CN109651232A - The method for preparing 4- bromine carbazole and its derivative - Google Patents
The method for preparing 4- bromine carbazole and its derivative Download PDFInfo
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- CN109651232A CN109651232A CN201811594888.0A CN201811594888A CN109651232A CN 109651232 A CN109651232 A CN 109651232A CN 201811594888 A CN201811594888 A CN 201811594888A CN 109651232 A CN109651232 A CN 109651232A
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 48
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 28
- 238000006482 condensation reaction Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000460 chlorine Substances 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 239000011630 iodine Substances 0.000 claims abstract description 6
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 238000006884 silylation reaction Methods 0.000 claims description 8
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 150000007530 organic bases Chemical class 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical group [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000012805 post-processing Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 37
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000002994 raw material Substances 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 239000007790 solid phase Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- DWNYXIICDFVJEX-UHFFFAOYSA-N 1,2-dibromo-3-fluorobenzene Chemical compound FC1=CC=CC(Br)=C1Br DWNYXIICDFVJEX-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 4
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001716 carbazoles Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000002305 electric material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000009790 rate-determining step (RDS) Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- OFGJZUBGZYMANZ-UHFFFAOYSA-N (2-bromophenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC=C1Br OFGJZUBGZYMANZ-UHFFFAOYSA-N 0.000 description 1
- KEURHSDOWCBXFX-UHFFFAOYSA-N 1-(2-bromophenyl)-2-nitrobenzene Chemical group [O-][N+](=O)C1=CC=CC=C1C1=CC=CC=C1Br KEURHSDOWCBXFX-UHFFFAOYSA-N 0.000 description 1
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical group BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 1
- YOJKKXRJMXIKSR-UHFFFAOYSA-N 1-nitro-2-phenylbenzene Chemical group [O-][N+](=O)C1=CC=CC=C1C1=CC=CC=C1 YOJKKXRJMXIKSR-UHFFFAOYSA-N 0.000 description 1
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical compound Br1=CC=CC=C1 SODQFLRLAOALCF-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
- JDLGBNVBFOLSMR-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3NC12.[Br] Chemical compound C1=CC=CC=2C3=CC=CC=C3NC12.[Br] JDLGBNVBFOLSMR-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- ZBCKWHYWPLHBOK-UHFFFAOYSA-N cyclohexylphosphane Chemical compound PC1CCCCC1 ZBCKWHYWPLHBOK-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
Abstract
The present invention relates to organic chemical synthesis fields, disclose a kind of method for preparing 4- bromine carbazole and its derivative, this method comprises: 1) contact the compound of structure shown in formula (1) with the compound of structure shown in formula (2) to carry out condensation reaction, the compound of structure shown in formula (3) is obtained；2) compound of structure shown in formula (3) is subjected to cyclization reaction, obtains 4- bromine carbazole or derivatives thereof；Wherein, in formula (2) and formula (3), R1Selected from chlorine, bromine or iodine.4- bromine carbazole and its derivative are prepared using this method, has that reaction condition is mild, post-processing purifying is simple, high income and the advantages such as at low cost.
Description
Technical field
The present invention relates to organic chemical synthesis fields, more particularly to the preparation side of a kind of 4- bromine carbazole and its derivative
Method.
Background technique
Carbazole analog derivative is the intermediate that a major class has extensive use.It is with good photoelectric properties, with carbazole
It is widely used in the fields such as oled light electric material, medicine, dyestuff and pesticide for the derivative that raw material is prepared.
The halides that different location replaces on carbazole are prepared by different methods.3- bromine carbazole, 2- bromine click at present
The carbazoles analog derivatives such as azoles, 1- bromine carbazole are widely reported, mainly by more direct bromo, card cyclizations or are taken
Xie Er indoles method is made.Its derivative is widely used in the fields such as oled light electric material, medicine, dyestuff and pesticide.
Currently, the preparation method of 4- bromine carbazole and its derivative also report it is less, be mostly by ortho-nitrophenyl boric acid and
After adjacent bromo-iodobenzene carries out Suzuki coupling, then it is cyclized and obtains under triethyl phosphite or triphenylphosphine high temperature action.But
Such method expensive raw material price, wherein triethyl phosphite smell it is larger, with triphenylphosphine carry out cyclisation preparation when during
The by-products such as a large amount of triphenylphosphinc oxide can be generated, and since product is in high temperature progress, final products color is relatively deep, purifies more
It is difficult.
CN 103936656A discloses a kind of method for synthesizing 4- bromine carbazole, and this method is using bromophenyl boric acid as raw material, warp
It crosses Suzuki to react to obtain the bromo- 2 '-nitrobiphenyl of 2-, then bromo- the 2 '-nitrobiphenyl of 2- is closed by reducing agent of triphenyl phosphite
At product 4- bromine carbazole.It leads to the problem of a large amount of triphenylphosphine by-products and purification difficult during equally existing cyclization.
Therefore, it is necessary to the production technology of 4- bromine carbazole in the prior art is improved, it is growing to meet
Product demand.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of 4- bromine carbazole and its derivative, with solve 4- bromine carbazole and its
The problem that expensive raw material price, smell are big in derivative preparation process and separation and purification of products is difficult.
To achieve the goals above, the present invention provides a kind of method for preparing 4- bromine carbazole and its derivative, this method packet
It includes:
1) compound of structure shown in formula (1) is contacted with the compound of structure shown in formula (2) to carry out condensation reaction, is obtained
Obtain the compound of structure shown in formula (3)；
2) compound of structure shown in formula (3) is subjected to cyclization reaction, obtains 4- bromine carbazole or derivatives thereof；
Wherein, in formula (2) and formula (3), R1Selected from chlorine, bromine or iodine；
In formula (1), formula (2) and formula (3), R2、R3、R4、R5、R6、R7And R8It is each independently selected from-H ,-D ,-CN ,-
NO2,-CF3, boric acid ester group, substituted or unsubstituted silylation, substituted or unsubstituted C1-12Alkyl, it is substituted or unsubstituted
C1-12Alkoxy, it is substituted or unsubstituted containing be selected from the heteroatomic C of at least one of O and S2-12Alkyl, replace or not
Substituted C6-C10Aryl or R7And R8C is collectively formed6-C10Aromatic group；
Wherein R2、R3、R4、R5、R6、R7And R8In the substituent group that is optionally present be each independently selected from C1-6Alkyl, C1-6
Alkoxy or C6-C10Aryl.
Two kinds of preferred embodiments of the invention presented below illustrate present invention preparation 4- bromine carbazole and its derivative
The method of object.
Specific embodiment 1:
A method of 4- bromine carbazole is prepared, this method comprises:
1) compound of structure shown in formula (1) is contacted with the compound of structure shown in formula (2) to carry out condensation reaction, is obtained
Obtain the compound of structure shown in formula (3)；
2) compound of structure shown in formula (3) is subjected to cyclization reaction, obtains 4- bromine carbazole；
Wherein, in formula (2) and formula (3), R1Selected from chlorine, bromine or iodine；
In formula (1), formula (2) and formula (3), R2、R3、R4、R5、R6、R7And R8It is H.
Specifically, the synthetic route for preparing 4- bromine carbazole is as follows:
Specific embodiment 2:
A method of 4- bromine carbazole derivates are prepared, this method comprises:
1) compound of structure shown in formula (1) is contacted with the compound of structure shown in formula (2) to carry out condensation reaction, is obtained
Obtain the compound of structure shown in formula (3)；
2) compound of structure shown in formula (3) is subjected to cyclization reaction, obtains 4- bromine carbazole derivates；
Wherein, in formula (2) and formula (3), R1Selected from chlorine, bromine or iodine；
In formula (1), formula (2) and formula (3), R2、R3、R4、R5、R6、R7And R8It is each independently selected from-H ,-D ,-CN ,-
NO2,-CF3, boric acid ester group, substituted or unsubstituted silylation, substituted or unsubstituted C1-12Alkyl, it is substituted or unsubstituted
C1-12Alkoxy, it is substituted or unsubstituted containing be selected from the heteroatomic C of at least one of O and S2-12Alkyl, replace or not
Substituted C6-C10Aryl or R7And R8C is collectively formed6-C10Aromatic group；
Wherein R2、R3、R4、R5、R6、R7And R8In the substituent group that is optionally present be each independently selected from C1-6Alkyl, C1-6
Alkoxy or C6-C10Aryl；
And R2、R3、R4、R5、R6、R7And R8It is not all H.
Specifically, the synthetic route for preparing 4- bromine carbazole derivates is as follows:
Through the above technical solutions, the preparation method of 4- bromine carbazole provided by the invention and its derivative, avoids use
The pyroreactions such as triethyl phosphite, triphenylphosphine prepare 4- bromine carbazole and its derivative, post-processing mild with reaction condition
Purifying is simple, high income and the advantages such as at low cost, reduces requirement of the industrialized production to conditions such as equipment, saves the same of the energy
When, it is advantageously implemented industrialized production.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
As previously mentioned, the present invention provides a kind of method for preparing 4- bromine carbazole and its derivative, this method comprises:
1) compound of structure shown in formula (1) is contacted with the compound of structure shown in formula (2) to carry out condensation reaction, is obtained
Obtain the compound of structure shown in formula (3)；
2) compound of structure shown in formula (3) is subjected to cyclization reaction, obtains 4- bromine carbazole or derivatives thereof；
Wherein, in formula (2) and formula (3), R1Selected from chlorine, bromine or iodine；
In formula (1), formula (2) and formula (3), R2、R3、R4、R5、R6、R7And R8It is each independently selected from-H ,-D ,-CN ,-
NO2,-CF3, boric acid ester group, substituted or unsubstituted silylation, substituted or unsubstituted C1-12Alkyl, it is substituted or unsubstituted
C1-12Alkoxy, it is substituted or unsubstituted containing be selected from the heteroatomic C of at least one of O and S2-12Alkyl, replace or not
Substituted C6-C10Aryl or R7And R8C is collectively formed6-C10Aromatic group；
Wherein R2、R3、R4、R5、R6、R7And R8In the substituent group that is optionally present be each independently selected from C1-6Alkyl, C1-6
Alkoxy or C6-C10Aryl.
In the present invention, with R2For carry out it is explained below:
" boric acid ester group " indicates, works as R2When for " boric acid ester group ", R2Contain boric acid ester group, such as R in as long as2
It can be group shown in group shown in formula (1-1) or formula (1-2).
" substituted or unsubstituted silylation " indicates, works as R2When for " substituted or unsubstituted silylation ", wherein unsubstituted
Shown in the structural formula of silylation such as formula (1-3), the H in " substituted silylation " expression (1-3) is independently selected from institute of the present invention
In the substituent group of description any one or it is two or more.
" substituted or unsubstituted C1-12Alkyl " indicate, work as R2For " substituted or unsubstituted C1-12Alkyl " when, R2's
The total number of carbon atoms is 1-12, and can be alkyl group or naphthenic base；If " substituted C1-12Alkyl ", taking on alkyl
Dai Jike in substituent group described in the present invention any one or it is two or more.
" substituted or unsubstituted C1-12Alkoxy " indicate, work as R2For " substituted or unsubstituted C1-12Alkoxy " when,
R2The total number of carbon atoms be 1-12, and can be chain alkoxy or cyclic alkoxy, if " substituted C1-12Alcoxyl
Base ", substituent group on alkoxy can in substituent group described in the present invention any one or it is two or more.
It is " substituted or unsubstituted containing selected from the heteroatomic C of at least one of O and S2-12Alkyl " indicate, work as R2For
It is " substituted or unsubstituted containing selected from the heteroatomic C of at least one of O and S2-12Alkyl " when, R2The total number of carbon atoms be 2-
12, and containing selected from least one of O and S hetero atom；If " substituted containing is selected from the miscellaneous original of at least one of O and S
The C of son2-12Alkyl ", substituent group on alkyl can in substituent group described in the present invention any one or two
Kind or more.
" substituted or unsubstituted C6-C10Aryl " indicate, work as R2For " substituted or unsubstituted C6-C10Aryl " when, R2
Middle the total number of carbon atoms is 6-10, and the member for forming the ring of aryl is carbon atom；If " substituted C6-C10Aryl " virtue
Substituent group on base can in substituent group described in the present invention any one or it is two or more.
" aryl " indicates, can be phenyl, naphthalene by the group of phenyl derivative.
According to the present invention, work as R2、R3、R4、R5、R6、R7And R8When being H, that is, 4- bromine carbazole is prepared.
Work as R2、R3、R4、R5、R6、R7And R8When being not all H, that is, 4- bromine carbazole derivates are prepared.
In the case of, according to the invention it is preferred to, in step 1), the compound and the formula (2) of structure shown in the formula (1)
The dosage molar ratio of the compound of shown structure is (0.5-1.5): 1, further preferably (0.95-1.1): 1.
Preferably, in step 1), the condition of the condensation reaction includes: that reaction temperature is 80-160 DEG C, further excellent
It is selected as 120-150 DEG C；Reaction time is 8-35h, further preferably 18-26h.
According to the present invention, for the purpose of the present invention is better achieved, 4- bromine carbazole and its derivative are obtained prepared by raising
Yield, under preferable case, the condensation reaction carries out in the presence of a basic.
Preferably, the dosage molar ratio of the alkaline matter and the compound of structure shown in the formula (2) is (1-6): 1,
Preferably (2.5-4): 1.
The type of the alkaline matter is not particularly limited, as long as alkaline condition can be provided i.e. for the condensation reaction
Can, in the present invention, the alkaline matter is preferably at least one of cesium carbonate, potassium carbonate, triethylamine and pyridine.
Under preferable case, the step 1) condensation reaction carries out in the presence of solvent；It is further preferred that the solvent choosing
From at least one of N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone.
Rate-determining steps 1) in the dosage of solvent for use be more advantageous to and improve preparation-obtained 4- bromine carbazole and its derivative
Yield, it is preferable that the ratio between dosage of solvent=1g:(5- in the dosage of the compound of structure shown in the formula (2) and step 1)
15mL)。
It is particularly preferred that the condensation reaction carries out in the presence of solvent and alkaline matter in step 1).Specific
In embodiment, the compound of structure shown in formula (2) can be dissolved in solvent, then sequentially add structure shown in formula (1)
Compound and alkaline matter carry out the condensation reaction.
In accordance with the present invention it is preferred that the material of acquisition is successively filtered and is dried after carrying out the condensation reaction
To obtain the compound of structure shown in formula (3), the compound of structure shown in the formula (3) obtained after drying is then used for step 2)
In.Specifically, such as the material of acquisition can will be poured into water after the condensation reaction, is then filtered, after filtering
Obtained solid-phase material successively with water elution and ethanol rinse, is then placed in 75-85 DEG C of convection oven dry 1-4h, obtains
The compound of structure shown in formula (3).
In the case of, according to the invention it is preferred to, in step 2), the condition of the cyclization reaction includes: that reaction temperature is 80-
160 DEG C, preferably 140-160 DEG C；Reaction time is 0.5-12h, preferably 2-6h；
Preferably, the cyclization reaction carries out under inert gas protection, and this field institute can be used in the inert gas
Well known nitrogen.
In the present invention, under preferable case, in step 2), the cyclization reaction carries out in the presence of palladium catalyst.
Preferably, the dosage molar ratio of the compound Yu the palladium catalyst of structure shown in the formula (3) is 1:(0.005-
1), preferably 1:(0.01-0.15), more preferably 1:(0.01-0.05)；
Preferably, the palladium catalyst is tris(dibenzylideneacetone) dipalladium and/or two (dibenzalacetone) palladiums.
In the case of, according to the invention it is preferred to, in step 2), the cyclization reaction carries out in the presence of an organic base；Into one
Preferably, the compound of structure shown in the formula (3) and the dosage molar ratio of the organic base are 1:(2-4 to step).
Preferably, the organic base is in 1,8- diazabicylo, 11 carbon -7- alkene (DBU), sodium tert-butoxide, pyridine
It is at least one.
In the present invention, in order to which the present invention can react during more mild, it is preferable that in step 2)
In, the cyclization reaction carries out in the presence of ligand；It is further preferred that the compound of structure shown in the formula (3) with it is described
The dosage molar ratio of ligand is 1:(0.005-1), more preferably 1:(0.005-0.05)；It is particularly preferred that the ligand is three
Cyclohexyl phosphine and/or tri-tert-butylphosphine.
In the case of, according to the invention it is preferred to, the step 2) cyclization reaction carries out in the presence of solvent；Further preferably
Ground, the solvent are selected from least one of n,N-Dimethylformamide, n,N-dimethylacetamide and N-Methyl pyrrolidone
Rate-determining steps 2) in the dosage of solvent for use be more advantageous to and improve preparation-obtained 4- bromine carbazole and its derivative
Yield, it is preferable that the ratio between dosage of solvent=1g:(5- in the dosage of the compound of structure shown in the formula (3) and step 2)
15mL)。
It is particularly preferred that the cyclization reaction is in the presence of solvent, palladium catalyst, organic base and ligand in step 2)
It carries out.In a particular embodiment, it can then be sequentially added for the compound of structure shown in formula (3) to be dissolved in solvent
Organic base, palladium catalyst and ligand carry out the cyclization reaction.
It according to the present invention, is the purity and yield that further increase preparation-obtained 4- bromine carbazole and its derivative,
In step 2), the material that the compound of structure shown in formula (3) obtain after cyclization reaction can be isolated and purified.Specifically
, then described isolate and purify can be filtered, after filtering for the material obtained after the cyclization reaction to be poured into water
Obtained solid-phase material successively uses water and ethanol rinse, is then placed in 75-85 DEG C of convection oven dry 1-4h, and will dry
The product obtained afterwards, which is added in 10 times of toluene for being equivalent to product quality, to be dissolved, and is carried out with the active carbon of 10% product quality ratio
It decolourizes, then solvent of the distillation filtrate to product quality than 1 times.And gained filtrate after distillation is down to room temperature and carries out crystallization, it obtains
Obtain the higher 4- bromine carbazole of purity and its derivative product.
It below will the present invention will be described in detail by example.In following instance, in case of no particular description,
The raw material is all from commercially available.
Preparation example 1
(1) bis- bromofluoro benzene of 2, the 3- of 0.197mol is dissolved in the n,N-dimethylacetamide solvent of 600ml, is sequentially added
0.197mol aniline, 0.5909mol cesium carbonate carry out condensation reaction under the conditions of 140 DEG C, react detection raw material reaction after 20h
It finishes, reaction solution is then cooled to room temperature, be added in 1L water, the solid-phase material obtained after filtering is used in stirring 30min filtering
The elution of 200ml water, 100ml ethanol rinse are then placed in 80 DEG C of convection oven dry 2h, obtain 0.1734mol intermediate a
(yield 88%)；
Calculated value C12H9Br2N:327.01 ± 1.δ=3.98~4.05 1H-NMR (400MHz, CDCl3) (ppm) (1H,
S), 6.43~6.48 (1H, m), 6.81~6.88 (3H, m), 7.19~7.29 (4H, m).
(2) 0.1734mol intermediate a is dissolved in the n,N-dimethylacetamide solvent of 500ml, is stirred under a nitrogen,
Then DBU, 0.0017mol tris(dibenzylideneacetone) dipalladium, the 0.0017mol tri-tert-butylphosphine of 0.4335mol are sequentially added,
Cyclization reaction is carried out at 160 DEG C, detects raw material end of reaction after 2h, and reaction solution is cooled to room temperature, is added in 1L water, stirring
It filters, the solid-phase material obtained after filtering 300ml water is eluted, 200ml ethanol rinse is then placed in 80 DEG C of drums after 30min
Wind oven drying 2h, addition are equivalent in 10 times of toluene of product quality and dissolve, with the active carbon of 10% product quality ratio into
Row decoloration, then solvent of the distillation filtrate to product quality than 1 times, is then down to room temperature for gained filtrate and carries out crystallization, obtain
The 4- bromine carbazole (yield 93.1%, purity 99.67%) of 0.1614mol；
Calculated value C12H8BrN:246.1 ± 1.δ=7.26~7.34 (3H, m) 1H-NMR (400MHz, CDCl3) (ppm),
7.50~7.63 (3H, m), 8.10~8.14 (1H, d), 9.98~10.05 (1H, s).
Preparation example 2
(1) bis- bromofluoro benzene of 2, the 3- of 0.197mol is dissolved in the n,N-Dimethylformamide solvent of 400ml, is sequentially added
0.187mol aniline, 0.4925mol potassium carbonate carry out condensation reaction under the conditions of 120 DEG C, detect raw material end of reaction after 26h,
Then reaction solution is cooled to room temperature, be added in 2L water, stirring 30min filtering, the solid-phase material 200ml that will be obtained after filtering
Water elution, 100ml ethanol rinse are then placed in 80 DEG C of convection oven dry 2h, obtain 0.1533mol intermediate a (yield
82%)；
Calculated value C12H9Br2N:327.01 ± 1.δ=3.98~4.05 1H-NMR (400MHz, CDCl3) (ppm) (1H,
S), 6.43~6.48 (1H, m), 6.81~6.88 (3H, m), 7.19~7.29 (4H, m).
(2) 0.1533mol intermediate a is dissolved in the n,N-Dimethylformamide solvent of 500ml, is stirred under a nitrogen,
Then DBU, 0.0038mol bis- (dibenzalacetone) palladium, the 0.00076mol tricyclohexyl phosphine of 0.3066mol are sequentially added,
Cyclization reaction is carried out at 140 DEG C, detects raw material end of reaction after 6h, and reaction solution is cooled to room temperature, is added in 2L water, stirring
It filters, the solid-phase material obtained after filtering 300ml water is eluted, 200ml ethanol rinse is then placed in 80 DEG C after 30min
Dry 2h in convection oven, addition, which is equivalent in 10 times of toluene of product quality, dissolves, with the activity of 10% product quality ratio
Charcoal decolourizes, then solvent of the distillation filtrate to product quality than 1 times, and gained filtrate is then down to room temperature and carries out crystallization,
Obtain the 4- bromine carbazole (yield 90.2%, purity 99.35%) of 0.1383mol；
Calculated value C12H8BrN:246.1 ± 1.δ=7.26~7.34 (3H, m) 1H-NMR (400MHz, CDCl3) (ppm),
7.50~7.63 (3H, m), 8.10~8.14 (1H, d), 9.98~10.05 (1H, s).
Preparation example 3
(1) bis- bromofluoro benzene of 2, the 3- of 0.197mol is dissolved in the N-Methyl pyrrolidone solvent of 750ml, is sequentially added
The aniline of 0.217mol, 0.788mol triethylamine carry out condensation reaction under the conditions of 150 DEG C, and detection raw material has reacted after 18h
Finish, reaction solution is then cooled to room temperature, be added in 3L water, the solid-phase material obtained after filtering is used in stirring 30min filtering
The elution of 200ml water, 100ml ethanol rinse are then placed in 80 DEG C of convection oven dry 2h, obtain 0.167mol intermediate a
(yield 85%)；
Calculated value C12H9Br2N:327.01 ± 1.δ=3.98~4.05 1H-NMR (400MHz, CDCl3) (ppm) (1H,
S), 6.43~6.48 (1H, m), 6.81~6.88 (3H, m), 7.19~7.29 (4H, m).
(2) 0.167mol intermediate a is dissolved in 500ml triethylamine solvent, stirs, then sequentially adds under a nitrogen
DBU, 0.00835mol tris(dibenzylideneacetone) dipalladium of 0.668mol, 0.00835mol tri-tert-butylphosphine, at 150 DEG C into
Row cyclization reaction detects raw material end of reaction after 3h, and reaction solution is cooled to room temperature, is added in 3L water, mistake after 30min is stirred
Filter, the solid-phase material obtained after filtering 300ml water is eluted, and it is dry to be then placed in 80 DEG C of convection ovens for 200ml ethanol rinse
2h, addition, which is equivalent in 10 times of toluene of product quality, dissolves, and is decolourized with the active carbon of 10% product quality ratio, then
Then gained filtrate is down to room temperature and carries out crystallization, obtains the 4- of 0.158mol by solvent of the distillation filtrate to product quality than 1 times
Bromine carbazole (yield 94.6%, purity 99.42%)；
Calculated value C12H8BrN:246.1 ± 1.δ=7.26~7.34 (3H, m) 1H-NMR (400MHz, CDCl3) (ppm),
7.50~7.63 (3H, m), 8.10~8.14 (1H, d), 9.98~10.05 (1H, s).
Preparation example 4
(1) according to preparation method similar with preparation example 1, only raw material is different, is made intermediate b (yield 78%)；
Calculated value C12H9BrClN:282.56 ± 1.δ=3.98~4.05 1H-NMR (400MHz, CDCl3) (ppm) (1H,
S), 6.43~6.48 (1H, m), 6.81~6.90 (3H, m), 6.80~7.29 (4H, m).
(2) preparation method similar with preparation example 1 is used, the difference is that preparing 4- bromine carbazole (yield using intermediate b
82.7%, purity 99.01%)；
Calculated value C12H8BrN:246.1 ± 1.δ=7.26~7.34 (3H, m) 1H-NMR (400MHz, CDCl3) (ppm),
7.50~7.63 (3H, m), 8.10~8.14 (1H, d), 9.98~10.05 (1H, s).
Preparation example 5
(1) according to preparation method similar with preparation example 1, only raw material is different, is made intermediate c (yield 75%)；
Calculated value C16H11Br2N:377.07 ± 1.δ=3.96~4.02 1H-NMR (400MHz, CDCl3) (ppm) (1H,
S), 6.85~6.88 (2H, m), 7.42~7.48 (1H, m), 7.30~7.50 (3H, m), 7.74~7.90 (4H, m).
(2) preparation method similar with preparation example 1 is used, is spread out the difference is that 4- bromine carbazole is prepared using intermediate c
Biological A (yield 73.8%, purity 99.13%)；
Calculated value C16H10BrN:296.16 ± 1.δ=7.26~7.34 1H-NMR (400MHz, CDCl3) (ppm) (2H,
M), 7.57~7.67 (5H, m), 8.14~8.18 (1H, m), 8.50~8.58 (1H, m), 10.00-10.12 (1H, s).
Preparation example 6
(1) according to preparation method similar with preparation example 1, only raw material is different, is made intermediate d (yield 76%)；
Calculated value C18H13Br2N:403.11 ± 1.δ=3.96~4.02 1H-NMR (400MHz, CDCl3) (ppm) (1H,
S), 6.45~6.48 (1H, m), 6.68~6.72 (2H, m), 6.85~6.88 (2H, m), 7.41~7.54 (7H, m).
(2) preparation method similar with preparation example 1 is used, the difference is that preparing 4- bromine carbazole derivates B using intermediate d
(yield 75.4%, purity 99.28%)；
Calculated value C18H12BrN:322.20 ± 1.δ=7.26~7.58 1H-NMR (400MHz, CDCl3) (ppm) (8H,
M), 7.67~7.78 (2H, m), 7.85~7.88 (1H, m), 9.98~10.02 (1H, m).
Preparation example 7
According to the method for preparation example 1, the difference is that: in step (1), the dosage molar ratio of 2,3- bis- bromofluoro benzenes and aniline is
1.5:1 is made intermediate a (yield 75.8%)；
Intermediate a preparation 4- bromine carbazole (yield 83.7%, purity 85.9%) obtained using this preparation example.
Preparation example 8
According to the method for preparation example 1, unlike: in step (2), intermediate a and tris(dibenzylideneacetone) dipalladium
Dosage molar ratio is 0.005:1, is made 4- bromine carbazole (yield 77.2%, purity 84.7%).
Preparation example 9
According to the method for preparation example 1, the difference is that: in step (1), replace cesium carbonate that intermediate a (yield is made with pyridine
For 62.3%).
Intermediate a preparation 4- bromine carbazole (yield 57.0%, purity 85.3%) obtained using this preparation example.
Can be seen that by above-mentioned preparation example can be prepared high yield and high-purity using the method for the invention
4- bromine carbazole and its derivative, in addition, the present invention is using more mild process instead of triethyl phosphite, triphenylphosphine etc.
Pyroreaction, the mild preparation for realizing 4- bromine carbazole and its derivative.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of method for preparing 4- bromine carbazole and its derivative, this method comprises:
1) compound of structure shown in formula (1) is contacted to carry out condensation reaction with the compound of structure shown in formula (2), obtains formula
(3) compound of structure shown in；
2) compound of structure shown in formula (3) is subjected to cyclization reaction, obtains 4- bromine carbazole or derivatives thereof；
Wherein, in formula (2) and formula (3), R1Selected from chlorine, bromine or iodine；
In formula (1), formula (2) and formula (3), R2、R3、R4、R5、R6、R7And R8It is each independently selected from-H ,-D ,-CN ,-NO2,-
CF3, boric acid ester group, substituted or unsubstituted silylation, substituted or unsubstituted C1-12Alkyl, substituted or unsubstituted C1-12
Alkoxy, it is substituted or unsubstituted containing be selected from the heteroatomic C of at least one of O and S2-12Alkyl, replace or do not take
The C in generation6-C10Aryl or R7And R8C is collectively formed6-C10Aromatic group；
Wherein R2、R3、R4、R5、R6、R7And R8In the substituent group that is optionally present be each independently selected from C1-6Alkyl, C1-6Alcoxyl
Base or C6-C10Aryl.
2. according to the method described in claim 1, wherein, in step 1), the compound of structure shown in the formula (1) and described
The dosage molar ratio of the compound of structure shown in formula (2) is (0.5-1.5): 1, preferably (0.95-1.1): 1.
3. method according to claim 1 or 2, wherein in step 1), the condition of the condensation reaction includes: reaction
Temperature is 80-160 DEG C, preferably 120-150 DEG C；Reaction time is 8-35h, preferably 18-26h.
4. method described in any one of -3 according to claim 1, wherein in step 1), the condensation reaction is in alkalinity
It is carried out in the presence of substance；
Preferably, the dosage molar ratio of the alkaline matter and the compound of structure shown in the formula (2) is (1-6): 1, preferably
For (2.5-4): 1；
Preferably, the alkaline matter is selected from least one of cesium carbonate, potassium carbonate, triethylamine and pyridine.
5. method described in any one of -4 according to claim 1, wherein in step 2), the condition of the cyclization reaction
Include: reaction temperature be 80-160 DEG C, preferably 140-160 DEG C；Reaction time is 0.5-12h, preferably 2-6h；
Preferably, the cyclization reaction carries out under inert gas protection.
6. method described in any one of -5 according to claim 1, wherein in step 2), the cyclization reaction is urged in palladium
It is carried out in the presence of agent；
Preferably, the dosage molar ratio of the compound Yu the palladium catalyst of structure shown in the formula (3) is 1:(0.005-1),
Preferably 1:(0.01-0.15)；
Preferably, the palladium catalyst is tris(dibenzylideneacetone) dipalladium and/or two (dibenzalacetone) palladiums.
7. method described in any one of -6 according to claim 1, wherein in step 2), the cyclization reaction is organic
It is carried out in the presence of alkali；
Preferably, the dosage molar ratio of the compound Yu the organic base of structure shown in the formula (3) is 1:(2-4)；
Preferably, the organic base is selected from least one of 1,8- diazabicylo, 11 carbon -7- alkene, sodium tert-butoxide, pyridine.
8. method according to claim 6 or 7, wherein in step 2), the cyclization reaction in the presence of ligand into
Row；
Preferably, the dosage molar ratio of the compound Yu the ligand of structure shown in the formula (3) is 1:(0.005-1)；
Preferably, the ligand is tricyclohexyl phosphine and/or tri-tert-butylphosphine.
9. method described in any one of -8 according to claim 1, wherein the condensation reaction and/or the cyclization reaction
It carries out in the presence of solvent；
Preferably, the ratio between dosage of solvent=1g:(5- in the dosage Yu step 1) of the compound of structure shown in the formula (2)
15mL)；
Preferably, the ratio between dosage of solvent=1g:(5- in the dosage Yu step 2) of the compound of structure shown in the formula (3)
15mL)；
Preferably, the solvent of optional use is selected from N, N- dimethyl formyl in the condensation reaction and the cyclization reaction
At least one of amine, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone.
10. method described in any one of -9 according to claim 1, wherein this method further include: carrying out, the condensation is anti-
Should after the material of acquisition is successively filtered and is dried with the compound of structure shown in acquisition formula (3).
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