CN111266133B - Manganese metal catalyst and synthetic method thereof, and synthetic method of vegetable oil-based amide compound - Google Patents
Manganese metal catalyst and synthetic method thereof, and synthetic method of vegetable oil-based amide compound Download PDFInfo
- Publication number
- CN111266133B CN111266133B CN202010169799.2A CN202010169799A CN111266133B CN 111266133 B CN111266133 B CN 111266133B CN 202010169799 A CN202010169799 A CN 202010169799A CN 111266133 B CN111266133 B CN 111266133B
- Authority
- CN
- China
- Prior art keywords
- vegetable oil
- metal catalyst
- formula
- manganese metal
- manganese
- 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.)
- Active
Links
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 78
- -1 amide compound Chemical class 0.000 title claims abstract description 61
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 235000015112 vegetable and seed oil Nutrition 0.000 title claims abstract description 46
- 239000008158 vegetable oil Substances 0.000 title claims abstract description 46
- 238000010189 synthetic method Methods 0.000 title claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001308 synthesis method Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 claims abstract 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 28
- 230000003647 oxidation Effects 0.000 claims description 26
- 238000007254 oxidation reaction Methods 0.000 claims description 26
- 239000011572 manganese Substances 0.000 claims description 23
- 229910052748 manganese Inorganic materials 0.000 claims description 23
- 238000007259 addition reaction Methods 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 10
- 238000006464 oxidative addition reaction Methods 0.000 claims description 10
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims description 6
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 6
- 229940073769 methyl oleate Drugs 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000003495 polar organic solvent Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 4
- 239000001149 (9Z,12Z)-octadeca-9,12-dienoate Substances 0.000 claims description 3
- WTTJVINHCBCLGX-UHFFFAOYSA-N (9trans,12cis)-methyl linoleate Natural products CCCCCC=CCC=CCCCCCCCC(=O)OC WTTJVINHCBCLGX-UHFFFAOYSA-N 0.000 claims description 3
- LNJCGNRKWOHFFV-UHFFFAOYSA-N 3-(2-hydroxyethylsulfanyl)propanenitrile Chemical compound OCCSCCC#N LNJCGNRKWOHFFV-UHFFFAOYSA-N 0.000 claims description 3
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 claims description 3
- PKIXXJPMNDDDOS-UHFFFAOYSA-N Methyl linoleate Natural products CCCCC=CCCC=CCCCCCCCC(=O)OC PKIXXJPMNDDDOS-UHFFFAOYSA-N 0.000 claims description 3
- XKGDWZQXVZSXAO-ADYSOMBNSA-N Ricinoleic Acid methyl ester Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC XKGDWZQXVZSXAO-ADYSOMBNSA-N 0.000 claims description 3
- XKGDWZQXVZSXAO-SFHVURJKSA-N Ricinolsaeure-methylester Natural products CCCCCC[C@H](O)CC=CCCCCCCCC(=O)OC XKGDWZQXVZSXAO-SFHVURJKSA-N 0.000 claims description 3
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 claims description 3
- 229940093471 ethyl oleate Drugs 0.000 claims description 3
- ZYNDJIBBPLNPOW-UHFFFAOYSA-N eurucic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCCCCCC(=O)OC ZYNDJIBBPLNPOW-UHFFFAOYSA-N 0.000 claims description 3
- ZYNDJIBBPLNPOW-KHPPLWFESA-N methyl erucate Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(=O)OC ZYNDJIBBPLNPOW-KHPPLWFESA-N 0.000 claims description 3
- 229940049964 oleate Drugs 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- XKGDWZQXVZSXAO-UHFFFAOYSA-N ricinoleic acid methyl ester Natural products CCCCCCC(O)CC=CCCCCCCCC(=O)OC XKGDWZQXVZSXAO-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 235000013311 vegetables Nutrition 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 81
- 238000001228 spectrum Methods 0.000 description 36
- 239000000047 product Substances 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- 239000012071 phase Substances 0.000 description 19
- 150000001556 benzimidazoles Chemical class 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000002390 rotary evaporation Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000004809 thin layer chromatography Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 239000013067 intermediate product Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- WGTASENVNYJZBK-UHFFFAOYSA-N 3,4,5-trimethoxyamphetamine Chemical compound COC1=CC(CC(C)N)=CC(OC)=C1OC WGTASENVNYJZBK-UHFFFAOYSA-N 0.000 description 3
- RXYIGKSGQKMGAG-UHFFFAOYSA-N CCCCCCCCC=CC(NCCC1=CC=CC=C1)=O Chemical compound CCCCCCCCC=CC(NCCC1=CC=CC=C1)=O RXYIGKSGQKMGAG-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- KISVAASFGZJBCY-UHFFFAOYSA-N methyl undecenate Chemical compound COC(=O)CCCCCCCCC=C KISVAASFGZJBCY-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- LPYWLLPAGRMCLL-KTKRTIGZSA-N (Z)-N-(2-phenylethyl)octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCC1=CC=CC=C1 LPYWLLPAGRMCLL-KTKRTIGZSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- FEYDZHNIIMENOB-UHFFFAOYSA-N 2,6-dibromopyridine Chemical compound BrC1=CC=CC(Br)=N1 FEYDZHNIIMENOB-UHFFFAOYSA-N 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- DJBNUMBKLMJRSA-UHFFFAOYSA-N Flecainide Chemical compound FC(F)(F)COC1=CC=C(OCC(F)(F)F)C(C(=O)NCC2NCCCC2)=C1 DJBNUMBKLMJRSA-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000001430 anti-depressive effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 229960000449 flecainide Drugs 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229940028300 tigan Drugs 0.000 description 1
Images
Classifications
-
- 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
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
-
- 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
- B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
- B01J2531/0233—Aza-Cp ligands, i.e. [CnN(5-n)Rn]- in which n is 0-4 and R is H or hydrocarbyl, or analogous condensed ring systems
-
- 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
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a manganese metal catalyst and a synthesis method thereof, and a synthesis method of a vegetable oil-based amide compound, belonging to the technical field of organic synthesis. The invention firstly synthesizes a manganese metal catalyst, and the vegetable oil-based amide compound can be obtained by only one-step reaction by using the catalyst. The manganese metal catalyst provided by the invention takes the easily prepared nitrogen heterocyclic ring bridged benzimidazole salt as a raw material, has a simple synthesis method and high yield, and has a good catalytic effect when being used for preparing the vegetable oil-based amide compound. The synthetic method of the vegetable oil-based amide compound provided by the invention is simple, the cost is low, the vegetable oil-based amide compound can be obtained by only one-step reaction, and toxic byproducts are not generated. The results of the examples show that the yield of the vegetable oil-based amide compound obtained by the method can reach more than 70%.
Description
Technical Field
The invention relates to the technical field of organic synthesis, and particularly relates to a manganese metal catalyst and a synthesis method thereof, and a synthesis method of a vegetable oil-based amide compound.
Background
The vegetable oil-based amide compounds are important medicine molecules with antiviral and antidepressant effects. At present, the vegetable oil-based amide compound medicines comprise the following medicines:
the traditional synthetic method of the medicine is mainly obtained by reacting carboxylic acid compounds with acyl chloride and then reacting with amine compounds under the action of equivalent coupling reagents, and the method has the problems of multiple steps, non-conformity with atom economy and the like; in addition, expensive coupling reagents or high-temperature conditions are required in the reaction process, and the reaction cost is high.
Disclosure of Invention
In view of this, the present invention aims to provide a manganese metal catalyst and a synthesis method thereof, and a synthesis method of a vegetable oil-based amide compound. The manganese metal catalyst provided by the invention can be used for preparing the vegetable oil-based amide compound in a one-step catalytic manner.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a manganese metal catalyst, which has a chemical structural formula shown as formula 1a, formula 1b, formula 1c or formula 1 d:
the invention provides a synthesis method of a manganese metal catalyst, which comprises the following steps:
mixing nitrogen heterocyclic bridged benzimidazole salt, manganese pentacarbonyl bromide, potassium tert-butoxide and a polar organic solvent, and carrying out metal oxidation addition reaction to obtain a manganese metal catalyst;
the nitrogen heterocyclic ring bridged benzimidazole salt has a structure shown in a formula 2:
in the formula 2, X is I or Br;
when X is I, R is one of Me, n-Pr and n-Bu;
when X is Br, R is n-Pr.
Preferably, the mole ratio of the nitrogen heterocyclic bridged benzimidazole salt to the manganese pentacarbonyl bromide to the potassium tert-butoxide is 1: 0.5-0.8: 0.4 to 0.6.
Preferably, the temperature of the metal oxidation addition reaction is 50-80 ℃, and the time is 18-20 h.
Preferably, after the metal oxidation addition, the method further comprises performing post-treatment on the metal oxidation addition liquid, wherein the post-treatment comprises the following steps:
and cooling, distilling, recrystallizing, filtering and drying the metal oxidation addition reaction liquid in sequence to obtain the manganese metal catalyst solid.
The invention provides a synthetic method of a vegetable oil-based amide compound, which comprises the following steps:
mixing vegetable oil ester compounds, amine compounds, sodium tert-butoxide, manganese metal catalysts and organic solvents, and carrying out oxidation addition reaction to obtain vegetable oil-based amide compounds;
the vegetable oil ester compound is one of methyl oleate, ethyl oleate, methyl linoleate, methyl erucate, methyl ricinoleate, methyl 10-undecylenate and epoxidized derivatives of vegetable oleate;
the amine compound has a structure shown in formula 3:
in formula 3, R 1 And R 2 Independently one of hydrogen, alkyl and aryl;
the manganese metal catalyst is the manganese metal catalyst.
Preferably, the molar ratio of the vegetable oil ester compound to the amine compound to the sodium tert-butoxide to the manganese metal catalyst is 1: 1.2-2: 0.2 to 0.5:0.01 to 0.05.
Preferably, the alkyl group is a primary or secondary alkyl group; the aryl group is a primary or secondary aryl group.
Preferably, the temperature of the oxidation addition reaction is 60-90 ℃ and the time is 18-24 h.
Preferably, the post-treatment of the oxidation addition reaction liquid after the oxidation addition reaction comprises the following steps:
and sequentially carrying out extraction, organic phase evaporation and thin-layer chromatographic column separation on the oxidation addition reaction liquid to obtain a pure vegetable oil-based amide compound.
The invention provides a manganese metal catalyst which has a good catalytic effect when used for preparing a vegetable oil-based amide compound. In the invention, the valence of manganese metal in the manganese metal catalyst is positive and monovalent, the positive and monovalent manganese is reduced into zero-valent manganese under the alkaline condition, the zero-valent manganese can be inserted into an ester group of a vegetable oil ester compound to generate an intermediate product, and then the intermediate product reacts with an amine compound to generate a target product, and manganese is removed, thereby completing the catalytic process.
The invention provides a method for synthesizing a manganese metal catalyst, which takes easily prepared nitrogen heterocyclic ring bridged benzimidazole salt as a raw material, and has simple synthesis method and high yield. The results of the examples show that the yield of the manganese metal catalyst of the synthesis method provided by the invention is 70-80%.
The invention provides a method for synthesizing a vegetable oil-based amide compound, which uses vegetable oil ester to perform oxidation addition reaction with amines under the action of manganese catalysis to obtain a product, has simple synthetic route and low cost, can obtain the vegetable oil-based amide compound by only one-step reaction, and does not generate toxic by-products. The results of the examples show that the yield of the vegetable oil-based amide compounds obtained by the method can reach more than 70%.
Drawings
FIG. 1 is a hydrogen spectrum of a manganese metal catalyst 1a obtained in example 1;
FIG. 2 is a hydrogen spectrum of the manganese metal catalyst 1b obtained in example 2;
FIG. 3 is a hydrogen spectrum of the manganese metal catalyst 1c obtained in example 3;
FIG. 4 is a hydrogen spectrum of the manganese metal catalyst 1d obtained in example 4;
FIG. 5 is a chart of a hydrogen spectrum of N-phenethyl oleamide obtained in example 5;
FIG. 6 is a carbon spectrum of N-phenethyloleamide obtained in example 5;
FIG. 7 is a hydrogen spectrum of 8- (3-octyloxa-2-yl) -N-phenethyloctanamide obtained in example 6;
FIG. 8 is a carbon spectrum of 8- (3-octyloxa-2-yl) -N-phenethyloctanamide obtained in example 6;
FIG. 9 is a hydrogen spectrum of N-phenethylundeceneamide obtained in example 7;
FIG. 10 is a carbon spectrum of N-phenethylundeceneamide obtained in example 7;
FIG. 11 is a hydrogen spectrum of 8- (3-octyloxa-2-yl) -N-phenyloctanoyl amide obtained in example 8;
FIG. 12 is a carbon spectrum of 8- (3-octyloxa-2-yl) -N-phenyloctanamide obtained in example 8.
Detailed Description
The invention provides a manganese metal catalyst, which has a chemical structural formula shown as formula 1a, formula 1b, formula 1c or formula 1 d:
in the invention, me is methyl, n-Pr is n-propyl, and n-Bu is n-butyl.
In the invention, the manganese metal catalyst is firstly reduced into zero-valent manganese by the action of alkali in a reaction cycle, then the zero-valent manganese is inserted into methyl ester to form an intermediate product, and then the intermediate product reacts with amine, manganese is removed to generate a product, and the reaction is finished. The manganese metal catalyst provided by the invention can be used for preparing known medicines, such as amide medicines, such as Moclobiemide, tigan, flecainide and the like, by catalysis.
The invention provides a preparation method of the manganese metal catalyst, which comprises the following steps:
mixing nitrogen heterocyclic bridged benzimidazole salt, manganese pentacarbonyl bromide, potassium tert-butoxide and a polar organic solvent, and carrying out metal oxidation addition reaction to obtain a manganese metal catalyst;
in the invention, the nitrogen heterocyclic ring bridged benzimidazole salt has a structure shown in a formula 2:
in the formula 2, X is I or Br;
when X is I, R is one of Me, n-Pr and n-Bu;
when X is Br, R is n-Pr.
In the present invention, the mole ratio of the nitrogen heterocyclic bridged benzimidazole salt, the manganese pentacarbonyl bromide and the sodium tert-butoxide is preferably 1:0.5 to 0.8:0.4 to 0.6, more preferably 1:0.6:0.5. in the present invention, the solvent is preferably a polar organic solvent, and the polar organic solvent is preferably one of tetrahydrofuran, acetonitrile and methanol, and more preferably tetrahydrofuran. In the present invention, the amount ratio of the nitrogen heterocyclic bridged benzimidazole salt to the solvent is preferably 1mmol: 1-2 mL. In the invention, the potassium tert-butoxide plays a role in removing active hydrogen on the nitrogen heterocyclic ring bridged benzimidazole salt and playing a role in oxidation. In the invention, the nitrogen heterocyclic bridged benzimidazole salt is easy to prepare and has wide sources. In the invention, the preparation method of the nitrogen heterocyclic bridged benzimidazole salt comprises the following steps:
firstly, carrying out substitution reaction on 2, 6-dibromopyridine and benzimidazole under the conditions of DMSO and CuI to obtain a substitution reaction product;
the temperature of the substitution reaction is 110 ℃, and the time is 12h;
reacting the substituted alkyl halide in acetonitrile solution to obtain nitrogen heterocyclic ring bridged benzimidazole salt;
the alkyl halide is one of methyl iodide, iodopropane, iodobutane and bromopropane;
the reaction temperature is 80 ℃ and the reaction time is 6h.
When X of the nitrogen heterocyclic bridged benzimidazole salt is I and R is Me, the reaction formula for preparing the nitrogen heterocyclic bridged benzimidazole salt is shown as the formula I:
the invention does not require any particular mixing means, such as stirring, known to the person skilled in the art. In the present invention, the reaction temperature of the metal oxidation addition reaction is preferably 50 to 80 ℃, more preferably 60 to 70 ℃; the reaction time is preferably 18 to 20 hours, more preferably 19 hours. In the present invention, the time for raising the temperature to the reaction temperature is preferably 3min. The metal oxidation addition reaction is preferably carried out under the condition of stirring, and the stirring speed is preferably 500r/min.
In the invention, the reaction formula of the metal oxidation addition reaction is shown as formula II:
in the present invention, it is preferable that the metal oxide addition liquid is subjected to a post-treatment after the metal oxide addition, and the post-treatment preferably comprises the steps of:
and cooling, distilling, recrystallizing, filtering and drying the metal oxidation addition reaction liquid in sequence to obtain the manganese metal catalyst solid.
The present invention does not require any particular cooling means, as those known to those skilled in the art, such as natural cooling to room temperature. In the present invention, the distillation mode is preferably reduced pressure rotary distillation, and the solid mixture containing the catalyst and the reactant is obtained by recrystallization. The recrystallization is preferably carried out by adding acetonitrile, and in the present invention, the recrystallized solid mixture is distilled, and the residual reactant is removed by recrystallization. The present invention does not require any particular means of filtration, and filtration methods well known to those skilled in the art may be used. In the present invention, the drying temperature is preferably room temperature, and the time is preferably 2 hours.
The invention provides a synthetic method of a vegetable oil-based amide compound, which comprises the following steps:
mixing vegetable oil ester compounds, amine compounds, sodium tert-butoxide, manganese metal catalysts and solvents, and carrying out oxidation addition reaction to obtain vegetable oil-based amide compounds;
the vegetable oil ester compound has a structure shown in a formula 4:
the vegetable oil ester compound is one of methyl oleate, ethyl oleate, methyl linoleate, methyl erucate, methyl ricinoleate, 10-methyl undecylenate and epoxidized derivatives of vegetable oleate. The amine compound has a structure shown in formula 3:
in the formula 3, R 1 And R 2 Independently one of hydrogen, alkyl and aryl; in the present invention, the alkyl group is preferably a primary or secondary alkyl group, and the aryl group is preferably a primary or secondary aryl group, and in the present invention, the amine compound is preferably one of pentylamine, dibutylamine, aniline, and diphenylamine.
The manganese metal catalyst is the manganese metal catalyst provided by the invention.
The vegetable oil-based amide compound is prepared by mixing vegetable oil ester compounds, amine compounds, sodium tert-butoxide, manganese metal catalysts and organic solvents, and performing oxidation addition reaction. In the present invention, the molar ratio of the vegetable oil ester compound, the amine compound, sodium tert-butoxide and the manganese metal catalyst is preferably 1: 1.2-2: 0.2 to 0.5:0.01 to 0.05, more preferably 1: 1.5-1.8: 0.2:0.01.
in the present invention, the organic solvent is preferably one or more of toluene, 1, 4-dioxane, methanol, ethanol, N-dimethylformamide, N-dimethylacetamide, acetonitrile, ethyl acetate, dichloromethane, tetrahydrofuran, a nitrogen heterocyclic compound, chloroform and acetone. In the present invention, the solvent is preferably an untreated solvent. In the present invention, the molar ratio of the vegetable oil ester compound to the organic solvent is preferably 1:15.
in the invention, sodium tert-butoxide is used for generating sodium iodide or sodium bromide from iodide or bromide of the catalyst and leaving the sodium iodide or sodium bromide to ensure that the catalyst is in positive valence and attracts electrons.
The invention does not require any particular mixing means, as is known to those skilled in the art, such as stirring.
In the present invention, the reaction temperature of the oxidative addition reaction is preferably 60 to 90 ℃, more preferably 70 to 80 ℃; the reaction time is preferably 18 to 24 hours, more preferably 20 to 22 hours. In the present invention, the time for raising the temperature to the reaction temperature is preferably 5 minutes. The oxidative addition reaction is preferably carried out under stirring, preferably at a rate of 500r/min.
In the invention, the valence of manganese metal in the manganese metal catalyst is monovalent, sodium tert-butoxide provides alkaline conditions for reaction, monovalent manganese is reduced to zero-valent manganese under the action of alkali, and the zero-valent manganese is inserted into an ester group of a vegetable oil ester compound to generate an intermediate product
Then reacting with amine compound to generate target product, and removing manganese to complete the catalysis process. In the present invention, the chemical reaction formula of the oxidative addition is shown as formula III:
in the present invention, it is preferable that the oxidative addition reaction liquid is subjected to a post-treatment after the oxidative addition reaction, the post-treatment comprising the steps of:
and sequentially carrying out extraction, organic phase evaporation and thin-layer chromatographic column separation on the oxidation addition reaction liquid to obtain a pure vegetable oil-based amide compound.
In the present invention, the oxidative addition reaction solution is preferably extracted with dichloromethane and a saturated common salt solution, and the number of times of extraction is preferably 3. In the present invention, the volume ratio of the dichloromethane to the saturated saline solution is preferably 1: in the present invention, the saturated saline solution has the effects of preventing emulsification and reducing the solubility of organic compounds in water. After extraction, the organic phase obtained is evaporated according to the invention. The present invention does not require any particular means for said evaporation, and can be carried out using methods known to the person skilled in the art, such as rotary evaporation. The present invention removes the dichloromethane phase by the evaporation. In the present invention, the mobile phase separated by the thin layer chromatography column is preferably petroleum ether: ethyl acetate =5:1.
the invention uses vegetable oil ester to react with amine compounds under the action of manganese catalysis to obtain products, and has the advantages of mild conditions, no need of solvent treatment, simple steps and high atom economy. The vegetable oil-based amide compounds obtained by the synthesis method of the invention preferably include the following compounds shown in table 1:
TABLE 1 vegetable oil-based amides obtained by the Synthesis method of the invention
The manganese metal catalyst and the synthesis method thereof and the synthesis method of the vegetable oil-based amide compound provided by the present invention are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding 2mL of tetrahydrofuran solution into a reaction tube, adding 1mmol of nitrogen heterocyclic bridged benzimidazole salt (R = Me at the moment, X = I), then adding 0.8mmol of manganese pentacarbonyl bromide, adding 0.6mmol of potassium tert-butoxide, heating to 50 ℃, stirring for 18h (stirring speed is 500R/min), cooling to room temperature after the reaction is completed, carrying out reduced pressure rotary distillation on the product, adding acetonitrile for recrystallization, filtering, and drying at room temperature for 2 hours to obtain the manganese metal catalyst 1a with the mass of 289mg and the yield of 76%.
The hydrogen spectrum of the obtained product is shown in figure 1, and the hydrogen spectrum data is as follows:
1 H NMR(DMSO,400MHz):δ9.07(brs,1H),8.49(d,J＝36.8Hz,2H),8.25(brs,1H),7.94(brs,1H),7.57(brs,3H),4.29(s,3H).HRMS(ESI)calcd for C 16 H 11 IMnN 3 O 3 [M-I] + 348.0175,found 348.0179。
example 2
Adding 2mL of tetrahydrofuran solution into a reaction tube, adding 1mmol of nitrogen heterocyclic bridged benzimidazole salt (R = n-Pr at the moment, and X = I), then adding 0.8mmol of manganese pentacarbonyl bromide, adding 0.6mmol of potassium tert-butoxide, heating to 60 ℃, stirring for 20h (stirring speed 500R/min), cooling to room temperature after the reaction is completed, carrying out reduced pressure rotary distillation on the product, adding acetonitrile for recrystallization, filtering, and drying at room temperature for 2h to obtain the manganese metal catalyst 1b with the mass of 294mg and the yield of 73%.
The hydrogen spectrum of the obtained product is shown in figure 2, and the hydrogen spectrum data are as follows:
1 H NMR(DMSO,400MHz):δ9.07(brs,1H),8.49(d,J＝34.8Hz,2H),8.25(brs,1H),8.01(brs,1H),7.56(brs,3H),4.70(s,2H),2.07(brs,2H),1.06(s,3H).HRMS(ESI)calcd for C 18 H 15 IMnN 3 O 3 [M-I] + 376.0488,found 376.0496。
example 3
Adding 2mL of tetrahydrofuran solution into a reaction tube, adding 1mmol of nitrogen heterocyclic ring bridged benzimidazole salt (R = n-Bu and X = I), then adding 0.8mmol of manganese pentacarbonyl bromide and 0.6mmol of potassium tert-butoxide, heating to 70 ℃, stirring for 22h (stirring speed 500R/min), cooling to room temperature after the reaction is completed, carrying out reduced pressure rotary distillation on the product, adding acetonitrile for recrystallization, filtering, and drying at room temperature for 2h to obtain the manganese metal catalyst 1c with the mass of 281mg and the yield of 68%.
The hydrogen spectrum of the obtained product is shown in figure 3, and the hydrogen spectrum data is as follows:
1 H NMR(DMSO,400MHz):δ9.07(brs,1H),8.49(d,J＝35.2Hz,2H),8.24(brs,1H),7.98(brs,1H),7.57(brs,3H),4.73(s,2H),2.07(brs,2H),1.50(brs,2H),1.06(s,3H).HRMS(ESI)calcd for C 19 H 17 IMnN 3 O 3 [M-I] + 390.0645,found 390.0656。
example 4
2ml of tetrahydrofuran solution was added to the reaction tube, and 1mmol of the azacyclo-bridged benzimidazole salt (in this case R = n-Pr, X = PF) was added 6 ) Then adding 0.8mmol of manganese pentacarbonyl bromide and 0.6mmol of potassium tert-butoxide, heating to 80 ℃, stirring for 24h (stirring speed 500 r/min), cooling to room temperature after the reaction is finished, carrying out reduced pressure rotary distillation on the product, adding acetonitrile, recrystallizing, filtering, and drying at room temperature for 2h to obtain the manganese metal catalyst 1d with the mass of 295mg and the yield of 81%.
The hydrogen spectrum of the obtained product is shown in figure 4, and the hydrogen spectrum data is as follows:
1 H NMR(DMSO,400MHz):δ8.46-7.62(m,8H),4.77(brs,2H),2.08(brs,2H),1.24-1.09(m,3H).HRMS(ESI)calcd for C 18 H 15 BrMnN 3 O 3 [M-Br] + 376.0488,found 376.0502。
example 5
Stirring 1mmol of methyl oleate, 1.2mmol of phenethylamine, 0.2mmol of sodium tert-butoxide, 0.01mmol of manganese metal catalyst 1a and 2mL of untreated toluene solvent at the temperature of 90 ℃ for 18h, extracting the required product for 3 times by dichloromethane and saturated saline after the reaction is finished, putting the required product in a dichloromethane phase, carrying out rotary evaporation on the dichloromethane phase, removing the dichloromethane phase, and carrying out thin-layer chromatography column separation on the residue to obtain the N-phenethyl oleamide, wherein the structural formula is shown in the specification
The yield reaches 70 percent.
The hydrogen spectrum of the obtained product is shown in figure 5, and the hydrogen spectrum data is as follows:
1 H NMR(CDCl 3 ,400MHz):δ7.19(t,J＝7.2Hz,2H),7.13-7.08(m,3H),5.95(brs,1H),5.27-5.24(m,2H),3.39(q,J＝7.2Hz,2H),2.71(t,J＝7.2Hz,2H),2.03(t,J＝7.2Hz,2H),1.95-1.90(m,3H),2.03(t,J＝6.8Hz,2H),1.21-1.18(m,21H),0.81-0.78(m,3H).
the carbon spectrum of the obtained product is shown in FIG. 6, and the carbon spectrum data are as follows:
13 C NMR(CDCl 3 ,100MHz):δ173.38,139.02,129.97,129.72,128.72,128.55,126.42,40.65,36.70,35.75,31.93,29.79,29.76,29.69,29.56,29.40,29.35,29.31,29.19,27.25,27.21,25.84,22.71,14.14.
example 6
1mmol of epoxidized methyl oleate
Mixing with 1.2mmol phenethylamine, 0.2mmol sodium tert-butoxide, 0.01mmol manganese metal catalyst 1b and 2mL untreated toluene solvent, stirring at 60 deg.C for 18h, extracting the desired product with dichloromethane and saturated saline water for 3 times, subjecting the desired product to rotary evaporation in dichloromethane phase, removing dichloromethane phase, separating the residue with thin layer chromatography to obtain 8- (3-octyloxa-2-yl) -N-phenethyl octanoamide with structural formula of
The yield reaches 75 percent.
The hydrogen spectrum of the obtained product is shown in figure 7, and the hydrogen spectrum data are as follows:
1 H NMR(CDCl 3 ,400MHz):δ7.29(t,J＝6.8Hz,2H),7.23-7.17(m,3H),5.57(brs,1H),3.50(q,J＝7.2Hz,2H),2.90-2.87(m,2H),2.80(t,J＝6.8Hz,2H),2.10(t,J＝7.6Hz,2H),1.60-1.26(m,26H),0.88-0.85(m,3H).
the carbon spectrum of the obtained product is shown in figure 8, and the carbon spectrum data are as follows:
13 C NMR(CDCl 3 ,100MHz):δ173.08,138.98,128.76,128.61,126.48,57.24,57.21,40.51,36.75,35.74,31.86,29.56,29.54,29.34,29.25,29.23,29.14,27.84,27.79,26.61,26.60,25.68,22.67,14.11.
example 7
1mmol of methyl 10-undecenoate, 1.2mmol of phenethylamine, 0.6mmol of sodium tert-butoxide, 0.01mmol of manganese metal catalyst 1c,2mL of untreated catalystStirring the toluene solvent at the temperature of 70 ℃ for 18 hours, extracting the required product for 3 times by dichloromethane and saturated saline after the reaction is finished, putting the required product in a dichloromethane phase, carrying out rotary evaporation on the dichloromethane phase, removing the dichloromethane phase, and carrying out thin-layer chromatography column separation on the residue to obtain the N-phenethyl undeceneamide with the structural formula of
The yield reaches 79 percent.
The hydrogen spectrum of the obtained product is shown in figure 9, and the hydrogen spectrum data are as follows:
1 H NMR(CDCl 3 ,400MHz):δ7.29(t,J＝6.8Hz,2H),7.23-7.17(m,3H),5.82-5.74(m,2H),4.94(qq,J＝12.0,1.6Hz,2H),3.49(q,J＝6.0Hz,2H),2.80(t,J＝7.2Hz,2H),2.11(t,J＝7.2Hz,2H),2.05-2.00(m,2H),1.59-1.56(m,2H),1.38-1.26(m,10H).
the carbon spectrum of the obtained product is shown in FIG. 10, and the carbon spectrum data is as follows:
13 C NMR(CDCl 3 ,100MHz):δ173.26,139.14,139.01,128.75,128.59,126.46,114.19,40.58,36.77,35.75,33.80,29.34,29.29,29.09,28.91,25.79,24.74.
example 8
1mmol of epoxidized methyl oleate, 1.2mmol of aniline, 0.6mmol of sodium tert-butoxide, 0.01mmol of manganese metal catalyst 1d, and 2mL of untreated toluene solvent are stirred at 80 ℃ for 20h, after the reaction is finished, the required product is extracted for 3 times by dichloromethane and saturated saline water, the required product is in a dichloromethane phase, the dichloromethane phase is subjected to rotary evaporation, the dichloromethane phase is removed, and the residue is subjected to thin-layer chromatography column separation to obtain 8- (3-octyloxa-2-yl) -N-phenyloctanamide, wherein the structural formula is shown in the specification
The yield reaches 70 percent.
The hydrogen spectrum of the obtained product is shown in figure 11, and the hydrogen spectrum data are as follows:
1 H NMR(CDCl 3 ,400MHz):δ7.50(d,J＝7.6Hz,2H),7.40(brs,1H),7.30(t,J＝7.6Hz,2H),7.08(t,J＝7.6Hz,1H),2.93-2.88(m,2H),2.34(t,J＝7.2Hz,2H),1.72-1.70(m,2H),1.50-1.24(m,24H),0.89-0.86(m,3H).
the carbon spectrum of the obtained product is shown in FIG. 12, and the carbon spectrum data are as follows:
13 C NMR(CDCl 3 ,100MHz):δ171.46,138.06,128.97,124.12,119.77,57.29,37.73,31.87,31.50,29.56,29.54,29.28,29.23,29.20,29.10,27.86,27.76,26.62,26.61,25.55,22.68,14.12.HRMS(ESI)calcd for C 24 H 39 NO 2 [M+H] + 374.3054,found 374.3058.
example 9
Stirring 1mmol of methyl oleate, 1.2mmol of naphthylamine, 0.6mmol of sodium tert-butoxide, 0.01mmol of manganese metal catalyst 1b and 2mL of untreated toluene solvent at the temperature of 90 ℃ for 22h, extracting the required product for 3 times by using dichloromethane and saturated saline after the reaction is finished, putting the required product in a dichloromethane phase, performing rotary evaporation on the dichloromethane phase, removing the dichloromethane phase, and performing thin-layer chromatography column separation on the residue to obtain N- (naphthalene-1-yl) oleamide, wherein the structural formula is shown in the specification
The yield reaches 74 percent.
Example 10
Stirring 1mmol methyl oleate, 1.2mmol p-methylaniline, 0.6mmol sodium tert-butoxide, 0.01mmol manganese metal catalyst 1d,2mL untreated toluene solvent at 90 ℃ for 24h, extracting the required product for 3 times by dichloromethane and saturated saline after the reaction is finished, putting the required product in a dichloromethane phase, carrying out rotary evaporation on the dichloromethane phase, removing the dichloromethane phase, carrying out thin-layer chromatography column separation on the residue to obtain N- (p-tolyl) oleamide, wherein the structural formula is shown in the specification
The yield reaches 74 percent.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A synthetic method of a vegetable oil-based amide compound is characterized by comprising the following steps:
mixing vegetable oil ester compounds, amine compounds, sodium tert-butoxide, manganese metal catalysts and organic solvents, and carrying out oxidation addition reaction to obtain vegetable oil-based amide compounds;
the vegetable oil ester compound is one of methyl oleate, ethyl oleate, methyl linoleate, methyl erucate, methyl ricinoleate, 10-methyl undecylenate and epoxidized derivatives of vegetable oleate;
the amine compound has a structure shown in formula 3:
in formula 3, R 1 And R 2 Independently one of hydrogen, alkyl and aryl;
the chemical structural formula of the manganese metal catalyst is shown as formula 1a, formula 1b, formula 1c or formula 1 d:
2. the synthesis method according to claim 1, characterized in that the synthesis method of the manganese metal catalyst comprises the following steps:
mixing nitrogen heterocyclic bridged benzimidazole salt, manganese pentacarbonyl bromide, potassium tert-butoxide and a polar organic solvent, and carrying out metal oxidation addition reaction to obtain a manganese metal catalyst;
the nitrogen heterocyclic bridged benzimidazole salt has a structure shown in a formula 2:
in the formula 2, X is I or Br;
when X is I, R is one of Me, n-Pr and n-Bu;
when X is Br, R is n-Pr.
3. The synthesis method according to claim 2, wherein the molar ratio of the nitrogen heterocyclic bridged benzimidazole salt to the manganese pentacarbonyl bromide to the potassium tert-butoxide is 1: 0.5-0.8: 0.4 to 0.6.
4. The synthesis method according to claim 2, characterized in that the temperature of the metal oxidative addition reaction is 50-80 ℃ and the time is 18-20 h.
5. The synthesis method according to claim 2 or 4, further comprising, after the metal oxidation addition, performing a post-treatment on the metal oxidation addition solution, wherein the post-treatment comprises the following steps:
and (3) sequentially cooling, distilling, recrystallizing, filtering and drying the metal oxidation addition reaction liquid to obtain the manganese metal catalyst solid.
6. The synthesis method according to claim 1, wherein the molar ratio of the vegetable oil ester compound to the amine compound to the sodium tert-butoxide to the manganese metal catalyst is 1: 1.2-2: 0.2 to 0.5:0.01 to 0.05.
7. The method of synthesis of claim 1, wherein the alkyl group is a primary or secondary alkyl group; the aryl group is a primary aryl group or a secondary aryl group.
8. The synthesis method according to claim 1, wherein the temperature of the oxidative addition reaction is 60-90 ℃ and the time is 18-24 h.
9. The synthesis method according to claim 1, further comprising post-treating the oxidative addition reaction solution after the oxidative addition reaction, wherein the post-treating comprises the steps of:
and sequentially carrying out extraction, organic phase evaporation and thin-layer chromatographic column separation on the oxidation addition reaction liquid to obtain a pure vegetable oil-based amide compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010169799.2A CN111266133B (en) | 2020-03-12 | 2020-03-12 | Manganese metal catalyst and synthetic method thereof, and synthetic method of vegetable oil-based amide compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010169799.2A CN111266133B (en) | 2020-03-12 | 2020-03-12 | Manganese metal catalyst and synthetic method thereof, and synthetic method of vegetable oil-based amide compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111266133A CN111266133A (en) | 2020-06-12 |
| CN111266133B true CN111266133B (en) | 2022-10-04 |
Family
ID=70991449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010169799.2A Active CN111266133B (en) | 2020-03-12 | 2020-03-12 | Manganese metal catalyst and synthetic method thereof, and synthetic method of vegetable oil-based amide compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111266133B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734667A (en) * | 2018-12-18 | 2019-05-10 | 五邑大学 | A kind of polysubstituted imidazolium compounds and its synthetic method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7223859B2 (en) * | 2003-03-17 | 2007-05-29 | Pfizer Inc. | Method for producing (R)-3-[4-(trifluoromethyl) phenylamino]-pentanoic acid amide derivative |
-
2020
- 2020-03-12 CN CN202010169799.2A patent/CN111266133B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734667A (en) * | 2018-12-18 | 2019-05-10 | 五邑大学 | A kind of polysubstituted imidazolium compounds and its synthetic method and application |
Non-Patent Citations (3)
| Title |
|---|
| Exploring the effect of axial ligand substitution (X = Br, NCS, CN) on the photodecomposition and electrochemical activity of [MnX(N–C)(CO)3] complexes;Jay Agarwal,et.al.;《Dalton Trans》;20141204;第44卷;图1 * |
| Jay Agarwal,et.al..Exploring the effect of axial ligand substitution (X = Br, NCS, CN) on the photodecomposition and electrochemical activity of [MnX(N–C)(CO)3] complexes.《Dalton Trans》.2014,第44卷 * |
| Manganese-Catalyzed Direct Conversion of Ester to Amide with Liberation of H2;Akash Mondal,et.al.;《Org. Lett.》;20180523;第20卷;摘要，摘要附图，Scheme 3 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111266133A (en) | 2020-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Regioselective and stereoselective sulfonylation of alkynylcarbonyl compounds in water | |
| JP6516856B2 (en) | Method for producing formamide compounds | |
| CN102516151B (en) | 3-substituted-3-hydroxyindazolone derivatives, and preparation method and application thereof | |
| CN111205279B (en) | Polysubstituted benzodihydrofuran heterocyclic compound and preparation method and application thereof | |
| CN108148069B (en) | Synthetic method of furanone pyridone compound | |
| CN108690007B (en) | C-H coupling reaction catalyzed by transition metal for efficiently preparing o-cyanoated aromatic ring or unsaturated aliphatic ring compound | |
| CN106349147A (en) | Synthetic method of pyrrole derivatives | |
| Okada et al. | One-Pot Synthesis of Isocyanides from Alcohols | |
| CN111974458B (en) | Iridium catalyst loaded by PBS microspheres as well as preparation method and application thereof | |
| CN111266133B (en) | Manganese metal catalyst and synthetic method thereof, and synthetic method of vegetable oil-based amide compound | |
| CN112812091A (en) | Synthetic method of cyclic carbonate | |
| CN109535120B (en) | Preparation method of 7-substituted-3, 4,4, 7-tetrahydrocyclobutane coumarin-5-ketone | |
| CN108314647B (en) | Preparation method of quinoline-2-formic acid and quinoline-2-formic acid derivative | |
| CN102617260B (en) | Method for removing boric acid group by using aryl boric acid compound | |
| CN113387886B (en) | 2-aminodibenzo [ c, e ] azepine compound and synthetic method thereof | |
| WO2021242807A1 (en) | Methods for preparing methyl (s)-2-amino-3-(4-(2,3-dimethylpyridin-4-yl)phenyl)propionate and hydrochloric acid salts thereof | |
| CN111018779B (en) | 2- (3-isoquinolyl) -ethyl propionate derivative and synthetic method thereof | |
| CN113527367A (en) | Chiral diphosphine ligand rhodium complex containing tetra (3, 5-bistrifluoromethylphenyl) boron anion and preparation method and application thereof | |
| CN108456172B (en) | Chiral N-heterocyclic carbene precursor compound with benzimidazole skeleton and preparation method and application thereof | |
| CN109053543A (en) | A kind of preparation method of cis- 3- alkoxy -1- methylene isoindole derivatives | |
| JP5645494B2 (en) | Method for producing amine body | |
| Sakai et al. | Chemoselective isomerization of secondary-type propargylic alcohols to propargylic/allenic bromides, and brominated dienes with Appel-Type reaction conditions | |
| CN103864548A (en) | Method for rapidly and efficiently preparing 1-haloalkyne | |
| CN108558750B (en) | Process for synthesizing 3-nitroquinoline derivative by solvent-free method | |
| TW201540743A (en) | Method for producing polyalkylene glycol derivative with narrow molecular weight distribution, and acetal group-containing alcohol compound for use therein and alkali metal salt 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |