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Synthesis method of RAFT chain transfer agent containing terminal hydroxyl

A technology of chain transfer agent and terminal hydroxyl group is applied in the field of organic synthesis of RAFT chain transfer agent, which can solve the problem that RAFT chain transfer agent cannot be directly applied, and achieve the effect of fast reaction rate and simple and mild reaction conditions.

Inactive Publication Date: 2014-05-28
NANJING UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] At present, most of the RAFT chain transfer agents that have been synthesized do not contain terminal initiator groups, so these RAFT chain transfer agents cannot be directly applied to the method of combining RAFT polymerization and ROP ring-opening polymerization to prepare block copolymers, and we designed The synthetic route of the RAFT chain transfer agent can solve this problem well, making the method of combining RAFT polymerization and ROP ring-opening polymerization to prepare block copolymers a reality

Method used

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  • Synthesis method of RAFT chain transfer agent containing terminal hydroxyl
  • Synthesis method of RAFT chain transfer agent containing terminal hydroxyl
  • Synthesis method of RAFT chain transfer agent containing terminal hydroxyl

Examples

Experimental program
Comparison scheme
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Embodiment 1

[0030] 4-bromomethylbenzyl alcohol can be purchased directly, or prepared by the following experimental method:

[0031] Dissolve 2.34 g of methyl p-bromomethylbenzoate in dry 15 mL of CH 2 Cl 2 , and cooled to 0 ° C, magnetic stirring, nitrogen protection. Slowly add 22 mL of DIBAL-H n-hexane solution dropwise with a dropping funnel. After the dropwise addition, continue stirring at 0°C for 10 minutes, and then react at room temperature for 24 hours. After the reaction, add 30mLCH to the reaction solution 2 Cl 2 , pour the mixture into the dropping funnel, and slowly drop it into a mixture of 30% hydrochloric acid and crushed ice, and stir it with a magnetic force. The organic phase was separated and the aqueous phase was extracted twice with 20 mL of ether. The mixed organic phase was washed 3 times with saturated sodium bicarbonate solution, then washed 3 times with saturated sodium chloride solution, and the finally obtained organic phase was washed with MgSO 4 Dryin...

Embodiment 2

[0033] (0.48g, 20mmol) of sodium hydride was added to a 100mL round bottom flask filled with 20mL of dimethyl sulfoxide, and (1.4mL, 20mmol) of pyrrole was slowly added dropwise with a dropping funnel. After the addition, the brown reaction solution was magnetically stirred at room temperature for 30 minutes, and then carbon disulfide (1.2 mL, 20 mmol) was slowly added dropwise. The reaction solution continued to be magnetically stirred at room temperature for 30 minutes, then weighed 4 g of 4-bromomethylbenzyl alcohol, dissolved in a small amount of dimethyl sulfoxide, and slowly added dropwise with a dropping funnel. After reacting for 1 hour, 20 mL of water was added, followed by 20 mL of diethyl ether. The orange liquid layer was separated, the aqueous phase was extracted twice with 20 mL of diethyl ether, the combined organic phases were dried over anhydrous magnesium sulfate, filtered and the solvent was removed. The crude product was chromatographed with 10% ethanol an...

Embodiment 3

[0035] Dithiobenzoic acid can be purchased directly, prepared by other synthetic methods, or prepared by the following experimental method:

[0036] Take bromobenzene (62.8g, 0.40mol) and magnesium chips (10g, 0.42mol) and add them to a 500mL round-bottomed flask filled with 300mL of dry tetrahydrofuran, and heat to 40°C, and (30.4g, 0.41mol) of carbon disulfide Add dropwise slowly over 15 minutes, maintaining a reaction temperature of 40°C. After reacting for 1 hour, cool, add 30% hydrochloric acid to mix, then pour into a separatory funnel, extract with ether, the obtained ether solution is dried with anhydrous magnesium sulfate, filtered, and rotary evaporated to obtain violet dithiobenzoic acid, the product structure through 1 H NMR with 13 C NMR identification.

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Abstract

The invention belongs to the field of organic synthesis, and provides a synthesis method of an RAFT chain transfer agent containing terminal hydroxyl; the synthesis method has the advantages of mild conditions, no need of catalysts and high reaction speed, and is applied to the preparation of segmented copolymers by combining the RAFT polymerization with the hydroxyl-triggered ring opening polymerization. Pyrrole reacts with sodium hydride and carbon disulfide, or a grignard reagent reacts with the carbon disulfide to generate disulfo-carboxylate; the disulfo-carboxylate is reacted with 4-bromine methyl benzyl alcohol for 1 hour at room temperature with dimethyl sulfoxide as a solvent; the generated crude product is implemented with such experimental methods as extraction and column chromatography to finally obtain the RAFT chain transfer agent containing the terminal hydroxyl (see attached drawing). The RAFT chain transfer agent synthesized by the method, provided by the invention, overcomes the defect that only the RAFT polymerization can be implemented in the existing preparation of the RAFT chain transfer agent. The RAFT chain transfer agent containing a trigger radical at the terminal can synchronously realize the combination of the RAFT and the ring opening polymerization (ROP) to prepare the segmented copolymers with certain structures and functions, and has a broad application prospect in a plurality of fields of drug release, bioengineering materials, material separation and immunoassay.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and refers to an organic synthesis method of a RAFT chain transfer agent containing a terminal hydroxyl group. Background technique [0002] RAFT polymerization, also known as Reversible Addition-Fragmentation Chain Transfer Polymerization (Reversible Addition-Fragmentation Chain Transfer Polymerization), as an important free radical polymerization method, has received extensive attention and research. In 1998, the Australian research team Ezio Rizzardo et al. (Chiefari J, Chong Y, Ercole F, et al. Living free-radical polymerization by reversible addition-fragmentation chain transfer: the RAFT process[J]. Macromolecules, 1998, 31(16) :5559-5562), first proposed this concept, and laid a solid foundation for the later research and application of RAFT aggregation. [0003] Compared with traditional free radical polymerization, RAFT polymerization has almost no restrictions on the selectio...

Claims

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Application Information

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IPC IPC(8): C07D207/32C07C327/36
CPCC07C327/36C07D207/32
Inventor 李振江梁彬麒王鑫张启国纪钰峰金玉何晓将
Owner NANJING UNIV OF TECH
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