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Ring-opening diiodination reaction method of cyclopropenone and oxygen heterocyclic compound

A cyclopropenone, iodination reaction technology, applied in the preparation of organic compounds, chemical instruments and methods, organic chemistry and other directions, can solve the problem of inability to prepare 3-iodoacrylate, etc., and achieve excellent substrate range, reaction Simple operation, high atomic economy effect

Pending Publication Date: 2022-01-07
WENZHOU UNIVERSITY
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  • Abstract
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Problems solved by technology

However, these methods still require noble metals, toxic CO or a large excess of highly corrosive acids that limit their application in the complex synthesis of 3-iodoacrylates, and these known synthetic methods can only prepare 3-chloro / Bromoacrylates, but 3-iodoacrylates cannot be prepared (references: (1) Smith, A.B.; Kilenyl, S.N. Avermectin-milbemycin studies.4. An expedient two-step preparation of p-hydroxybenzoates. Tetrahedron Lett.1985 ,26,4419; (2) Bey,P.; Vevert,J.P.Stereospecific alkylation of the Schiffbase ester of alanine with 2-substituted-(E)-and-(Z)-vinyl bromides.An efficient synthesis of2-methyl-(E )-3,4-didehydroglutamic acid, a potent substrate-induced irreversible inhibitor of L-glutamate-1-decarboxylase. J.Org.Chem.1980,45,3249; (3)Ege,G.;Franz,H.Aminopyrazoles.IV. Pyrazol-3-and 5-amines from 2,3-dihaloalkanenitroles or 3-chloroacrylonitriles and hydrazines. J.Heterocycl.Chem.1982,19,1267; (4) Larock, R.C.; Narayanan, K.; Hershberger, S.S. Mercury in organic chemistry. 25.Rhodium(I)-catalyzed alkenylation of arylmercurials.J.Org.Chem.1983,48,4377;(5)Zhang,C.;Lu,X.StereoselectiveSynthesis of Methyl(Z)-3-Iodo-2-(1 -hydroxyalkyl)prop-2-enoates and TheirFurther Transformation toα-(Z)-Iodomethylene-β- lactones.Synthesis 1996,586; (6)Crousse,B.;Alami,M.;Linstrumelle,G.A stereocontrolled method for synthesis of conjugatedpolyenes.Tetrahedron Lett.1995,36,4245.)

Method used

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  • Ring-opening diiodination reaction method of cyclopropenone and oxygen heterocyclic compound
  • Ring-opening diiodination reaction method of cyclopropenone and oxygen heterocyclic compound
  • Ring-opening diiodination reaction method of cyclopropenone and oxygen heterocyclic compound

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Experimental program
Comparison scheme
Effect test

Embodiment 22

[0035]

[0036] Cyclopropenone (0.2mmol, 1.0 equivalents) shown in formula 1b, I 2 (0.4mmol, 2.0 equivalents), tetrahydrofuran (0.3mmol, 1.5 equivalents) and CH 3 CN (2 mL) was loaded into a 10 mL reaction tube. The reaction mixture was stirred at 120°C for 10 hours. After completion of the reaction, 2.0 ml of water was added to the reaction mixture, the reaction solution was extracted with ethyl acetate (3 x 2 mL), the combined organic layers were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The remaining residue was purified by silica gel column chromatography to obtain the 3-iodoacrylate compound represented by formula 3b with a yield of 50%. Structure Characterization: 1 H NMR (500MHz, Chloroform-d) δ7.19–7.11(m, 6H), 6.98(d, J=8.4Hz, 2H), 4.30(t, J=6.2Hz, 2H), 3.19(t, J= 6.8Hz,2H),1.99–1.93(m,2H),1.90–1.83(m,2H),1.25(s,9H),1.22(s,9H). 13 C NMR (125MHz, Chloroform-d) δ169.0, 151.4, 150.9, 143.1, 139.1, 132.2, 129.1, 128....

Embodiment 23

[0038]

[0039] Cyclopropenone (0.2mmol, 1.0 equivalents) shown in formula 1c, I 2 (0.4mmol, 2.0 equivalents), tetrahydrofuran (0.3mmol, 1.5 equivalents) and CH 3 CN (2 mL) was loaded into a 10 mL reaction tube. The reaction mixture was stirred at 120°C for 10 hours. After completion of the reaction, 2.0 ml of water was added to the reaction mixture, the reaction solution was extracted with ethyl acetate (3 x 2 mL), the combined organic layers were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The remaining residue was purified by silica gel column chromatography to obtain the 3-iodoacrylate compound represented by formula 3c with a yield of 56%. Structure Characterization: 1 H NMR (500MHz, Chloroform-d) δ7.18–7.14(m,2H),7.07–7.03(m,2H),6.89-6.83(m,4H),4.30(t,J=6.2Hz,2H), 3.20(t,J=6.8Hz,2H),1.97–1.91(m,2H),1.89–1.82(m,2H). 13 C NMR (125MHz, Chloroform-d) δ168.3, 162.2(J=247.8Hz), 162.2(J=248.5Hz), 142.9, 137.9(J=3.7Hz), 130.9...

Embodiment 24

[0041]

[0042] Cyclopropenone (0.2mmol, 1.0 equivalents) shown in formula 1d, I 2 (0.4mmol, 2.0 equivalents), tetrahydrofuran (0.3mmol, 1.5 equivalents) and CH 3 CN (2 mL) was loaded into a 10 mL reaction tube. The reaction mixture was stirred at 120°C for 10 hours. After completion of the reaction, 2.0 ml of water was added to the reaction mixture, the reaction solution was extracted with ethyl acetate (3 x 2 mL), the combined organic layers were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The remaining residue was purified by silica gel column chromatography to obtain the 3-iodoacrylate compound represented by formula 3d with a yield of 50%. Structure Characterization: 1 H NMR (500MHz, Chloroform-d) δ7.18–7.09(m,6H),7.02–7.00(m,2H),4.31–4.28(m,2H),3.19(t,J=6.6Hz,2H), 1.93(m,2H),1.84(m,2H). 13 C NMR (125MHz, Chloroform-d) δ168.1, 143.0, 140.2, 134.5, 134.4, 133.3, 130.6, 130.0, 128.7, 128.5, 99.5, 64.8, 29.9, 29.3, 5.3. H...

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Abstract

The invention discloses a ring-opening diiodination reaction method of cyclopropenone and an oxygen heterocyclic compound. The method comprises the following steps: in the presence of an iodine source such as I2, N-iodosuccinimide and / or AlI3, heating to 60-150 DEG C under an air atmosphere condition, and carrying out a stirring reaction to conveniently prepare various required 3-iodoacrylate compounds. According to the method, two C-I bonds and one C-O bond can be constructed in one step, and cracking of the two C-O bonds and one C-C bond can be realized; and the method has the advantages of simple reaction operation, high atom economy and excellent substrate range.

Description

technical field [0001] The application belongs to the technical field of organic synthesis methodology, and in particular relates to a ring-opening diiodination reaction method of cyclopropenone and oxygen heterocyclic compounds. Background technique [0002] β-Unsaturated esters are an important chemical structure widely found in pesticides, natural products, additives, polymer modifiers, and plasticizers. Among them, 3-iodoacrylates are valuable building blocks in organic synthetic chemistry, and their derivatives show a series of physiological and pharmacological activities. Given their importance, various efficient methods to obtain 3-iodoacrylates have been successively reported. However, these methods still require noble metals, toxic CO or a large excess of highly corrosive acids that limit their application in the complex synthesis of 3-iodoacrylates, and these known synthetic methods can only prepare 3-chloro / Bromoacrylates, but 3-iodoacrylates cannot be prepared...

Claims

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Application Information

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IPC IPC(8): C07C67/00C07C69/65
CPCC07C67/00C07C69/65
Inventor 刘妙昌张新缪威航周云兵吴华悦
Owner WENZHOU UNIVERSITY
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