CN110835308A - Preparation method of halogenated o-aminobenzoic acid - Google Patents
Preparation method of halogenated o-aminobenzoic acid Download PDFInfo
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- CN110835308A CN110835308A CN201810926160.7A CN201810926160A CN110835308A CN 110835308 A CN110835308 A CN 110835308A CN 201810926160 A CN201810926160 A CN 201810926160A CN 110835308 A CN110835308 A CN 110835308A
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- anthranilic acid
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- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical class NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 230000002140 halogenating effect Effects 0.000 claims abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 12
- 238000010992 reflux Methods 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052794 bromium Inorganic materials 0.000 claims description 14
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- -1 halo C1-C6Alkylthio radical Chemical class 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- LQZMLBORDGWNPD-UHFFFAOYSA-N N-iodosuccinimide Chemical compound IN1C(=O)CCC1=O LQZMLBORDGWNPD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- VRLDVERQJMEPIF-UHFFFAOYSA-N dbdmh Chemical compound CC1(C)N(Br)C(=O)N(Br)C1=O VRLDVERQJMEPIF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims description 3
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 2
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 2
- SZCPTRGBOVXVCA-UHFFFAOYSA-N 2-amino-6-chlorobenzoic acid Chemical compound NC1=CC=CC(Cl)=C1C(O)=O SZCPTRGBOVXVCA-UHFFFAOYSA-N 0.000 description 1
- RWSFZKWMVWPDGZ-UHFFFAOYSA-N 2-amino-6-fluorobenzoic acid Chemical compound NC1=CC=CC(F)=C1C(O)=O RWSFZKWMVWPDGZ-UHFFFAOYSA-N 0.000 description 1
- DYZDIWNRWSNVPT-UHFFFAOYSA-N 2-amino-6-methoxybenzoic acid Chemical compound COC1=CC=CC(N)=C1C(O)=O DYZDIWNRWSNVPT-UHFFFAOYSA-N 0.000 description 1
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
Landscapes
- 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 halogenated anthranilic acid compounds, which comprises the steps of adding proper reagents and halogenating reagents into a general formula (II), reacting for 0.1-24 hours at the temperature of-20 ℃ to the reflux temperature range, and preparing halogenated anthranilic acid salts shown in the general formula (I). The definitions of the reaction formula and each substituent group in the formula are shown in the specification.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of a halogenated anthranilic acid compound.
Background
Halogenated anthranilic acid compounds are important intermediates in organic synthesis, especially in the fields of medicine and pesticides. WO 2007/090752A 1 discloses a process for the preparation of halogenated anthranilic acids, but the reaction times are long, the yields are low and there is still much room for improvement. Technical research and development personnel are dedicated to continuously research and develop a more updated, simpler and high-yield preparation method so as to reduce the production cost and improve the production benefit.
Disclosure of Invention
In order to meet the requirement of industrial production, the invention provides a novel method for preparing the halogenated anthranilic acid compound, which is simple, high in yield and low in cost.
The technical scheme of the invention is as follows:
a process for the preparation of a halogenated anthranilic acid of the general formula (I):
in the formula: r1Selected from halogen, CN, NO2、NH2、CHO、C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C1-C6Alkylthio, halo C1-C6Alkylthio radical, C3-C8Cycloalkyl, halo C3-C8Cycloalkyl radical, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C2-C6Alkynyl, halo C2-C6An alkynyl group; x is selected from halogen;
the method is characterized by comprising the following reaction steps:
adding a proper solvent and a halogenating reagent into anthranilic acid shown in a general formula (II), reacting for 0.1-24 hours at the temperature of-20 ℃ to the reflux temperature range, and preparing halogenated anthranilic acid shown in a general formula (I); the halogenating reagent is selected from fluorine gas, chlorine gas, sulfonyl chloride, N-chlorosuccinimide, 1, 3-dichloro-5, 5-dimethylhydantoin, bromine simple substance, N-bromosuccinimide, 1, 3-dibromo-5, 5-dimethylhydantoin, iodine simple substance and N-iodosuccinimide, and the feeding molar ratio of the anthranilic acid to the halogenating reagent is 1: 1-20; the solvent is selected from dichloromethane, dichloroethane, chloroform, carbon tetrachloride, hexane, acetonitrile, propionitrile, dioxane, toluene, formamide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, formic acid and acetic acid, and the dosage of the solvent is 1-20 times of the weight of the anthranilic acid shown in the general formula (II).
The preferred technical scheme of the invention is as follows:
the halogenating reagent is selected from chlorine, sulfonyl chloride, N-chlorosuccinimide, 1, 3-dichloro-5, 5-dimethylhydantoin, bromine simple substance, N-bromosuccinimide, 1, 3-dibromo-5, 5-dimethylhydantoin, iodine simple substance and N-iodosuccinimide, and the charging molar ratio of the anthranilic acid to the halogenating reagent is 1: 2-10; the solvent is selected from dichloromethane, dichloroethane, chloroform, carbon tetrachloride, hexane, acetonitrile, dioxane, toluene, formamide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, formic acid and acetic acid, and the dosage of the solvent is 1-10 times of the weight of the anthranilic acid shown in the general formula (II); the reaction temperature is in the range of 0 ℃ to reflux temperature; the reaction time is 0.1-12 hours.
The further preferable technical scheme of the invention is as follows:
the halogenating agent is selected from chlorine, sulfonyl chloride, N-chlorosuccinimide, bromine simple substance and N-bromosuccinimide; the solvent is selected from dichloromethane, dichloroethane, chloroform, carbon tetrachloride, acetonitrile, dioxane, toluene, formamide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, formic acid and acetic acid; r1Selected from F, Cl, Br, I, CN, NO2、NH2、CHO、CH3、OCH3、SCH3(ii) a X is selected from Cl and Br.
The halogenated anthranilic acid compounds represented by part of general formula (I) produced by the process of the present invention are shown in Table 1, but the process of the present invention is not limited to the production of only the compounds shown in Table 1.
TABLE 1
Detailed Description
The following specific examples are intended to further illustrate the invention, but the invention is by no means limited to these examples.
EXAMPLE 1 preparation of Compound 1-1
To a 2000 ml reaction flask were added 2-amino-6-fluorobenzoic acid (1.50mol,232.65g) and 814 ml of N, N-dimethylformamide, and the temperature was raised to 90 ℃. N-chlorosuccinimide (3.12mol, 416.52g) was then added portionwise, the temperature being controlled not to exceed 100 ℃. After the addition is finished, the reaction is carried out at 100 ℃, TLC tracking detection is carried out, after the reaction is finished, the reaction solution is cooled to room temperature, then the reaction solution is poured into 2849mL of water, the product is separated out, and the product is filtered, washed by water to obtain 319.72g of product with the yield of 95%. MS: 224.1.
EXAMPLE 2 preparation of Compounds 1-2
2-amino-6-chlorobenzoic acid (0.80mol,137.28g) and 480 ml of N, N-dimethylformamide were added to a 1000 ml reaction flask and the temperature was raised to 80 ℃. N-chlorosuccinimide (1.66mol, 221.61g) was then added portionwise, the temperature being controlled not to exceed 90 ℃. After the addition is finished, the reaction is carried out at 90 ℃, TLC tracking detection is carried out, after the reaction is finished, the reaction solution is cooled to room temperature, then the reaction solution is poured into 1680mL of water, the product is separated out, and the product is filtered, washed by water to obtain 181.58g of product with the yield of 94%. MS: 240.0.
EXAMPLE 3 preparation of Compounds 1-5
To a 1000 ml reaction flask were added 2-amino-6-methoxybenzoic acid (1.0mol,167.20g), 585 ml of N, N-dimethylformamide, followed by the addition of N-chlorosuccinimide (2.08mol, 277.68g) in portions, with the temperature controlled not to exceed 60 ℃. After the addition is finished, the reaction is carried out at 60 ℃, TLC tracking detection is carried out, after the reaction is finished, the reaction solution is cooled to room temperature, then the reaction solution is poured into 2048mL of water, the product is separated out, and the product is filtered, washed by water to obtain 208.16g of product with 88% yield. MS: 236.1.
Claims (7)
1. a preparation method of halogenated anthranilic acid compounds comprises the following steps:
in the formula: r1Selected from halogen, CN, NO2、NH2、CHO、C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C1-C6Alkylthio, halo C1-C6Alkylthio radical, C3-C8Cycloalkyl, halo C3-C8Cycloalkyl radical, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C2-C6Alkynyl, halo C2-C6An alkynyl group; x is selected from halogen;
the method is characterized by comprising the following reaction steps:
adding a proper solvent and a halogenating reagent into anthranilic acid shown in a general formula (II), reacting for 0.1-24 hours at the temperature of-20 ℃ to the reflux temperature range, and preparing halogenated anthranilic acid shown in a general formula (I); the halogenating reagent is selected from fluorine gas, chlorine gas, sulfonyl chloride, N-chlorosuccinimide, 1, 3-dichloro-5, 5-dimethylhydantoin, bromine simple substance, N-bromosuccinimide, 1, 3-dibromo-5, 5-dimethylhydantoin, iodine simple substance and N-iodosuccinimide, and the feeding molar ratio of the anthranilic acid to the halogenating reagent is 1: 1-20; the solvent is selected from dichloromethane, dichloroethane, chloroform, carbon tetrachloride, hexane, acetonitrile, propionitrile, dioxane, toluene, formamide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, formic acid and acetic acid, and the dosage of the solvent is 1-20 times of the weight of the anthranilic acid shown in the general formula (II).
2. The method of claim 1, wherein: the halogenating reagent is selected from chlorine, sulfonyl chloride, N-chlorosuccinimide, 1, 3-dichloro-5, 5-dimethylhydantoin, bromine simple substance, N-bromosuccinimide, 1, 3-dibromo-5, 5-dimethylhydantoin, iodine simple substance and N-iodosuccinimide, and the charging molar ratio of the anthranilic acid to the halogenating reagent is 1: 2-10; the solvent is selected from dichloromethane, dichloroethane, chloroform, carbon tetrachloride, hexane, acetonitrile, dioxane, toluene, formamide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, formic acid and acetic acid, and the dosage of the solvent is 1-10 times of the weight of the anthranilic acid shown in the general formula (II); the reaction temperature is in the range of 0 ℃ to reflux temperature; the reaction time is 0.1-12 hours.
3. The method of claim 2, wherein: the halogenating agent is selected from chlorine, sulfonyl chloride, N-chlorosuccinimide, bromine simple substance and N-bromosuccinimide; the solvent is selected from dichloromethane, dichloroethane, chloroform, carbon tetrachloride, acetonitrile, dioxane, toluene, formamide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, formic acid and acetic acid.
4. The production method according to claim 3, characterized in that: the halogenating agent is selected from chlorine, sulfonyl chloride and N-chlorosuccinimide; the solvent is selected from dichloroethane, chloroform, carbon tetrachloride, acetonitrile, dioxane, formamide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
5. The method of claim 1, wherein: r1Selected from F, Cl, Br, I, CN, NO2、NH2、CHO、C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C1-C6Alkylthio, halo C1-C6Alkylthio radical, C3-C8Cycloalkyl, halo C3-C8A cycloalkyl group; x is selected from F, Cl, Br and I.
6. The method of claim 5, wherein: r1Selected from F, Cl, Br, I, CN, NO2、NH2、CHO、CH3、CF3、OCH3、OCF3、SCH3、SCF3(ii) a X is selected from F, Cl and Br.
7. The method of claim 6, wherein: r1Selected from F, Cl, Br, CN, OCH3、SCH3(ii) a X is selected from Cl and Br.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115057768A (en) * | 2022-08-19 | 2022-09-16 | 济南国鼎医药科技有限公司 | Synthetic method of 3, 5-dichloro-4-methoxybenzoic acid |
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Application publication date: 20200225 |