CN106866545A - 1 cycloalkane 5 nitro 1H benzo [D] glyoxaline compound and preparation method thereof - Google Patents
1 cycloalkane 5 nitro 1H benzo [D] glyoxaline compound and preparation method thereof Download PDFInfo
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- CN106866545A CN106866545A CN201710204976.4A CN201710204976A CN106866545A CN 106866545 A CN106866545 A CN 106866545A CN 201710204976 A CN201710204976 A CN 201710204976A CN 106866545 A CN106866545 A CN 106866545A
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- compound
- nitro
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- cycloalkane
- benzo
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- -1 glyoxaline compound Chemical class 0.000 title claims abstract description 19
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 title abstract description 5
- 125000005605 benzo group Chemical group 0.000 title abstract description 3
- 150000001924 cycloalkanes Chemical class 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 238000004366 reverse phase liquid chromatography Methods 0.000 claims abstract description 5
- 229940126214 compound 3 Drugs 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims 1
- 238000013019 agitation Methods 0.000 abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 abstract 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- 229940049706 benzodiazepine Drugs 0.000 description 2
- 244000045947 parasite Species 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 150000004941 2-phenylimidazoles Chemical class 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 240000005308 Juniperus chinensis Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 230000001857 anti-mycotic effect Effects 0.000 description 1
- 230000003356 anti-rheumatic effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 239000002543 antimycotic Substances 0.000 description 1
- 239000003435 antirheumatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OSVHLUXLWQLPIY-KBAYOESNSA-N butyl 2-[(6aR,9R,10aR)-1-hydroxy-9-(hydroxymethyl)-6,6-dimethyl-6a,7,8,9,10,10a-hexahydrobenzo[c]chromen-3-yl]-2-methylpropanoate Chemical compound C(CCC)OC(C(C)(C)C1=CC(=C2[C@H]3[C@H](C(OC2=C1)(C)C)CC[C@H](C3)CO)O)=O OSVHLUXLWQLPIY-KBAYOESNSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles 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 in position 2
Abstract
The invention discloses 1 cycloalkane of a class 5 nitro 1H benzo [D] glyoxaline compound and preparation method thereof, in the flask with magnetic agitation, add N ' (nitrobenzene of 2 F 5) N of 0.4mmol, N dimethyl carbonamidines, the amine of 0.5mL dry HMPA and 2.8mmol, reactant mixture heats 70 120min at 150 230 DEG C, and product is by obtaining target product compound after Reverse phase chromatography.Preparation method of the present invention is simple, one pot process such compound (amine replaces fluorine and cyclization), high selectivity is shown compared with conventional method, raw material is easy to get, benzimidazole group exists in many drug molecules in gained compound structure, nitro in molecule can be reduced to amino, therefore, such compound can be used widely.
Description
Technical field
The present invention relates to the benzimidazole compound of the cycloalkyl of class N- substitutions, and in particular to 1- cycloalkane -5- nitros -
1H- benzos [D] glyoxaline compound and preparation method thereof.
Background technology
In decades, the synthesis and application study of benzimidazole and its derivative is the study hotspot of Minute Organic Synthesis；
Benzimidazoles compound is a kind of containing two Benzoheterocyclic compounds of nitrogen-atoms, and benzimidazole and its derivative are anti-
The aspect such as cancer, antimycotic, easing pain and diminishing inflammation, antirheumatic, expelling parasite has critically important medical value.Benzimidazoles compound or one
Plant the excellent corrosion inhibiter corroded in sour environment for carbon steel；Su Guoqiang, Guo Diliang, Liu Yu, Zhu Lan, Bian Jun, Zhu Chongliang are reported
The road preparation method (CN1425654A) of 2- alkoxybenzimidazole compounds.
Li Yan, Ma Huiqiang, Wang Yulu report a series of benzimidazoles and derivative (organic chemistry, the 2nd phase in 2008,
210~217).
Zeng Qingle etc. reports the synthetic method (A of CN 103755642) of 2- aryl benzimidazoles.
Hao Xinqi etc. discloses 3- (2- nitro -1- phenethyls) -2- (2- phenylimidazoles simultaneously [1,2- α] pyridine) class compound
(CN 105085520 A)。
Old Chinese juniper China, Lin Weizhong are condensed to form the double Schiff's bases of intramolecular using o-phenylenediamine and two molecule aldehyde, by occurring to divide
Reset in sub and synthesized 1- substitution -2- aryl benzimidizole derivatives.
Benzimidazoles compound not only has the bioactivity such as sterilized, antitumor, expelling parasite, and due to being deposited in its structure
In strong electron-withdrawing group nitro, the nitro in molecule can also be reduced to amino, therefore, such compound can be used widely.
In sum, research and development structure novelty, the benzimidazoles compound of performance efficiency have important reality meaning
Justice and scientific value.There is no 1- cycloalkane -5- nitro -1H- benzene in published benzimidazoles compound documents and materials
And [D] glyoxaline compound.
The content of the invention
It is an object of the invention to provide 1- cycloalkane -5- nitro -1H- benzos [D] glyoxaline compounds and its preparation side
Method, to solve above-mentioned technical problem.
To achieve the above object, the technical solution adopted by the present invention is:
1- cycloalkane -5- nitro -1H- benzo [D] glyoxaline compound, the compound is the compound shown in below general formula
3：
Wherein：R be △,,
Present invention also offers the preparation method of 1- cycloalkane -5- nitro -1H- benzo [D] glyoxaline compound, carrying
In the flask of magnetic agitation, add N ' (2-F-5- nitrobenzene)-N, N- dimethyl-formamidines, 0.5mL of 0.4mmol dry
The amine 2 of HMPA and 2.8mmol, 70-120min is heated by reactant mixture at 150-230 DEG C, and product is by anti-phase color
Spectrum obtains target product compound 3 after purification.
Beneficial effects of the present invention are：Preparation method of the present invention is simple, and (amine replaces fluorine for one pot process such compound
And cyclization), high selectivity is shown compared with conventional method, raw material is easy to get, benzo miaow in gained compound structure
Oxazolyl group exists in many drug molecules, and the nitro in molecule can be reduced to amino, and such compound is widely used.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated.
Embodiment 1
Preparation method：
In a reaction tube with magnetic agitation, N ' (2-F-5- nitrobenzene)-N, N- dimethyl-formamidines are added
(0.4mmol), 0.5mL dry HMPA and amine 2a (2.8mmol), reactant mixture heats 100min at 180 DEG C, and reaction is produced
Thing is by obtaining target product compound 3a after Reverse phase chromatography.Yield is 22%.1H NMR(500MHz,MeOD)：δppm
1.07-1.17 (m, 2H), 1.21-1.32 (m, 2H), 3.60 (dt, J=7.02,3.51Hz, 1H), 7.81-7.88 (m, 1H),
8.22-8.32 (m, 1H), 8.45 (s, 1H), 8.55 (br.s., 1H)；13C NMR (126MHz, MeOD)：δ ppm 5.32,
42.80,11.31,115.63,118.80,139.51,142.57,144.46,148.01；HRMS calcd.for C10H9N3O2：
203.0695, found：203.0682.
Embodiment 2
Preparation method：In a reaction tube with magnetic agitation, N ' (2-F-5- nitrobenzene)-N, N- diformazans are added
Base-carbonamidine (0.4mmol), 0.5mL dry HMPA and amine 2b (3.3mmol), reactant mixture heats 80min at 230 DEG C,
Product is by obtaining target product compound 3b after Reverse phase chromatography.Yield is 51%.
1H NMR(500MHz,MeOD)：δ ppm 1.94-2.15 (m, 2H), 2.51-2.73 (m, 4H), 4.98-5.10 (m,
1H), 7.72 (d, J=8.85Hz, 1H), 8.20 (d, J=8.85Hz, 1H), 8.54 (d, J=8.85Hz, 2H)；13C NMR
(126MHz,MeOD)：δ ppm 15.12,29.83,47.50,47.66,47.84,48.01,48.18,48.35,48.52,
48.63,48.66,50.46,111.27,115.61,118.50,137.66,142.76,144.22,145.75；HRMS
calcd.for C11H11N3O2：217.0851, found：217.0838.
Embodiment 3
Preparation method：In a reaction tube with magnetic agitation, N ' (2-F-5- nitrobenzene)-N, N- diformazans are added
Base-carbonamidine (0.4mmol), 0.5mL dry HMPA and amine 2c (3.3mmol), reactant mixture heats 90min at 220 DEG C,
Product is by obtaining target product compound 3c after Reverse phase chromatography.Yield is 37%.1H NMR(500MHz,
MeOD)：δ ppm 1.47-1.58 (m, 4H), 1.81-2.06 (m, 4H), 3.79-3.86 (m, 1H), 7.71 (d, J=8.85Hz,
1H), 8.19 (d, J=8.85Hz, 1H), 8.53 (d, J=8.85Hz, 2H)；HRMS calcd.for C12H13N3O2：
231.1008, found：231.1004.
Obviously, embodiments described above is only a part of embodiment of the invention, rather than whole embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art obtained under the premise of creative work is not made it is all its
His embodiment, belongs to the scope of protection of the invention.
Claims (2)
1.1- cycloalkane -5- nitro -1H- benzo [D] glyoxaline compound, it is characterised in that the compound is below general formula institute
The compound 3 for showing：
Wherein：R is
The preparation method of 2.1- cycloalkane -5- nitro -1H- benzo [D] glyoxaline compound, it is characterised in that with magnetic force
In the flask of stirring, add 0.4mmol N ' (2-F-5- nitrobenzene)-N, N- dimethyl-formamidines, the dry HMPA of 0.5mL and
The amine 2 of 2.8mmol, 70-120min is heated by reactant mixture at 150-230 DEG C, and product is by Reverse phase chromatography
After obtain target product compound 3.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107445899A (en) * | 2017-07-19 | 2017-12-08 | 枣庄学院 | A kind of benzimidazoles compound and preparation method thereof |
| CN108863820A (en) * | 2018-07-30 | 2018-11-23 | 枣庄学院 | A kind of synthetic method of substituted o-phenylenediamine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004092181A1 (en) * | 2003-04-11 | 2004-10-28 | Smithkline Beecham Corporation | Heterocyclic mchr1 antagonists |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004092181A1 (en) * | 2003-04-11 | 2004-10-28 | Smithkline Beecham Corporation | Heterocyclic mchr1 antagonists |
Non-Patent Citations (3)
| Title |
|---|
| GHOTAS EVINDAR ET AL.,: "Copper- and Palladium-Catalyzed Intramolecular Aryl Guanidinylation: An Efficient Method for the Synthesis of 2-Aminobenzimidazoles", 《ORG. LETT.》 * |
| HAMDAN S. AL-EBAISAT: "Synthesis and Biological Activities of Some Benzimidazoles Derivatives", 《J. APPL. SCI. ENVIRON. MANAGE. SEPT》 * |
| ZHANG HU ET AL.,: "Synthesis and biological evaluation of 1-cyano-2-aminobenzimidazole derivatives as a novel class of antitumor agents", 《MED CHEM RES》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107445899A (en) * | 2017-07-19 | 2017-12-08 | 枣庄学院 | A kind of benzimidazoles compound and preparation method thereof |
| WO2019015112A1 (en) * | 2017-07-19 | 2019-01-24 | 鲁南煤化工工程技术研究院 | Benzoimidazole compound and preparation method therefor |
| US20200002291A1 (en) * | 2017-07-19 | 2020-01-02 | Engineering And Technology Institute Of Lunan Coal Chemical Engineering | Benzimidazole Compound and Preparation Method Thereof |
| JP2020518661A (en) * | 2017-07-19 | 2020-06-25 | シャンドン ルーナン リサーチ インスティテュート オブ コール ケミカル エンジニアリング アンド テクノロジーＳｈａｎｄｏｎｇ Ｌｕｎａｎ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ ｏｆ Ｃｏａｌ Ｃｈｅｍｉｃａｌ Ｅｎｇｉｎｅｅｒｉｎｇ ａｎｄ Ｔｅｃｈｎｏｌｏｇｙ | Benzimidazole compound and method for producing the same |
| US10787420B2 (en) * | 2017-07-19 | 2020-09-29 | Shandong Engineering And Technology Institute Of Lunan Coal Chemical Engineering | Benzimidazole compound and preparation method thereof |
| CN108863820A (en) * | 2018-07-30 | 2018-11-23 | 枣庄学院 | A kind of synthetic method of substituted o-phenylenediamine |
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