CN100412047C - Method for quick preparation of phenyl pyruvic acid and its aryl substituted derivatives - Google Patents
Method for quick preparation of phenyl pyruvic acid and its aryl substituted derivatives Download PDFInfo
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- CN100412047C CN100412047C CNB2005101230711A CN200510123071A CN100412047C CN 100412047 C CN100412047 C CN 100412047C CN B2005101230711 A CNB2005101230711 A CN B2005101230711A CN 200510123071 A CN200510123071 A CN 200510123071A CN 100412047 C CN100412047 C CN 100412047C
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- aryl
- pyruvic acid
- phenyl
- substituted derivative
- glycolylurea
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- BTNMPGBKDVTSJY-UHFFFAOYSA-N keto-phenylpyruvic acid Chemical group OC(=O)C(=O)CC1=CC=CC=C1 BTNMPGBKDVTSJY-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 43
- 239000001903 2-oxo-3-phenylpropanoic acid Substances 0.000 title claims abstract description 33
- DEDGUGJNLNLJSR-UHFFFAOYSA-N alpha-hydroxycinnamic acid Natural products OC(=O)C(O)=CC1=CC=CC=C1 DEDGUGJNLNLJSR-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 72
- 230000005855 radiation Effects 0.000 claims abstract description 8
- PWKBVLCOBAZTTP-UHFFFAOYSA-N C(C1=CC=CC=C1)=NC(NC(CO)=O)=O Chemical compound C(C1=CC=CC=C1)=NC(NC(CO)=O)=O PWKBVLCOBAZTTP-UHFFFAOYSA-N 0.000 claims description 22
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 241001597008 Nomeidae Species 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 3
- VJUNTPRQTFDQMF-UHFFFAOYSA-N 1-benzylimidazolidine-2,4-dione Chemical compound O=C1NC(=O)CN1CC1=CC=CC=C1 VJUNTPRQTFDQMF-UHFFFAOYSA-N 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 85
- 238000006243 chemical reaction Methods 0.000 description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 239000012043 crude product Substances 0.000 description 24
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 14
- 238000004821 distillation Methods 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 14
- 238000000605 extraction Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 238000001953 recrystallisation Methods 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000001143 conditioned effect Effects 0.000 description 13
- 230000007062 hydrolysis Effects 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 7
- -1 oxazole ketone Chemical class 0.000 description 7
- 229940107700 pyruvic acid Drugs 0.000 description 7
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 5
- 238000005810 carbonylation reaction Methods 0.000 description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 4
- WEJRYKSUUFKMBC-UHFFFAOYSA-N 1-(4-chlorophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C(Cl)C=C1 WEJRYKSUUFKMBC-UHFFFAOYSA-N 0.000 description 3
- 230000006315 carbonylation Effects 0.000 description 3
- RYWYCWBZCMMLMA-UHFFFAOYSA-N 3-(dimethylamino)-2-oxo-3-phenylpropanoic acid Chemical compound CN(C)C(C(C(=O)O)=O)C1=CC=CC=C1 RYWYCWBZCMMLMA-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- NWCHELUCVWSRRS-SECBINFHSA-N (2r)-2-hydroxy-2-phenylpropanoic acid Chemical compound OC(=O)[C@@](O)(C)C1=CC=CC=C1 NWCHELUCVWSRRS-SECBINFHSA-N 0.000 description 1
- UDTSPKADQGPZFS-VURMDHGXSA-N (5z)-5-benzylideneimidazolidine-2,4-dione Chemical class N1C(=O)NC(=O)\C1=C\C1=CC=CC=C1 UDTSPKADQGPZFS-VURMDHGXSA-N 0.000 description 1
- LQQFFJFGLSKYIR-UHFFFAOYSA-N 3,4-dihydroxyphenylpyruvic acid Chemical compound OC(=O)C(=O)CC1=CC=C(O)C(O)=C1 LQQFFJFGLSKYIR-UHFFFAOYSA-N 0.000 description 1
- VUDRYTCMXUBSEV-UHFFFAOYSA-N 3-(3,4-dimethoxyphenyl)-2-oxopropanoic acid Chemical compound COC1=CC=C(CC(=O)C(O)=O)C=C1OC VUDRYTCMXUBSEV-UHFFFAOYSA-N 0.000 description 1
- WSXSTYQPGBHIPN-UHFFFAOYSA-N C1=CC(=C(C(=C1C=NC(=O)NC(=O)CO)F)F)F Chemical compound C1=CC(=C(C(=C1C=NC(=O)NC(=O)CO)F)F)F WSXSTYQPGBHIPN-UHFFFAOYSA-N 0.000 description 1
- IGACHHCPHNRLOR-UHFFFAOYSA-N C1=CC(=C(C=C1C=NC(=O)NC(=O)CO)O)O Chemical compound C1=CC(=C(C=C1C=NC(=O)NC(=O)CO)O)O IGACHHCPHNRLOR-UHFFFAOYSA-N 0.000 description 1
- OBDOAAMVPYWWTI-UHFFFAOYSA-N C1=CC(=CC=C1C=NC(=O)NC(=O)CO)[N+](=O)[O-] Chemical compound C1=CC(=CC=C1C=NC(=O)NC(=O)CO)[N+](=O)[O-] OBDOAAMVPYWWTI-UHFFFAOYSA-N 0.000 description 1
- HEUICSXLXKYZDM-UHFFFAOYSA-N C1=CC=C(C(=C1)C=NC(=O)NC(=O)CO)O Chemical compound C1=CC=C(C(=C1)C=NC(=O)NC(=O)CO)O HEUICSXLXKYZDM-UHFFFAOYSA-N 0.000 description 1
- HBGSIEQHSPMACX-UHFFFAOYSA-N CC1=CC=CC=C1C=NC(=O)NC(=O)CO Chemical compound CC1=CC=CC=C1C=NC(=O)NC(=O)CO HBGSIEQHSPMACX-UHFFFAOYSA-N 0.000 description 1
- ZBDVHYKDFPYSES-UHFFFAOYSA-N CN(C)N(C(=O)CO)C(=O)N=CC1=CC=CC=C1 Chemical compound CN(C)N(C(=O)CO)C(=O)N=CC1=CC=CC=C1 ZBDVHYKDFPYSES-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- VBUMUQPCMBNYLF-UHFFFAOYSA-N benzene 2-oxopropanoic acid Chemical class C1=CC=CC=C1.C(C(=O)C)(=O)O VBUMUQPCMBNYLF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a novel method for quickly preparing phenylpyruvic acid and aryl substitutive derivatives thereof, which is characterized in that under the condition of microwave radiation, sub-benzyl hydantoin or aryl substitutive derivatives thereof and sodium hydroxide are used as raw materials to prepare the phenylpyruvic acid or aryl substitutive derivatives thereof, wherein the molar ratio of the medium benzyl hydantoin or aryl substitutive derivatives thereof to the sodium hydroxide is 1:2 to 4.
Description
Technical field
The present invention relates to a kind of quick preparation phenyl-pyruvic acid and the substituted derivative method of aryl thereof, promptly under microwave radiation, with benzylidene glycolylurea or the substituted derivative of its aryl and sodium hydroxide is raw material, carries out the quick preparation that phenyl-pyruvic acid or its aryl are substituted derivative.
Background technology
Phenyl-pyruvic acid and aryl substituted derivatives thereof are important intermediates, can be applicable to medicine, agricultural chemicals and chemical industry, are used to prepare phenylalanine and derivative thereof and phenyl-lactic acid and derivative thereof etc.In recent years, along with going deep into of research, they enlarge just gradually in the application in above-mentioned field.
The preparation method of bibliographical information phenyl-pyruvic acid and aryl substituted derivatives thereof has alpha-acetamido-styracin hydrolysis method, the two carbonylation methods of benzyl chloride high pressure, replaces glycolylurea hydrolysis method and substituted oxazole ketone hydrolysis method etc.Japanese Patent has been reported by the hydrolysis of substituted oxazole ketone and has been prepared various substituted benzene pyruvic acid (JP08109152A2).Japanese Patent (JP 63048244A2) and (JP 62158240A2) have reported also by the two carbonylation methods of high pressure and have prepared phenyl-pyruvic acid and 4-fluorobenzene pyruvic acid that yield is respectively 80.2 and 73%.Chinese patent (CN 1112346C, 2003) has also been reported by benzyl chloride and aryl substituted derivatives thereof and has been prepared phenyl-pyruvic acid and aryl substituted derivatives thereof by two carbonylation reactions.But two carbonylation methods need high pressure and expensive catalysts, and the actually operating cost is bigger; And alpha-acetamido-styracin hydrolysis method and substituted oxazole ketone hydrolysis method feedstock production difficulty and seldom adopting.Replace the glycolylurea hydrolysis method is considered to simple possible because of characteristics such as its raw material are easy to get, cheap and equipment is simple method.Japanese Patent (JP 61167641A2) and Chinese patent (CN 1176060C) have been reported respectively by normal pressure and high pressure alkaline hydrolysis benzylidene glycolylurea and have been prepared phenyl-pyruvic acid.But the former is long the reaction times, and almost can't hydrolysis to some benzylidene hydantoin derivatives.Although the latter can make the quick hydrolysis of benzylidene glycolylurea, because the temperature of reaction height, the product phenyl-pyruvic acid decomposes easily, and reaction yield reduces.
Summary of the invention
The purpose of this invention is to provide a kind ofly by replacing the novel method that the glycolylurea hydrolysis method prepares phenyl-pyruvic acid and the substituted derivative of aryl thereof fast, this method has reduced cost, has improved reaction efficiency, has reduced side reaction, has higher economic value.
Purpose of the present invention specifically can reach by following measure:
The substituted derivative method of a kind of preparation phenyl-pyruvic acid and aryl thereof, promptly under microwave radiation, with benzylidene glycolylurea or the substituted derivative of its aryl and sodium hydroxide is feedstock production phenyl-pyruvic acid or the substituted derivative of its aryl, and wherein the mol ratio of benzylidene glycolylurea or substituted derivative of its aryl and sodium hydroxide is 1: 2～4; Detailed process is as follows:
Wherein, R is H, 2-F, 3-F, 4-F, 2-Cl, 3-Cl, 4-Cl, 2-Br, 3-Br, 4-Br, 2-CH
3, 4-CH
3, 4-CH
3O, 2-HO, 4-HO, 3-NO
2, 4-NO
2, 3,4-dichloro, 3,4-dihydroxyl, 3,4-dimethoxy, 4-(CH
3)
2N, 3-HO, 2,3,4-trifluoro, 2,4,5-trichlorine or 2,3,4-trimethoxy.
Concrete technology: 0.05～0.25mol benzylidene glycolylurea or the substituted derivative of its aryl, 0.1～1.0mol NaOH, 100mL water join in the 250mL single port flask, insert then in the microwave reactor (frequency 2450MHz), setting power 280～600W, reaction 5～60min.After reaction finishes, regulate pH value to 3.0～6.5, extracted with diethyl ether is to colourless, and ether extraction liquid merges the back underpressure distillation and removes ether, and the low-temperature vacuum drying residue gets phenyl-pyruvic acid or the substituted derivative crude product of its aryl.Crude product gets phenyl-pyruvic acid or the substituted derivative elaboration of its aryl through ethyl alcohol recrystallization.
Purpose of the present invention can also reach by following measures:
The substituted derivative optimum quantity of benzylidene glycolylurea or its aryl is 0.05～0.25mol, and the NaOH optimum quantity is 0.1～0.6mol;
Setting power the best is 300～500W;
Optimum reacting time is 10～30min;
After reaction finished, regulating pH value the best was 5.0～6.0.
The present invention has following advantage:
1, adopts auxiliary alkaline hydrolysis benzylidene glycolylurea of microwave radiation and aryl substituted derivatives thereof, reduced alkali consumption 30～100%, reduced cost;
2, adopt auxiliary alkaline hydrolysis benzylidene glycolylurea of microwave radiation and aryl substituted derivatives thereof, shortened the reaction times greatly, avoided the synthesis under normal pressure overlong time, the problem of phenyl-pyruvic acid and a large amount of oxygenolysis of aryl substituted derivatives thereof;
3, adopt auxiliary alkaline hydrolysis benzylidene glycolylurea of microwave radiation and aryl substituted derivatives thereof, avoid reaction under high pressure phenyl-pyruvic acid and aryl substituted derivatives thereof to be subject to the pyrolysated problem, reduced the generation of side reaction;
4, adopt auxiliary alkaline hydrolysis benzylidene glycolylurea of microwave radiation and aryl substituted derivatives thereof, can make under some normal condition the benzylidene glycolylurea aryl substituted derivatives alkaline hydrolysis of alkaline hydrolysis hardly, pitch glycolylurea etc. as 4-chlorine benzylidene glycolylurea, terephthaldehyde;
Embodiment
Embodiment 1
0.1mol benzylidene glycolylurea, 0.2mol NaOH, 100mL water join in the 250mL single port flask, insert in the microwave reactor (frequency 2450MHz) setting power 300W, backflow 10min then.After reaction finishes, conditioned reaction pH value to 6.0, the 200mL ether divides and is extracted to for three times colourlessly, and ether extraction liquid merges back underpressure distillation removal ether, and the low-temperature vacuum drying residue gets phenyl-pyruvic acid crude product 14.2g.Crude product gets phenyl-pyruvic acid elaboration 12.6g, purity 99.8%, yield 76.65% through ethyl alcohol recrystallization.
Embodiment 2
0.1mol 4-fluorine benzylidene glycolylurea, 0.2mol NaOH, 100mL water join in the 250mL single port flask, insert in the microwave reactor (frequency 2450MHz) setting power 300W, backflow 10min then.After reaction finishes, conditioned reaction pH value to 5.5, the 200mL ether divides and is extracted to for three times colourlessly, and ether extraction liquid merges back underpressure distillation removal ether, and the low-temperature vacuum drying residue gets 4-fluorobenzene pyruvic acid crude product 16.5g.Crude product gets 4-fluorobenzene pyruvic acid elaboration 13.5g, purity 99.9%, yield 74.93% through ethyl alcohol recrystallization.
Embodiment 3
0.05mol 4-chlorine benzylidene glycolylurea, 0.2mol NaOH, 100mL water join in the 250mL single port flask, insert in the microwave reactor (frequency 2450MHz) setting power 500W, backflow 30min then.After reaction finishes, conditioned reaction pH value to 6.0, the 200mL ether divides and is extracted to for three times colourlessly, and ether extraction liquid merges back underpressure distillation removal ether, and the low-temperature vacuum drying residue gets 4-chlorophenyl acetone acid crude 6.8g.Crude product gets 4-chlorophenyl acetone acid elaboration 5.4g, purity 99.7%, yield 54.38% through ethyl alcohol recrystallization.
Embodiment 4
0.1mol 3-bromine benzylidene glycolylurea, 0.2mol NaOH, 100mL water join in the 250mL single port flask, insert in the microwave reactor (frequency 2450MHz) setting power 400W, backflow 20min then.After reaction finishes, conditioned reaction pH value to 6.0, the 200mL ether divides and is extracted to for three times colourlessly, and ether extraction liquid merges back underpressure distillation removal ether, and the low-temperature vacuum drying residue gets 3-brom-acetophenone acid crude 20.7g.Crude product gets 4-chlorophenyl acetone acid elaboration 17.9g, purity 99.5%, yield 73.29% through ethyl alcohol recrystallization.
Embodiment 5
0.15mol 2-methyl benzylidene glycolylurea, 0.6mol NaOH, 100mL water join in the 250mL single port flask, insert in the microwave reactor (frequency 2450MHz) setting power 500W, backflow 25min then.After reaction finishes, conditioned reaction pH value to 6.0, the 200mL ether divides and is extracted to for three times colourlessly, and ether extraction liquid merges back underpressure distillation removal ether, and the low-temperature vacuum drying residue gets 2-methyl phenyl ketone acid crude 19.5g.Crude product gets 2-methyl phenyl ketone acid elaboration 16.8g, purity 99.8%, yield 62.8% through ethyl alcohol recrystallization.
Embodiment 6
0.1mol 4-methoxyl group benzylidene glycolylurea, 0.2mol NaOH, 100mL water join in the 250mL single port flask, insert in the microwave reactor (frequency 2450MHz) setting power 300W, backflow 15min then.After reaction finishes, conditioned reaction pH value to 6.0, the 200mL ether divides and is extracted to for three times colourlessly, and ether extraction liquid merges back underpressure distillation removal ether, and the low-temperature vacuum drying residue gets 4-anisole pyruvic acid crude product 16.8g.Crude product gets 4-anisole pyruvic acid elaboration 15.3g, purity 99.7%, yield 78.63% through ethyl alcohol recrystallization.
Embodiment 7
0.05mol 2-hydroxyl benzylidene glycolylurea, 0.1mol NaOH, 100mL water join in the 250mL single port flask, insert in the microwave reactor (frequency 2450MHz) setting power 300W, backflow 10min then.After reaction finishes, conditioned reaction pH value to 5.5, the 200mL ether divides and is extracted to for three times colourlessly, and ether extraction liquid merges back underpressure distillation removal ether, and the low-temperature vacuum drying residue gets 2-hydroxypropiophenonepreparation acid crude 8.6g.Crude product gets 2-hydroxyphenylphruvic acid elaboration 6.2g, purity 99.9%, yield 68.82% through ethyl alcohol recrystallization.
Embodiment 8
0.1mol 4-nitro benzylidene glycolylurea, 0.3mol NaOH, 100mL water join in the 250mL single port flask, insert in the microwave reactor (frequency 2450MHz) setting power 400W, backflow 25min then.After reaction finishes, conditioned reaction pH value to 6.0, the 200mL ether divides and is extracted to for three times colourlessly, and ether extraction liquid merges back underpressure distillation removal ether, and the low-temperature vacuum drying residue gets 4-oil of mirbane pyruvic acid crude product 17.4g.Crude product gets 4-oil of mirbane pyruvic acid elaboration 14.1g, purity 99.8%, yield 67.33% through ethyl alcohol recrystallization.
Embodiment 9
0.1mol dimethylamino benzylidene glycolylurea, 0.4mol NaOH, 100mL water are joined in the 250mL single port flask, insert in the microwave reactor (frequency 2450MHz) setting power 400W, backflow 30min then.After reaction finishes, conditioned reaction pH value to 6.0, the 200mL ether divides and is extracted to for three times colourlessly, and ether extraction liquid merges back underpressure distillation removal ether, and the low-temperature vacuum drying residue must be to dimethylamino phenyl-pyruvic acid crude product 15.7g.Crude product must be to dimethylamino phenyl-pyruvic acid elaboration 12.8g, purity 99.6%, yield 61.59% through ethyl alcohol recrystallization.
Embodiment 10
0.15mol 3,4-dihydroxyl benzylidene glycolylurea, 0.45mol NaOH, 100mL water join in the 250mL single port flask, insert in the microwave reactor (frequency 2450MHz) setting power 300W, backflow 10min then.After reaction finishes, conditioned reaction pH value to 5.0, the 200mL ether divides and is extracted to for three times colourlessly, and ether extraction liquid merges back underpressure distillation removal ether, and the low-temperature vacuum drying residue gets 3,4-dihydroxyphenyl pyruvic acid crude product 26.8g.Crude product gets 3 through ethyl alcohol recrystallization, 4-dihydroxyphenyl pyruvic acid elaboration 23.4g, purity 99.6%, yield 79.27%.
Embodiment 11
0.1mol 3,4-dimethoxybenzylidenegroup group glycolylurea, 0.2mol NaOH, 100mL water join in the 250mL single port flask, insert in the microwave reactor (frequency 2450MHz) setting power 300W, backflow 10min then.After reaction finishes, conditioned reaction pH value to 6.0, the 200mL ether divides and is extracted to for three times colourlessly, and ether extraction liquid merges back underpressure distillation removal ether, and the low-temperature vacuum drying residue gets 3,4-dimethoxy phenyl-pyruvic acid crude product 18.6g.Crude product gets 3 through ethyl alcohol recrystallization, 4-dimethoxy phenyl-pyruvic acid elaboration 16.9g, purity 99.8%, yield 75.3%.
Embodiment 12
0.1mol 3-hydroxyl-4-methoxyl group benzylidene glycolylurea, 0.2mol NaOH, 100mL water join in the 250mL single port flask, insert in the microwave reactor (frequency 2450MHz) setting power 300W, backflow 15min then.After reaction finishes, conditioned reaction pH value to 5.0, the 200mL ether divides and is extracted to for three times colourlessly, and ether extraction liquid merges back underpressure distillation removal ether, and the low-temperature vacuum drying residue gets 3-hydroxyl-4-anisole pyruvic acid crude product 17.9g.Crude product gets 3-hydroxyl-4-anisole pyruvic acid elaboration 15.2g, purity 99.8%, yield 72.24% through ethyl alcohol recrystallization.
Embodiment 13
0.05mol 2,3,4-trifluoro benzylidene glycolylurea, 0.2mol NaOH, 100mL water join in the 250mL single port flask, insert in the microwave reactor (frequency 2450MHz) setting power 500W, backflow 20min then.After reaction finishes, conditioned reaction pH value to 6.0, the 200mL ether divides and is extracted to for three times colourlessly, and ether extraction liquid merges back underpressure distillation removal ether, and the low-temperature vacuum drying residue gets 2,3,4-trifluoro-benzene pyruvic acid crude product 8.9g.Crude product gets 2,3 through ethyl alcohol recrystallization, 4-trifluoro-benzene pyruvic acid elaboration 7.6g, purity 99.8%, yield 69.59%.
Claims (9)
1. one kind prepares phenyl-pyruvic acid and the substituted derivative method of aryl thereof, it is characterized in that under microwave radiation, with benzylidene glycolylurea or the substituted derivative of its aryl and sodium hydroxide is feedstock production phenyl-pyruvic acid or the substituted derivative of its aryl, and wherein the mol ratio of benzylidene glycolylurea or substituted derivative of its aryl and sodium hydroxide is 1: 2～4; The substituted derivant structure formula of phenyl-pyruvic acid or its aryl is as follows:
Wherein, R is H, 2-F, 3-F, 4-F, 2-Cl, 3-Cl, 4-Cl, 2-Br, 3-Br, 4-Br, 2-CH
3, 4-CH
3, 4-CH
3O, 2-HO, 4-HO, 3-NO
2, 4-NO
2, 3,4-dichloro, 3,4-dihydroxyl, 3,4-dimethoxy, 4-(CH
3)
2N, 3-HO, 2,3,4-trifluoro, 2,4,5-trichlorine or 2,3,4-trimethoxy.
2. the substituted derivative method of preparation phenyl-pyruvic acid according to claim 1 and aryl thereof is characterized in that setting power is 280～600W in the microwave reactor.
3. the substituted derivative method of preparation phenyl-pyruvic acid according to claim 2 and aryl thereof is characterized in that setting power is 300～500W in the microwave reactor.
4. the substituted derivative method of preparation phenyl-pyruvic acid according to claim 1 and aryl thereof is characterized in that the substituted derivative amount of benzylidene glycolylurea or its aryl is 0.05～0.25mol, and the NaOH amount is 0.1～1.0mol.
5. the substituted derivative method of preparation phenyl-pyruvic acid according to claim 4 and aryl thereof is characterized in that the substituted derivative amount of benzylidene glycolylurea or its aryl is 0.05～0.15mol, and the NaOH amount is 0.1～0.6mol.
6. the substituted derivative method of preparation phenyl-pyruvic acid according to claim 1 and aryl thereof is characterized in that the reaction times is 5～60min.
7. the substituted derivative method of preparation phenyl-pyruvic acid according to claim 6 and aryl thereof is characterized in that the reaction times is 10～30min.
8. the substituted derivative method of preparation phenyl-pyruvic acid according to claim 1 and aryl thereof, after it is characterized in that reacting end, regulating the pH value is 3.0～6.5.
9. the substituted derivative method of preparation phenyl-pyruvic acid according to claim 8 and aryl thereof, after it is characterized in that reacting end, regulating the pH value is 5.0～6.0.
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| CNB2005101230711A CN100412047C (en) | 2005-12-15 | 2005-12-15 | Method for quick preparation of phenyl pyruvic acid and its aryl substituted derivatives |
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| CNB2005101230711A CN100412047C (en) | 2005-12-15 | 2005-12-15 | Method for quick preparation of phenyl pyruvic acid and its aryl substituted derivatives |
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| CN1789227A CN1789227A (en) | 2006-06-21 |
| CN100412047C true CN100412047C (en) | 2008-08-20 |
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| CN102503894B (en) * | 2011-11-17 | 2014-08-20 | 天津医科大学 | 5-substituted methylene imidazolidine-2, 4-diketone derivative as well as pharmaceutical composition and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6122042A (en) * | 1984-07-10 | 1986-01-30 | Mitsui Toatsu Chem Inc | Production of alpha-keto acid |
| JPS61167641A (en) * | 1985-01-21 | 1986-07-29 | Showa Denko Kk | Production of phenylpyruvic acid |
| JP2003104932A (en) * | 2001-09-28 | 2003-04-09 | Mitsubishi Rayon Co Ltd | Method for producing 4-hydroxyphenylpyruvic acid |
| CN1425641A (en) * | 2002-12-23 | 2003-06-25 | 南京工业大学 | Process for preparing sodium phenyl pyruvate by pressure hydrolizing benzal hydantoin |
-
2005
- 2005-12-15 CN CNB2005101230711A patent/CN100412047C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6122042A (en) * | 1984-07-10 | 1986-01-30 | Mitsui Toatsu Chem Inc | Production of alpha-keto acid |
| JPS61167641A (en) * | 1985-01-21 | 1986-07-29 | Showa Denko Kk | Production of phenylpyruvic acid |
| JP2003104932A (en) * | 2001-09-28 | 2003-04-09 | Mitsubishi Rayon Co Ltd | Method for producing 4-hydroxyphenylpyruvic acid |
| CN1425641A (en) * | 2002-12-23 | 2003-06-25 | 南京工业大学 | Process for preparing sodium phenyl pyruvate by pressure hydrolizing benzal hydantoin |
Non-Patent Citations (4)
| Title |
|---|
| 《亚苄基海因水解制备苯丙酮酸的动力学》. 周华等.《化工学报》，第52卷第2期. 2001 |
| 《亚苄基海因水解制备苯丙酮酸的动力学》. 周华等.《化工学报》，第52卷第2期. 2001 * |
| 《苯丙酮酸的合成进展》. 肖慧萍等.《内蒙古工业大学学报》，第21卷第1期. 2002 |
| 《苯丙酮酸的合成进展》. 肖慧萍等.《内蒙古工业大学学报》，第21卷第1期. 2002 * |
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|---|---|
| CN1789227A (en) | 2006-06-21 |
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