CN112916048A - Vanillin synthesis catalyst and preparation method thereof - Google Patents
Vanillin synthesis catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN112916048A CN112916048A CN201911230475.9A CN201911230475A CN112916048A CN 112916048 A CN112916048 A CN 112916048A CN 201911230475 A CN201911230475 A CN 201911230475A CN 112916048 A CN112916048 A CN 112916048A
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- CN
- China
- Prior art keywords
- catalyst
- product
- vanillin
- bromo
- sulfopyridine
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 235000012141 vanillin Nutrition 0.000 title claims abstract description 32
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims abstract description 44
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 42
- -1 alkyl pyridine Chemical compound 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 28
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 28
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 claims abstract description 21
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 238000007792 addition Methods 0.000 claims description 18
- 229960002510 mandelic acid Drugs 0.000 claims description 14
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 claims description 12
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 12
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
- VJXRKZJMGVSXPX-UHFFFAOYSA-N 4-ethylpyridine Chemical compound CCC1=CC=NC=C1 VJXRKZJMGVSXPX-UHFFFAOYSA-N 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- BWWVCOAABZLXRO-UHFFFAOYSA-N 2-bromopyridine-4-sulfonic acid Chemical compound C1=CN=C(C=C1S(=O)(=O)O)Br BWWVCOAABZLXRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 229960002089 ferrous chloride Drugs 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- LWMDPZVQAMQFOC-UHFFFAOYSA-N 4-butylpyridine Chemical compound CCCCC1=CC=NC=C1 LWMDPZVQAMQFOC-UHFFFAOYSA-N 0.000 claims description 4
- JAWZAONCXMJLFT-UHFFFAOYSA-N 4-propylpyridine Chemical compound CCCC1=CC=NC=C1 JAWZAONCXMJLFT-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 3
- IPOXZBCXKICZEH-UHFFFAOYSA-N (2,5-dimethylphenyl)phosphane Chemical compound CC1=CC=C(C)C(P)=C1 IPOXZBCXKICZEH-UHFFFAOYSA-N 0.000 claims description 2
- KYLUAQBYONVMCP-UHFFFAOYSA-N (2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P KYLUAQBYONVMCP-UHFFFAOYSA-N 0.000 claims description 2
- DIXCBXVJFXDLST-UHFFFAOYSA-N CC(C(Br)=NC=C1)=C1S(O)(=O)=O Chemical compound CC(C(Br)=NC=C1)=C1S(O)(=O)=O DIXCBXVJFXDLST-UHFFFAOYSA-N 0.000 claims description 2
- GUJPCUARQNBRBX-UHFFFAOYSA-N COC(C(Br)=NC=C1)=C1S(O)(=O)=O Chemical compound COC(C(Br)=NC=C1)=C1S(O)(=O)=O GUJPCUARQNBRBX-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 22
- 238000006482 condensation reaction Methods 0.000 abstract description 15
- 229910052742 iron Inorganic materials 0.000 abstract description 15
- 239000003446 ligand Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 50
- 239000000243 solution Substances 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 21
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 229960001867 guaiacol Drugs 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000009616 inductively coupled plasma Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- BTNMPGBKDVTSJY-UHFFFAOYSA-N keto-phenylpyruvic acid Chemical compound OC(=O)C(=O)CC1=CC=CC=C1 BTNMPGBKDVTSJY-UHFFFAOYSA-N 0.000 description 6
- 238000004611 spectroscopical analysis Methods 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001903 2-oxo-3-phenylpropanoic acid Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- DEDGUGJNLNLJSR-UHFFFAOYSA-N alpha-hydroxycinnamic acid Natural products OC(=O)C(O)=CC1=CC=CC=C1 DEDGUGJNLNLJSR-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CCWKLNIRBZGQRT-UHFFFAOYSA-N CC(C(S(O)(=O)=O)=C1)=CN=C1Br Chemical compound CC(C(S(O)(=O)=O)=C1)=CN=C1Br CCWKLNIRBZGQRT-UHFFFAOYSA-N 0.000 description 2
- LBWCDAGZFOPRQA-UHFFFAOYSA-N CC(C(S(O)(=O)=O)=C1C)=CN=C1Br Chemical compound CC(C(S(O)(=O)=O)=C1C)=CN=C1Br LBWCDAGZFOPRQA-UHFFFAOYSA-N 0.000 description 2
- CGQCWMIAEPEHNQ-UHFFFAOYSA-N Vanillylmandelic acid Chemical compound COC1=CC(C(O)C(O)=O)=CC=C1O CGQCWMIAEPEHNQ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DNHOTKSRZCSWOZ-UHFFFAOYSA-N COC(C(S(O)(=O)=O)=C1OC)=CN=C1Br Chemical compound COC(C(S(O)(=O)=O)=C1OC)=CN=C1Br DNHOTKSRZCSWOZ-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- ZPLQIPFOCGIIHV-UHFFFAOYSA-N Gimeracil Chemical group OC1=CC(=O)C(Cl)=CN1 ZPLQIPFOCGIIHV-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 244000263375 Vanilla tahitensis Species 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
- C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
- C07D213/71—Sulfur atoms to which a second hetero atom is attached
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention provides a vanillin synthetic catalyst and a preparation method thereof, wherein the catalyst is a coordination compound and has the following structural expression:
Description
Technical Field
The invention relates to a preparation method, in particular to a vanillin synthesis catalyst and a preparation method thereof, and belongs to the technical field of catalysts.
Background
Vanillin, commonly known as vanillin, chemical name 3-methoxy-4-hydroxybenzaldehyde, has the unique aroma of vanilla, is usually white or pale yellow crystalline powder, is the most productive synthetic perfume in the world, and has an annual energy production of about 3 ten thousand tons. At present, more than 80% of vanillin is synthesized by adopting a glyoxylic acid route, and the route comprises the steps of glyoxylic acid condensation, mandelic acid oxidation, acidification and decarboxylation and the like. The glyoxylic acid method has the following problems: 1. the condensation reaction has low selectivity, generates a large amount of ortho-position byproducts and di-condensation byproducts, and the COD of the wastewater is higher due to the difficult recovery of the condensation byproducts; 2. the mainstream oxidation process still adopts copper oxide as an oxidant, although the yield is high, the reaction rate is slow, a large amount of copper oxide needs to be added to participate in the reaction, and a large amount of cuprous oxide is generated as a byproduct, so that inconvenience is brought to the filtration, regeneration and the like of the oxidant in the later period.
In order to solve the problem of low yield of the condensation reaction, the U.S. Pat. No. 5, 4165341A uses alumina as a cocatalyst, and the selectivity of the condensation reaction is improved to 90%; U.S. Pat. No. 4, 5354897A discloses a method for increasing the selectivity of condensation reaction, which can synthesize ortho-mandelic acid product with high selectivity by the synergistic effect of metal salts and organic base, but does not provide a method for synthesizing para-mandelic acid compound with high selectivity. The Gimeracil group discloses the improvement of the condensation reaction of vanillin synthesis by glyoxylic acid method in Chinese patent CN101012161A, adopting quaternary ammonium salt catalyst, the mol ratio of the raw materials of glyoxylic acid, guaiacol and sodium hydroxide is 1: 1.1-1.2: 2.2-2.3, the reaction temperature is 27-29 ℃, the reaction time is 3.5-5 hours, and the condensation reaction yield reaches 81.3-85.8%. The mainstream technology at present is to add excessive guaiacol to improve the yield of condensation reaction, but the unreacted guaiacol needs to be extracted and recovered by adding alkali, and the technology is complicated.
In order to solve the problem of the oxidation rate, British patent GB1377243A discloses an oxidation method, wherein the target product vanillin can be obtained by reacting excessive ferric trichloride with 3-methoxy-4-hydroxymandelic acid solution at high temperature under acidic condition. The process route is simple, guaiacol is directly oxidized after being recycled under an acidic condition, so that the consumption of alkali liquor is reduced, vanillin can be obtained in one step through oxidation, but the greatest defect is that vanillin is unstable and can further react under a high-temperature acidic condition, and the yield of vanillin is low. Chinese patent CN102260150A discloses a method for efficiently oxidizing mandelic acid aqueous solution, which adopts a self-suction reaction kettle to introduce oxygen, effectively reduces reaction time and realizes catalyst recycling, but has the problems that the reaction end point is difficult to control and insufficient oxidation or excessive oxidation is easy to occur.
Disclosure of Invention
The invention aims to provide a vanillin synthesis catalyst and a preparation method thereof, which are suitable for catalyzing glyoxylate condensation reaction and mandelic acid oxidation reaction in a vanillin synthesis process at the same time.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a vanillin synthesis catalyst, which is a coordination compound; the structural expression of the catalyst is as follows:
in the formula, R1、R2Is an alkyl or alkoxy group having 0 to 1 carbon atom, preferably H, -CH3、-OCH3One of (1); r is an alkyl group having 0 to 4 carbon atoms, preferably-CH3、-C2H5。
A preparation method of a vanillin synthesis catalyst comprises the following steps:
1) dropwise adding butyl lithium into alkyl pyridine, and then adding trimethyl tin chloride to react to obtain a product 1;
2) mixing the product 1, the 2-bromine-4-sulfonic pyridine compound and a catalyst, and reacting to obtain a product 2;
3) and (3) mixing and stirring a ferrous compound and the product 2 in a solvent to prepare the catalyst.
Further, the molar ratio of the alkyl pyridine to the trimethyl tin chloride to the butyl lithium in the step 1) is 1 (1-2): (1-2), preferably 1 (1.1-1.3): (1.2-1.5).
Further, the molar ratio of the 2-bromo-4-sulfonic pyridine compound to the product 1 in the step 2) is (2-5): 1, preferably (2.2-3): 1, the molar ratio of the catalyst to the product 1 is 0.1-0.5: 100.
further, the molar ratio of the product 2 to the ferrous iron compound is (1-4) to 1, preferably (2-3): 1.
further, the alkyl pyridine in the step 1) is pyridine, 4-methylpyridine, 4-ethylpyridine, 4-propylpyridine or 4-butylpyridine;
the initial reaction temperature of the step 1) during the dropwise addition of the butyl lithium is preferably-100 to-50 ℃, and more preferably-78 ℃; after the trimethyltin chloride is added, the reaction temperature is preferably controlled to be 20-100 ℃, and more preferably 30-50 ℃.
Further, in the step 2), the 2-bromo-4-sulfopyridine compound is 2-bromo-4-sulfopyridine, 2-bromo-3-methyl-4-sulfopyridine, 2-bromo-4-sulfopyridine-5-methylpyridine, 2-bromo-3-methyl-4-sulfopyridine-5-methylpyridine, 2-bromo-3-methoxy-4-sulfopyridine, 2-bromo-4-sulfopyridine-5-methoxypyridine or 2-bromo-3-methoxy-4-sulfopyridine-5-methoxypyridine;
the catalyst in the step 2) is preferably one or more of tetrakis (triphenylphosphine) palladium, tetrakis (2-methylphenyl phosphine) palladium, tetrakis (2, 5-dimethylphenyl phosphine) palladium and palladium acetylacetonate;
the reaction temperature in the step 2) is preferably 60-200 ℃, and more preferably 80-120 ℃.
Further, the ferrous compound in step 3) is one or more of ferrous sulfate, ferrous nitrate, ferrous chloride and ferrous hydroxide, preferably one or two of ferrous sulfate and ferrous chloride;
the solvent in the step 3) is preferably one or more of DMF (dimethylformamide), DMAC (dimethylacetamide), DMSO (dimethyl sulfoxide), methanol and acetonitrile.
The reaction temperature in the step 3) is preferably 10-80 ℃, and preferably 20-40 ℃.
Further, the reaction conditions of the step 1) and the step 2) are anhydrous and anaerobic conditions.
The catalyst or the catalyst prepared by the method is used for catalyzing glyoxylic acid condensation and mandelic acid oxidation reactions in a vanillin glyoxylic acid method synthesis process.
The invention synthesizes the iron ligand catalyst and applies the iron ligand catalyst to the vanillin glyoxylic acid method synthesis process, which can greatly improve the yield of oxidation reaction and condensation reaction, thereby improving the production efficiency and yield of vanillin.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
[ example 1 ]
Preparation of the catalyst:
injecting pyridine and tetrahydrofuran solvent into an anhydrous and oxygen-free closed three-neck flask, slowly dropwise adding butyl lithium solution into a reaction system at-100 ℃, heating to room temperature after dropwise adding, continuing to react for 3h, quickly adding trimethyltin chloride solution into the reaction bottle, heating to 80 ℃, reacting for 6h, and separating and purifying to obtain a product 1. The addition molar ratio of the pyridine to the trimethyl tin chloride to the butyl lithium is 1: 1: 1.
dissolving the product 1 in a toluene solution, adding 2-bromo-4-sulfopyridine, heating to 60 ℃, carrying out reflux reaction for 12h, and separating and purifying to obtain a product 2. The addition molar ratio of the 2-bromo-4-sulfopyridine to the product 1 is 2: 1. to give birth toThe substance 2 was subjected to hydrogen nuclear magnetic resonance spectroscopy, and the results were as follows:1H NMR(600MHz,CDCl3):δ2.0(2H),7.79(2H),7.82(1H),8.69(2H),9.04(2H),9.17(2H)。
and mixing the product 2 and ferrous sulfate solid according to the molar ratio of 1:1, dissolving in a DMF solvent, stirring for 3 hours at room temperature to show that flocculent solid is separated out, filtering and washing to obtain the iron ion ligand catalyst. The catalyst was subjected to elemental analysis by means of an inductively coupled plasma emission spectrometer (ICP) model HK-8100, with the following results: c44.65%, H3.52%, Fe 6.29%, N9.47%, O21.63%, S14.45%.
[ example 2 ]
Preparation of the catalyst:
injecting 4-methylpyridine and tetrahydrofuran solvent into an anhydrous and oxygen-free closed three-neck flask, slowly dropwise adding butyl lithium solution into a reaction system at-80 ℃, heating to room temperature after dropwise adding, continuing to react for 3h, quickly adding trimethyltin chloride solution into the reaction flask, heating to 50 ℃, reacting for 8h, and separating and purifying to obtain a product 1. The addition molar ratio of the 4-methylpyridine to the trimethyl tin chloride to the butyl lithium is 1: 1: 2
Dissolving the product 1 in a toluene solution, adding 2-bromo-3-methyl-4-sulfonic pyridine, heating to 200 ℃, carrying out reflux reaction for 12 hours, and separating and purifying to obtain a product 2. The addition molar ratio of the 2-bromo-3-methyl-4-sulfonic pyridine to the product 1 is 5: 1. The product 2 was subjected to nmr hydrogen spectroscopy and the results were as follows:1HNMR(600MHz,CDCl3):δ2.0(2H),2.31(6H),2.36(6H),8.61(2H),8.66(2H),9.08(2H)。
and mixing the product 2 and ferrous nitrate solid according to a molar ratio of 2:1, dissolving in a DMAC solvent, stirring for 3 hours at room temperature to show that flocculent solid is separated out, filtering and washing to obtain the iron ion ligand catalyst. Elemental analysis of the catalyst by ICP gave the following results: 47.18% of C, 3.96% of H, 5.93% of Fe, 8.92% of N, 20.39% of O and 13.62% of S.
[ example 3 ]
Preparation of the catalyst:
injecting 4-ethyl pyridine and tetrahydrofuran solvent into an anhydrous and oxygen-free closed three-neck flask, slowly dropwise adding butyl lithium solution into a reaction system at-50 ℃, heating to room temperature after dropwise adding, continuing to react for 3h, quickly adding trimethyltin chloride solution into the reaction flask, heating to 30 ℃, reacting for 12h, and separating and purifying to obtain a product 1. The addition molar ratio of the 4-ethylpyridine to the trimethyltin chloride to the butyllithium is 1: 2: 2
Dissolving the product 1 in a toluene solution, adding 2-bromo-4-sulfo-5-methylpyridine, heating to 80 ℃, carrying out reflux reaction for 12 hours, and separating and purifying to obtain a product 2. The addition molar ratio of the 2-bromo-4-sulfo-5-methylpyridine to the product 1 is 2.5: 1. The product 2 was subjected to nmr hydrogen spectroscopy and the results were as follows:1H NMR(600MHz,CDCl3):δ1.25(3H),2.31(6H),2.60(2H),8.61(2H),8.66(2H),9.08(2H)。
and mixing the product 2 and ferrous nitrate solid according to a molar ratio of 2.5:1, dissolving in a DMAC solvent, stirring for 3 hours at room temperature to show that flocculent solid is separated out, filtering and washing to obtain the iron ion ligand catalyst. Elemental analysis of the catalyst by ICP gave the following results: 48.30% of C, 4.26% of H, 5.76% of Fe, 8.67% of N, 19.80% of O and 13.22% of S.
[ example 4 ]
Preparation of the catalyst:
injecting 4-propylpyridine and tetrahydrofuran solvent into an anhydrous and oxygen-free closed three-neck flask, slowly dropwise adding butyl lithium solution into a reaction system at-78 ℃, heating to room temperature after dropwise adding, continuing to react for 3h, quickly adding trimethyltin chloride solution into the reaction flask, heating to 40 ℃, reacting for 10h, and separating and purifying to obtain a product 1. The addition molar ratio of the 4-propylpyridine to the trimethyl tin chloride to the butyl lithium is 1: 1.2: 2
Dissolving the product 1 in a toluene solution, adding 2-bromo-3-methoxy-4-sulfonic pyridine, heating to 120 ℃, carrying out reflux reaction for 12 hours, and separating and purifying to obtain a product 2. The addition molar ratio of the 2-bromo-3-methoxy-4-sulfonic pyridine to the product 1 is 3: 1. The product 2 was subjected to nmr hydrogen spectroscopy and the results were as follows:1H NMR(600MHz,CDCl3):δ0.9(3H),1.65(2H),2.0(2H),2.65(2H),2.83(6H),8.47(2H),8.66(2H),9.32(2H)。
and mixing the product 2 and ferrous chloride solid according to the molar ratio of 3:1, dissolving in a methanol solvent, stirring for 3 hours at room temperature to show that flocculent solid is separated out, filtering and washing to obtain the iron ion ligand catalyst. Elemental analysis of the catalyst by ICP gave the following results: c46.37%, H4.27%, Fe 5.26%, N7.91%, O24.11%, S12.08%.
[ example 5 ]
Preparation of the catalyst:
injecting 4-butylpyridine and tetrahydrofuran solvent into an anhydrous and oxygen-free closed three-necked bottle, slowly dropwise adding a butyllithium solution into the reaction system at-90 ℃, heating to room temperature after dropwise adding, continuing to react for 3 hours, quickly adding a trimethyltin chloride solution into the reaction bottle, heating to 100 ℃, reacting for 4 hours, and separating and purifying to obtain a product 1. The addition molar ratio of the 4-butylpyridine to the trimethyltin chloride to the butyllithium is 1: 1.2: 1.3
Dissolving the product 1 in a toluene solution, adding 2-bromo-3-methyl-4-sulfo-5-methylpyridine, heating to 110 ℃, refluxing for reaction for 12 hours, and separating and purifying to obtain a product 2. The addition molar ratio of the 2-bromo-3-methyl-4-sulfo-5-methylpyridine to the product 1 is 3: 1. The product 2 was subjected to nmr hydrogen spectroscopy and the results were as follows:1H NMR(600MHz,CDCl3):δ0.9(3H),1.31(2H),1.60(2H),2.0(2H),2.31(12H),2.65(2H),2.83(6H),8.57(2H),8.66(2H)。
and mixing the product 2 and ferrous hydroxide solid according to a molar ratio of 4:1, dissolving in an acetonitrile solvent, stirring for 3 hours at room temperature to show that flocculent solid is separated out, filtering and washing to obtain the iron ion ligand catalyst. Elemental analysis of the catalyst by ICP gave the following results: c52.17%, H5.31%, Fe 5.16%, N7.77%, O17.74%, S11.85%.
[ example 6 ]
Preparation of the catalyst:
injecting 4-ethyl pyridine and tetrahydrofuran solvent into an anhydrous and oxygen-free closed three-neck flask, slowly dropwise adding butyl lithium solution into a reaction system at-78 ℃, heating to room temperature after dropwise adding, continuing to react for 3h, quickly adding trimethyltin chloride solution into the reaction flask, heating to 80 ℃, reacting for 6h, and separating and purifying to obtain a product 1. The addition molar ratio of the 4-ethylpyridine to the trimethyltin chloride to the butyllithium is 1: 1.1: 1.5.
dissolving the product 1 in a toluene solution, adding 2-bromo-3-methoxy-4-sulfo-5-methoxypyridine into the toluene solution, heating the mixture to 110 ℃, carrying out reflux reaction for 12 hours, and separating and purifying to obtain a product 2. The addition molar ratio of the 2-bromo-3-methoxy-4-sulfonic-5-methoxypyridine to the product 1 is 2.8: 1. The product 2 was subjected to nmr hydrogen spectroscopy and the results were as follows:1H NMR(600MHz,CDCl3):δ1.25(3H),2.0(2H),2.60(2H),3.83(12H),8.23(2H),8.66(2H)。
and mixing the product 2 and ferrous sulfate solid according to the molar ratio of 2:1, dissolving in a DMF solvent, stirring for 3 hours at room temperature to show that flocculent solid is separated out, filtering and washing to obtain the iron ion ligand catalyst. Elemental analysis of the catalyst by ICP gave the following results: 44.75% of C, 4.28% of H, 4.84% of Fe, 7.28% of N, 27.73% of O and 11.11% of S.
[ example 7 ]
Injecting 4-methylpyridine and tetrahydrofuran solvent into an anhydrous and oxygen-free closed three-neck flask, slowly dropwise adding butyl lithium solution into a reaction system at-80 ℃, heating to room temperature after dropwise adding, continuing to react for 3h, quickly adding trimethyltin chloride solution into the reaction flask, heating to 50 ℃, reacting for 8h, and separating and purifying to obtain a product 1. The addition molar ratio of the pyridine to the trimethyl tin chloride to the butyl lithium is 1: 1.3: 1.2.
dissolving the product 1 in a toluene solution, adding 2-bromo-3-methyl-4-sulfonic pyridine, heating to 200 ℃, carrying out reflux reaction for 12 hours, and separating and purifying to obtain a product 2. The addition molar ratio of the 2-bromo-4-sulfopyridine to the product 1 is 2.2: 1. The product 2 was subjected to nmr hydrogen spectroscopy and the results were as follows:1H NMR(600MHz,CDCl3):δ2.1(2H),2.29(6H),2.36(6H),8.61(2H),8.66(2H),9.12(2H)。
and mixing the product 2 and ferrous nitrate solid according to a molar ratio of 3:1, dissolving in a DMAC solvent, stirring for 3 hours at room temperature to show that flocculent solid is separated out, filtering and washing to obtain the iron ion ligand catalyst. Elemental analysis of the catalyst by ICP gave the following results: 47.19 percent of C, 3.96 percent of H, 5.92 percent of Fe, 8.92 percent of N, 20.41 percent of O and 13.60 percent of S.
The catalysts prepared in the examples were tested for activity:
0.2g of catalyst, 62g of guaiacol and 70g of glyoxylic acid solution (50%) are dissolved in 600g of water and reacted at 40 ℃ for 2 hours, and then sampled and analyzed. Then, 1MPa of oxygen gas was introduced into the reaction solution, the temperature was raised to 95 ℃ and the mixture was refluxed with stirring for 0.5 hour, the reaction solution was taken to conduct Agilent liquid phase analysis on the contents of glyoxylic acid, mandelic acid and phenylpyruvic acid, and the yield of the glyoxylic acid condensation reaction and the mandelic acid oxidation reaction was calculated, and the results are shown in Table 1.
Comparative example 1
62g of guaiacol and 70g of glyoxylic acid solution (50%) are dissolved in 600g of water, reacted for 2 hours at 40 ℃, sampled and analyzed, and 35g of 50% dilute sulfuric acid is added to extract the unreacted guaiacol. Then, 0.2g of copper oxide was added to the extracted aqueous phase, 1MPa of oxygen was introduced, the temperature was raised to 95 ℃ and the mixture was stirred and refluxed for 0.5h, the reaction solution was taken to perform Agilent liquid phase analysis on the contents of glyoxylic acid, mandelic acid and phenylpyruvic acid, and the yield of the condensation reaction of glyoxylic acid and the oxidation reaction of mandelic acid was calculated, and the results are shown in Table 1.
Comparative example 2
62g of guaiacol and 70g of glyoxylic acid solution (50%) are dissolved in 600g of water, reacted for 2 hours at 40 ℃, sampled and analyzed, and 35g of 50% dilute sulfuric acid is added to extract the unreacted guaiacol. Then, 12g of copper oxide was added to the extracted aqueous phase, 1MPa of oxygen was introduced, the temperature was raised to 95 ℃ and the mixture was stirred and refluxed for 0.5h, the reaction solution was taken to perform Agilent liquid phase analysis on the contents of glyoxylic acid, mandelic acid and phenylpyruvic acid, and the yields of the condensation reaction of glyoxylic acid and the oxidation reaction of mandelic acid were calculated, and the results are shown in Table 1.
TABLE 1 results of catalyst Performance testing
Yield of glyoxylic acid condensation reaction | Yield of mandelic acid oxidation reaction | |
Example 1 | 90.2% | 96.3% |
Example 2 | 92.7% | 97.7% |
Example 3 | 92.8% | 97.7% |
Example 4 | 91.2% | 96.0% |
Example 5 | 90.2% | 94.3% |
Example 6 | 90.5% | 95.7% |
Example 7 | 92.5% | 97.4 |
Comparative example 1 | 76.7% | 78.2% |
Comparative example 2 | 75.4% | 85.2% |
According to the test results, the catalyst with different substituent groups is screened, and the yield of the oxidation reaction and the condensation reaction in the vanillin glyoxylic acid method synthesis process is greatly improved by optimizing the ligand structural unit compared with the test results of a comparative example.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (10)
1. A vanillin synthetic catalyst is characterized in that the catalyst is a coordination compound; the structural expression of the catalyst is as follows:
in the formula, R1、R2Is an alkyl or alkoxy group having 0 to 1 carbon atom, preferably H, -CH3、-OCH3One of (1); r is an alkyl group having 0 to 4 carbon atoms, preferably-CH3、-C2H5。
2. A method for preparing a vanillin synthesis catalyst according to claim 1, comprising the steps of:
1) dropwise adding butyl lithium into alkyl pyridine, and then adding trimethyl tin chloride to react to obtain a product 1;
2) mixing the product 1, the 2-bromine-4-sulfonic pyridine compound and a catalyst, and reacting to obtain a product 2;
3) and (3) mixing and stirring a ferrous compound and the product 2 in a solvent to prepare the catalyst.
3. The vanillin synthesis catalyst according to claim 2, wherein the molar ratio of the alkyl pyridine to the trimethyl tin chloride to the butyl lithium in the step 1) is 1 (1-2): (1-2), preferably 1 (1.1-1.3): (1.2-1.5).
4. The method for preparing a vanillin synthesis catalyst according to claim 2 or 3, wherein the molar ratio of the 2-bromo-4-sulfopyridine compound to the product 1 in the step 2) is (2-5): 1, preferably (2.2-3): 1, the molar ratio of the catalyst to the product 1 is 0.1-0.5: 100.
5. the method for preparing the vanillin synthesis catalyst according to claim 4, wherein the molar ratio of the product 2 to the ferrous compound is (1-4) to 1, preferably (2-3): 1.
6. the method for preparing a vanillin synthesis catalyst according to any one of claims 2 to 5, wherein the alkyl pyridine in the step 1) is pyridine, 4-methylpyridine, 4-ethylpyridine, 4-propylpyridine or 4-butylpyridine;
the initial reaction temperature of the step 1) during the dropwise addition of the butyl lithium is preferably-100 to-50 ℃, and more preferably-78 ℃; after the trimethyltin chloride is added, the reaction temperature is preferably controlled to be 20-100 ℃, and more preferably 30-50 ℃.
7. The method for preparing a vanillin synthesis catalyst according to any one of claims 2 to 6, wherein the 2-bromo-4-sulfopyridine compound in the step 2) is 2-bromo-4-sulfopyridine, 2-bromo-3-methyl-4-sulfopyridine, 2-bromo-4-sulfopyridine-5-methylpyridine, 2-bromo-3-methyl-4-sulfopyridine-5-methylpyridine, 2-bromo-3-methoxy-4-sulfopyridine, 2-bromo-4-sulfopyridine-5-methoxypyridine or 2-bromo-3-methoxy-4-sulfopyridine-5-methoxypyridine;
the catalyst in the step 2) is preferably one or more of tetrakis (triphenylphosphine) palladium, tetrakis (2-methylphenyl phosphine) palladium, tetrakis (2, 5-dimethylphenyl phosphine) palladium and palladium acetylacetonate;
the reaction temperature in the step 2) is preferably 60-200 ℃, and more preferably 80-120 ℃.
8. The preparation method of the vanillin synthesis catalyst according to any one of claims 2 to 7, wherein the ferrous compound in the step 3) is one or more of ferrous sulfate, ferrous nitrate, ferrous chloride and ferrous hydroxide, preferably one or both of ferrous sulfate and ferrous chloride;
the solvent in the step 3) is preferably one or more of DMF, DMAC, DMSO, methanol and acetonitrile.
The reaction temperature in the step 3) is preferably 10-80 ℃, and preferably 20-40 ℃.
9. The method for preparing a vanillin synthesis catalyst according to any one of claims 2 to 8, wherein the reaction conditions of the steps 1) and 2) are anhydrous and anaerobic conditions.
10. The catalyst of claim 1 or the catalyst prepared by the method of any one of claims 2 to 9, wherein the catalyst is used for catalyzing glyoxylate condensation and mandelic acid oxidation reactions in a vanillin glyoxylic acid method synthesis process.
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CN101774897A (en) * | 2009-01-09 | 2010-07-14 | 华东理工大学 | Method for preparing vanillin and analogue thereof |
CN102040495A (en) * | 2010-11-22 | 2011-05-04 | 天津市职业大学 | Method for synthesizing vanillin by using glyoxylic acid and guaiacol together |
CN102381950A (en) * | 2011-09-05 | 2012-03-21 | 浙江新和成股份有限公司 | Catalytic oxidation method for preparing vanillin |
WO2013166946A1 (en) * | 2012-05-07 | 2013-11-14 | Rhodia Operations | Process for production of vanillin and vanillin derivatives |
WO2016000664A1 (en) * | 2014-06-30 | 2016-01-07 | 嘉兴市中华化工有限责任公司 | Method of preparing vanillin |
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CN101774897A (en) * | 2009-01-09 | 2010-07-14 | 华东理工大学 | Method for preparing vanillin and analogue thereof |
CN102040495A (en) * | 2010-11-22 | 2011-05-04 | 天津市职业大学 | Method for synthesizing vanillin by using glyoxylic acid and guaiacol together |
CN102381950A (en) * | 2011-09-05 | 2012-03-21 | 浙江新和成股份有限公司 | Catalytic oxidation method for preparing vanillin |
WO2013166946A1 (en) * | 2012-05-07 | 2013-11-14 | Rhodia Operations | Process for production of vanillin and vanillin derivatives |
WO2016000664A1 (en) * | 2014-06-30 | 2016-01-07 | 嘉兴市中华化工有限责任公司 | Method of preparing vanillin |
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