CN106631992A - Synthesis method of 4-oxy-3,4-dihydro-2H-pyridine-1-tert-butyl formate - Google Patents
Synthesis method of 4-oxy-3,4-dihydro-2H-pyridine-1-tert-butyl formate Download PDFInfo
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- CN106631992A CN106631992A CN201710007600.4A CN201710007600A CN106631992A CN 106631992 A CN106631992 A CN 106631992A CN 201710007600 A CN201710007600 A CN 201710007600A CN 106631992 A CN106631992 A CN 106631992A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/80—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D211/84—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen directly attached to ring carbon atoms
- C07D211/86—Oxygen atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The invention relates to a synthesis method of 4-oxy-3,4-dihydro-2H-pyridine-1-tert-butyl formate, which mainly solves the technical problems that the cost is high and the environment is polluted due to the use of a noble metal reagent in the existing synthesis method, and severe reaction conditions are not easy to control. The synthesis method comprises the following steps: taking N-tert-butyloxycarboryl-4-piperidone as the raw material to react with iodine in the presence of sodium methoxide, so as to obtain 3-hydroxy-4,4-dimethoxy-piperidine-1-tert-butyl formate; allowing the 3-hydroxy-4,4-dimethoxy-piperidine-1-tert-butyl formate to react with an activating group to obtain 3-activating group-4,4-dimethoxy-piperidine-1-tert-butyl formate; under the action of alkali, carrying out an eliminating reaction to obtain 4,4-dimethoxy-3,4-dihydro-2H-pyridine-1-tert-butyl formate; and finally, removing a protecting group to obtain 4-oxy-3,4-dihydro-2H-pyridine-1-tert-butyl formate. This type compound is an important drug compound structure modification small molecule in the research field of new drug.
Description
Technical field
The present invention relates to 4- oxygen -3, the synthetic method of 4- dihydro -2H- pyridine -1- t-butyl formates, such compound is new
Medicine research field is important medical compounds structural modification small molecule.
Background technology
4- oxygen -3,4- dihydros -2H- pyridines -1- t-butyl formates compound and its derivative are one in organic synthesis field
Class by extensive concern compound, it has, and chemical property is special, reactivity is high, unique structure the characteristics of.This kind of compound
Usually as the intermediate of Michael addition reaction, so as to build C-C keys, other reactions are compared, this kind of reaction has more preferable official
Tolerance can be rolled into a ball, more efficiently synthetic route, it is simpler that skeleton framework is carried out to molecule.Recently as similar structures
Drug candidate is developed in succession, and the application that this kind of compound is in terms of C-C bond formeds, molecular skeleton is built rapidly is also more next
It is more extensive.In biological medicine research field, the compound with piperidines and pyridine ring synthesis cancer therapy drug, antineoplastic,
The aspects such as anti-deterioration medicine have more application.4- oxygen -3,4- dihydro -2H- pyridine -1- t-butyl formates are to build such
The key intermediate of compound structure, can be widely used in medicament research and development and synthesis aspect.
4- oxygen -3, the actually rare report of synthetic method of 4- dihydro -2H- pyridine -1- t-butyl formates, and similar compound
Synthetic method it is also few.A kind of synthetic method therein is presented herein below：
1.《American Chemical Society's magazine》N- t-butoxycarbonylpiperidins ketone is disclosed with oxygen in catalyst：The catalysis of trifluoracetic acid palladium
Under prepare 4- oxygen -3,4- dihydro -2H- pyridine -1- t-butyl formates（Formula 1, Journal of the American
Chemical Society, 2011 ,vol. 133,# 37p. 14566 - 14569）；
Although the method route is short, palladium metal catalyst and oxygen are used, the use of noble metal can bring environmental pollution,
Environment is unfriendly.The intervention of oxygen can make reaction acutely, wayward, be not suitable for quick preparation, accomplish low cost, need very
More extra control.
Formula 1：
2. Li Lai companies are disclosed by methoxypyridine, after plurality of reagents reaction, finally give 4- oxygen -3,
4- dihydro -2H- pyridine -1- t-butyl formates（Formula 2, EP1204659 B1）；
Although the method route is brief, equally there is reaction reagent to methoxypyridine costliness, and be not readily available.Reaction is received
The problems such as rate is not high.In addition the route needs low-temp reaction, maintains reaction temperature at -40 DEG C, and this also brings to synthesis device
Certain difficulty.
Formula 2：
The content of the invention
The invention aims to providing one kind can efficiently obtain 4- oxygen -3,4- dihydro -2H- pyridine -1- formic acid
The synthetic method of tert-butyl ester compound, mainly solving the use noble metal reagent of existing synthetic method presence causes high cost
The violent uppity technical problem of enterprise, environmental pollution, and reaction condition.
Technical solution of the present invention：A kind of synthetic method of 4- oxygen -3,4- dihydros -2H- pyridine -1- t-butyl formates（Formula 3）,
Comprise the following steps：The first step, is reacted in the basic conditions as raw material with N- tertbutyloxycarbonyl -4- piperidones with elemental halogen,
Obtain 3- hydroxyls -4,4- dimethoxys-piperidines -1- t-butyl formates；Second step, 3- hydroxyl -4,4- dimethoxys-piperidines -1-
T-butyl formate reacts with activated group G, obtains 3-G-4,4- dimethoxys-piperidines -1- t-butyl formates；3rd step, 3-G-
In the presence of highly basic, elimination reaction obtains 4,4- dimethoxy -3,4- bis- to 4,4- dimethoxys-piperidines -1- t-butyl formates
Hydrogen -2H- pyridine -1- t-butyl formates；4th step, 4,4- dimethoxy -3,4- dihydro -2H- pyridine -1- t-butyl formates are in acid
Deprotection obtains 4- oxygen -3,4- dihydro -2H- pyridine -1- t-butyl formates under the conditions of property.
Formula 3：
。
The activated group G is all kinds of sulphonyl fat, halogen etc..The sulphonyl fat is Trifluoromethanesulfonic anhydride or Loprazolam
Acid anhydride.
The alkalescence condition（The first step）It is related to compound for potassium hydroxide or sodium methoxide.The highly basic（3rd step）Can be with
For organic base（For -5- the alkene of 1,5- diazabicylos [5.4.0] 11, pyridine, triethylamine, N, N-2 picolines, potassium tert-butoxide,
Caustic alcohol or Sodamide etc.）, or inorganic base（NaOH, potassium hydroxide, cesium carbonate etc.）.Described acid condition
（4th step）It is related to compound for the one kind in p-methyl benzenesulfonic acid, hydrochloric acid or acidic silica gel.
Beneficial effects of the present invention：The raw material N- tertbutyloxycarbonyl -4- piperidones used in the present invention（6000 yuan/1.0
kg）Low price, it is easy to get, the reagent that other are used also is conventional reagent, preparation cost is very cheap, it is to avoid use high risk
Triisopropyl potassium borohydride or and its costliness rare heavy metal catalyst.By four step popular responses, operation side
Just, post-process it is simple, product be easy to get to, it is to avoid high-temperature high-voltage reaction condition or heavy metal catalyst, the controllability of reaction and
Repeatability is all fine.
Specific embodiment
Embodiment 1
1）3- hydroxyls -4,4- dimethoxys-piperidines -1- t-butyl formates
In a 10 dry L there-necked flasks, 3800 mL methyl alcohol and 311g potassium hydroxide are added.Reactant liquor is cooled into 0
DEG C, 38 g N- tertbutyloxycarbonyl -4- piperidones are in reactant liquor.532 g iodines are dissolved in 3000 mL methyl alcohol, slow drop
In being added to reactant liquor.Reactant liquor is stirred at room temperature to raw material and disappears.Concentration of reaction solution removes most of methyl alcohol.Add 1500 mL first
Benzene is stirred 30 minutes in reaction bulb.It is filtered to remove inorganic salts.Vacuum distillation removes solvent.400 mL petroleum ethers are added to arrive
In reaction bulb, stir 30 minutes.Yellow solid is obtained after filtration.Drying under reduced pressure obtains 30g products, yield 60%.1H-NMR
(300 MHz, CDCl3): δ4.10-3.72 (m, 3H), 3.24 (s, 3H), 3.23 (s, 3H), 3.12-3.09
(broad d, 1H), 2.87-2.81 (broad t, 1H), 2.29 (broad s, 1H), 1.81-1.78 (m,
1H), 1.73-1.69 (m, 1H), 1.44 (s, 9H)。
）3- trifluoromethayl sulfonic acid ester group -4,4- dimethoxys-piperidines -1- t-butyl formates
In a 100 dry mL there-necked flasks, 2.0 g 3- hydroxyl -4, the 4- dimethoxys-tertiary fourth of piperidines -1- formic acid are added
Ester and 20 mL anhydrous methylene chlorides.2.0 mL pyridines are added in the reactant liquor.Reactant liquor is cooled into -15 ~ 0 DEG C.Will
2.28 g Trifluoromethanesulfonic anhydrides are slowly added drop-wise in reactant liquor.Reactant liquor is stirred 1 hour at -15 ~ 0 DEG C.Add 20 mL
Water urges reaction of going out in reaction bulb.Divide liquid, retain organic layer.Water layer continues to extract secondary with 15 mL dichloromethane.Merge organic
Layer simultaneously uses anhydrous sodium sulfate drying.Reduced pressure concentration removes solvent and obtains the g of light brown product liquid 2.8.1H-NMR (300 MHz,
CDCl3): δ4.87-4.80 (m, 1H), 4.48-4.34 (m, 1H), 4.20-3.89 (m, 1H), 3.27 (s,
6H), 3.26-3.16 (m, 1H), 2.90-2.78 (m, 1H), 1.90-1.78 (m, 2H), 1.46 (s, 9H)。
）4,4- dimethoxy -3,4- dihydro -2H- pyridine -1- t-butyl formates
In a 50 dry mL there-necked flasks, 0.5 g 3- trifluoromethayl sulfonic acids ester group -4,4- dimethoxy-piperidines-are added
1- carboxylic acid tert-butyl esters and 4.0 mL toluene.0.77 g sodium methoxides are added in the mixture.The mixture is heated to 50 degree,
And react 3 hours at such a temperature.As adding 10 mL water and 6mL methyl tertiary butyl ether(MTBE)s in reactant liquor.Retain organic layer, be used in combination
6 mL methyl tertiary butyl ether(MTBE)s extract remaining water layer twice.Merge organic layer.It is evaporated to dry, obtains 4,4- dimethoxy -3,4-
The g of dihydro -2H- pyridine -1- t-butyl formates 0.28.Yield 90%.1H-NMR (300 MHz, CDCl3): δ7.01-6.84
(dd, 1H), 4.96-4.85 (dd, 1H), 3.65-3.60(m, 2H), 3.25 (s, 6H), 1.92 (m, 2H),
1.49 (s, 9H)。
）4- oxygen -3,4- dihydro -2H- pyridine -1- t-butyl formates
In a 50 dry mL there-necked flasks, 0.28 g 4,4- dimethoxy -3,4- dihydro -2H- pyridine -1- formic acid are added
The tert-butyl ester and 4.0 mL acetone.0.01 g p-methyl benzenesulfonic acid is added in the mixture.The mixture is heated to 30 degree, and at this
At a temperature of react 1 hour.It is evaporated to dry, obtains 44- oxygen -3, the g of 4- dihydro -2H- pyridine -1- t-butyl formates 0.52.Yield
40%。1H-NMR (300 MHz, CDCl3): δ7.81 (d, 1H), 5.30-5.28 (d, 1H), 3.98-3.94 (t,
2H), 2.56-2.52 (t, 2H), 1.48 (s, 9H)。
Embodiment 2：
2）3- Loprazolam ester group -4,4- dimethoxys-piperidines -1- t-butyl formates
In a 100 dry mL there-necked flasks, 1.0 g 3- hydroxyl -4, the 4- dimethoxys-tertiary fourth of piperidines -1- formic acid are added
Ester and 10 mL anhydrous methylene chlorides.1.0 mL pyridines are added in the reactant liquor.Reactant liquor is cooled into 0 DEG C.By 0.46 g
Loprazolam acid anhydride is slowly added drop-wise in reactant liquor.Reactant liquor is stirred 1 hour at 0 DEG C.20 mL water are added to urge in reaction bulb
Go out reaction.Divide liquid, retain organic layer.Water layer continues to extract secondary with 15 mL dichloromethane.Merge organic layer and use anhydrous slufuric acid
Sodium is dried.Reduced pressure concentration removes solvent and obtains the g of light brown product liquid 1.1.By the silica gel group chromatographic purifying crude product, obtain
The 3- Loprazolam ester group -4,4- dimethoxys-g of piperidines -1- t-butyl formates 0.5.1H-NMR (300 MHz, CDCl3): δ
4.77-4.72 ( m, 1H), 4.45-4.30 (m, 1H), 4.20-3.87 (m, 1H), 3.12 (s, 6H), 3.10-
3.02 (m, 1H), 2.89-2.80 (m, 1H), 1.85-1.78 (m, 2H), 1.47 (s, 9H)。
）4,4- dimethoxy -3,4- dihydro -2H- pyridine -1- t-butyl formates
In a 50 dry mL there-necked flasks, 0.2 g 3- Loprazolams ester group -4,4- dimethoxys-piperidines -1- first are added
Tert-butyl acrylate crude product and the carbon -7- alkene of 4.0 mL 1,8- diazabicylos 11（DBU）.The mixture is heated to 90 DEG C, and at this
At a temperature of react 3 hours.As adding 20 mL water and 20mL methyl tertiary butyl ether(MTBE)s in reactant liquor.Retain organic layer, and use 10 mL
Methyl tertiary butyl ether(MTBE) extracts remaining water layer twice.Merge organic layer.It is evaporated to dry, obtains 4,4- dimethoxy -3,4- dihydros -
The g of 2H- pyridine -1- t-butyl formates 0.072.Yield 51%.1H-NMR (300 MHz, CDCl3): δ7.01-6.84 (dd,
1H), 4.96-4.85 (dd, 1H), 3.65-3.60(m, 2H), 3.25 (s, 6H), 1.92 (m, 2H), 1.49
(s, 9H)。
Embodiment 3, it is sodium methoxide that first step alkalescence condition is related to compound, and the 4th step acid condition is related to compound for salt
Acid, remaining is with embodiment 1.
Embodiment 4, the activated group G is bromine, and highly basic described in the 3rd step is potassium hydroxide, and the 4th step acid condition is related to
Compound is acidic silica gel, and remaining is with embodiment 1.
Embodiment 5, the activated group G is Trifluoromethanesulfonic anhydride, and highly basic described in the 3rd step is pyridine, and remaining is with enforcement
Example 1.
Claims (9)
1. a kind of 4- oxygen -3, the synthetic method of 4- dihydro -2H- pyridine -1- t-butyl formates, is characterized in that comprising the following steps：
The first step, is reacted in the basic conditions as raw material with N- tertbutyloxycarbonyl -4- piperidones with elemental halogen, obtains 3- hydroxyl -4,
4- dimethoxys-piperidines -1- t-butyl formates；Second step, 3- hydroxyl -4,4- dimethoxys-piperidines -1- t-butyl formates and work
Change group G reactions, obtain 3-G-4,4- dimethoxys-piperidines -1- t-butyl formates；3rd step, 3-G-4,4- dimethoxy-piperazine
In the presence of highly basic, elimination reaction obtains 4,4- dimethoxy -3,4- dihydro -2H- pyridine -1- first to pyridine -1- t-butyl formates
Tert-butyl acrylate；4th step, 4,4- dimethoxy -3,4- dihydro -2H- pyridine -1- t-butyl formates deprotection in acid condition
Base obtains 4- oxygen -3, and 4- dihydro -2H- pyridine -1- t-butyl formates, reaction equation is as follows：
。
2. a kind of 4- oxygen -3 according to claim 1, the synthetic method of 4- dihydro -2H- pyridine -1- t-butyl formates, its
It is characterized in that alkalescence condition described in the first step is related to compound for potassium hydroxide or sodium methoxide.
3. a kind of 4- oxygen -3 according to claim 1, the synthetic method of 4- dihydro -2H- pyridine -1- t-butyl formates, its
The activated group G is characterized in that for sulphonyl fat or halogen.
4. a kind of 4- oxygen -3 according to claim 3, the synthetic method of 4- dihydro -2H- pyridine -1- t-butyl formates, its
The sulphonyl fat is characterized in that for Trifluoromethanesulfonic anhydride or Loprazolam acid anhydride.
5. a kind of 4- oxygen -3 according to claim 3, the synthetic method of 4- dihydro -2H- pyridine -1- t-butyl formates, its
It is characterized in that the halogen is iodine, bromine or chlorine.
6. a kind of 4- oxygen -3 according to claim 1, the synthetic method of 4- dihydro -2H- pyridine -1- t-butyl formates, its
Highly basic described in the 3rd step is characterized in that for organic base or inorganic base.
7. a kind of 4- oxygen -3 according to claim 6, the synthetic method of 4- dihydro -2H- pyridine -1- t-butyl formates, its
Described organic base is characterized in that for -5- the alkene of 1,5- diazabicylos [5.4.0] 11, pyridine, triethylamine, N, N-2 picolines,
One kind in potassium tert-butoxide, caustic alcohol or Sodamide.
8. a kind of 4- oxygen -3 according to claim 6, the synthetic method of 4- dihydro -2H- pyridine -1- t-butyl formates, its
It is characterized in that described inorganic base is the one kind in NaOH, potassium hydroxide or cesium carbonate.
9. a kind of 4- oxygen -3 according to claim 1, the synthetic method of 4- dihydro -2H- pyridine -1- t-butyl formates, its
It is characterized in that the 4th step acid condition is related to compound for the one kind in p-methyl benzenesulfonic acid, hydrochloric acid or acidic silica gel.
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Cited By (1)
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| CN112250616A (en) * | 2020-10-26 | 2021-01-22 | 南京合巨药业有限公司 | Preparation method of 4-oxo-3, 4-dihydropyridine-1 (2H) -carboxylic acid tert-butyl ester |
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| CN103298801A (en) * | 2010-11-23 | 2013-09-11 | 辉瑞大药厂 | 4- (5-cyano-pyrazol-1-yl) -piperidine derivatives as GPR 119 modulators |
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| CN103298801A (en) * | 2010-11-23 | 2013-09-11 | 辉瑞大药厂 | 4- (5-cyano-pyrazol-1-yl) -piperidine derivatives as GPR 119 modulators |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112250616A (en) * | 2020-10-26 | 2021-01-22 | 南京合巨药业有限公司 | Preparation method of 4-oxo-3, 4-dihydropyridine-1 (2H) -carboxylic acid tert-butyl ester |
| CN112250616B (en) * | 2020-10-26 | 2022-03-18 | 南京合巨药业有限公司 | Preparation method of 4-oxo-3, 4-dihydropyridine-1 (2H) -carboxylic acid tert-butyl ester |
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