Preparation method of beta-amino acrylonitrile compounds

An aminoacrylonitrile and compound technology, which is applied in the field of preparation of beta-aminoacrylonitrile compounds, can solve problems such as the inability to well solve the problem of product geometry selectivity, and achieves simplified and smooth method, good yield, and three wastes. easy effect

Active Publication Date: 2020-05-08
CHINA AGRI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, these methods reported so far are mixtures of E / Z configurations, which cannot solve the problem of product geometric configuration selectivity.

Method used

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  • Preparation method of beta-amino acrylonitrile compounds
  • Preparation method of beta-amino acrylonitrile compounds
  • Preparation method of beta-amino acrylonitrile compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] Embodiment 1: Preparation of (E) 3-phenyl-3-(phenylamino)-acrylonitrile (l)

[0037] Add β-aminocyanoacrylate (8mmol, 1eq), lithium chloride (16mmol, 2eq), dimethyl sulfoxide (40mL), water (10mL) in sequence into a 100mL three-neck flask as shown in formula 1-1 , stir to dissolve, and heat to 160°C for 12 hours until the reaction of the raw materials is complete. After cooling to room temperature (25°C), 100 mL of ethyl acetate was added, the organic phase was washed with (2×50 mL) water and 50 mL of saturated saline solution, and the crude product was washed with petroleum ether: ethyl acetate = 4:1 after precipitation under reduced pressure. Recrystallization gave 1.23 g of white solid (E) 3-phenyl-3-(phenylamino)-acrylonitrile (1 in Table 1, formula 1), with a yield of 70.0%.

[0038]

[0039] The product has undergone a single crystal structure, 1 H NMR, 13 C NMR and MS confirmed:

[0040] Its single crystal structure is figure 1 shown. 1 H NMR (300MHz, DMS...

Embodiment 2

[0041] Embodiment 2, the preparation of (E) 3-((4-methoxyphenyl) amino)-3-cinnamonitrile (n)

[0042]Add β-aminocyanoacrylate (8mmol, 1eq), lithium chloride (16mmol, 2eq), dimethyl sulfoxide (40mL), water (10mL) in sequence into a 100mL three-necked flask as shown in formula n-1 , stir to dissolve, and heat to 160°C for 12 hours until the reaction of the raw materials is complete. After cooling to room temperature, 100 mL of ethyl acetate was added, and the organic phase was washed with (2×50 mL) water and 50 mL of saturated saline solution respectively. After precipitation under reduced pressure, the crude product was recrystallized with petroleum ether: ethyl acetate = 4:1 to obtain 1.52 g of gray solid (E) 3-((4-methoxyphenyl)amino)-3-cinnamonitrile (n in Table 1, formula n), yield 76.0%.

[0043]

[0044] product through 1 H NMR, 13 C NMR and MS confirmed:

[0045] 1 H NMR (300MHz, DMSO-d 6 )δ8.80(s,1H),7.63(m,2H),7.58–7.49(m,3H),7.24–7.13(m,2H),7.00–6.91(m,2H),4....

Embodiment 3

[0046] Embodiment 3, the preparation of (E) 3-(tert-butylamino)-3-phenylacrylonitrile (j)

[0047] Add β-aminocyanoacrylate (8mmol, 1eq), lithium chloride (16mmol, 2eq), dimethyl sulfoxide (40mL), water (10mL) in sequence into a 100mL three-necked flask as shown in formula j-1 , stir to dissolve, and heat to 160°C for 12 hours until the reaction of the raw materials is complete. After cooling to room temperature, 100 mL of ethyl acetate was added, and the organic phase was washed with (2×50 mL) water and 50 mL of saturated saline solution respectively. After precipitation under reduced pressure, the crude product was recrystallized with petroleum ether: ethyl acetate = 4:1 to obtain 1.3 g of yellow solid (E) 3-(tert-butylamino)-3-phenylacrylonitrile (j in Table 1, formula j), yield 81.0%.

[0048]

[0049] The product has been single crystal, 1 H NMR, 13 C NMR and MS confirmed:

[0050] Its single crystal structure is figure 1 shown. 1 H NMR (300MHz, DMSO-d 6 )δ7.53–...

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Abstract

The invention discloses a preparation method of beta-amino acrylonitrile compounds. Beta-aminocyanoacrylate represented by formula I reacts in a solvent under the action of a catalyst to obtain the beta-aminoacrylonitrile compounds represented by formula II; and in the formulas, R<1> is a C1-C12 alkyl group, a halogenated C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C2-C12 alkenyl group, a C2-C12 alkynyl group, an aryl group, a substituted aryl group, a benzyl group or a substituted benzyl group, and R<2> is hydrogen, halogen, a hydroxyl group, an amino group, a cyano group, a nitro group,a C1-C12 alkyl group or a halogenated C1-C12 alkyl group. The method has the characteristics of good stereoselectivity, high yield, simplicity preparation of the raw material beta-aminocyanoacrylate,and great practical value.

Description

technical field [0001] The invention relates to a preparation method of β-aminoacrylonitrile compounds, which belongs to the field of preparation of important intermediates of pesticides and medicines. Background technique [0002] As a kind of polarized ethylene, β-aminoacrylonitrile compounds are important intermediates for the synthesis of thiazoles, quinolines, indoles and azaheterocycles. At the same time, chiral β-aminonitrile can also be synthesized by asymmetric catalytic hydrogenation, which can be used to simulate the construction of peptide skeleton structure. For many years, β-aminoacrylonitrile compounds have received extensive attention due to their flexible reaction characteristics, but there are few reports on the synthesis methods of such compounds. There are few reports on the control of stereoselectivity and configuration confirmation of β-aminoacrylonitrile compounds. [0003] [0004] Scheme 1: Synthetic route of β-aminoacrylonitrile compounds [0...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C253/30C07C255/42C07D213/38
CPCC07B2200/09C07C253/30C07D213/38C07C2601/02C07C2601/14C07C255/42
Inventor 凌云张学博杨新玲金小宇孙腾达马航宇张晓鸣
Owner CHINA AGRI UNIV
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