CN107915587B - Method for alkyl-alkoxylation of olefin compounds - Google Patents
Method for alkyl-alkoxylation of olefin compounds Download PDFInfo
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Abstract
The application discloses a preparation method of a compound IV, which is characterized in that in the presence of a catalyst, a compound I containing carbon-carbon double bonds, a peroxide II and an alcohol compound III are subjected to alkoxylation reaction to prepare the compound IV; the compound I containing the carbon-carbon double bond is at least one selected from compounds containing structural units shown in formula I in a structural formula; the peroxide II is selected from one of a compound with a structural formula shown in a formula II-1-1 and a compound with a structural formula shown in a formula II-1-2; the carboxylic acid compound II-2 is selected from one of compounds with a structural formula shown in a formula II-2; the alcohol compound III is selected from one of compounds with a structural formula shown in a formula III; the compound IV is at least one compound with a structural unit shown in formula IV. The method has the advantages of cheap raw materials and catalysts, mild reaction conditions, simple operation, high reaction efficiency and the like.
Description
Technical Field
The application relates to an olefin compound alkyl-alkoxylation method, belonging to the field of organic synthesis.
Background
The bifunctional of olefins is an effective method for simultaneously inserting two functional groups into an olefin compound which is inexpensive and present in a large amount. The C-C bond and the C-O bond are the two most common chemical bonds in nature. The selective functionalization of olefins with carbon and oxygen groups enables efficient simultaneous construction of C-C and C-O bonds. The efficient aryloxyation of olefins was subsequently reported by Toste, Lloyd-Jones, Heinrich, Studer et al. However, the alkyl oxidation of olefins still presents significant challenges. Beta hydrogen elimination from alkyl electrophiles is a difficulty. To overcome this problem, the subject groups of Tuder, Buchwald, Loh, Alexanian, Wang and Lei use radical precursors and Togni's reagent as alkyl electrophiles. Among these alkyl electrophiles, the Tempo-type reagent, the Togni's reagent and the allyl sulfone are relatively specific when the alkyl halide is limited to electrophiles without β -H, such as bromoacetonitrile and benzyl bromide. It is very difficult to alkoxylation olefins with conventional alkyl electrophiles by a free radical strategy. Using Re2(CO)10The catalyst can be used for esterification and alkylation of styrene compounds by using high-price iodine reagent as an alkylating reagent, but the catalyst of the system is expensive, the high-price iodine reagent is not easy to obtain, and only primary alkylation reaction can be realized.
The alkyl carboxylic acid compounds have the characteristics of low price, stable physicochemical property and no toxicity, and are widely used chemical raw materials. Li Shuizhi, McMillan, Sammis et al, reported examples of decarboxylation of alkyl carboxylic acids to generate alkyl radicals and subsequent reaction. At present, many scientists are constantly searching for new alkyl electrophiles.
Disclosure of Invention
According to one aspect of the present application, there is provided a process for the preparation of compound IV (i.e., alkyl-alkoxylation of olefin compounds) which utilizes an alkyl carboxylic acid as an alkyl electrophile to synthesize an unprecedented decarboxylated alkoxy intermediate of an olefin over an iron catalyst. The method has the advantages of cheap raw materials and catalysts, mild reaction conditions, simple operation, high reaction efficiency and the like.
The preparation method of the compound IV is characterized in that in the presence of a catalyst, a compound I containing carbon-carbon double bonds, peroxide II and an alcohol compound III are subjected to alkyl-alkoxylation reaction to prepare a compound IV;
the compound I containing the carbon-carbon double bond is at least one compound containing a structural unit shown in the formula I in the structural formula:
the peroxide II is selected from one of a compound with a structural formula shown in a formula II-1 and a compound with a structural formula shown in a formula II-2;
the alcohol compound III is selected from one of compounds with a structural formula shown in a formula III:
R2-OH formula III
The compound IV is at least one compound containing a structural unit shown in a formula IV:
wherein R is1、R2Independently selected from hydrocarbyl, substituted hydrocarbyl, heteroaryl, substituted heteroaryl.
The peroxide II and the carbon-carbon double bond in the compound I containing the carbon-carbon double bond are subjected to alkyl-alkoxylation reaction; the compound I containing a carbon-carbon double bond may be a compound having a cyclic structure or a compound having a chain structure, and the position of the carbon-carbon double bond may be in the chain structure or the cyclic structure. The bond between formula I and formula IV is with other groups or atoms.
Preferably, the compound I containing a carbon-carbon double bond is at least one selected from compounds having a chemical structural formula shown in formula I-1:
wherein R is3、R4、R5、R6Independently selected from one of hydrogen, alkyl, substituted alkyl, heteroaryl, substituted heteroaryl and non-hydrocarbon substituent.
Further preferably, the compound I containing a carbon-carbon double bond is selected from at least one of a compound having a chemical structural formula shown in formula I-2, a compound having a chemical structural formula shown in formula I-3, and a compound having a chemical structural formula shown in formula I-4:
wherein n is 0, 1, 2, 3, 4 or 5;
R7at least one selected from the group consisting of a hydrocarbyl group, a substituted hydrocarbyl group, and a non-hydrocarbon substituent;
R8，R9，R10，R11，R12，R13independently selected from one of hydrogen, alkyl, substituted alkyl and non-hydrocarbon substituent.
As an embodiment, the compound having the formula represented by formula II-1 may be prepared from a raw material containing the compound having the formula represented by formula II-0 and hydrogen peroxide;
as an embodiment, the compound having the formula shown in formula II-2 can be prepared from a starting material comprising a compound having the formula shown in formula II-0 and t-butyl hydroperoxide:
wherein R is1Selected from the group consisting of alkyl, substituted alkyl, heteroaryl, substituted heteroaryl.
Preferably, R1、R2Independently selected from C1～C20Hydrocarbyl radical, C1～C20Substituted hydrocarbyl radical, C3～C20Heteroaryl group, C3～C20One of the substituted heteroaryl groups.
Preferably, R3、R4、R5、R6Independently selected from hydrogen, C1～C20Hydrocarbyl radical, C1～C20One of the substituted hydrocarbon groups.
Preferably, R7Is selected from C1～C20Hydrocarbyl radical, C1～C20At least one of substituted hydrocarbon group and non-hydrocarbon substituent.
Preferably, R8，R9，R10，R11，R12，R13Independently selected from hydrogen, C1～C20Hydrocarbyl radical, C1～C20At least one of substituted hydrocarbon group and non-hydrocarbon substituent.
When the compound I containing the carbon-carbon double bond is selected from compounds with a chemical structural formula shown in I-1, the structural formula of the compound IV is shown in a formula IV-1:
when the compound I containing the carbon-carbon double bond is selected from compounds with a chemical structural formula shown in I-2, the structural formula of the compound IV is shown as a formula IV-2:
when the compound I containing the carbon-carbon double bond is selected from compounds with a chemical structural formula shown in I-3, the structural formula of the compound IV is shown as a formula IV-3:
when the compound I containing the carbon-carbon double bond is selected from compounds with a chemical structural formula shown in I-4, the structural formula of the compound IV is shown as the formula IV-4:
in the present application, the substituents in the substituted hydrocarbyl, substituted heteroaryl groups are non-hydrocarbon substituents; the non-hydrocarbon substituent is at least one selected from oxygen, halogen, a group with a structural formula shown in a formula (1), a group with a structural formula shown in a formula (2), a group with a structural formula shown in a formula (3) and a group with a structural formula shown in a formula (4):
in the formula (1), M11Selected from hydrogen, C1～C10An alkyl group of (a);
in the formula (2), M21Selected from hydrogen, C1～C10An alkyl group of (a);
M31-O-formula (3)
In formula (3), M31Selected from hydrogen, C1～C10An alkyl group of (1).
Preferably, the catalyst is selected from at least one of metal salts containing iron element. I.e. the catalyst is selected from organic salts of iron and/or inorganic salts of iron. Further preferably, the catalyst is at least one selected from ferrous chloride, ferrous acetate, ferric p-toluenesulfonate, ferrous trifluoromethanesulfonate, and ferric trifluoromethanesulfonate.
The person skilled in the art can select a suitable raw material ratio according to specific needs. In a preferred embodiment, the molar ratio of the compound I containing a carbon-carbon double bond, the peroxide II, the alcohol compound III and the catalyst is:
compound I containing a carbon-carbon double bond: peroxide II: alcohol compound III: catalyst and process for preparing same
＝1：1～3：3～9：0.05～0.1。
The temperature and time of the alkyl-alkoxylation reaction can be selected by one skilled in the art depending on the starting materials and the specific production requirements. Preferably, the reaction temperature of the alkoxylation reaction does not exceed 80 ℃ and the reaction time is not less than 30 minutes. Further preferably, the reaction temperature of the alkyl-alkoxylation reaction is 40 to 70 ℃, and the reaction time is 0.5 to 5 hours.
As an embodiment, the alkyl-alkoxylation reaction system contains an organic solvent. The kind and amount of the organic solvent can be selected by those skilled in the art according to the raw materials and the specific production requirements. Preferably, the organic solvent is at least one selected from the group consisting of toluene, acetonitrile, trifluorotoluene, tetrahydrofuran, and dioxane.
Preferably, the ratio of the organic solvent (volume) to the compound I containing a carbon-carbon double bond (mole number) is 2mL/mmol to 6 mL/mmol. Further preferably, the ratio of the organic solvent (volume) to the compound I having a carbon-carbon double bond (mole number) is 3mL/mmol to 4 mL/mmol.
As an embodiment, the method for preparing compound IV comprises at least the following steps:
a) placing a compound I containing carbon-carbon double bonds, a peroxide II, an alcohol compound III, a catalyst and an organic solvent in a reaction container, stirring for 0.5-5 hours at 20-80 ℃, and cooling to room temperature;
b) diluting with dichloromethane, filtering with diatomite, distilling under reduced pressure to remove solvent, and separating with column chromatography to obtain compound IV.
In this application, C1～C10、C1～C20Etc. all ofRefers to the number of carbon atoms contained in the group.
As used herein, a "hydrocarbyl group" is a group formed by the loss of any hydrogen atom from a hydrocarbon compound molecule; the hydrocarbon compounds include alkane compounds, alkene compounds, alkyne compounds, and aromatic hydrocarbon compounds. Such as p-tolyl group in which toluene loses the hydrogen atom para to the methyl group on the phenyl ring, or benzyl group in which toluene loses any of the hydrogen atoms on the methyl group, and the like.
In the present application, the "alkyl group" is a group formed by losing any one hydrogen atom on the molecule of the alkane compound.
In the present application, the "aromatic hydrocarbon group" is a group formed by losing one hydrogen atom on an aromatic ring on an aromatic compound molecule; such as p-tolyl, formed by toluene losing the hydrogen atom para to the methyl group on the phenyl ring.
In the present application, the "heteroaryl" is a group formed by losing any one of hydrogen atoms on an aromatic ring on an aromatic compound (referred to as a heteroaryl compound for short) having O, N, S heteroatoms in the aromatic ring; such as piperazine ring, by the loss of any one of the hydrogen atoms.
In the present application, the "halogen" refers to at least one of fluorine, chlorine, bromine and iodine.
In the present application, the term "non-hydrocarbon substituent" refers to a group formed by a compound containing an element other than H and C (e.g., halogen, S, O, P, N, etc.) by the loss of any one hydrogen atom.
In the present application, the carbon atoms of the "substituted hydrocarbon group", "substituted aromatic hydrocarbon group" and "substituted heteroaryl group" are defined to mean the number of carbon atoms contained in the hydrocarbon group, aromatic hydrocarbon group and heteroaryl group themselves, not the number of carbon atoms after substitution. Such as C1～C10The substituted hydrocarbon group of (2) means a group having a carbon atom number of C1～C10At least one hydrogen atom on the hydrocarbon group of (1) is substituted with a substituent. Such as a group containing 11 carbon atoms formed by substituting a hydrogen on adamantyl with-C.ident.N.
In the present application, when the substituent is oxygen, it means that two H atoms on any one C atom in the group are replaced with O to form a C ═ O bond.
Benefits of the present application include, but are not limited to:
(1) the method provided by the application has the advantages of cheap raw materials and catalysts, mild reaction conditions, simplicity in operation, high reaction efficiency and the like.
(2) The method provided by the application has the advantages of wide application range, good functional group tolerance and the like.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
In the examples, t-butyl hydroperoxide is abbreviated as TBHP, dicyclohexylcarbodiimide as DCC and 4-dimethylaminopyridine as DMAP.
In the examples, NMR spectra1H-NMR was measured on a 400AVANCE model III Spectrometer (Spectrometer) from Bruker, 400MHz, CDCl3(ii) a Carbon spectrum13C-NMR，400MHz，CDCl3。
The product separation adopts an RF + UV-VIS type full-automatic rapid preparation chromatographic system of Teledyne Isco.
Electron impact Mass Spectrometry MS (EI) A6224 TOF type mass spectrometer from AGILENT was used.
The yield of the compound IV is calculated by the following formula based on the amount of the compound I having a carbon-carbon double bond:
yield = (mass actually obtained by target product ÷ mass theoretically to be obtained by target product) × 100%.
Example 1
5 mol% of catalyst Fe (OTf) is added into the reaction tube312.7mg, 2mL of 1, 4-dioxane as a solvent, 102. mu.L (0.5mmol) of p-tert-butylstyrene 1-1,120uL (3mmol) of methanol 1-2, 214.7mg (0.75mmol) of peroxide 1-3, magnetic stirring, and reacting in an oil bath at 50 ℃ for 3 hours. Cooling to room temperature after the reaction is finished, diluting with dichloromethane, and distilling and concentrating under reduced pressure to remove solventThe crude product was separated by column chromatography and a sample of the product was obtained as 1-4, 137.9mg total, 95% yield.
The nuclear magnetic data for product samples 1-4 are as follows:
1H NMR(400MHz,CDCl3)δ7.34(d,J＝8.3Hz,2H),7.19(d,J＝8.3Hz,2H),4.08-4.02(m,1H),3.19(s,3H),1.85-1.73(m,1H),1.61(dt,J＝8.7,5.5Hz,1H),1.45-1.36(m,1H),1.32(s,9H),1.29-1.20(m,11H),0.86(t,J＝6.8Hz,3H)。
13C NMR(100MHz,CDCl3)δ150.16,139.49,126.36,125.15,83.98,56.57,38.25,34.49,31.92,31.44,29.65,29.57,29.33,25.97,22.70,14.13。
example 2
5 mol% of catalyst Fe (OTf) is added into the reaction tube312.7mg, 2mL of 1, 4-dioxane as a solvent, 102. mu.L (0.5mmol) of p-t-butylstyrene 2-1,120uL (3mmol) of methanol 2-2, 172.6mg (0.75mmol) of peroxide 2-3, magnetic stirring, and reacting in an oil bath at 50 ℃ for 3 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, diluted with dichloromethane, concentrated by distillation under reduced pressure to remove the solvent, and the crude product was isolated by column chromatography, giving a sample of 2-4, which was 94.4mg total, in 72% yield.
The nuclear magnetic data for product samples 2-4 are as follows:
1H NMR(400MHz,CDCl3)δ7.35(d,J＝8.3Hz,2H),7.20(d,J＝8.3Hz,2H),3.99(dd,J＝7.6,5.6Hz,1H),3.19(s,3H),1.84-1.70(m,1H),1.66-1.53(m,1H),1.46-1.36(m,1H),1.32(s,9H),1.14-1.03(m,1H),0.85(s,9H)。
13C NMR(100MHz,CDCl3)δ150.20,139.51,126.38,125.21,125.18,84.83,56.61,40.23,34.52,33.43,31.45,30.12,29.39。
example 3
5 mol% of catalyst Fe (OTf) is added into the reaction tube312.7mg, 2mL of 1, 4-dioxane as a solvent, 102. mu.L (0.5mmol) of p-t-butylstyrene 3-1,120uL (3mmol) of methanol 3-2, 211.6mg (0.75mmol) of peroxide 3-3, magnetic stirring, and reacting in an oil bath at 50 ℃ for 3 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, diluted with dichloromethane, and concentrated by distillation under reduced pressure to remove the solvent, and the crude product was separated by column chromatography, and a total of 100.9mg of the product was obtained as a sample of 3 to 4, with a yield of 70%.
The nuclear magnetic data for product samples 3-4 are as follows:
1H NMR(400MHz,CDCl3)δ7.34(d,J＝8.3Hz,2H),7.19(d,J＝8.3Hz,2H),4.05(dd,J＝7.4,5.9Hz,1H),3.18(s,3H),1.86-1.75(m,1H),1.70(d,J＝8.4Hz,3H),1.65-1.52(m,3H),1.52-1.39(m,3H),1.31(s,9H),1.30-1.24(m,3H),1.10-0.95(m,3H)。
13C NMR(100MHz,CDCl3)δ150.14,139.53,126.36,125.16,83.98,56.59,40.15,38.54,36.18,34.50,32.78,32.73,31.46,25.21,25.18。
example 4
5 mol% of catalyst Fe (OTf) is added into the reaction tube312.7mg, 2mL of 1, 4-dioxane as a solvent, 102. mu.L (0.5mmol) of p-tert-butylstyrene 4-1,120uL (3mmol) of methanol 4-2, 232.7mg (0.75mmol) of peroxide 4-3, magnetic stirring, and reacting in an oil bath at 50 ℃ for 3 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, diluted with dichloromethane, concentrated by distillation under reduced pressure to remove the solvent, and the crude product was isolated by column chromatography, giving a sample of 4-4, totaling 120.0mg, in 77% yield.
The nuclear magnetic data for product samples 4-4 are as follows:
1H NMR(400MHz,CDCl3)δ7.35(d,J＝8.3Hz,2H),7.27-7.21(m,2H),7.18(d,J＝8.3Hz,2H),7.14(t,J＝8.5Hz,3H),4.05(dd,J＝12.0,4.0Hz,1H),3.19(s,3H),2.61-2.53(m,2H),1.91-1.77(m,1H),1.71-1.55(m,3H),1.54-1.40(m,1H),1.32(s,9H),1.27(d,J＝10.3Hz,1H)。
13C NMR(100MHz,CDCl3)δ142.75,139.34,128.40,128.26,126.36,125.62,125.22,83.82,56.64,38.03,35.91,34.54,31.53,31.46,25.69。
example 5
5 mol% of catalyst Fe (OTf) is added into the reaction tube312.7mg, 2mL of 1, 4-dioxane as a solvent, 102. mu.L (0.5mmol) of p-tert-butylstyrene 5-1, 230. mu.L (3mmol) of isopropanol 5-2, and 232.7mg (0.75mmol) of peroxide 5-3, and reacting under a 50 ℃ oil bath for 3 hours with magnetic stirring. After the reaction was complete, the reaction mixture was cooled to room temperature, diluted with dichloromethane, concentrated by distillation under reduced pressure to remove the solvent, and the crude product was isolated by column chromatography, giving a sample of 5-4, total 123.4mg, 85% yield.
The nuclear magnetic detection data for product samples 5-4 are as follows:
1H NMR(400MHz,CDCl3)δ7.33(d,J＝8.3Hz,2H),7.21(d,J＝8.3Hz,2H),4.27(dd,J＝8.0,5.3Hz,1H),3.52–3.40(m,1H),1.79–1.66(m,1H),1.61–1.50(m,1H),1.49–1.38(m,1H),1.32(s,9H),1.28–1.21(m,7H),1.13(d,J＝6.0Hz,3H),1.08(d,J＝6.2Hz,3H),0.89–0.82(m,3H)。
13C NMR(100MHz,CDCl3)δ149.82,141.03,126.15,125.00,79.00,68.48,38.98,34.47,31.85,31.44,29.26,26.13,23.54,22.66,21.21,14.10。
example 6
5 mol% of catalyst Fe (OTf) is added into the reaction tube312.7mg, 2mL of 1, 4-dioxane as a solvent, 102. mu.L (0.5mmol) of p-t-butylstyrene 6-1,120uL (3mmol) of methanol 6-2, 148.6mg (0.75mmol) of peroxide 6-3, magnetic stirring, and reacting in an oil bath at 50 ℃ for 3 hours. Reaction junctionAfter cooling to room temperature, the mixture was diluted with dichloromethane, concentrated by distillation under reduced pressure to remove the solvent, and the crude product was isolated by column chromatography, giving a sample of 6-4, a total of 87.3mg, and a yield of 71%.
The nuclear magnetic detection data of the product sample 6-4 is as follows:
1H NMR(400MHz,CDCl3)δ7.35(d,J＝8.28Hz,2H),7.19(d,J＝8.28Hz,2H),5.83-5.72(m,1H),4.99-4.91(m,2H),4.06(t,J＝5.84Hz,1H),3.20(s,3H),2.07-2.02(m,2H),1.84-1.77(m,1H),1.68-1.59(m,2H),1.55-1.49(m,1H),1.32(s,9H)。
13C NMR(100MHz,CDCl3)δ150.27,139.27,138.75,126.31,125.19,114.51,83.73,56.62,37.61,33.70,31.41,25.23。
example 7
5 mol% of catalyst Fe (OTf) is added into the reaction tube312.7mg, 2mL of 1, 4-dioxane as a solvent, 102. mu.L (0.5mmol) of p-t-butylstyrene 7-1,120uL (3mmol) of methanol 7-2, 196.6mg (0.75mmol) of peroxide 7-3, magnetic stirring, and reacting in an oil bath at 50 ℃ for 3 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, diluted with dichloromethane, concentrated by distillation under reduced pressure to remove the solvent, and the crude product was isolated by column chromatography, giving a sample of 7-4, which was 94.6mg in total, giving a yield of 68%.
The nuclear magnetic detection data for product sample 7-4 is as follows:
1H NMR(400MHz,CDCl3)δ7.35(d,J＝8.3Hz,2H),7.19(d,J＝8.3Hz,2H),4.07(dd,J＝7.2,5.4Hz,1H),3.64(s,3H),3.19(s,3H),2.31(m,2H),1.79(m,2H),1.71-1.53(m,2H),1.32(s,9H)。
13C NMR(100MHz,CDCl3)δ173.94,150.38,138.89,126.28,125.24,83.39,56.57,51.42,37.49,34.49,33.91,31.39,21.46。
example 8
5 mol% of catalyst Fe (OTf) is added into the reaction tube312.7mg, 2mL of 1, 4-dioxane as a solvent, 8-1 of 0.5mmol of styrene, 8-2 of 120uL (3mmol) of methanol, 8-3 of 172.6mg (0.75mmol) of peroxide, and reacting for 3 hours in an oil bath at 50 ℃ under magnetic stirring. After the reaction was complete, the reaction mixture was cooled to room temperature, diluted with dichloromethane, concentrated by distillation under reduced pressure to remove the solvent, and the crude product was isolated by column chromatography, giving a sample of 8-4, which amounted to 75.3mg, giving a yield of 73%.
The nuclear magnetic detection data for product sample 8-4 is as follows:
1H NMR(400MHz,CDCl3)δ7.35-7.32(m,2H),7.28-7.24(m,3H),4.07(t,J＝6.44Hz,1H),3.20(s,3H),1.83-1.77(m,1H),1.65-1.59(m,1H),1.41-1.33(m,1H),1.31-1.18(m,7H),0.86(t,J＝7.08Hz,3H)。
13C NMR(100MHz,CDCl3)δ142.58,128.32,127.41,126.71,84.20,56.61,38.23,31.79,29.26,25.81,22.62,14.08。
example 9
5 mol% of catalyst Fe (OTf) is added into the reaction tube312.7mg, 2mL of 1, 4-dioxane as a solvent, 9-1,120uL (3mmol) of 3-methylstyrene (9-2), 172.6mg (0.75mmol) of peroxide (9-3), magnetic stirring, and reacting in an oil bath at 50 ℃ for 3 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, diluted with dichloromethane, concentrated by distillation under reduced pressure to remove the solvent, and the crude product was isolated by column chromatography, giving a sample of 9-4, 92.5mg total, 84% yield.
The nuclear magnetic data for product sample 9-4 is as follows:
1H NMR(400MHz,CDCl3)7.28-7.24(m,1H),7.12-7.09(m,3H),4.07(t,J＝7.04Hz,1H),3.23(s,3H),2.39(s,3H),1.87-1.78(m,1H),1.66-1.60(m,1H),1.45-1.37(m,1H),1.33-1.24(m,7H),0.89(t,J＝7.04Hz,3H)。
13C NMR(100MHz,CDCl3)142.51,137.89,128.17,128.16,127.33,123.82,84.22,56.62,38.21,31.78,29.26,25.87,22.63,21.49,14.09。
example 10
5 mol% of catalyst Fe (OTf) is added into the reaction tube312.7mg, 2mL of 1, 4-dioxane as a solvent, 10-1 of 0.5mmol of 2, 5-dimethylstyrene, 10-2 of 10-120 uL (3mmol) of methanol, 10-3 of 172.6mg (0.75mmol) of peroxide, magnetic stirring, and reacting for 3 hours in an oil bath at 50 ℃. After the reaction was completed, the reaction mixture was cooled to room temperature, diluted with dichloromethane, and concentrated by distillation under reduced pressure to remove the solvent, and the crude product was separated by column chromatography, and a sample of the obtained product was recorded as 10-4, 96.0mg in total, and the yield was 82%.
The nuclear magnetic data for the product sample 10-4 is as follows:
1H NMR(400MHz,CDCl3)7.15(s,1H),7.01(d,J＝7.68Hz,1H),6.96(d,J＝7.60Hz,1H),4.35-4.32(m,1H),3.20(s,3H),2.32(s,3H),2.27(s,3H),1.74-1.67(m,1H),1.62-1.57(m,1H),1.50-1.45(m,1H),1.29-1.26(m,7H),0.87(t,J＝6.96Hz,3H)。
13C NMR(100MHz,CDCl3)150.41,142.01,125.64,125.33,74.50,38.98,34.51,31.79,31.38,29.23,25.92,22.63,14.08。
example 11
5 mol% of catalyst Fe (OTf) is added into the reaction tube312.7mg, 2mL of 1, 4-dioxane as a solvent, 11-1,120uL (3mmol) of 4-methoxystyrene (11-2), 172.6mg (0.75mmol) of peroxide (11-3), magnetic stirring, and reacting in an oil bath at 50 ℃ for 3 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, diluted with dichloromethane, concentrated by distillation under reduced pressure to remove the solvent, and the crude product was isolated by column chromatography, giving a sample of 11-4, which was 76.8mg in total, 65% yield.
The nuclear magnetic data for product sample 11-4 is as follows:
1H NMR(400MHz,CDCl3)7.19(d,J＝8.56Hz,2H),6.88d(d,J＝8.56Hz,2H),4.02(t,J＝6.76Hz,1H),3.80(s,3H),3.17(s,3H),1.83-1.75(m,1H),1.63-1.54(M,1H),1.38-1.32(m,1H),1.28-1.21(m,7H),0.86(t,J＝6.96Hz,3H)。
13C NMR(100MHz,CDCl3)158.98,134.53,127.90,113.69,83.71,56.34,55.24,38.09,31.78,29.24,25.83,22.60,14.06。
example 12
5 mol% of catalyst Fe (OTf) is added into the reaction tube312.7mg, 2mL of 1, 4-dioxane as a solvent, 12-1,120uL (3mmol) of 3-chlorostyrene 12-1, 12-2 of methanol (3mmol), 172.6mg (0.75mmol) of peroxide 12-3, magnetic stirring, and reacting for 3 hours in an oil bath at 50 ℃. After the reaction was complete, the reaction mixture was cooled to room temperature, diluted with dichloromethane, concentrated by distillation under reduced pressure to remove the solvent, and the crude product was isolated by column chromatography, giving a sample of 12-4, amounting to 85.2mg, giving a yield of 71%.
The NMR data for product sample 12-4 are as follows:
1H NMR(400MHz,CDCl3))δ7.30-7.21(m,3H),7.17-7.13(m,1H),4.04(dd,J＝8.0,4.0Hz,1H),3.20(s,3H),1.84-1.71(m,1H),1.64-1.53(m,1H),1.43-1.32(m,1H),1.30-1.16(m,7H),0.86(t,J＝6.9Hz,3H)。
13C NMR(100MHz,CDCl3)δ144.93,134.32,129.62,127.54,126.75,124.82,83.61,56.78,38.13,31.73,29.19,25.66,22.59,14.05。
example 13
5 mol% of catalyst Fe (OTf) is added into the reaction tube312.7mg of 1, 4-dioxane 2 as solventmL,0.5mmol of 4-chloromethylstyrene 13-1,120uL (3mmol) of methanol 13-2, 172.6mg (0.75mmol) of peroxide 13-3, magnetic stirring, and reacting in an oil bath at 50 ℃ for 3 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, diluted with dichloromethane, concentrated by distillation under reduced pressure to remove the solvent, and the crude product was isolated by column chromatography, giving a sample of 13-4, totaling 101.7mg, in 80% yield.
The nuclear magnetic data for the product sample 13-4 is as follows:
1H NMR(400MHz,CDCl3)δ7.37(d,J＝8.1Hz,2H),7.27(d,J＝8.2Hz,2H),4.59(s,2H),4.08(t,J＝8.0Hz,1H),3.20(s,3H),1.85-1.67(m,1H),1.65-1.54(m,1H),1.43-1.32(m,1H),1.27-1.16(m,7H),0.86(t,J＝6.9Hz,3H)。
13C NMR(100MHz,CDCl3)δ143.01,136.55,128.62,127.04,83.81,56.71,46.11,38.19,31.76,29.22,25.73,22.60,14.07。
example 14
5 mol% of catalyst Fe (OTf) is added into the reaction tube28.8mg, 2mL of 1, 4-dioxane as a solvent, 14-1 of 0.5mmol of 1-propenylbenzene (14-1), 14-2 of 120uL (3mmol) of methanol, and 14-3 of 172.6mg (0.75mmol) of peroxide, and reacting for 3 hours under a 50 ℃ oil bath with magnetic stirring. After the reaction was complete, the reaction mixture was cooled to room temperature, diluted with dichloromethane, concentrated by distillation under reduced pressure to remove the solvent, and the crude product was isolated by column chromatography, giving a sample of 14-4, total 76.0mg, 69% yield.
The nuclear magnetic data for product sample 14-4 is as follows:
1H NMR(400MHz,CDCl3)7.33(t,J＝7.36Hz,2H),7.25(t,J＝9.48Hz,3H),3.90(d,J＝6.16Hz,0.64H),3.82(d,J＝7.24Hz,0.32H),3.20(s,2H),3.18(s,1H),1.82-1.71(m,1H),1.30-1.17(m,8H),0.91(d,J＝6.72Hz,2H),0.88-0.83(m,3H),0.68(d,J＝6.80Hz,1H)。
13C NMR(100MHz,CDCl3)141.28,140.97,128.00,127.98,127.59,127.34,127.28,127.14,88.68,88.21,57.08,56.89,39.83,39.53,32.91,32.78,32.23,32.03,26.80,26.71,22.71,22.63,15.66,15.13,14.11,14.07。
example 15
5 mol% of catalyst Fe (OTf) is added into the reaction tube312.7mg, 2mL of 1, 4-dioxane as a solvent, 0.5mmol of an olefin compound 15-1,120uL (3mmol) of methanol 15-2, 172.6mg (0.75mmol) of peroxide 15-3, magnetic stirring, and reacting in an oil bath at 50 ℃ for 3 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, diluted with dichloromethane, concentrated by distillation under reduced pressure to remove the solvent, and the crude product was isolated by column chromatography, giving a sample of 15-4, total 76.0mg, 66% yield.
The nuclear magnetic data for product sample 15-4 is as follows:
1H NMR(400MHz,CDCl3)δ7.47-7.41(m,2H),7.32-7.27(m,3H),4.16(t,J＝6.5Hz,1H),3.47(s,3H),1.88-1.70(m,2H),1.56-1.45(m,2H),1.37-1.27(m,6H),0.89(d,J＝8.0Hz,3H)。
13C NMR(100MHz,CDCl3)δ131.73,128.24,128.23,122.91,88.22,85.83,71.81,56.46,35.73,31.77,29.72,29.07,25.31,22.61,14.08。
example 16
5 mol% of catalyst Fe (OTf) is added into the reaction tube312.7mg, 2mL of 1, 4-dioxane as a solvent, 16-1 of trans-1-phenyl-1, 3-butadiene (0.5mmol), 16-2 of methanol (3mmol), 172.6mg (0.75mmol) of peroxide (16-3), magnetic stirring, and reacting in an oil bath at 50 ℃ for 3 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, diluted with dichloromethane, and concentrated by distillation under reduced pressure to remove the solvent, and the crude product was separated by column chromatography, and a total of 70.0mg of 16-4 was obtained as a sample, which was 60% yield.
The nuclear magnetic data for the product sample 16-4 is as follows:
1H NMR(400MHz,CDCl3)7.40(d,7.32Hz,2H),7.32(t,J＝7.32Hz,2H),7.24(d,J＝5.52Hz,1H),6.52(d,J＝15.96Hz,1H),6.07-6.01(dd,J＝7.96Hz,J＝7.96Hz,1H),3.70-3.65(m,1H),3.31(s,3H),1.71-1.64(m,1H),1.57-1.50(m,1H),1.39-1.35(m,1H),1.30-1.26(m,7H),0.87(t,J＝6.96Hz,3H)。
13C NMR(100MHz,CDCl3)136.74,132.16,130.58,128.58,127.62,126.46,82.68,56.25,35.77,31.81,29.31,25.38,22.62,14.08。
example 17
6mmol of acid 17-1, 0.45mmol of DCC, 0.05mmol of DMAP and 0.6mmol of TBHP are added into a reaction tube, and a magnetic stirrer is added for reaction for 3 hours at the temperature of minus 10 to minus 15 ℃. After the reaction is finished, the reaction product is cooled to room temperature and filtered to obtain the peroxide 17-2. Then 5 mol% of catalyst Fe (OTf) is added312.7mg, 6mL of 1, 4-dioxane as a solvent, 1.5mmol of 17-3 parts of an olefin compound, and 10.5mmol of 17-4 parts of methanol, magnetically stirring, and reacting in an oil bath at 50 ℃ for 3 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, diluted with dichloromethane, concentrated by distillation under reduced pressure to remove the solvent, and the crude product was isolated by column chromatography, giving a sample of 17-5, total 391.5mg, 80% yield.
The nuclear magnetic assay data for product sample 17-5 are as follows:
1H NMR(400MHz,CDCl3)δ7.34(d,J＝8.28Hz,2H),7.19(d,J＝8.28,2H),4.24-4.21(m,1H),3.15(s,3H),2.02-1.89(m,3H),1.69-1.62(m,8H),1.57(d,J＝2.24Hz,6H),1.33-1.28(m,9H)。
13C NMR(100MHz,CDCl3)δ149.96,140.99,126.07,125.21,80.03,56.11,53.24,43.04,37.17,31.44,28.83。
example 18
5 mol% of catalyst Fe (OTf) is added into the reaction tube312.7mg, 2mL of 1, 4-dioxane as a solvent, 18-1,3.5mmol of p-tert-butylstyrene (0.5mmol) and 18-2 of methanol (279.2 mg, 1.5mmol) of peroxide (18-3), magnetically stirring, and reacting in an oil bath at 50 ℃ for 3 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, diluted with dichloromethane, concentrated by distillation under reduced pressure to remove the solvent, and the crude product was isolated by column chromatography, giving a sample of 18-4, amounting to 114.5mg, in 88% yield.
The NMR data for product sample 18-4 are as follows:
1H NMR(400MHz,CDCl3)δ7.35(d,J＝8.0Hz,2H),7.20(d,J＝8.0,2H),4.08(t,J＝8.0Hz,1H),3.19(s,3H),1.89-1.73(m,4H),1.63-1.56(m,3H),1.52-1.45(m,2H),1.32(s,9H),1.16-1.08(m,2H)。
13C NMR(100MHz,CDCl3)δ150.23,139.56,126.34,125.17,83.26,56.56,44.70,36.63,32.84,32.73,31.42,25.16,25.01。
although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (8)
1. The preparation method of the compound IV is characterized in that in the presence of a catalyst, a compound I containing carbon-carbon double bonds, peroxide II and an alcohol compound III are subjected to alkoxylation reaction to prepare a compound IV;
the compound I containing the carbon-carbon double bond is at least one compound containing a structural unit shown in the formula I in the structural formula:
the peroxide II is selected from one of a compound with a structural formula shown in a formula II-1 and a compound with a structural formula shown in a formula II-2;
the alcohol compound III is selected from one of compounds with a structural formula shown in a formula III:
R2-OH formula III
The compound IV is at least one compound containing a structural unit shown in a formula IV:
wherein R is1、R2Independently selected from hydrocarbyl, substituted hydrocarbyl, heteroaryl, substituted heteroaryl;
the catalyst is selected from at least one of metal salts containing iron element;
the compound I containing the carbon-carbon double bond is at least one of a compound with a chemical structural formula shown in a formula I-2, a compound with a chemical structural formula shown in a formula I-3 and a compound with a chemical structural formula shown in a formula I-4:
wherein n is 0, 1, 2, 3, 4 or 5;
R7at least one selected from alkyl, substituted alkyl and non-hydrocarbon substituent;
R8，R9，R10，R11，R12，R13independently selected from one of hydrogen, alkyl, substituted alkyl and non-hydrocarbon substituent;
the substituents in the substituted alkyl group are non-hydrocarbon substituents;
the non-hydrocarbon substituent is at least one selected from halogen, a group with a structural formula shown in a formula (1), a group with a structural formula shown in a formula (2) and a group with a structural formula shown in a formula (3):
in the formula (1), M11Is selected from C1～C10An alkyl group of (a);
in the formula (2), M21Selected from hydrogen, C1～C10An alkyl group of (a);
M31-O-formula (3)
In formula (3), M31Selected from hydrogen, C1～C10An alkyl group of (1).
2. The method of claim 1, wherein R is1、R2Independently selected from C1～C20Hydrocarbyl radical, C1～C20Substituted hydrocarbyl radical, C3～C20Heteroaryl group, C3～C20One of the substituted heteroaryl groups.
3. The method of claim 1, wherein the catalyst is selected from at least one of ferrous chloride, ferrous acetate, ferric p-toluenesulfonate, ferrous trifluoromethanesulfonate, and ferric trifluoromethanesulfonate.
4. The method of claim 1, wherein the compound having the formula shown in formula II-1 is prepared from a raw material comprising the compound having the formula shown in formula II-0 and hydrogen peroxide; the compound having the structural formula shown in formula II-2 is prepared from a raw material containing the compound having the structural formula shown in formula II-0 and tert-butyl hydroperoxide:
wherein R is1Selected from the group consisting of alkyl, substituted alkyl, heteroaryl, substituted heteroaryl.
5. The method according to claim 1, wherein the molar ratio of the compound I containing a carbon-carbon double bond, the peroxide II, the alcohol compound III and the catalyst is as follows:
compound I containing a carbon-carbon double bond: peroxide II: alcohol compound III: catalyst 1: 1-3: 3-9: 0.05 to 0.1.
6. The process of claim 1, wherein the alkoxylation reaction is carried out at a reaction temperature of no more than 80 ℃ and for a reaction time of no less than 30 minutes.
7. The method of claim 1, wherein the alkoxylation reaction system comprises an organic solvent; the organic solvent is at least one of toluene, acetonitrile, trifluorotoluene, tetrahydrofuran and dioxane.
8. Method according to claim 7, characterized in that it comprises at least the following steps:
a) placing a compound I containing carbon-carbon double bonds, a peroxide II, an alcohol compound III, a catalyst and an organic solvent in a reaction container, stirring for 0.5-5 hours at 20-80 ℃, and cooling to room temperature;
b) diluting with ethyl acetate, filtering with diatomite, distilling under reduced pressure to remove solvent, and separating with column chromatography to obtain compound IV.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0482860A (en) * | 1990-07-26 | 1992-03-16 | Nippon Oil & Fats Co Ltd | Fluoroalkyl group-containing styrene derivative and production thereof |
| EP0512035B1 (en) * | 1990-01-26 | 1994-11-30 | Henkel Kommanditgesellschaft auf Aktien | Alkoxylated compounds produced from epoxylated carboxylic acid derivatives |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0512035B1 (en) * | 1990-01-26 | 1994-11-30 | Henkel Kommanditgesellschaft auf Aktien | Alkoxylated compounds produced from epoxylated carboxylic acid derivatives |
| JPH0482860A (en) * | 1990-07-26 | 1992-03-16 | Nippon Oil & Fats Co Ltd | Fluoroalkyl group-containing styrene derivative and production thereof |
Non-Patent Citations (3)
| Title |
|---|
| Alkene Oxyalkylation Enabled by Merging Rhenium Catalysis with Hypervalent Iodine(III) Reagents via Decarboxylation;Wang Yin;《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 》;20131117;第135卷(第48期);全文 * |
| Convenient preparation of difluoromethylene-functionalized compounds from chlorodifluoroacetic acid;MasatoYoshida等;《Journal of Fluorine Chemistry》;19940731;第68卷(第1期);全文 * |
| Copper-Catalyzed Regioselective 1,2-Alkylesterification of Dienes to Allylic Esters;Li Yougui;《Organic Letters》;20160205;第18卷(第3期);全文 * |
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