CN114671796A - Method for synthesizing N-alkyl phthalimide through photocatalysis - Google Patents
Method for synthesizing N-alkyl phthalimide through photocatalysis Download PDFInfo
- Publication number
- CN114671796A CN114671796A CN202210429375.4A CN202210429375A CN114671796A CN 114671796 A CN114671796 A CN 114671796A CN 202210429375 A CN202210429375 A CN 202210429375A CN 114671796 A CN114671796 A CN 114671796A
- Authority
- CN
- China
- Prior art keywords
- reaction tube
- ethyl acetate
- alkylphthalimide
- phthalimide
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title abstract description 12
- 238000007146 photocatalysis Methods 0.000 title abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 32
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012074 organic phase Substances 0.000 claims abstract description 18
- 239000003208 petroleum Substances 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 12
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical compound CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000004440 column chromatography Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000007865 diluting Methods 0.000 claims abstract description 4
- 238000004821 distillation Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000003480 eluent Substances 0.000 claims abstract description 4
- 238000000605 extraction Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 24
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- -1 alkyl silicon Chemical compound 0.000 claims description 8
- 238000001308 synthesis method Methods 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 229910000799 K alloy Inorganic materials 0.000 claims 3
- 239000000047 product Substances 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 description 13
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 6
- 150000003141 primary amines Chemical class 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000003818 flash chromatography Methods 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 238000006800 Gabriel amine synthesis reaction Methods 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001343 alkyl silanes Chemical class 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003862 amino acid derivatives Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 125000005543 phthalimide group Chemical group 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
Abstract
The invention provides a method for synthesizing N-alkyl phthalimide by photocatalysis, which comprises the following steps: s1: to a reaction tube with a stirrer was added N-alkenylphthalimide and a photosensitizer Ir [ dF (CF)3)ppy]2(dtbbpy)PF6Then adding a radical precursor silicon alkyl to the reaction tube; s2: adding dimethyl sulfoxide into the reaction tube, evacuating the reaction tube, exchanging nitrogen, placing the reaction tube under a 9W blue light LED lamp for irradiation, stirring, diluting the reaction solution with ethyl acetate and water, and extracting with ethyl acetate; s3: combining the organic phases obtained by extraction, drying with anhydrous sodium sulfate, filtering again to obtain an organic phase solution, and removing the solvent by a rotary evaporator; then the mixed solution of petroleum ether and ethyl acetate is used as eluent to carry out column chromatography separation, and finally the product N-alkyl phthalimide is obtained by distillation of a rotary evaporator. The method can be used for efficiently preparing the N-alkyl phthalimide, and has high production efficiency and few byproducts.
Description
Technical Field
The invention relates to the field of photocatalytic synthesis, in particular to a method for synthesizing N-alkyl phthalimide through photocatalysis.
Background
Primary amines are a basic and important class of organic compounds, and are also important intermediates in chemical reactions. Hydrolysis of N-alkylphthalimides is one of the important processes for the synthesis of primary amines and is known as the Gabriel amine synthesis. The synthesis method has no side reaction problem of secondary and tertiary amine, so that the method can be used for synthesizing primary amine with higher purity. In the process for preparing N-substituted phthalimides, the conventional method commonly used is to react phthalimide with a halogenated hydrocarbon under the action of a base (e.g., reaction formula (1)). However, this synthesis method is suitable for primary halogenated hydrocarbons having high reactivity, and is not efficient in secondary halogenated hydrocarbons and involves many side reactions.
The free radical addition reaction of N-alkenyl phthalimide as an acceptor provides a good alternative strategy to the low efficiency between secondary halides and phthalimides. For example, synthesis of unnatural amino acid derivatives can be achieved using an olefin as a radical precursor under iron-catalyzed conditions (e.g., equation (2)). In addition, an addition reaction is carried out by using aldehyde as a radical precursor and generating an acyl radical and N-alkenylphthalimide through the cleavage of a C-H bond under the catalysis of tetrabutylammonium decatungstate (TBADT) (as shown in the reaction formula (3)). The catalytic system can generate C-H bond breakage to generate alkyl free radical and perform addition reaction for the hydrogen at benzyl position and tertiary position, but the efficiency is general.
In view of the universality and universality of the Gabriel amine synthesis method in primary amine synthesis, the development of a high-efficiency N-alkylphthalimide synthesis method still has important significance, and particularly the N-alkylphthalimide synthesis method which is mild in reaction conditions, simple in operation, good in universality and high in efficiency is more important.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for synthesizing N-alkyl phthalimide by photocatalysis, so as to solve the problems of low reaction efficiency, more byproducts, and poor universality and universality in the conventional reaction.
In order to solve the problems, the invention provides a method for synthesizing N-alkyl phthalimide by photocatalysis, which comprises the following specific steps:
s1: adding N-alkenyl phthalimide and photosensitizer Ir [ dF (CF) into a reaction tube with a stirrer3)ppy]2(dtbbpy)PF6Then adding a radical precursor silicon alkyl to the reaction tube;
s2: adding dimethyl sulfoxide into the reaction tube obtained after the operation of the step S1, evacuating the reaction tube, replacing nitrogen, placing the reaction tube under a 9W blue LED lamp for irradiation, stirring, diluting the reaction solution with ethyl acetate and water, and extracting with ethyl acetate;
s3: combining the organic phases obtained by the extraction in the step S2, drying the combined organic phases by using anhydrous sodium sulfate, filtering the combined organic phases again to obtain an organic phase solution, and removing the solvent by using a rotary evaporator; then the mixed solution of petroleum ether and ethyl acetate is used as eluent to carry out column chromatography separation, and finally the product N-alkyl phthalimide is obtained by distillation of a rotary evaporator.
Preferably, in step S1, the N-alkenylphthalimide is reacted with Ir [ dF (CF)3)ppy]2(dtbbpy)PF6In a molar ratio of 1: (0.01-0.03).
Preferably, in step S1, the molar ratio of N-alkenylphthalimide to radical precursor alkylsilane is 1: (1.5-2.5).
Preferably, in step S1, the alkylsilane serving as the radical precursor is one of chloropropylbis (catechol) silicate-18-crown ether-6-potassium, cyclohexylbis (catechol) silicate-18-crown ether-6-potassium and ethylbis (catechol) silicate-18-crown ether-6-potassium.
Preferably, in step S2, the stirring conditions are: stirred at room temperature for 24 hours.
Preferably, in the step S1 and the step S2, the molar ratio of the N-alkenyl phthalimide to the dimethyl sulfoxide is 1: (400-450).
Preferably, in the step S3, the volume ratio of the petroleum ether to the ethyl acetate in the mixed solution of the petroleum ether and the ethyl acetate is 10: 1.
Preferably, in the step S3, the length of the silica gel column in the column chromatography separation is 10 cm.
Preferably, the reaction formula of the method is as follows:
the beneficial effects of the invention are: the invention relates to a method for synthesizing N-alkyl phthalimide by photocatalysis, and provides a novel method for modularizing and synthesizing N-alkyl phthalimide; the invention has the advantages of wide substrate application range, good functional group compatibility, mild and efficient reaction conditions and simple and convenient operation; the invention provides a novel method for synthesizing N-alkyl phthalimide by taking high-valence organic silicon as a free radical precursor and N-alkenyl phthalimide as a free radical acceptor under the mild visible light irradiation condition without alkali and an additional reducing agent, and the method has the advantages of low preparation cost, simple condition, higher universality and universality, fewer reaction byproducts, high reaction efficiency and higher popularization value and commercial value.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides the following method for obtaining N-alkyl phthalimide by photocatalytic synthesis:
the invention provides a method for synthesizing N-alkyl phthalimide by photocatalysis, which comprises the following steps:
s1: to a reaction tube with a stirrer was added N-alkenylphthalimide and a photosensitizer Ir [ dF (CF)3)ppy]2(dtbbpy)PF6Then adding a radical precursor silicon alkyl to the reaction tube;
s2: adding dimethyl sulfoxide into the reaction tube obtained after the operation of the step S1, evacuating the reaction tube, replacing nitrogen, placing the reaction tube under a 9W blue LED lamp for irradiation, stirring, diluting the reaction solution with ethyl acetate and water, and extracting with ethyl acetate;
s3: combining the organic phases obtained by the extraction in the step S2, drying the combined organic phases by using anhydrous sodium sulfate, filtering the combined organic phases again to obtain an organic phase solution, and removing the solvent by using a rotary evaporator; then the mixed solution of petroleum ether and ethyl acetate is used as eluent to carry out column chromatography separation, and finally the product N-alkyl phthalimide is obtained by distillation of a rotary evaporator.
Preferably, in step S1, the N-alkenylphthalimide is reacted with Ir [ dF (CF)3)ppy]2(dtbbpy)PF6In a molar ratio of 1: (0.01-0.03).
Preferably, in step S1, the molar ratio of N-alkenylphthalimide to radical precursor silane is 1: (1.5-2.5).
Preferably, in step S1, the alkyl silicon as the radical precursor is one of chloropropyl bis (catechol) silicate-18-crown ether-6-potassium, cyclohexyl bis (catechol) silicate-18-crown ether-6-potassium and ethyl bis (catechol) silicate-18-crown ether-6-potassium.
Preferably, in step S2, the stirring conditions are: stirred at room temperature for 24 hours.
Preferably, in the step S1 and the step S2, the molar ratio of N-alkenyl phthalimide to dimethyl sulfoxide is 1: (400-450).
Preferably, in the step S3, the volume ratio of the petroleum ether to the ethyl acetate in the mixed solution of the petroleum ether and the ethyl acetate is 10: 1.
Preferably, in the step S3, in the column chromatography separation, the length of the silica gel column is 10 cm.
Preferably, the reaction formula of the process is as follows:
the above method is described below with reference to specific data:
example one
S1: put magneton into reaction tube, add Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(4.5mg,0.004mmol,0.02equiv), ethyl 2- (N-phthalimide) acrylate (49.0mg,0.2mmol,1.0 equiv); placing the reaction tube into a glove box, and weighing chloropropylbis (catechol) silicate-18-crown ether-6-potassium complex (249.8mg,0.4mmol,2.0equiv) in the glove box;
s2: the reaction tube was stoppered with a rubber stopper, dried dimethyl sulfoxide (6mL) was added under nitrogen, and the rubber stopper was sealed with a sealing film. Irradiating the reaction tube under a 9W blue light LED lamp, stirring at room temperature for 24h, stopping the illumination reaction, adding 6mL of water into the reaction solution, and extracting with ethyl acetate (4X 10 mL);
s3: the organic phases were combined, washed with 5mL of saturated brine, dried over anhydrous sodium sulfate, filtered, the solvent was removed by rotary evaporation of the filtrate, and the residue was washed with a mixture of petroleum ether and ethyl acetate (V)Petroleum ether：VEthyl acetate10: 1) the target product 45.9mg is obtained by flash column chromatography, the yield is 71 percent, and the product is faint yellow viscous liquid. The analytical data are as follows:
1H NMR(500MHz,CDCl3):δ7.88-7.86(m,2H),7.77-7.75(m,2H),4.83(dd,J＝10.4Hz,5.2Hz,1H),4.23-4.16(m,2H),3.51-3.48(m,2H),2.32-2.21(m,2H),1.88-1.74(m,2H),1.51-1.41(m,2H),1.22(t,J＝7.2Hz,3H)；13C NMR(125MHz,CDCl3):δ169.1,167.7,134.2,131.7,123.6,61.9,52.0,44.5,31.8,27.9,23.6,14.1；HRMS(ESI)calculated for C16H19ClNO4[M+H]+324.1003,found 324.1007.
the general reaction formula of the above example is as follows:
example two
S1: put magneton into reaction tube, add Ir [ dF (CF)3)ppy]2(dtbbpy)PF6(4.5mg,0.004mmol,0.02equiv), ethyl 2- (N-phthalimide) acrylate (49.0mg,0.2mmol,1.0 equiv); the reaction tube was placed in a glove box, and cyclohexylbis (catechol) silicate-18-crown-6-potassium complex (252.0mg,0.4mmol,2.0equiv) was weighed in the glove box;
s2: the reaction tube was stoppered with a rubber stopper, dried dimethyl sulfoxide (6mL) was added under nitrogen, and the rubber stopper was sealed with a sealing film. Irradiating the reaction tube under a 9W blue light LED lamp, stirring at room temperature for 24h, stopping the illumination reaction, adding 6mL of water into the reaction solution, and extracting with ethyl acetate (4X 10 mL);
s3: the organic phase was combined, washed with 5mL of saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was evaporated to remove the solvent, and then mixed with a mixture of petroleum ether and ethyl acetate (V)Petroleum ether：VEthyl acetate10: 1) the target product 54.6mg is obtained by flash column chromatography, the yield is 83 percent, and the product is light yellow viscous liquid. The analytical data are as follows:
1H NMR(500MHz,CDCl3):δ7.87-7.84(m,2H),7.75-7.72(m,2H),4.95(dd,J＝11.5Hz,4.4Hz,1H),4.21-4.14(m,2H),2.29-2.23(m,1H),2.04-1.98(m,1H),1.87(d,J＝12.7Hz,1H),1.71-1.60(m,4H),1.20(t,J＝7.1Hz,3H),1.15-1.09(m,4H),1.02-0.97(m,1H),0.95-0.86(m,1H)；13C NMR(125MHz,CDCl3):δ169.8,167.7,134.1,131.8,123.4,61.7,50.1,35.9,34.3,33.7,31.6,26.3,26.1,25.8,14.0.
the general reaction formula of example 2 above is as follows:
EXAMPLE III
S1: a magneton is put into the reaction tube, and Ir [ dF (CF) is added3)ppy]2(dtbbpy)PF6(4.5mg,0.004mmol,0.02equiv), 1- (N-phthalimide) styrene (49.0mg,0.2mmol,1.0 equiv); the reaction tube was placed in a glove box, and ethyl bis (catechol) silicate-18-crown ether-6-potassium complex (230.4mg,0.4mmol,2.0equiv) was weighed in the glove box;
s2: the reaction tube was stoppered with a rubber stopper, dried dimethyl sulfoxide (6mL) was added under nitrogen, and the rubber stopper was sealed with a sealing film. Irradiating the reaction tube under a 9W blue light LED lamp, stirring at room temperature for 24h, stopping the illumination reaction, adding 6mL of water into the reaction solution, and extracting with ethyl acetate (4X 10 mL);
s3: the organic phases were combined and washed with 5mL of saturated brine, the organic phase was dried over anhydrous sodium sulfate and filtered, the solvent was removed by rotary evaporation of the filtrate, and then a mixture of petroleum ether and ethyl acetate (V)Petroleum ether：VEthyl acetate10: 1) the target product 37.4mg is obtained by flash column chromatography, the yield is 67 percent, and the product is pale yellow viscous liquid. The analytical data are as follows:
1H NMR(500MHz,CDCl3):δ7.71-7.70(m,2H),7.59-7.58(m,2H),7.46(d,J＝7.8Hz,2H),7.25-7.22(m,2H),7.18-7.15(m,1H),5.28-5.25(m,1H),2.53-2.46(m,1H),2.18-2.11(m,1H),1.31-1.22(m,2H),0.88(t,J＝7.3Hz,3H)；13C NMR(125MHz,CDCl3):δ168.4,139.8,133.9,131.8,128.4,128.1,127.7,123.1,54.6,32.9,20.2,13.7.
the general reaction formula of example 3 above is as follows:
through the preparation reactions and the product tests of the above examples 1-3, the invention further illustrates that the invention provides a new method for synthesizing N-alkylphthalimide by using high-valence organosilicon as a radical precursor and N-alkenylphthalimide as a radical acceptor under the mild visible light irradiation condition without alkali and an additional reducing agent, and simultaneously solves the problems of low yield and more byproducts in the conventional preparation method.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, and such changes and modifications will fall within the scope of the present invention.
Claims (9)
1. A method for photocatalytic synthesis of N-alkylphthalimide, comprising the steps of:
s1: to a reaction tube with a stirrer was added N-alkenylphthalimide and a photosensitizer Ir [ dF (CF)3)ppy]2(dtbbpy)PF6Then adding a radical precursor silicon alkyl to the reaction tube;
s2: adding dimethyl sulfoxide into the reaction tube operated in the step S1, evacuating the reaction tube, exchanging nitrogen, placing the reaction tube under a 9W blue LED lamp for irradiation, stirring, diluting the reaction solution with ethyl acetate and water, and extracting with ethyl acetate;
s3: combining the organic phases obtained by the extraction in the step S2, drying the combined organic phases by using anhydrous sodium sulfate, filtering the combined organic phases again to obtain an organic phase solution, and removing the solvent by using a rotary evaporator; then the mixed solution of petroleum ether and ethyl acetate is used as eluent to carry out column chromatography separation, and finally the product N-alkyl phthalimide is obtained by distillation of a rotary evaporator.
2. The photocatalytic synthesis of N-alkylphthalimide according to claim 1 wherein: in the step S1, the N-alkenyl phthalimide is reacted with Ir [ dF (CF)3)ppy]2(dtbbpy)PF6In a molar ratio of 1: (0.01-0.03).
3. The photocatalytic synthesis of N-alkylphthalimide according to claim 1 wherein: in the step S1, the molar ratio of the N-alkenyl phthalimide to the radical precursor alkyl silicon is 1 (1.5-2.5).
4. The photocatalytic synthesis method of N-alkylphthalimide as claimed in claim 1 wherein: in the step S1, the alkyl silicon as the radical precursor is one of chloropropyl bis (catechol) silicate-18-crown ether-6-potassium alloy, cyclohexyl bis (catechol) silicate-18-crown ether-6-potassium alloy, and ethyl bis (catechol) silicate-18-crown ether-6-potassium alloy.
5. The photocatalytic synthesis method of N-alkylphthalimide as claimed in claim 1 wherein: in step S2, the stirring conditions are as follows: stirred at room temperature for 24 hours.
6. The photocatalytic synthesis of N-alkylphthalimide according to claim 1 wherein: in the step S1 and the step S2, the molar ratio of N-alkenyl phthalimide to dimethyl sulfoxide is 1: (400-450).
7. The photocatalytic synthesis of N-alkylphthalimide according to claim 1 wherein: in the step S3, the volume ratio of petroleum ether to ethyl acetate in the mixed solution of petroleum ether and ethyl acetate is 10: 1.
8. The photocatalytic synthesis method of N-alkylphthalimide as claimed in claim 1 wherein: in the step S3, the length of the silica gel column is 10cm in the column chromatography separation.
9. The photocatalytic synthesis process for an N-alkylphthalimide as claimed in any one of claims 1 to 8, wherein the reaction scheme of the process is as follows:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210429375.4A CN114671796B (en) | 2022-04-22 | 2022-04-22 | Method for synthesizing N-alkyl phthalimide by photocatalysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210429375.4A CN114671796B (en) | 2022-04-22 | 2022-04-22 | Method for synthesizing N-alkyl phthalimide by photocatalysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114671796A true CN114671796A (en) | 2022-06-28 |
| CN114671796B CN114671796B (en) | 2024-06-11 |
Family
ID=82080077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210429375.4A Active CN114671796B (en) | 2022-04-22 | 2022-04-22 | Method for synthesizing N-alkyl phthalimide by photocatalysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114671796B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257042A (en) * | 2005-03-18 | 2006-09-28 | Central Glass Co Ltd | Method for producing 2-fluoro-6-(trifluoromethyl)benzyl bromide and 2-fluoro-6-(trifluoromethyl)benzylamine |
| WO2007076655A1 (en) * | 2005-12-31 | 2007-07-12 | Sun Yat-Sen University | METHOD FOR SYNTHESIS OF CHOLEST-3β,5α,6β,19-TETRAHYDROXY-24-ONE AND ITS DERIVATIVES |
| WO2018103509A1 (en) * | 2016-12-05 | 2018-06-14 | 华南理工大学 | Synthesis method for cyclopropane phosphoramidate compound comprising continuous quaternary carbon center |
| CN108516992A (en) * | 2018-03-29 | 2018-09-11 | 宁波工程学院 | Photocatalytic synthesis at 1- aryl cyclopropyl phosphonate esters method |
| CN110041361A (en) * | 2019-05-07 | 2019-07-23 | 宁波工程学院 | Photocatalysis allylation/Cyclopropanated tandem reaction synthesis bis- substituted cyclopropane of 1,1- method |
| CN110041362A (en) * | 2019-05-07 | 2019-07-23 | 宁波工程学院 | Photocatalytic synthesis at 1- alkyl -1- phosphono cyclopropane method |
| CN111153920A (en) * | 2020-01-15 | 2020-05-15 | 宁波工程学院 | Method for synthesizing N-methyl imine diacyl boron substituted cyclopropane by photocatalytic reaction |
| CN112679435A (en) * | 2021-01-04 | 2021-04-20 | 南昌航空大学 | Alkylation/acylation method adopting photo-oxidation reduction/copper co-catalysis |
| CN112794821A (en) * | 2021-01-04 | 2021-05-14 | 南昌航空大学 | Free radical mediated decarboxylation C (sp) of diacyl peroxide and nitrogen-containing nucleophile3) -N cross-coupling reaction |
| WO2021232791A1 (en) * | 2020-05-22 | 2021-11-25 | 深圳市老年医学研究所 | Method for preparing efficient anti-tumor active polypeptide tubulysin m |
| CN114105738A (en) * | 2021-11-24 | 2022-03-01 | 宁波工程学院 | Method for photocatalytic synthesis of alkyl alkenyl ether |
-
2022
- 2022-04-22 CN CN202210429375.4A patent/CN114671796B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257042A (en) * | 2005-03-18 | 2006-09-28 | Central Glass Co Ltd | Method for producing 2-fluoro-6-(trifluoromethyl)benzyl bromide and 2-fluoro-6-(trifluoromethyl)benzylamine |
| WO2007076655A1 (en) * | 2005-12-31 | 2007-07-12 | Sun Yat-Sen University | METHOD FOR SYNTHESIS OF CHOLEST-3β,5α,6β,19-TETRAHYDROXY-24-ONE AND ITS DERIVATIVES |
| WO2018103509A1 (en) * | 2016-12-05 | 2018-06-14 | 华南理工大学 | Synthesis method for cyclopropane phosphoramidate compound comprising continuous quaternary carbon center |
| CN108516992A (en) * | 2018-03-29 | 2018-09-11 | 宁波工程学院 | Photocatalytic synthesis at 1- aryl cyclopropyl phosphonate esters method |
| CN110041361A (en) * | 2019-05-07 | 2019-07-23 | 宁波工程学院 | Photocatalysis allylation/Cyclopropanated tandem reaction synthesis bis- substituted cyclopropane of 1,1- method |
| CN110041362A (en) * | 2019-05-07 | 2019-07-23 | 宁波工程学院 | Photocatalytic synthesis at 1- alkyl -1- phosphono cyclopropane method |
| CN111153920A (en) * | 2020-01-15 | 2020-05-15 | 宁波工程学院 | Method for synthesizing N-methyl imine diacyl boron substituted cyclopropane by photocatalytic reaction |
| WO2021232791A1 (en) * | 2020-05-22 | 2021-11-25 | 深圳市老年医学研究所 | Method for preparing efficient anti-tumor active polypeptide tubulysin m |
| CN112679435A (en) * | 2021-01-04 | 2021-04-20 | 南昌航空大学 | Alkylation/acylation method adopting photo-oxidation reduction/copper co-catalysis |
| CN112794821A (en) * | 2021-01-04 | 2021-05-14 | 南昌航空大学 | Free radical mediated decarboxylation C (sp) of diacyl peroxide and nitrogen-containing nucleophile3) -N cross-coupling reaction |
| CN114105738A (en) * | 2021-11-24 | 2022-03-01 | 宁波工程学院 | Method for photocatalytic synthesis of alkyl alkenyl ether |
Non-Patent Citations (5)
| Title |
|---|
| CORCE, VINCENT，等: "Silicates as Latent Alkyl Radical Precursors: Visible-Light Photocatalytic Oxidation of Hypervalent Bis-Catecholato Silicon Compounds", ANGEWANDTE CHEMIE, vol. 54, no. 39, pages 1 - 3 * |
| 方文智，等: "烷基氯代物在光照下铜催化的三氟甲基化反应", 安徽化工, vol. 05, no. 03, pages 115 - 119 * |
| 王伟佳，等: "自由基类型的三氟甲硫基化反应的研究进展", 国际药学研究杂志, vol. 35, no. 11, pages 1 - 9 * |
| 粱波颖，等: "光诱导单电子转移反应合成硫杂、氮杂冠醚", 有机化学, vol. 11, no. 09, pages 1511 - 1517 * |
| 金英学，等: "氮-(ω-三丁基锡)烷基邻苯二甲酰亚胺的光诱导单电子转移环化反应", 黑龙江八一农垦大学学报, vol. 19, no. 03, 15 June 2007 (2007-06-15), pages 90 - 94 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114671796B (en) | 2024-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109879731B (en) | Diaryl methane halogenated olefin derivative and preparation method thereof | |
| CN109438317B (en) | Preparation method of nitrogen-alkyl (deuterated alkyl) aromatic heterocycle and alkyl (deuterated alkyl) aryl ether compound | |
| CN114671796B (en) | Method for synthesizing N-alkyl phthalimide by photocatalysis | |
| CN102675415B (en) | Method for preparing bortezomib | |
| JPH07316111A (en) | Production of n,n-disubstituted (meth)acrylamide derivative | |
| CN111454216A (en) | Process for the preparation of HMG-CoA reductase inhibitors and intermediates thereof | |
| CN113754544B (en) | Preparation method of polysubstituted (E) -trifluoromethyl olefin | |
| CN113045496B (en) | Method for selectively synthesizing dihydrophenanthridine or phenanthridine compounds | |
| CN112174893B (en) | Synthesis method and application of 2,4, 5-trimethyl-1H-imidazoline formate | |
| CN113248396A (en) | Preparation method of chlorobenzene para-aminated compound mediated by high-valence iodine reagent | |
| WO2009157386A1 (en) | Method for producing optically active amine compound | |
| CN112194548A (en) | Alpha-amino-gamma-butyrolactone compound and preparation method thereof | |
| CN114920652B (en) | Method for synthesizing 1-alkylstyrene derivative by photocatalysis | |
| CN109879829B (en) | Synthesis method of trans-4-hydroxy-5-amino-1, 2-oxazinane compounds | |
| CN112778352B (en) | Organosilicon compound and synthesis method thereof | |
| CN115368292B (en) | Benzondoles compound and synthesis method thereof | |
| CN112321398B (en) | Method for synthesizing alpha-fluorinated ketone by hydrazonating aliphatic chain monoketone | |
| JP3477631B2 (en) | Purification method of 1,3-bis (3-aminopropyl) -1,1,3,3-tetraorganodisiloxane | |
| CN115819207B (en) | Method for synthesizing 1, 1-disubstituted diene by nickel catalysis | |
| CN117486747B (en) | Synthesis method of N- (4-amino-2, 5-diethoxyphenyl) benzamide | |
| JP2005112820A (en) | Method for producing 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane | |
| CN114835646B (en) | Imidazole trifluoro methylthio reagent and synthesis application thereof | |
| CN103476763B (en) | 3,5-dioxo capronate is prepared with two steps | |
| CN114773229B (en) | 1,6 Diene compound and preparation method and application thereof | |
| CN113024464B (en) | Method for preparing [60] fullerene tetrahydroquinoline derivative based on triflic acid/p-toluenesulfonic acid catalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |