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Synthesis method of axially chiral dinaphthalene ligand precursor (s)-2,2'-dinaphthyl-1,1'-dicarboxylic acid

A technology of dicarboxylic acid and axial chirality, which is applied in the fields of oxidation, hydrolysis, coupling reaction and bromination. It can solve the problems of poor economy of reagents, harsh conditions and difficulties in industrialization, and achieve high yield, simple operation, Good economical effect

Inactive Publication Date: 2016-05-04
YANGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Ye Kang, Cao Mang and others have improved the synthesis of racemic binaphtalic acid, but the reagents used in some steps are not economical, the conditions are harsh, and industrialization is difficult

Method used

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  • Synthesis method of axially chiral dinaphthalene ligand precursor (s)-2,2'-dinaphthyl-1,1'-dicarboxylic acid
  • Synthesis method of axially chiral dinaphthalene ligand precursor (s)-2,2'-dinaphthyl-1,1'-dicarboxylic acid
  • Synthesis method of axially chiral dinaphthalene ligand precursor (s)-2,2'-dinaphthyl-1,1'-dicarboxylic acid

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Experimental program
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Effect test

Embodiment 1

[0014] 1) Add 10.05g of 2-methylnaphthalene, 6.42g of sodium acetate and 30mL of acetic acid solution in a 250mL round bottom flask. Add 20mL of acetic acid and 4mL of liquid bromine into the dropping funnel, and add them dropwise into the round bottom flask. The solution turns yellow, and continue to stir for 15 minutes to stop the reaction. After extraction, drying and concentration, 13.5 g of light yellow oily product (1-bromo-2-methylnaphthalene) was obtained with a yield of 86.3%.

[0015] 2) Add 10.2g of 1-bromo-2-methylnaphthalene and 8.2g of NBS and 100mL of CCl in a 250mL round bottom flask 4 In the solution, add 0.06g benzoyl peroxide (BPO) again, reflux and stir for 3h, then add 0.06g benzoyl peroxide (BPO), reflux for 3h, the solution is overnight at room temperature, then the suspension is heated to the boiling point, multiplied Hot filtration, filtrate directly with CCl 4 The solution was recrystallized and recrystallized three times to obtain 10.0 g of light y...

Embodiment 2

[0023] 1) In a 250mL round bottom flask, add 10.05g of 2-methylnaphthalene, 12.80g of sodium acetate and 30mL of acetic acid solution. Add 20mL of acetic acid and 4mL of liquid bromine into the dropping funnel, and add them dropwise into the round bottom flask. The solution turns yellow, and continue to stir for 15 minutes to stop the reaction. After extraction, drying and concentration, 13.7 g of light yellow oily product (1-bromo-2-methylnaphthalene) was obtained with a yield of 87.6%.

[0024] 2) Add 10.2g of 1-bromo-2-methylnaphthalene and 8.2g of NBS and 100mL of CCl in a 250mL round bottom flask 4 In the solution, add 0.06g benzoyl peroxide (BPO) again, reflux and stir for 3h, then add 0.06g benzoyl peroxide (BPO), reflux for 3h, the solution is overnight at room temperature, then the suspension is heated to the boiling point, multiplied Hot filtration, filtrate directly with CCl 4 The solution was recrystallized and recrystallized three times to obtain 10.0 g of light...

Embodiment 3

[0032] 1) Add 10.05g of 2-methylnaphthalene, 6.42g of sodium acetate and 30mL of acetic acid solution in a 250mL round bottom flask. Add 20mL of acetic acid and 4mL of liquid bromine into the dropping funnel, and add them dropwise into the round bottom flask. The solution turns yellow, and continue to stir for 15 minutes to stop the reaction. After extraction, drying and concentration, 13.5 g of light yellow oily product (1-bromo-2-methylnaphthalene) was obtained with a yield of 86.3%.

[0033] 2) Add 10.2g of 1-bromo-2-methylnaphthalene and 8.2g of NBS and 100mL of benzene solution into a 250mL round bottom flask, then add 0.06g of benzoyl peroxide (BPO), stir at reflux for 3 hours, and then add 0.06g of peroxide Benzoyl Oxygen (BPO), reflux for 3h, the solution was overnight at room temperature, then the suspension was heated to the boiling point, filtered while hot, and the filtrate was directly washed with CCl 4 The solution was recrystallized and recrystallized three tim...

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Abstract

The invention relates to the technical field of bromination, hydrolysis, oxidation and coupling reaction in organic synthesis, particularly a synthesis method of an axially chiral dinaphthalene ligand precursor (s)-2,2'-dinaphthyl-1,1'-dicarboxylic acid. The method comprises the following steps: synthesizing a compound 1-bromo-2-methylnaphthalene from an initial raw material 2-bromomethylnaphthalene, carrying out bromination, hydrolysis and oxidation on the 1-bromo-2-methylnaphthalene to obtain 1-bromo-2-naphthoic acid, generating an ester under the actions of methanol and thionyl chloride, protecting the carboxyl group, carrying out Ullmann reaction under the action of copper powder to perform coupling, carrying out hydrolysis to obtain 2,2'-dinaphthyl-1,1'-dicarboxylic acid, and finally, resolving to obtain the (s)-2,2'-dinaphthyl-1,1'-dicarboxylic acid. The method is simple to operate, and has the advantages of higher yield and favorable economical efficiency.

Description

technical field [0001] The invention relates to the technical field of bromination, hydrolysis, oxidation and coupling reactions in organic synthesis. Specifically, it relates to a synthesis method of an axial chiral binaphthyl ligand precursor (s)-2,2'-dicarboxylic acid-1,1'-binaphthyl. Background technique [0002] Axial chiral compounds are a large class of chiral ligands. Axial chirality comes from the restricted rotation relative to a single bond. This rotational barrier is sufficient to allow enantiomeric compounds to be resolved. Axichiral compounds play an important role in chiral synthesis because they are both rigid and flexible, and their angle can be changed by structural modification and adding groups. Optically active 1,1'-binaphthyl compounds are C2-axis biaromatic compounds that have been studied more since the 1990s, and their optically active isomers and derivatives have been obtained through asymmetric synthesis and catalysis. Many applications, such as ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C51/487C07C63/38
CPCC07C51/487C07B2200/07C07C29/124C07C51/16C07C67/08C07C67/343C07C63/38C07C69/76C07C63/72C07C33/46
Inventor 袁宇于梦轩王碧莹
Owner YANGZHOU UNIV
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