CN102633623A - Methylphenylacetic acid preparation method - Google Patents
Methylphenylacetic acid preparation method Download PDFInfo
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- CN102633623A CN102633623A CN2012100873742A CN201210087374A CN102633623A CN 102633623 A CN102633623 A CN 102633623A CN 2012100873742 A CN2012100873742 A CN 2012100873742A CN 201210087374 A CN201210087374 A CN 201210087374A CN 102633623 A CN102633623 A CN 102633623A
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- acetic acid
- methylphenyl acetic
- acid
- preparation
- methylphenylacetic acid
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- YPGCWEMNNLXISK-UHFFFAOYSA-N hydratropic acid Chemical compound OC(=O)C(C)C1=CC=CC=C1 YPGCWEMNNLXISK-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010992 reflux Methods 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005864 Sulphur Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- RZWGTXHSYZGXKF-UHFFFAOYSA-N 2-(2-methylphenyl)acetic acid Chemical compound CC1=CC=CC=C1CC(O)=O RZWGTXHSYZGXKF-UHFFFAOYSA-N 0.000 claims description 4
- GJMPSRSMBJLKKB-UHFFFAOYSA-N 3-methylphenylacetic acid Chemical compound CC1=CC=CC(CC(O)=O)=C1 GJMPSRSMBJLKKB-UHFFFAOYSA-N 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 13
- 239000007787 solid Substances 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000012043 crude product Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- LSBDFXRDZJMBSC-UHFFFAOYSA-N 2-phenylacetamide Chemical compound NC(=O)CC1=CC=CC=C1 LSBDFXRDZJMBSC-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 239000010977 jade Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N methyl cyanide Natural products CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 2
- 241000722917 Cacosmia Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 208000012898 Olfaction disease Diseases 0.000 description 1
- AHIBWURJLGCHAY-UHFFFAOYSA-N [S].C1=CC=CC=C1 Chemical compound [S].C1=CC=CC=C1 AHIBWURJLGCHAY-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- -1 aryl acetonitrile Chemical compound 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000019546 parosmia Nutrition 0.000 description 1
- NRNHJIRMWBDTJE-UHFFFAOYSA-N pentan-3-one;toluene Chemical compound CCC(=O)CC.CC1=CC=CC=C1 NRNHJIRMWBDTJE-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a methylphenylacetic acid preparation method, which includes: adding methylphenylacetic acid, morpholine and sulphur in a reactor, performing reflux stirring for 8-10h, adding methyl alcohol and heating and dissolving after reaction is completed, decoloring with activated carbon, filtering, cooling, adding a mixed solution of 50-70%sodium hydroxide solution and 50%sodium hydroxide solution to lead pH (potential of hydrogen) to be kept at 8-10, performing heating reflux for 4-6h, filtering after reaction, recovering solvent under reduced pressure, adding water, acidizing to pH of 1-2 by inorganic acid, separating out solid, filtering to obtain a methylphenylacetic acid crude product, recrystallizing with 60% of ethanol, and drying so that methylphenylacetic acid is obtained. The methylphenylacetic acid preparation method is simple in process, stable, high in yield, low in cost and suitable for industrial production.
Description
Technical field
The present invention relates to organic chemistry synthetic field, particularly a kind of preparation method of methylphenyl acetic acid.
Background technology
Methylphenyl acetic acid as adjacent (to) methylphenyl acetic acid, its () is one type of important organic chemical industry's fine chemicals midbody, is mainly used in to make agricultural chemicals and medicine and corresponding ester class etc.In the prior art; Preparing method's report of methylphenyl acetic acid is also few; But the synthetic and preparation method of its analogue toluylic acid is very many; Its synthesis route mainly contains following several kinds: (1) benzyl cyanide hydrolysis method: at first in the presence of solvent, generate benzyl cyanide with chlorine joint and sodium cyanide, further react then aryl acetonitrile, in dilute sulphuric acid, be hydrolyzed into Arylacetic acids at last.This step yield of this method hydrolysis is high, but synthetic benzyl cyanide yield is low, and the order sodium cyanide has severe toxicity.(2) phenylacetamide hydrolysis method: with vinylbenzene is raw material, and warp and ammoniacal liquor, sulfur reaction generate phenylacetamide, continue to react arylacetamide, generate Arylacetic acids through hydrolysis again.This method technology is simple, and operational condition is easy to control, and raw material and intermediate product toxicity are little, but the by product benzene sulfur alcohol of this step reaction of vinylbenzene and ammoniacal liquor, sulphur, the flavor cacosmia, and contaminate environment, and also the reaction needed pressurization carries out, and limited the utilization of this reaction.(3) carbon back synthesis method: under the carbonylation catalyst action, the chloro arylmethane carries out the carbonylation reaction under lower pressure and mild temperature in sodium hydroxide and organic solvent two-phase system, generate Arylacetic acids sodium, becomes Arylacetic acids through acidifying then.The product purity of this method is high, and reaction conditions is gentle, but has technical requirements height in the technological process, needs operation meticulously to prevent shortcomings such as catalyst deactivation or loss, and the order yield still awaits improving.
Summary of the invention
The technical problem that the present invention mainly solves provides a kind of preparation method of methylphenyl acetic acid, and this method technology is simple, process stabilization, and efficient is high, is easy to suitability for industrialized production.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of preparation method of methylphenyl acetic acid in reactor drum, adds methylphenyl acetic acid, morpholine and sulphur, refluxing and stirring 6-8h; After reaction finishes, add methyl alcohol, heating for dissolving, activated carbon decolorizing filters; Cooling is adding the mixed solution that 50%-70% and 50% sodium hydroxide solution are formed, and PH maintains 8-10, and reflux 4-6h is after reaction finishes; Filter, decompression and solvent recovery adds water, and it is 2-3 that mineral acid is acidified to PH, separates out cabinet; Filter, get the methylphenyl acetic acid bullion, 60% ethyl alcohol recrystallization, drying gets methylphenyl acetic acid.
In preferred embodiment of the present invention, described methylphenyl acetic acid, the mol ratio of morpholine and sulphur is 1:3-4:1-2.
In preferred embodiment of the present invention, described material methylphenyl acetic acid includes o-Tolylacetic acid, to methylphenyl acetic acid and m-Tolylacetic acid.
In preferred embodiment of the present invention, described mineral acid comprises hydrochloric acid and sulfuric acid.
Because adopt technique scheme, the present invention has the reaction conditions gentleness, raw material cheaply is easy to get, and operating process is simple, stable, productive rate is higher, cost is low, is more suitable for suitability for industrialized production.
Embodiment
A kind of preparation method of methylphenyl acetic acid in reactor drum, adds methylphenyl acetic acid, morpholine and sulphur, refluxing and stirring 6-8h; After reaction finishes, add methyl alcohol, heating for dissolving, activated carbon decolorizing filters; Cooling is adding the mixed solution that 50%-70% and 50% sodium hydroxide solution are formed, and PH maintains 8-10, and reflux 4-6h is after reaction finishes; Filter, decompression and solvent recovery adds water, and it is 2-3 that mineral acid is acidified to PH, separates out cabinet; Filter, get the methylphenyl acetic acid bullion, 60% ethyl alcohol recrystallization, drying gets methylphenyl acetic acid.
Wherein, in reaction, methylphenyl acetic acid, the mol ratio of morpholine and sulphur is 1:3-4:1-2; Methylphenyl acetic acid includes o-Tolylacetic acid, to methylphenyl acetic acid and m-Tolylacetic acid; Mineral acid comprises hydrochloric acid and sulfuric acid.
Embodiment 1
In the exsiccant three-necked flask, add 3g (0. 02 mol) o-methyl-benzene ethyl ketone, 6.098 mL (0. 075mol) beautiful jade and 0.96g (0. 03mol) sulphur; Refluxing and stirring 8h after reaction finishes, adds methyl alcohol 25 mL; Heating makes dissolving, and activated carbon decolorizing filters; Cooling adds the mixing solutions that 20 rnL, 70% ethanol and 3. 7 mL, 50% sodium hydroxide solution are formed, reflux 4h again.Reaction is finished, and filters, and after filtrate decompression reclaimed solvent, it was an amount of to add water, transfers to pH 1-2 with Hydrogen chloride, separates out solid, and suction filtration obtains bullion.Bullion is heavily tied article with 60% ethanol, and ten is dry, obtains o-Tolylacetic acid 2.32g, yield 70%, fusing point 88-90 ℃.
Embodiment 2
In the exsiccant three-necked flask, add methyl acetophenone between 30g (0.2 mol), 65.34 mL (0.75 mol) beautiful jade and 10.56g (0.33mol) sulphur; Refluxing and stirring 8h after reaction finishes, adds methyl alcohol 25 mL; Heating makes dissolving, and activated carbon decolorizing filters; Cooling adds the mixing solutions that 20 rnL, 70% ethanol and 3. 7 mL, 50% sodium hydroxide solution are formed, reflux 4h again.Reaction is finished, and filters, and after filtrate decompression reclaimed solvent, it was an amount of to add water, transfers to pH 1-2 with Hydrogen chloride, separates out solid, and suction filtration obtains bullion.Bullion is heavily tied article with 60% ethanol, and ten is dry, gets m-Tolylacetic acid 24.9g, yield 75%, fusing point 88-90 ℃.
Embodiment 3
In the exsiccant three-necked flask, add 30g (0.2 mol) p-methyl aceto phenone, 69.70 mL (0.8mol) beautiful jade and 12.8g (0.4mol) sulphur; Refluxing and stirring 8h after reaction finishes, adds methyl alcohol 25 mL; Heating makes dissolving, and activated carbon decolorizing filters; Cooling adds the mixing solutions that 20 rnL, 70% ethanol and 3. 7 mL, 50% sodium hydroxide solution are formed, reflux 4h again.Reaction is finished, and filters, and after filtrate decompression reclaimed solvent, it was an amount of to add water, transfers to pH 1-2 with Hydrogen chloride, separates out solid, and suction filtration obtains bullion.Bullion is heavily tied article with 60% ethanol, and ten is dry, obtains to methylphenyl acetic acid 2.32g yield 70%, fusing point 92-93 ℃.
The above is merely embodiments of the invention; Be not so limit claim of the present invention; Everyly utilize specification sheets of the present invention and equivalent structure of being done or equivalent flow process conversion; Or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (4)
1. the preparation method of a methylphenyl acetic acid is characterized in that, in reactor drum, adds methylphenyl acetic acid, morpholine and sulphur, refluxing and stirring 6-8h; After reaction finishes, add methyl alcohol, heating for dissolving, activated carbon decolorizing filters; Cooling is adding the mixed solution that 50%-70% and 50% sodium hydroxide solution are formed, and PH maintains 8-10, and reflux 4-6h is after reaction finishes; Filter, decompression and solvent recovery adds water, and it is 2-3 that mineral acid is acidified to PH, separates out cabinet; Filter, get the methylphenyl acetic acid bullion, 60% ethyl alcohol recrystallization, drying gets methylphenyl acetic acid.
2. the preparation method of methylphenyl acetic acid according to claim 1 is characterized in that, described methylphenyl acetic acid, and the mol ratio of morpholine and sulphur is 1:3-4:1-2.
3. the preparation method of methylphenyl acetic acid according to claim 1 is characterized in that, described material methylphenyl acetic acid includes o-Tolylacetic acid, to methylphenyl acetic acid and m-Tolylacetic acid.
4. the preparation method of methylphenyl acetic acid according to claim 1 is characterized in that, described mineral acid comprises hydrochloric acid and sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100873742A CN102633623A (en) | 2012-03-29 | 2012-03-29 | Methylphenylacetic acid preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100873742A CN102633623A (en) | 2012-03-29 | 2012-03-29 | Methylphenylacetic acid preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102633623A true CN102633623A (en) | 2012-08-15 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100873742A Pending CN102633623A (en) | 2012-03-29 | 2012-03-29 | Methylphenylacetic acid preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102633623A (en) |
-
2012
- 2012-03-29 CN CN2012100873742A patent/CN102633623A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| S. J. ROWLAND ET AL.: "Monocyclic and monoaromatic naphthenic acids: synthesis and characterisation", 《ENVIRON CHEM LETT》 * |
| 郑丽玲等: "Willgerodt-Kindler 法合成系列芳基乙酸化合物", 《化学试剂》 * |
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Application publication date: 20120815 |