CN113121310A - Preparation method of 1- (4-chlorphenyl) -2-methylbut-3-en-1-ol - Google Patents
Preparation method of 1- (4-chlorphenyl) -2-methylbut-3-en-1-ol Download PDFInfo
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- CN113121310A CN113121310A CN201911406816.3A CN201911406816A CN113121310A CN 113121310 A CN113121310 A CN 113121310A CN 201911406816 A CN201911406816 A CN 201911406816A CN 113121310 A CN113121310 A CN 113121310A
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- methylbut
- chlorphenyl
- chlorobenzaldehyde
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- silica gel
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- UUZUQJOJASRJBK-UHFFFAOYSA-N 1-(4-chlorophenyl)-2-methylbut-3-en-1-ol Chemical compound C=CC(C)C(O)C1=CC=C(Cl)C=C1 UUZUQJOJASRJBK-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 claims abstract description 25
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 239000000741 silica gel Substances 0.000 claims abstract description 13
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 7
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims 1
- UFNOUKDBUJZYDE-UHFFFAOYSA-N 2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol Chemical compound C1=NC=NN1CC(O)(C=1C=CC(Cl)=CC=1)C(C)C1CC1 UFNOUKDBUJZYDE-UHFFFAOYSA-N 0.000 abstract description 8
- 239000005757 Cyproconazole Substances 0.000 abstract description 8
- 241000233866 Fungi Species 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- OILXMJHPFNGGTO-UHFFFAOYSA-N (22E)-(24xi)-24-methylcholesta-5,22-dien-3beta-ol Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)C=CC(C)C(C)C)C1(C)CC2 OILXMJHPFNGGTO-UHFFFAOYSA-N 0.000 description 1
- RQOCXCFLRBRBCS-UHFFFAOYSA-N (22E)-cholesta-5,7,22-trien-3beta-ol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CCC(C)C)CCC33)C)C3=CC=C21 RQOCXCFLRBRBCS-UHFFFAOYSA-N 0.000 description 1
- OQMZNAMGEHIHNN-UHFFFAOYSA-N 7-Dehydrostigmasterol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CC(CC)C(C)C)CCC33)C)C3=CC=C21 OQMZNAMGEHIHNN-UHFFFAOYSA-N 0.000 description 1
- DNVPQKQSNYMLRS-NXVQYWJNSA-N Ergosterol Natural products CC(C)[C@@H](C)C=C[C@H](C)[C@H]1CC[C@H]2C3=CC=C4C[C@@H](O)CC[C@]4(C)[C@@H]3CC[C@]12C DNVPQKQSNYMLRS-NXVQYWJNSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OATYEVJXAXMWIA-UHFFFAOYSA-K [Cl-].C1=CC=CCCCC1.[Ru+3].[Cl-].[Cl-] Chemical group [Cl-].C1=CC=CCCCC1.[Ru+3].[Cl-].[Cl-] OATYEVJXAXMWIA-UHFFFAOYSA-K 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- YTKRILODNOEEPX-NSCUHMNNSA-N crotyl chloride Chemical compound C\C=C\CCl YTKRILODNOEEPX-NSCUHMNNSA-N 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- DNVPQKQSNYMLRS-SOWFXMKYSA-N ergosterol Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H](CC[C@]3([C@H]([C@H](C)/C=C/[C@@H](C)C(C)C)CC[C@H]33)C)C3=CC=C21 DNVPQKQSNYMLRS-SOWFXMKYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 1- (4-chlorphenyl) -2-methylbut-3-en-1-ol, which comprises the following steps of reacting p-chlorobenzaldehyde and chlorodibutyl-diene as raw materials under the action of zinc powder, saturated aqueous solution of ammonium chloride and silica gel to generate a compound 1- (4-chlorphenyl) -2-methylbut-3-en-1-ol shown in a formula (III), wherein the specific reaction formula is as follows:
the invention provides a brand new preparation method of 1- (4-chlorphenyl) -2-methylbut-3-ene-1-ol as an intermediate for preparing cyproconazole, the purity of the 1- (4-chlorphenyl) -2-methylbut-3-ene-1-ol prepared by the method can reach 98.9 percent, the yield reaches 93.8 percent, the quality is extremely high, and the method is greatly used for preparing cyproconazoleThe purity of the cyproconazole is improved.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a preparation method of 1- (4-chlorphenyl) -2-methylbut-3-en-1-ol.
Background
1- (4-chlorphenyl) -2-methylbut-3-en-1-ol is an intermediate for synthesizing cyproconazole, and the cyproconazole is a triazole fungicide, can inhibit demethylation of ergosterol which is an important substance in fungus cell membranes, and has the effects of preventing and treating fungi.
U4849449 reports that p-chlorobenzaldehyde as raw material and 1-chloro-2-butene undergo Grignard reaction to obtain the target compound, magnesium strips and a large amount of organic solvent are added, the reaction is carried out at low temperature in an anhydrous and oxygen-free manner, the reaction conditions are harsh, and the safety is low.
The article reports that p-chlorobenzaldehyde is used as a raw material to react with allyl alcohol to obtain a target compound, but the required catalyst is cyclooctadiene ruthenium chloride, the catalyst is not easy to obtain, the reaction time is long, 11 hours are needed, and the industrialization is difficult to realize.
In summary, the existing production process of 1- (4-chlorophenyl) -2-methylbut-3-en-1-ol generally has the defects of high risk, high cost, difficulty in realizing industrial production and the like, so that a safe and efficient method for preparing 1- (4-chlorophenyl) -2-methylbut-3-en-1-ol is needed.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a brand-new preparation method of 1- (4-chlorphenyl) -2-methylbut-3-en-1-ol as an intermediate for producing cyproconazole aiming at the defects of the prior art.
The technical scheme is as follows: the invention relates to a preparation method of 1- (4-chlorphenyl) -2-methylbut-3-en-1-ol, which takes p-chlorobenzaldehyde and chlorodibutyl-diene as raw materials to react under the action of zinc powder, saturated aqueous solution of ammonium chloride and silica gel to generate a compound 1- (4-chlorphenyl) -2-methylbut-3-en-1-ol shown in a formula (III), and the specific reaction formula is as follows:
further, the method specifically comprises the following steps:
(1) weighing p-chlorobenzaldehyde, zinc powder and a saturated ammonium chloride aqueous solution, controlling the temperature at 0-5 ℃, dropwise adding monochlorodibutene, preserving heat for 6-10 hours after dropwise adding, sending samples to detect, wherein the p-chlorobenzaldehyde is less than or equal to 0.2%, and obtaining a crude product after reaction;
(2) and adding hydrochloric acid into the crude product, stirring for 0.5-1 h, carrying out suction filtration, wherein the filter residue is silica gel, drying and then repeatedly using, adding toluene into the filtrate for extraction, and drying with anhydrous sodium sulfate to obtain the 1- (4-chlorphenyl) -2-methylbut-3-en-1-ol.
Furthermore, the molar ratio of the p-chlorobenzaldehyde to the chlorodibutyl carbonate to the zinc powder is 1: 1-2: 0.1-0.3, the molar ratio of the p-chlorobenzaldehyde to the saturated ammonium chloride aqueous solution is 1: 0.5-1, and the reaction temperature is 0-5 ℃.
Further, the silica gel is C18 silica gel.
Has the advantages that: (1) the invention provides a brand new preparation method of 1- (4-chlorphenyl) -2-methylbut-3-ene-1-ol as an intermediate for preparing cyproconazole, the purity of the 1- (4-chlorphenyl) -2-methylbut-3-ene-1-ol prepared by the method can reach 98.9 percent, the yield reaches 93.8 percent, the quality is extremely high, and the method is used for preparing cyproconazole and greatly improving the purity of cyproconazole;
(2) in the method provided by the invention, the reactant silica gel can be recycled, so that the material waste is greatly reduced, and the production cost is reduced.
Drawings
FIG. 1 is a NMR chart of 1- (4-chlorophenyl) -2-methylbut-3-en-1-ol in example 1.
Detailed Description
The technical solution of the present invention is described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the embodiments.
Example 1: (1) weighing p-chlorobenzaldehyde, zinc powder and a saturated ammonium chloride aqueous solution, controlling the temperature at 0-5 ℃, dropwise adding monochlorodibutene, preserving heat for 6-10 hours after dropwise adding, sending samples to detect, wherein the p-chlorobenzaldehyde is less than or equal to 0.2%, and obtaining a crude product after reaction;
(2) and adding hydrochloric acid into the crude product, stirring for 0.5-1 h, carrying out suction filtration, wherein the filter residue is silica gel, drying and then repeatedly using, adding toluene into the filtrate for extraction, and drying with anhydrous sodium sulfate to obtain the 1- (4-chlorphenyl) -2-methylbut-3-en-1-ol.
Wherein the molar ratio of the p-chlorobenzaldehyde to the chlorodibutyl and the zinc powder is 1:1.5:0.2, and the molar ratio of the p-chlorobenzaldehyde to the saturated aqueous solution of ammonium chloride is 1: 0.8.
The 1- (4-chlorophenyl) -2-methylbut-3-en-1-ol prepared in this example was found to have a purity of 98.9% and a yield of 93.8%. The hydrogen spectrum of the product prepared in this example as shown in fig. 1 can be read as follows:
1h NMR (400MHz, CDCl3) δ 7.33-7.26 (m,2H), 7.25-7.15 (m,2H), 5.86-5.60 (m,1H), 5.22-5.10 (m,1H),5.03(m,1H),4.41(m,1H), 2.59-2.45 (m,1H),0.92(d, J ═ 6.8Hz, 3H). The above data demonstrate the successful synthesis of 1- (4-chlorophenyl) -2-methylbut-3-en-1-ol.
Example 2: (1) weighing p-chlorobenzaldehyde, zinc powder and a saturated ammonium chloride aqueous solution, controlling the temperature at 0-5 ℃, dropwise adding monochlorodibutene, preserving heat for 6-10 hours after dropwise adding, sending samples to detect, wherein the p-chlorobenzaldehyde is less than or equal to 0.2%, and obtaining a crude product after reaction;
(2) and adding hydrochloric acid into the crude product, stirring for 0.5-1 h, carrying out suction filtration, wherein the filter residue is silica gel, drying and then repeatedly using, adding toluene into the filtrate for extraction, and drying with anhydrous sodium sulfate to obtain the 1- (4-chlorphenyl) -2-methylbut-3-en-1-ol.
Wherein the molar ratio of the p-chlorobenzaldehyde to the chlorodibutyl carbonate to the zinc powder is 1:1:0.1, and the molar ratio of the p-chlorobenzaldehyde to the saturated aqueous solution of ammonium chloride is 1: 0.5.
The 1- (4-chlorophenyl) -2-methylbut-3-en-1-ol prepared in this example was found to have a purity of 97.9% and a yield of 93.5%.
Example 3: (1) weighing p-chlorobenzaldehyde, zinc powder and a saturated ammonium chloride aqueous solution, controlling the temperature at 0-5 ℃, dropwise adding monochlorodibutene, preserving heat for 6-10 hours after dropwise adding, sending samples to detect, wherein the p-chlorobenzaldehyde is less than or equal to 0.2%, and obtaining a crude product after reaction;
(2) and adding hydrochloric acid into the crude product, stirring for 0.5-1 h, carrying out suction filtration, wherein the filter residue is silica gel, drying and then repeatedly using, adding toluene into the filtrate for extraction, and drying with anhydrous sodium sulfate to obtain the 1- (4-chlorphenyl) -2-methylbut-3-en-1-ol.
Wherein the molar ratio of the p-chlorobenzaldehyde to the chlorodibutyl carbonate to the zinc powder is 1:2:0.3, and the molar ratio of the p-chlorobenzaldehyde to the saturated aqueous solution of ammonium chloride is 1:1.
The 1- (4-chlorophenyl) -2-methylbut-3-en-1-ol prepared in this example was found to have a purity of 97.8% and a yield of 93.4%.
As noted above, while the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limited thereto. Various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (4)
1. A preparation method of 1- (4-chlorphenyl) -2-methylbut-3-en-1-ol is characterized in that: p-chlorobenzaldehyde and chlorodibutyl phthalate are used as raw materials to react under the action of zinc powder, saturated aqueous solution of ammonium chloride and silica gel to generate a compound 1- (4-chlorphenyl) -2-methylbut-3-en-1-ol shown in a formula (III), and the specific reaction formula is as follows:
2. the process for the preparation of 1- (4-chlorophenyl) -2-methylbut-3-en-1-ol according to claim 1, characterized by comprising the following steps:
(1) weighing p-chlorobenzaldehyde, zinc powder and a saturated ammonium chloride aqueous solution, controlling the temperature at 0-5 ℃, dropwise adding monochlorodibutene, preserving heat for 6-10 hours after dropwise adding, sending samples to detect, wherein the p-chlorobenzaldehyde is less than or equal to 0.2%, and obtaining a crude product after reaction;
(2) and adding hydrochloric acid into the crude product, stirring for 0.5-1 h, carrying out suction filtration, wherein the filter residue is silica gel, drying and then repeatedly using, adding toluene into the filtrate for extraction, and drying with anhydrous sodium sulfate to obtain the 1- (4-chlorphenyl) -2-methylbut-3-en-1-ol.
3. The process for the preparation of 1- (4-chlorophenyl) -2-methylbut-3-en-1-ol according to claim 1, characterized in that: the mol ratio of p-chlorobenzaldehyde to the chlorodibutyl carbonate to zinc powder is 1: 1-2: 0.1-0.3, the mol to volume ratio of the p-chlorobenzaldehyde to the saturated aqueous solution of ammonium chloride is 1: 0.5-1, and the reaction temperature is 0-5 ℃.
4. The process for the preparation of 1- (4-chlorophenyl) -2-methylbut-3-en-1-ol according to claim 1, characterized in that: the silica gel is C18 silica gel.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4849449A (en) * | 1985-12-10 | 1989-07-18 | Roussel Uclaf | Novel cyclopropane carboxylates |
| CN1035494A (en) * | 1987-12-14 | 1989-09-13 | 山道士有限公司 | The preparation method of cyclopropane derivative |
| US5770741A (en) * | 1988-12-12 | 1998-06-23 | Sandoz Ltd. | Process for cylopropane derivatives |
-
2019
- 2019-12-31 CN CN201911406816.3A patent/CN113121310A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4849449A (en) * | 1985-12-10 | 1989-07-18 | Roussel Uclaf | Novel cyclopropane carboxylates |
| CN1035494A (en) * | 1987-12-14 | 1989-09-13 | 山道士有限公司 | The preparation method of cyclopropane derivative |
| US5770741A (en) * | 1988-12-12 | 1998-06-23 | Sandoz Ltd. | Process for cylopropane derivatives |
Non-Patent Citations (4)
| Title |
|---|
| MASUYAMA, YOSHIRO: "α-Regioselective carbonyl allylation by an allylic tin compound prepared from 1-bromobut-2-ene and tin(II) bromide at a nonpolar organic-aqueous interface", JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS * |
| SINHA, PRADIPTA: "Barbier Reaction in the Regime of Metal Oxide: Carbonyl Allylation over β-SnO/Cu2O and Surface Diagnostics", ORGANOMETALLICS * |
| SINHA, PRADIPTA: "Transition metal catalyzed Grignard-like allylic activation across tetragonal tin(II) oxide", PROCEEDINGS - INDIAN ACADEMY OF SCIENCES, CHEMICAL SCIENCES * |
| YAMATAKA, HIROSHI;: "Reaction pathway and transition state of the Zn-promoted Barbier-type reactions of benzaldehyde and benzophenone with allylic iodides", BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN * |
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