CN105175412B - A kind of synthetic method of 2- amino -1,10- Phen - Google Patents
A kind of synthetic method of 2- amino -1,10- Phen Download PDFInfo
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- CN105175412B CN105175412B CN201510511148.6A CN201510511148A CN105175412B CN 105175412 B CN105175412 B CN 105175412B CN 201510511148 A CN201510511148 A CN 201510511148A CN 105175412 B CN105175412 B CN 105175412B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention provides a kind of 2- amino -1; the synthetic method of 10- Phen; this method are as follows: in aprotic solvent, in the presence of a base, 1; 10- Phen -2- ketone and sulfochlorides occur sulfonylation and obtain 1; 10- Phen -2- sulphonic acid ester, 1,10- Phen -2- sulphonic acid ester is without isolation; with ammonium hydroxide heating reaction, isolated 2- amino -1,10- Phen.The optional toluene of the aprotic solvent used in this method, dimethylbenzene, dimethyl sulfoxide, diethylene glycol dimethyl ether etc.；The optional triethylamine of alkali, 1- methyl piperidine, pyridine, sodium carbonate etc.；The optional p-methyl benzene sulfonic chloride of sulfochlorides, benzene sulfonyl chloride, arylsulfonyl chloride, mesyl chloride etc., wherein it is preferred that p-methyl benzene sulfonic chloride.
Description
Technical field
The present invention relates to the preparation methods of 2- amino -1,10- Phen.
Background technique
1,10- Phen is a classical ligand, and 1,10- Phen and its derivative play in Coordinative Chemistry
Important role, as good metal ligand, they antibacterial it is antitumor, catalysis reaction, supramolecular chemistry, DNA probe, divide
Sub switch etc. is widely used.It is to obtain 1,10- Phen to spread out that structural modification is carried out on the basis of 1,10- Phen
The important channel of biology, the derivative that the method obtains is concentrated mainly on 2,9-, 3,8-, 5,6- positions, wherein 5,6- derivatives
Object is most.
2- amino -1,10- Phen is 2 bit derivants important in 1,10- derivative of phenanthroline, main synthesis
Method be by 2- it is halogenated -1,10- Phen aminating reaction obtains, since access approaches are less, 2- amino-reported in the literature
1,10- Phen performance and application study are also relatively fewer.
Summary of the invention
It is an object of the invention to: a kind of synthetic method of 2- amino -1,10- Phen is provided, increases target and produces
The available sources of object.The present invention synthesizes 2- amino -1,10- Phen using following route thus:
The reaction method for raw material, obtains intermediate 1 through sulfonylation, 10- is adjacent with 1,10- Phen -2- ketone (2)
Phenanthroline -2- sulphonic acid ester (3), intermediate react to obtain 2- amino -1,10- Phen (1) without isolation with ammonium hydroxide.
2- amino -1,10- Phen preparation method is as follows: in aprotic solvent, in the presence of a base, 1,10- neighbour's Féraud
Quinoline -2- ketone (2) and sulfochlorides occur sulfonylation and obtain 1,10- Phen -2- sulphonic acid ester (3), 1,10- neighbour's Féraud
Quinoline -2- sulphonic acid ester (3) heats reaction, isolated 2- amino -1,10- Phen (1) with ammonium hydroxide without isolation.The program
In the optional toluene of aprotic solvent, dimethylbenzene, dimethyl sulfoxide, the diethylene glycol dimethyl ether etc. used；The optional triethylamine of alkali, 1-
Methyl piperidine, pyridine, sodium carbonate etc.；The optional p-methyl benzene sulfonic chloride of sulfochlorides, benzene sulfonyl chloride, arylsulfonyl chloride, methylsulphur
Acyl chlorides etc., wherein it is preferred that p-methyl benzene sulfonic chloride, and the impurity in products that mesyl chloride eventually forms is more, yield is lower.
Specific embodiment
Embodiment 1
Addition 20mL toluene, 1.96g (10mmol) 1,10- Phen -2- ketone, 9.53g (50mmol) are right in flask
Toluene sulfonyl chloride, 5g (50mmol) 1- methyl piperidine, stirring are heated to 112 DEG C of back flow reaction 12h (TLC tracking), slightly cold
But, concentrated ammonia liquor 20mL, heating reflux reaction 4h is added, it is cooling, 20mL water is added, is layered, water layer is extracted with 20mL chloroform, is merged
Organic layer is concentrated to dryness, and residue purifies (mobile phase is ethyl acetate) with silica gel column chromatography, obtains white solid 1.53g, yield
187~189 DEG C of 78%, Mp.
Embodiment 2
20mL dimethylbenzene, 1.96g (10mmol) 1,10- Phen -2- ketone, 11.4g (100mmol) are added in flask
Mesyl chloride, 10.1g (100mmol) triethylamine, stirring are heated to 70 DEG C of reaction 6h (TLC tracking), slightly cooling, and dense ammonia is added
Water 20mL, heating reflux reaction 6h, it is cooling, 40mL water is added, is layered, water layer is extracted with 20mL chloroform, merges organic layer, concentration
To doing, residue purifies (mobile phase is ethyl acetate) with silica gel column chromatography, obtains white solid 0.22g, yield 11%, Mp 187
~189 DEG C.
Embodiment 3
20mL dimethyl sulfoxide, 1.96g (10mmol) 1,10- Phen -2- ketone, 9.53g are added in flask
(50mmol) arylsulfonyl chloride, 5.4g (50mmol) sodium carbonate, stirring are heated to 90 DEG C of reaction 6h (TLC tracking), slightly cooling,
Concentrated ammonia liquor 20mL, heating reflux reaction 4h is added, solvent is concentrated under reduced pressure, residue adds 20mL water, and water layer is extracted with 20mL*2 chloroform
It takes, extract liquor is concentrated to dryness, and residue purifies (mobile phase is ethyl acetate) with silica gel column chromatography, obtains white solid 1.0g, is received
Rate 51%, 187~189 DEG C of Mp.
Embodiment 4
20mL diethylene glycol dimethyl ether, 1.96g (10mmol) 1,10- Phen -2- ketone, 3.53g are added in flask
(20mmol) benzene sulfonyl chloride, 1.58g (20mmol) pyridine, stirring are heated to 120 DEG C of reaction 8h (TLC tracking), slightly cooling, add
Entering concentrated ammonia liquor 20mL, heating reflux reaction 4h, solvent is concentrated under reduced pressure, residue adds 20mL water, and water layer is extracted with 20mL*2 chloroform,
Extract liquor is concentrated to dryness, and residue purifies (mobile phase is ethyl acetate) with silica gel column chromatography, obtains white solid 1.10g, yield
187~189 DEG C of 56%, Mp.
Claims (5)
1. a kind of synthetic method of 2- amino -1,10- Phen, the method is as follows: in aprotic solvent, in the presence of a base, 1,
10- Phen -2- ketone and sulfochlorides occur sulfonylation and obtain 1,10- Phen -2- sulphonic acid ester, and 1,10- is adjacent
Phenanthroline -2- sulphonic acid ester heats reaction, isolated 2- amino -1,10- Phen with ammonium hydroxide without isolation.
2. a kind of synthetic method of 2- amino -1,10- Phen according to claim 1, it is characterised in that: method institute
The optional p-methyl benzene sulfonic chloride of the sulfochlorides stated, benzene sulfonyl chloride, arylsulfonyl chloride, mesyl chloride.
3. a kind of synthetic method of 2- amino -1,10- Phen according to claim 1, it is characterised in that: method institute
The molar ratio of the sulfochlorides and 1,10- Phen -2- ketone stated is 10:1~2:1.
4. a kind of synthetic method of 2- amino -1,10- Phen according to claim 1, it is characterised in that: method institute
The optional toluene of the aprotic solvent stated, dimethylbenzene, dimethyl sulfoxide, diethylene glycol dimethyl ether.
5. a kind of synthetic method of 2- amino -1,10- Phen according to claim 1, it is characterised in that: method institute
The optional triethylamine of the alkali stated, 1- methyl piperidine, pyridine, sodium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510511148.6A CN105175412B (en) | 2015-08-19 | 2015-08-19 | A kind of synthetic method of 2- amino -1,10- Phen |
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| CN201510511148.6A CN105175412B (en) | 2015-08-19 | 2015-08-19 | A kind of synthetic method of 2- amino -1,10- Phen |
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| CN105175412A CN105175412A (en) | 2015-12-23 |
| CN105175412B true CN105175412B (en) | 2019-05-24 |
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| CN105884769B (en) * | 2016-04-06 | 2017-07-07 | 苏州杉洋医药科技有限公司 | The method of one kind synthesis amine of 1,10 phenanthroline 2 |
| CN106588765A (en) * | 2016-09-06 | 2017-04-26 | 天津科技大学 | Method for hydroxylation of nitrogen oxide C2-position |
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| CN103183677B (en) * | 2013-05-03 | 2015-07-01 | 南京信息工程大学 | Application of ammonium thiosulfate as reducing agent in preparation of 5-amino-1,10-phenanthroline |
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Effective date of registration: 20200713 Address after: Room 101, building d6-1, No. 555, Chuangye Road, Dayun Town, Jiashan County, Jiaxing City, Zhejiang Province Patentee after: Zhejiang saifute New Material Technology Co.,Ltd. Address before: 318000, No. 1139, City Avenue, Jiaojiang District, Zhejiang, Taizhou Co-patentee before: Guo Haichang Patentee before: TAIZHOU University |
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Effective date of registration: 20230411 Address after: Room 1901, Building E1, Zhihui Zhongchuang Center, No. 3 Xiyuanba Road, Xihu District, Hangzhou City, Zhejiang Province, 310012 Patentee after: Hangzhou Shengda Applied Materials Co.,Ltd. Address before: Room 101, building d6-1, 555 Chuangye Road, Dayun Town, Jiashan County, Jiaxing City, Zhejiang Province, 314100 Patentee before: Zhejiang saifute New Material Technology Co.,Ltd. |
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