CN106065004A - The preparation method of D HPPA - Google Patents
The preparation method of D HPPA Download PDFInfo
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- CN106065004A CN106065004A CN201610355826.9A CN201610355826A CN106065004A CN 106065004 A CN106065004 A CN 106065004A CN 201610355826 A CN201610355826 A CN 201610355826A CN 106065004 A CN106065004 A CN 106065004A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Providing the new method utilizing new catalyst to prepare D HPPA, this method synthesis technique is simple, is suitable for industrialization.
Description
Technical field
The present invention relates to the preparation method of a kind of D-HPPA, specifically, one utilizes catalyst Pd-G to prepare D-HPPA
Method.
Background technology
D-HPPA is the important intermediate for synthesis of phenoxy phenoxy propionic acid herbicide.Chinese be (R)-(+)-2-
(4-hydroxyphenoxy) propanoic acid, chemical formula is
The preparation technology flow process of current industrial use is as follows:
Specifically, hydroquinone is added to the water, with 30% liquid caustic soda regulation pH=10-11, is allowed to the most molten.Dropping (S)-
2-chloropropionic acid and 30% liquid caustic soda, control pH=9.Reaction terminates regulation pH=6-7, with MIBK extraction and recovery hydroquinone, water-soluble
Liquid is acidified to pH=1-2, separates out solid, filters, is dried to obtain product.
This reaction has an impurity to need to control, the most di-substituted, not only affects content, and reduces yield.In order to
Making singly to exhaust possibility many, general industry way is hydroquinone excess one times, and reaction is reclaimed after terminating, and the response rate is 60-80%.
This process water makees solvent, low cost；Technique is simple, easily operates；It is suitable for industrialization.But, shortcoming is waste water
Amount is big；Hydroquinone one times of recycling of excess causes the bad process of phenol wastewater；Repeatedly it is acidified, alkalizes, waste water high salt, also difficulty
Reason；The method waste water processes the difficult problem being to perplex industry, it is difficult to overcome, and general employing burning method processes sewage, and cost is high, environment
Pollute big.In today that the cry of environmental conservation is the highest, the improvement to this technique is imperative.
The present inventor it has surprisingly been found that, by use 1,1,3,3-tetramethyl-2-(3-trimethoxy is silica-based
Propyl group) catalyst that obtains of guanidine and palladium complexation replaces the base catalyst in existing technique, process simplification can be suitable for industry raw
Produce.
Summary of the invention
The preparation method of 1. 1 kinds of D-HPPA of embodiment, it is characterised in that make parachlorophenol and (S)-2-chloropropionic acid molten
In agent in the presence of catalyst Pd-G dehalogenation.
Embodiment 2. method as tdescribed in embodiment 1, wherein said solvent is dichloroethanes.
Embodiment 3. method as tdescribed in embodiment 1, wherein said reaction is carried out under nitrogen protection.
Embodiment 4. method as tdescribed in embodiment 1, wherein said reaction is carried out under reflux.
Embodiment 5. method as tdescribed in embodiment 1, the most also includes by water and the step of absorbent charcoal fine purification.
Detailed description of the invention
The molecular formula of 1,1,3,3-tetramethyl-2-(the silica-based propyl group of 3-trimethoxy) guanidine is:
With the molecular formula of the catalyst obtained after palladium complexation it is:
It is referred to as catalyst Pd-G in this application.
The new preparation process flow process of the present invention is as follows:
Specifically, parachlorophenol and (S)-2-chloropropionic acid is made to react in the presence of the catalyst that the present invention proposes, one
Step directly obtains D-HPPA.Compared with the prior art, new technology has the advantage that
1, reactions steps is few, and synthesis technique is simple, is suitable for industrialization；
2, reaction condition is gentle, and configuration inversion does not occur；
3, not taking hydroquinone excess, content of phenol in waster is few, disposable；
4, solvent method synthesis, wastewater flow rate is few, beneficially environmental protection；And
5, high-salt wastewater is not produced.
Embodiment
Embodiment uses following chemical reagent:
Embodiment 1.1,1, the preparation of 3,3-tetramethyl-2-(the silica-based propyl group of 3-trimethoxy) guanidine
1,1,3,3-tetramethyl guanidine (17.39 grams, 0.151mol) and dimethylbenzene 200 milliliters is added in 250ml there-necked flask,
Nitrogen purge three times.It is warming up to 120 DEG C, dropping 3-r-chloropropyl trimethoxyl silane (14.93 grams, 0.076mol), within 2 hours, drip
Complete, then insulation reaction 7 hours, nitrogen sustainable protection.It is cooled to room temperature, is filtered to remove tetramethyl guanidine hydrochlorate, filtrate reduced in volume
Remove part dimethylbenzene, residual liquid cooling crystallization, filter, be vacuum dried off-white powder is product 1,1,3,3-tetramethyl-
2-(the silica-based propyl group of 3-trimethoxy) guanidine, yield 18%.
The synthesis of embodiment 2. catalyst
1,1,3,3-tetramethyl-2-(the silica-based propyl group of 3-trimethoxy) guanidine (5.0 grams) is added in 100 milliliters of there-necked flasks,
With toluene 50 milliliters, stirring is lower adds palladium carbon 10% (3.2 grams), nitrogen purge, protection, reacts 12 hours in 55 degree, is cooled to room
Temperature, filters, and is dried, obtains black powder and be catalyst, numbered Pd-G.
The synthesis of embodiment 3.D-HPPA
Parachlorophenol (12.8 grams, 0.1mol), Pd-G 0.1 gram, dichloroethanes 120 milli is added in 500 milliliters of there-necked flasks
Rising, nitrogen purge, nitrogen is protected.It is warming up to backflow, is slowly added dropwise (S)-2-chloropropionic acid (11 grams, 0.1mol), within 2 hours, drips off,
Back flow reaction 5 hours again, heat filtering, reclaim catalyst, filtrate is lowered the temperature, and removes solvent under reduced pressure, and crude product is with 32 grams of pure water and a little
Absorbent charcoal fine purification, obtains 15.2 grams of white crystals.Optics content 99.4%, fusing point 144-145 DEG C, yield 83%.
Structure determines:1H NMR (500MHz, DMSO-d6), δ: 1.53 (d, 3H, J=7.2Hz, CH3), 4.69 (q, 1H,
CH), 6.57-7.12 (m, 4H, ArH), 8.90 (s, 1H, OH), 12.81 (s, 1H, COOH)；IR(KBr)v/cm-1: 3 223,1
707,1 511,1 452,1 371,1 232,1 198,1 134,827；MS (70eV) m/z (%): 182 (M+, 50), 137
(33), 109 (100), 93 (12), 81 (48), 74 (39), 65 (32), 53 (31), 39 (24).
Embodiment 4:
Parachlorophenol (12.8 grams, 0.1mol), Pd-G 0.12 gram, dichloroethanes 120 is added in 500 milliliters of there-necked flasks
Milliliter, nitrogen purge, nitrogen is protected.It is warming up to backflow, is slowly added dropwise (S)-2-chloropropionic acid (11 grams, 0.1mol), within 2 hours, drips
Complete, then back flow reaction 5 hours, heat filtering, reclaim catalyst, filtrate is lowered the temperature, and removes solvent under reduced pressure, and crude product is with 32 grams of pure water and lacks
Permitted absorbent charcoal fine purification, obtained 15.6 grams of white crystals.Optics content 99.3%, fusing point 144-145 DEG C, yield 84%.Structural confirmation
Unanimously.
Embodiment 5:
In 500 milliliters of there-necked flasks, add parachlorophenol (12.8 grams, 0.1mol), reclaim Pd-G 0.12 gram, dichloroethanes
120 milliliters, nitrogen purge, nitrogen is protected.It is warming up to backflow, is slowly added dropwise (S)-2-chloropropionic acid (11 grams, 0.1mol), 2 hours
Dripping off, then back flow reaction 5 hours, heat filtering, reclaim catalyst, filtrate is lowered the temperature, and removes solvent under reduced pressure, crude product with 32 grams of pure water with
A little absorbent charcoal fine purification, obtains 15.4 grams of white crystals.Optics content 99.3%, fusing point 144-145 DEG C, yield 83%.Structure is true
Recognize consistent.
Claims (5)
1. the preparation method of a D-HPPA, it is characterised in that make parachlorophenol and (S)-2-chloropropionic acid in a solvent at catalyst
Reacting in the presence of Pd-G, described Pd-G is
2. the method for claim 1, wherein said solvent is dichloroethanes.
3. the method for claim 1, wherein said reaction is carried out under nitrogen protection.
4. the method for claim 1, wherein said reaction is carried out under reflux.
5. the method for claim 1, the most also includes by water and the step of absorbent charcoal fine purification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610355826.9A CN106065004A (en) | 2016-05-27 | 2016-05-27 | The preparation method of D HPPA |
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| CN201610355826.9A Pending CN106065004A (en) | 2016-05-27 | 2016-05-27 | The preparation method of D HPPA |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112718415A (en) * | 2020-12-02 | 2021-04-30 | 江苏三房巷薄膜有限公司 | Transparent high-barrier film and preparation method thereof |
-
2016
- 2016-05-27 CN CN201610355826.9A patent/CN106065004A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| CHUANHAI XIA ET AL: "The Pd-catalyzed hydrodechlorination of chlorophenols in aqueous solutions under mild conditions: A promising approach to practical use in wastewater", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| 朱洪法等: "《石油化工催化剂基础知识》", 30 April 2010, 中国石化出版社 * |
| 邓红英等: "Pd负载磁性多壁碳纳米管催化对氯苯酚脱氯的研究", 《应用化工》 * |
| 黄应昌等: "《弹性密封胶与胶黏剂》", 30 September 2003, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112718415A (en) * | 2020-12-02 | 2021-04-30 | 江苏三房巷薄膜有限公司 | Transparent high-barrier film and preparation method thereof |
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Effective date of registration: 20170830 Address after: Jinzhou City, Liaoning province Yixian Liu long Gou Xiang Da Qi Gou Cun Applicant after: Jinzhou Sihai biochemistry Co., Ltd. Applicant after: Zhao Hongyang Address before: Liaoning Province, Jinzhou economic and Technological Development Zone Xingshan Street No. 29 Pang Tun Cun Applicant before: Jinzhou West Sea Chemical Co., Ltd. Applicant before: Zhao Hongyang |
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