CN114349683A - Amido protection and deprotection method of carbazole and carbazole similar derivatives - Google Patents
Amido protection and deprotection method of carbazole and carbazole similar derivatives Download PDFInfo
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- CN114349683A CN114349683A CN202210059662.0A CN202210059662A CN114349683A CN 114349683 A CN114349683 A CN 114349683A CN 202210059662 A CN202210059662 A CN 202210059662A CN 114349683 A CN114349683 A CN 114349683A
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- carbazole
- chloroethyl
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- dichloroethane
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 229
- 238000000034 method Methods 0.000 title claims abstract description 63
- 238000010511 deprotection reaction Methods 0.000 title claims abstract description 30
- 125000003368 amide group Chemical group 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 230000008569 process Effects 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 alkali metal salt Chemical class 0.000 claims abstract description 19
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- 150000001716 carbazoles Chemical class 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 238000005859 coupling reaction Methods 0.000 claims abstract description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 41
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 239000012074 organic phase Substances 0.000 claims description 32
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 26
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 22
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 125000003277 amino group Chemical group 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000008878 coupling Effects 0.000 claims description 7
- 238000010168 coupling process Methods 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 6
- 238000004537 pulping Methods 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims 1
- 239000000047 product Substances 0.000 description 51
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- MYKQKWIPLZEVOW-UHFFFAOYSA-N 11h-benzo[a]carbazole Chemical compound C1=CC2=CC=CC=C2C2=C1C1=CC=CC=C1N2 MYKQKWIPLZEVOW-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 125000006239 protecting group Chemical group 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 150000004756 silanes Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XPEIJWZLPWNNOK-UHFFFAOYSA-N (4-phenylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1C1=CC=CC=C1 XPEIJWZLPWNNOK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The invention discloses an amido protection and deprotection method of carbazole and carbazole similar derivatives, which comprises the following steps: step 1: and in the protection process, reacting carbazole and carbazole similar derivatives A with 1, 2-dichloroethane to generate-N-chloroethyl protection products B, and continuing to perform C-C or C-N coupling reaction on the B to convert the B 'into B', wherein the molar ratio of the carbazole and carbazole similar derivatives A to the 1, 2-dichloroethane is 1: 5-10; step 2: deprotection process, reaction of N-chloroethyl protection product B or B ' with alkali metal salt of alcohol to remove-N-chloroethyl and generate corresponding carbazole and carbazole analog derivative A or A ', wherein the molar ratio of-N-chloroethyl protection product B or B ' to alkali metal salt of alcohol is 1: 1 to 1.5.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to an amino protection and deprotection method of carbazole and carbazole-like derivatives.
Background
Carbazole and similar derivatives have wide and important applications in the field of OLED materials, and mature and stable technical methods are available for relevant synthetic methods at present. Along with the gradual connection and fusion of domestic and international markets, related OLED materials and synthesis technologies are also improved and improved day by day, the international high standard becomes a consensus of the industry, the important point is that the synthesis of important small molecules and derivatives thereof such as carbazole, furan, thiophene and the like which are high-frequency key intermediate fragments used at present is pursued to be high in purity (99.9% +), impurities are effectively controlled from the source, and the establishment of the index of ideal high purity of the final terminal material is achieved. In the prior art, the processes of C-C and C-N coupling of carbazole and similar derivatives in the specific process of relevant synthesis of OLED materials are difficult to avoid using high-activity catalysts mainly comprising palladium, platinum and the like, and the reaction process is difficult to avoid other relevant side reactions caused by catalysis if the catalysts of the type are used. Examples are as follows: in order to realize the SUZUKI butt-joint reaction of 3-bromocarbazole and 4-biphenylboronic acid to prepare the compound 1- (3- (4' -biphenyl) -9-H-carbazole), common catalysts such as zero-valent or divalent palladium and related ligands are used in the reaction process, and the conversion rate of the two compounds is close to 98% by using a good catalytic system in the reaction process. However, the reaction process cannot avoid the generation of 2- (9- (4 ' -biphenyl) -3-bromocarbazole) which is a main byproduct and 3- (9- (4 ' -biphenyl) -3- (4 ' -biphenyl) carbazole) which is a byproduct. Although the byproducts 2 and 3 are generated rarely, the byproducts are very difficult to remove completely in the purification process of the compound 1, so that the byproducts are inevitably introduced into the next reaction to the final product, and the final product cannot realize high purity to affect the electrochemical performance and quality stability of the terminal material. In order to obtain the high-purity target compound 1, various companies and scientific research institutions in the market continuously innovate catalyst selection and synthesis schemes, strive for technical and method breakthroughs, and strive for market initiatives. For the reasons mentioned above, it is a convenient and effective method to protect the active hydrogen of carbazole and its derivatives and then carry out the relevant reaction.
At present, the method for protecting carbazole amine mainly comprises two main types of the traditional silanes and benzyl, wherein the process of protecting carbazole and similar derivatives by the silanes is realized by using high-activity substances such as sodium hydride, active lithium reagents and the like, and can be generally realized at a lower temperature, and the conversion rate of upper protection is unstable and is generally between 70 and 95 percent; and the products after silane protection are sensitive to common acids such as hydrochloric acid, acetic acid, sulfuric acid and the like, and can be easily removed even in the environment of strong acid and weak base salts, so that the use is limited. The other is a benzyl protecting group which is generally protected at a higher temperature, the conversion rate of the benzyl protecting process is generally over 90 percent, the cost of reaction raw materials is lower, and the stability of the obtained product is very high. However, the benzyl protection product has high stability, so that the removal process is very difficult, and the complete removal of the protecting group is often impossible, so that the method is greatly limited. At present, the conventional methods such as high-pressure hydrogenation and the like can not remove the benzyl protecting group on carbazole and similar derivatives, or can be carried out at high temperature and high pressure. Other methods are to remove benzyl group by forced transfer with strong lewis acid such as anhydrous aluminum trichloride or by oxidation with strong oxidant such as DDQ, and under these severe reaction conditions, the product will also generate a large amount of other by-products, which makes the solution difficult to use; another method is to use K (t-BuO) and O in a strong polar solvent such as DMSO and the like2Or the benzyl group is removed by matching with silanes, but the reaction operation is inconvenient, and the removal of the protective agent is incomplete, so that the application of the method is also greatly limited.
The silane has large fluctuation of the protection conversion rate on carbazole and similar derivatives, and the products after protection are sensitive and unstable to inorganic acids such as hydrochloric acid, sulfuric acid, acetic acid, strong acid and weak base salt and the like, so that the silane protection products can not play a role in protection in the reaction processes of preparing boric acid, bromination and the like in the preparation process of OLED materials, thereby limiting the practical application; the stability of the benzyl protecting group in carbazole and carbazole derivatives is too high, and the benzyl protecting group is difficult to remove; therefore, it is necessary to develop an amino protection and deprotection method, which is convenient for protection, free from limitation, convenient for deprotection and free from byproducts.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an amino protection and deprotection method of carbazole and similar derivatives, which ensures the conversion rate of protection on carbazole and similar derivatives, ensures the stability of products subjected to protection, has moderate stability on common inorganic acid and alkali, is relatively mild in the protection removal process, is easy to realize and has high deprotection conversion rate.
In order to solve the technical problem, the technical scheme of the invention is as follows: a method for protecting and deprotecting amine groups of carbazole and carbazole-like derivatives comprises the following steps:
step 1: and in the protection process, reacting carbazole and carbazole similar derivatives A with 1, 2-dichloroethane to generate-N-chloroethyl protection products B, and continuing to perform C-C or C-N coupling reaction on the B to convert the B 'into B', wherein the molar ratio of the carbazole and carbazole similar derivatives A to the 1, 2-dichloroethane is 1: 5-10;
step 2: deprotection process, reaction of N-chloroethyl protection product B or B ' with alkali metal salt of alcohol to remove-N-chloroethyl and generate corresponding carbazole and carbazole analog derivative A or A ', wherein the molar ratio of-N-chloroethyl protection product B or B ' to alkali metal salt of alcohol is 1: 1 to 1.5.
Preferably, the step 1 specifically comprises: reacting carbazole and carbazole similar derivatives A with 1, 2-dichloroethane in a solution of potassium hydroxide in heavy pyridine to protect active hydrogen of amino groups to generate an-N-chloroethyl protection product B, and continuing C-C or C-N coupling on the B to convert the product into B', wherein the molar ratio of carbazole and carbazole similar derivatives A to potassium hydroxide is 1: 3-5, wherein the molar ratio of the carbazole and the carbazole similar derivative A to the heavy pyridine solution is 1: 4 to 6.
Preferably, the step 1 specifically comprises:
step 1-1: dissolving carbazole and carbazole similar derivative A into a heavy pyridine solution;
step 1-2: adding potassium hydroxide into the mixture obtained in the step 1-1 in batches, heating to 60-80 ℃, stirring and activating for 3-4 h;
step 1-3: cooling the activated solution obtained in the step 1-2 to 20-25 ℃, and then adding 1, 2-dichloroethane at one time;
step 1-4: after the steps 1-3 are finished, the temperature is raised to 70-80 ℃ again, the reaction is kept for 6-8 h until the protection is complete, a-N-chloroethyl protection product B reaction system is obtained, and the B can be converted into B' by reaction after the C-C or C-N coupling is continuously carried out.
Preferably, the solution of the heavy pyridine is a quinoline solution or an isoquinoline solution.
Preferably, the post-treatment of the reaction system of the-N-chloroethyl protection product B in the steps 1 to 4 is as follows: cooling the reaction system of the-N-chloroethyl protection product B to 20-25 ℃, then fully acidifying with hydrochloric acid, then extracting with dichloroethane, extracting an organic phase, fully washing solvent quinoline with hydrochloric acid to remove the solvent quinoline, then washing the organic phase with water to be neutral, then drying the organic phase with anhydrous sodium sulfate, and finally concentrating the organic phase under reduced pressure to obtain an oily crude product-N-chloroethyl protection product B.
Preferably, the step 2 specifically comprises:
step 2-1: dissolving the-N-chloroethyl protection product B or B 'into DMF, wherein the dosage ratio of the-N-chloroethyl protection product B or B' to the DMF is 1 g: 5ml of the solution;
step 2-2: and (3) adding alkali metal salt of alcohol into the solution obtained in the step (2-1), slowly heating to 120-135 ℃ under stirring, and reacting for 3-4 h under heat preservation to obtain a reaction system of carbazole and carbazole similar derivatives A or A'.
Preferably, the reaction system post-treatment of carbazole and carbazole analog derivative a or a' in step 2-2 is: extracting a reaction system of carbazole and carbazole similar derivative A or A 'by using dichloroethane, washing to remove DMF (dimethyl formamide), drying an dichloroethane organic phase by using anhydrous sodium sulfate, concentrating under reduced pressure to dry, pulping and dispersing by using N-heptane to obtain a de-N-chloroethyl group, and generating corresponding carbazole and carbazole similar derivative A or A'.
Preferably, the alkali metal salt of the alcohol is sodium methoxide or sodium ethoxide.
Compared with the prior art, the invention has the advantages that:
(1) the method realizes the upper protection of carbazole or similar carbazole derivatives (aromatic secondary amine) by using 1, 2-dichloroethane as a protective group, and performs deprotection of carbazole or similar carbazole derivatives by using alkali metal salt of alcohol, so that the product of the upper protection has moderate stability, the deprotection process is relatively mild, the preparation and the use are convenient, and a reference scheme is provided for the protection of other types of halogenated alkanes as secondary amine;
(2) the stability of the upper protection product prepared by the invention is more stable than silanes and lower than benzyl, and the upper protection product is stable to common acids (hydrochloric acid, dilute sulfuric acid, dilute nitric acid, acetic acid and the like) and inorganic bases (potassium carbonate, sodium hydroxide, potassium hydroxide and the like); the stability to organic alkali is better in a non-polar solvent;
(3) the prepared upper protection product has good tolerance to most of aryl substituted functional groups, the upper protection group used in carbazole and carbazole derivatives has little influence on the transformation and reaction processes of other substituent groups on benzene rings, the implementation process of the reaction is greatly facilitated, and the protection and deprotection processes have better comprehensive practical value than benzyl and silyl protection groups;
(4) the raw materials used in the invention are easily available and safe, the operation in the experimental process is relatively mild, the conversion rate of the upper protection and the deprotection is high, and the method is suitable for further amplifying the preparation process.
Drawings
FIG. 1, hydrogen spectrum of a1 product in example 1 of the present invention;
FIG. 2, the hydrogen spectrum of the b1 product in inventive example 2.
Detailed Description
The present invention is illustrated below with reference to specific examples, wherein the raw materials, solvents and catalysts are all conventional commercial products, and the following examples are provided to illustrate the present invention but are not intended to limit the scope of the present invention.
The invention discloses an amido protection and deprotection method of carbazole and carbazole similar derivatives, which comprises the following steps:
step 1: and in the protection process, reacting carbazole and carbazole similar derivatives A with 1, 2-dichloroethane to generate-N-chloroethyl protection products B, and continuing to perform C-C or C-N coupling reaction on the B to convert the B 'into B', wherein the molar ratio of the carbazole and carbazole similar derivatives A to the 1, 2-dichloroethane is 1: 5-10;
step 2: deprotection process, reaction of N-chloroethyl protection product B or B ' with alkali metal salt of alcohol to remove-N-chloroethyl and generate corresponding carbazole and carbazole analog derivative A or A ', wherein the molar ratio of-N-chloroethyl protection product B or B ' to alkali metal salt of alcohol is 1: 1 to 1.5.
Preferably, the step 1 specifically comprises: reacting carbazole and carbazole similar derivatives A with 1, 2-dichloroethane in a solution of potassium hydroxide in heavy pyridine to protect active hydrogen of amino groups to generate an-N-chloroethyl protection product B, and continuing C-C or C-N coupling on the B to convert the product into B', wherein the molar ratio of carbazole and carbazole similar derivatives A to potassium hydroxide is 1: 3-5, wherein the molar ratio of the carbazole and the carbazole similar derivative A to the heavy pyridine solution is 1: 4 to 6.
Preferably, the step 1 specifically comprises:
step 1-1: dissolving carbazole and carbazole similar derivative A into a heavy pyridine solution;
step 1-2: adding potassium hydroxide into the mixture obtained in the step 1-1 in batches, heating to 60-80 ℃, stirring and activating for 3-4 h;
step 1-3: cooling the activated solution obtained in the step 1-2 to 20-25 ℃, and then adding 1, 2-dichloroethane at one time;
step 1-4: after the steps 1-3 are finished, the temperature is raised to 70-80 ℃ again, the reaction is kept for 6-8 h until the protection is complete, a-N-chloroethyl protection product B reaction system is obtained, and the B can be converted into B' by reaction after the C-C or C-N coupling is continuously carried out.
Preferably, the solution of the heavy pyridine is a quinoline solution or an isoquinoline solution.
Preferably, the post-treatment of the reaction system of the-N-chloroethyl protection product B in the steps 1 to 4 is as follows: cooling the reaction system of the-N-chloroethyl protection product B to 20-25 ℃, then fully acidifying with hydrochloric acid, then extracting with dichloroethane, extracting an organic phase, fully washing solvent quinoline with hydrochloric acid to remove the solvent quinoline, then washing the organic phase with water to be neutral, then drying the organic phase with anhydrous sodium sulfate, and finally concentrating the organic phase under reduced pressure to obtain an oily crude product-N-chloroethyl protection product B.
Preferably, the step 2 specifically comprises:
step 2-1: dissolving the-N-chloroethyl protection product B or B 'into DMF, wherein the dosage ratio of the-N-chloroethyl protection product B or B' to the DMF is 1 g: 5ml of the solution;
step 2-2: and (3) adding alkali metal salt of alcohol into the solution obtained in the step (2-1), slowly heating to 120-135 ℃ under stirring, and reacting for 3-4 h under heat preservation to obtain a reaction system of carbazole and carbazole similar derivatives A or A'.
Preferably, the reaction system post-treatment of carbazole and carbazole analog derivative a or a' in step 2-2 is: extracting a reaction system of carbazole and carbazole similar derivative A or A 'by using dichloroethane, washing to remove DMF (dimethyl formamide), drying an dichloroethane organic phase by using anhydrous sodium sulfate, concentrating under reduced pressure to dry, pulping and dispersing by using N-heptane to obtain a de-N-chloroethyl group, and generating corresponding carbazole and carbazole similar derivative A or A'.
Preferably, the alkali metal salt of the alcohol is sodium methoxide or sodium ethoxide.
Example 1
The process of the protection and deprotection of 3-bromocarbazole comprises the following steps:
and (3) protection process:
step 1-1: weighing 123.05g (1eq) of 3-bromocarbazole and dissolving in 387g of quinoline (3 eq);
step 1-2: adding KOH84.15g (3eq) into the solution obtained in the step 1-1 in batches, heating to 60-80 ℃, and stirring and activating for 3-4 h;
step 1-3: after the activated solution is cooled to 20-25 ℃, 396g (8eq) of dichloroethane is added at one time;
step 1-4: after the reaction is finished, the temperature is raised to 70-80 ℃ again, and the reaction is kept for 6-8 h until the 3-bromocarbazole is completely protected.
And (3) post-treatment: cooling the reaction system to 20-25 deg.c, acidifying with hydrochloric acid and extracting with dichloroethane. And extracting an organic phase, fully washing quinoline with hydrochloric acid to remove the quinoline, washing the organic phase to be neutral with water, drying the organic phase with anhydrous sodium sulfate, and concentrating the organic phase under reduced pressure to obtain an oily crude product. The crude product was freeze-crystallized from ethanol and filtered to obtain a white solid powder, which was then dried to obtain 140.4g of (a1), 99.8% in yield 91%.
The hydrogen spectrum of the a1 product is: 1H NMR (500MHz, Chloroform) δ 8.22-8.12 (m,1H),8.05(d, J ═ 2.8Hz,1H), 7.59-7.52 (m,2H), 7.47-7.28 (m,3H),4.77(t, J ═ 14.9Hz,2H),4.05(t, J ═ 14.9Hz, 2H).
The carbon spectrum data of the a1 product are as follows: 13CNMR (CDCl3,75MHZ) d42.5,60.5,101.9,108.7,109.1,118.7,110.5,121.1,124.6,126.0,128.2,129.8,134.2,138.6.
Deprotection process:
step 2-1: 51.7g (1.0eq) of a1 prepared were taken and dissolved in 250ml of DMF solution;
step 2-2: and adding 13.6g (1.5eq) of sodium methoxide into the system in the step 2-1, slowly heating to 120-135 ℃ under stirring, and keeping the temperature for reaction for 3-4 h until the TLC tracking reaction of a1 is complete.
And (3) post-treatment: extracting a reaction system by using dichloroethane, washing the reaction system by using water to remove DMF (dimethyl formamide), drying a dichloroethane organic phase by using anhydrous sodium sulfate, concentrating the dried dichloroethane organic phase under reduced pressure, pulping the dried dichloroethane organic phase by using n-heptane, and dispersing the obtained product to obtain 39.16g of white 3-bromocarbazole, wherein the content is 99.5 percent by HPLC (high performance liquid chromatography) detection, and the yield is 95 percent.
Example 2
The up-protection and deprotection process of 11H-benzo [ a ] carbazole comprises the following specific reaction processes:
and (3) protection process:
step 1-1: weighing 54.31g (1eq) of 11H-benzo [ a ] carbazole and dissolving in 129g of quinoline (4 eq);
step 1-2: adding KOH42.07g (3eq) into the solution obtained in the step 1-1 in batches, and then heating the system to 60-80 ℃, stirring and activating for 3-4 h;
step 1-3: cooling the activated solution to 20-25 ℃, and adding 198g (8eq) of dichloroethane at one time;
step 1-4: after the reaction is finished, the temperature is raised to 70-80 ℃ again, and the reaction is kept for 6-8H until the 11H-benzo [ a ] carbazole is completely protected.
And (3) post-treatment: cooling the reaction system to 20-25 deg.c, acidifying with hydrochloric acid and extracting with dichloroethane. And extracting an organic phase, fully washing quinoline with hydrochloric acid to remove the quinoline, washing the organic phase to be neutral with water, drying the organic phase with anhydrous sodium sulfate, and concentrating the organic phase under reduced pressure to obtain a viscous crude product. The crude product is frozen and crystallized by ethanol, and is filtered to obtain white solid powder, and 60.8g (b1) is obtained after drying, the content is 99.6 percent, and the yield is 87 percent.
b1 product hydrogen spectrum: 1H NMR (500MHz, Chloroform) δ 8.59-8.45 (m,1H),8.34(dd, J ═ 15.0,3.1Hz,1H), 8.21-8.03 (m,1H), 7.90-7.58 (m,5H),7.41(td, J ═ 15.0,3.0Hz,1H),7.14(td, J ═ 15.0,3.1Hz,1H),4.77(t, J ═ 14.8Hz,2H),4.05(t, J ═ 14.8Hz, 2H).
b1 carbon spectrum data of product: 13CNMR (CDCl3,75 MHZ): d43.1,61.9,103.3,108.9,111.2,118.7,121.4,121.6,121.9,122.2,123.0,124.5,127.6,128.0,133.2,135.4,139.5,143.8.
Deprotection process:
step 2-1: 41.96g (1eq) of prepared b1 was taken and dissolved in 280ml of DMF solution;
step 2-2: and adding 12.15g (1.5eq) of sodium methoxide into the system in the step 2-1, slowly heating to 120-135 ℃ under stirring, and keeping the temperature for reaction for 3-4 h until the TLC tracking reaction of the b1 is complete.
And (3) post-treatment: extracting a reaction system by using dichloroethane, washing by using water to remove DMF (dimethyl formamide), drying a dichloroethane organic phase by using anhydrous sodium sulfate, concentrating under reduced pressure to be dry, pulping by using n-heptane to disperse to obtain gray-white 11H-benzo [ a ] carbazole 31,28g, wherein the content is 99.1% by HPLC (high performance liquid chromatography) detection, and the yield is 96%.
Example 3
The upper protection and deprotection process of carbazole and carbazole analog derivative A, the upper protection process:
step 1-1: weighing carbazole and carbazole similar derivatives A (1eq) and dissolving the carbazole and carbazole similar derivatives A (1eq) into a quinoline solution or an isoquinoline solution (4-6 eq);
step 1-2: adding KOH (3-5 eq) into the solution obtained in the step 1-1 in batches, heating to 60-80 ℃, and stirring and activating for 3-4 hours;
step 1-3: cooling the activated solution to 20-25 ℃, and adding dichloroethane (5-10 eq) at one time;
step 1-4: after the reaction is finished, the temperature is raised to 70-80 ℃ again, and the reaction is kept for 6-8 h until the 3-bromocarbazole is completely protected.
And (3) post-treatment: cooling the reaction system to 20-25 deg.c, acidifying with hydrochloric acid and extracting with dichloroethane. And extracting an organic phase, fully washing quinoline with hydrochloric acid to remove the quinoline, washing the organic phase to be neutral with water, drying the organic phase with anhydrous sodium sulfate, and concentrating the organic phase under reduced pressure to obtain an oily crude product. And (3) freezing and crystallizing the crude product by using ethanol, filtering to obtain white solid powder, and drying to obtain the-N-chloroethyl protection product B.
Deprotection process:
step 2-1: dissolving the-N-chloroethyl protection product B or B' (1.0eq) in a DMF solution;
step 2-2: and adding sodium methoxide (1-1.5 eq) into the system in the step 2-1, slowly heating to 120-135 ℃ under stirring, and carrying out heat preservation reaction for 3-4 h until the TLC tracking reaction of the-N-chloroethyl protection product B or B' is complete.
And (3) post-treatment: extracting reaction system with dichloroethane, washing to remove DMF, drying dichloroethane organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, pulping with n-heptane, and dispersing to obtain carbazole and carbazole similar derivative A or A'.
The basic process of the reaction of the present invention can be briefly described by the chemical formula shown below:
the protection process is a common SN2 reaction process, carbazole and carbazole similar derivatives A are used for protecting active hydrogen of amino in quinoline solution of potassium hydroxide by using 1, 2-dichloroethane (dichloroethane mentioned in the article refers to 1, 2-dichloroethane) as a raw material (the protection reaction temperature on the carbazole and carbazole similar derivatives A is generally finished between 70 ℃ and 80 ℃, the reaction time is generally 6h to 8h), an N-chloroethyl protection product B is generated, the B can be continuously subjected to a conventional C-C or C-N coupling reaction process and converted into B', the B is stable to common acids (hydrochloric acid, dilute nitric acid, dilute sulfuric acid, acetic acid and the like) and inorganic bases (potassium carbonate, sodium hydroxide, potassium hydroxide and the like), and the carbazole and carbazole similar derivatives A also have good stability to organic bases (potassium acetate, sodium tert-butoxide, potassium tert-butoxide) in a non-polar solvent.
The mechanism of the deprotection reaction is described as follows:
reacting the-N-chloroethyl protection product B or B 'in a DMF solution in the presence of sodium methoxide at 120-135 ℃ to remove-N-chloroethyl to generate corresponding A or A', wherein the reaction time is 3-4 h, the sodium methoxide reacts with DMF to form an active intermediate a, the a and the-N-chloroethyl protection product B or B 'form a transition state B, the B is further converted into a five-membered ring transition state c, the c forms d through intramolecular electron transfer and proton transfer, and then forms e, and the e is further dissociated to generate the corresponding A or A'.
The method mainly aims at the protection of carbazole and carbazole derivatives, and other secondary amines can also be used; the experimental scheme uses dichloroethane as a protective group, and other similar halogenated hydrocarbons like dichloroethane may also be suitable; the protecting group is suitable for quinoline or isoquinoline as a solvent, and other solvents with similar properties to quinoline or isoquinoline are also suitable; deprotection is carried out using sodium methoxide, sodium ethoxide and like bases will also have the same or similar effect.
The method realizes the upper protection of carbazole or similar carbazole derivatives (aromatic secondary amine) by using 1, 2-dichloroethane as a protective group, and performs deprotection of carbazole or similar carbazole derivatives by using alkali metal salt of alcohol, so that the product of the upper protection has moderate stability, the deprotection process is relatively mild, the preparation and the use are convenient, and a reference scheme is provided for the protection of other types of halogenated alkanes as secondary amine.
The stability of the upper protection product prepared by the invention is more stable than silanes and lower than benzyl, and the upper protection product is stable to common acids (hydrochloric acid, dilute sulfuric acid, dilute nitric acid, acetic acid and the like) and inorganic bases (potassium carbonate, sodium hydroxide, potassium hydroxide and the like); the non-polar solvent also has better stability to organic base.
The upper protection product prepared by the invention has good tolerance to most aryl substituted functional groups, the upper protection group used in carbazole and carbazole derivatives has little influence on the transformation and reaction processes of other substituent groups on benzene rings, the implementation process of the reaction is greatly facilitated, and the protection and deprotection processes have better comprehensive practical value than benzyl and silyl protection groups.
The raw materials used in the invention are easily available and safe, the operation in the experimental process is relatively mild, the conversion rate of the upper protection and the deprotection is high, and the method is suitable for further amplifying the preparation process.
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 can 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 can 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 (8)
1. An amino protection and deprotection method of carbazole and carbazole analog derivatives is characterized by comprising the following steps:
step 1: and in the protection process, reacting carbazole and carbazole similar derivatives A with 1, 2-dichloroethane to generate-N-chloroethyl protection products B, and continuing to perform C-C or C-N coupling reaction on the B to convert the B 'into B', wherein the molar ratio of the carbazole and carbazole similar derivatives A to the 1, 2-dichloroethane is 1: 5-10;
step 2: deprotection process, reaction of N-chloroethyl protection product B or B ' with alkali metal salt of alcohol to remove-N-chloroethyl and generate corresponding carbazole and carbazole analog derivative A or A ', wherein the molar ratio of-N-chloroethyl protection product B or B ' to alkali metal salt of alcohol is 1: 1 to 1.5.
2. The method for protecting and deprotecting amine groups of carbazole and carbazole-like derivatives according to claim 1, wherein step 1 specifically comprises: reacting carbazole and carbazole similar derivatives A with 1, 2-dichloroethane in a solution of potassium hydroxide in heavy pyridine to protect active hydrogen of amino groups to generate an-N-chloroethyl protection product B, and continuing C-C or C-N coupling on the B to convert the product into B', wherein the molar ratio of carbazole and carbazole similar derivatives A to potassium hydroxide is 1: 3-5, wherein the molar ratio of the carbazole and the carbazole similar derivative A to the heavy pyridine solution is 1: 4 to 6.
3. The method for protecting and deprotecting amine groups of carbazole and carbazole-like derivatives according to claim 2, wherein step 1 specifically comprises:
step 1-1: dissolving carbazole and carbazole similar derivative A into a heavy pyridine solution;
step 1-2: adding potassium hydroxide into the mixture obtained in the step 1-1 in batches, heating to 60-80 ℃, stirring and activating for 3-4 h;
step 1-3: cooling the activated solution obtained in the step 1-2 to 20-25 ℃, and then adding 1, 2-dichloroethane at one time;
step 1-4: after the steps 1-3 are finished, the temperature is raised to 70-80 ℃ again, the reaction is kept for 6-8 h until the protection is complete, a-N-chloroethyl protection product B reaction system is obtained, and the B can be converted into B' by reaction after the C-C or C-N coupling is continuously carried out.
4. The method for protecting and deprotecting amine groups in carbazole and carbazole-like derivatives according to claim 3, wherein said solution of bipyridine is quinoline solution or isoquinoline solution.
5. The method for protecting and deprotecting amine groups of carbazole and carbazole-like derivatives according to claim 3, wherein the post-treatment of the reaction system of-N-chloroethyl protection product B in steps 1 to 4 is: cooling the reaction system of the-N-chloroethyl protection product B to 20-25 ℃, then fully acidifying with hydrochloric acid, then extracting with dichloroethane, extracting an organic phase, fully washing solvent quinoline or isoquinoline with hydrochloric acid to remove, then washing the organic phase to neutrality with water, then drying the organic phase with anhydrous sodium sulfate, and finally concentrating and drying the organic phase under reduced pressure to obtain an oily crude product-N-chloroethyl protection product B.
6. The method for protecting and deprotecting amine groups of carbazole and carbazole-like derivatives according to claim 1, wherein said step 2 specifically comprises:
step 2-1: dissolving the-N-chloroethyl protection product B or B 'into DMF, wherein the dosage ratio of the-N-chloroethyl protection product B or B' to the DMF is 1 g: 5ml of the solution;
step 2-2: and (3) adding alkali metal salt of alcohol into the solution obtained in the step (2-1), slowly heating to 120-135 ℃ under stirring, and reacting for 3-4 h under heat preservation to obtain a reaction system of carbazole and carbazole similar derivatives A or A'.
7. The method for protecting and deprotecting amine groups of carbazole and carbazole-like derivatives according to claim 6, wherein the reaction system of carbazole and carbazole-like derivatives a or a' in step 2-2 is post-treated by: extracting a reaction system of carbazole and carbazole similar derivative A or A 'by using dichloroethane, washing to remove DMF (dimethyl formamide), drying an dichloroethane organic phase by using anhydrous sodium sulfate, concentrating under reduced pressure to dry, pulping and dispersing by using N-heptane to obtain a de-N-chloroethyl group, and generating corresponding carbazole and carbazole similar derivative A or A'.
8. The method for protecting and deprotecting the amine groups of carbazole and carbazole-like derivatives according to claim 6, wherein said alkali metal salt of alcohol is sodium methoxide or sodium ethoxide.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1061746A (en) * | 1963-08-26 | 1967-03-15 | Ibm | Novel carbazole derivatives,and their preparation |
| CN101531655A (en) * | 2009-04-08 | 2009-09-16 | 中北大学 | 9-((2-methyl-1H-imidazole-1-group) ethyl)-9H-carbazole and preparation method thereof |
| CN106046054A (en) * | 2016-05-19 | 2016-10-26 | 南京工业大学 | Vinyl polymer main body material with electron donor-acceptor structure and preparation and application methods therefor |
| CN106397304A (en) * | 2016-08-31 | 2017-02-15 | 河南省科学院化学研究所有限公司 | Production method of 1-bromocarbazole |
| CN106957381A (en) * | 2017-05-12 | 2017-07-18 | 南京工业大学 | Design, synthesis and the application of the hole mobile material of one perovskite-like solar cell |
| CN107235891A (en) * | 2017-05-24 | 2017-10-10 | 北京八亿时空液晶科技股份有限公司 | A kind of preparation method of 4 bromine carbazole |
| CN113549169A (en) * | 2021-06-15 | 2021-10-26 | 南京工业大学 | Phenylfluorenamine polymer hole transport material and preparation method and application thereof |
| CN113582910A (en) * | 2021-08-27 | 2021-11-02 | 中钢集团南京新材料研究院有限公司 | Synthesis method of 1-bromocarbazole by taking carbazole as raw material |
-
2022
- 2022-01-19 CN CN202210059662.0A patent/CN114349683B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1061746A (en) * | 1963-08-26 | 1967-03-15 | Ibm | Novel carbazole derivatives,and their preparation |
| CN101531655A (en) * | 2009-04-08 | 2009-09-16 | 中北大学 | 9-((2-methyl-1H-imidazole-1-group) ethyl)-9H-carbazole and preparation method thereof |
| CN106046054A (en) * | 2016-05-19 | 2016-10-26 | 南京工业大学 | Vinyl polymer main body material with electron donor-acceptor structure and preparation and application methods therefor |
| CN106397304A (en) * | 2016-08-31 | 2017-02-15 | 河南省科学院化学研究所有限公司 | Production method of 1-bromocarbazole |
| CN106957381A (en) * | 2017-05-12 | 2017-07-18 | 南京工业大学 | Design, synthesis and the application of the hole mobile material of one perovskite-like solar cell |
| CN107235891A (en) * | 2017-05-24 | 2017-10-10 | 北京八亿时空液晶科技股份有限公司 | A kind of preparation method of 4 bromine carbazole |
| CN113549169A (en) * | 2021-06-15 | 2021-10-26 | 南京工业大学 | Phenylfluorenamine polymer hole transport material and preparation method and application thereof |
| CN113582910A (en) * | 2021-08-27 | 2021-11-02 | 中钢集团南京新材料研究院有限公司 | Synthesis method of 1-bromocarbazole by taking carbazole as raw material |
Non-Patent Citations (4)
| Title |
|---|
| JAN PIELICHOWSKI ET AL.: "A Novel Synthesis of N-Vinylcarbazoles: Reaction Conditions and Mechanism of the Side Reaction", 《JOURNAL OF POLYMER SCIENCE: POLYMER LETTERS EDITION》, vol. 23, pages 387 - 393 * |
| JOHN WILEY ET AL.: "POLY-N-VINYLHALOGENOCARBAZOLE I. ON THE SYNTHESIS OF N-VINYLHALOGENOCARBAZOLE", 《POLYMER LETTERS EDITION》, vol. 12, pages 257 - 260 * |
| MARCO A. DE LA MORA ET AL.: "Synthesis of tricyclic-2-aminoindoles by intramolecular 1,3-dipolar cycloaddition of 1-w-azidoalkylindoles", 《TETRAHEDRON LETTERS》, vol. 42, pages 5351, XP004254957, DOI: 10.1016/S0040-4039(01)01006-1 * |
| 黄雄飞 等: "咔唑一偶氮二元化合物的 合成及其二阶非线性光学研究", 《中山大学学报 自然科学版》, vol. 40, no. 4, pages 66 - 69 * |
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