CN107986972A - A kind of 3- (4-nitrophenoxy) propionic acid preparation method - Google Patents
A kind of 3- (4-nitrophenoxy) propionic acid preparation method Download PDFInfo
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- CN107986972A CN107986972A CN201711107743.9A CN201711107743A CN107986972A CN 107986972 A CN107986972 A CN 107986972A CN 201711107743 A CN201711107743 A CN 201711107743A CN 107986972 A CN107986972 A CN 107986972A
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- propionic acid
- nitrophenoxy
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- acid preparation
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- RRQDYEMTBDVXQY-UHFFFAOYSA-N 3-(4-nitrophenoxy)propanoic acid Chemical compound OC(=O)CCOC1=CC=C([N+]([O-])=O)C=C1 RRQDYEMTBDVXQY-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003426 co-catalyst Substances 0.000 claims abstract description 11
- 150000002118 epoxides Chemical class 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 230000003068 static effect Effects 0.000 claims abstract description 7
- 238000009413 insulation Methods 0.000 claims abstract description 6
- 239000012044 organic layer Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- -1 oxygen radical compound Chemical class 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- CPZHJYJSCCEDQX-UHFFFAOYSA-N [O]C1=CC=C([N+]([O-])=O)C=C1 Chemical compound [O]C1=CC=C([N+]([O-])=O)C=C1 CPZHJYJSCCEDQX-UHFFFAOYSA-N 0.000 abstract description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical group [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 5
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 2
- DHXNZYCXMFBMHE-UHFFFAOYSA-N 3-bromopropanoic acid Chemical class OC(=O)CCBr DHXNZYCXMFBMHE-UHFFFAOYSA-N 0.000 description 2
- QEYMMOKECZBKAC-UHFFFAOYSA-N 3-chloropropanoic acid Chemical class OC(=O)CCCl QEYMMOKECZBKAC-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- OYYFEDUOOFSUGM-UHFFFAOYSA-N 2-(4-nitrophenoxy)propanoic acid Chemical compound OC(=O)C(C)OC1=CC=C([N+]([O-])=O)C=C1 OYYFEDUOOFSUGM-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000242680 Schistosoma mansoni Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 229940049706 benzodiazepine Drugs 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of 3 (4 nitro-phenoxy) propionic acid preparation methods, p-nitrophenyl epoxide propyl alcohol is dissolved in solvent by a.；B. water and NaHCO are added in the reactor3After stirring and dissolving, co-catalyst is added, after reaction solution is cooled to 05 DEG C, oxygen radical compound is added and stirs evenly；C. by the liquid in a steps in 05 DEG C of reaction solutions for instilling in b. steps, rear insulation reaction 30min is dripped off, reaction is thorough, and static layering, separates organic layer；Water layer concentrated hydrochloric acid tune PH to 23, has a large amount of white solids to separate out, when insulated and stirred 12 is small after product is obtained by filtration；Using organic oxidizing reaction, aoxidize to obtain 3 (4 nitro-phenoxy) propionic acid with p-nitrophenyl oxygen propyl alcohol, since using organic oxidizing reaction, its reaction condition is gentle, its yield improves the earning rate of product up to 85%, adds benefit.
Description
Technical field
The present invention relates to 3- (4-nitrophenoxy) propionic acid production method technical field, more particularly to a kind of 3- (4- nitros
Phenoxy group) propionic acid preparation method.
Background technology
3- (4-nitrophenoxy) propionic acid is bis- hydrocarbon amino methyl -6- substituent benzos oxygen six of Schistosoma mansoni disease medicine 3-
The important intermediate of garden -4- ketone.The preparation method of document J.Indian chem..Soc.1949,16, P639-44 reports is to adopt
Reacted with nitrophenol and 3- chloropropionic acids or 3- bromo-propionic acids, its yield about 30% or so.Acta Pharmaceutica Sinica 1959, Vol7No5P180-
The preparation method of 192 reports is not obtain product with 3- chloropropionic acids using nitrophenol, and only 3- bromo-propionic acids obtain 29% yield.
Therefore, it is necessary to develop a kind of preparation method of the 3- of high income (4-nitrophenoxy) propionic acid.
The content of the invention
The technical problem to be solved in the present invention is to provide one kind to use organic oxidizing reaction, and reaction condition is gentle, and yield reaches
85% 3- (4-nitrophenoxy) propionic acid preparation method.
In order to solve the above-mentioned technical problem, the technical scheme is that：It is prepared by a kind of 3- (4-nitrophenoxy) propionic acid
P-nitrophenyl epoxide propyl alcohol is dissolved in solvent by method, a.；B. water and NaHCO are added in the reactor3After stirring and dissolving, then add
Enter co-catalyst, after reaction solution is cooled to 0-5 DEG C, adds oxygen radical compound and stir evenly；C. by the liquid in a steps
Body drips off rear insulation reaction 30min, reaction is thorough, and static layering, has separated in the 0-5 DEG C of reaction solution for instilling in b. steps
Machine layer；Water layer concentrated hydrochloric acid tune PH to 2-3, has a large amount of white solids to separate out, when insulated and stirred 1-2 is small after product is obtained by filtration.
As a kind of preferred embodiment, oxygen radical compound includes tempo, 4-Meotempo or 4- methyl tempo.
As a kind of preferred embodiment, solvent includes dichloromethane or dichloroethanes.
As a kind of preferred embodiment, co-catalyst includes KI, tetrabutylammonium bromide and NaClO.
As a kind of preferred embodiment, co-catalyst includes KBr, benzyltriethylammoinium chloride and NaClO.
As a kind of preferred embodiment, co-catalyst includes KBr, benzyltriethylammoinium chloride and NaClO.
As a kind of preferred embodiment, co-catalyst includes KBr, benzyltriethylammoinium chloride and NaBrO.
Had the beneficial effect that using what the above-mentioned technical proposal present invention obtained：Using organic oxidizing reaction, with p-nitrophenyl oxygen
Propyl alcohol aoxidizes to obtain 3- (4-nitrophenoxy) propionic acid, since using organic oxidizing reaction, its reaction condition is gentle, and we
Method p-nitrophenyl oxygen propyl alcohol aoxidizes to obtain 3- (4-nitrophenoxy) propionic acid its yield up to 85%, therefore improves the income of product
Rate, adds benefit.
Embodiment
The embodiment of the present invention is described further.It should be noted that for these embodiments
Explanation be used to help understand the present invention, but do not form limitation of the invention.In addition, invention described below is each
As long as involved technical characteristic does not form conflict and is mutually combined each other in embodiment.
Real row one,
30g p-nitrophenyl epoxide propyl alcohol is dissolved in 300mlCH2Cl2；750ml water and 52.5gNaHCO are added in reaction bulb3
After stirring and dissolving, 3gKI, 2g tetrabutylammonium bromide and 450ml NaClO (13%) are added；Reaction solution is cooled to 0-5 DEG C
Afterwards, 0.24gtempo is added, is stirred evenly；P-nitrophenyl epoxide propyl alcohol is instilled in above-mentioned reaction solution at 0-5 DEG C, is protected after dripping off
Temperature reaction 30min, reaction are thorough；Static layering, separates organic layer；Water layer concentrated hydrochloric acid tune PH to 2-3, there is a large amount of white solids
Separate out, when insulated and stirred 1-2 is small after filter to obtain 28 grams of product.
Example two,
30g p-nitrophenyl epoxide propyl alcohol is dissolved in 300mlCH2Cl2；750ml water and 52.5gNaHCO are added in reaction bulb3
After stirring and dissolving, 2gKBr, 1.65g benzyltriethylammoinium chlorides and 450ml NaClO (13%) are added；Reaction solution is cold
But after arriving 0-5 DEG C, 0.24gtempo is added, is stirred evenly；P-nitrophenyl epoxide propyl alcohol is instilled into above-mentioned reaction solution at 0-5 DEG C
In, it is thorough to drip off rear insulation reaction 30min. reactions；Static layering, separates organic layer；Water layer concentrated hydrochloric acid tune PH to 2-3, has
A large amount of white solids separate out, when insulated and stirred 1-2 is small after filter to obtain 29 grams of product.
Example three,
30g p-nitrophenyl epoxide propyl alcohol is dissolved in 300mlCH2Cl2；750ml water and 52.5gNaHCO are added in reaction bulb3
After stirring and dissolving, 2gKBr, 1.65g benzyltriethylammoinium chlorides and 450ml NaClO (13%) are added；Reaction solution is cold
But after arriving 0-5 DEG C, 0.5g4-Meotempo is added, is stirred evenly；P-nitrophenyl epoxide propyl alcohol is above-mentioned anti-in 5-10 DEG C of instillation
Answer in liquid, drip off rear insulation reaction 30min, reaction is thorough；Static layering, separates organic layer；Water layer concentrated hydrochloric acid tune PH to 2-
3, there are a large amount of white solids to separate out, when insulated and stirred 1-2 is small after filter to obtain 25 grams of product.
Example four,
30g p-nitrophenyl epoxide propyl alcohol is dissolved in 300mlCH2Cl2；750ml water and 52.5gNaHCO are added in reaction bulb3
After stirring and dissolving, 2gKBr, 1.65g benzyltriethylammoinium chlorides and 600ml NaBrO (10%) are added；Reaction solution is cold
But after arriving 0-5 DEG C, 0.24gtempo is added, is stirred evenly；P-nitrophenyl epoxide propyl alcohol is instilled into above-mentioned reaction solution at 0-5 DEG C
In, rear insulation reaction 30min is dripped off, reaction is thorough；Static layering, separates organic layer；Water layer concentrated hydrochloric acid tune PH to 2-3, has
A large amount of white solids separate out, when insulated and stirred 1-2 is small after filter to obtain 30 grams of product.
Embodiments of the present invention are explained in detail above, but the invention is not restricted to described embodiment.It is right
For those skilled in the art, in the case where not departing from the principle of the invention and spirit, these embodiments are carried out more
Kind change, modification, replacement and modification, still fall within protection scope of the present invention.
Claims (7)
- A kind of 1. 3- (4-nitrophenoxy) propionic acid preparation method, it is characterised in that：A. p-nitrophenyl epoxide propyl alcohol is dissolved in solvent；B. water and NaHCO are added in the reactor3After stirring and dissolving, co-catalyst is added, reaction solution is cooled to 0-5 DEG C Afterwards, oxygen radical compound is added to stir evenly；C. by the liquid in a steps in the 0-5 DEG C of reaction solution for instilling in b. steps, rear insulation reaction 30min is dripped off, reaction is thorough Bottom, static layering, separates organic layer；Water layer concentrated hydrochloric acid tune PH to 2-3, has a large amount of white solids to separate out, and insulated and stirred 1-2 is small When after product is obtained by filtration.
- 2. 3- (4-nitrophenoxy) propionic acid preparation method according to claim 1, it is characterised in that：Oxygen radical chemical combination Thing includes tempo, 4-Meotempo or 4- methyl tempo.
- 3. 3- (4-nitrophenoxy) propionic acid preparation method according to claim 2, it is characterised in that：Solvent includes dichloro Methane or dichloroethanes.
- 4. 3- (4-nitrophenoxy) propionic acid preparation method according to claim 3, it is characterised in that：Co-catalyst includes KI, tetrabutylammonium bromide and NaClO.
- 5. 3- (4-nitrophenoxy) propionic acid preparation method according to claim 3, it is characterised in that：Co-catalyst includes KBr, benzyltriethylammoinium chloride and NaClO.
- 6. 3- (4-nitrophenoxy) propionic acid preparation method according to claim 3, it is characterised in that：Co-catalyst includes KBr, benzyltriethylammoinium chloride and NaClO.
- 7. 3- (4-nitrophenoxy) propionic acid preparation method according to claim 3, it is characterised in that：Co-catalyst includes KBr, benzyltriethylammoinium chloride and NaBrO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711107743.9A CN107986972A (en) | 2017-11-10 | 2017-11-10 | A kind of 3- (4-nitrophenoxy) propionic acid preparation method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711107743.9A CN107986972A (en) | 2017-11-10 | 2017-11-10 | A kind of 3- (4-nitrophenoxy) propionic acid preparation method |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174061A (en) * | 2011-03-08 | 2011-09-07 | 上海统麦生物科技有限公司 | Novel method for synthesizing 4-carboxybutyl triphenyl phosphonium bromide |
| KR20130090144A (en) * | 2012-02-03 | 2013-08-13 | 서울대학교산학협력단 | Novel pyrimidine derivatives or pharmaceutically acceptable salts thereof, process for the preparation thereof and pharmaceutical composition for prevention or treatment of rage receptor related diseases containing the same as an active ingredient |
| CN104513283A (en) * | 2013-09-27 | 2015-04-15 | 广东东阳光药业有限公司 | Glucopyranosyl derivative and application thereof in medicine |
-
2017
- 2017-11-10 CN CN201711107743.9A patent/CN107986972A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174061A (en) * | 2011-03-08 | 2011-09-07 | 上海统麦生物科技有限公司 | Novel method for synthesizing 4-carboxybutyl triphenyl phosphonium bromide |
| KR20130090144A (en) * | 2012-02-03 | 2013-08-13 | 서울대학교산학협력단 | Novel pyrimidine derivatives or pharmaceutically acceptable salts thereof, process for the preparation thereof and pharmaceutical composition for prevention or treatment of rage receptor related diseases containing the same as an active ingredient |
| CN104513283A (en) * | 2013-09-27 | 2015-04-15 | 广东东阳光药业有限公司 | Glucopyranosyl derivative and application thereof in medicine |
Non-Patent Citations (2)
| Title |
|---|
| JENNIFER M. GALVIN等: "《e-EROS Encyclopedia of Reagents for Organic Synthesis》", 15 May 2013 * |
| PIER LUCIO ANELLI等: "Fast and Selective Oxidation of Primary Alcohols to Aldehydes or to Carboxylic Acids and of Secondary Alcohols to Ketones Mediated by Oxoammonium Salts under Two-Phase Conditions", 《J. ORG. CHEM.》 * |
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Application publication date: 20180504 |