CN116410073A - Method for preparing methylene quinone compound by deamination of Mannich base - Google Patents
Method for preparing methylene quinone compound by deamination of Mannich base Download PDFInfo
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- CN116410073A CN116410073A CN202310203689.7A CN202310203689A CN116410073A CN 116410073 A CN116410073 A CN 116410073A CN 202310203689 A CN202310203689 A CN 202310203689A CN 116410073 A CN116410073 A CN 116410073A
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- mannich base
- deamination
- amino acid
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- 238000000034 method Methods 0.000 title claims abstract description 26
- -1 methylene quinone compound Chemical class 0.000 title claims abstract description 20
- 238000006481 deamination reaction Methods 0.000 title claims abstract description 13
- 230000009615 deamination Effects 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 150000001413 amino acids Chemical class 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 4
- 235000001014 amino acid Nutrition 0.000 claims description 10
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 3
- 235000004279 alanine Nutrition 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004472 Lysine Substances 0.000 claims description 2
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 238000004821 distillation Methods 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract description 3
- 150000008064 anhydrides Chemical class 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- JPUUAYFQHNNDBM-UHFFFAOYSA-N bicyclo[4.1.0]hepta-1(6),3-diene-2,5-dione Chemical class O=C1C=CC(=O)C2=C1C2 JPUUAYFQHNNDBM-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NSELNWPKMNRMRP-UHFFFAOYSA-N C(C)(C)(C)C1=C(C(=CC(=C1)C(C1=CC=C(C=C1)C)N1CCCCC1)C(C)(C)C)O Chemical compound C(C)(C)(C)C1=C(C(=CC(=C1)C(C1=CC=C(C=C1)C)N1CCCCC1)C(C)(C)C)O NSELNWPKMNRMRP-UHFFFAOYSA-N 0.000 description 3
- PZSYEZUGGGAMTF-UHFFFAOYSA-N CC1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C Chemical compound CC1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C PZSYEZUGGGAMTF-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 2
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 2
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- VPDSZFFCLBKLKX-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(2-hydroxyphenyl)-piperidin-1-ylmethyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C(N2CCCCC2)C=2C(=CC=CC=2)O)=C1 VPDSZFFCLBKLKX-UHFFFAOYSA-N 0.000 description 1
- QHKJIFLLPMPEIW-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3-nitrophenyl)-piperidin-1-ylmethyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C(N2CCCCC2)C=2C=C(C=CC=2)[N+]([O-])=O)=C1 QHKJIFLLPMPEIW-UHFFFAOYSA-N 0.000 description 1
- RKRMNTKNIMMDCP-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3-nitrophenyl)methylidene]cyclohexa-2,5-dien-1-one Chemical compound C1=C(C(C)(C)C)C(=O)C(C(C)(C)C)=CC1=CC1=CC=CC([N+]([O-])=O)=C1 RKRMNTKNIMMDCP-UHFFFAOYSA-N 0.000 description 1
- YUOVZJMEWHMILQ-UHFFFAOYSA-N OC1=C(C=CC=C1)C=C1C=C(C(C(=C1)C(C)(C)C)=O)C(C)(C)C Chemical compound OC1=C(C=CC=C1)C=C1C=C(C(C(=C1)C(C)(C)C)=O)C(C)(C)C YUOVZJMEWHMILQ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 229940124350 antibacterial drug Drugs 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- 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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing a methylene quinone compound by deamination of a Mannich base. The method is that amino acid reacts with Mannich base, organic amine on the Mannich base and the amino acid form water-soluble amide compound, and the product is separated by water washing after the reaction. The method of the invention avoids the problems of environmental pollution and larger energy consumption caused by the traditional use of inorganic acid or anhydride and deamination by distillation, has high reaction efficiency, is green and environment-friendly, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of organic synthesis, and relates to a deamination method which is particularly suitable for a process of preparing methylene quinone compounds from Mannich base.
Background
The methylene quinone compound is an important intermediate for organic synthesis, and can be used for synthesizing bioactive compounds such as natural melanin, lignin, anticancer drugs, antibacterial drugs and the like. The methylene quinone compounds can be classified into o-methylene quinone and p-methylene quinone. Compared with o-methylene quinone, the 2, 6-di-tert-butyl-7-substituted methylene quinone compound is relatively stable to methylene quinone compounds, can be used as a plurality of organic matters and intermediates of bioactive compounds, and can also be used as a polymerization inhibitor of unsaturated hydrocarbons.
The currently reported synthesis methods of 2, 6-di-tert-butyl-7-substituted methylene quinone compounds mainly comprise three types, wherein the methylene oxidation method uses benzene with strong toxicity and potassium ferricyanide serving as an oxidant, the phenyl lithium method or the Grignard reagent method needs to use high-price phenyl lithium or Grignard reagent, and the reaction needs to be carried out under the anhydrous and anaerobic condition.
The Mannich method takes 2, 6-di-tert-butylphenol, benzaldehyde and secondary amine as raw materials, firstly generates Mannich base, and then deaminates to obtain a product. EP0744392A1 and CN109354571 report that the use of hydrochloric acid and sulfuric acid for deamination to give the hydrochloride and sulfate of an amine has the problems of poor control of the addition amount of acid, easy corrosion to equipment, and severe reaction and high risk. EP0744392A1 also reports a process for deamination using anhydrides, but the amide formed by the reaction is difficult to separate by distillation from the system completely, affecting the product purity. Wang reports a method for deamination by distillation under reduced pressure, but the method has higher requirements on equipment and higher reaction energy consumption.
Disclosure of Invention
The invention aims to solve the problems of low efficiency and dangerous reaction process of the existing Mannich base deamination reaction, and provides a method for preparing a methylene quinone compound by the Mannich base deamination, which has the advantages of high efficiency, low toxicity, easy product separation and suitability for industrial production.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a methylene quinone compound by deamination of a mannich base, the method comprising:
reacting amino acid, mannich base and solvent at 70-110 ℃, washing the reaction system with water after the reaction to obtain an organic phase, and crystallizing to obtain a product;
wherein the structural formula of the Mannich base compound is as follows:
wherein R1 is one of methyl, ethyl, isopropyl, tert-butyl, phenyl, hydroxy, nitrile, methoxy, ethoxy, isopropoxy, butoxy, phenoxy, carboxyl, nitro, halogen and acetyl, R2 is one of methyl, hydroxy, cyano, methoxy and halogen, and R3 is one of hydroxy, nitrile, methoxy, nitro and halogen; the X element in the nitrogen-containing six-membered ring is one of carbon, oxygen and nitrogen.
In the above method of the present invention, the molar ratio of the amino acid to the mannich base is preferably 1.8 to 1.1:1, more preferably a molar ratio of 1.5 to 1.2:1.
in the method of the invention, the reaction temperature is preferably 80-90 ℃; the reaction time is preferably 1.5 to 3.5 hours, more preferably 2 to 3 hours.
The amino acid compound is one of lysine, serine, glycine, glutamic acid and alanine.
According to the method, amino acid and Mannich base are used for deamination, carboxyl on the amino acid and amine are subjected to amidation reaction to generate amide, and the generated amide can be easily separated from a reaction system through washing due to hydrophilic groups on the amino acid, so that the reaction condition is mild, the selectivity is good, and meanwhile, the byproduct amide can be recycled as an organic synthesis intermediate, so that the method has a good industrial prospect.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
Example 1
A three-necked flask was charged with 0.394g (1 mmol) of 2, 6-di-t-butyl-4- [ (4-methylphenyl) -1-piperidylmethyl ] phenol and 50ml of toluene, the mixture was heated to 80℃with stirring, 20ml of an aqueous solution containing 0.09g (1.2 mmol) of glycine was added, the reaction was stopped after stirring for 2 hours, the aqueous phase was separated, the organic phase was washed three times with 100ml of water, toluene was removed, and crystallization was carried out with ethanol to obtain 0.286g of 4-p-methylphenyl methylene-2, 6-di-t-butyl-2, 5-cyclohexadien-1-one as a product in 93% yield.
Example two
A three-necked flask was charged with 0.396g (1 mmol) of 2, 6-di-t-butyl-4- [ (2-hydroxyphenyl) -1-piperidylmethyl ] phenol and 50ml of toluene, the mixture was heated to 85℃with stirring, 20ml of an aqueous solution containing 0.116g (1.3 mmol) of alanine was added, the reaction was stopped after stirring for 2 hours, the aqueous phase was separated, the organic phase was washed three times with 100ml of water, toluene was removed, and crystallization was carried out with ethanol to obtain 0.295g of 4-o-hydroxyphenylmethylene-2, 6-di-t-butyl-2, 5-cyclohexadien-1-one as a product in a yield of 95%.
Example III
A three-necked flask was charged with 0.425g (1 mmol) of 2, 6-di-t-butyl-4- [ (3-nitrophenyl) -1-piperidylmethyl ] phenol and 50ml of toluene, the mixture was heated to 90℃with stirring, 20ml of an aqueous solution containing 0.206g (1.4 mmol) of glutamic acid was added, the reaction was stopped after stirring for 2 hours, the aqueous phase was separated, the organic phase was washed three times with 100ml of water, toluene was removed, and crystallization was carried out with ethanol to obtain 0.316g of 4-m-nitrophenylmethylene-2, 6-di-t-butyl-2, 5-cyclohexadien-1-one as a product in 93% yield.
Comparative example one
To a three-necked flask, 0.394g (1 mmol) of 2, 6-di-t-butyl-4- [ (4-methylphenyl) -1-piperidylmethyl ] phenol and 50ml of toluene were added, the mixture was stirred and heated to 80℃and HCl gas was continuously introduced into the system, the reaction was stopped after stirring for 5 hours, the organic phase was washed three times with 100ml of water, toluene was removed, and crystallization with ethanol was performed to obtain 0.268g of 4-p-methylphenyl methylene-2, 6-di-t-butyl-2, 5-cyclohexadien-1-one as a product in a yield of 87%.
Comparative example two
A three-necked flask was charged with 0.394g (1 mmol) of 2, 6-di-t-butyl-4- [ (4-methylphenyl) -1-piperidylmethyl ] phenol, and after distillation under reduced pressure at 200℃under 1000Pa of vacuum for 6 hours, the reaction was stopped, and the residue was crystallized from ethanol to give 0.246g of 4-p-methylphenyl methylene-2, 6-di-t-butyl-2, 5-cyclohexadien-1-one as a product in 80% yield.
Claims (5)
1. A method for preparing a methylene quinone compound by deamination of a mannich base, comprising the steps of:
reacting amino acid, mannich base and solvent at 70-110 ℃, washing the reaction system with water after the reaction to obtain an organic phase, and crystallizing to obtain a product;
wherein the structural formula of the Mannich base compound is as follows:
wherein R1 is one of methyl, ethyl, isopropyl, tert-butyl, phenyl, hydroxy, nitrile, methoxy, ethoxy, isopropoxy, butoxy, phenoxy, carboxyl, nitro, halogen and acetyl, R2 is one of methyl, hydroxy, cyano, methoxy and halogen, and R3 is one of hydroxy, nitrile, methoxy, nitro and halogen; the X element in the nitrogen-containing six-membered ring is one of carbon, oxygen and nitrogen.
2. The method according to claim 1, wherein the molar ratio of the amino acid to the mannich base is 1.1 to 1.8:1.
3. the method according to claim 2, wherein the molar ratio of the amino acid to the mannich base is 1.5-1.2: 1.
4. the method according to claim 1, wherein the reaction temperature is 80-90 ℃; the reaction time is 1.5-3.5 h.
5. The method of claim 1, wherein the amino acid compound is one of lysine, serine, glycine, glutamic acid, and alanine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310203689.7A CN116410073A (en) | 2023-03-06 | 2023-03-06 | Method for preparing methylene quinone compound by deamination of Mannich base |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310203689.7A CN116410073A (en) | 2023-03-06 | 2023-03-06 | Method for preparing methylene quinone compound by deamination of Mannich base |
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| Publication Number | Publication Date |
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| CN116410073A true CN116410073A (en) | 2023-07-11 |
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| CN202310203689.7A Pending CN116410073A (en) | 2023-03-06 | 2023-03-06 | Method for preparing methylene quinone compound by deamination of Mannich base |
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| Country | Link |
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- 2023-03-06 CN CN202310203689.7A patent/CN116410073A/en active Pending
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