CN102336750A - Method for preparing Chiral pyridinebis(oxazoline) ligand - Google Patents
Method for preparing Chiral pyridinebis(oxazoline) ligand Download PDFInfo
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Abstract
The invention discloses a method for preparing Chiral pyridinebis(oxazoline) ligand, which belongs to the technical field of chemical synthesis. The method comprises the following steps of: using 2, 6-pyridine-dimethyl phthalate as a raw material in an organic solvent, reacting at a temperature of 110-120 DEG C for 16-24 hours under the action of chiral alkamine, lowering pressure, evaporating to remove the solvent, and separating by column chromatography to obtain bisamide; and combining rings to obtain a final product. The invention has the advantages of single synthesized product, high total yield (higher than 92%), high purity (higher than 99%), easy raw material acquisition, low cost, easiness for storage, simple reaction steps, high efficiency, low emission of pollutants and environment friendliness.
Description
Technical field
The invention belongs to chemosynthesis technical field, relate to a kind of preparation method of chirality pyridine double-oxazoline part, relate in particular to a kind ofly with 2,6-dinicotinic acid dimethyl ester and chiral amino alcohol are the method for raw material synthesis of chiral pyridine double-oxazoline part.
Background technology
Chirality is the ubiquitous a kind of phenomenon of occurring in nature; All contain unsymmetrical carbon in many material molecules with physiologically active, the high-efficiency synthesis method that chiral carbon atom is constructed in development is a very important research topic that is faced in the asymmetric synthesis field.Chirality pyridine double-oxazoline class part with C-2 symmetry axis has been widely used in the asymmetric catalysis, in many asymmetric reactions, has all shown excellent chiral induction effect.Like cyclopropanization reaction, aldol reaction, Michael addition, ammoxidation.Chirality pyridine double-oxazoline is to be easy to preparation as the advantage of chiral ligand, and is cheap.It can be through being that feedstock production obtains by chiral amino alcohol, and the chiral amino acid that nature extensively exists is easy to obtain chiral amino alcohol through hydrogenating reduction.Ling Wai ， oxazoline is very near from coordination center as the chiral radicals of chiral ligand, therefore in the metal ion catalysis process, can play a very strong and direct chiral induction effect.
About synthesizing of chirality bisoxazoline part, domestic and foreign literature has been reported many methods.Can be divided into three types from initial used raw material type, specific as follows:
The first kind: proposed by Nishiyama in 1989: at first 2, reaction generates amide compound 3 to 6-pyridine dimethyl chloride 1 with chiral amino alcohol, with thionyl chloride with hydroxy chloride for generating compound 4.Have chirality if connect the carbon of hydroxyl, then constant by its configuration after the chlorination.Cyclization generates Shou Xing bisoxazoline pyridine compounds and their 5 under alkaline condition at last.Reaction formula is following:
The raw material 2 of this method, 6-dinicotinic acid chlorine instability especially are not easy to store, and this synthesis step is loaded down with trivial details, and productive rate is lower.
Second type: 1999, Chelucci was a raw material with the pyridine dintrile, at ZnCl
2Catalysis under, when the mol ratio of amino alcohol and dinitrile is 1:1, generate monocycle product (26% ~ 44% productive rate) and dicyclo product (20% ~ 30% productive rate) simultaneously; When the mol ratio of amino alcohol and dinitrile is 3:1, have to the dicyclo product.Reaction formula is following:
Though this method step is simple, its raw material pyridine dintrile is very expensive, so this method is not suitable for suitability for industrialized production.
The 3rd type: Shogo Takahashi group in 2010 is with 2, and 6-pyridine dicarbaldehyde is a raw material, with the chiral amino alcohol reaction, at K
2CO
3Effect directly generates the bisoxazoline chiral ligand down.Reaction formula is following:
Raw material 2 in this method, 6-pyridine dicarbaldehyde are relatively more expensive, and environmental pollution is serious, and productive rate is not high, therefore are not suitable for suitability for industrialized production.
Summary of the invention
The objective of the invention is provides a kind of novel preparation method of chirality pyridine double-oxazoline part to the problem that exists in the prior art.
The present invention prepares the method for chirality pyridine double-oxazoline part; Be cheaply to be easy to get; And store 2 easily, 6-dinicotinic acid dimethyl ester is an initial feed, generates key intermediate pyridine-2 with different chiral amino alcohol reactions; 6-diacid bisamide obtains final product (seeing Scheme 1) through cyclization again.Its concrete synthetic method craft is following:
(1) be solvent with toluene, with 2,6-dinicotinic acid dimethyl ester and chiral amino alcohol, reacted 24 ~ 30 hours in 110 ~ 120 ℃ with the mol ratio of 1:2.0 ~ 1:2.5, boiled off solvent, and column chromatography for separation obtains midbody pyridine-2,6-diacid bisamide.
Said chiral amino alcohol is L-phenylalaninol, L-benzene glycinol, L-aminopropanol.
(2) be solvent with the methylene dichloride, make pyridine-2,6-diacid bisamide, Tosyl chloride, triethylamine, reacted 12 ~ 18 hours in 50 ~ 60 ℃ with the mol ratio of 1:2:15 ~ 1:2.5:30, filter, column chromatography for separation, both title product.
Concrete synthetic route is:
Wherein R represents the alkyl or aryl substituting group, concrete nail base, phenyl or benzyl.
The product of the inventive method preparation through data characterizations such as hydrogen spectrum, carbon spectrums, shows that it is the chirality pyridine double-oxazoline part.
The present invention has the following advantages with respect to prior art:
1, the present invention is with 2, and 6-dinicotinic acid dimethyl ester is an initial feed, generates key intermediate pyridine-2 with different chiral amino alcohol reactions, and 6-diacid bisamide obtains final product through cyclization again.To compare this synthesis step simple with existing compound method, and total recovery higher (91 ~ 92 %).
2, the present invention is with respect to other compound method, and raw material cheaply is easy to get, and cost is lower, and stores easily.
3, disposal of pollutants is light, and is environmentally friendly.
Embodiment
Through specific embodiment the method that the present invention prepares the chirality pyridine double-oxazoline part is further specified below.
Embodiment one, 2, the preparation of 6-two [4 ' (S)-Bian oxazolins-2 '-] pyridine
(1) pyridine-2; The preparation of 6-diacid two [((S)-2-hydroxyl-1-benzyl ethyl) acid amides]: with 2; 6-dinicotinic acid dimethyl ester (8.80 g, 0.04 mol) and L-phenylalaninol (13.3 g, 0.08 mol) join in the single port bottle of 250 mL; Add 200 mL toluene, refluxed 24 hours at 120 ℃.After steaming toluene, column chromatography (ETHYLE ACETATE: sherwood oil=2:1), obtain white solid 15.9 g, productive rate 86 %, fusing point: 87 ℃ ~ 88 ℃.
The preparation of (2) 2,6-two [4 ' (S)-Bian oxazolins-2 '-] pyridine: with pyridine-2,6-diacid two [((S)-2-hydroxyl-1-benzyl ethyl) acid amides] (11 g, 0.02 mol) and 60 mL methylene dichloride add in the 250 mL single port bottles; Add Tosyl chloride (7.6 g, 0.04 mmol) again, 0 ℃ slowly drips triethylamine (30.3 g, 0.3 mol down in batches; 15 equiv), stirred overnight refluxed 12 hours at 60 ℃; TLC detects raw material and disappears, filters, column chromatography (ETHYLE ACETATE: sherwood oil=2:1); Get white solid (7.7 g, 0.02 mol), productive rate 90 %.Fusing point: 175 ℃ ~ 177 ℃.
Above-mentioned synthetic 2,6-pair [4 ' (S)-Bian oxazolins-2 '-] pyridine, warp
1HNMR,
13CNMR detects, and its product is pure target compound.Its each performance index or characterization data are following:
1HNMR?(CDCl
3,?400?MHz)，δ?(ppm):?2.72-2.78(d,?J=24.0Hz,?2H)，3.25-3.30?(d,?J=16.0Hz,?2H),?4.25?(t,?
J?=?16?Hz,,?2H),?4.46（t,?
J?=?20?Hz,?2H),?4..61-4.69?(m,?2H),?7.24-7.33?(m,?10H),?7.89?(t,?
J?=?16?Hz,?1H),?8.2?(d,?J=8..0Hz,?2H)；
13CNMR?(CDCl
3,?400?MHz),?δ?(ppm):?41.6,?68.0,?72.6,?125.8,?126.5,?128.5,?129.1,?137.3,?137.7,?146.8,162.6。
Embodiment two, 2, the preparation of 6-two [4 ' (S)-Bian oxazolins-2 '-] pyridine
(1) pyridine-2; The preparation of 6-diacid two [((S)-2-hydroxyl-1-benzyl ethyl) acid amides]: with 2; 6-dinicotinic acid dimethyl ester (8.80 g, 0.04 mol) and L-phenylalaninol (14.9 g, 0.1 mol) join in the single port bottle of 250 mL; Add 200 mL toluene, refluxed 24 hours at 120 ℃.After steaming toluene, column chromatography (ETHYLE ACETATE: sherwood oil=2:1), obtain white solid 17.6 g, productive rate 95 %.
The preparation of (2) 2,6-two [4 ' (S)-Bian oxazolins-2 '-] pyridine: with pyridine-2,6-diacid two [((S)-2-hydroxyl-1-benzyl ethyl) acid amides] (11 g, 0.02 mol) and 60 mL methylene dichloride add in the 250 mL single port bottles; Add Tosyl chloride (7.6 g, 0.04 mol) again, 0 ℃ slowly drips triethylamine (30.3 g, 0.3 mol down in batches; 15 equiv), stirred overnight refluxed 12 hours at 60 ℃; TLC detects raw material and disappears, filters, column chromatography (ETHYLE ACETATE: sherwood oil=2:1); Get white solid (7.7 g, 0.02 mol), productive rate 90 %.
Above-mentioned synthetic 2,6-pair [4 ' (S)-Bian oxazolins-2 '-] pyridine, warp
1HNMR,
13CNMR detects, and its product is pure target compound.Its each performance index or characterization data are with embodiment one.
Embodiment three, 2, the preparation of 6-two [4 ' (S)-Bian oxazolins-2 '-] pyridine
(1) pyridine-2; The preparation of 6-diacid two [((S)-2-hydroxyl-1-benzyl ethyl) acid amides]: with 2; (14.9 g 0.1mol) join in the single port bottle of 250 mL for 6-dinicotinic acid dimethyl ester (8.80 g, 0.04 mol) and L-phenylalaninol; Add 200 mL toluene, refluxed 24 hours at 120 ℃.After steaming toluene, column chromatography (ETHYLE ACETATE: sherwood oil=2:1), obtain white solid 17.6 g, productive rate 95 %.
The preparation of (2) 2,6-two [4 ' (S)-Bian oxazolins-2 '-] pyridine: with pyridine-2, two [((S)-2-hydroxyl-1-benzyl ethyl) acid amides] (11 g, 0.02 mol of 6-diacid;) and 60 mL methylene dichloride add in the 250 mL single port bottles, add Tosyl chloride (9.53 g, 0.05 mol) more in batches, 0 ℃ drips down slowly triethylamine (30.3 g; 0.3 mol, 15 equiv), stirred overnight; Refluxed 12 hours at 60 ℃, TLC detects raw material and disappears, and filters; Column chromatography (ETHYLE ACETATE: sherwood oil=2:1), get white solid (8.25 g, 0.02 mol).Productive rate 96 %.
Above-mentioned synthetic 2,6-pair [4 ' (S)-Bian oxazolins-2 '-] pyridine, warp
1HNMR,
13CNMR detects, and its product is pure target compound.Its each performance index or characterization data are with embodiment one.
Embodiment four, 2, the preparation of 6-two [4 ' (S)-Ben oxazolins-2 '-] pyridine
(1) pyridine-2; The preparation of 6-diacid two [((S)-2-hydroxyl-1-phenylethyl) acid amides]: with 2; 6-dinicotinic acid dimethyl ester (8.80 g, 0.04 mol) and L-benzene glycinol (10.8 g, 0.08 mol) join in the single port bottle of 250 mL; Add 200 mL toluene, refluxed 26 hours at 120 ℃.After steaming toluene, column chromatography (ETHYLE ACETATE: sherwood oil=2:1), obtain white solid 15.6 g, productive rate 90 %.Fusing point: 117 ℃ ~ 119 ℃.
The preparation of (2) 2,6-two [4 ' (S)-Ben oxazolins-2 '-] pyridine: with pyridine-2,6-diacid two [((S)-2-hydroxyl-1-phenylethyl) acid amides] (2 g, 4.6 mmol) and 60 mL methylene dichloride add in the 250 mL single port bottles; Adding Tosyl chloride (1.75 g, 9.2 mmol), 0 ℃ slowly drips triethylamine (13.9 g, 138 mmol down in batches; 30 equiv), stirred overnight refluxed 12 hours at 60 ℃; TLC detects raw material and disappears, filters, column chromatography (ETHYLE ACETATE: sherwood oil=2:1); Get white solid (1.65 g, 4.1 mmol), productive rate 90 %.Fusing point: 174 ℃ ~ 176 ℃.
Above-mentioned synthetic 2,6-pair [4 ' (S)-Ben oxazolin-2 '-] pyridine, warp
1HNMR,
13CNMR detects, and its product is pure target compound.Its each performance index or characterization data are following:
1HNMR?(CDCl
3,?400?MHz)，δ?(ppm):?4.43(t,?
J?=?20.0?Hz,?2H)，4.93?(d,?J=20.0Hz,?2H),?5.46?(t,?
J?=?20.0?Hz,?2H),?7.26-7.39?(m,?9H),?7.92?(t,?
J?=?16.0?Hz,?1H),?8.34(d,?J=8.0Hz,?2H)；
13CNMR?(CDCl
3,?400?MHz),?δ?(ppm):?70.3,?75.5,?126.3,?126.8,?127.8,?128.5,?137.4,?141.7,?146.8,?163.5。
Embodiment five, 2, the preparation of 6-two [4 ' (S)-Ben oxazolins-2 '-] pyridine
(1) pyridine-2; The preparation of 6-diacid two [((S)-2-hydroxyl-1-phenylethyl) acid amides]: with 2; (13.5 g 0.1mol) join in the single port bottle of 250 mL for 6-dinicotinic acid dimethyl ester (8.80 g, 0.04 mol) and L-benzene glycinol; Add 200 mL toluene, refluxed 24 hours at 120 ℃.After steaming toluene, column chromatography (ETHYLE ACETATE: sherwood oil=2:1), obtain white solid 16.5 g, productive rate 95 %.
The preparation of (2) 2,6-two [4 ' (S)-Ben oxazolins-2 '-] pyridine: with pyridine-2,6-diacid two [((S)-2-hydroxyl-1-phenylethyl) acid amides] (2 g, 4.6 mmol) and 60 mL methylene dichloride add in the 250 mL single port bottles; Adding Tosyl chloride (1.75 g, 9.2 mmol), 0 ℃ slowly drips triethylamine (13.9 g, 138 mmol down in batches; 30 equiv), stirred overnight refluxed 12 hours at 60 ℃; TLC detects raw material and disappears, filters, column chromatography (ETHYLE ACETATE: sherwood oil=2:1); Get white solid (1.65 g, 4.1 mmol), productive rate 90 %.
Above-mentioned synthetic 2,6-pair [4 ' (S)-Ben oxazolin-2 '-] pyridine, warp
1HNMR,
13CNMR detects, and its product is pure target compound.Its each performance index or characterization data are with embodiment four.
Embodiment six, 2, the preparation of 6-two [4 ' (S)-Ben oxazolins-2 '-] pyridine
(1) pyridine-2; The preparation of 6-diacid two [((S)-2-hydroxyl-1-phenylethyl) acid amides]: with 2; 6-dinicotinic acid dimethyl ester (8.80 g, 0.04 mol) and L-benzene glycinol (13.5 g, 0.1 mol) join in the single port bottle of 250 mL; Add 200 mL toluene, refluxed 24 hours at 120 ℃.After steaming toluene, column chromatography (ETHYLE ACETATE: sherwood oil=2:1), obtain white solid 16.5 g, productive rate 95 %.
The preparation of (2) 2,6-two [4 ' (S)-Ben oxazolins-2 '-] pyridine: with pyridine-2, two [((S)-2-hydroxyl-1-phenylethyl) acid amides] (2 g, 4.6 mmol of 6-diacid;) and 60 mL methylene dichloride add in the 250 mL single port bottles, adding Tosyl chloride (2.19 g, 11.5 mmol) in batches, 0 ℃ drips down slowly triethylamine (13.9 g; 138 mmol, 30 equiv), stirred overnight refluxed 12 hours at 60 ℃; TLC detects raw material and disappears, filters, column chromatography (ETHYLE ACETATE: sherwood oil=2:1); Get white solid (1.68 g, 4.2 mmol), productive rate 92 %.
Above-mentioned synthetic 2,6-pair [4 ' (S)-Ben oxazolin-2 '-] pyridine, warp
1HNMR,
13CNMR detects, and its product is pure target compound.Its each performance index or characterization data are with embodiment four.
Embodiment seven, 2, the preparation of 6-two [4 ' (S)-Jia oxazolins-2 '-] pyridine
(1) pyridine-2; The preparation of 6-diacid two [((S)-2-hydroxyl-1-phenylethyl) acid amides]: with 2; 6-dinicotinic acid dimethyl ester (8.80 g, 0.04 mol) and L-aminopropanol (6.0 g, 0.08 mol) join in the single port bottle of 250 mL; Add 200 mL toluene, refluxed 24 hours at 120 ℃.After steaming toluene, column chromatography (ETHYLE ACETATE: sherwood oil=3:1), obtain white solid 7.89 g, productive rate 93 %.Fusing point: 196 ℃ ~ 198 ℃.
The preparation of (2) 2,6-two [4 ' (S)-Jia oxazolins-2 '-] pyridine: with pyridine-2, two [((S)-2-hydroxyl-1-methylethyl) acid amides] (2 g, 6.4 mmol of 6-diacid;) and 60 mL methylene dichloride add in the 250 mL single port bottles, adding Tosyl chloride (2.44 g, 12.8 mmol) in batches, 0 ℃ drips down slowly triethylamine (19.4 g; 192 mmol, 30 equiv), stirred overnight refluxed 12 hours at 60 ℃; TLC detects raw material and disappears, filters, column chromatography (ETHYLE ACETATE: sherwood oil=2:1); Get white solid (1.57 g, 5.1 mmol), productive rate 90 %.Fusing point: 173 ℃ ~ 175 ℃.
Above-mentioned synthetic 2,6-pair [4 ' (S)-Jia oxazolin-2 '-] pyridine, warp
1HNMR,
13CNMR detects, and its product is pure target compound.Its each performance index or characterization data are following:
1HNMR?(CDCl
3,?400?MHz)，δ?(ppm):?1.32?(d,?J=8..0Hz,?6H)，4.02?(t,?
J?=?16.0?Hz,?2H),?4.36-4.44?(m,?2H),?4.56?(t,?
J?=?16.0?Hz,?2H),?7.82?(t,?
J?=?20.0?Hz,?1H),?8.11(d,?J=8.0Hz,?2H)；
13CNMR?(CDCl
3,?400?MHz),?δ?(ppm):?21.2,?62.1,?125.5,?137.2,?146.7,162.1。
Embodiment eight, 2, the preparation of 6-two [4 ' (S)-Jia oxazolins-2 '-] pyridine
(1) pyridine-2; The preparation of 6-diacid two [((S)-2-hydroxyl-1-phenylethyl) acid amides]: with 2; (7.5 g 0.1mol) join in the single port bottle of 250 mL for 6-dinicotinic acid dimethyl ester (8.80 g, 0.04 mol) and L-aminopropanol; Add 200 mL toluene, refluxed 24 hours at 120 ℃.After steaming toluene, column chromatography (ETHYLE ACETATE: sherwood oil=3:1), obtain white solid 12.07 g, productive rate 98 %.
The preparation of (2) 2,6-two [4 ' (S)-Jia oxazolins-2 '-] pyridine: with pyridine-2, two [((S)-2-hydroxyl-1-methylethyl) acid amides] (2 g, 6.4 mmol of 6-diacid;) and 60 mL methylene dichloride add in the 250 mL single port bottles, adding Tosyl chloride (2.44 g, 12.8 mmol) in batches, 0 ℃ drips down slowly triethylamine (19.4 g; 192 mmol, 30 equiv), stirred overnight refluxed 12 hours at 60 ℃; TLC detects raw material and disappears, filters, column chromatography (ETHYLE ACETATE: sherwood oil=2:1); Get white solid (1.57 g, 5.1 mmol), productive rate 90 %.
Above-mentioned synthetic 2,6-pair [4 ' (S)-Jia oxazolins-2 '-] pyridine, warp
1HNMR,
13CNMR detects, and its product is pure target compound.Its each performance index or characterization data are with embodiment seven.
Embodiment nine, 2, the preparation of 6-two [4 ' (S)-Jia oxazolins-2 '-] pyridine
(1) pyridine-2; The preparation of 6-diacid two [((S)-2-hydroxyl-1-phenylethyl) acid amides]: with 2; (7.5 g 0.1mol) join in the single port bottle of 250 mL for 6-dinicotinic acid dimethyl ester (8.80 g, 0.04 mol) and L-aminopropanol; Add 200 mL toluene, refluxed 24 hours at 120 ℃.After steaming toluene, column chromatography (ETHYLE ACETATE: sherwood oil=3:1), obtain white solid 12.07 g, productive rate 98 %.
The preparation of (2) 2,6-two [4 ' (S)-Jia oxazolins-2 '-] pyridine: with pyridine-2, two [((S)-2-hydroxyl-1-methylethyl) acid amides] (2 g, 6.4 mmol of 6-diacid;) and 60 mL methylene dichloride add in the 250 mL single port bottles, adding Tosyl chloride (3.05 g, 16 mmol) in batches, 0 ℃ drips down slowly triethylamine (19.4 g; 192 mmol, 30 equiv), stirred overnight refluxed 12 hours at 60 ℃; TLC detects raw material and disappears, filters, column chromatography (ETHYLE ACETATE: sherwood oil=2:1); Get white solid (1.85 g, 6.0 mmol), productive rate 94 %.
Above-mentioned synthetic 2,6-pair [4 ' (S)-Jia oxazolins-2 '-] pyridine, warp
1HNMR,
13CNMR detects, and its product is pure target compound.Its each performance index or characterization data are with embodiment seven.
Claims (2)
1. the preparation method of a chirality pyridine double-oxazoline part is to be solvent with toluene, with 2; 6-dinicotinic acid dimethyl ester and chiral amino alcohol are with the mixed in molar ratio of 1:2.0 ~ 1:2.5; In 110 ~ 120 ℃ of back flow reaction 24 ~ 30 hours, boil off solvent, column chromatography for separation; Obtain midbody pyridine-2,6-diacid bisamide; Be solvent with the methylene dichloride again, make pyridine-2,6-diacid bisamide, Tosyl chloride, triethylamine, filter in 50 ~ 60 ℃ of reactions 12 ~ 18 hours with the mol ratio of 1:2:15 ~ 1:2.5:30, column chromatography for separation, both title product.
2. the preparation method of chirality pyridine double-oxazoline part according to claim 1, it is characterized in that: said chiral amino alcohol is L-phenylalaninol, L-benzene glycinol or L-aminopropanol.
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| WO2022222913A1 (en) * | 2021-04-21 | 2022-10-27 | 黄冈中有生物科技有限公司 | Preparation method for l-nicotine |
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| CN107033342A (en) * | 2017-04-25 | 2017-08-11 | 清华大学 | A kind of preparation method of the solid supported chiral bisoxazoline parts of PEG |
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