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3-Substituted allyl carbamate compound and synthetic method thereof

A technology of allyl carbamic acid and allyl chloride compound, which is applied in the preparation of carbamic acid derivatives, chemical instruments and methods, organic compounds/hydrides/coordination complex catalysts, etc. problem, to achieve the effect of a wide range of substrates, mild conditions, and mild reaction conditions

Inactive Publication Date: 2015-06-24
TONGJI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

(a) E.Chae, H.J.Yi, Y.Choi, H.Cho, K.Lee, H.Moon, Bioorg.Med.Chem.Lett.2012, 22, 2434-2439; (b) S.Wang, M.B. Onaran, C.T. Seto, Org. Lett. 2010, 12, 2690-2693; (c) R. Naito, Y. Yonetoku, Y. Okamoto, A. Toyoshima, K. Ikeda, M. Takeuchi, J. Med. Chem. 2005, 48, 6597-6606; some carbamates were applied as insecticides, see: either (d) US20090068242A1 or (e) WO2010055267A1. Due to its particularity (the main source of the greenhouse effect and also a cheap carbon source), carbon dioxide is relatively researched Relatively mature, there have been a series of work reports on its activation, but there are few reports on related cascade reactions
However, there are few reports on the construction of chirality in tandem reactions.

Method used

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  • 3-Substituted allyl carbamate compound and synthetic method thereof
  • 3-Substituted allyl carbamate compound and synthetic method thereof
  • 3-Substituted allyl carbamate compound and synthetic method thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1～20

[0028] Additives, temperature and solvents for the tandem allylation of carbon dioxide, n-propylamine and cinnamon chloride catalyzed by iridium complexes, and the effect of different ligands on the reaction.

[0029] The amine is selected from n-propylamine, the allyl chloride compound is selected from cinnamyl chloride, and the carbon dioxide is an atmospheric pressure. In the case of different ligands, different additives, different solvents, different raw material ratios and reaction temperatures, the reaction product and yield are investigated. .

[0030]

[0031] In the formula, Add refers to the additive, Solv refers to the solvent, and T refers to the temperature.

[0032] In Examples 1-10, allyl chloride compound, amine, [Ir(COD)C1] 2 , ligands, additives in a molar ratio of 1.2:1:0.04:0.08:2, in Example 11, allyl chloride compound, amine, [Ir(COD)Cl] 2 , ligand, the mol ratio of additive is 1.2:1:0.02:0.04:2, in embodiment 12, allyl chloride compound, amine, [Ir(C...

Embodiment 21～31

[0039] The reaction equation of the asymmetric series reaction of carbon dioxide, amine and allyl chloride compound catalyzed by iridium complex is:

[0040]

[0041] In a dry argon-protected reaction tube, sequentially add [Ir(COD)Cl] 2 (0.004mmol), chiral ligand (0.008mmol), n-propylamine (0.2mL) and THF (0.5mL), reacted at 50°C for 30 minutes, cooled naturally to room temperature and pumped dry. Amine (0.2mmol) and DABCO (0.4mmol) were added to the reaction tube, carbon dioxide was bubbled in for 10 minutes, then allyl chloride compound (0.24mmol) and toluene (2.5mL) were added, and the reaction was stirred at room temperature. After the reaction, the solvent was removed under reduced pressure and the residue was subjected to thin-layer chromatography to obtain the target product 4 (petroleum ether / ethyl acetate=10:1, v / v).

[0042] When R1, R2, and R3 are different, the structure and properties of the target product 4 are as follows:

Embodiment 21

[0044] Target product 4: (R)-1-phenylallyl n-propyl carbamate

[0045]

[0046] Colorless liquid, 51% yield, 94% ee [chiral column OD-H (0.46cm x25cm); n-hexane / isopropanol=90 / 10; flow rate=1.0mL / min; detection wavelength=214nm; t R =6.019(major),7.008(minor)min].

[0047] [α] D 20 =+16.6°(c0.4, CHCl 3 ).

[0048] 1 HNMR (400MHz, CDCl 3 )δ=7.38(d, J=4.4Hz, 4H), 7.33-7.28(m, 1H), 6.18(d, J=5.6Hz, 1H), 6.02(ddd, J=16.8, 10.4, 6.0Hz, 1H ), 5.30(d, J=17.2Hz, 1H), 5.23(dt, J=10.4, 1.2Hz, 1H), 4.79(br, 1H), 3.18-3.12(m, 2H), 1.51(sext, J= 7.2Hz, 2H), 0.91ppm (t, J=7.2Hz, 3H).

[0049] 13 CNMR (100MHz, CDCl 3 )δ=155.6, 139.4, 136.8, 128.5, 128.0, 127.0, 116.5, 76.5, 42.8, 23.2, 11.2ppm.

[0050] IR (KBr): v max (cm -1 )=3476, 2964, 2918, 2843, 1696 (C=O), 1523, 1262, 1263, 698.

[0051] HRMS(ESI+)calcd for C 13 h 17 NNaO 2 [M+Na] + : 242.1151, Found: 242.1134.

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Abstract

The invention relates to a 3-substituted allyl carbamate compound and a synthetic method thereof. The 3-substituted allyl carbamate compound is prepared through a serial reaction of raw materials comprising carbon dioxide, amine and an allyl chloride compound in an organic solvent at a controlled reaction temperature of -10-40DEG C for 1-12h under the action of an additive with an iridium complex generated through a reaction of [Ir(COD)Cl]2 and a ligand as a catalyst. Compared with the prior art, the method is suitable for different types of aminated compounds and allyl chloride compounds, and has the advantages of mild reaction conditions, simple operation, good reaction yield (the yield of a two-step serial reaction is 38-74% generally), high regioselectivity (generally not lower than 90:10), high antipodal selectivity (generally 70-94%), easily available catalyst, high catalytic activity and wide substrate application range.

Description

technical field [0001] The invention relates to a carbamate compound and a synthesis method thereof, in particular to a 3-substituted allyl carbamate compound and a synthesis method thereof. Background technique [0002] Carbamate compounds are a class of highly biologically active compounds that are widely used in agriculture and biomedicine. The well-known pesticide carbofuran is a kind of carbamate derivatives, which is also widely used in medicine. Nuxinslimin is also a carbamate derivative, which is very effective in the treatment of glaucoma. At the same time, this type of compound contains chemically active groups such as amide groups, which are also good leaving groups and play an important role in the synthesis of organic intermediates. (a) E.Chae, H.J.Yi, Y.Choi, H.Cho, K.Lee, H.Moon, Bioorg.Med.Chem.Lett.2012, 22, 2434-2439; (b) S.Wang, M.B. Onaran, C.T. Seto, Org. Lett. 2010, 12, 2690-2693; (c) R. Naito, Y. Yonetoku, Y. Okamoto, A. Toyoshima, K. Ikeda, M. Take...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C271/12C07C269/04B01J31/24
Inventor 赵晓明张敏
Owner TONGJI UNIV