CN114230468A - Method for catalytic synthesis of nitrobenzaldehyde - Google Patents
Method for catalytic synthesis of nitrobenzaldehyde Download PDFInfo
- Publication number
- CN114230468A CN114230468A CN202110883472.6A CN202110883472A CN114230468A CN 114230468 A CN114230468 A CN 114230468A CN 202110883472 A CN202110883472 A CN 202110883472A CN 114230468 A CN114230468 A CN 114230468A
- Authority
- CN
- China
- Prior art keywords
- reaction
- nitrotoluene
- nitrobenzaldehyde
- reactor
- sba
- 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
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000013335 mesoporous material Substances 0.000 claims abstract description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 21
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 239000000010 aprotic solvent Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 5
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 17
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 11
- 230000002194 synthesizing effect Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 7
- 238000001308 synthesis method Methods 0.000 abstract description 7
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- -1 methyl free radical Chemical class 0.000 abstract description 4
- 230000026030 halogenation Effects 0.000 abstract 1
- 238000005658 halogenation reaction Methods 0.000 abstract 1
- 238000003541 multi-stage reaction Methods 0.000 abstract 1
- 239000012074 organic phase Substances 0.000 description 33
- 238000005406 washing Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 230000007935 neutral effect Effects 0.000 description 22
- 239000000047 product Substances 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000012071 phase Substances 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000005119 centrifugation Methods 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 11
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- ZETIVVHRRQLWFW-UHFFFAOYSA-N 3-nitrobenzaldehyde Chemical class [O-][N+](=O)C1=CC=CC(C=O)=C1 ZETIVVHRRQLWFW-UHFFFAOYSA-N 0.000 description 4
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical class [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000006396 nitration reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- XAWCLWKTUKMCMO-UHFFFAOYSA-N 2-nitroethylbenzene Chemical compound [O-][N+](=O)CCC1=CC=CC=C1 XAWCLWKTUKMCMO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- BVJSGOYEEDZAGW-UHFFFAOYSA-N [chloro(nitro)methyl]benzene Chemical compound [O-][N+](=O)C(Cl)C1=CC=CC=C1 BVJSGOYEEDZAGW-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- XUZLXCQFXTZASF-UHFFFAOYSA-N nitro(phenyl)methanol Chemical compound [O-][N+](=O)C(O)C1=CC=CC=C1 XUZLXCQFXTZASF-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BXCBUWKTXLWPSB-UHFFFAOYSA-N 1-(chloromethyl)-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1CCl BXCBUWKTXLWPSB-UHFFFAOYSA-N 0.000 description 1
- APGGSERFJKEWFG-UHFFFAOYSA-N 1-(chloromethyl)-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(CCl)=C1 APGGSERFJKEWFG-UHFFFAOYSA-N 0.000 description 1
- YVLNDCLPPGIRCP-UHFFFAOYSA-N 2-nitro-3-phenylprop-2-enoic acid Chemical compound OC(=O)C([N+]([O-])=O)=CC1=CC=CC=C1 YVLNDCLPPGIRCP-UHFFFAOYSA-N 0.000 description 1
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 1
- BWWHTIHDQBHTHP-UHFFFAOYSA-N 2-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=CC=C1C(Cl)=O BWWHTIHDQBHTHP-UHFFFAOYSA-N 0.000 description 1
- PIAOLBVUVDXHHL-UHFFFAOYSA-N 2-nitroethenylbenzene Chemical compound [O-][N+](=O)C=CC1=CC=CC=C1 PIAOLBVUVDXHHL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 206010062717 Increased upper airway secretion Diseases 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 206010023644 Lacrimation increased Diseases 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- JBDGDEWWOUBZPM-XYPYZODXSA-N ambroxol Chemical compound NC1=C(Br)C=C(Br)C=C1CN[C@@H]1CC[C@@H](O)CC1 JBDGDEWWOUBZPM-XYPYZODXSA-N 0.000 description 1
- 229960005174 ambroxol Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 230000004317 lacrimation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- KGCNHWXDPDPSBV-UHFFFAOYSA-N p-nitrobenzyl chloride Chemical compound [O-][N+](=O)C1=CC=C(CCl)C=C1 KGCNHWXDPDPSBV-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 208000026435 phlegm Diseases 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for catalytically synthesizing nitrobenzaldehyde, which is an atom economic method for synthesizing nitrobenzaldehyde with high selectivity by catalyzing molecular oxygen and nitrotoluene to carry out oxidation reaction by using an SBA-15 mesoporous material, wherein an oxidized substrate is prepared into a solution in a solvent or a substrate raw material solvent, and the SBA-15 mesoporous material is catalyzed to act on molecular oxygen under certain reaction temperature and pressure conditions to enable the substrate to carry out side chain methyl free radical oxidation reaction to synthesize the nitrobenzaldehyde substance. The method is used for replacing the traditional industrial synthesis method, namely, through multi-step reactions such as nitrotoluene side chain halogenation, hydrolysis, oxidation and the like, the atom utilization rate of the synthesis reaction is improved, energy is saved, emission is reduced, and the method has industrial application development sustainability.
Description
One, the technical field
The invention relates to a method for catalytically synthesizing nitrobenzaldehyde, in particular to an atom economic method for realizing high-selectivity synthesis of nitrobenzaldehyde by catalyzing molecular oxygen and nitrotoluene to perform oxidation reaction by using an SBA-15 mesoporous material.
Second, background Art
Nitrobenzaldehyde having the formula C7H5NO3The relative molecular mass is 151.1, three isomers of o-, m-and p-nitrobenzaldehyde exist, as shown in figure 1, the product is a yellowish solid which is insoluble in water and easily soluble in organic solvents such as aromatic hydrocarbon, halogenated hydrocarbon, alcohol, ether and ester.
Nitrobenzaldehyde is an important drug intermediate and a multipurpose organic functional material, is mainly used for synthesizing a drug for preventing and treating hypertension and cardiovascular diseases, such as the flat class, and the like, and is also used for synthesizing phlegm-eliminating and inflammation-diminishing drugs, such as ambroxol, and the like. In addition, nitrobenzaldehyde can also be used as a plant growth regulator for synthesizing racemization tetraporphyrinase antibody and indwellate, and can be applied to synthesizing organic intermediate products such as nitrostyrene, nitrocinnamic acid and the like. Therefore, the new synthesis method of nitrobenzaldehyde has the advantages of environmental protection, economic development and wide social benefits.
According to the characteristics of basic raw materials, the synthesis method of nitrobenzaldehyde mainly uses toluene, nitrotoluene, nitroethylbenzene and nitrobenzoyl chloride as raw materials, and finishes the reaction through a multi-step unit reaction process. For example, in the synthesis method using petroleum toluene as a raw material, benzyl chloride is generated by chlorination of toluene serving as a substrate through chlorine gas, nitrobenzyl chloride is generated by nitration through a nitric acid/solid superacid system, nitrobenzyl chloride is further hydrolyzed to form nitrobenzyl alcohol, nitrobenzaldehyde is obtained by nitric acid oxidation, and a target product is synthesized through four-step unit reaction. In the process of the synthesis method, chlorine is required to be applied in the first step of reaction, formed benzyl chloride has the stimulation effect of strong lacrimation, and a mixture of nitric acid and niobium pentoxide solid superacid is used as a nitrating agent in the second step of nitration reaction to form three isomer mixtures of o-nitrobenzyl chloride, m-nitrobenzyl chloride and p-nitrobenzyl chloride. Therefore, the synthesis reaction has complex technological process, harsh technological process control such as chlorination, nitration and the like, high energy consumption for treating a large amount of waste acid and waste brine, serious environmental pollution and no meeting of the environmental economic development requirement. However, the method using nitrotoluene or nitroethylbenzene as the basic raw material has the advantages of abundant raw material sources, simple implementation of the synthetic reaction process and certain economical efficiency. For example, the substrate nitrotoluene is oxidized in the acetic anhydride medium by using chromium oxide, dichromate, potassium permanganate or high-pressure oxygen as an oxidant to synthesize nitrobenzaldehyde by oxidizing side chain methyl. However, the characteristics of the synthesis reaction process show that the reaction selectivity is poor, a large amount of oxidation by-product nitrobenzoic acid is formed, the yield of the product nitrobenzaldehyde is low, particularly, the applied inorganic oxidant generates a large amount of acidic wastewater containing heavy metal salts which is difficult to biodegrade, the environmental pollution is serious, and the requirements of environmental economic development are not met.
In view of this, the current industrial synthesis method uses nitrotoluene as a raw material, firstly forms nitrobromobenzyl through molecular bromine reaction, then forms nitrobenzyl alcohol through sodium carbonate catalytic hydrolysis, and further synthesizes nitrobenzaldehyde through oxidation. Particularly, in the oxidation unit reaction, the oxidation agent nitric acid is selected to oxidize the nitrobenzol, the transition metal organic complex is selected to catalyze oxygen to oxidize the nitrobenzol, the inorganic base such as alkali metal hydroxide is selected to catalyze hydrogen peroxide to oxidize the nitrobenzol and the like, the development of the oxidation methods improves the reaction selectivity, avoids the separation difficulty of the intermediate or the product isomer, and improves the yield. However, the whole synthesis reaction process is a unit reaction process including three steps of bromination, hydrolysis and oxidation, the application cost of the industrial raw material of liquid bromine in the first bromination reaction procedure is high, bromine has irritant influence on the operation production environment, the transition metal organic complex catalyst used in the third oxidation reaction procedure is difficult to regenerate, and the safety and controllability of a hydrogen peroxide oxidation system are poor. Therefore, the synthesis reaction process is complex, multiple reaction procedures exist, the final yield is low, the synthesis reaction atom economy is not high, and the synthesis methods have no sustainable development characteristic.
Third, the invention
The invention aims to provide a novel method for synthesizing nitrobenzaldehyde, which has high reaction atom utilization rate and environmental economic characteristics and industrial sustainable application characteristics.
In order to achieve the purpose of the invention, the method for catalytically synthesizing nitrobenzaldehyde comprises the following steps:
A. adding a mesoporous material catalyst, a nitrotoluene substrate and an oxidant into a reactor;
B. setting the reaction temperature to be between room temperature and 150 ℃ and the reaction pressure to be between normal pressure and 5 MPa;
C. fully reacting in a reactor;
wherein, the mesoporous material catalyst is SBA-15, and the nitrotoluene substrate is: one of o-nitrotoluene, m-nitrotoluene and p-nitrotoluene, wherein the oxidant is pure oxygen or air.
The more preferable technical scheme for achieving the purpose is that the SBA-15 is metal element modified SBA-15, and the metal element is preferably Fe, Co, Ni, Ag, Cu, Zn, La or Pd.
The technical scheme for realizing the aim is that air is used as the oxidant.
The technical scheme for realizing the aim is that the oxidant is pure oxygen.
The more preferable technical scheme for realizing the purpose is that the reaction temperature is preferably room temperature (25 ℃) to 120 ℃, and the reaction pressure is preferably normal pressure (0.1MPa) to 0.5 MPa.
The technical scheme for realizing the aim is that the reactor can be a kettle type reactor or a tower type reactor.
The technical scheme for realizing the aim is that the reaction mode can adopt batch reaction or continuous reaction.
The technical scheme for realizing the aim is that the method also comprises the step of adding an aromatic hydrocarbon aprotic solvent or an aliphatic hydrocarbon aprotic solvent into the reactor. The aromatic hydrocarbon aprotic solvent is o-nitrotoluene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene or nitrobenzene and the like; the aliphatic hydrocarbon aprotic solvent is N-hexane, acetonitrile, dichloromethane, dichloroethane, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or methylpyrrolidone or the like. If the substrate is in solid form, the reaction requires the addition of a solvent, and the choice of an aromatic aprotic solvent helps to increase the yield and selectivity.
The oxidation principle of the method of the invention is as follows: preparing an oxidized substrate into a solution in a solvent or a solvent of a substrate raw material, and catalytically acting an SBA-15 mesoporous material on molecular oxygen under certain reaction temperature and pressure conditions to enable the substrate to generate side chain methyl free radical oxidation reaction to synthesize the nitrobenzaldehyde substance.
The technological process of nitrobenzaldehyde synthesis reaction is as follows: introducing air or pure oxygen oxidant into an oxidized substrate and catalyst system, reacting for a certain time under the conditions of certain temperature and pressure, separating a product from a reaction mixture after the reaction is finished, and recycling the catalyst after centrifugal separation and washing.
The preparation reaction mode can be batch reaction or continuous reaction, the reaction phase is heterogeneous reaction, and the reactor can be a kettle reactor or a tower reactor, which does not influence the selective synthesis of the nitrobenzaldehyde substance.
Compared with the traditional method, the method of the invention has obvious advantages, and is mainly characterized in that:
(1) the method uses nitrotoluene as a raw material, and the nitrotoluene is catalyzed by a SBA-15 mesoporous material and oxidized into a nitrobenzaldehyde substance in one step, so that the traditional three-step synthesis process of bromination, hydrolysis and oxidation of the nitrotoluene raw material is replaced, the atom economy of the synthesis reaction is improved, and the method has industrial application sustainability.
(2) The method of the invention uses air or pure oxygen as an oxidant to replace oxidant such as dichromate, potassium permanganate and the like in an acetic anhydride medium related to the traditional method, obviously reduces the influence of heavy metal salt on environmental pollution, is beneficial to economically preparing the nitroaldehyde substance in industrial environment, saves energy, reduces emission and has clean synthesis process.
(3) The method of the invention uses air or pure oxygen to oxidize nitrotoluene to synthesize nitrobenzaldehyde, and has high selectivity.
(4) The method of the invention applies SBA-15 with excellent catalytic performance and transition metal elements (Fe, Co, Ni, Ag, Cu, Zn, La or Pd) to modify the SBA-15 mesoporous material, and the catalyst material has good catalytic activity, catalytic selectivity, chemical stability and thermal stability.
(5) The method can realize the synthesis of nitrobenzaldehyde by the catalytic oxidation of nitrotoluene with molecular oxygen under mild reaction conditions of certain pressure, certain temperature and the like. The milder reaction temperature is from room temperature (25 ℃) to 150 ℃ and the milder pressure is from normal pressure (0.1MPa) to 5 MPa.
(6) The method can react in a solvent-free or aprotic organic solvent medium, wherein the solvent-free medium refers to a reaction substrate serving as a solvent, and the aprotic solvent mainly comprises aromatic hydrocarbons and aliphatic hydrocarbon substances, such as o-nitrotoluene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, nitrobenzene, N-hexane, acetonitrile, dichloromethane, dichloroethane, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or methyl pyrrolidone and the like, wherein the aromatic hydrocarbons such as chlorobenzene and the like have excellent solvent characteristics.
Fourthly, explanation of the attached drawings:
FIG. 1 shows the chemical structural formulas of three isomers of nitrobenzaldehyde.
FIG. 2 shows the result of hydrogen nuclear magnetic resonance spectroscopy analysis of o-nitrobenzaldehyde 1HNMR (500MHz, CDCl3), delta 10.42(s, 1H), 8.11(d, J ═ 8.0Hz, 1H), 7.96-7.93(m, 1H), 7.82-7.73 (m, 2H)
FIG. 3 is a graph showing the results of hydrogen nuclear magnetic resonance spectroscopy analysis of the product m-nitrobenzaldehyde 1HNMR (500MHz, DMSO-d6), Δ 10.12(s, 1H), 8.65(s, 1H), 8.50(s, 1H), 8.31(s, 1H), 7.88(s, 1H)
FIG. 4 shows the results of hydrogen nuclear magnetic resonance spectroscopy analysis of p-tolualdehyde, p-nitrobenzaldehyde 1HNMR (500MHz, DMSO-d6), delta 10.14(s, 1H), 8.38(d, J. 8.6Hz, 2H), 8.13(d, J. 8.7Hz, 2H)
Fifth, detailed description of the invention
The following is a detailed description of the present method using a specific exemplary embodiment, which is to say, the nitrotoluene substrate is oxidized by air or oxygen oxidant to be converted into nitrobenzaldehyde product under the action of the catalyst of the mesoporous material SBA-15, but the present invention is not limited thereto.
Example 1
The reaction was carried out in a reactor containing 1.37g of o-nitrotoluene and 0.015g of SBA-15 at 25 ℃ under 0.1MPa (normal pressure) of oxygen for 20 hours. After the reaction, methylene chloride was added to the reaction mixture, and the catalyst was separated by centrifugation. Washing the filtrate with 5% (m/m) sodium bicarbonate water solution to neutral, washing with distilled water until the organic phase is neutral, separating the organic phase from the water phase, and analyzing the content of the product component by gas chromatography after the organic phase is evaporated and concentrated under reduced pressure. The conversion rate of o-nitrotoluene is 6%, the yield of o-nitrobenzaldehyde is 6%, and the selectivity of the reaction product is 100%.
Example 2
The reaction was carried out in a reactor containing 1.37g of o-nitrotoluene and 0.030g of SBA-15 at 25 ℃ and 5MPa of oxygen for 20 hours. After the reaction, methylene chloride was added to the reaction mixture, and the catalyst was separated by centrifugation. Washing the filtrate with 5% (m/m) sodium bicarbonate water solution to neutral, washing with distilled water until the organic phase is neutral, separating the organic phase from the water phase, and analyzing the content of the product component by gas chromatography after the organic phase is evaporated and concentrated under reduced pressure. The conversion rate of o-nitrotoluene is 10%, the yield of o-nitrobenzaldehyde is 9%, and the selectivity of the reaction product is 90%.
Example 3
The reaction was carried out in a reactor containing 1.37g of o-nitrotoluene and 0.015g of SBA-15 at 150 ℃ under 5MPa of oxygen for 20 hours. After the reaction, methylene chloride was added to the reaction mixture, and the catalyst was separated by centrifugation. Washing the filtrate with 5% (m/m) sodium bicarbonate water solution to neutral, washing with distilled water until the organic phase is neutral, separating the organic phase from the water phase, and analyzing the content of the product component by gas chromatography after the organic phase is evaporated and concentrated under reduced pressure. The conversion rate of o-nitrotoluene is 16%, the yield of o-nitrobenzaldehyde is 13%, and the selectivity of the reaction product is 81%.
Example 4
The reaction was carried out in a reactor containing 1.37g of o-nitrotoluene and 0.015g of SBA-15 at 120 ℃ under 2.5MPa of oxygen for 20 hours. After the reaction, methylene chloride was added to the reaction mixture, and the catalyst was separated by centrifugation. Washing the filtrate with 5% (m/m) sodium bicarbonate water solution to neutral, washing with distilled water until the organic phase is neutral, separating the organic phase from the water phase, and analyzing the content of the product component by gas chromatography after the organic phase is evaporated and concentrated under reduced pressure. The conversion rate of o-nitrotoluene was 15%, the yield of o-nitrobenzaldehyde was 14%, and the selectivity of the reaction product was 93%.
Example 5
The reaction was carried out in a reactor containing 1.37g of o-nitrotoluene and 0.015g of AgSBA-15 at 120 ℃ under 0.1MPa of oxygen for 12 hours. After the reaction, methylene chloride was added to the reaction mixture, and the catalyst was separated by centrifugation. Washing the filtrate with 5% (m/m) sodium bicarbonate water solution to neutral, washing with distilled water until the organic phase is neutral, separating the organic phase from the water phase, and analyzing the content of the product component by gas chromatography after the organic phase is evaporated and concentrated under reduced pressure. The conversion rate of o-nitrotoluene is 29%, the yield of o-nitrobenzaldehyde is 26%, and the selectivity of the reaction product is 90%.
Example 6
The reaction was carried out in a reactor containing 5.00g of chlorobenzene, 1.37g of m-nitrotoluene and 0.015g of AgSBA-15 at 120 ℃ under 0.1MPa of oxygen for 12 hours. After the reaction, methylene chloride was added to the reaction mixture, and the catalyst was separated by centrifugation. Washing the filtrate with 5% (m/m) sodium bicarbonate water solution to neutral, washing with distilled water until the organic phase is neutral, separating the organic phase from the water phase, and analyzing the content of the product component by gas chromatography after the organic phase is evaporated and concentrated under reduced pressure. The conversion rate of m-nitrotoluene is 43%, the yield of m-nitrobenzaldehyde is 41%, and the selectivity of the reaction product is 95%.
Example 7
The reaction was carried out in a reactor containing 5.00g of chlorobenzene, 1.37g of p-nitrotoluene and 0.015g of AgSBA-15 at 120 ℃ under 0.1MPa of oxygen for 12 hours. After the reaction, methylene chloride was added to the reaction mixture, and the catalyst was separated by centrifugation. Washing the filtrate with 5% (m/m) sodium bicarbonate water solution to neutral, washing with distilled water until the organic phase is neutral, separating the organic phase from the water phase, and analyzing the content of the product component by gas chromatography after the organic phase is evaporated and concentrated under reduced pressure. The conversion rate of p-nitrotoluene was 44%, the yield of p-nitrobenzaldehyde was 41%, and the selectivity of the reaction product was 93%.
Example 8
The reaction was carried out in a reactor containing 1.37g of o-nitrotoluene and 0.030g of AgSBA-15 at 120 ℃ under 0.5MPa of oxygen for 15 hours. After the reaction, methylene chloride was added to the reaction mixture, and the catalyst was separated by centrifugation. Washing the filtrate with 5% (m/m) sodium bicarbonate water solution to neutral, washing with distilled water until the organic phase is neutral, separating the organic phase from the water phase, and analyzing the content of the product component by gas chromatography after the organic phase is evaporated and concentrated under reduced pressure. The conversion rate of o-nitrotoluene is 56%, the yield of o-nitrobenzaldehyde is 50%, and the selectivity of the reaction product is 89%.
Example 9
The reaction was carried out in a reactor containing 1.37g of o-nitrotoluene and 0.015g of FeSBA-15 at 120 ℃ under 0.5MPa of oxygen for 15 hours. After the reaction, methylene chloride was added to the reaction mixture, and the catalyst was separated by centrifugation. Washing the filtrate with 5% (m/m) sodium bicarbonate water solution to neutral, washing with distilled water until the organic phase is neutral, separating the organic phase from the water phase, and analyzing the content of the product component by gas chromatography after the organic phase is evaporated and concentrated under reduced pressure. The conversion rate of o-nitrotoluene is 35%, the yield of o-nitrobenzaldehyde is 32%, and the selectivity of the reaction product is 91%.
Example 10
The reaction was carried out in a reactor containing 1.37g of o-nitrotoluene and 0.015g of PdSBA-15 at 120 ℃ under 0.5MPa of oxygen for 15 hours. After the reaction, methylene chloride was added to the reaction mixture, and the catalyst was separated by centrifugation. Washing the filtrate with 5% (m/m) sodium bicarbonate water solution to neutral, washing with distilled water until the organic phase is neutral, separating the organic phase from the water phase, and analyzing the content of the product component by gas chromatography after the organic phase is evaporated and concentrated under reduced pressure. The conversion rate of o-nitrotoluene was 46%, the yield of o-nitrobenzaldehyde was 44%, and the selectivity of the reaction product was 96%.
Example 11
The reaction was carried out in a reactor containing 5.00g of chlorobenzene, 1.37g of p-nitrotoluene and 0.015g of PdSBA-15 at 90 ℃ under 0.5MPa of oxygen for 15 hours. After the reaction, methylene chloride was added to the reaction mixture, and the catalyst was separated by centrifugation. Washing the filtrate with 5% (m/m) sodium bicarbonate water solution to neutral, washing with distilled water until the organic phase is neutral, separating the organic phase from the water phase, and analyzing the content of the product component by gas chromatography after the organic phase is evaporated and concentrated under reduced pressure. The conversion rate of p-nitrotoluene is 68%, the yield of p-nitrobenzaldehyde is 65%, and the selectivity of the reaction product is 96%.
The detection results of the structures of the products o-nitrobenzaldehyde, m-nitrobenzaldehyde and p-tolualdehyde in the above examples are respectively shown in the attached drawings 2, 3 and 4, and the detection and analysis results of the hydrogen nuclear magnetic resonance spectrum show that the nitrobenzaldehyde is successfully and directly synthesized by one-step reaction.
The above description is only an exemplary embodiment of the present invention, and it should be noted that, for those skilled in the art, it is possible to make several improvements, extensions and modifications to the mesoporous material catalyst, the methyl aromatic hydrocarbon substrate, the reaction conditions, etc. without departing from the principle of the present invention, and these improvements, extensions and modifications should be considered as the protection scope of the present invention. Structures, devices, and methods of operation not specifically described or illustrated herein are generally practiced in the art without specific recitation or limitation.
Claims (7)
1. The catalytic synthesis method of nitrobenzaldehyde is characterized by comprising the following steps:
A. adding a mesoporous material catalyst, a nitrotoluene substrate and an oxidant into a reactor;
B. setting the reaction temperature to be between room temperature and 150 ℃ and the reaction pressure to be between normal pressure and 5 MPa;
C. fully reacting in a reactor;
the mesoporous material catalyst is SBA-15, the nitrotoluene substrate is one of o-nitrotoluene, m-nitrotoluene and p-nitrotoluene, and the oxidant is pure oxygen or air.
2. The process according to claim 1 for the catalytic synthesis of nitrobenzaldehydes, characterized in that: the SBA-15 is metal element modified SBA-15, and the metal element is Fe, Co, Ni, Ag, Cu, Zn, La or Pd.
3. The process for the catalytic synthesis of nitrobenzaldehydes according to claim 1 or 2, characterized in that: the reaction temperature is between room temperature and 120 ℃, and the reaction pressure is between normal pressure and 0.5 MPa.
4. The process for the catalytic synthesis of nitrobenzaldehydes according to claim 1 or 2, characterized in that: the reactor may be a tank reactor or a column reactor.
5. The process for the catalytic synthesis of nitrobenzaldehydes according to claim 1 or 2, characterized in that: the reaction mode may be a batch reaction or a continuous reaction.
6. The process for the catalytic synthesis of nitrobenzaldehydes according to claim 1 or 2, characterized in that: the method also comprises the step of adding an aromatic aprotic solvent into the reactor, wherein the aromatic aprotic solvent is as follows: one of o-nitrotoluene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, and nitrobenzene.
7. The process for the catalytic synthesis of nitrobenzaldehydes according to claim 1 or 2, characterized in that: further comprising the step of adding an aliphatic hydrocarbon aprotic solvent to the reactor, the aliphatic hydrocarbon aprotic solvent being: one of N-hexane, acetonitrile, dichloromethane, dichloroethane, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and methylpyrrolidone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110883472.6A CN114230468A (en) | 2021-08-02 | 2021-08-02 | Method for catalytic synthesis of nitrobenzaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110883472.6A CN114230468A (en) | 2021-08-02 | 2021-08-02 | Method for catalytic synthesis of nitrobenzaldehyde |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114230468A true CN114230468A (en) | 2022-03-25 |
Family
ID=80742507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110883472.6A Pending CN114230468A (en) | 2021-08-02 | 2021-08-02 | Method for catalytic synthesis of nitrobenzaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114230468A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989499A (en) * | 2012-12-18 | 2013-03-27 | 陕西省石油化工研究设计院 | Catalyst for preparing p-tertbutyl benzaldehyde and preparation method |
| CN103880574A (en) * | 2014-04-04 | 2014-06-25 | 湖南大学 | Method for preparing aromatic aldehyde by catalytic oxidation of toluene compound |
| CN105348107A (en) * | 2014-08-22 | 2016-02-24 | 南京理工大学 | Preparation method of p-nitrobenzaldehyde |
-
2021
- 2021-08-02 CN CN202110883472.6A patent/CN114230468A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989499A (en) * | 2012-12-18 | 2013-03-27 | 陕西省石油化工研究设计院 | Catalyst for preparing p-tertbutyl benzaldehyde and preparation method |
| CN103880574A (en) * | 2014-04-04 | 2014-06-25 | 湖南大学 | Method for preparing aromatic aldehyde by catalytic oxidation of toluene compound |
| CN105348107A (en) * | 2014-08-22 | 2016-02-24 | 南京理工大学 | Preparation method of p-nitrobenzaldehyde |
Non-Patent Citations (5)
| Title |
|---|
| A. COSTINE ET AL.: "Reactivity of electrophilic oxygen species generated over mesoporous iron-containing catalysts", 《CATALYSIS TODAY》, vol. 112, no. 1, pages 103 - 106, XP025116699, DOI: 10.1016/j.cattod.2005.11.032 * |
| P. VISUVAMITHIRAN ET AL.: "Oxidation of alkyl aromatics over SBA-15 supported cobalt oxide", 《JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY》, vol. 13, no. 4, pages 2528 - 2537 * |
| RIMA BISWAS ET AL.: "AgNPs Immobilized over Functionalized 2D Hexagonal SBA-15 for Catalytic C-H Oxidation of Hydrocarbons with Molecular Oxygen under Solvent-Free Conditions", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》, vol. 8, no. 15, pages 5856 - 5867 * |
| WENZHOU ZHONG ET AL.: "Solvent-free selective oxidation of toluene by oxygen over MnOx/SBA-15 catalysts: Relationship between catalytic behavior and surface structure", 《CHEMICAL ENGINEERING JOURNAL》, vol. 280, pages 737 - 747 * |
| 张金峰: "Ti-Co-SBA-15的制备、表征及其选择氧化催化性能", 《无机化学学报》, vol. 30, no. 5, pages 1063 - 1067 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ballini et al. | Synthetic procedures for the preparation of nitroalkanes | |
| CN112920066A (en) | Alpha-substituted-alpha-amino acid ester compound and preparation method thereof | |
| CN113816874B (en) | Process method for synthesizing 4-cyano-2-fluorobenzyl alcohol | |
| Base et al. | A versatile method for the conversion of oximes to nitroalkanes | |
| US20060167313A1 (en) | Process for preparing encapsulated metalloporphyrin catalyst and process for oxidation of alcohols | |
| CN114230468A (en) | Method for catalytic synthesis of nitrobenzaldehyde | |
| CN108003031B (en) | Method for preparing nitro compound by catalyzing nitrogen dioxide with graphene | |
| CN108003029B (en) | Method for preparing nitro compound by catalyzing nitric oxide with graphene | |
| CN108047001B (en) | Method for synthesizing 2, 5-dimethylphenol | |
| Wang et al. | A metal-free aerobic oxidation of nitrotoluenes catalyzed by N, N′, N ″-trihydroxyisocyanuric acid (THICA) and a novel approach to the catalyst | |
| JP2984047B2 (en) | Method for producing 1-amino-4-alkoxybenzenes | |
| CN109678741B (en) | Preparation method of 4-amino-3-fluorobenzoic acid | |
| Liu et al. | Efficient Synthesis of Oxazolidin‐2‐one via (Chitosan‐Schiff Base) cobalt (II)‐Catalyzed Oxidative Carbonylation of 2‐Aminoalkan‐1‐ols | |
| EP1468983B1 (en) | Process for producing 2,5-bis(trifluoromethyl)nitrobenzene | |
| CN118439966B (en) | Synthesis method of p-nitroaniline compound | |
| CN106995372B (en) | A method of (E)-beta-nitrostyrene derivative is catalyzed and synthesized based on tetaraary porphyrin iron | |
| CN111170837A (en) | Synthetic method of methyl ketone compound | |
| CN114560759A (en) | Method for catalytically synthesizing aromatic aldehyde | |
| CN115490597B (en) | Synthetic method of fluorotoluene derivative | |
| US6977313B2 (en) | Production process of 2,7-dibromofluorenone | |
| CN108689894B (en) | Synthesis method of green high-conversion-number sulfoxide compound | |
| CN107417535A (en) | A kind of One-step Synthesis method of high selectivity (E) β nitrostyrene derivatives | |
| CN109369357B (en) | Method for preparing symmetrical diaryl ketone by catalytic oxidation carbonylation | |
| US4618714A (en) | Process for preparation of 3,3'- or 3,4'-diaminobenzophenones | |
| CN118558321A (en) | Application of iron-copper oxide compound as catalyst in preparation of aniline or derivatives thereof by catalyzing reduction of nitrobenzene or derivatives thereof |
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: 20220325 |
|
| WD01 | Invention patent application deemed withdrawn after publication |