CN110294727B - Method for producing enamine compound - Google Patents
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- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
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Abstract
The invention relates to the field of preparation of enamine compounds, and discloses a preparation method of enamine compounds shown in a formula (I), which comprises the following steps: in the presence of a baseReacting a compound represented by the formula (II) with a compound represented by the formula (III) in the presence of an organic substance;
wherein R is1Is hydrogen or C1‑C4An alkyl group; r2、R3And R4Are the same or different and are each independently C1‑C4An alkyl group; n is 0 or 1. The invention has the advantages of simpler process, easily obtained raw materials, lower cost, high reaction conversion rate and high selectivity.
Description
Technical Field
The invention relates to the field of preparation of enamine compounds, and particularly relates to a preparation method of enamine compounds.
Background
So far, the preparation methods of 3-dimethylaminomethylenyl-2-benzofuranone compounds reported at home and abroad are few, and the preparation method mainly adopts N, N-dimethylformamide dimethyl acetal as a substitution reagent for substitution reaction, so that the method has the defects of high reaction requirement temperature, incomplete reaction and the like, and has low yield and high price when preparing the N, N-dimethylformamide dimethyl acetal as a raw material, and the cost for preparing the 3-dimethylaminomethylenyl-2-benzofuranone compounds is increased. The other one is prepared by adopting a 3-methoxy methyl alkenyl-2-benzofuranone raw material and reacting the 3-methoxy methyl alkenyl-2-benzofuranone with an amine compound, wherein the preparation of the 3-methoxy methyl alkenyl-2-benzofuranone raw material in the method is complex and the cost is higher.
Pharmaceutical Chemistry Journal,41(10), 549-; 2007 reports a process for the preparation of 3-dimethylaminomethylenyl-2-benzofuranone, obtained by reacting benzofuranone with twice the equivalent of N, N-dimethylformamide dimethyl acetal in the presence of isopropanol, with a yield of only 71%.
Journal of Heterocyclic Chemistry,18(4), 845-6; 1981 reported a process for the preparation of 3-dimethylaminomethylene-2-benzofuranone in the presence of phosphorus oxychloride by reacting N, N-dimethylformamide with benzofuranone in a yield of only 24%.
CN 1219537A discloses a preparation method of 3-methoxy methyl-2-benzofuranone, which takes acetic anhydride as solvent to react with methyl orthoformate at 105 ℃ for 20 hours at 100 ℃, the reaction not only needs high temperature, but also has incomplete conversion of raw materials after 20 hours of reaction.
In conclusion, the existing methods for preparing benzofuranone enamine and 3-isochromone enamine compounds have the defects of low reaction yield, incomplete conversion of raw materials and the like.
Disclosure of Invention
The invention aims to solve the problems of low reaction yield and incomplete raw material conversion in the preparation of enamine compounds in the prior art, and provides a preparation method of enamine compounds.
In order to achieve the above object, the present invention provides, in one aspect, a method for preparing an enamine compound represented by the formula (I), which comprises: reacting a compound represented by the formula (II) with a compound represented by the formula (III) in the presence of a basic substance;
wherein R is1Is hydrogen or C1-C4An alkyl group; r2、R3And R4Are the same or different and are each independently C1-C4An alkyl group; n is 0 or 1.
Through the technical scheme, the compound with the general formula (II) is adopted to replace N, N-dimethylformamide dimethyl acetal raw materials for carrying out complex reaction, and the technological process for preparing the N, N-dimethylformamide dimethyl acetal raw materials is omitted. Therefore, the method has the advantages of simpler process, easily obtained raw materials, lower cost, high reaction conversion rate and high selectivity.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a preparation method of an enamine compound shown in a formula (I), which comprises the following steps: reacting a compound represented by the formula (II) with a compound represented by the formula (III) in the presence of a basic substance;
wherein R is1Is hydrogen or C1-C4An alkyl group; r2、R3And R4Are the same or different and are each independently C1-C4An alkyl group; n is 0 or 1.
In the present invention, said C1-C4Alkyl means a straight-chain, branched or cyclic alkyl group, and may be, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, cyclopropyl, cyclobutyl.
The invention adopts the compound of the general formula (II) to replace the N, N-dimethyl formamide dimethyl acetal raw material in the prior art, omits the process for preparing the N, N-dimethyl formamide dimethyl acetal raw material, has low raw material cost, is easy to carry out complex reaction with the compound of the general formula (III), and is easy to eliminate under the alkaline action
And R3OH is more beneficial to the rapid reaction, so that the conversion of raw materials is more complete, and the reaction conversion rate and the reaction selectivity are further improved.
Preferably, R1Is hydrogen or C1-C4Straight chain alkyl radical, R2、R3And R4Are the same or different, andeach independently is C1-C4A linear alkyl group.
Particularly preferably, R1Is hydrogen, methyl or ethyl, R2、R3And R4Identical or different and are each independently methyl or ethyl.
In the present invention, the reaction is carried out in an organic solvent for the sake of simple subsequent treatment process. Among them, the organic solvent may be various conventional choices in the art.
In the present invention, the organic solvent is used in an amount of 1 to 50mol, for example, 1mol, 3mol, 5mol, 8mol, 10mol, 12mol, 15mol, 18mol, 20mol, 22mol, 25mol, 28mol, 30mol, 32mol, 35mol, 38mol, 40 mol, 42mol, preferably 5 to 30mol, based on 1mol of the compound of the general formula (III).
In the invention, in order to make the subsequent treatment process simpler and lower in cost, the organic solvent is at least one of aromatic hydrocarbon, nitrile and alcohol. Preferably, the organic solvent is at least one of a monocyclic aromatic hydrocarbon, a linear saturated aliphatic nitrile, and a linear saturated aliphatic alcohol. The monocyclic aromatic hydrocarbon may be, for example, toluene, xylene, ethylbenzene, cumene, or the like; examples of the straight-chain saturated aliphatic nitrile include acetonitrile, propionitrile, and butyronitrile; examples of the straight-chain saturated aliphatic alcohol include methanol, ethanol, and propanol.
More preferably, the organic solvent is at least one selected from the group consisting of toluene, xylene, methanol, ethanol, acetonitrile and butyronitrile, and the target product is easier to separate and the subsequent separation treatment can be reduced. Particularly preferably, the organic solvent is at least one selected from the group consisting of toluene, methanol and acetonitrile.
In the present invention, the compound of the general formula (II) is used in an amount of 1 to 7mol, for example, 1mol, 2mol, 3mol, 4mol, 5mol, 6mol, 7mol and any two of these values, preferably 1 to 3mol, based on 1mol of the compound of the general formula (III).
In the present invention, the amount of the basic substance to be used is 0.6 to 3mol, for example, 0.6mol, 0.7mol, 0.8mol, 0.9mol, 1mol, 1.1mol, 1.2mol, 1.3mol, 1.4mol, 1.5mol, 1.6mol, 1.7mol, 1.8mol, 1.9mol, 2mol, 2.2mol, 2.4mol, 2.6mol, 2.8mol, 3mol and any two of these values, preferably 0.8 to 1.5mol, relative to 1mol of the compound of the general formula (III).
In the present invention, in order to improve the reaction conversion rate and the reaction selectivity, the reaction conditions include: the temperature is-20 to 100 ℃, and may be, for example, -20 ℃, -10 ℃, 30 ℃, 50 ℃, 70 ℃, 90 ℃, 100 ℃, or any value in the range of any two of these values, preferably-10 to 30 ℃; the time is 1 to 24 hours, and may be, for example, 1 hour, 2 hours, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours, 24 hours, or any value in the range of any two of these points, and preferably 2 to 10 hours.
According to the present invention, in order to improve the reaction conversion rate and the reaction selectivity, the compound of the general formula (II) is N, N-dimethylformamide dimethyl sulfate complex, N-dimethylformamide diethyl sulfate complex, N-methylformamide dimethyl sulfate complex, N-diethylformamide dimethyl sulfate complex, or N, N-diethylformamide diethyl sulfate complex. Wherein, the compound of the general formula (II) can be prepared by referring to the preparation process of N, N-dimethylformamide dimethyl acetal raw material reported in No. 38, No. 5, No. 2008 and No. 10 months of fine chemical intermediates of persevere, and can also be obtained by commercial purchase.
In the present invention, in order to facilitate elimination
And R3OH is more beneficial to the rapid reaction, and the alkaline substance is at least one of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, triethylamine, diisopropylethylamine, pyridine and N, N-diethylaniline.
Preferably, the base is at least one of sodium carbonate, sodium hydroxide, triethylamine and pyridine.
The present invention will be described in detail below by way of examples. In the following examples:
the amounts of reactants and products were determined by liquid chromatography (Agilent HPLC 1260).
The conversion and selectivity of the reaction are calculated by the following formulas:
conversion rate (molar amount of raw material charged-molar amount of raw material remaining in product)/molar amount of raw material charged X100%
Selectivity is the actual molar amount of target product/theoretical molar amount of target product x 100%.
In the case where no particular mention is made, commercially available products are used as the starting materials.
Example 1
This example illustrates the preparation of 3-dimethylaminomethylenyl-2-benzofuranone, a compound of formula (Ia).
1. Preparation of the Complex of formula (IIa)
Adding 289g (3.96mol) of DMF into a reaction bottle, heating and stirring, dropwise adding 450g (3.57mol) of dimethyl sulfate at the temperature of 60-70 ℃, completing the addition for about 1h, stirring, reacting at the temperature of 70-80 ℃ for 3h to obtain an imine complex compound shown as a formula (IIa), and cooling to the temperature below 0 ℃ in an ice bath for later use.
2. Preparation of 3-dimethylaminomethylene-2-benzofuranone
134g (1mol) of benzofuranone, 219g of a complex represented by the formula (IIa) (1.1mol) and 500mL of methanol were put into a four-necked flask equipped with a mechanical stirrer, a thermometer and a condenser, stirred and mixed thoroughly, and then 2.5mol of sodium carbonate solid was added to the mixture in portions at 30 ℃ and reacted at 30 ℃ for 2 hours after the completion of the addition to obtain the target product 3-dimethylaminomethylenyl-2-benzofuranone. The conversion of the reaction was measured to be 99% and the selectivity was measured to be 98%. 1H NMR DMSO-d6(δ,ppm)：3.33，3.37，3.55(s,6H,N(CH3)2)，7.00，7.34，7.48(m,4H,4–7-H)，7.58，7.83(s,1H,1-H)。
Example 2
This example illustrates the preparation of 3-dimethylaminomethylenyl-2-benzofuranone, a compound of formula (Ia).
134g (1mol) of benzofuranone and 249.7g of formula (II) were placed in a four-necked flask equipped with mechanical stirring, thermometer and condenserb) The complex (1.1mol) and 500mL of methanol are stirred to be fully mixed, then 2.5mol of sodium carbonate solid is added into the mixture in batches at 30 ℃, and after the addition is finished, the reaction is carried out for 2 hours at 30 ℃ to obtain the target product 3-dimethylamine methylene-2-benzofuranone. The conversion of the reaction was measured to be 99% and the selectivity was measured to be 98%.
Example 3
This example illustrates the formula (I)b) A preparation method of a compound 3-methylamine-methyl-alkenyl-2-benzofuranone.
134g (1mol) of benzofuranone and 203.5g of formula (II) were placed in a four-necked flask equipped with mechanical stirring, thermometer and condenserC) The complex (1.1mol) and 500mL of methanol are stirred to be fully mixed, then 2.5mol of sodium carbonate solid is added into the mixture in batches at 30 ℃, and after the addition is finished, the reaction is carried out for 2 hours at 30 ℃ to obtain the target product 3-methylamine-methyl-alkenyl-2-benzofuranone. The conversion of the reaction was measured to be 99% and the selectivity to 97%. 1H NMR DMSO-d6(δ,ppm)：2.91，2.96(s,3H,N-CH3)，7.00，7.34，7.48(m,4H,4–7-H)，7.32，7.56(s,1H,1-H)。
Example 4
This example illustrates the formula (I)c) A preparation method of a compound 3-diethylamine methyl alkenyl-2-benzofuranone.
134g (1mol) of benzofuranone and 249.7g of formula (II) were placed in a four-necked flask equipped with mechanical stirring, thermometer and condenserd) The complex (1.1mol) and 500mL of methanol are stirred and fully mixed, then 2.5mol of solid is added into the mixture in batches at 30 ℃, and after the addition is finished, the reaction is carried out for 2 hours at 30 ℃ to obtain the target product, namely 3-diethylamine methyl alkenyl-2-benzofuranone. The conversion of the reaction was measured to be 99% and the selectivity was measured to be 98%. 1H NMR DMSO-d6(δ,ppm)：1.12，1.16，1.33(t，6H，-(CH3)3)，3.33，3.37，3.55(q，4H，N-(CH2)2)，7.00，7.34，7.48(m,4H,4–7-H)，7.58，7.83(s,1H,1-H)。
Example 5
This example illustrates the preparation of 4-dimethylaminomethylenyl-3-isochromone, a compound of formula (Id).
148g (1mol) of 3-isochromone, 219g of the complex represented by the formula (IIa) (1.1mol) and 800mL of methanol were put into a four-necked flask equipped with a mechanical stirrer, a thermometer and a condenser, and stirred to mix them thoroughly, and then 2.5mol of sodium carbonate solid was added to the mixture in portions at 30 ℃ and reacted at 30 ℃ for 2 hours after the completion of the addition to obtain the objective 4-dimethylaminomethylenyl-3-isochromone. The conversion of the reaction was measured to be 99% and the selectivity was measured to be 98%. 1H NMR DMSO-d6(δ,ppm)：3.34，3.36，3.52(s,6H,N(CH3)2)，5.32(s，2H，-CH2)，7.02，7.37，7.46(m，4H，4–7-H)，7.58，7.84(s，1H,，1-H)。
Example 6
This example illustrates the preparation of 4-dimethylaminomethylenyl-3-isochromone, a compound of formula (Id)).
Into a four-necked flask equipped with a mechanical stirrer, a thermometer and a condenser were charged 148g (1mol) of 3-isochromone and 249.7g of formula (II)b) The complex (1.1mol) and 800mL of methanol are stirred to be fully mixed, then 2.5mol of sodium carbonate solid is added into the mixture in batches at 30 ℃, and after the addition is finished, the reaction is carried out for 2 hours at 30 ℃ to obtain the target product, namely 4-dimethylamine methylene-3-isochromone. The conversion of the reaction was measured to be 99% and the selectivity was measured to be 98%.
Example 7
This example illustrates the preparation of 4-methylaminomethyl-3-isochromone, a compound of formula (ie).
Into a four-necked flask equipped with a mechanical stirrer, a thermometer and a condenser were charged 148g (1mol) of 3-isochromone and 203.5g of the compound of formula (II)C) The complex (1.1mol) and 800mL of methanol are stirred to be fully mixed, then 2.5mol of sodium carbonate solid is added into the mixture in batches at 30 ℃, and after the addition is finished, the reaction is carried out for 2 hours at 30 ℃ to obtain the target product 4-methylamine methylene-3-isochromone. The conversion of the reaction was measured to be 99% and the selectivity to 97%. 1H NMR DMSO-d6(δ，ppm)：2.82，2.91(s，3H，N-CH3)，5.32(s，2H，-CH2)，7.02，7.37，7.46(m，4H，4–7-H)，7.58，7.84(s，1H，1-H)。
Example 8
This example illustrates the preparation of 3-diethylamino-2-isochromone, a compound of formula (if).
Into a four-necked flask equipped with a mechanical stirrer, a thermometer and a condenser were charged 148g (1mol) of 3-isochromone and 249.7g of formula (II)d) The complex (1.1mol) and 500mL of methanol were mixed and charged with stirringMixing, adding 2.5mol of sodium carbonate solid into the mixture in batches at 30 ℃, and reacting for 2 hours at 30 ℃ after the addition is finished to obtain the target product 3-diethylamine methylene-2-isochromone. The conversion of the reaction was measured to be 99% and the selectivity was measured to be 98%. 1H NMR DMSO-d6(δ,ppm)：1.12，1.16，1.33(t，6H，-(CH3)3)，3.32，3.38，3.54(q，4H，N-(CH2)2)，5.32(s，2H，-CH2)，7.00，7.34，7.48(m，4H，4–7-H)，7.58，7.83(s，1H，1-H)。
Example 9
3-Diaminomethylnenyl-2-benzofuranone was prepared according to the method of example 1 except that the methanol was replaced with toluene to obtain the objective product. The conversion of the reaction was measured to be 99% and the selectivity to 94%.
Example 10
3-Diaminomethyllene-2-benzofuranone was prepared according to the procedure of example 1, except that the sodium carbonate was replaced with triethylamine to obtain the objective product, and the conversion of the reaction was found to be 99% with a selectivity of 96%.
In conclusion, the reaction conversion rate can reach 99% and the selectivity can reach more than 94% by adopting the method for preparing the enamine compound in the embodiments 1-10.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (19)
1. A method for producing an enamine compound of the formula (I), comprising: reacting a compound represented by the formula (II) with a compound represented by the formula (III) in the presence of a basic substance;
wherein R is1Is hydrogen or C1-C4An alkyl group; r2、R3And R4Are the same or different and are each independently C1-C4An alkyl group; n is 0 or 1.
2. The method of claim 1, wherein R is1Is hydrogen or C1-C4Straight chain alkyl radical, R2、R3And R4Are the same or different and are each independently C1-C4A linear alkyl group.
3. The method of claim 2, wherein R is1Is hydrogen, methyl or ethyl, R2、R3And R4Identical or different and are each independently methyl or ethyl.
4. The process according to claim 1, characterized in that the reaction is carried out in an organic solvent.
5. The method according to claim 4, wherein the organic solvent is used in an amount of 1 to 50mol relative to 1mol of the compound represented by formula (III).
6. The method according to claim 5, wherein the organic solvent is used in an amount of 5 to 30mol relative to 1mol of the compound represented by formula (III).
7. The method according to claim 4, wherein the organic solvent is at least one of aromatic hydrocarbons, nitriles, and alcohols.
8. The method according to claim 7, wherein the organic solvent is at least one of a monocyclic aromatic hydrocarbon, a linear saturated aliphatic nitrile, and a linear saturated aliphatic alcohol.
9. The method according to claim 8, wherein the organic solvent is selected from at least one of toluene, xylene, methanol, ethanol, acetonitrile and butyronitrile.
10. The method of claim 9, wherein the organic solvent is selected from at least one of toluene, methanol, and acetonitrile.
11. The method according to any one of claims 1 to 4, wherein the compound represented by the formula (II) is used in an amount of 1 to 7mol relative to 1mol of the compound represented by the formula (III).
12. The method according to claim 11, wherein the compound represented by the formula (II) is used in an amount of 1 to 3mol with respect to 1mol of the compound represented by the formula (III).
13. The method according to any one of claims 1 to 4, wherein the basic substance is used in an amount of 0.6 to 3mol relative to 1mol of the compound represented by formula (III).
14. The method according to claim 13, wherein the basic substance is used in an amount of 0.8 to 1.5mol with respect to 1mol of the compound represented by formula (III).
15. The method according to any one of claims 1 to 4, wherein the reaction conditions comprise: the temperature is-20-100 ℃; the time is 1-24 h.
16. The method of claim 15, wherein the reaction conditions comprise: the temperature is-10-30 ℃; the time is 2-10 h.
17. The method according to any one of claims 1 to 4, wherein the compound of the general formula (II) is N, N-dimethylformamide dimethyl sulfate complex, N-dimethylformamide diethyl sulfate complex, N-methylformamide dimethyl sulfate complex, N-diethylformamide dimethyl sulfate complex, or N, N-diethylformamide diethyl sulfate complex.
18. The method according to any one of claims 1 to 4, wherein the basic substance is at least one of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, triethylamine, diisopropylethylamine, pyridine, and N, N-diethylaniline.
19. The method of claim 18, wherein the basic substance is at least one of sodium carbonate, sodium hydroxide, triethylamine, and pyridine.
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