CN116874411B - Synthesis method of 1-bromocarbazole - Google Patents
Synthesis method of 1-bromocarbazole Download PDFInfo
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- VCDOOGZTWDOHEB-UHFFFAOYSA-N 1-bromo-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C(Br)=CC=C2 VCDOOGZTWDOHEB-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000001308 synthesis method Methods 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 121
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 50
- SSIZLKDLDKIHEV-UHFFFAOYSA-N 2,6-dibromophenol Chemical compound OC1=C(Br)C=CC=C1Br SSIZLKDLDKIHEV-UHFFFAOYSA-N 0.000 claims abstract description 30
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 claims abstract description 28
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006798 ring closing metathesis reaction Methods 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 56
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 33
- 239000012074 organic phase Substances 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 239000002274 desiccant Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000000741 silica gel Substances 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 8
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 7
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 7
- 235000011009 potassium phosphates Nutrition 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- AIVAIUMRPBQMLT-UHFFFAOYSA-N 3-acetylpentane-2,4-dione;nickel Chemical compound [Ni].CC(=O)C(C(C)=O)C(C)=O AIVAIUMRPBQMLT-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 238000010009 beating Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 150000003738 xylenes Chemical class 0.000 claims description 4
- SFUIGUOONHIVLG-UHFFFAOYSA-N (2-nitrophenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1[N+]([O-])=O SFUIGUOONHIVLG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 8
- 125000003277 amino group Chemical group 0.000 abstract description 6
- 230000008878 coupling Effects 0.000 abstract description 5
- 238000010168 coupling process Methods 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 5
- 210000001503 joint Anatomy 0.000 abstract description 4
- 229940124530 sulfonamide Drugs 0.000 abstract description 4
- -1 sulfonamide compound Chemical class 0.000 abstract description 4
- 239000007858 starting material Substances 0.000 abstract 1
- 230000008569 process Effects 0.000 description 16
- 239000002994 raw material Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- PHCYUJRYSFMJMG-UHFFFAOYSA-N (2-bromophenyl)hydrazine;hydron;chloride Chemical compound Cl.NNC1=CC=CC=C1Br PHCYUJRYSFMJMG-UHFFFAOYSA-N 0.000 description 1
- RFWWDDNZOQXTBD-UHFFFAOYSA-N 1-(3-bromophenyl)-2-nitrobenzene Chemical group [O-][N+](=O)C1=CC=CC=C1C1=CC=CC(Br)=C1 RFWWDDNZOQXTBD-UHFFFAOYSA-N 0.000 description 1
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 1
- UBPDKIDWEADHPP-UHFFFAOYSA-N 2-iodoaniline Chemical compound NC1=CC=CC=C1I UBPDKIDWEADHPP-UHFFFAOYSA-N 0.000 description 1
- OYFFSPILVQLRQA-UHFFFAOYSA-N 3,6-ditert-butyl-9h-carbazole Chemical compound C1=C(C(C)(C)C)C=C2C3=CC(C(C)(C)C)=CC=C3NC2=C1 OYFFSPILVQLRQA-UHFFFAOYSA-N 0.000 description 1
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 description 1
- 238000005600 Cadogan reaction Methods 0.000 description 1
- 229930195212 Fischerindole Natural products 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of 1-bromocarbazole, which is prepared by taking o-nitrobenzoic acid and 2, 6-dibromophenol which are easily purchased in the market and are produced in mass as starting materials, obtaining a compound a1 after nickel-catalyzed C-C coupling butt joint, performing nitroreduction on the compound a1 by iron powder to obtain a compound a2, preparing an amino group of the compound a2 into a sulfonamide compound a3 by using trifluoromethanesulfonic anhydride, and finally performing ring closure preparation on the compound a3 under the catalysis of p-toluenesulfonic acid to obtain a target product 1-bromocarbazole.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a synthesis method of 1-bromocarbazole.
Background
Carbazole and various substituted intermediates of carbazole are important intermediates commonly used in the field of fine chemical industry, in particular in the field of OLED. In terms of the prior art, the 2-position, 3-position and 4-position bromine substitutes of carbazole are all prepared in a quantitative production manner in the current market, and the 1-position bromine substitutes are not prepared in an industrialized mass manner. The 1-bromocarbazole commercially available in the current market comes from small-batch production in a laboratory and is high in price, so that the use and quantitative popularization of a plurality of OLED materials using the 1-bromocarbazole as an intermediate are limited.
The current mainstream laboratory synthesis method of 1-bromocarbazole is to synthesize indole by using o-bromophenylhydrazine hydrochloride and cyclohexanone through a Fischer indole cyclization method and then prepare 1-bromocarbazole through DDQ oxidative dehydrogenation. The method has the advantages that the raw materials are easy to obtain, but the DDQ dehydrogenation conversion rate in the second step is very low, and the DDQ byproducts are very difficult to separate from the system, so that the production popularization is greatly limited, the environment pollution caused by the DDQ treatment process is serious, and the industrialized application of the method is limited. The other method is that 2-nitro-3' -bromobiphenyl is prepared through Cadogan reaction, but the method mainly generates isomer 3-bromocarbazole, but the target compound 1-bromocarbazole is less, the product separation is difficult, the method is not suitable for mass production and preparation, and the method is rarely used. Other methods also report that the 3, 6-di-tert-butyl carbazole is brominated to the 1 position and then is removed by Lewis acid to remove the di-tert-butyl, but the di-substitution is not easy to control in the bromination process, the reaction operation stability is not high when the Lewis acid is used for removing the tert-butyl, and the method is not practically popularized; another patent with publication number CN107325037a discloses a process for preparing monobromocarbazole, which is prepared by palladium-catalyzed coupling of o-iodoaniline and o-bromoiodobenzene, and then palladium-catalyzed ring closure. In the process, a large amount of palladium is used, the cost reduction is difficult to realize in large-scale production, and the actual application and popularization are not achieved.
In summary, the existing method for synthesizing 1-bromocarbazole is difficult to realize industrialized mass production, has difficult product purification, low yield, heavy pollution in the reaction treatment process, uses a large amount of noble metal catalysts, and has difficult mass preparation cost reduction, so that the research on a novel 1-bromocarbazole synthesis method has a market prospect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a synthesis method of 1-bromocarbazole.
In order to solve the technical problems, the technical scheme of the invention is as follows: the synthesis method of the 1-bromocarbazole comprises the following four steps:
Step 1: the o-nitrobenzoic acid and the 2, 6-dibromophenol are coupled and butted through the C-C catalyst by nickel to obtain a compound a1, the equivalent ratio of the o-nitrobenzoic acid to the 2, 6-dibromophenol is 1:1-1.1, and the structural formula of the compound a1 is as follows
Step 2: performing nitroreduction on the compound a1 by using iron powder to obtain a compound a2, wherein the equivalent ratio of the compound a1 to the iron powder is 1:7-8, and the structural formula of the compound a2 is as follows
Step 3: the compound a2 and the trifluoromethanesulfonic anhydride react to prepare a compound a3, the equivalent ratio of the compound a2 to the trifluoromethanesulfonic anhydride is 1:1-1.2, and the structural formula of the compound a3 is as follows
Step 4: under the catalysis of p-toluenesulfonic acid, the compound a3 is subjected to ring closure to prepare the target product 1-bromocarbazole, and the equivalent ratio of the compound a3 to the p-toluenesulfonic acid is 1:1.8-2.2.
Preferably, the step 1 specifically includes: adding o-nitrobenzoic acid and 2, 6-dibromophenol into a reaction bottle, adding dioxane and water, stirring, adding potassium phosphate, replacing a system with argon, adding nickel diacetylacetone, DPPF and CuCl, replacing with argon, heating to a reflux temperature of 90-92 ℃ for heat preservation reaction for 6-8 hours until the o-nitrobenzoic acid is reacted completely, and obtaining a compound a1, wherein the dosage ratio of the o-nitrobenzoic acid to the dioxane and the water is 0.5mol:800mL:200mL of o-nitrobenzeneboronic acid with respect to the equivalent ratio of potassium phosphate, nickel diacetylacetonate, DPPF and CuCl is 1:1.5:0.0025:0.005:0.05.
Preferably, the post-treatment of the compound a1 is: after the reaction of the reaction liquid is finished, standing and separating the reaction liquid, concentrating the upper organic phase under reduced pressure, adding toluene for dissolving, washing the organic phase with water to remove residual salts, adding a drying agent for drying, filtering the toluene organic phase to remove the drying agent, concentrating the toluene under reduced pressure, and crystallizing with ethanol to obtain a yellowish solid compound a1.
Preferably, the step 2 specifically includes: adding the compound a1 into a methanol solution, adding ammonium chloride, heating to 55-62 ℃, then adding Fe powder in batches for a small amount for many times after adding concentrated hydrochloric acid dropwise, and obtaining a compound a2, wherein the dosage ratio of the compound a1 to the methanol is 0.4mol:840mL of compound a1 with an equivalent ratio of 1 to ammonium chloride and concentrated hydrochloric acid: 5:0.05.
Preferably, the post-treatment of the compound a2 is: cooling to 20-30 ℃ after the reaction is finished, passing through a diatomite funnel, collecting filtrate, concentrating the filtrate under reduced pressure to dryness, adding ethyl acetate to dissolve, washing an organic phase with water to wash and remove residual inorganic salt, and then removing residual small amount of ferric salt from the ethyl acetate organic phase through a silica gel funnel, concentrating the ethyl acetate phase under reduced pressure to dryness; then petroleum ether is used for beating and dispersing to obtain the white-like solid powder compound a2.
Preferably, the step 3 specifically includes: adding a compound a2 into a three-mouth bottle under the protection of argon, adding dichloromethane, stirring for dissolution, adding pyridine, cooling the system to between 10 ℃ below zero and 0 ℃, slowly dripping trifluoromethanesulfonic anhydride into the dichloromethane system under stirring, controlling the reaction temperature to between 10 ℃ below zero and 0 ℃, and keeping the temperature for reaction for 1h to 2h until the compound a2 is completely reacted after the dripping is finished to obtain a compound a3; the dosage ratio of compound a2 to dichloromethane was 0.3mol:500mL, equivalent ratio of compound a2 to pyridine of 1:1.2.
Preferably, the post-treatment of the compound a3 is: after completion of the reaction, the reaction mixture was added to water, separated, and the dichloromethane phase was washed with water to neutrality, and then concentrated under reduced pressure to dryness to obtain the light gray solid compound a3.
Preferably, the step 4 specifically includes: adding a compound a3 into a dimethylbenzene solution, adding p-toluenesulfonic acid, heating the system to reflux after stirring, and reacting at a temperature for 15-20 h until the compound a3 is reacted thoroughly to obtain 1-bromocarbazole, wherein the dosage ratio of the compound a3 to the dimethylbenzene solution is 0.25mol:400mL.
Preferably, the post-treatment of the 1-bromocarbazole is as follows: cooling to 20-30 ℃ after the reaction is finished, adding water into the system, separating liquid after dissolving the p-toluenesulfonic acid, washing the xylenes organic phase with water for 2-3 times successively to enable the p-toluenesulfonic acid to be washed and removed fully, adding anhydrous sodium sulfate for drying after washing the organic phase with water, removing the large polar impurities from the dried organic phase through a silica gel column, concentrating the column liquid under reduced pressure to obtain a thick matter crude product, and recrystallizing the crude product with n-heptane to obtain yellowish to white solid powder 1-bromocarbazole.
Compared with the prior art, the invention has the advantages that:
(1) The invention discloses a synthesis method of 1-bromocarbazole, which is prepared by taking o-nitrobenzoic acid and 2, 6-dibromophenol which are reaction raw materials which are easy to purchase in the market and are produced in quantity as starting raw materials, obtaining a compound a1 after nickel-catalyzed C-C coupling butt joint, carrying out nitroreduction on the compound a1 by iron powder to obtain a compound a2, preparing an amino group of the compound a2 into a sulfonamide compound a3 by using trifluoromethanesulfonic anhydride, and finally carrying out ring closure preparation on the compound a3 under the catalysis of p-toluenesulfonic acid to obtain a target product 1-bromocarbazole, wherein the pollution in the reaction treatment process is small, the large-scale preparation cost is low, and the industrialized mass amplification production can be realized;
(2) The invention discloses a brand new synthesis method of 1-bromocarbazole, which comprises the steps of carrying out intramolecular dehydration on 2-trifluoromethanesulfonamide-2 '-hydroxy-3' -bromo-biphenyl through p-toluenesulfonic acid to obtain 1-bromocarbazole, wherein isomers are not easy to generate in the reaction process, the purification is easy, and the yield is high;
(3) The synthesis process of the invention avoids using a great deal of noble metal catalysts such as palladium, effectively reduces the cost and improves the comprehensive benefit; the synthetic process of the invention avoids the use of the oxidant DDQ with great pollution, reduces the pollution of byproducts to the environment and has better product quality;
(4) The invention has the advantages of simple post-treatment process of each step, high yield and industrial production potential.
Drawings
FIG. 1 shows a nuclear magnetic spectrum of the 1-bromocarbazole prepared by the invention.
Detailed Description
The invention will now be described with reference to the following examples, which are given by way of illustration of the invention, but are not intended to limit the scope of the invention, using conventional commercial products as raw materials, solvents and catalysts.
The invention discloses a synthesis method of 1-bromocarbazole, which comprises the following four steps:
Step 1: the o-nitrobenzoic acid and the 2, 6-dibromophenol are coupled and butted through the C-C catalyst by nickel to obtain a compound a1, the equivalent ratio of the o-nitrobenzoic acid to the 2, 6-dibromophenol is 1:1-1.1, and the structural formula of the compound a1 is as follows
Step 2: performing nitroreduction on the compound a1 by using iron powder to obtain a compound a2, wherein the equivalent ratio of the compound a1 to the iron powder is 1:7-8, and the structural formula of the compound a2 is as follows
Step 3: the compound a2 and the trifluoromethanesulfonic anhydride react to prepare a compound a3, the equivalent ratio of the compound a2 to the trifluoromethanesulfonic anhydride is 1:1-1.2, and the structural formula of the compound a3 is as follows
Step 4: under the catalysis of p-toluenesulfonic acid, the compound a3 is subjected to ring closure to prepare the target product 1-bromocarbazole, and the equivalent ratio of the compound a3 to the p-toluenesulfonic acid is 1:1.8-2.2.
Preferably, the step 1 specifically includes: adding o-nitrobenzoic acid and 2, 6-dibromophenol into a reaction bottle, adding dioxane and water, stirring, adding potassium phosphate, replacing a system with argon, adding nickel diacetylacetone, DPPF and CuCl, replacing with argon, heating to a reflux temperature of 90-92 ℃ for heat preservation reaction for 6-8 hours until the o-nitrobenzoic acid is reacted completely, and obtaining a compound a1, wherein the dosage ratio of the o-nitrobenzoic acid to the dioxane and the water is 0.5mol:800mL:200mL of o-nitrobenzeneboronic acid with respect to the equivalent ratio of potassium phosphate, nickel diacetylacetonate, DPPF and CuCl is 1:1.5:0.0025:0.005:0.05.
Preferably, the post-treatment of the compound a1 is: after the reaction of the reaction liquid is finished, standing and separating the reaction liquid, concentrating the upper organic phase under reduced pressure, adding toluene for dissolving, washing the organic phase with water to remove residual salts, adding a drying agent for drying, filtering the toluene organic phase to remove the drying agent, concentrating the toluene under reduced pressure, and crystallizing with ethanol to obtain a yellowish solid compound a1.
Preferably, the step 2 specifically includes: adding the compound a1 into a methanol solution, adding ammonium chloride, heating to 55-62 ℃, then adding Fe powder in batches for a small amount for many times after adding concentrated hydrochloric acid dropwise, and obtaining a compound a2, wherein the dosage ratio of the compound a1 to the methanol is 0.4mol:840mL of compound a1 with an equivalent ratio of 1 to ammonium chloride and concentrated hydrochloric acid: 5:0.05.
Preferably, the post-treatment of the compound a2 is: cooling to 20-30 ℃ after the reaction is finished, passing through a diatomite funnel, collecting filtrate, concentrating the filtrate under reduced pressure to dryness, adding ethyl acetate to dissolve, washing an organic phase with water to wash and remove residual inorganic salt, and then removing residual small amount of ferric salt from the ethyl acetate organic phase through a silica gel funnel, concentrating the ethyl acetate phase under reduced pressure to dryness; then petroleum ether is used for beating and dispersing to obtain the white-like solid powder compound a2.
Preferably, the step 3 specifically includes: adding a compound a2 into a three-mouth bottle under the protection of argon, adding dichloromethane, stirring for dissolution, adding pyridine, cooling the system to between 10 ℃ below zero and 0 ℃, slowly dripping trifluoromethanesulfonic anhydride into the dichloromethane system under stirring, controlling the reaction temperature to between 10 ℃ below zero and 0 ℃, and keeping the temperature for reaction for 1h to 2h until the compound a2 is completely reacted after the dripping is finished to obtain a compound a3; the dosage ratio of compound a2 to dichloromethane was 0.3mol:500mL, equivalent ratio of compound a2 to pyridine of 1:1.2.
Preferably, the post-treatment of the compound a3 is: after completion of the reaction, the reaction mixture was added to water, separated, and the dichloromethane phase was washed with water to neutrality, and then concentrated under reduced pressure to dryness to obtain the light gray solid compound a3.
Preferably, the step 4 specifically includes: adding a compound a3 into a dimethylbenzene solution, adding p-toluenesulfonic acid, heating the system to reflux after stirring, and reacting at a temperature for 15-20 h until the compound a3 is reacted thoroughly to obtain 1-bromocarbazole, wherein the dosage ratio of the compound a3 to the dimethylbenzene solution is 0.25mol:400mL.
Preferably, the post-treatment of the 1-bromocarbazole is as follows: cooling to 20-30 ℃ after the reaction is finished, adding water into the system, separating liquid after dissolving the p-toluenesulfonic acid, washing the xylenes organic phase with water for 2-3 times successively to enable the p-toluenesulfonic acid to be washed and removed fully, adding anhydrous sodium sulfate for drying after washing the organic phase with water, removing the large polar impurities from the dried organic phase through a silica gel column, concentrating the column liquid under reduced pressure to obtain a thick matter crude product, and recrystallizing the crude product with n-heptane to obtain yellowish to white solid powder 1-bromocarbazole.
Example 1
Step 1 synthesis of compound a 1: 83.46g (1 eq) of o-nitrobenzoic acid and 132.24g (1.05 eq) of 2, 6-dibromophenol are added into a reaction bottle, 800mL of dioxane, 200mL of water are added, and 159g (1.5 eq) of potassium phosphate is added after stirring is started; after the system is replaced by argon, 0.32g (0.0025 eq) of nickel diacetylacetone, 1.38g (0.005 eq) of DPPF, 2.47g (0.05 eq) of CuCl and the argon are used for replacing, the temperature is raised to reflux at 90-92 ℃ for heat preservation reaction for 6-8 h until the o-nitrobenzoic acid is reacted completely. After the reaction of the reaction liquid is finished, standing for liquid separation, concentrating the upper organic phase under reduced pressure, adding toluene for dissolving, washing the organic phase with water to remove residual salts, and then adding a drying agent for drying. The toluene organic phase was filtered to remove the drying agent, concentrated under reduced pressure to dry toluene, and crystallized with ethanol to give 120.5g of a yellowish solid with a purity of 98.4% and a yield of 82.0%. LC-MS detection molecular weight: 292.91.
Step 2, synthesizing a compound a 2: 120.5g of compound a1 was added to 840mL of methanol solution, 109.6g (5 eq) of ammonium chloride was added thereto, the temperature was raised to 55℃to 62℃and then 2.0g (0.05 eq) of concentrated hydrochloric acid was added dropwise thereto, followed by starting to add 160.2g (7 eq) of Fe powder in small portions a plurality of times until the reaction of compound a1 was completed. Cooling to 20-30 ℃ after the reaction is completed, passing through a diatomite funnel, and collecting filtrate. The filtrate was concentrated to dryness under reduced pressure, dissolved in ethyl acetate and the organic phase was washed with water to remove the residual salts. Then the ethyl acetate organic phase is concentrated to dryness under reduced pressure after a small amount of residual ferric salt is removed by a silica gel funnel; then, petroleum ether was used for beating and dispersion to obtain 79.0g of white solid powder with purity of 99.2% and yield of 73.1%. LC-MS detection molecular weight: 262.90.
Step 3, synthesizing a compound a 3: under the protection of argon, 79.0g (1 eq) of compound a2 solid is added into a 1L three-mouth bottle, 500mL of dichloromethane is added, stirring is carried out for dissolution, 28.4g (1.2 eq) of pyridine is added, and then the system is cooled to between-10 ℃ and 0 ℃. 88.8g (1.05 eq) of trifluoromethanesulfonic anhydride is slowly dripped into the dichloromethane system under stirring, and the reaction temperature is controlled between-10 ℃ and 0 ℃. After the dripping is finished, the reaction is carried out for 1 to 2 hours at a constant temperature until the compound a2 is completely reacted. After the completion of the reaction, the reaction mixture was added to water, separated, and the dichloromethane phase was washed with water to neutrality, and then concentrated under reduced pressure to obtain a3 as a pale gray solid, which weighed 114.8g and had a purity of 95.3% and a yield of 97.0%. LC-MS detection molecular weight: 396.89.
Step 4, synthesizing 1-bromocarbazole: then, 399.0g (1 eq) of compound a is added into 400mL of xylene solution, 86.1g (2 eq) of p-toluenesulfonic acid is added, stirring is started, the system is heated to reflux (135 ℃ to 140 ℃) and the reaction is carried out for 15h to 20h under heat preservation, and the reaction of the compound a3 is complete. Cooling to 20-30 ℃ after the reaction is finished, adding water into the system, separating liquid after dissolving the p-toluenesulfonic acid, and washing the xylenes organic phase by water for 2-3 times to fully remove the p-toluenesulfonic acid. And (3) after the organic phase is washed, adding anhydrous sodium sulfate for drying, removing the large-polarity impurities from the dried organic phase through a silica gel column, and concentrating the column passing liquid under reduced pressure for drying to obtain a thick crude product. The crude product was recrystallized from n-heptane to give yellowish to off-white solid powder weighing 48.0g with a purity of 98.7% and a yield of 78.1%. LC-MS detection molecular weight: 244.95.
As shown in FIG. 1, the 1-bromocarbazole nuclear magnetic spectrum obtained in this example ,NMR(400MHz,)δ11.39(s),8.10(d,J＝7.7Hz),7.56(ddd,J＝8.2,2.2,0.8Hz),7.44–7.38(m),7.17(dd,J＝11.4,4.3Hz),7.07(t,J＝7.7Hz).
Referring to example 1, comparative experiments were conducted on the molar equivalent of the key materials involved in the reaction steps 1 to 4, keeping the reaction conditions such as the order of addition, the reaction temperature, the reaction time period, the auxiliary material ratio, etc., and experimental data obtained by data acquisition and verification are shown in table 1 below. As can be seen from Table 1 below, the molar equivalent of the key material has an effect on the reaction results, but the effect fluctuates less.
TABLE 1
The design reaction process of the invention is as follows:
The invention discloses a synthesis method of 1-bromocarbazole, which is prepared by taking o-nitrobenzoic acid and 2, 6-dibromophenol which are reaction raw materials which are easy to purchase in the market and are produced in quantity as starting raw materials, obtaining a compound a1 after nickel-catalyzed C-C coupling butt joint, performing nitroreduction on the compound a1 by using iron powder to obtain a compound a2, preparing an amino group of the compound a2 into a sulfonamide compound a3 by using trifluoromethanesulfonic anhydride (Tf 2 0), and finally performing ring closure preparation on the compound a3 under the catalysis of p-toluenesulfonic acid T S OH to obtain a target product 1-bromocarbazole, wherein the pollution in the reaction treatment process is small, the large-scale preparation cost is low, and the industrialized mass production can be realized.
From the design of a synthetic route and experimental data, the situation that bromine at another position is replaced by reaction to connect two molecules of nitrobenzene in the synthesis process of a1 can be effectively avoided by properly improving the equivalent weight of 2, 6-dibromophenol in the synthesis process of a1, so that a1 with higher purity can be obtained by the route. In the next reaction, the a1 is subjected to nitro reduction, the trifluoro methanesulfonyl group on the amino group, and each reaction link is mild in reaction and high in selectivity in the dehydration process of the p-toluenesulfonic acid, so that the reliable guarantee is provided for guaranteeing the quality of the 1-bromocarbazole. The route avoids the occurrence of the further participation of bromine in the product 1-bromocarbazole in other side reactions (such as the removal of bromine, the continuous reaction of bromine and the product internal amino group and other side reactions) in the prior art process.
The invention discloses a synthesis method of 1-bromocarbazole, which is prepared by taking o-nitrobenzoic acid and 2, 6-dibromophenol which are reaction raw materials which are easy to purchase in the market and are produced in quantity as starting raw materials, obtaining a compound a1 after nickel-catalyzed C-C coupling butt joint, carrying out nitroreduction on the compound a1 by iron powder to obtain a compound a2, preparing an amino group of the compound a2 into a sulfonamide compound a3 by using trifluoromethanesulfonic anhydride, and finally carrying out ring closure preparation on the compound a3 under the catalysis of p-toluenesulfonic acid to obtain a target product 1-bromocarbazole.
The invention discloses a brand new synthesis method of 1-bromocarbazole, which is characterized in that 2-trifluoromethanesulfonamide-2 '-hydroxy-3' -bromo-biphenyl is subjected to intramolecular dehydration through p-toluenesulfonic acid to obtain 1-bromocarbazole, and isomers are not easy to generate in the reaction process, and the method is easy to purify and high in yield.
The synthesis process of the invention avoids using a great deal of noble metal catalysts such as palladium, effectively reduces the cost and improves the comprehensive benefit; the synthetic process of the invention avoids the use of the oxidant DDQ with great pollution, reduces the pollution of byproducts to the environment and has better product quality.
The invention has the advantages of simple post-treatment process of each step, high yield and industrial production potential.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Many other changes and modifications may be made without departing from the spirit and scope of the invention. It is to be understood that the invention is not to be limited to the specific embodiments, but only by the scope of the appended claims.
Claims (7)
1. The synthesis method of the 1-bromocarbazole is characterized by comprising the following four steps:
Step 1: the o-nitrobenzoic acid and the 2, 6-dibromophenol are coupled and butted through the C-C catalyst by nickel to obtain a compound a1, the equivalent ratio of the o-nitrobenzoic acid to the 2, 6-dibromophenol is 1:1-1.1, and the structural formula of the compound a1 is as follows
Step 2: performing nitroreduction on the compound a1 by using iron powder to obtain a compound a2, wherein the equivalent ratio of the compound a1 to the iron powder is 1:7-8, and the structural formula of the compound a2 is as follows
Step 3: the compound a2 and the trifluoromethanesulfonic anhydride react to prepare a compound a3, the equivalent ratio of the compound a2 to the trifluoromethanesulfonic anhydride is 1:1-1.2, under the protection of argon, the compound a2 is added into a three-mouth bottle, dichloromethane is added for stirring and dissolving, pyridine is then added, the system is cooled to between minus 10 ℃ and 0 ℃, the trifluoromethanesulfonic anhydride is slowly dripped into the dichloromethane system under stirring, the reaction temperature is controlled between minus 10 ℃ and 0 ℃, and the reaction is carried out for 1h to 2h after the dripping is finished, until the compound a2 is completely reacted, thus obtaining the compound a3; the dosage ratio of the compound a2 to the dichloromethane is 0.3mol:500mL, and the equivalent ratio of the compound a2 to the pyridine is 1:1.2; after the reaction is confirmed, adding the reaction solution into water, separating the solution, washing a dichloromethane phase to be neutral by using water, and concentrating the dichloromethane phase under reduced pressure to obtain a light gray solid compound a3;
Step 4: under the catalysis of p-toluenesulfonic acid, the compound a3 is subjected to ring closure to prepare the target product 1-bromocarbazole, and the equivalent ratio of the compound a3 to the p-toluenesulfonic acid is 1:1.8-2.2.
2. The method for synthesizing 1-bromocarbazole according to claim 1, wherein the step 1 is specifically: adding o-nitrobenzoic acid and 2, 6-dibromophenol into a reaction bottle, adding dioxane and water, stirring, adding potassium phosphate, replacing a system with argon, adding nickel diacetylacetone, DPPF and CuCl, replacing with argon, heating to a reflux temperature of 90-92 ℃ for heat preservation reaction for 6-8 hours until the o-nitrobenzoic acid is reacted completely, and obtaining a compound a1, wherein the dosage ratio of the o-nitrobenzoic acid to the dioxane and the water is 0.5mol:800mL:200mL of o-nitrobenzeneboronic acid with respect to the equivalent ratio of potassium phosphate, nickel diacetylacetonate, DPPF and CuCl is 1:1.5:0.0025:0.005:0.05.
3. The method for synthesizing 1-bromocarbazole according to claim 2, wherein the post-treatment of the compound a1 is: after the reaction of the reaction liquid is finished, standing and separating the reaction liquid, concentrating the upper organic phase under reduced pressure, adding toluene for dissolving, washing the organic phase with water to remove residual salts, adding a drying agent for drying, filtering the toluene organic phase to remove the drying agent, concentrating the toluene under reduced pressure, and crystallizing with ethanol to obtain a yellowish solid compound a1.
4. The method for synthesizing 1-bromocarbazole according to claim 1, wherein the step 2 specifically comprises: adding the compound a1 into a methanol solution, adding ammonium chloride, heating to 55-62 ℃, then adding Fe powder in batches for a small amount for many times after adding concentrated hydrochloric acid dropwise, and obtaining a compound a2, wherein the dosage ratio of the compound a1 to the methanol is 0.4mol:840mL of compound a1 with an equivalent ratio of 1 to ammonium chloride and concentrated hydrochloric acid: 5:0.05.
5. The method for synthesizing 1-bromocarbazole according to claim 4, wherein the post-treatment of the compound a2 is: cooling to 20-30 ℃ after the reaction is finished, passing through a diatomite funnel, collecting filtrate, concentrating the filtrate under reduced pressure to dryness, adding ethyl acetate to dissolve, washing an organic phase with water to wash and remove residual inorganic salt, and then removing residual small amount of ferric salt from the ethyl acetate organic phase through a silica gel funnel, concentrating the ethyl acetate phase under reduced pressure to dryness; then petroleum ether is used for beating and dispersing to obtain the white-like solid powder compound a2.
6. The method for synthesizing 1-bromocarbazole according to claim 1, wherein the step 4 specifically comprises: adding a compound a3 into a dimethylbenzene solution, adding p-toluenesulfonic acid, heating the system to reflux after stirring, and reacting at a temperature for 15-20 h until the compound a3 is reacted thoroughly to obtain 1-bromocarbazole, wherein the dosage ratio of the compound a3 to the dimethylbenzene solution is 0.25mol:400mL.
7. The method for synthesizing 1-bromocarbazole according to claim 6, wherein the post-treatment of 1-bromocarbazole is: cooling to 20-30 ℃ after the reaction is finished, adding water into the system, separating liquid after dissolving the p-toluenesulfonic acid, washing the xylenes organic phase with water for 2-3 times successively to enable the p-toluenesulfonic acid to be washed and removed fully, adding anhydrous sodium sulfate for drying after washing the organic phase with water, removing the large polar impurities from the dried organic phase through a silica gel column, concentrating the column liquid under reduced pressure to obtain a thick matter crude product, and recrystallizing the crude product with n-heptane to obtain yellowish to white solid powder 1-bromocarbazole.
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