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3-aryl-2-naphthalene acetaldehyde and 3-aryl-2-anthracene acetaldehyde compound as well as synthetic method and application thereof

A synthesis method and technology of naphthaleneacetaldehyde, applied in the oxidation preparation of carbonyl compounds, chemical instruments and methods, organic chemistry, etc., can solve the problems of inconvenient operation of arylacetaldehyde and difficulty in the synthesis of metal complexes

Inactive Publication Date: 2017-06-13
SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The above step of synthesizing aryl acetaldehyde from basic raw materials is inconvenient, and the metal complexes and ligands used are difficult to synthesize

Method used

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  • 3-aryl-2-naphthalene acetaldehyde and 3-aryl-2-anthracene acetaldehyde compound as well as synthetic method and application thereof
  • 3-aryl-2-naphthalene acetaldehyde and 3-aryl-2-anthracene acetaldehyde compound as well as synthetic method and application thereof
  • 3-aryl-2-naphthalene acetaldehyde and 3-aryl-2-anthracene acetaldehyde compound as well as synthetic method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0051] Embodiment 1 --- the general operating procedure of synthetic compound 2

[0052] Synthesis of 3-aryl-2-naphthylacetaldehyde 2: In a clean reaction tube filled with argon, add methylenecyclopropane-substituted 1,5-enyne (1, 0.20 mmol), 3,5-dibromo Pyridine oxynitride (0.3mmol), gold catalyst JohnPhosAu(NCMe)SbF 6 (0.01 mmol), heated to 95°C in toluene for 4 hours. Flash column chromatography (SiO 2 , the eluent is petroleum ether / ethyl acetate=25:1) to obtain the corresponding product 2.

[0053] Compound 2a(R 1 =Ph,R 2 =Ph,R 3 =H): 59mg, 92%, white solid, melting point: 143-145°C; IR(CH 2 Cl 2 ):ν3055,2954,2923,2826,1722,1488,1442,1382,1109,1028,892,751,703cm -1 ; 1 HNMR (400MHz, CDCl 3 ,TMS):δ3.63(s,2H),7.26(d,2H,J=7.2Hz),7.33-7.40(m,4H),7.42-7.49(m,7H),7.80(s,1H), 7.85(d,1H,J=8.4Hz),9.41(s,1H); 13 C NMR (100MHz, CDCl 3 MS( 323.1(M+H + ,100); HRMS (ESI) calculated value Calcd.forC 24 h 19 o + Measured value requires: 323.1430, Found: 323.1442.

[00...

Embodiment 2

[0079] The synthesis of embodiment 2 compound 3r

[0080] Synthesis of polycyclic aromatic hydrocarbons benzo[α]anthracene 3r: In a 25mL clean reaction tube, add 3-aryl-2-naphthylacetaldehyde (2, 0.20mmol), Lewis acid In(OTf) 3 (0.01 mmol), heated to 50° C. in DCE (dichloroethane) for 2 hours. Flash column chromatography (SiO 2 , the eluent is petroleum ether) to obtain the corresponding product 3r.

[0081]

[0082] Compound 3r: 69mg, 90%, white solid, melting point: 185-187℃; IR(CH 2 Cl 2 ):ν2958,2920,2851,1654,1633,1469,1075,1019,873,822,742,700cm -1 ; 1 H NMR (400MHz, CD 2 Cl 2 ,TMS):δ7.28(d,2H,J=8.4Hz),7.40-7.44(m,2H),7.49(d,1H,J=8.8Hz),7.53(td,1H,J 1 =8.0Hz,J 2 =1.2Hz),7.58-7.62(m,2H),7.66-7.71(m,3H),7.79(d,1H,J=7.6Hz),8.14(d,1H,J=8.0Hz),8.86(d ,1H,J=8.0Hz),9.23(s,1H); 13 C NMR (100MHz, CD 2 Cl 2 ,TMS):δ121.7,121.9,123.0,125.1,125.6,126.0,126.3,127.0,127.19,127.23,128.47,128.52,128.53,128.7,130.3,130.6,131.39,131.42,135.9 (MS ESI)m / z:383.0(M+H + ,100); ...

Embodiment 3

[0083] The synthesis of embodiment 3 compound 4r

[0084] Synthesis of anticancer drug 4r: In a 25mL clean reaction tube filled with argon, add polycyclic aromatic hydrocarbon 3r (0.2mmol), catalyst Pd 2 (dba) 3 (0.01mmol), ligand XantPhos (0.02mmol), base Cs 2 CO 3 (0.4mmol), morpholine (0.4mmol), heated to 100°C in toluene, reacted for 4 hours. Flash column chromatography (SiO 2 , the eluent is petroleum ether / ethyl acetate=10 / 1) to obtain the corresponding product 4r.

[0085]

[0086] Compound 4r: 49mg, 63%, white solid, melting point: 218-220℃; IR(CH 2 Cl 2 ):ν2962,2919,2848,2820,1645,1607,1515,1502,1446,1257,1234,1122,928,831,822,803,770,751cm -1 ; 1 H NMR (400MHz, CD 2 Cl 2 ,TMS): δ3.03(t, 4H, J=4.0Hz), 3.94(t, 4H, J=4.0Hz), 7.09(d, 2H, J=7.6Hz), 7.33(d, 2H, J= 8.4Hz), 7.42(t, 1H, J=7.6Hz), 7.54(t, 1H, J=7.6Hz), 7.58-7.62(m, 3H), 7.68(d, 1H, J=8.0Hz), 7.73 (t, 1H, J=8.4Hz), 7.81(d, 1H, J=8.0Hz), 8.15(d, 1H, J=8.4Hz), 8.89(d, 1H, J=8.4Hz), 9.23(s ,1H); 1...

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Abstract

The invention relates to a 3-aryl-2-naphthalene acetaldehyde and 3-aryl-2-anthracene acetaldehyde compound as well as a synthetic method and application thereof. The compound has the structural formula shown in the specification. The compound is prepared from methylene cyclopropane substituted 1,5-eneyne through cycloisomerization-oxidation reaction under the gold-catalysis action. The method is simple and convenient, and a synthetic intermediate and a medical intermediate can be used for preparing anti-tumor drugs.

Description

technical field [0001] The present invention relates to the synthesis of multi-substituted 3-aryl-2-naphthaleneacetaldehyde / anthracetaldehyde by cycloisomerization / oxidation process of 1,5-enyne substituted by methylene cyclopropane under the catalysis of gold catalyst new method. Background technique [0002] The carbonyl functional group has a prominent position in many organic functional groups and plays an important part in contemporary organic synthesis. Its special natural advantages include stability, compatibility, and the diversity of functional group transformations, making carbonyls widely used in chemical, pharmaceutical, and pesticide fields. In organic synthesis, including total organic synthesis, the most commonly used method for introducing carbon groups is the oxidative cleavage of alkenes. Among them, the ozonation method is particularly common. However, the ozonation method has problems that cannot be ignored, such as the tolerance of functional groups,...

Claims

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Application Information

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IPC IPC(8): C07C45/27C07C47/23C07C47/277C07C47/24C07C47/235C07D333/22C07D333/16C07D295/033
CPCC07C17/35C07C47/23C07C47/235C07C47/24C07C47/277C07D295/033C07D333/16C07D333/22C07C25/22
Inventor 余刘柱施敏
Owner SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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