CN109020865A - 3,3- bis- replaces Oxoindole and preparation method thereof - Google Patents
3,3- bis- replaces Oxoindole and preparation method thereof Download PDFInfo
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- CN109020865A CN109020865A CN201811064128.9A CN201811064128A CN109020865A CN 109020865 A CN109020865 A CN 109020865A CN 201811064128 A CN201811064128 A CN 201811064128A CN 109020865 A CN109020865 A CN 109020865A
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- 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
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
- C07D209/32—Oxygen atoms
- C07D209/34—Oxygen atoms in position 2
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
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- 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
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
- C07D209/32—Oxygen atoms
- C07D209/38—Oxygen atoms in positions 2 and 3, e.g. isatin
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Abstract
The invention discloses 3,3- bis- to replace Oxoindole and preparation method thereof, and reaction includes the following steps, is reducing agent using alkenyl active methylene compound as substrate, metal hydride, palladium compound is catalyst, and reduction reaction obtains reduzate；It is reacted with reduzate with electrophilic reagent, obtains 3,3- bis- and replace Oxoindole.Reduction system of the invention is the simple and easy method for restoring alkenyl active methylene compound, hydride and palladium compound catalyst used is all the reagent being easy to get in laboratory, compared to common hydrogen method for hydrogenation and reducing agent restoring method, the method is easier to operate, safety is higher, mild condition, and reaction yield is high, and can have very high Atom economy and step economy with one pot of two-step reaction.
Description
Technical field
The invention belongs to technical field of organic synthesis, are related to metal hydride/palladium compound system in the active methylene of alkenyl
Application in based compound reduction and one pot reaction, and in particular to 3,3- bis- replace Oxoindole and preparation method thereof.
Background technique
Sodium hydride is a kind of laboratory and the highly basic being industrially commonly used, for a long time, few as reducing agent quilt
The relevant report used, and existing reaction needs large excess of reducing agent (3 equivalent), while needing the iodine of at least 2 equivalents
Change sodium as promotor.The reduction reaction of alkenyl active methylene compound is usually to be restored using hydrogen/palladium carbon condition；
In addition, some negative reagents of hydrogen, such as [(Ph3P)CuH]6 (Stryker reagent), R3SiH, Hantzsch ester etc. can also be completed
The reduction of this electron deficient double bond.But these reducing conditions or the hydrogen with certain risk, such as explosive；
Reagent is more expensive, reaction lack Atom economy and needs to handle more waste, such as [(Ph after reacting3P)
CuH]6 (Stryker reagent), R3Need to handle a large amount of waste water after SiH, Hantzsch ester etc. or some reactions, so
Also there is certain limitation in industrial application.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of applications of metal hydride/palladium compound system, to mention
The method that 3,3- bis- replaces Oxoindole is prepared for a kind of reduction of alkenyl active methylene compound.
The present invention realizes that the technological means of above-mentioned reduction alkenyl active methylene compound is with metal hydride
For reducing agent, palladium and its esters are catalyst, and reaction obtains the sodium salt product of double bond reduction in a solvent, then anti-with electrophilic reagent
It answers, obtains disubstituted product.Specific technical solution is as follows:
Metal hydride/palladium compound system is preparing the application in the substitution Oxoindole of 3,3- bis-.
3,3- bis- replace the preparation method of Oxoindole, using alkenyl active methylene compound as substrate, metal hydride
It is catalyst for reducing agent, palladium compound, reduction reaction obtains reduzate；It is reacted, is obtained with electrophilic reagent with reduzate
3,3- bis- replaces Oxoindole.
In above-mentioned technical proposal, reduzate and electrophilic reagent after reaction, are added saturated aqueous ammonium chloride and stop
Reaction, then process is extracted, is spin-dried for, column chromatographic purifying obtains reduzate.
In the present invention, the chemical structural formula of alkenyl active methylene compound is as follows:
Wherein, R1、R2It is independent to be selected from hydrogen, alkyl, phenyl, substituted-phenyl, naphthalene, pyridyl group, quinolyl.
In the chemical structural formula of alkenyl active methylene compound, alkyl can be methyl, and substituted-phenyl can be halogen
Substituted-phenyl, methoxy substitution phenyl.
In the present invention, the metal hydride includes sodium hydride, lithium hydride, hydrofining, calcium hydride, preferably sodium hydride, hydrogen
Change lithium, more preferable sodium hydride；The palladium compound includes for palladium chloride, palladium acetate, Pd (MeCN)2Cl2、[(η3-C3H5)PdCl
]2、Pd(TFA)2、Pd(dppp)Cl2、Pd2(dba)3、Pd(C6H5CN)2Cl2、Pd(OH)2、Pd/C、Pd(PPh3)4、Pd(PPh3)2Cl2, preferably palladium chloride, palladium acetate, more preferable palladium chloride.
In the present invention, the electrophilic reagent is cylite, iodomethane, methyl acrylate or hydrogen peroxide.
In the present invention, the palladium compound, metal hydride, alkenyl active methylene compound molar ratio be (0.01
~1): (1~5): 1, preferably (0.03~0.1): (1~3): 1, more preferably 0.05: (1.5~2.5): 1, it is optimal
It is selected as 0.05: 2: 1.
In the present invention, reaction carries out in a nitrogen atmosphere, in solvent；The solvent includes DMA (N, N- dimethylacetamide
Amine), DMF, THF, DME or dioxane.
In the present invention, the temperature of reduction reaction is -50 DEG C~120 DEG C, preferably 0~50 DEG C, more preferable room temperature；Reduction reaction
Time be 0.3~10 hour, preferably 0.4~5 hour, more preferable 0.5 hour.The ring that reduzate is reacted with electrophilic reagent
Border, temperature are consistent with reduction reaction.
Sodium hydride of the present invention/palladium reduction alkenyl active methylene compound has following advantage: 1) compared to hydroboration
Sodium, sodium hydride price are more cheap (industrial sodium borohydride is prepared by raw material of sodium hydride)；Also compared to hydrogen/palladium carbon
The safety of original, sodium hydride method is higher；2) sodium hydride molecular weight is small and composition is simple, and usage amount is few in reaction, so with
Sodium hydride is a kind of method of atom economy as reducing agent；By-product is generated in addition to harmless sodium salt without other wastes；3)
It is sodium salt, this point and existing reduction side before post-processing that alkenyl active methylene compound, which is hydrogenated the product after sodium reduction,
Method is all different, and the sodium salt with reactivity can continue to react with electrophilic reagent, obtains disubstituted product, has expanded alkene
The application of base active methylene compound.And in this one pot reaction, the reproducibility and alkalinity of sodium hydride are all fully utilized,
The Atom economy and step economy for substantially increasing reaction, reduce reaction cost.
Technical solution of the present invention specifically can be as described below: under nitrogen protection, palladium compound and metal hydride being hanged
Float in solvent and stir, substrate alkenyl active methylene compound is then added, it is small that 0.3~10 is reacted at -50 DEG C to 120 DEG C
When；Electrophilic reagent is added, the reaction was continued until raw material fully reacting, saturated aqueous ammonium chloride stopped reaction is then added,
It with solvent extraction, is evaporated, column chromatographic purifying obtains product.
The reduction of alkenyl active methylene compound is the chemical reaction being commonly used in organic synthesis, generally uses two classes
Method: one kind is to carry out hydro-reduction using hydrogen/palladium carbon, and in this process, the use of hydrogen is one potential dangerous
Factor, misoperation will cause kindling, explosion；Another kind of restored using reducing agent, and price is higher and needs to handle
A large amount of waste water.The present invention replaces hydrogen and reducing agent to be used for alkenyl using relatively safe and cheap metal hydride
The reduction of active methylene compound has great importance；And importantly, the method has given full play to sodium hydride
Reproducibility and alkalinity can carry out one pot reaction.
Reduction system of the invention is the simple and easy method for restoring alkenyl active methylene compound, hydride and palladium used
Compound catalyst is all the reagent being easy to get in laboratory, compared to common hydrogen method for hydrogenation and reducing agent reduction side
Method, the method is easier to operate, and safety is higher, mild condition, and reaction yield is high, and can have very with one pot of two-step reaction
High Atom economy and step economy.
Specific embodiment
Embodiment 1
Under nitrogen protection, palladium chloride (1.7 mg, 0.01 mmol, 5 mol%) and sodium hydride (60% in oil, 16 mg,
0.4 mmol, 2 equiv) it is suspended in DMA (1.0 mL), it is stirred at room temperature 5 minutes, compound 1a (0.2 mmol) is added and exists
The solution of DMA (0.5 mL) after raw material fully reacting, is added cylite (1.5eq.) then in room temperature reaction 30 minutes, after
It is continuous to be stirred to react.After raw material has reacted, add saturated aqueous ammonium chloride quenching reaction, be extracted with ethyl acetate, collects organic
Phase is spin-dried for solvent and obtains crude product, and column chromatography finally obtains compound 3a, yield 98%.1H NMR (400 MHz, CDCl3):
δ 7.38-7.27 (m, 4H), 7.13-7.04 (m, 7H), 7.02-6.94 (m, 5H), 6.64 (d, J = 7.3
Hz, 2H), 6.21 (d, J = 7.7 Hz, 1H), 3.47 (d, J = 12.9 Hz, 2H), 3.25 (d, J =
12.9 Hz, 2H). 13C NMR (151 MHz, CDCl3): δ 177.80, 144.12, 136.08, 134.37,
130.26, 130.14, 129.49, 128.06, 127.85, 127.76, 126.81, 126.65, 124.42,
122.23, 108.88, 56.67, 43.83. LR-MS (ESI): m/z 390.3 [M+H]+。
Embodiment 2
Under nitrogen protection, palladium chloride (1.7 mg, 0.01 mmol, 5 mol%) and sodium hydride (60% in oil, 16 mg,
0.4 mmol, 2 equiv) it is suspended in DMA (1.0 mL), it is stirred at room temperature 5 minutes, compound 1a (0.2 mmol) is added and exists
The solution of DMA (0.5 mL) after raw material fully reacting, is added iodomethane (2.5eq.) then in room temperature reaction 30 minutes, after
It is continuous to be stirred to react.After raw material has reacted, add saturated aqueous ammonium chloride quenching reaction, be extracted with ethyl acetate, collects organic
Phase is spin-dried for solvent and obtains crude product, and column chromatography finally obtains compound 3b, yield 98%.1H NMR (400 MHz,
Chloroform-d): δ 7.41 (t, J = 7.5 Hz, 2H), 7.37-7.28 (m, 2H), 7.15-7.02 (m,
5H), 6.94 (d, J = 7.6 Hz, 2H), 6.86 (d, J = 7.1 Hz, 2H), 6.55-6.45 (m, 1H),
3.27 (d, J = 12.8 Hz, 1H), 3.09 (d, J = 12.8 Hz, 1H), 1.63 (s, 3H). 13C NMR
(151 MHz, CDCl3): δ 179.27, 143.52, 136.20, 134.51, 132.95, 129.99, 129.56,
128.04, 127.85, 127.73, 126.77, 126.70, 123.47, 122.70, 109.15, 50.41, 45.56,
23.10. LR-MS (ESI): m/z 314.2 [M+H]+。
Embodiment 3
Under nitrogen protection, palladium chloride (1.7 mg, 0.01 mmol, 5 mol%) and sodium hydride (60% in oil, 16 mg,
0.4 mmol, 2 equiv) it is suspended in DMA (1.0 mL), it is stirred at room temperature 5 minutes, compound 1a (0.2 mmol) is added and exists
The solution of DMA (0.5 mL) after raw material fully reacting, is added methyl acrylate (6 eq.) then in room temperature reaction 30 minutes,
Continue to be stirred to react.After raw material has reacted, adds saturated aqueous ammonium chloride quenching reaction, be extracted with ethyl acetate, collection has
Machine phase is spin-dried for solvent and obtains crude product, and column chromatography finally obtains compound 3c, yield 97%.1H NMR (400 MHz,
CDCl3): δ 7.45-7.28 (m, 4H), 7.15-7.01 (m, 5H), 6.91 (d, J = 7.4 Hz, 2H),
6.84 (d, J = 7.1 Hz, 2H), 6.51-6.42 (m, 1H), 3.56 (s, 3H), 3.29 (d, J = 12.8
Hz, 1H), 3.11 (d, J = 12.7 Hz, 1H), 2.59-2.48 (m, 1H), 2.45-2.34 (m, 1H),
2.32-2.20 (m, 1H), 2.11-1.98 (m, 1H).13C NMR (151 MHz, CDCl3): δ 177.80,
173.27, 144.23, 135.51, 134.29, 130.04, 129.84, 129.60, 128.26, 128.19,
127.72, 126.76, 126.74, 123.83, 122.86, 109.24, 54.40, 51.77, 44.92, 32.04,
29.73. LR-MS (ESI): m/z 386.2 [M+H]+。
Embodiment 4
Under nitrogen protection, palladium chloride (1.7 mg, 0.01 mmol, 5 mol%) and sodium hydride (60% in oil, 16 mg,
0.4 mmol, 2 equiv) it is suspended in DMA (1.0 mL), it is stirred at room temperature 5 minutes, compound 1a (0.2 mmol) is added and exists
The solution of DMA (0.5 mL) after raw material fully reacting, is added hydrogen peroxide (3 eq.), continues then in room temperature reaction 30 minutes
It is stirred to react.After raw material has reacted, add saturated aqueous ammonium chloride quenching reaction, be extracted with ethyl acetate, collects organic phase,
It is spin-dried for solvent and obtains crude product, column chromatography finally obtains compound 3d, yield 93%.1H NMR (400 MHz, CDCl3): δ
7.46-7.38 (m, 3H), 7.38-7.32 (m, 1H), 7.21-7.08 (m, 5H), 6.97 (d, J = 7.5 Hz,
2H), 6.92 (d, J = 7.2 Hz, 2H), 6.51 (d, J = 7.5 Hz, 1H), 3.45 (br, 1H), 3.37
(q, J = 12.5 Hz, 2H). 13C NMR (151 MHz, CDCl3): δ 177.21, 143.56, 133.92,
133.82, 130.35, 129.73, 129.68, 129.04, 128.36, 127.99, 127.09, 126.55,
124.61, 123.46, 109.55, 78.09, 45.99. LR-MS (ESI): m/z 316.1 [M+H]+。
Claims (10)
1. metal hydride/palladium compound system is preparing the application in the substitution Oxoindole of 3,3- bis-.
2. application according to claim 1, which is characterized in that the metal hydride includes sodium hydride, lithium hydride, hydrogenation
Potassium, calcium hydride；The palladium compound includes for palladium chloride, palladium acetate, Pd (MeCN)2Cl2、[(η3-C3H5)PdCl]2、Pd
(TFA)2、Pd(dppp)Cl2、Pd2(dba)3、Pd(C6H5CN)2Cl2、Pd(OH)2、Pd/C、Pd(PPh3)4、Pd(PPh3)2Cl2。
3. application according to claim 1, which is characterized in that active with alkenyl when preparation 3,3- bis- replaces Oxoindole
Methylene compound, electrophilic reagent are raw material；The chemical structural formula of the alkenyl active methylene compound is as follows:
Wherein, R1、R2It is independent to be selected from hydrogen, alkyl, phenyl, substituted-phenyl, naphthalene, pyridyl group, quinolyl；The electrophilic reagent
For cylite, iodomethane, methyl acrylate or hydrogen peroxide.
4. application according to claim 1, which is characterized in that the active methylene of the palladium compound, metal hydride, alkenyl
The molar ratio of based compound is (0.01~1): (1~5): 1.
5.3,3- bis- replace the preparation method of Oxoindole, are by substrate, metal hydride of alkenyl active methylene compound
Reducing agent, palladium compound are catalyst, and reduction reaction obtains reduzate；It is reacted with reduzate with electrophilic reagent, obtains 3,
3- bis- replaces Oxoindole.
6. according to the method described in claim 5, it is characterized in that, reduzate and electrophilic reagent after reaction, are added and satisfy
With aqueous ammonium chloride solution stopped reaction, then process is extracted, is spin-dried for, column chromatographic purifying obtains reduzate.
7. according to the method described in claim 5, it is characterized in that, the chemical structural formula of alkenyl active methylene compound such as
Under:
Wherein, R1、R2It is independent to be selected from hydrogen, alkyl, phenyl, substituted-phenyl, naphthalene, pyridyl group, quinolyl；
The metal hydride includes sodium hydride, lithium hydride, hydrofining, calcium hydride；
The palladium compound includes for palladium chloride, palladium acetate, Pd (MeCN)2Cl2、[(η3-C3H5)PdCl]2、Pd(TFA)2、Pd
(dppp)Cl2、Pd2(dba)3、Pd(C6H5CN)2Cl2、Pd(OH)2、Pd/C、Pd(PPh3)4、Pd(PPh3)2Cl2；The electrophilic examination
Agent is cylite, iodomethane, methyl acrylate or hydrogen peroxide.
8. according to the method described in claim 5, it is characterized in that, the active methylene of the palladium compound, metal hydride, alkenyl
The molar ratio of based compound is (0.01~1): (1~5): 1.
9. according to the method described in claim 5, it is characterized in that, reduction reaction carries out in a nitrogen atmosphere, in solvent；Reduction
The temperature of reaction is -50 DEG C~120 DEG C, and the time is 0.3~10 hour.
10. the 3,3- bis- of preparation replaces Oxoindole according to the method for claim 5.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020051853A1 (en) * | 2018-09-13 | 2020-03-19 | 南通纺织丝绸产业技术研究院 | 3,3-disubstituted oxindole and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012241A (en) * | 2013-01-23 | 2013-04-03 | 中国科学院上海有机化学研究所 | Polysubstitution indole, synthesis method for same and synthesis application of polysubstitution indole to indomethacin |
| CN108218672A (en) * | 2018-01-30 | 2018-06-29 | 苏州大学 | Application of the metal compound/palladium compound catalytic reduction system in de- allyl reaction and deuterated reaction |
| CN108358760A (en) * | 2018-01-30 | 2018-08-03 | 苏州大学 | Application of the metal compound/palladium compound catalytic reduction system in debenzylation and deuterated reaction |
-
2018
- 2018-09-12 CN CN201811064128.9A patent/CN109020865B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012241A (en) * | 2013-01-23 | 2013-04-03 | 中国科学院上海有机化学研究所 | Polysubstitution indole, synthesis method for same and synthesis application of polysubstitution indole to indomethacin |
| CN108218672A (en) * | 2018-01-30 | 2018-06-29 | 苏州大学 | Application of the metal compound/palladium compound catalytic reduction system in de- allyl reaction and deuterated reaction |
| CN108358760A (en) * | 2018-01-30 | 2018-08-03 | 苏州大学 | Application of the metal compound/palladium compound catalytic reduction system in debenzylation and deuterated reaction |
Non-Patent Citations (3)
| Title |
|---|
| BING ZHOU，等: "Copper(I)-Catalyzed Aryl or Vinyl Addition to Electron-Deficient Alkenes Cascaded by Cationic Cyclization", 《ORG. LETT.》 * |
| QIANG WU，等: "Preparation of pyridyltriazole ruthenium complexes as effective catalysts for the selective alkylation and one-pot C–H hydroxylation of 2-oxindole with alcohols and mechanism exploration", 《ORGANIC CHEMISTRY FRONTIERS》 * |
| STN-REGISTRY: "RN:1026538-68-0", 《STN-REGISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020051853A1 (en) * | 2018-09-13 | 2020-03-19 | 南通纺织丝绸产业技术研究院 | 3,3-disubstituted oxindole and preparation method thereof |
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