CN112010722B - Synthesis method of E-type beta-thiocyanatelamide derivative - Google Patents
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Abstract
The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing an E-type beta-thiocyanatelamide derivative, which has the following specific reaction equation:
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing an E-type beta-thiocyanatelamide derivative.
Background
The enamide compounds are important pharmaceutical and biological intermediates, and widely appear in natural products and bioactive compounds as important synthetic raw materials, so that the construction of C-C bonds and C-X (X = O, S, P, si) bonds through direct C (sp 2) -H functional group reaction is concerned by researchers in related fields. In addition, the thiocyanic acid compounds are a precursor for constructing sulfur-containing compounds, including thioether and sulfur-containing heterocycle, and the compounds have certain bactericidal and cancer-inhibiting effects. Heretofore, thiocyanidation of aromatic and heterocyclic compounds has been studied, but the reaction of thiocyanidation of olefinic compounds has been sought.
The traditional beta-thiocyanatemide derivative is prepared by taking potassium thiocyanate as a thiocyano source and N-bromosuccinimide as an oxidant through reaction in N, N-dimethylformamide or ethanol, and the reaction does not generally relate to stereoselectivity, so that the method for synthesizing the E-type beta-thiocyanatemide derivative by developing regioselectivity and stereoselectivity has higher theoretical and practical application values.
Disclosure of Invention
Aiming at the problems, the invention provides a synthetic method of the E-type beta-thiocyanenamide derivative, which has the advantages of good selectivity, high yield, mild reaction conditions and simple and convenient post-treatment.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for synthesizing E type beta-thiocyanatelamide derivatives has the following specific reaction equation:
the first compound is an enamide derivative, and the second compound is ammonium thiocyanate;
wherein R is 1 Is phenyl, substituted phenyl, naphthyl, thiophene; r 2 Is methyl, ethyl, n-propyl; r 3 Is methyl, benzyl, substituted benzyl, propynyl, propenyl, methyl.
Preferably, the oxidizing agent is potassium persulfate; the solvent is acetic acid.
Preferably, the reaction temperature of the method for synthesizing the E-type beta-thiocyanatelenamide derivative is 60 ℃, and the reaction time is 6-12h.
Preferably, the molar ratio of the first compound to the second compound is 1.0: 1.5, the molar ratio of the second compound to the oxidizing agent is 1.0: 1.0, and 3mL of the reaction solvent is used per millimole of the first compound.
The invention has the beneficial effects that:
1. the E-type beta-thiocyanatelenamide compound is synthesized for the first time by taking the enamide derivative and ammonium thiocyanate as substrates.
2. The method has the advantages of good selectivity, high yield, mild reaction conditions and simple and convenient post-treatment.
Detailed Description
The technical solutions of the present invention are further illustrated and described below by specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
(E)-N-benzyl-N-(2-thiocyanato-1-(p-tolyl)vinyl)acetamide
Mixing 0.3mmol of enamide derivative, 0.45mmol of ammonium thiocyanate, 0.45mmol of potassium persulfate as oxidant and 3mL of acetic acid in an air atmosphereReacting for 6 hours at 60 ℃; adding proper amount of water or sodium chloride solution to stop reaction, and cooling to room temperature. The reaction solution was washed with brine, extracted with ethyl acetate 3 times, and the organic phase was collected. Anhydrous Mg for organic phase 2 SO 4 Drying, filtering, concentrating and purifying by column chromatography to obtain 84.1mg of target product, wherein the yield is 87%, and the nuclear magnetic data of the target product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.31-7.26(m,5H),7.19-7.10(m,4H),5.85(s,1H),4.56(s,2H),2.42(s,3H),2.19(s,3H). 13 C NMR(100MHz,CDCl 3 )δ170.1,145.7,141.2,136.5,129.9,129.3,128.6,128.5,128.1,127.7,111.3,109.6,49.7,22.4,21.4.
example 2
(F)-N-benzyl-N-(1-phenyl-2-thiocyanatovinyl)acetamide
Mixing 0.3mmol of enamide derivative, 0.45mmol of ammonium thiocyanate, 0.45mmol of potassium persulfate oxidant and 3mL of acetic acid, and reacting at 60 ℃ for 6 hours in an air atmosphere; the reaction was stopped by adding an appropriate amount of water or sodium chloride solution and cooled to room temperature. The reaction solution was washed with brine, extracted with ethyl acetate 3 times, and the organic phase was collected. Anhydrous Mg for organic phase 2 SO 4 Drying, filtering, concentrating and purifying by column chromatography to obtain 78.6mg of target product, wherein the yield is 85%, and the nuclear magnetic data of the target product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.50-7.44(m,3H),7.34-7.28(m,3H),7.24-7.22(m,2H),7.18-7.13(m,2H),5.92(s,1H),4.57(s,2H),2.21(s,3H). 13 C NMR(100MHz,CDCl 3 )δ170.2,145.5,136.4,132.2,130.7,129.3,128.6,128.5,128.2,127.8,112.2,109.4,49.8,22.4.
example 3
(E)-N-benzyl-N-(1-phenyl-2-thiocyanatovinyl)acetamide
0.3mmol of an enamide derivative, 0.45mmol of ammonium thiocyanate, and,0.45mmol of potassium persulfate oxidant and 3mL of acetic acid react for 6h at 60 ℃ in the air atmosphere; the reaction was stopped by adding an appropriate amount of water or sodium chloride solution and cooled to room temperature. The reaction solution was washed with brine, extracted with ethyl acetate 3 times, and the organic phase was collected. Anhydrous Mg for organic phase 2 SO 4 Drying, filtering, concentrating and purifying by column chromatography to obtain 82.2mg of target product, wherein the yield is 81%, and the nuclear magnetic data of the target product are as follows: 1 H NMR(400MHz,CDCl 3 )：δ7.32-7.29(m,3H),7.18-7.15(m,4H),6.97(d,J＝8.8Hz,2H),5.80(s,1H),4.57(s,2H),3.87(s,3H),2.19(s,3H). 13 C NMR(100MHz,CDCl 3 )δ170.2,161.3,145.7,136.5,129.9,128.7,128.6,127.8,124.2,114.7,110.1,109.7,55.4,49.8,22.4.
example 4
(E)-N-(1-([1,1'-biphenyl]-4-yl)-2-thiocyanatovinyl)-N-benzylacetamide
Mixing 0.3mmol of enamide derivative, 0.45mmol of ammonium thiocyanate, 0.45mmol of potassium persulfate oxidant and 3mL of acetic acid, and reacting at 60 ℃ for 6 hours in an air atmosphere; the reaction was stopped by adding an appropriate amount of water or sodium chloride solution and cooled to room temperature. The reaction solution was washed with brine, extracted with ethyl acetate 3 times, and the organic phase was collected. Anhydrous Mg for organic phase 2 SO 4 Drying, filtering, concentrating, and purifying by column chromatography to obtain 88.7mg of target product with a yield of 77%, wherein the nuclear magnetic data of the target product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.69-7.67(m,2H),7.63-7.61(m,2H),7.50-7.46(m,2H),7.42-7.38(m,1H),7.32-7.26(m,5H),7.20-7.17(m,2H),5.93(s,1H),4.61(s,2H),2.22(s,3H). 13 C NMR(100MHz,CDCl 3 )δ170.1,145.3,143.5,139.4,136.5,130.9,128.9,128.8,128.7,128.6,128.1,127.8,127.8,127.0,112.1,109.4,49.9,22.4.
example 5
(E)-N-benzyl-N-(2-thiocyanato-1-(4-(trifluoromethyl)phenyl)vinyl)acetamide
Mixing 0.3mmol of enamide derivative, 0.45mmol of ammonium thiocyanate, 0.45mmol of potassium persulfate oxidant and 3mL of acetic acid, and reacting at 60 ℃ for 6 hours in an air atmosphere; the reaction was stopped by adding an appropriate amount of water or sodium chloride solution and cooled to room temperature. The reaction solution was washed with brine, extracted with ethyl acetate 3 times, and the organic phase was collected. Anhydrous Mg for organic phase 2 SO 4 Drying, filtering, concentrating, and purifying by column chromatography to obtain 90.3mg of target product with yield of 80%, wherein the nuclear magnetic data of the target product is as follows: 1 H NMR(400MHz,CDCl 3 )δ7.73(d,J＝8.1Hz,2H),7.37-7.30(m,5H),7.16-7.13(m,2H),6.06(s,1H),4.59(s,2H),2.21(s,3H). 13 C NMR(100MHz,CDCl 3 )δ170.5,145.4,139.1,137.2,131.1(q,J C-F ＝33Hz),129.0,128.4,127.5,126.1(2C),126.0(q,J C-F ＝4Hz),123.8(d,J C-F ＝271Hz),116.7,49.9,22.0.
example 6
(E)-N-benzyl-N-(1-(4-fluorophenyl)-2-thiocyanatovinyl)acetamide
Mixing 0.3mmol of enamide derivative, 0.45mmol of ammonium thiocyanate, 0.45mmol of potassium persulfate oxidant and 3mL of acetic acid, and reacting at 60 ℃ for 6 hours in an air atmosphere; adding proper amount of water or sodium chloride solution to stop reaction, and cooling to room temperature. The reaction solution was washed with brine, extracted with ethyl acetate 3 times, and the organic phase was collected. Anhydrous Mg for organic phase 2 SO 4 Drying, filtering, concentrating and purifying by column chromatography to obtain 81.2mg of target product, wherein the yield is 83 percent, and the nuclear magnetic data of the target product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.33-7.28(m,3H),7.25-7.21(m,2H),7.18-7.13(m,4H),5.93(s,1H),4.56(s,2H),2.20(s,3H). 13 C NMR(100MHz,CDCl 3 )δ170.0,163.6(d,J C-F ＝251Hz),144.9,136.3,130.4(d,J C-F ＝8Hz),128.7,128.6,128.3(d,J C-F ＝4Hz),127.9,116.6(d,J C-F ＝22Hz),112.0,109.1,49.9,22.4.
example 7
(E)-N-benzyl-N-(1-(4-chlorophenyl)-2-thiocyanatovinyl)acetamide
Mixing 0.3mmol of enamide derivative, 0.45mmol of ammonium thiocyanate, 0.45mmol of potassium persulfate oxidant and 3mL of acetic acid, and reacting at 60 ℃ for 6 hours in an air atmosphere; the reaction was stopped by adding an appropriate amount of water or sodium chloride solution and cooled to room temperature. The reaction solution was washed with brine, extracted with ethyl acetate 3 times, and the organic phase was collected. Anhydrous Mg for organic phase 2 SO 4 Drying, filtering, concentrating and purifying by column chromatography to obtain 81.2mg of target product, wherein the yield is 80 percent, and the nuclear magnetic data of the target product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.45-7.43(m,2H),7.32-7.29(m,3H),7.18-7.13(m,4H),5.95(s,1H),4.57(s,2H),2.19(s,3H). 13 C NMR(100MHz,CDCl 3 )δ167.0,144.7,136.8,136.2,130.7,129.6,129.5,128.7,128.6,127.9,112.6,109.0,49.9,22.4.
example 8
(E)-N-benzyl-N-(1-(4-bromophenyl)-2-thiocyanatovinyl)acetamide
Mixing 0.3mmol of enamide derivative, 0.45mmol of ammonium thiocyanate, 0.45mmol of potassium persulfate oxidant and 3mL of acetic acid, and reacting at 60 ℃ for 6 hours in an air atmosphere; the reaction was stopped by adding an appropriate amount of water or sodium chloride solution and cooled to room temperature. The reaction solution was washed with brine, extracted with ethyl acetate 3 times, and the organic phase was collected. Anhydrous Mg for organic phase 2 SO 4 Drying, filtering, concentrating, and purifying by column chromatography to obtain 98.4mg of target product with yield of 85%, wherein the nuclear magnetic data of the target product is as follows: 1 H NMR(400MHz,CDCl 3 )δ7.60(d,J＝8.3Hz,2H),7.31-7.28(m,3H),7.15–7.08(m,4H),5.96(s,1H),4.56(s,2H),2.19(s,3H). 13 C NMR(100MHz,CDCl 3 )δ170.0,144.6,136.1,132.5,131.1,129.7,128.6,128.5,127.8,125.0,112.6,108.9,49.9,22.4.
example 9
(E)-N-methyl-N-(1-phenyl-2-thiocyanatovinyl)acetamide
Mixing 0.3mmol of enamide derivative, 0.45mmol of ammonium thiocyanate, 0.45mmol of potassium persulfate oxidant and 3mL of acetic acid, and reacting at 60 ℃ for 6 hours in an air atmosphere; the reaction was stopped by adding an appropriate amount of water or sodium chloride solution and cooled to room temperature. The reaction solution was washed with brine, extracted with ethyl acetate 3 times, and the organic phase was collected. Anhydrous Mg for organic phase 2 SO 4 Drying, filtering, concentrating and purifying by column chromatography to obtain 59.2mg of target product, wherein the yield is 85 percent, and the nuclear magnetic data of the target product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.49-7.48(m,3H),7.31-7.29(m,2H),6.27(s,1H),3.03(s,3H),2.13(s,3H). 13 C NMR(100MHz,CDCl 3 )δ170.5,147.6,132.5,130.7,129.3,128.1,110.5,109.6,35.6,22.2.
example 10
(E)-N-(1-phenyl-2-thiocyanatovinyl)-N-(prop-2-yn-1-yl)acetamide
Mixing 0.3mmol of enamide derivative, 0.45mmol of ammonium thiocyanate, 0.45mmol of potassium persulfate oxidant and 3mL of acetic acid, and reacting at 60 ℃ for 6 hours in an air atmosphere; adding proper amount of water or sodium chloride solution to stop reaction, and cooling to room temperature. The reaction solution was washed with brine, extracted with ethyl acetate 3 times, and the organic phase was collected. Anhydrous Mg for organic phase 2 SO 4 Drying, filtering, concentrating and purifying by column chromatography to obtain 63.8mg of target product, wherein the yield is 83 percent, and the nuclear magnetic data of the target product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.49-7.47(m,3H),7.34-7.32(m,2H),6.43(s,1H),4.25(d,J＝2.4Hz,2H),2.30(t,J＝2.5Hz,1H),2.14(s,3H). 13 C NMR(100MHz,CDCl 3 )δ13C NMR(101MHz,CDCl3)δ169.7,144.7,132.1,130.8,129.3,128.1,112.7,109.5,77.9,72.9,36.4,22.3.
example 11
(E)-N-allyl-N-(1-phenyl-2-thiocyanatovinyl)acetamide
Mixing 0.3mmol of enamide derivative, 0.45mmol of ammonium thiocyanate, 0.45mmol of potassium persulfate oxidant and 3mL of acetic acid, and reacting at 60 ℃ for 6 hours in an air atmosphere; the reaction was stopped by adding an appropriate amount of water or sodium chloride solution and cooled to room temperature. The reaction solution was washed with brine, extracted with ethyl acetate 3 times, and the organic phase was collected. Anhydrous Mg for organic phase 2 SO 4 Drying, filtering, concentrating and purifying by column chromatography to obtain 62.7mg of target product, wherein the yield is 81 percent, and the nuclear magnetic data of the target product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.48-7.47(m,3H),7.31-7.26(m,2H),6.24(s,1H),5.79(ddt,J＝16.6,10.1,6.3Hz,1H),5.18(d,J＝10.1Hz,1H),5.05(d,J＝17.2Hz,1H),4.02(d,J＝6.2Hz,2H),2.16(s,3H). 13 C NMR(100MHz,CDCl 3 )δ169.9,145.9,132.5,132.2,130.6,129.2,128.1,118.8,111.6,109.6,49.7,22.4.
example 12
(E)-N-(2-bromobenzyl)-N-(1-phenyl-2-thiocyanatovinyl)acetamide
Mixing 0.3mmol of enamide derivative, 0.45mmol of ammonium thiocyanate, 0.45mmol of potassium persulfate oxidant and 3mL of acetic acid, and reacting at 60 ℃ for 6 hours in an air atmosphere; adding proper amount of water or sodium chloride solution to stop reaction, and cooling to room temperature. The reaction solution was washed with brine, extracted with ethyl acetate 3 times, and the organic phase was collected. Anhydrous Mg for organic phase 2 SO 4 Drying, filtering, concentrating and purifying by column chromatography to obtain 84.5mg of target product, wherein the yield is 73%, and the nuclear magnetic data of the target product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.54-7.44(m,4H),7.27-7.25(m,1H),7.21-7.14(m,4H),6.09(s,1H),4.77(s,2H),2.23(s,3H). 13 C NMR(100MHz,CDCl 3 )δ170.4,145.2,135.5,133.0,132.2,130.8,130.7,129.5,129.2(2C),128.2(2C),127.7,123.9,112.8,109.5,49.8,22.4.
example 13
(E)-N-benzyl-N-(1-phenyl-2-thiocyanatovinyl)propionamide
Mixing 0.3mmol of enamide derivative, 0.45mmol of ammonium thiocyanate, 0.45mmol of potassium persulfate oxidant and 3mL of acetic acid, and reacting at 60 ℃ for 6 hours in an air atmosphere; the reaction was stopped by adding an appropriate amount of water or sodium chloride solution and cooled to room temperature. The reaction solution was washed with brine, extracted with ethyl acetate 3 times, and the organic phase was collected. Anhydrous Mg for organic phase 2 SO 4 Drying, filtering, concentrating and purifying by column chromatography to obtain 79.2mg of target product, wherein the yield is 82%, and the nuclear magnetic data of the target product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.48-7.46(m,3H),7.32-7.30(m,3H),7.23-7.21(m,2H),7.19-7.17(m,2H),5.91(s,1H),4.58(s,2H),2.44(q,J＝7.4Hz,2H),1.20(t,J＝7.4Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ173.8,145.3,136.7,132.5,130.8,129.4,128.8,128.7,128.3,127.9,112.1,109.6,50.2,27.7,10.0.
example 14
(E)-N-benzyl-N-(1-phenyl-2-thiocyanatovinyl)butyramide
Mixing 0.3mmol of enamide derivative, 0.45mmol of ammonium thiocyanate, 0.45mmol of potassium persulfate oxidant and 3mL of acetic acid, and reacting at 60 ℃ for 6 hours in an air atmosphere; the reaction was stopped by adding an appropriate amount of water or sodium chloride solution and cooled to room temperature. The reaction solution was washed with brine, extracted with ethyl acetate 3 times, and the organic phase was collected. Anhydrous Mg for organic phase 2 SO 4 Drying, filtering and concentratingAnd (3) performing column chromatography purification to obtain 88.7mg of a target product, wherein the yield is 88%, and the nuclear magnetic data of the target product is as follows: 1 H NMR(400MHz,CDCl 3 )δ7.48-7.46(m,3H),7.34-7.28(m,3H),7.24-7.21(m,2H),7.18-7.16(m,2H),5.88(s,1H),4.58(s,2H),2.40(t,J＝7.4Hz,2H),1.74(q,J＝7.3Hz,2H),0.96(t,J＝7.4Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ172.9,145.3,136.7,132.4,130.7,129.3,128.7,128.6,128.2,127.8,111.9,109.5,50.0,36.1,19.1,13.9.
example 15
(E)-N-benzyl-N-(2-thiocyanato-1-(thiophen-3-yl)vinyl)acetamide
Mixing 0.3mmol of enamide derivative, 0.45mmol of ammonium thiocyanate, 0.45mmol of potassium persulfate oxidant and 3mL of acetic acid, and reacting at 60 ℃ for 6 hours in an air atmosphere; the reaction was stopped by adding an appropriate amount of water or sodium chloride solution and cooled to room temperature. The reaction solution was washed with brine, extracted with ethyl acetate 3 times, and the organic phase was collected. Anhydrous Mg for organic phase 2 SO 4 Drying, filtering, concentrating and purifying by column chromatography to obtain 78.2mg of target product, wherein the yield is 83 percent, and the nuclear magnetic data of the target product are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.45(dd,J＝5.1,2.9Hz,1H),7.37-7.36(m,1H),7.34-7.29(m,3H),7.21-7.19(m,2H),7.07(d,J＝5.0Hz,1H),5.84(s,1H),4.64(s,2H),2.13(s,3H). 13 C NMR(100MHz,CDCl 3 )δ169.9,140.4,136.5,134.1,128.8,128.6,127.9,127.8,127.7,126.3,112.0,109.1,50.3,22.2.
example 16
(E)-N-benzyl-N-(1-phenyl-2-selenocyanatovinyl)acetamide
Mixing 0.3mmol of enamide derivative, 0.45mmol of ammonium thiocyanate, 0.45mmol of potassium persulfate oxidant and 3mL of acetic acid, and reacting at 60 ℃ for 6 hours in an air atmosphere; adding a proper amount of waterOr stopping the reaction by using sodium chloride solution, and cooling to room temperature. The reaction solution was washed with brine, extracted with ethyl acetate 3 times, and the organic phase was collected. Anhydrous Mg for organic phase 2 SO 4 Drying, filtering, concentrating and purifying by column chromatography to obtain 91.9mg of target product, wherein the yield is 86%, and the nuclear magnetic data of the target product is as follows: 1 H NMR(400MHz,CDCl 3 )δ7.50-7.46(m,3H),7.34-7.28(m,3H),7.18-7.14(m,4H),6.26(s,1H),4.58(s,2H),2.21(s,3H). 13 C NMR(100MHz,CDCl 3 )δ170.2,145.4,136.5,133.7,130.8,129.6,128.6(2C),127.8,127.5,111.0,100.2,49.9,22.4.
in conclusion, the E-type beta-thiocyano enamide compound is obtained by taking an enamide compound as a raw material, adding ammonium thiocyanate and potassium persulfate, and reacting at room temperature by taking acetic acid as a solvent. Compared with the traditional method, the method has the advantages of better yield, regioselectivity and stereoselectivity, mild reaction conditions, no metal participation and convenient raw material acquisition.
It is to be understood that the present invention is not limited to the details shown herein, but is rather well known to those skilled in the art.
The above examples are only for further illustrating the synthesis method of the E-type β -thiocyanenamide derivative of the present invention, but the present invention is not limited to the examples, and all equivalent changes and modifications made to the above examples according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (3)
1. A method for synthesizing E type beta-thiocyanenamide derivatives is characterized in that the specific reaction equation is as follows:
the first compound is an enamide derivative, and the second compound is ammonium thiocyanate;
wherein R is 1 Is phenyl, substituted phenyl, naphthyl, thiophene; r 2 Is methyl, ethyl, n-propyl; r is 3 Is methyl, benzylSubstituted benzyl, propynyl, propenyl;
the oxidant is potassium persulfate; the solvent is acetic acid.
2. The method for synthesizing the E-type beta-thiocyanenamide derivative according to claim 1, wherein the reaction temperature of the method for synthesizing the E-type beta-thiocyanenamide derivative is 60 ℃, and the reaction time is 6-12h.
3. The method for synthesizing the E type beta-thiocyanatenamide derivative according to claim 1, wherein the molar ratio of the first compound to the second compound is 1.0: 1.5, the molar ratio of the second compound to the oxidizing agent is 1.0: 1.0, and each millimole of the first compound corresponds to 3mL of the reaction solvent.
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| CN103787802A (en) * | 2014-02-11 | 2014-05-14 | 华东师范大学 | Aryl alkyl thioether compounds and synthesis method thereof |
| CN104447686A (en) * | 2014-11-13 | 2015-03-25 | 华侨大学 | Polysubstituted 2-pyrrolopyridine derivative and preparation method thereof |
| CN107501328A (en) * | 2017-09-08 | 2017-12-22 | 江苏强盛功能化学股份有限公司 | A kind of β thiocyanogens alkenyl phosphono analog derivative and preparation method thereof |
| CN107973779A (en) * | 2018-01-08 | 2018-05-01 | 华侨大学 | A kind of N-（2- pyridines/pyrimidine radicals）The preparation method of indole derivatives |
| CN109021033A (en) * | 2018-07-23 | 2018-12-18 | 中国科学院海洋研究所 | A kind of chitosan oligosaccharide derivative and preparation method thereof containing thiocarbamide and diethoxy phosphinylidyne amine structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787802A (en) * | 2014-02-11 | 2014-05-14 | 华东师范大学 | Aryl alkyl thioether compounds and synthesis method thereof |
| CN104447686A (en) * | 2014-11-13 | 2015-03-25 | 华侨大学 | Polysubstituted 2-pyrrolopyridine derivative and preparation method thereof |
| CN107501328A (en) * | 2017-09-08 | 2017-12-22 | 江苏强盛功能化学股份有限公司 | A kind of β thiocyanogens alkenyl phosphono analog derivative and preparation method thereof |
| CN107973779A (en) * | 2018-01-08 | 2018-05-01 | 华侨大学 | A kind of N-（2- pyridines/pyrimidine radicals）The preparation method of indole derivatives |
| CN109021033A (en) * | 2018-07-23 | 2018-12-18 | 中国科学院海洋研究所 | A kind of chitosan oligosaccharide derivative and preparation method thereof containing thiocarbamide and diethoxy phosphinylidyne amine structure |
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