field of preparation of free radical initiators, in particular to a recyclable free radical initiator and application thereof in oxidation reaction.
Background
The selective oxidation of alkylbenzenes with molecular oxygen is a very important class of selective oxidation reactions for the production of bulk and fine chemicals, such as benzoic acid, terephthalic acid, and the like. At present, transition metals (such as organic acid salts of cobalt, manganese and the like) and oxidation promoters (bromides) are widely used as catalysts in industry, and the catalytic system needs to be carried out under the conditions of high temperature and high pressure, so that the energy consumption is high, the price is high, equipment is corroded, and environmental pollution to a certain extent is caused.
In recent years, the application of N-hydroxyphthalimide (NHPI) and its analogues in organic oxidation reactions has attracted great attention. They are widely used in oxidation reactions of aromatic hydrocarbons, alkanes, alkenes, alkynes, alcohols, ethers, amides and acetals as electrochemical oxidation substrates or catalysts. In particular, the catalytic oxidation of many organic compounds can be achieved under mild conditions of atmospheric pressure and 25-100 ℃ with the aid of transition metal salts.
However, a major limitation of NHPI applications is that N-hydroxyphthalimide radicals (PINO) undergo self-decomposition under certain conditions, especially at high temperatures. The literature (Guangzhou chemical, 2016, 44 (18): 37-40) reports that decomposition of PINO occurs primarily at the C-N bond. In which the yield of trimer produced by decomposition polymerization of PINO was 71%, phthalic acid and phthalic anhydride were also found as by-products. Therefore, when the NHPI compound is repeatedly used, it is necessary to supplement the deteriorated catalyst, which increases the production cost to some extent. Therefore, the development of simple, low cost NHPI alternatives and their improved recovery, recycle are key to the use of this catalytic system for bulk chemical production.
N-hydroxy-Tetrachlorophthalimide (TCNHPI) is used as one of substituted N-hydroxy-phthalimides (NHPI), and as four hydrogen atoms on a benzene ring of the NHPI are substituted by four chlorine atoms, the chlorine atoms and the benzene ring generate P-pi conjugation, the stability and the reaction activity of N-OH are greatly increased. There are few publications and patents on the synthesis of TCNHPI. The document (molecular catalysis, 2007, 21 (2): 97-98) reports that TCNHPI is prepared by using tetrachlorophthalic anhydride and hydroxylamine hydrochloride as substrates and triethylamine as an accelerator, wherein the triethylamine belongs to organic amines, has strong basicity, is toxic, has strong stimulation effect on eyes and upper respiratory tracts after being inhaled in a small amount, belongs to an organic compound which is difficult to degrade, is expensive, and triethylamine wastewater belongs to toxic wastewater, has high N/C ratio and is difficult to treat.
The invention aims to overcome the technical defects and provides a free radical initiator capable of being recycled in molecular oxygen oxidation reaction, and particularly relates to a method for preparing TCNHPI (trichlorophthalic anhydride) from tetrachlorophthalic anhydride and recycling performance of TCNHPI in the preparation of 2-chloro-4-methylsulfonylbenzoic acid by molecular oxygen oxidation of 2-chloro-4-methylsulfonyltoluene.
Disclosure of Invention
In view of the above, the first aspect of the present invention provides a recyclable radical initiator TCNHPI, wherein four hydrogen atoms on the benzene ring of NHPI are replaced by four chlorine atoms, and the chlorine atoms and the benzene ring undergo P-pi conjugation, such that the stability and reactivity of N-OH are greatly increased.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of preparing a free radical initiator comprising the steps of:
(1) feeding hydroxylamine raw material, inorganic base and water in proportion, and carrying out acid-base neutralization reaction for 1-4h at 0-25 ℃ to dissociate hydroxylamine and avoid volatilization loss of hydroxylamine;
(2) adding tetrachlorophthalic anhydride, stirring at room temperature for reaction for 0.5-4h, then reacting at 50-100 ℃ for 4-24h, washing with water, and drying at 60-80 ℃ for 8-36h to obtain a crude product of N-hydroxy tetrachlorophthalimide; although tetrachlorophthalic anhydride and hydroxylamine can react at room temperature, the reaction rate is slow, resulting in lower yields of TCNHPI; the later temperature rise can accelerate the reaction, so that the reaction is more thorough, and meanwhile, the volatilization of hydroxylamine and the ineffective decomposition of tetrachlorophthalic anhydride caused by the direct reaction at high temperature are avoided;
(3) recrystallizing the crude N-hydroxy tetrachlorophthalimide in a mixed solvent of toluene and ethanol, filtering, and drying at 60-80 ℃ for 8-36h to obtain the refined N-hydroxy tetrachlorophthalimide radical initiator.
Preferably, in the above one method for producing a radical initiator, the molar ratio of the hydroxylamine starting material, the inorganic base and water is 1: (1.0-6.0): (100-1500), preferably 1: (1.1-3.0): (600-1000).
If the amount of water is too low, the solution is easily thickened in the preparation process, and mass and heat transfer are not facilitated; the use of too much water results in a low concentration of reactants, which affects the progress of the reaction and reduces the yield of N-hydroxy tetrachlorophthalimide.
Preferably, in one of the above-mentioned methods for producing a radical initiator, the hydroxylamine starting material is hydroxylamine sulfate or hydroxylamine hydrochloride.
Preferably, in the above preparation method of one radical initiator, the inorganic base is one or more of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, lithium hydroxide, magnesium hydroxide, zinc hydroxide and copper hydroxide, and preferably sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.
Preferably, in one of the above-mentioned processes for the preparation of a free radical initiator, the ratio of free hydroxylamine to tetrachlorophthalic anhydride is (1.0-1.5): 1, preferably (1.1-1.3): 1.
preferably, in the above one of the preparation methods of the radical initiator, the reaction temperature in the step (2) is 70 to 90 ℃ and the reaction time is 6 to 12 hours.
The invention also discloses an application of the free radical initiator prepared by the method in oxidation reaction, wherein the oxidation reaction is to prepare 2-chloro-4-methylsulfonylbenzoic acid by molecular oxygen oxidation of 2-chloro-4-methylsulfonyltoluene.
Preferably, in the application of the free radical initiator in the oxidation reaction, 2-chloro-4-methylsulfonyl toluene is used as a substrate, acetonitrile or acetic acid is used as a solvent, oxygen is used as an oxidant, N-hydroxy-tetrachlorophthalimide is used as an initiator, and a supported multi-metal oxide is used as a catalyst to prepare 2-chloro-4-methylsulfonylbenzoic acid at a certain temperature and under a certain pressure
According to the technical scheme, compared with the prior art, the invention discloses the recyclable free radical initiator TCNHPI and the application thereof in the oxidation reaction, and the recyclable free radical initiator TCNHPI has the following beneficial effects: the method has the advantages of simple adopted raw materials, easily controlled conditions, green and environment-friendly preparation process and good preparation repeatability, and the free radical initiator is used in the oxidation reaction to obtain products with high purity and high yield, and the products obtained after being recycled for multiple times still have high separation yield and purity.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a Fourier transform infrared spectrogram of TCNHPI obtained in example 1 and example 4 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the supported multi-metal oxide catalyst in the following examples was prepared by the following steps:
washing rice hull to remove mud, oven drying at 50 deg.C, grinding, sieving to obtain powder of 60 meshes above, collecting a certain amount of 60 meshes rice hull powder, activating at 105 deg.C for 4 hr (SiO)2Content 20.5%), 50g are weighed for use(ii) a In accordance with MnO2In an amount of 15%, WO3Supported in an amount of 10%, a metal ion assistant (Co)2+、Mg2+、Ca2+、Na+) Preparing aqueous solution of manganese acetate, phosphotungstic acid, cobalt acetate, magnesium acetate, calcium acetate and sodium acetate with the molar ratio of 1 percent to Mn, then impregnating rice hull powder by adopting an isometric impregnation method to obtain a precursor of the catalyst, aging the precursor for 24 hours at room temperature, drying the precursor at 110 ℃, grinding, and roasting at 600 ℃ for 6 hours to obtain the supported multi-metal oxide catalyst, wherein the molar ratio of the supported multi-metal oxide catalyst to Mn is 0.07 percent MgO-0.10 percent CaO-0.11 percent Na2O-0.13％CoO-10％WO3-15％MnO2/SiO2。
Example 1
Under the condition of ice-water bath, 2.2g of hydroxylamine sulfate, 2.2g of anhydrous sodium carbonate and 150mL of water are added into a flask and stirred to be dissolved, the mixture is reacted for 1.5h, then 6.0g of tetrachlorophthalic anhydride is added, the mixture is stirred and reacted for 1.0h at room temperature, then the temperature is raised to 85 ℃, the reaction is continued for 12h, after the reaction is finished, the mixture is cooled, filtered, washed by water, dried for 12h at 60 ℃, then mixed solvent of toluene and ethanol (1:1) is adopted for recrystallization, filtered, and dried for 12h at 60 ℃, so that light brown TCNHPI is obtained, the melting point is 238 ℃, the yield is 90.4%, and the purity is 99.1%.
The TCNHPI prepared by the embodiment is used as an initiator, the supported multi-metal oxide is used as a catalyst, glacial acetic acid is used as a solvent, and the recycling performance of catalyzing the molecular oxygen oxidation of the 2-chloro-4-methylsulfonyl toluene is evaluated according to the following method:
placing 20.5g of 2-chloro-4-methylsulfonyltoluene (100mmol), 3.0g of TCNHPI, 2.1g of supported multi-metal oxide and 150mL of glacial acetic acid in a high-pressure reaction kettle, wherein the oxygen pressure is 0.2MPa, the rotating speed of a stirrer is 200r/min, and reacting for 3h at 90 ℃; after the reaction is finished, cooling, discharging and filtering. Adding NaHCO into the filter cake3Then the catalyst and the filtrate are obtained after the treatment in the aqueous solution. Adjusting the pH of the filtrate to 2-3 with 6.0mol/L hydrochloric acid aqueous solution to generate a large amount of white crystals, filtering, and drying at 60 ℃ to obtain 2-chloro-4-methylsulfonylbenzoic acid with the yield of 95.3% and the high performance liquid chromatography purity of 98.4%.
Example 2
Under the condition of ice-water bath, 2.2g of hydroxylamine sulfate, 1.6g of anhydrous sodium carbonate and 240mL of water are added into a flask and stirred to be dissolved, the mixture is reacted for 3.0h, then 6.0g of tetrachlorophthalic anhydride is added, the mixture is stirred and reacted for 2.0h at room temperature, then the temperature is raised to 90 ℃, the reaction is continued for 8h, after the reaction is finished, the mixture is cooled, filtered, washed by water, dried for 12h at 60 ℃, recrystallized by adopting a mixed solvent of toluene and ethanol (1:1), filtered, and dried for 24h at 60 ℃, so that light brown TCNHPI is obtained, the melting point is 239 ℃, the yield is 89.0%, and the purity is 99.4%.
The TCNHPI prepared by the embodiment is used as an initiator, the supported multi-metal oxide is used as a catalyst, glacial acetic acid is used as a solvent, and the recycling performance of catalyzing the molecular oxygen oxidation of the 2-chloro-4-methylsulfonyl toluene is evaluated according to the following method:
placing 20.5g of 2-chloro-4-methylsulfonyltoluene (100mmol), 3.0g of TCNHPI, 2.1g of supported multi-metal oxide and 150mL of glacial acetic acid in a high-pressure reaction kettle, wherein the oxygen pressure is 0.2MPa, the rotating speed of a stirrer is 200r/min, and reacting for 3h at 90 ℃; after the reaction is finished, cooling, discharging and filtering. Adding NaHCO into the filter cake3Then the catalyst and the filtrate are obtained after the treatment in the aqueous solution. Adjusting the pH of the filtrate to 2-3 with 6.0mol/L hydrochloric acid aqueous solution to generate a large amount of white crystals, filtering, and drying at 60 ℃ to obtain 2-chloro-4-methylsulfonylbenzoic acid with the yield of 94.6% and the high performance liquid chromatography purity of 99.0%.
Example 3
Under the condition of ice-water bath, 1.9g of hydroxylamine sulfate, 1.7g of anhydrous sodium carbonate and 180mL of water are added into a flask and stirred to be dissolved, the mixture is reacted for 2.0h, then 6.0g of tetrachlorophthalic anhydride is added, the mixture is stirred and reacted for 4.0h at room temperature, then the temperature is raised to 75 ℃, the reaction is continued for 16h, after the reaction is finished, the mixture is cooled, filtered, washed by water and dried for 12h at 60 ℃, then mixed solvent of toluene and ethanol (1:1) is adopted for recrystallization, the filtration is carried out, and the drying is carried out for 12h at 70 ℃, so that light brown TCNHPI is obtained, the melting point is 237 ℃, the yield is 89.6%, and the purity is 98.8%.
The recycling performance of the supported multi-metal oxide as an initiator, the supported multi-metal oxide as a catalyst and glacial acetic acid as a solvent for catalyzing the molecular oxygen oxidation of 2-chloro-4-methylsulfonyltoluene is evaluated, and the method is specifically carried out as follows:
20.5g of 2-chloro-4-methylsulfonyltoluene (100mmol), 3.0g of TCNHPI, 2.1g of supported multi-metal oxide and 150mL of glacial acetic acid are placed in a high-pressure reaction kettle, the oxygen pressure is 0.2MPa, the rotating speed of a stirrer is 200r/min, the reaction is carried out for 3h at 90 ℃, and after the reaction is finished, the temperature is reduced, the material is discharged, and the filtration is carried out. Adding NaHCO into the filter cake3Then the catalyst and the filtrate are obtained after the treatment in the aqueous solution. Adjusting the pH of the filtrate to 2-3 with 6.0mol/L hydrochloric acid aqueous solution to generate a large amount of white crystals, filtering, and drying at 60 ℃ to obtain 2-chloro-4-methylsulfonylbenzoic acid with the yield of 94.2% and the high performance liquid chromatography purity of 98.0%.
Example 4
Under the condition of ice-water bath, 1.8g of hydroxylamine hydrochloride, 2.5g of sodium bicarbonate and 270mL of water are added into a flask and stirred for dissolution, the mixture is reacted for 3.0h, then 6.0g of tetrachlorophthalic anhydride is added, the mixture is stirred for reaction for 3.0h at room temperature, then the temperature is raised to 80 ℃, the reaction is continued for 24h, after the reaction is finished, the mixture is cooled, filtered, washed with water and dried for 12h at 70 ℃, then mixed solvent of toluene and ethanol (1:1) is adopted for recrystallization, filtered and dried for 12h at 70 ℃, light brown TCNHPI is obtained, the melting point is 238 ℃, the yield is 87.6%, and the purity is 98.3%.
The TCNHPI prepared by the embodiment is used as an initiator, the supported multi-metal oxide is used as a catalyst, glacial acetic acid is used as a solvent, and the recycling performance of catalyzing the molecular oxygen oxidation of the 2-chloro-4-methylsulfonyl toluene is evaluated according to the following method:
placing 20.5g of 2-chloro-4-methylsulfonyltoluene (100mmol), 3.0g of TCNHPI, 2.1g of supported multi-metal oxide and 150mL of glacial acetic acid in a high-pressure reaction kettle, wherein the oxygen pressure is 0.2MPa, the rotating speed of a stirrer is 200r/min, and reacting for 3h at 90 ℃; after the reaction is finished, cooling, discharging and filtering. Adding NaHCO into the filter cake3Then the catalyst and the filtrate are obtained after the treatment in the aqueous solution. Adjusting the pH of the filtrate to 2-3 with 6.0mol/L hydrochloric acid aqueous solution to generate a large amount of white crystals, filtering,Drying at 60 ℃ to obtain the 2-chloro-4-methylsulfonylbenzoic acid, wherein the yield is 92.7 percent and the high performance liquid chromatography purity is 98.9 percent.
Example 5
Under the condition of ice-water bath, 2.1g of hydroxylamine sulfate, 2.1g of potassium carbonate and 180mL of water are added into a flask and stirred for dissolution, the mixture is reacted for 3.0h, then 6.0g of tetrachlorophthalic anhydride is added, the mixture is stirred and reacted for 3.0h at room temperature, then the temperature is raised to 80 ℃, the reaction is continued for 24h, after the reaction is finished, the mixture is cooled, filtered, washed with water, dried for 12h at 70 ℃, recrystallized by using a mixed solvent of toluene and ethanol (1:1), filtered and dried for 12h at 80 ℃, so that light brown TCNHPI is obtained, the melting point is 238 ℃, the yield is 90.2%, and the purity is 99.5%.
The TCNHPI prepared by the embodiment is used as an initiator, the supported multi-metal oxide is used as a catalyst, glacial acetic acid is used as a solvent, and the recycling performance of catalyzing the molecular oxygen oxidation of the 2-chloro-4-methylsulfonyl toluene is evaluated according to the following method:
placing 20.5g of 2-chloro-4-methylsulfonyltoluene (100mmol), 3.0g of TCNHPI, 2.1g of supported multi-metal oxide and 150mL of glacial acetic acid in a high-pressure reaction kettle, wherein the oxygen pressure is 0.2MPa, the rotating speed of a stirrer is 200r/min, and reacting for 3h at 90 ℃; after the reaction is finished, cooling, discharging and filtering. Adding NaHCO into the filter cake3Then the catalyst and the filtrate are obtained after the treatment in the aqueous solution. Adjusting the pH of the filtrate to 2-3 with 6.0mol/L hydrochloric acid aqueous solution to generate a large amount of white crystals, filtering, and drying at 60 ℃ to obtain 2-chloro-4-methylsulfonylbenzoic acid with the yield of 93.9% and the high performance liquid chromatography purity of 98.3%.
Example 6
Under the condition of ice-water bath, 2.1g of hydroxylamine sulfate, 3.8g of potassium bicarbonate and 210mL of water are added into a flask and stirred to be dissolved, the mixture is reacted for 3.0h, then 6.0g of tetrachlorophthalic anhydride is added, the mixture is stirred and reacted for 3.0h at room temperature, then the temperature is raised to 80 ℃, the reaction is continued for 24h, after the reaction is finished, the mixture is cooled, filtered, washed with water and dried for 12h at 70 ℃, then mixed solvent of toluene and ethanol (1:1) is adopted for recrystallization, filtered and dried for 10h at 80 ℃, light brown TCNHPI is obtained, the melting point is 238 ℃, the yield is 90.1%, and the purity is 99.5%.
The TCNHPI prepared by the embodiment is used as an initiator, the supported multi-metal oxide is used as a catalyst, glacial acetic acid is used as a solvent, and the recycling performance of catalyzing the molecular oxygen oxidation of the 2-chloro-4-methylsulfonyl toluene is evaluated according to the following method:
placing 20.5g of 2-chloro-4-methylsulfonyltoluene (100mmol), 3.0g of TCNHPI, 2.1g of supported multi-metal oxide and 150mL of glacial acetic acid in a high-pressure reaction kettle, wherein the oxygen pressure is 0.2MPa, the rotating speed of a stirrer is 200r/min, and reacting for 3h at 90 ℃; after the reaction is finished, cooling, discharging and filtering. Adding NaHCO into the filter cake3Then the catalyst and the filtrate are obtained after the treatment in the aqueous solution. Adjusting the pH of the filtrate to 2-3 with 6.0mol/L hydrochloric acid aqueous solution to generate a large amount of white crystals, filtering, and drying at 60 ℃ to obtain 2-chloro-4-methylsulfonylbenzoic acid with the yield of 93.9% and the high performance liquid chromatography purity of 98.3%.
Comparative example 1
Under the condition of ice-water bath, 4.4g of hydroxylamine sulfate, 4.4g of anhydrous sodium carbonate and 300mL of water are added into a flask and stirred to be dissolved, the mixture is reacted for 1.5h, then 12.0g of tetrachlorophthalic anhydride is added, the mixture is stirred and reacted for 48h at room temperature, after the reaction is finished, the mixture is cooled, filtered, washed by water, dried for 12h at 60 ℃, then mixed solvent of toluene and ethanol (1:1) is adopted for recrystallization, filtered and dried for 12h at 60 ℃, and light brown TCNHPI with the melting point of 236 ℃, the yield of 28.5 percent and the purity of 90.2 percent is obtained.
The TCNHPI prepared by the embodiment is used as an initiator, the supported multi-metal oxide is used as a catalyst, glacial acetic acid is used as a solvent, and the recycling performance of catalyzing the molecular oxygen oxidation of the 2-chloro-4-methylsulfonyl toluene is evaluated according to the following method:
placing 20.5g of 2-chloro-4-methylsulfonyltoluene (100mmol), 3.0g of TCNHPI, 2.1g of supported multi-metal oxide and 150mL of glacial acetic acid in a high-pressure reaction kettle, wherein the oxygen pressure is 0.2MPa, the rotating speed of a stirrer is 200r/min, and reacting for 3h at 90 ℃; after the reaction is finished, cooling, discharging and filtering. Adding NaHCO into the filter cake3Then the catalyst and the filtrate are obtained after the treatment in the aqueous solution. Using 6.0mol/L of filtrate obtained in the previous stepAdjusting the pH of the filtrate to 2-3 with hydrochloric acid aqueous solution to generate a large amount of white crystals, filtering, and drying at 60 deg.C to obtain 2-chloro-4-methylsulfonylbenzoic acid with yield of 75.3% and high performance liquid chromatography purity of 96.4%.
It can be seen that the reaction of tetrachlorophthalic anhydride with hydroxylamine proceeds at room temperature, but the reaction rate is slow, the yield of TCNHPI is low and the purity is not high, as compared to example 1. The later temperature rise enables the reaction to be more thorough, the yield of TCNHPI is greatly improved, and the catalyst has good catalytic performance in the molecular oxygen oxidation reaction of 2-chloro-4-methylsulfonyl toluene.
Comparative example 2
The recycling performance of catalyzing the molecular oxygen oxidation of 2-chloro-4-methylsulfonyl toluene by adopting a commercially available NHPI as an initiator, the supported multi-metal oxide as a catalyst and glacial acetic acid as a solvent is evaluated, and the method is specifically carried out according to the following steps:
20.5g of 2-chloro-4-methylsulfonyltoluene (100mmol), 1.6g of NHPI, 2.1g of supported multi-metal oxide and 150mL of glacial acetic acid are placed in a high-pressure reaction kettle, the oxygen pressure is 0.2MPa, the rotating speed of a stirrer is 200r/min, the reaction is carried out for 3h at 90 ℃, and after the reaction is finished, the temperature is reduced, the material is discharged, and the suction filtration is carried out. Adding NaHCO into the filter cake3Then the catalyst and the filtrate are obtained after the treatment in the aqueous solution. Adjusting the pH of the filtrate to 2-3 with 6.0mol/L hydrochloric acid aqueous solution to generate a large amount of white crystals, filtering, and drying at 60 ℃ to obtain 2-chloro-4-methylsulfonylbenzoic acid with the yield of 91.7% and the high performance liquid chromatography purity of 83.6%.
Compared with examples 1-6, the comparative example shows that NHPI has higher catalytic activity in the molecular oxygen oxidation reaction of 2-chloro-4-methylsulfonyltoluene, but the purity of the product is lower, which indicates that NHPI has poor stability in the reaction process and is decomposed to generate a byproduct.
Test group 1
Test set 1 is presented to illustrate the recycling properties of the initiator obtained in example 1. The mother liquors (containing TCNHPI and NHPI) recovered in example 1 and comparative example 2 were subjected to the molecular oxygen oxidation reactions in example 1 and comparative example 2, respectively, and when the set of the mother liquors was repeated to compensate for the loss of the operation process, 2% of fresh initiator was added, and the catalytic results are shown in Table 1.
TABLE 1 recycle Properties of the initiators in example 1 and comparative example 1
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. For the scheme disclosed by the embodiment, the scheme corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A method for preparing a free radical initiator, comprising the steps of:
(1) feeding hydroxylamine raw material, inorganic base and water according to a proportion, and carrying out acid-base neutralization reaction for 1-4h at the temperature of 0-25 ℃ to free hydroxylamine;
(2) adding tetrachlorophthalic anhydride, stirring at room temperature for reaction for 0.5-4h, then reacting at 50-100 ℃ for 4-24h, washing with water, and drying at 60-80 ℃ for 8-36h to obtain a crude product of N-hydroxy tetrachlorophthalimide;
(3) recrystallizing the crude N-hydroxy tetrachlorophthalimide in a mixed solvent of toluene and ethanol, filtering, and drying at 60-80 ℃ to obtain the refined N-hydroxy tetrachlorophthalimide radical initiator.
2. The method according to claim 1, wherein the molar ratio of the hydroxylamine starting material to the inorganic base to the water is 1: (1.0-6.0): (100-1500).
3. The method according to claim 1, wherein the hydroxylamine is selected from the group consisting of hydroxylamine sulfate and hydroxylamine hydrochloride.
4. The method of claim 1, wherein the inorganic base is one or more of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, lithium hydroxide, magnesium hydroxide, zinc hydroxide, and copper hydroxide.
5. The method of claim 1, wherein the ratio of free hydroxylamine to tetrachlorophthalic anhydride is (1.0-1.5): 1.
6. the method according to claim 1, wherein the liquid-solid ratio of water to tetrachlorophthalic anhydride is 15 to 50 mL/g.
7. Use of a radical initiator prepared according to any one of claims 1 to 6 in an oxidation reaction for the molecular oxygen oxidation of 2-chloro-4-methylsulfonyltoluene to prepare 2-chloro-4-methylsulfonylbenzoic acid.
8. The application of the free radical initiator in oxidation reaction as claimed in claim 7, wherein 2-chloro-4-methylsulfonyltoluene is used as a substrate, acetonitrile or acetic acid is used as a solvent, oxygen is used as an oxidant, N-hydroxy-tetrachlorophthalimide is used as an initiator, and a supported polyoxometalate is used as a catalyst to prepare 2-chloro-4-methylsulfonylbenzoic acid at a certain temperature and pressure.
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Application publication date: 20211105 |