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Synthesis method of chlorinated allyl ester without transition metal catalysis

A chloroallyl ester and metal-catalyzed technology, which is applied in the field of preparation of pharmaceutical and chemical intermediates, can solve the problem of unfriendly cost and environmental protection, low yield of chloroallyl ester, and limited range of allene substrates and other problems, to achieve the effect of large use value and social and economic benefits, mild reaction conditions, and simple steps

Active Publication Date: 2022-07-26
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, these methods all require the use of transition metals and corresponding ligands in most cases, which are not friendly in terms of cost and environmental protection. In addition, there are problems of catalyst loss and residue, which limit the application of such methods. application
[0004]Recently, metal-free catalyzed addition of carboxylic acids to allenes has been reported [ACS Omega 2019,4,15312] using iodosuccinyl As a catalyst, imines attack allenes through iodonium ions, and undergo the process of iodonium ion intermediates. The substrate range of allenes is limited, and the yield for the synthesis of chloroallyl esters is low

Method used

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  • Synthesis method of chlorinated allyl ester without transition metal catalysis
  • Synthesis method of chlorinated allyl ester without transition metal catalysis
  • Synthesis method of chlorinated allyl ester without transition metal catalysis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] Example 1: Synthesis of 2-chloro-1-phenoxyallyl benzoate (3a)

[0037]

[0038] Weigh benzoic acid (36.6 mg, 0.3 mmol), phenoxy allenyl ether (58.5 μL, 0.45 mmol), and tert-butyl hypochlorite (101.8 μL, 0.9 mmol) into a 25 mL reaction tube, and then add CH 2 Br 2 (1 mL) was placed in an oil bath at 25°C for 2 h. After the reaction, the solvent was removed under reduced pressure, and the product was separated by silica gel column using petroleum ether / dichloromethane as the eluent, and the yield of the product was 72%.

[0039] 1 H NMR (400MHz, CDCl 3 )δ8.10(d,J=7.0Hz,2H),7.59(t,J=7.5Hz,1H),7.45(t,J=7.8Hz,2H),7.36–7.26(m,2H),7.08( dd,J=13.0,7.5Hz,3H),7.00(s,1H),5.90(d,J=1.9Hz,1H),5.63(d,J=2.0Hz,1H). 13 C NMR (100MHz, CDCl 3 )δ164.9,155.8,136.0,133.8,130.1,129.8,128.9,128.6,123.6,117.3,116.8,94.3.IR(KBr):ν3064,2927,2841,1731,1640,1492,1266,1062,69cm,9 -1 .HRMS(ESI)calcd for[C 16 H 13 ClNaO 3 ,M+Na] + :311.0445,found:311.0450.

Embodiment 2

[0040] Example 2: Synthesis of 2-chloro-1-phenoxyallyl 4-methylbenzoate (3b)

[0041]

[0042] Weigh p-toluic acid (40.8 mg, 0.3 mmol), phenoxy allenyl ether (58.5 μL, 0.45 mmol), and tert-butyl hypochlorite (101.8 μL, 0.9 mmol) into a 25 mL reaction tube, Then add CH 2 Cl 2 (1 mL) was placed in an oil bath at 25°C for 3 h. After the reaction, the solvent was removed under reduced pressure, and the product was separated by silica gel column using petroleum ether / dichloromethane as the eluent, and the yield of the product was 70%.

[0043] 1 H NMR (400MHz, CDCl 3 )δ7.98(d,J=8.3Hz,2H),7.32-7.22(m,4H),7.07(dd,J=15.0,7.6Hz,3H),6.99(s,1H),5.89(d,J =2.0Hz,1H),5.62(d,J=2.0Hz,1H),2.40(s,3H). 13 C NMR (100MHz, CDCl 3)δ165.0,155.8,144.8,136.1,130.2,129.8,129.3,126.1,123.6,117.3,116.7,94.2,21.8.IR(KBr):v 3042,2924,2847,1731,1639,1591,1418,1268 ,1018,750,690cm -1 .HRMS(ESI)calcd for[C 17 H 15 ClNaO 3 ,M+Na] + :325.0602,found:325.0603.

Embodiment 3

[0044] Example 3: Synthesis of 2-chloro-1-phenoxyallyl 4-nitrobenzoate (3c)

[0045]

[0046] Weigh p-nitrobenzoic acid (50.1 mg, 0.3 mmol), phenoloxy allenyl ether (78.0 μL, 0.6 mmol), and tert-butyl hypochlorite (136.0 μL, 1.2 mmol) into a 25 mL reaction tube, Then add CCl 4 (1 mL) was placed in an oil bath at 25°C for 6 h. After the reaction, the solvent was removed under reduced pressure, and the product was separated by silica gel column using petroleum ether / dichloromethane as the eluent, and the yield of the product was 80%.

[0047] 1 H NMR (400MHz, CDCl 3 )δ8.28(q,J=8.9Hz,4H),7.32(t,J=7.9Hz,2H),7.10(t,J=8.9Hz,3H),7.01(s,1H),5.94(d, J=2.0Hz, 1H), 5.68(d, J=1.5Hz, 1H). 13 C NMR (100MHz, CDCl 3 )δ163.2,155.5,151.0,135.4,134.2,131.2,129.9,124.0,123.7,117.5,117.3,94.9.IR(KBr):v 3051,2926,1739,1529,1347,1268,1085,1014,814cm70,7 - 1 .HRMS(ESI)calcd for[C 16 H 12 ClNNaO 5 ,M+Na] + :356.0296,found:356.0290.

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Abstract

The invention provides a synthetic method of chlorinated allyl ester without transition metal catalysis, which comprises the following steps: by taking a carboxylic acid compound and phenoloxy allene ether as raw materials, constructing a series of chlorinated allyl ester compounds containing C-Cl and C-O bonds in the presence of tert-butyl hypochlorite and an organic solvent. Chloro-allyl ester serves as an important ester, the structure exists in many natural products, in addition, the chloro-allyl ester is an intermediate with important application value in the field of organic synthesis, and the chloro-allyl ester has wide market prospects. The method disclosed by the invention has the advantages of simple steps, easily available raw materials, mild reaction conditions and the like. The method has great use value and social and economic benefits.

Description

technical field [0001] The invention relates to a preparation method of a pharmaceutical chemical intermediate, and relates to a synthesis method of a transition metal-free chloroallyl ester. Background technique [0002] As an important ester, allyl ester structure exists in many natural products, and it is also an intermediate with important application value in the field of organic synthesis. The traditional synthesis methods generally use the corresponding allyl alcohol to carry out acylation reaction with acid, acid chloride or acid anhydride [J.Am.Chem.Soc.2006,128,15572; J.Am.Chem.Soc.2010,132 , 1206], however, such methods are limited by factors such as difficult preparation of raw materials, limited scope of reactants and harsh conditions. [0003] In recent years, reports of transition metal-catalyzed reactions of carboxylic acids with allene compounds to linear or branched allyl ester products are receiving increasing attention [Org. Lett. 2008, 10, 513; ACS Cata...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/04C07C69/007C07C69/78C07C69/76C07C69/28C07C201/12C07C205/57C07C205/37C07D333/38
CPCC07C67/04C07C201/12C07D333/38C07C69/007C07C69/78C07C69/76C07C69/28C07C205/57C07C205/37
Inventor 冯秀娟李世鸿包明王泽优
Owner DALIAN UNIV OF TECH
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