CN114380713A - Synthesis method of o-methyl benzoyl cyanide - Google Patents
Synthesis method of o-methyl benzoyl cyanide Download PDFInfo
- Publication number
- CN114380713A CN114380713A CN202111155127.7A CN202111155127A CN114380713A CN 114380713 A CN114380713 A CN 114380713A CN 202111155127 A CN202111155127 A CN 202111155127A CN 114380713 A CN114380713 A CN 114380713A
- Authority
- CN
- China
- Prior art keywords
- cyanide
- methylbenzoyl
- copper
- chloride
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- WYXWANVHOUGOBI-UHFFFAOYSA-N 2-methylbenzoyl cyanide Chemical compound CC1=CC=CC=C1C(=O)C#N WYXWANVHOUGOBI-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000001308 synthesis method Methods 0.000 title abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- GPZXFICWCMCQPF-UHFFFAOYSA-N 2-methylbenzoyl chloride Chemical compound CC1=CC=CC=C1C(Cl)=O GPZXFICWCMCQPF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 18
- -1 potassium ferricyanide Chemical compound 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 34
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 11
- 239000005857 Trifloxystrobin Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- ONCZDRURRATYFI-TVJDWZFNSA-N trifloxystrobin Chemical compound CO\N=C(\C(=O)OC)C1=CC=CC=C1CO\N=C(/C)C1=CC=CC(C(F)(F)F)=C1 ONCZDRURRATYFI-TVJDWZFNSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- MMUFAGXJPKNAHT-UHFFFAOYSA-N copper;quinolin-8-ol Chemical compound [Cu].C1=CN=C2C(O)=CC=CC2=C1 MMUFAGXJPKNAHT-UHFFFAOYSA-N 0.000 claims description 8
- JLOULEJYJNBUMX-UHFFFAOYSA-L copper;quinoline-2-carboxylate Chemical compound [Cu+2].C1=CC=CC2=NC(C(=O)[O-])=CC=C21.C1=CC=CC2=NC(C(=O)[O-])=CC=C21 JLOULEJYJNBUMX-UHFFFAOYSA-L 0.000 claims description 6
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 5
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 5
- 229940045803 cuprous chloride Drugs 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract 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 abstract description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 abstract 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000000276 potassium ferrocyanide Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- 229930182692 Strobilurin Natural products 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QQGVWMIRCZEUBB-UHFFFAOYSA-N n-[1-[3-(trifluoromethyl)phenyl]ethylidene]hydroxylamine Chemical compound ON=C(C)C1=CC=CC(C(F)(F)F)=C1 QQGVWMIRCZEUBB-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 238000006146 oximation reaction Methods 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of o-methylbenzoyl cyanide, which takes o-methylbenzoyl chloride as a raw material and potassium ferricyanide as a cyaniding reagent to prepare the o-methylbenzoyl cyanide in a solvent or in the absence of the solvent under the catalysis of a copper catalyst. The synthesis method avoids the use of virulent sodium cyanide, cuprous cyanide and the like, is green and safe, has cheap and easily-obtained raw materials and mild reaction conditions, and has high industrial production value.
Description
Technical Field
The present invention relates to the field of organic synthesis. In particular to a novel synthesis method of o-methyl benzoyl cyanide.
Background
The trifloxystrobin belongs to strobilurin fungicides, and has the characteristics of high efficiency, broad spectrum, long lasting period and the like. The o-methylbenzoyl cyanide is a key intermediate for synthesizing trifloxystrobin, and the method reported in the literature at present is mainly prepared by taking o-methylbenzoyl chloride as a raw material and taking sodium cyanide, potassium cyanide and the like as cyaniding reagents.
The methods all need to use highly toxic cyanide, and the synthesis process has no characteristics of greenness, safety and the like. For example, the cyanidation synthesis methods described in chinese patents CN201210457928 and CN201811581239, etc. all use highly toxic cyanide as a cyanidation reagent; advanced Synthesis and Catalysis,2019,361(19),4474-4482 and Synlett,2006,15,2495-2497 report the use of potassium ferrocyanide as a cyaniding reagent and palladium acetate or silver iodide as a catalyst, which is expensive, costly to produce and not suitable for industrial production. Similarly, J.Braz.chem.Soc.2013,24(11),1739-1743 report benzoyl cyanidation, potassium ferrocyanide is used as a cyaniding reagent, and the reaction is carried out at a high temperature of 160 ℃, so that the energy consumption of industrial production is too high. Chinese patent CN201710177386 also reports a similar cyanidation synthesis method, potassium ferrocyanide and a phase transfer catalyst system are adopted for cyanidation reaction, and tests prove that o-methylbenzoyl chloride does not react under the synthesis method.
Therefore, an economic, environment-friendly and green and safe o-methyl benzoyl cyanide synthesis method is urgently needed in the field.
Disclosure of Invention
The invention aims to provide a brand-new o-methyl benzoyl cyanide synthesis method which has the advantages of economy, environmental protection, green and safe process and the like.
In a first aspect, the present invention provides a method for preparing trifloxystrobin, comprising the steps of:
1) synthesizing o-methylbenzoyl cyanide by using o-methylbenzoyl chloride in the presence of potassium ferricyanide and a copper catalyst and in the presence or absence of a solvent;
and
2) synthesizing the o-methyl benzoyl cyanide obtained in the step 1) to obtain trifloxystrobin.
In a specific embodiment, the molar ratio of the o-methylbenzoyl chloride to the potassium ferricyanide in the step 1) is 1: 0.16-0.3; preferably 1: 0.17-0.2; more preferably 1: 0.17-0.18.
In a particular embodiment, the copper catalyst in step 1) is selected from: oxine-copper, cuprous chloride, cuprous bromide, cuprous iodide, and the like; copper quinolinate is preferred.
In a specific embodiment, the amount of the copper catalyst used in the step 1) is 1% -10% of the amount of the o-methylbenzoyl chloride; preferably 1 to 5%; more preferably 1%.
In a particular embodiment, the solvent in step 1) is selected from any one or several of the following: dichloroethane, toluene, xylene, N-dimethylformamide, etc.; dichloroethane, toluene, etc. are preferable.
In a specific embodiment, the reaction temperature of the step 1) is 0-150 ℃, and the reaction time is 1-10 hours; the reaction temperature is preferably 70 to 110 ℃ and the reaction time is preferably 3 to 5 hours.
In a second aspect, the present invention provides a process for the preparation of o-methylbenzoyl cyanide, said process comprising the steps of:
1) synthesizing o-methylbenzoyl cyanide by using o-methylbenzoyl chloride in the presence of potassium ferricyanide and a copper catalyst and in the presence or absence of a solvent;
in a specific embodiment, the molar ratio of the o-methylbenzoyl chloride to the potassium ferricyanide in the step 1) is 1: 0.16-0.3; preferably 1: 0.17-0.2; more preferably 1: 0.17-0.18.
In a particular embodiment, the copper catalyst in step 1) is selected from: oxine-copper, cuprous chloride, cuprous bromide, cuprous iodide, and the like; copper quinolinate is preferred.
In a specific embodiment, the amount of the copper catalyst used in the step 1) is 1% -10% of the amount of the o-methylbenzoyl chloride; preferably 1 to 5%; more preferably 1%; and/or
The solvent in the step 1) is selected from any one or more of the following solvents: dichloroethane, toluene, xylene, N, N-dimethylformamide and the like; preferably dichloroethane, toluene, etc.; and/or
The reaction temperature of the step 1) is 0-150 ℃, and the reaction time is 1-10 hours; the reaction temperature is preferably 70 to 110 ℃ and the reaction time is preferably 3 to 5 hours.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Detailed Description
The inventor unexpectedly finds that potassium ferricyanide is used as a cyaniding reagent to carry out the acyl cyaniding reaction under a copper catalyst system, so that the method is more suitable for industrial production, and can be used for synthesizing o-methyl benzoyl cyanide safely and environmentally friendly to prepare the final trifloxystrobin. The synthesis method is simple, mild in reaction conditions and suitable for industrial scale-up production. The present invention has been completed based on this finding.
Method of the invention
In order to overcome various defects in the prior art, the invention provides a method for synthesizing o-methyl benzoyl cyanide. The method disclosed by the invention avoids the use of highly toxic cyanide, the used raw materials are cheap and easy to obtain, the process is green and safe, and the reaction conditions are mild; compared with other reported methods, the method disclosed by the invention adopts potassium ferricyanide as a cyaniding reagent, performs the cyaniding reaction under a copper catalyst system, and is more suitable for industrial production.
In a specific embodiment, the invention provides a synthesis method of o-methyl benzoyl cyanide, which comprises the following synthesis process route:
the synthesis method of o-methyl benzoyl cyanide comprises the following steps:
adding o-methylbenzoyl chloride, potassium ferricyanide and a copper catalyst into a reactor, and carrying out heat preservation reaction in the presence or absence of a solvent. After the reaction is finished, washing and layering, and carrying out vacuum distillation on the organic phase to obtain the o-methyl benzoyl cyanide.
In a preferred embodiment, potassium ferricyanide is used as the cyanating agent, and the molar ratio of o-methylbenzoyl cyanide to potassium ferricyanide is 1: 0.16-0.3; preferably 1: 0.17-0.2; more preferably 1: 0.17-0.18.
In a preferred embodiment, the copper catalyst is selected from the group consisting of copper quinolinate, cuprous chloride, cuprous bromide, cuprous iodide, and the like; copper quinolinate is preferred.
In a preferred embodiment, the amount of copper catalyst is 1% to 10% of the o-methylbenzoyl chloride; preferably 1 to 5%; more preferably 1%.
In a preferred embodiment, in the presence or absence of a solvent, which may be selected from any one or more of the following: dichloroethane, toluene, xylene, N-dimethylformamide, etc.; dichloroethane, toluene and the like are preferred.
In a preferred embodiment, the reaction temperature is 0 to 150 ℃ and the reaction time is 1 to 10 hours; the reaction temperature is preferably 70 to 110 ℃ and the reaction time is preferably 3 to 5 hours.
On the basis of the prepared o-methylbenzoyl cyanide, the invention further provides a method for preparing trifloxystrobin. The method for preparing trifloxystrobin by using o-methylbenzoyl cyanide is well known to those skilled in the art, and for example, WO2013144924, US5221762, and noro (fine chemical intermediate, 2016,46(2),19-21) and the like report that o-methylbenzoic acid is used as a raw material, and the intermediate is obtained through acyl chlorination, cyanidation, esterification, oximation and bromination and then condensed with m-trifluoromethyl acetophenone oxime to obtain trifloxystrobin. And therefore need not be described in detail herein.
The invention has the advantages that:
compared with the synthesis method provided by the prior art, the synthesis method provided by the invention has the following advantages:
1) the method for synthesizing o-methylbenzoyl cyanide adopts potassium ferricyanide as a cyaniding reagent, and compared with the traditional virulent cyanide, the method has the advantages that the raw materials are cheap and easy to obtain, and are nontoxic and harmless, and the reaction is safer;
2) the method of the invention simultaneously adopts oxine-copper as the catalyst, has less dosage and cheap and easily obtained raw materials, and is beneficial to industrial production;
3) the method is simple, has mild reaction conditions, and is suitable for industrial scale-up production.
The technical solution of the present invention will be further described with reference to the following specific embodiments, but the following embodiments are not intended to limit the present invention, and all of the various application methods adopted according to the principles and technical means of the present invention belong to the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
Example 1
200ml of dichloroethane as a solvent, 50g (0.32mol) of o-methylbenzoyl chloride and 18.1g (0.054mol) of potassium ferricyanide are added into a 500ml reaction bottle, 0.5g of oxine-copper is added, the temperature is controlled to be 80-85 ℃, the reaction is kept for 4 hours, water is used for layering after the reaction is finished, and after organic phase is desolventized, reduced pressure distillation is carried out to obtain 43.3g of o-methylbenzoyl cyanide, the purity is 97.8 percent, and the yield is 91.3 percent.
1H NMR(400MHz,CDCl3)δ2.64(s,3H),7.36(d,J=7.6Hz,1H),7.48(t,J=7.6Hz,1H),7.63(td,J1=7.6,J2=1.2Hz,1H),8.25(d,J=7.6Hz,1H).
13C NMR(100MHz,CDCl3)δ22.0,113.3,126.8,131.4,132.8,135.0,135.6,142.8,168.5.
GC-MS(EI)M+145.
Example 2
200ml of toluene solvent, 50g (0.32mol) of o-methylbenzoyl chloride and 18.1g (0.054mol) of potassium ferricyanide are added into a 500ml reaction bottle, 0.5g of oxine-copper is added, the temperature is controlled to be 80-85 ℃, the reaction is kept for 3 hours, water is used for layering after the reaction is finished, and after organic phase is desolventized, reduced pressure distillation is carried out to obtain 43.1g of o-methylbenzoyl cyanide, the purity is 98 percent, and the yield is 91.1 percent.
Example 3
50g (0.32mol) of o-methylbenzoyl chloride and 18.1g (0.054mol) of potassium ferricyanide are added into a 500ml reaction bottle, 0.5g of oxine-copper is added, the temperature is controlled at 80-85 ℃, the reaction is kept for 5 hours, water is washed for layering after the reaction is finished, and the organic phase is directly distilled under reduced pressure to obtain 42.8g of o-methylbenzoyl cyanide with the purity of 98.1% and the yield of 90.5%.
Comparative example 1
Refer to the method reported in Chinese patent 20171077386: weighing 21.5g (0.051mol) of potassium ferrocyanide, adding 86g of water and 111.8g of toluene, adding 0.69g of tetrabutylammonium bromide serving as a phase transfer catalyst, dropwise adding 50g (0.32mol) of o-methylbenzoyl chloride at 20-25 ℃, slowly heating to 35-38 ℃ after dropwise adding, stirring for 2 hours, and finding out that no o-methylbenzoyl cyanide product is generated and almost the benzoyl chloride is hydrolyzed into benzoic acid as a byproduct after reaction tracking.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (10)
1. A method for preparing trifloxystrobin, comprising the steps of:
1) synthesizing o-methylbenzoyl cyanide by using o-methylbenzoyl chloride in the presence of potassium ferricyanide and a copper catalyst and in the presence or absence of a solvent;
and
2) synthesizing the o-methyl benzoyl cyanide obtained in the step 1) to obtain trifloxystrobin.
2. The process according to claim 1, wherein the molar ratio of o-methylbenzoyl chloride to potassium ferricyanide in step 1) is 1:0.16 to 0.3; preferably 1: 0.17-0.2; more preferably 1: 0.17-0.18.
3. The method of claim 1, wherein the copper catalyst in step 1) is selected from the group consisting of: oxine-copper, cuprous chloride, cuprous bromide, cuprous iodide, and the like; copper quinolinate is preferred.
4. The method according to claim 1, wherein the amount of the copper catalyst used in step 1) is 1% to 10% of o-methylbenzoyl chloride; preferably 1 to 5%; more preferably 1%.
5. The method according to claim 1, wherein the solvent used in step 1) is selected from any one or more of the following: dichloroethane, toluene, xylene, N-dimethylformamide, etc.; dichloroethane, toluene, etc. are preferable.
6. The method according to claim 1, wherein the reaction temperature in step 1) is 0 to 150 ℃ and the reaction time is 1 to 10 hours; the reaction temperature is preferably 70 to 110 ℃ and the reaction time is preferably 3 to 5 hours.
8. the method according to claim 7, wherein the molar ratio of o-methylbenzoyl chloride to potassium ferricyanide in step 1) is 1:0.16 to 0.3; preferably 1: 0.17-0.2; more preferably 1: 0.17-0.18.
9. The method of claim 7, wherein the copper catalyst in step 1) is selected from the group consisting of: oxine-copper, cuprous chloride, cuprous bromide, cuprous iodide, and the like; copper quinolinate is preferred.
10. The method according to claim 7, wherein the amount of the copper catalyst used in the step 1) is 1% to 10% of o-methylbenzoyl chloride; preferably 1 to 5%; more preferably 1%; and/or
The solvent in the step 1) is selected from any one or more of the following solvents: dichloroethane, toluene, xylene, N, N-dimethylformamide and the like; preferably dichloroethane, toluene, etc.; and/or
The reaction temperature of the step 1) is 0-150 ℃, and the reaction time is 1-10 hours; the reaction temperature is preferably 70 to 110 ℃ and the reaction time is preferably 3 to 5 hours.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111155127.7A CN114380713A (en) | 2021-09-29 | 2021-09-29 | Synthesis method of o-methyl benzoyl cyanide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111155127.7A CN114380713A (en) | 2021-09-29 | 2021-09-29 | Synthesis method of o-methyl benzoyl cyanide |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114380713A true CN114380713A (en) | 2022-04-22 |
Family
ID=81194831
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111155127.7A Pending CN114380713A (en) | 2021-09-29 | 2021-09-29 | Synthesis method of o-methyl benzoyl cyanide |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114380713A (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1903030A1 (en) * | 2006-09-09 | 2008-03-26 | Saltigo GmbH | Method for catalytic manufacture of aromatic or heteroaromatic nitriles |
CN102952038A (en) * | 2012-11-15 | 2013-03-06 | 大连九信生物化工科技有限公司 | Synthesis method for 2-methylbenzoyl cyanide |
CN103833660A (en) * | 2014-03-26 | 2014-06-04 | 成都医路康医学技术服务有限公司 | Preparation method of lamotrigine and intermediate thereof |
CN104098486A (en) * | 2014-06-19 | 2014-10-15 | 浙江大学 | Preparation method for 2-nitro-4-trifluoromethyl cyanobenzene |
CN107043336A (en) * | 2017-03-22 | 2017-08-15 | 京博农化科技股份有限公司 | One kind 2(2 methylphenoxies)The preparation method of methylene benzoyl cyanide |
CN113666841A (en) * | 2021-09-23 | 2021-11-19 | 抚顺顺能化工有限公司 | Preparation method of o-methyl benzoyl nitrile |
-
2021
- 2021-09-29 CN CN202111155127.7A patent/CN114380713A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1903030A1 (en) * | 2006-09-09 | 2008-03-26 | Saltigo GmbH | Method for catalytic manufacture of aromatic or heteroaromatic nitriles |
CN102952038A (en) * | 2012-11-15 | 2013-03-06 | 大连九信生物化工科技有限公司 | Synthesis method for 2-methylbenzoyl cyanide |
CN103833660A (en) * | 2014-03-26 | 2014-06-04 | 成都医路康医学技术服务有限公司 | Preparation method of lamotrigine and intermediate thereof |
CN104098486A (en) * | 2014-06-19 | 2014-10-15 | 浙江大学 | Preparation method for 2-nitro-4-trifluoromethyl cyanobenzene |
CN107043336A (en) * | 2017-03-22 | 2017-08-15 | 京博农化科技股份有限公司 | One kind 2(2 methylphenoxies)The preparation method of methylene benzoyl cyanide |
CN113666841A (en) * | 2021-09-23 | 2021-11-19 | 抚顺顺能化工有限公司 | Preparation method of o-methyl benzoyl nitrile |
Non-Patent Citations (2)
Title |
---|
HAO LU 等: "Palladium-CatalyzedOne-Pot Four-Component Synthesisof β-Cyano-α, β-unsaturated KetonesUsingCalcium Carbide as an AcetyleneSource and Potassium Hexacyanoferrate(II)as anEco-Friendly Cyanide Source", 《ADV. SYNTH. CATAL.》, no. 361, pages 4474 - 4482 * |
ZHENG LI 等: "AgI–PEG400–KI Catalyzed Environmentally Benign Synthesis of Aroyl Cyanides Using Potassium Hexacyanoferrate(II) as the Cyanating Agent", 《SYNLETT》, no. 15, pages 2495 - 2497 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113372288A (en) | Synthetic method of topramezone pesticide intermediate | |
CN115772069A (en) | Synthesis method of vinyl methyl ether | |
CN105085420B (en) | A kind of method that compound phenazine is catalyzed and synthesized under the microwave radiation in aqueous phase | |
CN108530301B (en) | Synthetic method of 2,4, 6-trifluorobenzylamine | |
CN107118073A (en) | The method that two alcohol catalysis prepare dichloro alkyl halide | |
CN114380713A (en) | Synthesis method of o-methyl benzoyl cyanide | |
CN115417841B (en) | Synthesis method of cocoanut aldehyde | |
CN110950778A (en) | Process and catalyst system for preparing aromatic malononitrile | |
CN106986900B (en) | A kind of preparation method of N- alkyl glucose imines | |
CN113318730B (en) | δ-MnO2Catalyst, preparation method and application thereof | |
CN115417797A (en) | Preparation method of bifenazate | |
CN112194559B (en) | Synthesis method of chiral and achiral 2,2' -dihalogenated biaryl compound | |
CN111187146B (en) | Process for producing 2-methyl-3-buten-2-ol | |
CN114315575A (en) | Preparation method and application of photoinitiator intermediate | |
CN113582918A (en) | Method for preparing 2,3-dichloropyridine by chlorination | |
CN112010831A (en) | Green and efficient phenyl ether ketal bromination synthesis method | |
CN111153794A (en) | Method for synthesizing ethyl palmitate by using dodecyl trimethyl ammonium chloride-based eutectic solvent catalyst | |
CN111233654B (en) | Simple method for synthesizing tiglic acid | |
CN115073364B (en) | Preparation method of 6-nitropyridin-3-ol | |
CN107556188A (en) | A kind of method of phase-transfer Wittig reaction benzyl ester | |
CN112358442B (en) | Preparation method of 2-fluoro-5-formyl chloropyridine | |
CN109134312B (en) | Preparation method of 2-phenyl acrylonitrile | |
CN114478315B (en) | Method for catalytic reduction of irosartan biphenyl waste residues by using halogen-modified Pd/C catalyst | |
CN115368217B (en) | Synthesis method of 3,4, 5-trimethoxytoluene | |
CA2502360C (en) | Process for producing acetylene compound |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |