CN116535368A - Dicyanomethane compound and synthesis method and application thereof - Google Patents

Dicyanomethane compound and synthesis method and application thereof Download PDF

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CN116535368A
CN116535368A CN202310384586.5A CN202310384586A CN116535368A CN 116535368 A CN116535368 A CN 116535368A CN 202310384586 A CN202310384586 A CN 202310384586A CN 116535368 A CN116535368 A CN 116535368A
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dicyanomethane
compound according
dicyan
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沈永淼
梁尚闯
涂梦
苏淼
雷子俊
付飞亚
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Shaoxing Ruiyibo New Material Technology Co ltd
Zhejiang University Of Technology Shengzhou Innovation Research Institute Co ltd
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Shaoxing Ruiyibo New Material Technology Co ltd
Zhejiang University Of Technology Shengzhou Innovation Research Institute Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/16—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0231—Halogen-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/30—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/46—C-H or C-C activation

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Abstract

The application provides a dicyan methane compound and a synthesis method and application thereof, belonging to the technical field of heterocyclic compounds. Under the condition of light and room temperature, carbon tetrabromide is used as a catalyst to catalyze the alkenyl malononitrile compound in an organic solvent. The invention discloses a method for directly alkylating C-H bond by using carbon tetrabromide as a photocatalyst under mild conditions, which simplifies the synthesis steps and is suitable for large-scale industrial production.

Description

Dicyanomethane compound and synthesis method and application thereof
Technical Field
The application relates to a dicyan methane compound, a synthesis method and application thereof, and belongs to the technical field of heterocyclic compounds.
Background
The formation of C-H bond-activated C-C bond reactions have been the focus of the field of organic synthesis, whereby scientists have developed many compact, efficient synthetic routes. In 2008, chen Yingchun et al used asymmetric Michael addition to C-C couple malononitrile derivatives with aromatic ketones under primary amine catalysis, but the yields were not high. (Tetrahedron Letters,2008,49 (24): 3881-3884.). The group of the 2016 Nataraj Poomathi problem uses malononitriles as substrates for C-C bond coupling reactions with non-metallic participation, which have a broad spectrum of acceptors but are strictly required to be carried out under specific cytisine conditions (Org. Lett.2005,7 (23): 5293-5296.). With the development of single electron transfer induced formation of C-C bonds, several synthetic routes to malononitrile have recently emerged, mediated by free radicals. For example, yao reports the use of Et 3 B as free radical initiator, one-pot coupling of malononitrile with alkyl iodide (Tetrahedron letters,2006,47 (34): 6133-6137.). In the last decade, many methods for activating C (sp 3) -H under mild conditions have been made possible by the development of visible light catalysis, which has not been possible by other methods before. In 2018, evo's team established radical induced addition of ether to electron deficient olefins under visible light irradiation using Eosin Y as a photocatalyst, but with low alkyl yields and required reaction at 60 ℃ (Angewandte Chemie International Edition,2018,130 (28): 8650-8654.). At present, transition metal complexes such as Ir and Ru are the most widely used photocatalysts, and C-H bonds are activated to carry out alkylation by a metal-ligand charge transfer method, but the transition metal complexes are hindered from being applied to a large scale due to the defects of scarcity, high cost, low recoverability and the like of the transition metal.
Disclosure of Invention
In view of the above, the application provides a simple and effective synthesis process for C-H alkylation of dicyanomethane compounds through bromine free radical mediation under visible light catalysis, and the synthesis method is simple and easy to obtain raw materials and environment-friendly. The invention innovatively uses green and safe carbon tetrabromide as a photocatalyst, and realizes C-H alkylation by utilizing visible light induction under the condition of simple operation.
Based on the above, the technical scheme adopted by the application is as follows:
a dicyan methane compound having the structural formula:
r adopts one of aryl, substituted aryl, cyclobutyl, cyclohexyl and the like; r1 adopts tetrahydrofuran, 1, 3-dioxolane and derivatives thereof.
Meanwhile, the applicant also provides a synthesis method of the dicyanomethane compound: the method comprises the steps of taking an alkenyl malononitrile compound containing R as a raw material, adding R1, taking carbon tetrabromide as a catalyst, under the conditions of an organic solvent and irradiation of visible light, catalyzing and abstracting hydrogen of an alkylating reagent by bromine free radicals generated by the carbon tetrabromide, carrying out single electron transfer on the generated free radicals, and carrying out electrophilic substitution reaction with the raw material to obtain a C-H alkylated product.
Further, as preferable:
the R-containing alkenyl malononitrile compound is selected from any one of the following:
and R1 is any one of tetrahydrofuran, 1, 3-dioxolane and derivatives thereof.
The organic reagent is tetrahydrofuran, ethyl acetate, acetonitrile, dichloromethane and the like, wherein the preferable solvent is tetrahydrofuran.
In the reaction, the reaction time is 12-42h, and the dosage of carbon tetrabromide relative to the alkenyl malononitrile compound containing R is 0.1-0.3eq.
The product is purified after the reaction is finished, and the method comprises the following steps: petroleum ether and ethyl acetate are used as developing agents according to a certain proportion, column chromatography is used for separation, and drying is carried out after concentration. Carbon tetrabromide is used as an inexpensive and easy-to-synthesize organic micromolecule reagent, and can lead C-Br bond to generate high-activity bromine free radical through homologous cracking under the condition of heating or illumination, tetrahydrofuran is induced to generate tetrahydrofuran free radical, the tetrahydrofuran free radical and the malononitrile compound are alkylated, and the dicyanomethane compound with higher purity can be obtained after the simple purification.
Compared with the prior art, the method has the following advantages;
1) The invention provides a safe, green and simple operation method, which can induce the generation of C-C bonds by using visible light to complete the C-H alkylation, and has a larger invention prospect.
2) Under the condition of visible light, carbon tetrabromide is used for replacing an expensive metal catalyst, the cost is low, the reaction condition is mild, and the subsequent purification treatment is simple and convenient.
3) The reaction is carried out at room temperature, so that the potential safety hazard caused by high-temperature reaction is reduced, and the reaction is easy to control.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of the product prepared in example 1;
FIG. 2 is a nuclear magnetic resonance spectrum of the product prepared in example 1;
FIG. 3 is a nuclear magnetic resonance spectrum of the product prepared in example 2;
FIG. 4 is a nuclear magnetic resonance spectrum of the product prepared in example 2;
FIG. 5 is a nuclear magnetic resonance spectrum of the product prepared in example 3;
FIG. 6 is a nuclear magnetic resonance spectrum of the product prepared in example 3;
FIG. 7 is a nuclear magnetic resonance spectrum of the product prepared in example 4;
FIG. 8 is a nuclear magnetic resonance spectrum of the product prepared in example 4;
FIG. 9 is a nuclear magnetic resonance spectrum of the product prepared in example 5;
FIG. 10 is a nuclear magnetic resonance spectrum of the product prepared in example 5;
FIG. 11 is a nuclear magnetic resonance spectrum of the product prepared in example 6;
FIG. 12 is a nuclear magnetic resonance spectrum of the product prepared in example 6;
FIG. 13 is a nuclear magnetic resonance spectrum of the product prepared in example 7;
FIG. 14 is a nuclear magnetic resonance spectrum of the product prepared in example 7;
FIG. 15 is a nuclear magnetic resonance spectrum of the product prepared in example 8;
FIG. 16 is a nuclear magnetic resonance spectrum of the product prepared in example 8;
FIG. 17 is a nuclear magnetic resonance spectrum of the product prepared in example 9;
FIG. 18 is a nuclear magnetic resonance spectrum of the product prepared in example 9;
FIG. 19 is a nuclear magnetic resonance spectrum of the product prepared in example 10;
FIG. 20 is a nuclear magnetic resonance spectrum of the product prepared in example 10;
FIG. 21 is a nuclear magnetic resonance spectrum of the product prepared in example 11;
FIG. 22 is a nuclear magnetic resonance spectrum of the product prepared in example 11.
Detailed Description
Specific embodiments of the present invention will be described in detail with reference to fig. 1 to 22, but do not limit the claims of the present invention.
Example 1
To a 4mL reaction flask, benzylidene malononitrile (0.2 mmol), tetrahydrofuran (2.5 mL), carbon tetrabromide (0.02 mmol) and magneton were sequentially added, and after plugging the flask, the flask was vented under argon atmosphere for 15 minutes and reacted for 36 hours under irradiation of a 3W LED blue lamp. After the reaction was completed, the reacted solution was placed in an conical flask and concentrated by distillation under reduced pressure using a rotary evaporator to obtain a thick liquid. Finally, ethyl acetate and petroleum ether are mixed according to the ratio of 1:10 to be used as developing agents, column chromatography separation is carried out, and the obtained product is dried to obtain the yield of 93%.
The product was tested as shown in fig. 1 and 2:
1 H NMR(400MHz,CDCl 3 )δ7.46–7.28(m,11H),4.54(d,J＝4.0Hz,1H),4.40(d,J＝10.5Hz,3H),3.86(s,2H),3.73(t,J＝5.8Hz,2H),3.28(d,J＝10.5Hz,1H),3.04(dd,J＝10.3,3.9Hz,1H),1.92(qt,J＝13.8,7.0Hz,4H),1.78(dd,J＝11.6,6.2Hz,1H),1.51–1.32(m,3H)。
13 C NMR(101MHz,CDCl 3 )δ134.60(s),134.08(s),129.55–129.03(m),129.00(d,J＝3.8Hz),128.58(s),112.47(s),111.90(s),78.13(s),77.55(d,J＝6.0Hz),77.20(s),76.88(s),68.85(d,J＝12.9Hz),51.91(s),50.60(s),30.38(s),28.97(s),27.42(s),27.07(s),25.84(d,J＝1.6Hz)。
alternative 1
This embodiment is identical to the arrangement of embodiment 1, except that: the kinds of the organic solvents, the amounts of carbon tetrabromide, the reaction time, etc., were examined and their effects on the reaction were examined, respectively, and are shown in Table 1.
Table 1: influence of different parameters on the reaction
Note that: the sequence numbers 1-2 are carried out under the light-proof condition, and the sequence numbers 1-4 are carried out under the air condition.
As compared to example 1, it can be seen in connection with table 1: during the synthesis of the product: when THF is adopted as the solvent, the reaction yield can reach 88 percent (see sequence numbers 1-3 and 1-4) under the condition of argon exhaust and in the air, and the reaction is not easy to carry out under the condition of no light; with the increase of the catalyst addition amount, the yield is improved and then reduced, and 0.1eq is taken as a node; the reaction time plays a positive role in the reaction, but when the reaction time exceeds 36 hours, the significance of improving the yield is not obvious.
Example 2
This embodiment is identical to the arrangement of embodiment 1, except that: p-methyl benzylidene malononitrile (0.2 mmol) was used in place of benzylidene malononitrile (0.2 mmol) in 95% yield, and the results of the product detection are shown in FIGS. 3 and 4:
1 H NMR(400MHz,CDCl 3 )δ7.26(d,J＝8.1Hz,3H),7.23–7.14(m,4H),4.55–4.49(m,1H),4.48–4.31(m,3H),3.99–3.89(m,1H),3.89–3.81(m,1H),3.73(dd,J＝9.9,3.3Hz,1H),3.24(dd,J＝10.5,3.2Hz,1H),3.02(d,J＝4.1Hz,1H),2.35(d,J＝5.6Hz,3H),2.02–1.83(m,5H),1.83–1.72(m,1H),1.51–1.35(m,3H)。
13 C NMR(101MHz,CDCl 3 )δ139.13(s),138.80(s),131.58(s),131.03(s),130.00(s),129.75(s),129.21(s),128.45(s),111.98(s),78.21(s),77.61(d,J＝14.9Hz),77.22(s),76.90(s),68.85(d,J＝13.9Hz),51.66(s),50.36(s),30.40(s),29.00(s),27.56(s),27.17(s),25.88(d,J＝6.2Hz),21.22(s)。
example 3
This embodiment is identical to the arrangement of embodiment 1, except that: p-methoxybenzylidene malononitrile (0.2 mmol) was used in place of benzylidene malononitrile (0.2 mmol) in greater than 99%. The product detection results are shown in fig. 5 and 6:
1 H NMR(400MHz,CDCl 3 )δ7.31(d,J＝8.7Hz,2H),7.25(d,J＝8.7Hz,2H),6.92(dd,J＝14.8,8.7Hz,4H),4.53(d,J＝4.0Hz,1H),4.48–4.31(m,3H),3.94(d,J＝6.5Hz,1H),3.86(dd,J＝8.2,5.4Hz,1H),3.81(t,J＝3.5Hz,6H),3.78–3.70(m,2H),3.25(dd,J＝10.4,3.2Hz,1H),3.02(dd,J＝10.3,4.1Hz,1H),1.98–1.86(m,4H),1.77(d,J＝6.9Hz,1H),1.54–1.34(m,3H)。
13 C NMR(101MHz,CDCl 3 )δ160.03(d,J＝20.0Hz),130.47(s),129.71(s),126.56(s),125.93(s),114.64(s),114.38(s),112.64(d,J＝5.0Hz),112.04(s),78.23(s),77.63(d,J＝13.0Hz),77.25(s),76.93(s),68.82(d,J＝14.2Hz),55.30(d,J＝5.4Hz),51.22(s),49.91(s),30.35(s),28.97(s),27.64(s),27.28(s),25.83(d,J＝6.5Hz)。
example 4
This embodiment is identical to the arrangement of embodiment 1, except that: para-fluorobenzenemalononitrile (0.2 mmol) was used in place of benzylideenemalononitrile (0.2 mmol) in 82% yield. The product detection results are shown in fig. 7 and 8:
1 H NMR(400MHz,CDCl 3 )δ7.38(dd,J＝8.4,5.4Hz,2H),7.33(dd,J＝8.4,5.5Hz,2H),7.10(dt,J＝16.9,8.5Hz,4H),4.56(d,J＝4.1Hz,1H),4.49–4.42(m,1H),4.36(d,J＝10.4Hz,2H),3.95(dd,J＝14.7,6.6Hz,1H),3.86(dd,J＝14.3,7.1Hz,1H),3.75(t,J＝6.7Hz,2H),3.30(dd,J＝10.4,3.0Hz,1H),3.06(dd,J＝10.3,4.1Hz,1H),1.94(dt,J＝11.9,7.1Hz,4H),1.85–1.74(m,1H),1.42(ddd,J＝36.6,16.1,7.4Hz,3H)。
13 C NMR(101MHz,CDCl 3 )δ164.28(d,J＝12.8Hz),161.82(d,J＝12.5Hz),131.13(d,J＝8.2Hz),130.37(d,J＝8.4Hz),129.94(s),116.46(s),116.21(d,J＝8.7Hz),115.95(s),112.36(d,J＝8.0Hz),111.76(s),78.04(s),77.51(s),77.19(s),76.88(s),68.86(d,J＝7.6Hz),51.18(s),49.79(s),30.35(s),29.66(s),28.95(s),27.45(s),27.25(s),25.81(d,J＝1.5Hz)。
example 5
This embodiment is identical to the arrangement of embodiment 1, except that: para-tert-butylmalononitrile (0.2 mmol) was used instead of benzylidene malononitrile (0.2 mmol) in 94% yield. The product detection results are shown in fig. 9 and 10:
1 H NMR(400MHz,CDCl 3 )δ7.39(dd,J＝15.3,8.3Hz,4H),7.29(d,J＝8.4Hz,2H),7.23(d,J＝8.3Hz,2H),4.53(d,J＝4.0Hz,1H),4.48–4.33(m,3H),3.94(dt,J＝12.9,6.5Hz,1H),3.90–3.80(m,1H),3.79–3.68(m,2H),3.26(dd,J＝10.3,3.3Hz,1H),3.02(dd,J＝10.4,4.0Hz,1H),2.03–1.84(m,4H),1.78(dd,J＝9.1,4.5Hz,1H),1.45(dt,J＝13.1,5.7Hz,3H),1.31(d,J＝4.2Hz,18H)。
13 C NMR(101MHz,CDCl 3 )δ152.12(s),151.85(s),131.41(s),130.89(s),128.92(s),128.19(s),126.17(s),125.88(s),112.57(d,J＝2.6Hz),111.97(s),78.16(s),77.74(s),77.48(s),77.16(s),76.84(s),68.80(d,J＝13.0Hz),51.56(s),50.20(s),34.65(d,J＝4.2Hz),31.29(s),30.43(s),28.99(s),27.47(s),27.13(s),25.84(d,J＝6.4Hz)。
example 6
This embodiment is identical to the arrangement of embodiment 1, except that: 3, 4-dimethylbenzenemalononitrile (0.2 mmol) was substituted for benzylidene malononitrile (0.2 mmol) in 68% yield. Product detection is shown in fig. 11 and 12:
1 H NMR(400MHz,CDCl 3 )δ7.13(dd,J＝16.1,7.0Hz,4H),7.03(d,J＝9.0Hz,2H),4.50(d,J＝4.1Hz,1H),4.46–4.32(m,3H),3.93(dd,J＝14.4,6.7Hz,1H),3.84(dd,J＝14.2,7.1Hz,1H),3.73(t,J＝6.5Hz,2H),3.20(dd,J＝10.5,2.8Hz,1H),2.97(dd,J＝10.5,3.9Hz,1H),2.25(t,J＝6.6Hz,12H),1.99–1.84(m,4H),1.77(d,J＝6.7Hz,1H),1.45(dd,J＝12.0,5.2Hz,3H)。
13 C NMR(101MHz,CDCl 3 )δ137.48(dd,J＝36.2,18.0Hz),132.02(s),131.43(s),130.49(d,J＝9.4Hz),130.22(s),129.71(s),126.52(s),125.83(s),112.63(s),112.05(s),78.26(s),77.74(s),77.53(s),77.22(s),76.90(s),68.82(d,J＝15.2Hz),51.60(s),50.33(s),30.40(s),29.03(s),27.53(s),27.16(s),25.89(d,J＝13.7Hz),19.93(s),19.54(s)。
example 7
This embodiment is identical to the arrangement of embodiment 1, except that: p-n-propylmethylenemalononitrile (0.2 mmol) was used in place of benzylidene malononitrile (0.2 mmol) in 73% yield. The product detection results are shown in fig. 13 and 14:
1 H NMR(400MHz,CDCl 3 )δ7.28(d,J＝8.1Hz,2H),7.24–7.14(m,6H),4.52(d,J＝4.1Hz,1H),4.48–4.34(m,3H),3.99–3.89(m,1H),3.89–3.80(m,1H),3.79–3.69(m,2H),3.25(dd,J＝10.5,3.2Hz,1H),3.01(dd,J＝10.3,4.1Hz,1H),2.58(td,J＝7.7,4.6Hz,4H),2.01–1.82(m,4H),1.77(dd,J＝9.0,4.3Hz,1H),1.64(ddd,J＝15.0,7.5,3.6Hz,4H),1.49–1.35(m,3H),0.94(q,J＝7.2Hz,6H)。
13 C NMR(101MHz,CDCl 3 )δ143.79(s),143.47(s),131.78(s),131.20(s),129.47–128.88(m),128.38(s),112.57(s),111.98(s),78.21(s),77.59(d,J＝18.7Hz),77.18(s),76.87(s),68.82(d,J＝14.8Hz),51.66(s),50.36(s),37.69(d,J＝3.7Hz),30.40(s),28.98(s),27.50(s),27.12(s),25.83(d,J＝3.9Hz),24.29(d,J＝3.2Hz),13.87(d,J＝4.4Hz)。
as can be seen by comparing examples 2-7 with example 1: under the same conditions, the yield aspect: p-methoxybenzylidene malononitrile (99%) > methylbenzylidene malononitrile (95%) > p-tert-butylmalononitrile (94%) > benzylidene malononitrile (93%) > p-fluorobenzylidene malononitrile (82%) > p-n-propylmethylenemalononitrile (73%) > 3, 4-dimethylbenzenemalononitrile (68%).
Example 8
This embodiment is identical to the arrangement of embodiment 1, except that: 2-methyltetrahydrofuran was used as a starting material for R1 in 75% yield. The product detection results are shown in fig. 15 and 16:
1 H NMR(400MHz,CDCl 3 )δ7.48–7.36(m,10H),4.48(dd,J＝21.0,5.5Hz,2H),4.05–3.87(m,4H),3.38(d,J＝5.5Hz,1H),3.26(d,J＝5.6Hz,1H),2.19(dt,J＝12.4,8.7Hz,1H),2.06–1.92(m,4H),1.91–1.77(m,1H),1.67(d,J＝8.0Hz,2H),1.26(s,3H),1.21(s,3H)。
13 C NMR(101MHz,CDCl 3 )δ135.26(d,J＝8.0Hz),129.38(d,J＝15.0Hz),128.99(t,J＝8.6Hz),113.16(dd,J＝19.0,11.4Hz),83.80(d,J＝16.0Hz),77.42(s),77.11(s),76.79(s),68.24(s),67.70(s),55.58(s),55.19(s),37.80(s),33.64(s),26.88(s),25.66(d,J＝7.2Hz),24.90(s),24.65(s),23.96(s)。
example 9
This embodiment is identical to the arrangement of embodiment 1, except that: 1, 3-dioxolane was used as a starting material for R1 in place of tetrahydrofuran in a yield of 69%. The product detection results are shown in fig. 17 and 18:
1 H NMR(400MHz,CDCl 3 )δ7.49–7.35(m,5H),5.24(d,J＝2.7Hz,1H),4.30(d,J＝6.6Hz,1H),4.08(dt,J＝14.1,6.9Hz,2H),4.02–3.87(m,2H),3.52(dd,J＝6.4,2.7Hz,1H)。
13 C NMR(101MHz,CDCl 3 )δ133.21(s),129.33(d,J＝9.6Hz),129.02(s),112.19(s),112.03(d,J＝22.6Hz),102.93(s),77.47(s),77.15(s),76.83(s),65.98(s),65.10(s),49.26(s),24.34(s)。
as can be seen by comparing examples 8-9 with example 1: under the same conditions, in the R1 raw material, the contribution of tetrahydrofuran to the yield is better than that of 2-methyltetrahydrofuran, and the 2-methyltetrahydrofuran is better than that of 1, 3-dioxolane.
Example 10
This embodiment is identical to the arrangement of embodiment 1, except that: phenethyl benzylidene malononitrile (0.2 mmol) was substituted for benzylidene malononitrile (0.2 mmol) with a reaction time of 42h and a yield of 87%. The product detection results are shown in fig. 19 and 20:
1 H NMR(400MHz,CDCl 3 )δ7.52(d,J＝7.7Hz,2H),7.43(t,J＝6.8Hz,3H),7.37(dd,J＝14.6,7.0Hz,5H),4.81(s,1H),4.66(t,J＝7.3Hz,1H),4.29(s,1H),4.18(t,J＝7.3Hz,1H),3.95(dd,J＝14.2,6.6Hz,1H),3.85(dd,J＝14.8,7.0Hz,1H),3.76–3.63(m,2H),1.86(ddd,J＝23.4,14.0,7.5Hz,4H),1.72(dd,J＝12.2,7.1Hz,1H),1.66(s,3H),1.56(s,2H),1.48(dd,J＝12.2,7.5Hz,1H),1.35–1.23(m,1H),1.24–1.12(m,1H)。
13 C NMR(101MHz,CDCl 3 )δ138.30(s),136.76(s),128.99(s),128.88–128.33(m),127.75(s),126.72(s),112.23(d,J＝14.2Hz),82.61(s),80.94(s),77.53(s),77.21(s),76.89(s),48.32(s),48.06(s),34.44(s),33.18(s),27.29(d,J＝8.9Hz),26.34(s),25.86(s),19.52(s),16.51(s)。
example 11
This embodiment is identical to the arrangement of embodiment 1, except that: p-methyl phenethyl benzylidene malononitrile (0.2 mmol) was substituted for benzylidene malononitrile (0.2 mmol), the reaction time was 42h and the yield was 76%. The product detection results are shown in fig. 21 and 22:
1 H NMR(400MHz,CDCl 3 )δ7.44(d,J＝8.1Hz,2H),7.35(d,J＝8.1Hz,3H),7.26–7.19(m,3H),4.83(s,1H),4.70(t,J＝7.2Hz,1H),4.31(s,1H),4.21(t,J＝7.3Hz,1H),3.94(qd,J＝14.6,6.8Hz,2H),3.81–3.63(m,3H),2.38(d,J＝4.4Hz,6H),2.00–1.82(m,4H),1.76(dd,J＝13.1,6.2Hz,1H),1.68(s,4H),1.59(s,2H),1.52(dd,J＝12.1,7.5Hz,1H),1.42–1.32(m,1H),1.27–1.21(m,1H)。
13 C NMR(101MHz,CDCl 3 )δ138.47(s),138.23(s),135.23(s),133.65(s),129.67(s),129.46(s),127.59(s),126.56(s),112.31(d,J＝10.5Hz),82.62(s),80.89(s),77.50(s),77.18(s),76.86(s),69.55(s),69.06(s),48.08(s),47.82(s),34.57(s),33.22(s),32.38(s),27.27(d,J＝12.1Hz),26.37(s),25.93(s),21.02(s),19.53(s),16.50(s)。
as can be seen from comparative examples 10 and 11, under the same conditions, the yield of p-methylbenzene-methylene-malononitrile was smaller than that of phenethyl-benzylidene-malononitrile. In comparison with example 1, the yield was still lower than that of the alkenyl malononitrile compound of example 1, although the reaction time was prolonged.
Example 12
This example is based on example 1 and is carried out as an amplification reaction, the specific procedure being as follows:
1g of benzylidene malononitrile (0.0064 mol), 0.219g of carbon tetrabromide and 50ml of tetrahydrofuran were successively charged into a 100ml single-necked flask, and after adding a magnet, the single-necked flask was vented under argon for 30 minutes and reacted under 30W of blue light for 36 hours. Working up as in example 1 after the end of the reaction gave a yield of 54%.
The invention takes the dicyanomethane as the raw material, synthesizes the dicyanomethane derivative through the photocatalysis of the photo-mediated carbon tetrabromide, does not use noble metal for catalysis in the reaction, and has mild reaction conditions and short reaction time. Can be used for industrial mass production. When based on benzylidene malononitrile and tetrahydrofuran, the best conditions are: the reaction time is 36h, the dosage of carbon tetrabromide is 0.1eq of the raw material, and when tetrahydrofuran is used as a solvent, the yield of the obtained product is highest. And the substrate adaptability is expanded under the condition, and the substrate adaptability is good as can be seen from the examples. And after the amplification reaction, the yield can reach 54%, and the method is suitable for industrial production.
In the experiment, the highest yield can reach 94%, the applicability of the substrate is wide, the noble metal is avoided to catalyze, and the method has wide prospect in the field of organic synthesis.
It is to be understood that the foregoing detailed description of the invention is merely illustrative of the invention and is not limited to the embodiments of the invention. It will be understood by those of ordinary skill in the art that the present invention may be modified or substituted for elements thereof to achieve the same technical effects; the protection scope of the scheme is as long as the use requirement is met.

Claims (9)

1. The dicyanomethane compound is characterized in that the structural general formula of the dicyanomethane compound meets the following conditions:
r is any one of aryl, substituted aryl, cyclobutyl and cyclohexyl, and R1 is any one of tetrahydrofuran, 1, 3-dioxolane and derivatives thereof.
2. A dicyanomethane compound according to claim 1, characterized in that the dicyanomethane compound is any one of the following structures:
3. a process for the preparation of the dicyan methane compound according to claim 1, characterized in that: r1 and an alkenyl malononitrile compound with an R group are taken as raw materials, carbon tetrabromide is added as a catalyst, and the dicyanomethane compound is obtained by reaction under the conditions of an organic solvent and visible light irradiation.
4. A process for the preparation of a dicyan methane compound according to claim 3, characterized in that: the alkenyl malononitrile compound with R is any one of 3, 4-dimethylbenzenemalononitrile, p-chlorobenzenemalononitrile, p-trifluoromethyl benzylenemalononitrile, p-phenyl benzylenemalononitrile, p-methoxybenzylenemalononitrile, o-chlorobenzenemalononitrile, p-methylbenzenemalononitrile, p-cyanobenzenemalononitrile, p-n-propylbenzylenemalononitrile, 1-naphthalene benzylenemalononitrile and perfluoro benzylenemalononitrile.
5. A process for the preparation of a dicyan methane compound according to claim 3, characterized in that: the organic reagent is any one of tetrahydrofuran, ethyl acetate, acetonitrile and dichloromethane.
6. A process for the preparation of a dicyan methane compound according to claim 3, characterized in that: the dosage of the carbon tetrabromide relative to the alkenyl malononitrile compound with R groups is 0.1-0.3eq.
7. A process for the preparation of a dicyan methane compound according to claim 3, characterized in that: and R1 is any one of 2-methyltetrahydrofuran, tetrahydrofuran, 1, 3-dioxolane and derivatives thereof.
8. A process for the preparation of a dicyan methane compound according to claim 3, characterized in that: the visible light is blue light, and the reaction time is 12-42h.
9. The method for producing a dicyanomethane compound according to any one of claims 3 to 8, wherein the reaction further comprises a purification step of: the mixture of petroleum ether and ethyl acetate is used as a developing agent, column chromatography is used for separation, and the finished product of the dicyanomethane compound is obtained after concentration and drying.
CN202310384586.5A 2023-04-12 2023-04-12 Dicyanomethane compound and synthesis method and application thereof Pending CN116535368A (en)

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