CN1687031A - Method for synthesizing imide base substituted endo compound - Google Patents
Method for synthesizing imide base substituted endo compound Download PDFInfo
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Abstract
本发明涉及一种合成酰亚胺基取代化合物的方法，包括：以路易斯酸作为催化剂，如式(I)的酰亚胺基取代α，β－不饱和酮与如式(II)的五元环二烯烃在微波辐射下于－20～150℃在有机溶剂中进行Diels－Alder反应，后处理得产物；所述的合成方法收率高、反应时间短、反应温度低。
The invention relates to a method for synthesizing imide-substituted compounds, comprising: using Lewis acid as a catalyst, imide-substituted α, β-unsaturated ketones such as formula (I) and five-membered ketones such as formula (II) Cyclodiene is subjected to Diels-Alder reaction in an organic solvent at -20-150 DEG C under microwave radiation, and the product is obtained after post-treatment; the synthesis method has high yield, short reaction time and low reaction temperature.
Description
(1) technical field
The present invention relates to a kind of method of synthesizing imide base substitution compound.
(2) background technology
The compound that contains the imide carbonyl structure has certain biological activity, mainly is as sterilant, weedicide and the class medicine that kills mouse aspect biologic applications, is the important intermediate of tranquilizer, antituberculotic and depressor aspect medical.In addition, such material also is being with a wide range of applications aspect synthesis of chiral medicine and the natural goods.
The present inventor had once reported the method for the endocyclic compound of two kinds of synthesizing imide base carbonyl substituted.A kind of is to replace α by imide, the Diels-Alder reaction that alpha, beta-unsaturated ketone and cyclopentadiene hydrocarbon carry out in molecular solvent, there are shortcomings such as yield is low, long reaction time, temperature of reaction height in the cycloaddition product that has synthesized a series of imide carbonyl substituted, this method.A kind of is the Diels-Alder reaction of being carried out in ionic liquid by imide replacement alpha, beta-unsaturated ketone and five-ring diolefine, has synthesized the cycloaddition product of a series of imide carbonyl substituted, and this method yield is improved, but the reaction times is long.Microwave method is used for organic synthesis as a kind of novel Green Chemistry synthetic technology, have easy and simple to handle, accelerate speed of reaction, improve advantages such as product yield and environmental pollution are little.This technology is obtaining using widely aspect synthetic medicine, agricultural chemicals and the natural goods.
(3) summary of the invention
The object of the invention is to provide the method for the endocyclic compound that a kind of reaction times is short, yield is high, temperature of reaction is low synthesizing imide base replaces.
The method of the endocyclic compound that described synthesizing imide base replaces, comprise: with Lewis acid as catalyzer, imide suc as formula (I) replaces α, alpha, beta-unsaturated ketone with under microwave radiation, in organic solvent carry out Diels-Alder reaction in-20～150 ℃ suc as formula the five-ring diolefine of (II), aftertreatment gets product;
Wherein R is aryl or C
1～C
4Alkyl; R
1, R
2Respectively do for oneself hydrogen or form phenyl ring; X is one of following: C, S, O ,-NH-.Reaction formula is as follows:
Described aryl is preferably phenyl or nitrophenyl.
Described organic solvent can be molecular solvent or ionic liquid.Described molecular solvent such as methylene dichloride, toluene, chloroform, tetrahydrofuran (THF), tetracol phenixin, N, dinethylformamide, methyl-sulphoxide etc. are preferably toluene or methylene dichloride.Described ionic liquid is preferably alkyl imidazole a tetrafluoro borate or alkyl-imidazole hexafluorophosphate, described alkyl carbon atom quantity 1～18; Ionic liquid is preferably 1-butyl-3-methyl imidazolium tetrafluoroborate or 1-butyl-3-Methylimidazole hexafluorophosphate.
Described microwave apparatus is all kinds of experiments with microwave radiation device or household microwave oven.
In common Diels-Alder reaction, described Lewis acid is preferably zinc iodide, and it is as follows that synthesis step is recommended: imide is replaced alpha, beta-unsaturated ketone and the five-ring diolefine is dissolved in the methylene dichloride, under catalyst behind microwave radiation stoichiometric number minute, add saturated sodium bicarbonate solution, use dichloromethane extraction, washed several times with water, dry, concentrate,, get the cycloaddition product through recrystallization or column chromatography for separation.
In asymmetry catalysis Diels-Alder reaction, Lewis acid is preferably the chirality 1 of structure suc as formula (III), 4-glycol titanium complex:
Wherein, Ar represents phenyl, 3,5-3,5-dimethylphenyl or naphthyl; Y represents halogen atom.Synthesis step is recommended as follows: use nitrogen protection, with dry activatory molecular sieve powder and chirality 1, the 4-glycol is put into the tetrafluoroethylene reactor and is sealed.Charge into nitrogen and make reaction system anaerobic and adiabatic drying, add toluene with syringe, thorough mixing stirs, again with TiX
2(OPr
i)
2Toluene solution add reaction system, stirring at room, at low temperatures, the alpha, beta-unsaturated ketone that imide is replaced is dissolved in and adds reaction system in the toluene earlier, after the stirred for several minute, add the five-ring diolefine again, behind microwave radiation stoichiometric number minute, add saturated sodium bicarbonate solution, use dichloromethane extraction, washed several times with water, dry, concentrate, use column chromatography, get the cycloaddition product.The finished product are identified with infrared spectra, nuclear magnetic resonance spectrum and mass spectrum.
The temperature of reaction of described building-up reactions is preferably 25～110 ℃; Reaction times is preferably 0.1min～2h, more preferably 1min～30min.
The molar ratio that described imide replaces alpha, beta-unsaturated ketone and five-ring diolefine is preferably 1: 1～and 10, more preferably 1: 3～7.
Behind the organic solvent extraction product, ionic liquid can continue to use.
The present invention utilizes microwave radiation to promote reaction, has accelerated reaction process, has shortened the reaction times, and is easy and simple to handle, reduced temperature of reaction, saved energy consumption, improved product yield, is beneficial to suitability for industrialized production.Because ionic liquid-catalyzed system can be recycled, and has not only reduced cost, and has reduced the pollution of waste water to environment.
(4) embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1 1-succimide base-3-phenyl acrylketone and cyclopentadiene carry out the Diels-Alder reaction
In 50mL single port flask, add 5mL toluene and 0.23 gram (1mmol) 1-succimide base-3-phenyl acrylketone, add 0.15 gram (0.5mmol) zinc iodide and 0.5mL (5mmol) cyclopentadiene then, uncovered inserting in the microwave oven through microwave radiation (490W) 1min, add the 20mL saturated sodium bicarbonate solution, with dichloromethane extraction (3 * 5mL), washed several times with water, dry, concentrate, get white needle-like crystals 0.25 gram with ethyl alcohol recrystallization, 128～129 ℃ of fusing points (literature value: 127～128 ℃), yield 84.4%.
Embodiment 2 1-succimide base-2-butylene ketone and cyclopentadiene carry out the Diels-Alder reaction
In 50mL single port flask, add 5mL 1-butyl-3-methyl imidazolium tetrafluoroborate and 0.17 gram (1mmol) 1-succimide base-2-butylene ketone, add 0.15 gram (0.5mmol) zinc iodide and 0.5mL (5mmol) cyclopentadiene then, uncovered inserting in the microwave oven through microwave radiation (70W) 1min, with toluene extraction (3 * 5mL), washed several times with water, dry, concentrate, through column chromatography (sherwood oil: ethyl acetate=2: 1) get white needle-like crystals 0.22 gram, 88～89 ℃ of fusing points, yield 93.3%.IR：v＝2975，2872，1795，1746，1709，1429，1371，1317，1253，1183cm
-1。
1H?NMR(400MHz，CDCl
3)：δ＝1.18(d，J＝7.2，3H，Me-6)，1.46(dd，J＝9，1.6Hz，1H，H-7a)，1.63(d，J＝8.8，1H，H-7b)，2.05(m，1H，H-1)，2.54(s，1H，H-6)，2.8(s，4H，H-11，H-12)，3.07(s，1H，H-4)，3.24(dd，J＝3.6，4Hz，1H，H-5)，5.91(dd，J＝2.6，6Hz，1H，H-2)，6.24(dd，J＝3.4，6Hz，1H，H-3)。MS:m/z=233 (M
+, 0.2%), 168 (14.3%), 69 (76%), 66 (base peaks).
Embodiment 3 1-succimide base-2-butylene ketone and cyclopentadiene carry out the Diels-Alder reaction
In nitrogen gas stream, and dry activatory 4A molecular sieve powder 0.4 gram of general and optical activity (2R, 3R)-(-)-1,1,4,4-four-(1-naphthyl)-2,3-(acetone contracts)-1,4-butyleneglycol 0.15 gram (0.22mmol) is inserted in the 25mL tetrafluoroethylene reactor and is sealed.Charge into nitrogen and make reaction system anaerobic and adiabatic drying, add 3mL toluene with syringe, thorough mixing stirs, again with 0.2mLTiCl
2(OPr
i)
2Toluene solution (0.87mol/L) add reaction system, stirring at room 1 hour, cool the temperature to-10 ℃ again, 0.17 gram (1mmol) 1-succimide base-2-butylene ketone is dissolved in 4mL toluene and adds reaction system earlier, after the stirred for several minute, add cyclopentadiene 1mL (10mmol) again,, add the 20mL saturated sodium bicarbonate solution through microwave radiation (490W) 45s, with dichloromethane extraction (3 * 5mL), washed several times with water, drying concentrates, through column chromatography (sherwood oil: ethyl acetate=2: 1) get white needle-like crystals 0.2 gram, 113～114 ℃ of fusing points, yield 85.7%, enantiomeric excess 91%e.e..
Embodiment 4 1-succimide base-3-phenyl acrylketone and cyclopentadiene carry out the Diels-Alder reaction
In 50mL single port flask, add 5mL 1-butyl-3-Methylimidazole hexafluorophosphate and 0.23 gram (1mmol) 1-succimide base-3-phenyl acrylketone, add 0.15 gram (0.5mmol) zinc iodide and 0.5mL (5mmol) cyclopentadiene then, uncovered inserting in the microwave oven through microwave radiation (70W) 1min, with toluene extraction (3 * 5mL), washed several times with water, dry, concentrate, get white needle-like crystals 0.22 gram with ethyl alcohol recrystallization, 126～127 ℃ of fusing points (literature value: 127～128 ℃), yield 74.7%.
Embodiment 5 1-phthalimide-based-3-phenyl acrylketone and cyclopentadiene carry out the Diels-Alder reaction
In 50mL single port flask, add 5mL toluene and 0.28 gram (1mmol) 1-phthalimide-based-3-phenyl acrylketone, add 0.15 gram (0.5mmol) zinc iodide and 0.5mL (5mmo1) cyclopentadiene then, uncovered inserting in the microwave oven through microwave radiation (490W) 1min, add the 20mL saturated sodium bicarbonate solution, with dichloromethane extraction (3 * 5mL), washed several times with water, dry, concentrate, get white plates crystal 0.27 gram with ethyl alcohol recrystallization, 142～143 ℃ of fusing points (literature value: 141～142 ℃), yield 77.7%.
Embodiment 6 1-succimide bases-3-m-nitro base acrylketone and cyclopentadiene carry out the Diels-Alder reaction
In 50mL single port flask, add 5mL toluene and 0.27 gram (1mmol) 1-succimide base-3-m-nitro base acrylketone, add 0.15 gram (0.5mmol) zinc iodide and 0.5mL (5mmol) cyclopentadiene then, uncovered inserting in the microwave oven through microwave spoke (490W) 1min, add the 20mL saturated sodium bicarbonate solution, with dichloromethane extraction (3 * 5mL), washed several times with water, dry, concentrate, get white plates crystal 0.24 gram with ethyl alcohol recrystallization, 123～125 ℃ of fusing points (literature value: 123～124 ℃), yield 71.6%.
Embodiment 7 1-phthalimide-based-2-butylene ketone and cyclopentadiene carry out the Diels-Alder reaction
In 50mL single port flask, add 5mL methylene dichloride and 0.21 gram (1mmol) 1-phthalimide-based-2-butylene ketone, add 0.15 gram (0.5mmol) zinc iodide and 0.5mL ((5mmol) cyclopentadiene then, uncovered inserting in the microwave oven through microwave radiation (490W) 1min, add the 20mL saturated sodium bicarbonate solution, with dichloromethane extraction (3 * 5mL), washed several times with water, dry, concentrate, through column chromatography (sherwood oil: ethyl acetate=3: 1) get white particulate crystal 0.24 gram, 143～144 ℃ of fusing points, yield 87.4%.IR：ν＝2970，2869，1795，1751，1713，1469，1368，1323，1273，1176，1134，1113cm
-1。
1NMR(400MHz，CDCl
3)：δ＝1.2(d，J＝7.6，3H，Me-6)，1.47(dd，J＝8.8，1.6Hz，1H，H-7a)，1.70(d，J＝8.4，1H，H-7b)，2.18(m，1H，H-1)，2.56(s，1H，H-6)，3.16(s，1H，H-4)，3.49(dd，J＝3.6，4.4Hz，1H，H-5)，5.90(dd，J＝2.8，5.4Hz，1H，H-2)，6.36(dd，J＝3.2，5.6Hz，1H，H-3)，7.84(m，2H，ph-5)，7.96(m，2H，ph-5)。MS:m/z=281 (M
+, 0.3%), 216 (14.6%), 174 (14.7%), 69 (69%), 66 (base peak).
Embodiment 8 1-phthalimide-based-3-p-nitrophenyl acrylketone and cyclopentadiene carry out the Diels-Alder reaction
In 50mL single port flask, add 5mL toluene and 0.32 gram (1mmol) 1-phthalimide-based-3-p-nitrophenyl acrylketone, add 0.15 gram (0.5mmol) zinc iodide and 0.5mL (5mmol) cyclopentadiene then, uncovered inserting in the microwave oven through microwave radiation (490W) 1min, add the 20mL saturated sodium bicarbonate solution, with dichloromethane extraction (3 * 5mL), washed several times with water, dry, concentrate, get white particulate crystal 0.28 gram with ethyl alcohol recrystallization, 155～156 ℃ of fusing points, yield 72.6%.IR：ν＝2991，1793，1744，1711，1603，1519，1468，1349，1296cm
-1。
1NMR(400MHz，CDCl
3)：δ＝1.68(dd，J＝8.6，1.8Hz，1H，H-7a)，1.89(d，J＝8.7，1H，H-7b)，3.15(s，1H，H-1)，3.40(s，1H，H-6)，3.57(d，J＝4.88，1H，H-4)，4.14(dd，J＝4，4.5Hz，1H，H-5)，6.06(dd，J＝2.3，5.6Hz，1H，H-2)，6.54(dd，J＝3.0，5.6Hz，1H，H-3)，7.48(d，J＝8.5，2H，ph-6)，7.86(m，2H，ph-5)，7.97(m，2H，ph-5)，8.17(d，J＝8.5，2H，ph-6)。MS:m/z=322 (M
+, 36.9%), 176 (base peaks), 102 (93.7%), 76 (80.5%), 66 (70%).
Embodiment 9 1-phthalimide-based-3-m-nitro base acrylketone and cyclopentadiene carry out the Diels-Alder reaction
In 50mL single port flask, add 5mL toluene and 0.32 gram (1mmol) 1-phthalimide-based-3-m-nitro base acrylketone, add 0.15 gram (0.5mmol) zinc iodide and 0.5mL (5mmol) cyclopentadiene then, uncovered inserting in the microwave oven through microwave radiation (490W) 1min, add the 20mL saturated sodium bicarbonate solution, with dichloromethane extraction (3 * 5mL), washed several times with water, dry, concentrate, get white particulate crystal 0.29 gram with ethyl alcohol recrystallization, 142～144 ℃ of fusing points (literature value: 143～145 ℃), yield 75.2%.
Embodiment 10 1-succimide base-3-phenyl acrylketone and pyrroles carry out the Diels-Alder reaction
In 50mL single port flask, add 5mL 1-butyl-3-methyl imidazolium tetrafluoroborate and 0.23 gram (1mmol) 1-succimide base-3-phenyl acrylketone, add 0.32 gram (1mmol) zinc iodide and 0.67mL (10mmol) pyrroles then, uncovered inserting in the microwave oven through microwave radiation (70W) 2min, with toluene extraction (3 * 5mL), washed several times with water, dry, concentrate, through column chromatography (sherwood oil: ethyl acetate=2: 1) get white plates crystal 0.1 gram, 126～127 ℃ of fusing points, yield 33.5%.IR：ν＝cm
-1。
1H?NMR(400MHz，CDCl
3)：δ＝。MS:m/z=296 (M
+, 0.1%), 229 (34.1%), 131 (67.9%), 67 (base peaks).
Embodiment 11 1-succimide base-3-phenyl acrylketone and furans carry out the Diels-Alder reaction
In 50mL single port flask, add 5mL 1-butyl-3-methyl imidazolium tetrafluoroborate and 0.23 gram (1mmol) 1-succimide base-3-phenyl acrylketone, add 0.32 gram (1mmol) zinc iodide and 0.7mL (10mmol) furans then, uncovered inserting in the microwave oven through microwave radiation (70W) 2min, with toluene extraction (3 * 5mL), washed several times with water, dry, concentrate, through column chromatography (sherwood oil: ethyl acetate=3: 1) get white particulate crystal 0.14 gram, 123～124 ℃ of fusing points, yield 46.9%.IR：ν＝cm
-1。
1H?NMR(400MHz，CDCl
3)：δ＝。MS:m/z=297 (M
+, 0.2%), 229 (47.1%), 131 (77.5%), 68 (base peaks).
Embodiment 12 1-succimide base-2-butylene ketone and thiophene carry out the Diels-Alder reaction
In 50mL single port flask, add 5mL 1-butyl-3-methyl imidazolium tetrafluoroborate and 0.17 gram (1mmol) 1-succimide base-2-butylene ketone, add 0.32 gram (1mmol) zinc iodide and 0.8mL (10mmol) thiophene then, uncovered inserting in the microwave oven through microwave radiation (70W) 2min, with toluene extraction (3 * 5mL), washed several times with water, drying, concentrate, through column chromatography (sherwood oil: ethyl acetate=3: 1) get white needle-like crystals 0.08 gram, 94～95 ℃ of fusing points, yield 31.3%.IR：ν＝cm
-1。
1H?NMR(400MHz，CDCl
3)：δ＝。MS:m/z=251 (M
+, 0.3%), 168 (29.7%), 84 (base peak), 69 (71.9%).
Embodiment 13 1-succimide base-3-phenyl acrylketone and cyclopentadiene carry out the Diels-Alder reaction
In 50mL single port flask, add 5mL chloroform and 0.23 gram (1mmol) 1-succimide base-3-phenyl acrylketone, add 0.15 gram (0.5mmol) zinc iodide and 0.7mL (7mmol) cyclopentadiene then, uncovered inserting in the microwave oven through microwave radiation (70W) 1min, with toluene extraction (3 * 5mL), washed several times with water, drying, concentrate, get white needle-like crystals 0.23 gram, 126～127 ℃ of fusing points (literature value: 127～128 ℃), yield 78.0% with ethyl alcohol recrystallization.
Embodiment 14 1-phthalimide-based-3-phenyl acrylketone and cyclopentadiene carry out the Diels-Alder reaction
In 50mL single port flask, add 5mL methyl-sulphoxide and 0.28 gram (1mmol) 1-phthalimide-based-3-phenyl acrylketone, add 0.15 gram (0.5mmol) zinc iodide and 0.3mL (3mmol) cyclopentadiene then, uncovered inserting in the microwave oven through microwave radiation (490W) 1min, add the 20mL saturated sodium bicarbonate solution, with dichloromethane extraction (3 * 5mL), washed several times with water, dry, concentrate, get white plates crystal 0.22 gram with ethyl alcohol recrystallization, 142～143 ℃ of fusing points (literature value: 141～142 ℃), yield 63.3%.
Embodiment 15 1-succimide bases-3-m-nitro base acrylketone and cyclopentadiene carry out the Diels-Alder reaction
In 50mL single port flask, add 5mL tetracol phenixin and 0.27 gram (1mmol) 1-succimide base-3-m-nitro base acrylketone, add 0.15 gram (0.5mmol) zinc iodide and 0.5mL (5mmol) cyclopentadiene then, uncovered inserting in the microwave oven through microwave spoke (490W) 1min, add the 20mL saturated sodium bicarbonate solution, with dichloromethane extraction (3 * 5mL), washed several times with water, dry, concentrate, get white plates crystal 0.24 gram with ethyl alcohol recrystallization, 123～125 ℃ of fusing points (literature value: 123～124 ℃), yield 71.6%.
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| US4748183A (en) * | 1986-06-13 | 1988-05-31 | Warner-Lambert Company | N-1H-tetrazol-5-yl-2-thiophene carboxamides, N-1H-tetrazol-5-yl-2-pyrrole carboxamides, N-1H-tetrazol-5-yl-2-furan carboxamides, and anti-allergic and anti-inflammatory use thereof |
| JP3123137B2 (en) * | 1991-08-20 | 2001-01-09 | チッソ株式会社 | Method for producing optically active 3-substituted-2-norbornanone |
| JP3118939B2 (en) * | 1992-02-10 | 2000-12-18 | チッソ株式会社 | Method for producing optically active 2-hydroxy-2-norbornanecarboxylic acid |
| TW229214B (en) * | 1992-01-10 | 1994-09-01 | Shell Oil Co | |
| FR2771735B1 (en) * | 1997-12-02 | 2000-03-03 | Atochem Elf Sa | PROCESS AND REACTOR FOR THE MANUFACTURE OF NORBORNENE |
| US5993497A (en) * | 1998-08-28 | 1999-11-30 | Chevron Chemical Company Llc | Esters of polyalkyl or polyalkenyl N-hydroxyalkyl succinimides and fuel compositions containing the same |
| JP2006511628A (en) * | 2002-05-07 | 2006-04-06 | ハネウェル・インターナショナル・インコーポレーテッド | Fluorinated polymer |
| CN1266094C (en) * | 2003-08-14 | 2006-07-26 | 中国石化上海石油化工股份有限公司 | Method for preparing 2,5-norbornadiene from dicyclo pentadiene |
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