CN101792414B - Method for preparing 2-(3'-quinolyl) propenol - Google Patents
Method for preparing 2-(3'-quinolyl) propenol Download PDFInfo
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- CN101792414B CN101792414B CN2010101272151A CN201010127215A CN101792414B CN 101792414 B CN101792414 B CN 101792414B CN 2010101272151 A CN2010101272151 A CN 2010101272151A CN 201010127215 A CN201010127215 A CN 201010127215A CN 101792414 B CN101792414 B CN 101792414B
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- 0 O=C(CC[n+]1c[n](CCC(Nc2ccccc2)=O)cc1)*c1ccccc1 Chemical compound O=C(CC[n+]1c[n](CCC(Nc2ccccc2)=O)cc1)*c1ccccc1 0.000 description 1
- NZVFROAVTVGGTE-UHFFFAOYSA-N [O-][NH+](CCCl)Nc1ccccc1 Chemical compound [O-][NH+](CCCl)Nc1ccccc1 NZVFROAVTVGGTE-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a method for preparing 2-(3'- quinolyl) propenol and aims to provide a method for preparing the 2-(3'-quinolyl) propenol by using magnesium oxide solid alkali and independently designed and synthesized ionic liquid as a supported palladium catalyst and by using a Heck reaction, which comprises the following steps: adding 3-haloquinoline, 1,3-bis(N-phenylaminoformylethyl)imidazolium hexafluorophosphate ionic liquid, propenol, magnesium oxide, palladium diacetate and N-dimethylformamide into a three-neck flask in turn; stirring and heating the mixture; and after the reactions are finished, cooling the reaction solution, extracting the resulting product by methylbenzene, drying the extract by using anhydrous magnesium sulfate, concentrating the extract, and performing column chromatographic separation by using a mixed solvent of cyclohexane and acetone in a volume ratio of 1:1 as eluant to obtain the product of the 2-(3'-quinolyl) propenol compound. The method is easy to operate, less in waste water, gas and solid and convenient in post treatment, makes the reaction system reusable and avoids using organic phosphorous compounds. Thus, the method is an economic, practical, green and environmentally-friendly technique.
Description
Technical field
The present invention relates to the preparation method of a kind of 2-(3 '-quinolyl) vinyl carbinol; Especially utilize solid alkali Natural manganese dioxide and design synthetic 1 voluntarily; 3-two (N-phenylamino formyl radical ethyl) imidazoles hexafluorophosphate ionic liquid is as loaded palladium catalyst, adopts the method for Heck prepared in reaction 2-(3 '-quinolyl) vinyl carbinol.
Background technology
The quinoline medicine has important effect in pharmaceutical industries, and quinoline also is the important intermediate of many medicines, and the study on the synthesis of carrying out quinoline new drug and relative medicine midbody thereof is very important.2-(3 '-quinolyl) vinyl carbinol is the important intermediate of synthetic cardiovascular agent, and developing this compound has wide application prospect.
Heck reaction under the palladium catalysis is the important method that forms the C-C key, is having broad application prospects aspect many natural products of preparation and the pharmaceutical intermediate.Reaction has advantages of high catalytic activity to palladium catalytic system to Heck, still, and in this reaction system; Must use mineral alkali or organic amine as alkali, organic phosphine compound is prone to produce palladium black as the reaction part in reaction process; Be difficult to separate with reaction solution; Catalyst activity is reduced, and the mineral alkali that uses or organic amine be difficult to reclaim with organophosphorus ligand, and had a strong impact on the practical application that Heck reacts.
The more traditional fluent meterial of ionic liquid is compared, and ionic liquid has following advantage: 1. almost there is not vp, and not volatile, thus in use can not cause very big pollution to environment; 2. has bigger equilibrium temperature scope (100～200 ℃) and better chemical stability; 3. through its solvability of design adjustable of zwitterion, can construct functionalized ion liquid through the unitized design of certain zwitterion to inorganics, water, organism and polymkeric substance.In reaction process, ionic liquid both can be used as catalyzer, can be used as reaction medium again, also can be used for the function that catalyzed reaction has part and sorbent material, and ionic liquid was easy to recycle after reaction was accomplished.Therefore, develop the catalyzer that efficient recyclable regenerative uses, simplify reactions step, reduce disposal of pollutants,, become research direction from now on for suitability for industrialized production provides important green synthesis techniques.
Summary of the invention
The technical problem that the present invention will solve is: utilize solid alkali Natural manganese dioxide and design synthetic 1 voluntarily; 3-two (N-phenylamino formyl radical ethyl) imidazoles hexafluorophosphate ionic liquid is as loaded palladium catalyst; Adopt the method in Heck prepared in reaction 2-(3 '-quinolyl) vinyl carbinol, the green synthesis techniques an of Synthetic 2-(3 '-quinolyl) allyl alcohol compound is provided for suitability for industrialized production.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following:
A kind of 2-(3 '-quinolyl) is provided the preparation method of allyl alcohol compound, and step is following:
Will be suc as formula the 3-halogenated quinoline shown in (I), suc as formula 1 shown in (II); 3-two (N-phenylamino formyl radical ethyl) imidazoles hexafluorophosphate ionic liquid, vinyl carbinol, Natural manganese dioxide, palladium and N; Dinethylformamide adds in the there-necked flask successively, stirs, heats, and reaction finishes postcooling; Use extracted in toluene; Extraction liquid with anhydrous magnesium sulfate drying, concentrate, be 1: 1 hexanaphthene with volume ratio: acetone mixed solvent is as the eluent column chromatography for separation, obtains the allyl alcohol compound suc as formula the product 2-shown in (III) (3 '-quinolyl);
In the formula (I), X is Cl, Br or I.
The reaction formula of above-mentioned reaction is:
The temperature of reaction of said reaction is 10 ℃～150 ℃, and the reaction times is 1～30 hour;
Said 3-halogenated quinoline and 1,3-two (N-phenylamino formyl radical ethyl) the ion liquid mol ratio of imidazoles hexafluorophosphate is 1: 0.02～2;
The mol ratio of said 3-halogenated quinoline and vinyl carbinol is 1: 2～10;
Said 3-halogenated quinoline and magnesian mass ratio are 1: 2～10;
The mol ratio of said 3-halogenated quinoline and palladium is 1: 0.01～0.1;
Said 3-halogenated quinoline and N, the mass ratio of dinethylformamide are 1: 2～10.
Product is identified with nuclear magnetic resonance spectrum and mass spectrum.
As a kind of improvement, said temperature of reaction is 100 ℃～130 ℃.
As a kind of improvement, the said reaction times is 10～20 hours.
As a kind of improvement, the mol ratio of said 3-halogenated quinoline and vinyl carbinol is 1: 3～5.
As a kind of improvement, the mol ratio of said 3-halogenated quinoline and palladium is 1: 0.02～0.05.
As a kind of improvement, said 3-halogenated quinoline and 1,3-two (N-phenylamino formyl radical ethyl) the ion liquid mol ratio of imidazoles hexafluorophosphate is 1: 0.04～0.1.
As a kind of improvement, said 3-halogenated quinoline and magnesian mass ratio are 1: 3～5.
As a kind of improvement, said 3-halogenated quinoline and N, the mass ratio of dinethylformamide are 1: 3～5.
As a kind of improvement, the compound method of said 2-(3 '-quinolyl) allyl alcohol compound is carried out as follows: will be suc as formula 3-halogenated quinoline 1 mmole shown in (I), suc as formula 1 shown in (II); 3-two (N-phenylamino formyl radical ethyl) imidazoles hexafluorophosphate ionic liquid 0.08 mmole, vinyl carbinol 2.5 mmoles, Natural manganese dioxide are 3～5 times of 3-halogenated quinoline quality; Palladium 0.04 mmole; N, dinethylformamide are 3～5 times of 3-halogenated quinoline quality, place 50 milliliters of there-necked flasks; Stirring heating, anti-15 hours at 110 ℃.After reaction finished, cooling extracted with toluene 3 * 10mL; Extraction liquid is used anhydrous magnesium sulfate drying; Concentrating, is 1: 1 hexanaphthene with volume ratio: acetone mixed solvent is as the eluent column chromatography for separation, obtains the allyl alcohol compound suc as formula the product 2-shown in (III) (3 '-quinolyl).Product is identified with nuclear magnetic resonance spectrum and mass spectrum.
Among the present invention, said 1,3-two (N-phenylamino formyl radical ethyl) the ion liquid building-up reactions formula of imidazoles hexafluorophosphate is:
Its synthetic step is following:
0.2mol N-phenyl-3-chlorine propionic acid amide is dissolved in the acetonitrile of 30mL, adds the Methylimidazole of 0.1mol again, behind the reflux 24h; Acetonitrile is removed in distillation, gets white solid behind the ethyl alcohol recrystallization, adds in the beaker of 500mL; Add the KPF6 of 0.22mol and the water of 200mL again, stirring reaction 24h under the room temperature crosses and filters white solid; Get 1 behind the ethyl alcohol recrystallization, 3-two (N-phenylamino formyl radical ethyl) imidazoles hexafluorophosphate, yield 47.2%.
Beneficial effect of the present invention is embodied in:
Compared with prior art, it is should technology easy to operate, the three wastes are few, convenient post-treatment, reaction system are reusable, has avoided the use organo phosphorous compounds, is economical and practical green environmental protection technique.
Embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this.
Embodiment 1
1,3-two (N-phenylamino formyl radical ethyl) the ion liquid preparation of imidazoles hexafluorophosphate
N-phenyl-3-chlorine propionic acid amide (0.2mol) is dissolved in the acetonitrile of 30mL, adds the Methylimidazole of 0.1mol again, behind the reflux 24h, acetonitrile is removed in distillation, gets white solid behind the ethyl alcohol recrystallization, adds in the beaker of 500mL, adds the KPF of 0.22mol again
6With the water of 200mL, stirring reaction 24h under the room temperature crosses and to filter white solid, behind the ethyl alcohol recrystallization 1,3-two (N-phenylamino formyl radical ethyl) imidazoles hexafluorophosphate ionic liquid, yield 47.2%, m.p.171～173 ℃.
1H?NMR(400MHz，DMSO-d
6)δ：10.08(s，2H)，9.21(s，1H)，7.76(s，2H)，7.53(d，4H，J＝7.6Hz)，7.27(t，4H，J＝7.6Hz)，7.04(t，2H，J＝7.20Hz)，4.46(t，4H，J＝6.4Hz)，2.95(t，4H，J＝6.0Hz)；IR(KBr)v：3418，3147，1692，1599，1533，1444，1165，845，750，558cm
-1.
Embodiment 2
Prepare 2-(3 '-quinolyl) vinyl carbinol by the 3-bromoquinoline
With 208 milligrams of 3-bromoquinolines (1 mmole), 290 milligrams of vinyl carbinols (5 mmole), 9 milligrams of palladium (0.04 mmole); 1,3-two (N-phenylamino formyl radical ethyl) 41 milligrams of imidazoles hexafluorophosphate ionic liquids (0.08 mmole), 1040 milligrams in Natural manganese dioxide; N, 830 milligrams of dinethylformamides place 50 milliliters of there-necked flasks; Stirring heating was 110 ℃ of reactions 15 hours.After reaction finished, cooling extracted with toluene 3 * 10mL; Extraction liquid is used anhydrous magnesium sulfate drying, concentrates, and with the column chromatography hexanaphthene: the mixed solvent of acetone (volume ratio)=1: 1 is as eluent; Separate and to obtain 148 milligrams of product 2-(3 '-quinolyl) vinyl carbinols, yield 80%.
1H?NMR(CDCl
3)δppm：1.98(w，1H)，4.67(t，J＝0.64，0.58Hz，2H)，5.56(d，J＝0.58Hz，1H)，5.68(d，J＝0.51Hz，1H)，7.55(m，1H)，7.68(m，1H)，7.81(m，1H)，8.09(m，1H)，8.19(m，1H)，9.01(m，1H)；
13C?NMR(CDCl
3)δppm：65.20，115.31，127.40，128.08，128.48，129.34，129.93，131.64，132.93，144.83，147.74，149.41。
MS(m/z)：185(M
+)。
Embodiment 3
Prepare 2-(3 '-quinolyl) vinyl carbinol by the 3-SN-7618
With 164 milligrams of 3-SN-7618s (1 mmole), 232 milligrams of vinyl carbinols (4 mmole), 11 milligrams of palladium (0.05 mmole); 1,3-two (N-phenylamino formyl radical ethyl) 51 milligrams of imidazoles hexafluorophosphate ionic liquids (0.1 mmole), 1640 milligrams in Natural manganese dioxide; N, 820 milligrams of dinethylformamides place 50 milliliters of there-necked flasks; Stirring heating was 130 ℃ of reactions 10 hours.After reaction finished, cooling extracted with toluene 3 * 10mL; Extraction liquid is used anhydrous magnesium sulfate drying, concentrates, and with the column chromatography hexanaphthene: the mixed solvent of acetone (volume ratio)=1: 1 is as eluent; Separate and to obtain 148 milligrams of product 2-(3 '-quinolyl) vinyl carbinols, yield 69%.
Embodiment 4
Prepare 2-(3 '-quinolyl) vinyl carbinol by the 3-iodine quinoline
With 255 milligrams of 3-iodine quinolines (1 mmole), 175 milligrams of vinyl carbinols (3 mmole), 2 milligrams of palladium (0.01 mmole); 1,3-two (N-phenylamino formyl radical ethyl) 21 milligrams of imidazoles hexafluorophosphate ionic liquids (0.04 mmole), 1020 milligrams in Natural manganese dioxide; N, 2550 milligrams of dinethylformamides place 50 milliliters of there-necked flasks; Stirring heating was 100 ℃ of reactions 20 hours.After reaction finishes, cooling, with toluene 3 * 10mL extraction, extraction liquid use anhydrous magnesium sulfate drying, and is concentrated, and with the column chromatography hexanaphthene: the mixed solvent of acetone (volume ratio)=1: 1 is as eluent, and separation obtaining product
151 milligrams of 2-(3 '-quinolyl) vinyl carbinols, yield 82%.
Embodiment 5
With 255 milligrams of 3-iodine quinolines (1 mmole), 116 milligrams of vinyl carbinols (2 mmole), 5 milligrams of palladium (0.02 mmole); 1,3-two (N-phenylamino formyl radical ethyl) 11 milligrams of imidazoles hexafluorophosphate ionic liquids (0.02 mmole), 765 milligrams in Natural manganese dioxide; N, 510 milligrams of dinethylformamides place 50 milliliters of there-necked flasks; Stirring heating was 10 ℃ of reactions 30 hours.After reaction finished, cooling extracted with toluene 3 * 10mL; Extraction liquid is used anhydrous magnesium sulfate drying, concentrates, and with the column chromatography hexanaphthene: the mixed solvent of acetone (volume ratio)=1: 1 is as eluent; Separate and to obtain 116 milligrams of product 2-(3 '-quinolyl) vinyl carbinols, yield 63%.
Embodiment 6
With 255 milligrams of 3-iodine quinolines (1 mmole), 580 milligrams of vinyl carbinols (10 mmole), 22 milligrams of palladium (0.1 mmole); 1,3-two (N-phenylamino formyl radical ethyl) 1020 milligrams of imidazoles hexafluorophosphate ionic liquids (2 mmole), 510 milligrams in Natural manganese dioxide; N, 765 milligrams of dinethylformamides place 50 milliliters of there-necked flasks; Stirring heating was 150 ℃ of reactions 1 hour.After reaction finished, cooling extracted with toluene 3 * 10mL; Extraction liquid is used anhydrous magnesium sulfate drying, concentrates, and with the column chromatography hexanaphthene: the mixed solvent of acetone (volume ratio)=1: 1 is as eluent; Separate and to obtain 112 milligrams of product 2-(3 '-quinolyl) vinyl carbinols, yield 61%.
Embodiment 7
With 255 milligrams of 3-iodine quinolines (1 mmole), 175 milligrams of vinyl carbinols (3 mmole), 9 milligrams of palladium (0.04 mmole); 1,3-two (N-phenylamino formyl radical ethyl) 51 milligrams of imidazoles hexafluorophosphate ionic liquids (0.1 mmole), 2500 milligrams in Natural manganese dioxide; N, 2500 milligrams of dinethylformamides place 50 milliliters of there-necked flasks; Stirring heating was 120 ℃ of reactions 20 hours.After reaction finished, cooling extracted with toluene 3 * 10mL; Extraction liquid is used anhydrous magnesium sulfate drying, concentrates, and with the column chromatography hexanaphthene: the mixed solvent of acetone (volume ratio)=1: 1 is as eluent; Separate and to obtain 151 milligrams of product 2-(3 '-quinolyl) vinyl carbinols, yield 82%.
At last, it is also to be noted that what more than enumerate only is specific embodiment of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (10)
1. the preparation method of a 2-(3 '-quinolyl) allyl alcohol compound, step is following:
Will be suc as formula the 3-halogenated quinoline shown in (I), suc as formula 1 shown in (II); 3-two (N-phenylamino formyl radical ethyl) imidazoles hexafluorophosphate ionic liquid, vinyl carbinol, Natural manganese dioxide, palladium and N; Dinethylformamide adds in the there-necked flask successively, stirs, heats, and reaction finishes postcooling; Use extracted in toluene; Extraction liquid with anhydrous magnesium sulfate drying, concentrate, be 1: 1 hexanaphthene with volume ratio: acetone mixed solvent is as the eluent column chromatography for separation, obtains the allyl alcohol compound suc as formula the product 2-shown in (III) (3 '-quinolyl);
In the formula (I), X is Cl, Br or I;
The reaction formula of above-mentioned reaction is:
The temperature of reaction of said reaction is 10 ℃～150 ℃, and the reaction times is 1～30 hour;
Said 3-halogenated quinoline and 1,3-two (N-phenylamino formyl radical ethyl) the ion liquid mol ratio of imidazoles hexafluorophosphate is 1: 0.02～2;
The mol ratio of said 3-halogenated quinoline and vinyl carbinol is 1: 2～10;
Said 3-halogenated quinoline and magnesian mass ratio are 1: 2～10;
The mol ratio of said 3-halogenated quinoline and palladium is 1: 0.01～0.1;
Said 3-halogenated quinoline and N, the mass ratio of dinethylformamide are 1: 2～10.
2. the preparation method of 2-according to claim 1 (3 '-quinolyl) allyl alcohol compound is characterized in that, and is said 1, and 3-two (N-phenylamino formyl radical ethyl) the ion liquid building-up reactions formula of imidazoles hexafluorophosphate is:
Its synthetic step is following:
0.2mol N-phenyl-3-chlorine propionic acid amide is dissolved in the acetonitrile of 30mL, adds the imidazoles of 0.1mol again, behind the reflux 24h, acetonitrile is removed in distillation, gets white solid behind the ethyl alcohol recrystallization, adds in the beaker of 500mL, adds the KPF of 0.22mol again
6With the water of 200mL, stirring reaction 24h under the room temperature crosses and filters white solid, gets 1 behind the ethyl alcohol recrystallization, 3-two (N-phenylamino formyl radical ethyl) imidazoles hexafluorophosphate, yield 47.2%.
3. the preparation method of 2-according to claim 1 (3 '-quinolyl) allyl alcohol compound is characterized in that said temperature of reaction is 100 ℃～130 ℃.
4. the preparation method of 2-according to claim 1 (3 '-quinolyl) allyl alcohol compound is characterized in that the said reaction times is 10～20 hours.
5. the preparation method of 2-according to claim 1 (3 '-quinolyl) allyl alcohol compound is characterized in that the mol ratio of said 3-halogenated quinoline and vinyl carbinol is 1: 3～5.
6. the preparation method of 2-according to claim 1 (3 '-quinolyl) allyl alcohol compound is characterized in that the mol ratio of said 3-halogenated quinoline and palladium is 1: 0.02～0.05.
7. the preparation method of 2-according to claim 1 (3 '-quinolyl) allyl alcohol compound is characterized in that, said 3-halogenated quinoline and 1, and 3-two (N-phenylamino formyl radical ethyl) the ion liquid mol ratio of imidazoles hexafluorophosphate is 1: 0.04～0.1.
8. the preparation method of 2-according to claim 1 (3 '-quinolyl) allyl alcohol compound is characterized in that said 3-halogenated quinoline and magnesian mass ratio are 1: 3～5.
9. the preparation method of 2-according to claim 1 (3 '-quinolyl) allyl alcohol compound is characterized in that said 3-halogenated quinoline and N, the mass ratio of dinethylformamide are 1: 3～5.
10. the preparation method of 2-according to claim 1 (3 '-quinolyl) allyl alcohol compound is characterized in that, the compound method of said 2-(3 '-quinolyl) allyl alcohol compound is carried out as follows:
Will be suc as formula 3-halogenated quinoline 1 mmole shown in (I), suc as formula 1 shown in (II), 3-two (N-phenylamino formyl radical ethyl) imidazoles hexafluorophosphate ionic liquid 0.08 mmole; Vinyl carbinol 2.5 mmoles, Natural manganese dioxide are 3～5 times of 3-halogenated quinoline quality, palladium 0.04 mmole; N, dinethylformamide are 3～5 times of 3-halogenated quinoline quality, place 50 milliliters of there-necked flasks; Stirring heating was 110 ℃ of reactions 15 hours; After reaction finished, cooling extracted with toluene 3 * 10mL; Extraction liquid is used anhydrous magnesium sulfate drying; Concentrating, is 1: 1 hexanaphthene with volume ratio: acetone mixed solvent is as the eluent column chromatography for separation, obtains the allyl alcohol compound suc as formula the product 2-shown in (III) (3 '-quinolyl).
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