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Method for synthesizing dihydroisoquinoline by catalyzing selective dehydrogenation of tetrahydroisoquinoline

A technology of tetrahydroisoquinoline and dihydroisoquinoline, applied in the direction of organic chemistry, can solve the problems of narrow substrate application range, unfavorable industrial production, harsh reaction conditions, etc., and achieve convenient and practical reaction operation and easy product , Increase the effect of reactivity

Pending Publication Date: 2022-03-18
XI'AN PETROLEUM UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

As a noble metal catalyst, palladium carbon is expensive, and the amount of catalyst used in the reaction is large, which is not conducive to further industrial production
[0005] Although some research progress has been made in the synthesis of dihydroisoquinolines by transition metal-catalyzed oxidative dehydrogenation, there are still some problems, including poor dehydrogenation selectivity, expensive catalysts, harsh reaction conditions, and narrow scope of substrate application. , at present, the fundamental problem that urgently needs to be solved is how to suppress aromatization products and improve dehydrogenation selectivity

Method used

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  • Method for synthesizing dihydroisoquinoline by catalyzing selective dehydrogenation of tetrahydroisoquinoline
  • Method for synthesizing dihydroisoquinoline by catalyzing selective dehydrogenation of tetrahydroisoquinoline
  • Method for synthesizing dihydroisoquinoline by catalyzing selective dehydrogenation of tetrahydroisoquinoline

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Example 1 Synthesis of 1-phenyl-3,4-dihydrooquinoline

[0038] This example provides a synthetic method of 1-phenyl-3,4-dihydrooquinoline, which is called 1-phenyl-1,2,3,4-tetrahydroisoquinoline (104.6 mg), respectively. ), Iodide (9.5 mg), 4-dimethylaminopyridine (12.2 mg), added to 3 mL of acetonitrile, continuously stirred, heated to 60 ° C, reacted for 10 h, and using TLC detection, after completion EtOAc.

[0039]

[0040] 1-phenyl-3,4-dihydrooquinoline (1-Phenyl-3, 4-DihydroisoisoisoisoisoisoisoisoisoisoisoisoisoisoisoisoisoiSoisoisoisoisoisoisoiSoisoisoiSoisoisoiSoisoisoiSoiSoiSoiSoiSoisoiSoiSoiSoisoiSoiSoiSoiSoiSoiSoQuinoline): Pale Yellowoil, 95% yield.r f = 0.45 (Petroleum ether / ethyl acetate 2: 1). 1 H NMR (400MHz, CDCL 3 Δ7.65-7.53 (m, 2H), 7.49-7.33 (m, 4H), 7.24 (m, 3H), 4.00-3.70 (m, 2H), 2.86-2.70 (m, 2H). 13 C NMR (100MHz, CDCL 3 Δ167.3, 139.0, 138.9, 130.7, 129.3, 128.8, 128.2, 128.0, 127.4, 126.6, 47.7, 26.4. Hydrogen core magnetic spectrum figure 1 A...

Embodiment 2～14

[0041] Example 2 to 14 Synthesis of 1-phenyl-3,4-dihydrooquinoline

[0042] The synthesis of 1-phenyl-3,4-dihydrooquinoline is provided, and the synthesis method is substantially the same as that of Example 1, and the difference is only different from the raw material and part of the process parameters. The specific data is shown in Table 1.

[0043] Table 1: Process Parameters

[0044]

[0045] Other steps were the same as in Example 1, the reaction was 1-phenyl-1,2,3,4-tetrahydroisoquinoline synthesized 1-phenyl-3,4-dihydrogen isoquine in a dehydrogenation reaction. Porroline, its reaction equation is

[0046]

[0047] As can be seen from Examples 1-14, the catalytic effect of iodide and bromide copper copper is better than that of other catalysts, and the use of acetonitrile is better than other solvents, using additives 4-dimethyl Aminopyridine can greatly increase the yield of the target product.

Embodiment 15

[0048] Example 15 Synthesis of 1- (2-methylphenyl) -3,4-dihydroisoquinoline

[0049] This example provides a synthesis method of 1- (2-methylphenyl) -3, 4-dihydroisoquinoline, which is respectively weighing 1-phenyl-1, 2, 3, 4-tetrahydrogen Isoquinoline (111.7 mg), copper iodide (9.5 mg), 4-dimethylaminopyridine (12.2 mg), added to 3 ml of acetonitrile, continuously stirred, heated to 60 ° C, maintaining 60 ° C for 24 h, utilization After the TLC was completed, purified from the column chromatography, i.e., 103.3 mg of 1-phenyl-3,4-dihydroisoquinoline, yield of 93%, chemical reaction formula

[0050]

[0051] 1- (2-methylphenyl) -3,4-dihydroisoquinoline (1- (O-Tolyl) -3, 4-dihydroisoisoSoQuinoline): Pale Yellow Solid, 93% Yield.R f = 0.34 (Petroleum ether / ethyl acetate 2: 1). 1 H NMR (400MHz, CDCL 3 ) δ7.37-7.20 (m, 6H), 7.16 (t, j = 7.5 Hz, 1H), 6.91 (D, J = 7.6Hz, 1H), 3.91 (m, 2H), 2.85 (T, J = 7.4 Hz, 2H), 2.13 (S, 3H). 13 C NMR (100MHz, CDCL 3 δ168.2, 139.0, 137.4, 135.8,...

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Abstract

The invention provides a method for synthesizing dihydroisoquinoline by catalyzing selective dehydrogenation of tetrahydroisoquinoline, which comprises the following steps: adding a tetrahydroisoquinoline compound as shown in a formula (1) into an organic solvent, adding a catalyst and an organic alkali additive, and heating for dehydrogenation reaction to obtain a dihydroisoquinoline compound as shown in a formula (2), wherein R < x > is one or two of-H,-F,-Cl,-CH3 and-OCH3; r1 and R2 are respectively and independently-H,-CH3 or-OCH3; the catalyst is cuprous iodide, cuprous bromide, cuprous chloride, copper trifluoromethanesulfonate, cuprous acetate or copper iodide. According to the method, high-selectivity partial dehydrogenation can be realized, and the yield of the dihydroisoquinoline product is high.

Description

Technical field [0001] The present invention belongs to the field of organic synthesis, and a method of synthesizing a isoquinoline compound, in particular to a method of catalyzing tetrahydro isoquinoline selective dehydrogenation synthesis dihydroisoquinoline. Background technique [0002] The tetrahydrotoquinoline compound is widely present in natural products and biologically active molecules as an important type of organoamine compound. Chiral tetrahydrotoquinoline biologicoids typically have very good biological activity while is also an important type of drug intermediate. Among them, Sofah ((+) - Solifenacin) succinate (Aito, R.; YONETOKU, Y;; Toyoshima, a.; IKeda, k.; Takeuchi, MjsyNThesis and antimuscarinic property ofquinuclidin -3-YL 1, 2, 3, 4-Tetrahydroisoquinoline-2-Carboxylate DeriVATIVES Asnovel Muscarinic Receptor Antagonists [J] .j.med.Chem. 2005, 48, 6597-6606.) Is a quinish Porphyroline is a chiral amine compound of the core skeleton, which is a new muscarini...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D217/02C07D217/16C07D217/14
CPCC07D217/02C07D217/16C07D217/14Y02P20/584
Inventor 姬悦张学牛犇党泽林张豪毅王嗣昌韩薇薇
Owner XI'AN PETROLEUM UNIVERSITY
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