CN105820137B - A method of synthesizing two aminated aromatic hydrocarbons of ortho position using domino aryne precursor - Google Patents
A method of synthesizing two aminated aromatic hydrocarbons of ortho position using domino aryne precursor Download PDFInfo
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- CN105820137B CN105820137B CN201610177424.4A CN201610177424A CN105820137B CN 105820137 B CN105820137 B CN 105820137B CN 201610177424 A CN201610177424 A CN 201610177424A CN 105820137 B CN105820137 B CN 105820137B
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- China
- Prior art keywords
- domino
- ortho position
- aromatic hydrocarbons
- aryne precursor
- aryne
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/14—Thiadiazoles; Hydrogenated thiadiazoles condensed with carbocyclic rings or ring systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of new methods efficiently synthesizing two aminated aromatic hydrocarbons of ortho position using domino aryne precursor.Its synthesis path：The diamines (wherein the amine of bridging can be alkylamine or arylamine) and potassium carbonate, 18 crown ether six of sulfonyl bridging are mixed in reaction dissolvent second cyanogen; at 80 DEG C; it is slowly added to domino aryne precursor and reacts 8 hours, be efficiently prepared for two aminated aromatic hydrocarbons of ortho position.This patent efficiently synthesizes having the technical effect that for two aminated aromatic hydrocarbons of ortho position by domino aryne precursor：Reaction condition is mild, does not need transition metal participates in, synthesis step is short, yield is higher.The feature has important value in pharmaceutical synthesis and organic synthesis field.
Description
Technical field
The present invention proposes a kind of new method synthesizing two aminated aromatic hydrocarbons of ortho position using domino aryne precursor.
Background technology
Two amido aromatic hydrocarbons of ortho position is a kind of important feature in machine compound, this class formation be largely present in native compound,
In bioactive molecule, drug molecule, dyestuff and organic material.By the way that simple, efficiently method realizes aromatic ring ortho position diamines
Base is important research direction in synthetic organic chemistry.
The traditional preparation methods of two aminated aromatic hydrocarbons of ortho position generally require the reaction of experience multi-step chemical and purification step, limitation
The extensive use of this kind of compound.The conjunction of these two amidos aromatic hydrocarbons may be implemented using transition metal-catalyzed coupling reaction
At, multistep reaction is still needed for the synthesis of asymmetric product, meanwhile, the later stage of pharmaceutical synthesis generally requires to avoid using
Cross metal.Therefore, seek that a kind of simple, efficiently synthetic method realizes that two aminated have great importance.
This patent propose it is a kind of reacted with the diamines of sulfonyl bridging using domino aryne precursor, efficiently prepare
Ortho position two aminated aromatic hydrocarbons.Synthesis step is highly shortened, while in turn avoiding participating in reaction using transition metal.This
Outside, this method is not only applicable to symmetrical arylamine and alkylamine, and is suitable for asymmetrical various diamines substrates.This meets
It is economical in pharmaceutical synthesis organic chemistry, efficient to require.
Invention content
1, the main object of the present invention：It is a kind of important molecular structure, traditional conjunction in view of two aminated aromatic hydrocarbons of ortho position
It is cumbersome at method and step, need transition metal participate in reaction.The present invention utilizes domino aryne precursor and the two of sulfonyl bridging
Amine is reacted, and two aminated aromatic hydrocarbons of ortho position is efficiently prepared for, and by changing different bridged groups, has obtained different two
Aminated aromatic hydrocarbons.This has important value in the synthesis of drug molecule and native compound.
2, the principle of the present invention：The diamines for designing sulfonyl bridging is reacted as substrate with domino aryne, first
Behind No. 1 position of nucleophilic moiety attack aryne, No. 2 positions of another nucleophilic moiety aryne of the generation of attack second in the molecule obtain
To two aminated aromatic hydrocarbons of ortho position.
Specific implementation mode：
Below in conjunction with specific reaction, further illustrate the present invention.It is reacted with domino aryne with sulfonyl bridging diphenylamines
For.
First, by the diphenylamines substrate of sulfonyl bridging (50.0mg, 0.2mmol, 1.0 equiv.), K2CO3
(110.4mg, 0.8mmol, 4.0equiv.), 18 crown ether six (211.4 mg, 0.8mmol, 4.0equiv.) are dissolved in second cyanogen
In (10mL) reaction dissolvent, flow back 30 minutes at 80 DEG C.
Secondly, then by second cyanogen (10 mL) solution of TPBT (268.0mg, 0.6mmol, 1.5equiv) pass through 8 at 80 DEG C
Hour is slowly dropped in reaction solution, is uniformly mixed and reacts.
Finally, it post-processes：After reaction terminates, second cyanogen is removed with Rotary Evaporators, is obtained through silica gel chromatograph column separating purification
To two amido benzene of product ortho position, yield 85%.
Description of the drawings
Fig. 1 be chemical equation describe sulfonyl bridging diamines (in equation, R, R ' can be alkyl or
Person's aryl) two aminated aromatic hydrocarbons of ortho position is synthesized with domino aryne precursor.
Fig. 2 is the diphenylamines (when R, R ' are phenyl) and domino aryne that chemical equation describes sulfonyl bridging
Precursor synthesizes two amido benzene of ortho position.
Compound property
Two amido benzene of ortho position：
Mp:114-116℃；1H NMR(500MHz,CDCl3) δ 7.64 (d, J=7.5 Hz, 4H), 7.57 (t, J=
7.5Hz, 4H), 7.51 (t, J=7.5Hz, 2H), 6.98-6.94 (m, 2H), 6.72-6.68 (m, 2H) ppm；13C NMR
(125MHz,CDCl3)δ132.6,130.4, 130.3,129.8,128.6,122.3,109.5ppm；IR(thin film)
1592,1484,1330, 1301,1173,1155,947,738,691,568(cm-1)；HRMS-MALDI(m/z)calcd for
[C18H14NaN2O2S]+,345.0668；found,345.0673.
The drug used
Claims (1)
1. a kind of method synthesizing two amido benzene compound of ortho position using domino aryne precursor, characterized in that reaction equation is：
It is as follows：
Step 1：The diphenylamines of sulfonyl bridging and potassium carbonate, 18- crown ethers -6 are mixed, acetonitrile as solvents is added, it is anhydrous,
It flows back 30 minutes under oxygen free condition；
Step 2：It keeps at 80 DEG C, domino aryne precursor TPBT is slowly added in 8 hours and is reacted；
Step 3：Acetonitrile is removed with Rotary Evaporators, two amido benzene compound of ortho position has been obtained, has been purified through column chromatography, yield is
85%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610177424.4A CN105820137B (en) | 2016-03-25 | 2016-03-25 | A method of synthesizing two aminated aromatic hydrocarbons of ortho position using domino aryne precursor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610177424.4A CN105820137B (en) | 2016-03-25 | 2016-03-25 | A method of synthesizing two aminated aromatic hydrocarbons of ortho position using domino aryne precursor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105820137A CN105820137A (en) | 2016-08-03 |
| CN105820137B true CN105820137B (en) | 2018-10-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610177424.4A Expired - Fee Related CN105820137B (en) | 2016-03-25 | 2016-03-25 | A method of synthesizing two aminated aromatic hydrocarbons of ortho position using domino aryne precursor |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107935927A (en) * | 2017-12-01 | 2018-04-20 | 重庆大学 | A kind of synthesis of the more yuan of rings of benzo-aza |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177395A (en) * | 2014-07-31 | 2014-12-03 | 重庆大学 | Benzyne precursor and synthesis method thereof |
| CN104829553A (en) * | 2015-03-16 | 2015-08-12 | 重庆大学 | New method of synthesizing 2,4-di-substituted benzothiazole |
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2016
- 2016-03-25 CN CN201610177424.4A patent/CN105820137B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177395A (en) * | 2014-07-31 | 2014-12-03 | 重庆大学 | Benzyne precursor and synthesis method thereof |
| CN104829553A (en) * | 2015-03-16 | 2015-08-12 | 重庆大学 | New method of synthesizing 2,4-di-substituted benzothiazole |
Non-Patent Citations (1)
| Title |
|---|
| Vicinal Diamination of Arenes with Domino Aryne Precursors;Lu Li et al.;《Org. Lett.》;20160713;3726-3729 * |
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| CN105820137A (en) | 2016-08-03 |
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