CN107805232B - Synthetic method of derivative containing methylthio furan - Google Patents

Synthetic method of derivative containing methylthio furan Download PDF

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CN107805232B
CN107805232B CN201711054356.3A CN201711054356A CN107805232B CN 107805232 B CN107805232 B CN 107805232B CN 201711054356 A CN201711054356 A CN 201711054356A CN 107805232 B CN107805232 B CN 107805232B
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郭灿城
胡雨群
郭欣
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YUANJIANG HUALONG CATALYTIC TECHNOLOGY CO LTD
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    • 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
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
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Abstract

The invention discloses a synthetic method of a furan derivative containing methylthio groups, which comprises the steps of carrying out one-pot reaction on acetophenone compounds and dimethyl sulfoxide in the presence of an elemental iodine catalyst and a potassium persulfate oxidant to obtain the furan derivative containing methylthio groups; the method enriches the variety of furan derivatives, provides more intermediates for drug synthesis, has wide raw material source, simple steps, mild reaction conditions and high yield, and is beneficial to industrial production.

Description

Synthetic method of derivative containing methylthio furan
Technical Field
The invention relates to a synthetic method of substituted furan, in particular to a method for generating furan derivatives by oxidizing potassium persulfate through one-step reaction of acetophenone compounds and dimethyl sulfoxide under the catalysis of elemental iodine, and belongs to the field of synthesis of pharmaceutical intermediates.
Background
The furan derivative is an important raw material or intermediate for organic or pharmaceutical synthesis. In the prior art, relatively complex furan derivative medicines are often extracted from natural plants, for example, Chinese patent (publication No. 101830871A) discloses a method for extracting furan derivatives from snakegourd fruit, and particularly, the furan derivative medicines for treating various diseases caused by the transitional activation of a complement system are obtained by adopting ethanol extraction and chromatographic separation. The simple furan derivative can be synthesized by using furan raw materials, mainly by using the aromatic ring property of furan ring, and obtaining different substituted products by performing electrophilic substitution reaction such as halogenation, nitration, sulfonation, acylation and the like on the furan ring, for example, documents (2-acetylfuran synthesis, petrochemical, 2008, volume 37 supplement, 328-330) disclose a 2-acetylfuran which can be used for pharmaceutical intermediates and food additives, and acetic anhydride and furan are mainly used as catalysts to synthesize the 2-acetylfuran. The furan derivative can be further modified by simple furan derivatives, so that relatively complex furan derivatives can be obtained, for example, the document (the synthesis research of 2-furanboronic acid, the proceedings of Hebei science and technology university, 4 months 2012, 33, 2 nd vol. and 103-106 pages) discloses that 2-bromofuran and tributyl borate are used as raw materials, and n-butyllithium is adopted for the synthesis2-furanboronic acid is formed, and SP can be constructed by the 2-furanboronic acid through Suzuki cross-coupling reaction2A C-C single bond, so that furan derivatives of various substituent groups such as aromatic rings can be obtained. These methods for synthesizing furan derivatives by directly performing substitution reactions or the like on furan rings are affected by the electronic effects of furan rings, and the number and positions of the substitution group modifications are limited. At present, the synthesis of furan derivatives is also achieved by direct synthesis of furan rings, and complex substituent groups can be introduced directly from the starting materials, as compared with the classical Paal-Knorr reaction for the synthesis of furan derivatives, such as the dehydration of 1, 4-dicarbonyl compounds under anhydrous acidic conditions to yield furan and its derivatives, the reaction formula is as follows:
Figure BDA0001451662210000021
wherein the tert-butyl group can be replaced by other groups, so that furan derivatives substituted at the 2-position and the 5-position can be obtained. However, the method is difficult to obtain by adopting the 1, 4-diketone compound, so that the application of the method is limited.
Disclosure of Invention
Aiming at the defects of the existing method for synthesizing furan derivatives, the invention aims to provide a method for generating furan derivatives by oxidizing potassium persulfate through one-step reaction of acetophenone compounds and dimethyl sulfoxide under the catalysis of elemental iodine, the method enriches the variety of the furan derivatives, provides more intermediates for drug synthesis, has wide raw material source, simple steps, mild reaction conditions and high yield, and is beneficial to industrial production.
In order to realize the technical purpose, the invention provides a synthesis method of a furan derivative containing methylthio groups, wherein acetophenone compounds and dimethyl sulfoxide in a formula 1 are subjected to one-pot reaction in the presence of an elemental iodine catalyst and a potassium persulfate oxidant to obtain a furan derivative in a formula 2;
wherein R is hydrogen, halogen substituent, trifluoromethyl, nitro, alkyl, alkoxy or methylthio.
In a preferred embodiment, the substituted phenyl group in the acetophenone compound is, for example, o/m/p-bromophenyl, o/m/p-chlorophenyl, o/p-trifluoromethyl, o/m/p-tolyl, o/m-nitrophenyl, o/p-methoxy, p-methylthio, p-tert-butylphenyl or the like. The acetophenone compounds containing the substituents can obtain higher yield in the process of synthesizing corresponding furan derivatives.
In a preferable scheme, the concentration of the acetophenone compound in dimethyl sulfoxide is 0.1-1 mol/L; more preferably 0.2 to 0.3 mol/L.
In a preferable scheme, the molar weight of the tetraalkylammonium iodide is 20-40% of that of the acetophenone compound; more preferably 25 to 35%.
In a preferable scheme, the molar weight of the potassium persulfate oxidant is 2-3 times of that of the acetophenone compound. More preferably 2 to 2.5 times.
In a preferred embodiment, the reaction conditions are as follows: the reaction temperature is 90-140 ℃, and the reaction time is 5-11 h. Further preferred reaction conditions: the reaction temperature is 100-130 ℃, and the reaction time is 6-10 h; more preferred reaction conditions are: the reaction temperature is 115-125 ℃, and the reaction time is 7-9 h.
In the technical scheme of the invention, the elemental iodine is used as a catalyst, and the potassium persulfate is used as an oxidant. The furan derivative is formed by cyclizing two molecules of acetophenone compounds and one molecule of dimethyl sulfoxide, wherein one molecule of acetyl of the acetophenone compounds, one molecule of methyl of the acetophenone compounds and one molecule of methyl of the dimethyl sulfoxide are cyclized under the action of an elemental iodine catalyst and a potassium persulfate oxidant, so that the furan derivative with simultaneous substitution of 2, 3 and 5 positions is obtained. In the technical scheme of the invention, dimethyl sulfoxide has two important functions, on one hand, the dimethyl sulfoxide is used as an organic solvent with good solubility and can improve the reaction efficiency, and on the other hand, one methyl group of the dimethyl sulfoxide is used as a reaction substrate to participate in cyclization, and the other methyl group is modified on a formed furan ring in a methylthio form.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) the technical scheme of the invention realizes the oxidative cyclization of the acetophenone compound and dimethyl sulfoxide to obtain the furan derivative for the first time, and provides a brand new thought for synthesizing the furan derivative.
2) The technical scheme of the invention adopts the conventional acetophenone compound and the dimethyl sulfoxide as raw materials, and has the advantage of low cost compared with the existing 1, 4-diketone compound raw materials.
3) The technical scheme of the invention has simple steps and mild reaction conditions, can realize the synthesis of the furan derivative by a one-pot method, has high reaction yield and is beneficial to large-scale production.
4) The furan derivative synthesized by the technical scheme of the invention contains aryl and methylthio which are easy to modify, and has obvious advantages when being used as a synthetic intermediate of furan drugs.
Drawings
FIG. 1 is a 1H NMR spectrum of the furan derivative in example 1;
FIG. 2 is a 13C NMR spectrum of the furan derivative in example 1;
FIG. 3 is a 1H NMR spectrum of the furan derivative in example 2;
FIG. 4 is a 13C NMR spectrum of the furan derivative in example 2.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
The substrate starting materials, solvents and the like mentioned in the following examples were all commercial products (analytical reagents) on the market and were not further purified.
The product is separated by chromatography, column silica gel (300-400 mesh).
1H NMR (400MHz), 13C NMR (100MHz), in CDCl3As solvent, TMS was used as internal standard.
Multiplicity is defined as follows: s (singlet); d (doublet); t (triplet); q (quartet) and m (multiplet). Coupling constant J (Hertz).
Condition optimization experiment: the optimal reaction conditions were found by the following control experimental groups: acetophenone and dimethyl sulfoxide are used as reaction raw materials, and excessive dimethyl sulfoxide is used as a reaction solvent, so as to carry out an exemplary reaction, wherein the specific reaction is as follows:
weighing a catalyst, acetophenone and an oxidant, placing the catalyst, the acetophenone and the oxidant in a 25mL reaction tube, adding dimethyl sulfoxide (DMSO) as a solvent, heating the mixed solution to a certain temperature in an air atmosphere, and stirring for reaction. The reaction solution was cooled to room temperature, diluted with ethyl acetate (10mL), washed with water (5mL), and extracted with ethyl acetate (5mL × 3), and the organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and the solvent was then dried by rotary evaporator. The concentrated material was separated and purified by silica gel column chromatography (eluent petroleum ether/ethyl acetate) to obtain the final product.
Figure BDA0001451662210000041
Figure BDA0001451662210000042
Figure BDA0001451662210000051
Reaction conditions of control experiment groups 1-11 are acetophenone (0.5mmol), DMSO (2.0mL), catalyst (30 mol%), oxidant (1.0mmol), and reaction time is 8 h.
Control experiment 12 was in DMSO (1.0mL) under the same conditions as experiment 1.
DMSO (3.0mL) in control experiment 13 was the same as in experiment 1 except that the conditions were the same.
I of control experiment group 142(10 mol%), the other conditions were the same as in experimental group 1.
I of control group 152(50 mol%), other conditions were the same as in experimental group 1.
As can be seen from comparison of experimental groups 1-4 in the table, the reaction can be smoothly carried out under catalysis of elementary iodine, TBAB, TBAC, KI and the like, but the elementary iodine has better catalytic activity compared with TBAB, TBAC and the like and potassium iodide, and the yield of the corresponding obtained furan derivative is higher.
As can be seen from comparison of experimental groups 1 and 5-9 in the table, except that persulfate can enable the reaction to be carried out, other conventional oxidants such as hydrogen peroxide, oxygen, peroxide TBHP and the like can not realize the synthesis of furan derivatives, and potassium persulfate has the best effect in persulfate, so that the ideal yield can be obtained, and (NH)4)2S2O8、KHSO5Although the reaction proceeds, the yield is not satisfactory.
As can be seen from comparison of experimental groups 1 and 10-11 in the table, the yield is correspondingly reduced when the reaction temperature is too high or too low, and the optimal reaction effect can be achieved at about 120 ℃.
In summary, the optimal reaction conditions can be obtained by comparing the experimental groups 1-15: acetophenone (0.5mmol), and methyl sulfoxide (2mL), I2(0.15mmol)，K2S2O8(1.0mmol)，120℃，8h。
The following examples 1 to 18 were reacted under the optimized optimal reaction conditions described above:
example 1
Raw materials: acetophenone;
and (3) target products:
yield: 83 percent;
1H NMR(400MHz,CDCl3):δ8.05(dd,J＝13.7,7.6Hz,1H),7.65–7.59(m,1H),7.53(t,J＝7.1Hz,1H),7.48(t,J＝7.1Hz,1H),7.43–7.37(m,1H),7.35(s,1H),2.48(s,1H).
13C NMR(101MHz,CDCl3):δ181.8,153.8,150.3,137.2,132.6,129.5,129.3,129.1,128.7,128.5,126.5,124.1,118.1,18.1.
example 2
Raw materials: 2-bromoacetophenone;
and (3) target products:
yield: 62 percent;
1H NMR(400MHz,CDCl3):δ7.67(t,J＝7.7Hz,1H),7.52(d,J＝7.3Hz,1H),7.36(ddd,J＝26.3,15.5,7.6Hz,2H),7.22(s,1H),2.34(s,1H).
13C NMR(100MHz,CDCl3):δ182.4,155.4,150.8,139.1,133.4,133.4,132.3,131.7,131.3,130.1,129.4,127.1,127.1,123.6,123.4,120.9,120.0,18.1.
example 3
Raw materials: 2-trifluoromethylacetophenone;
and (3) target products:
Figure BDA0001451662210000071
yield: 50 percent;
1H NMR(400MHz,CDCl3):δ7.79–7.74(m,1H),7.67–7.60(m,2H),7.57(t,J＝6.4Hz,1H),7.30(s,1H),2.33(s,1H).
13C NMR(100MHz,CDCl3):δ182.4,153.6,151.3,136.4,132.2,131.5,131.3,130.3,130.0,129.6,129.3,128.4,127.0(q,J＝5.1Hz),126.7,126.7(dd,J＝8.7,3.9Hz),124.9,124.7,122.7,120.8,18.0.
example 4
Raw materials: 2-methylacetophenone;
and (3) target products:
Figure BDA0001451662210000072
yield: 74 percent;
1H NMR(400MHz,CDCl3):δ7.53(d,J＝7.5Hz,1H),7.40(t,J＝7.4Hz,1H),7.37–7.27(m,2H),7.15(s,1H),2.43(s,2H),2.40(s,1H),2.32(s,1H).
13C NMR(100MHz,CDCl3):δ184.5,156.8,151.4,137.8,137.3,137.2,131.2,130.9,130.7,130.2,129.8,128.4,128.3,125.5,125.1,123.7,119.,20.7,19.8,18.1.
example 5
Raw materials: 2-chloroacetophenone;
and (3) target products:
Figure BDA0001451662210000073
yield: 65 percent;
1H NMR(400MHz,CDCl3):δ7.55(t,J＝8.4Hz,1H),7.46(dd,J＝19.9,8.6Hz,1H),7.42–7.32(m,1H),7.23(s,1H),2.35(s,1H).
13C NMR(100MHz,CDCl3):δ181.6,154.0,151.2,137.1,133.9,131.9,131.8,131.7,131.3,131.1,130.3,130.3,129.4,128.0,126.5,123.4,121.1,18.0。
example 6
Raw materials: 2-nitroacetophenone;
and (3) target products:
Figure BDA0001451662210000081
yield: 64 percent;
1H NMR(400MHz,CDCl3):δ8.21(d,J＝8.2Hz,1H),7.92(d,J＝8.1Hz,1H),7.82(t,J＝7.5Hz,1H),7.72(dd,J＝21.5,7.4Hz,3H),7.59(dd,J＝15.5,7.6Hz,2H),7.40(s,1H),2.41(s,3H).
13C NMR(100MHz,CDCl3):δ180.5,151.2,150.6,148.1,146.8,134.2,133.9,132.7,131.4,131.2,130.4,129.2,124.7,124.4,123.0,121.6,121.4,17.9.
example 7
Raw materials: 2-methoxyacetophenone;
and (3) target products:
yield: 70 percent;
1H NMR(400MHz,CDCl3):δ7.53(d,J＝7.5Hz,1H),7.47(t,J＝8.9Hz,2H),7.39(dd,J＝14.8,6.8Hz,1H),7.14(s,1H),7.06–6.94(m,4H),3.86(s,3H),3.83(s,3H),2.32(s,3H).
13C NMR(100MHz,CDCl3):δ182.3,157.5,157.2,153.4,151.6,132.2,131.2,130.7,129.69,127.8,123.1,120.4,120.2,120.2,118.4,111.6,111.3,55.8,55.5,17.8.
example 8
Raw materials: 3-bromoacetophenone;
and (3) target products:
Figure BDA0001451662210000091
yield: 84%;
1H NMR(400MHz,CDCl3):δ8.19(s,1H),8.17(s,1H),7.96(dd,J＝15.7,7.8Hz,2H),7.74(d,J＝7.9Hz,1H),7.52(t,J＝9.6Hz,1H),7.41(t,J＝7.9Hz,1H),7.38–7.30(m,2H),2.49(s,3H).
13C NMR(100MHz,CDCl3):δ179.9,152.0,150.1,138.7,135.6,132.3,132.0,131.1,130.2,130.1,129.1,127.8,124.9,123.9,122.9,122.8,119.6,17.9.
example 9
Raw materials: 3-methylacetophenone;
and (3) target products:
Figure BDA0001451662210000092
yield: 79 percent;
1H NMR(400MHz,CDCl3):δ7.88(d,J＝8.9Hz,1H),7.82(s,1H),7.43(s,1H),7.36(t,J＝7.7Hz,1H),7.32(s,1H),7.21(d,J＝7.1Hz,1H),2.46(s,3H),2.43(s,2H).
13C NMR(100MHz,CDCl3):δ182.0,154.0,150.1,138.4,138.4,137.3,133.4,129.9,129.8,129.4,128.6,128.3,127.1,126.5,124.1,123.8,117.8,21.5,21.4,18.1.
example 10
Raw materials: 3-chloroacetophenone;
and (3) target products:
Figure BDA0001451662210000101
the yield is 80%;
1H NMR(400MHz,CDCl3):δ8.04(s,1H),8.00(s,1H),7.91(dd,J＝13.3,7.7Hz,2H),7.66(s,1H),7.59(d,J＝8.0Hz,1H),7.48(t,J＝7.7Hz,1H),7.41(t,J＝7.7Hz,1H),7.36(d,J＝7.5Hz,2H),2.49(s,3H).
13C NMR(100MHz,CDCl3):δ180.1,152.1,150.1,138.5,134.8,134.8,132.7,130.9,130.0,129.9,129.4,129.1,127.4,126.3,124.5,124.0,119.6,17.9.
example 11
Raw materials: 3-nitroacetophenone;
and (3) target products:
Figure BDA0001451662210000102
yield: 88 percent;
1H NMR(400MHz,CDCl3):δ9.00(s,1H),8.95(s,1H),8.51(d,J＝8.2Hz,1H),
8.38(dd,J＝13.2,7.8Hz,2H),8.25(d,J＝8.2Hz,1H),7.78(t,J＝8.0Hz,1H),7.69(t,J＝8.0Hz,1H),7.51(d,J＝13.0Hz,1H),2.57(s,4H).
13C NMR(100MHz,CDCl3):δ178.7,151.0,150.4,148.6,148.2,137.8,134.9,131.6,130.6,130.0,130.0,127.3,124.4,123.8,123.5,121.4,121.1,17.8.
example 12
Raw materials: 4-bromoacetophenone;
and (3) target products:
Figure BDA0001451662210000103
yield: 80 percent;
1H NMR(400MHz,CDCl3):δ7.90(t,J＝8.4Hz,1H),7.68(d,J＝7.7Hz,1H),7.60(d,J＝7.9Hz,1H),7.34(s,1H),2.48(s,1H).
13C NMR(100MHz,CDCl3):δ180.5,152.7,150.2,135.7,132.0,131.8,130.8,128.2,127.8,123.9,123.4,119.0,18.0.
example 13
Raw materials: 4-trifluoromethylacetophenone;
and (3) target products:
Figure BDA0001451662210000111
the yield is 78 percent;
(4-(methylthio)-5-(4-(trifluoromethyl)phenyl)furan-2-yl)(4-(trifluoromethyl)phenyl)methanone
1H NMR(400MHz,CDCl3):δ8.14(t,J＝9.4Hz,1H),7.82(d,J＝7.9Hz,1H),7.74(d,J＝8.0Hz,1H),7.39(s,1H),2.52(s,1H).
13C NMR(100MHz,CDCl3):δ180.5,151.9,150.4,139.8,134.3,132.4,129.6,129.1,128.3,126.6,126.5,125.7(dd,J＝7.5,3.7Hz),125.6(q,J＝3.7Hz),123.8,120.8,17.8.
example 14
Raw materials: 4-methylacetophenone;
and (3) target products:
Figure BDA0001451662210000112
yield: 73 percent
1H NMR(400MHz,CDCl3):δ7.99–7.92(m,1H),7.32(d,J＝6.6Hz,1H),7.27(d,J＝8.0Hz,1H),2.45(s,2H),2.40(s,1H).
13C NMR(100MHz,CDCl3):δ181.4,154.12,150.2,143.4,139.2,134.6,129.5,129.4,129.2,126.8,126.5,124.0,117.2,21.7,21.5,18.1.
Example 15
Raw materials: 4-chloroacetophenone;
and (3) target products:
Figure BDA0001451662210000121
yield: 80 percent;
1H NMR(400MHz,CDCl3):δ8.03–7.93(m,1H),7.51(d,J＝8.2Hz,1H),7.45(d,J＝8.3Hz,1H),7.35(s,1H),2.48(s,1H).
13C NMR(100MHz,CDCl3):δ180.3,152.7,150.2,139.2,135.3,135.1,130.7,129.0,128.9,127.8,127.7,123.9,118.8,18.0.
example 16
Raw materials: 4-methoxyacetophenone;
and (3) target products:
Figure BDA0001451662210000122
yield: 72 percent;
1H NMR(400MHz,CDCl3):δ8.05(dd,J＝16.5,7.6Hz,1H),7.33(s,1H),7.05–6.94(m,2H),3.91(s,1H),3.88(s,1H),2.45(s,1H).
13C NMR(100MHz,CDCl3):δ193.5,163.2,160.1,154.0,150.1,132.3,131.7,129.9,128.1,124.0,122.4,114.3,114.1,113.7,55.5,55.3,18.3.
example 17
Raw materials: 4-methylthioacetophenone;
and (3) target products:
Figure BDA0001451662210000131
the yield is 63%;
1H NMR(400MHz,CDCl3):δ7.98(d,J＝8.2Hz,1H),7.33(t,J＝6.4Hz,1H),7.26(s,1H),2.56(s,1H),2.53(s,1H),2.47(s,1H).
13C NMR(100MHz,CDCl3):δ180.5,153.4,150.2,145.5,140.3,133.3,129.8,126.7,126.0,125.9,125.0,123.9,117.6,18.1,15.2,14.8.
example 18
Raw materials: 4-tert-butyl acetophenone;
and (3) target products:
Figure BDA0001451662210000132
yield: 58 percent;
1H NMR(400MHz,CDCl3):δ8.01(d,J＝7.8Hz,1H),7.52(dd,J＝14.9,7.6Hz,1H),7.36(s,1H),2.47(s,1H),1.38(s,2H),1.36(s,2H).
13C NMR(100MHz,CDCl3):δ181.3,156.3,154.0,152.3,150.4,134.5,129.4,126.8,126.3,125.6,125.4,124.0,117.3,35.1,34.8,31.2,31.1,18.2.

Claims (7)

1. a synthetic method of a derivative containing methylthio furan is characterized in that: reacting acetophenone compounds and dimethyl sulfoxide in a formula 1 in the presence of an elemental iodine catalyst and a potassium persulfate oxidant in one pot to obtain furan derivatives in a formula 2;
Figure FDA0002104367140000011
wherein R is hydrogen, halogen substituent, trifluoromethyl, nitro, alkyl, alkoxy or methylthio;
the reaction conditions are as follows: the reaction temperature is 90-140 ℃, and the reaction time is 5-11 h.
2. The method for synthesizing the derivative containing methylthio furan according to claim 1, wherein: the concentration of the acetophenone compounds in dimethyl sulfoxide is 0.1-1 mol/L.
3. The method for synthesizing the derivative containing methylthiofuran according to claim 2, wherein: the concentration of the acetophenone compounds in dimethyl sulfoxide is 0.2-0.3 mol/L.
4. The method for synthesizing the derivative containing methylthio furan according to claim 1, wherein: the molar weight of the elementary iodine is 20-40% of that of the acetophenone compound.
5. The method for synthesizing the derivative containing methylthio furan according to claim 4, wherein: the molar weight of the elementary iodine is 25-35% of that of the acetophenone compound.
6. The method for synthesizing the derivative containing methylthio furan according to claim 1, wherein: the molar weight of the potassium persulfate oxidant is 2-3 times that of the acetophenone compound.
7. The method for synthesizing the derivative containing methylthio furan according to claim 1, wherein: the reaction conditions are as follows: the reaction temperature is 100-130 ℃, and the reaction time is 6-10 h.
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