CN111153787B - Preparation method of 1-naphthylacetic acid - Google Patents
Preparation method of 1-naphthylacetic acid Download PDFInfo
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- CN111153787B CN111153787B CN202010060687.3A CN202010060687A CN111153787B CN 111153787 B CN111153787 B CN 111153787B CN 202010060687 A CN202010060687 A CN 202010060687A CN 111153787 B CN111153787 B CN 111153787B
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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
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
Abstract
The invention belongs to the field of pesticide synthesis, and particularly relates to a preparation method of 1-naphthylacetic acid. The method specifically comprises the following steps: naphthalene and chloroacetic acid are added into a reactor for reaction to obtain a mixture containing 1-naphthylacetic acid and excessive chloroacetic acid; carrying out solid-liquid separation on the mixture to obtain 1-naphthylacetic acid and mother liquor; the mother liquor is recycled to the reaction; the naphthalene is in a molten liquid state during feeding, and the chloroacetic acid is in a gaseous state. The method for continuously producing the 1-naphthylacetic acid greatly reduces the generation of byproducts, solves the problem of recovering excessive chloroacetic acid, is efficient and environment-friendly, omits a complicated separation step, greatly reduces the production cost, and is suitable for large-scale continuous production of the 1-naphthylacetic acid.
Description
Technical Field
The invention belongs to the field of pesticide synthesis, and particularly relates to a preparation method of 1-naphthylacetic acid.
Background
The 1-naphthylacetic acid is a broad-spectrum plant growth regulator, it can quickly promote cell division and expansion (fruit swelling agent, swelling element, inducing to form adventitious root (rooting agent), at the same time it has the functions of regulating growth, promoting rooting, flowering, preventing flower and fruit drop, forming seedless fruit, promoting prematurity and increasing yield, and after it is used, it also can raise the drought-resisting, cold-resisting, salt-resisting, disease-resisting and dry-hot wind-resisting capabilities of plant.
There are various methods for synthesizing 1-naphthylacetic acid. The first method is a Condensation reaction of Naphthalene and Chloroacetic Acid to produce naphthylacetic Acid (Ogata Y, Ishiguro J.preparation of alpha-naphthylacetic Acid by the Condensation of Naphthalene with chlorophoacetic Acid [ J ]. J.Am.chem.Soc,1950,72: 4302; Malachi, Tanghong Bo. alpha-naphthylacetic Acid synthesis process research [ J ]. pesticide, 2004,43(9): 412-
The method has the advantages that the catalyst has various types and can be selected randomly, such as Fe powder and Fe2O3Powder A1, powder A1Cl3、MnO2And the like, KBr is generally adopted as a cocatalyst in experiments, and the method has the defects that the yield is generally not high and is 45-50%, in addition, the reaction time is more than 30h, the reaction temperature requirement is higher, meanwhile, the raw material consumption is higher, and the raw material is not easy to recover. Research on synthesis process of alpha-naphthylacetic acid, a plant growth regulator, in the literature, Chailaoli (Chailaoli, Kudzuvine mountain, Wang Guobao, etc.)]The A1 powder is used as a catalyst and iodine is used as a cocatalyst, the reaction time is greatly shortened by the method for synthesizing the target compound, the reaction time is reduced to about 10 hours, and although the reaction time is greatly shortened, iodine is used in the reaction, so that the cost is increased.
The second method is that naphthalene is chloromethylated to produce alpha-chloromethyl naphthalene, which is then condensed with sodium cyanide to produce alpha-naphthylacetonitrile, which is hydrolyzed under alkaline condition to produce naphthylacetic acid (Oliver G., Allen B.,1-Chloromethylnaphthalene [ J ]. Organic Syntheses, 1944,24.)
The synthetic route is very simple and convenient, has many advantages that other reactions do not have, for example, the reaction temperature is mild, alpha-chloromethyl naphthalene can be prepared at about 80 ℃, the reaction has no high requirement on equipment, the raw material naphthalene is cheap and easy to obtain, and meanwhile, the post-treatment is simple and convenient, thus being relatively suitable for industrial scale-up production. However, NaCN used in the experiment belongs to a highly toxic chemical, and the leakage caused by carelessness in use can affect the safety of people and animals and cause pollution to the environment.
The third method is that naphthalene and acetic anhydride generate naphthylacetic acid under the action of potassium permanganate (Xuanguang. synthesis of plant growth hormone naphthylacetic acid [ J ]. chemical world, 1985(12):451.)
The reaction time of synthesizing the naphthylacetic acid by the method is short, the reaction temperature is low, the operation is simple and convenient, but acetic anhydride used in the reaction belongs to a tube product, the acetic anhydride is not suitable for purchase, the total yield of the experiment is low and is about 45%, so that the loss of raw materials in the experiment is caused, and the cost is high. Meanwhile, potassium permanganate and acetic anhydride used in the reaction process have certain dangerousness at high temperature, so that the route is limited on an industrial road.
Disclosure of Invention
In view of the above, the present invention discloses a method for continuously producing 1-naphthylacetic acid. Greatly reduces the generation of byproducts, solves the problem of recovering excessive chloroacetic acid, is efficient and environment-friendly, omits complex separation steps, greatly reduces the production cost, and is suitable for large-scale continuous production of the 1-naphthylacetic acid.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a preparation method of 1-naphthylacetic acid, which comprises the following steps:
1) naphthalene and chloroacetic acid enter a reactor filled with a ZSM-5 or ZSM-11 molecular sieve, wherein naphthalene enters from a feed inlet at the upper part of the reactor, and raw materials react in the reactor to obtain a mixture containing 1-naphthylacetic acid;
2) a discharge port of the reactor is connected with solid-liquid separation equipment, a mixture containing the 1-naphthylacetic acid is subjected to solid-liquid separation in the solid-liquid separation equipment to obtain the 1-naphthylacetic acid and a mother solution, the discharge port of the solid-liquid separation equipment is communicated with a mother solution circulating pump, and a discharge port of the mother solution circulating pump is communicated with the upper part of the reactor through a pipeline; the mother liquor is recycled to the reactor for reuse.
In a preferred embodiment of the present invention, the naphthalene is fed in a molten liquid state. The molten naphthalene is directly fed by a constant flow pump, the constant flow pump is connected with a naphthalene storage tank, and an outlet of the constant flow pump is connected with a feed inlet at the upper part of the reactor.
As a preferable scheme of the invention, the feed inlet is connected with a distributor positioned at the upper part in the reactor through a pipeline, and the naphthalene is uniformly dispersed into the reactor through the distributor. Preferably, the distributor is a spray head.
As a preferable scheme of the invention, the naphthalene is continuously fed; the naphthalene storage tank and the constant flow pump are both positioned above the reactor.
As a preferable scheme of the invention, the reactor is provided with a jacket, and heat conducting oil is introduced into the jacket to control the temperature in the reactor.
As a preferable scheme of the invention, the discharge hole of the reactor is positioned at the bottom of the reactor; the solid-liquid separation equipment is positioned below the reactor, the discharge port is connected with the solid-liquid separation equipment through a pipeline, and the solid-liquid separation equipment is a centrifugal machine or a filter press.
In a preferred embodiment of the invention, the feeding molar ratio of naphthalene to chloroacetic acid is 1: 1-10.
As a preferable scheme of the invention, the temperature of the reaction in the step 1) is 190-215 ℃.
As a preferable embodiment of the present invention, chloroacetic acid as a raw material in the step 1) is fed in a liquid state, and a liquid feeding port for chloroacetic acid is provided in the upper part of the reactor.
As a preferable scheme of the invention, the raw material chloroacetic acid in the step 1) is fed in a gaseous state, the raw material chloroacetic acid is firstly gasified and then pressed into the reactor through a compressor, and a chloroacetic acid gaseous feed inlet is positioned at the lower part of the catalyst bed layer.
As a preferable scheme of the invention, the feeding speed of the naphthalene in the step 1) is 100-1000 kg/h; the feeding speed of the chloroacetic acid is 70-1000 kg/h.
The invention has the beneficial effects that:
in the method for continuously producing the 1-naphthylacetic acid, naphthalene and chloroacetic acid react in a reactor filled with a ZSM-5 or ZSM-11 molecular sieve, the naphthalene can be in a molten liquid state when being fed, and the chloroacetic acid can be in a liquid state or a gas state; the method adopts ZSM-5 or ZSM-11, so that the generation of 2-naphthylacetic acid is greatly reduced, the complicated separation step is saved, the problem of chloroacetic acid recovery can be solved, the raw material loss is reduced, the method is efficient and environment-friendly, the production cost is greatly reduced, and the method is suitable for large-scale production. The purity of the 1-naphthylacetic acid produced by the method can reach more than 98%, and the yield can reach more than 95%.
Drawings
FIG. 1 is a schematic view of a continuous production apparatus of 1-naphthylacetic acid in accordance with the present invention.
Detailed Description
In one embodiment of the present invention, the preparation method of the present invention is carried out using a reaction apparatus as shown in FIG. 1, which mainly comprises a naphthalene storage tank, a reactor, a solid-liquid separator and a circulation pump; the reactor is a tower reactor, ZSM-5 or ZSM-11 molecular sieve is filled in the tower as a catalyst, a spray nozzle is arranged at the top of the tower as a naphthalene distributor, and a product outlet is arranged at the bottom of the tower.
Naphthalene in the naphthalene storage tank can be fed into a top feeding port of the tower reactor in a molten liquid state, the feeding port is connected with a spray head, and the spray head disperses the naphthalene in the reaction tower; chloroacetic acid can enter a reactor in a gas form, naphthalene and chloroacetic acid react in the reactor to obtain a mixture containing 1-naphthylacetic acid, the obtained mixture containing 1-naphthylacetic acid enters a solid-liquid separator from the bottom of the reaction tower, and the solid-liquid separator separates to obtain a product 1-naphthylacetic acid; and recycling the separated liquid to the reactor.
Example 1: (molar ratio 1:1)
Feeding is carried out in a reactor 3 filled with 100kg of ZSM-5, the reaction temperature is 190 ℃, the naphthalene feeding speed is 95kg/h, the melted naphthalene is uniformly dispersed into the reactor through a spray head 2, the chloroacetic acid feeding speed is 70kg/h, the melted naphthalene is pressed into the reactor through a compressor after being gasified, 1-naphthylacetic acid and excessive liquid chloroacetic acid mother liquor are separated through a filter press, and the mother liquor is circulated into the reactor 3 through a pipeline through a circulating pump; the mother liquor returns to the reactor through a mother liquor circulating pump. The yield of the 1-naphthylacetic acid is 95.5 percent, and the purity of the dried product is 98.8 percent. IR (cm)-1):3300-2500,3065.1,2915.2,1699.0,1414.0,1220.5,935.1,781.2. Nuclear magnetic resonance hydrogen spectroscopy (CDCl)3)δ：11.9(S,1H),7.98-8.00(d,2H),7.88-7.90(d,2H),7.82-7.84(d,2H),7.51-7.57(m,2H) 7.43-7.48(m,2H),4.10-1.12(s, 2H). Nuclear magnetic resonance carbon spectroscopy (CDCl)3)δ：78.00,39.83，123.80，125.50，125.90，126.10，128.34,128.48,128.90，129.83，132.11，133.90，178.50。
Example 2: : (molar ratio 1:10)
Feeding is carried out in a reactor 3 filled with 100kg of ZSM-11, the reaction temperature is 215 ℃, the naphthalene feeding rate is 100kg/h, the melted naphthalene is uniformly dispersed into the reactor through a spray head 2, the chloroacetic acid feeding rate is 734kg/h, the melted naphthalene is pressed into the reactor through a compressor after being gasified, 1-naphthylacetic acid and excessive liquid chloroacetic acid mother liquor are separated through a filter press, and the mother liquor is circulated into the reactor 3 through a pipeline through a circulating pump; the yield of the 1-naphthylacetic acid is 95.5 percent, and the purity of the dried product is 98.9 percent.
Example 3: (molar ratio 1:1.36)
Feeding is carried out in a reactor 3 filled with 85kg of ZSM-11, the reaction temperature is 200 ℃, the naphthalene feeding rate is 1000kg/h, the melted naphthalene is uniformly dispersed into the reactor through a spray head 2, the chloroacetic acid feeding rate is 734kg/h, the melted naphthalene is pressed into the reactor through a compressor after being gasified, 1-naphthylacetic acid and excessive liquid chloroacetic acid mother liquor are separated through a filter press, and the mother liquor is circulated into the reactor 3 through a pipeline through a circulating pump; the yield of the 1-naphthylacetic acid is 96.5 percent, and the purity of the dried product is 98.7 percent.
Example 4: (molar ratio 1:2)
Feeding is carried out in a reactor 3 filled with 85kg of ZSM-5, the reaction temperature is 200 ℃, the naphthalene feeding rate is 681kg/h, the melted naphthalene is uniformly dispersed into the reactor through a spray head 2, the chloroacetic acid feeding rate is 1000kg/h, the melted naphthalene is pressed into the reactor through a compressor after being gasified, 1-naphthylacetic acid and excessive liquid chloroacetic acid mother liquor are separated through a filter press, and the mother liquor is circulated into the reactor 3 through a pipeline through a circulating pump; the yield of the 1-naphthylacetic acid is 96.7 percent, and the purity of the dried product is 98.8 percent.
Claims (10)
1. A preparation method of 1-naphthylacetic acid is characterized by comprising the following steps:
1) naphthalene and chloroacetic acid enter a reactor filled with a ZSM-5 or ZSM-11 molecular sieve, wherein naphthalene enters from a feed inlet at the upper part of the reactor, and raw materials react in the reactor to obtain a mixture containing 1-naphthylacetic acid;
2) a discharge port of the reactor is connected with solid-liquid separation equipment, a mixture containing the 1-naphthylacetic acid is subjected to solid-liquid separation in the solid-liquid separation equipment to obtain the 1-naphthylacetic acid and a mother liquor, the discharge port of the solid-liquid separation equipment is communicated with a mother liquor circulating pump, and the discharge port of the mother liquor circulating pump is communicated with the upper part of the reactor through a pipeline; the mother liquor is recycled to the reactor for reuse.
2. The method according to claim 1, wherein naphthalene is fed in a molten state, the feed port is connected to a distributor located at an upper portion of the reactor through a pipe, and naphthalene is uniformly dispersed into the reactor through the distributor.
3. The method of claim 2, wherein the method is a continuous process, and both naphthalene and chloroacetic acid are fed continuously; the resulting mixture containing 1-naphthylacetic acid is discharged continuously.
4. The method for preparing 1-naphthylacetic acid according to claim 1, wherein the reactor is provided with a jacket, and heat conducting oil is introduced into the jacket to control the temperature in the reactor.
5. The method for preparing 1-naphthylacetic acid according to claim 1, wherein the outlet of the reactor is located at the bottom of the reactor; the solid-liquid separation equipment is positioned below the reactor, the discharge port is connected with the solid-liquid separation equipment through a pipeline, and the solid-liquid separation equipment is a centrifugal machine or a filter press.
6. The method of claim 1, wherein the feed molar ratio of naphthalene to chloroacetic acid is from 1:1 to 10.
7. The method of claim 1, wherein the temperature of the reaction in step 1) is 190-215 ℃.
8. The process according to claim 1, characterized in that the starting material chloroacetic acid in step 1) is fed in liquid form, and the liquid feed inlet for chloroacetic acid is located in the upper part of the reactor.
9. The process according to claim 1, characterized in that the feed chloroacetic acid in step 1) is fed in gaseous form, the feed chloroacetic acid is first gasified and then pressed into the reactor by means of a compressor, and the gaseous feed inlet for chloroacetic acid is located at the lower part of the catalyst bed.
10. The method according to claim 1, wherein the feeding rate of naphthalene in step 1) is 100 to 1000 kg/h;
the feeding speed of the chloroacetic acid is 70-1000 kg/h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086400A (en) * | 2014-07-15 | 2014-10-08 | 四川国光农化股份有限公司 | Production process of sodium naphthalene acetate |
| CN109796324A (en) * | 2019-02-16 | 2019-05-24 | 河南大学 | Methyl α-naphthyl acetate preparation method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086400A (en) * | 2014-07-15 | 2014-10-08 | 四川国光农化股份有限公司 | Production process of sodium naphthalene acetate |
| CN109796324A (en) * | 2019-02-16 | 2019-05-24 | 河南大学 | Methyl α-naphthyl acetate preparation method |
Non-Patent Citations (4)
| Title |
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| Direct aromatic carboxymethylation;Southwick, Philip L.;《Synthesis》;197012(第12期);第628-635页 * |
| Mesoporous Beta Zeolite Catalysts for Benzylation of Naphthalene: Effect of Pore Structure and Acidity;Wenming Hao等;《Catalysts》;20181028;第8卷(第11期);第504/1-504/13页 * |
| 不同沸石分子筛催化剂上萘与异丙醇的烷基化反应;刘琪英等;《南京工业大学学报》;200405;第26卷(第3期);第12-14页 * |
| 纳米ZSM-5分子筛的酸脱铝改性及其催化萘和甲醇的烷基化反应性能;王文静等;《石油学报（石油加工）》;201408;第30卷(第4期);第620-628页 * |
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