CN105906486A - Synthetic method of sarpogrelate intermediate 2-[2-(3-methoxyphenyl)ethyl]phenol - Google Patents
Synthetic method of sarpogrelate intermediate 2-[2-(3-methoxyphenyl)ethyl]phenol Download PDFInfo
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- CN105906486A CN105906486A CN201610251703.0A CN201610251703A CN105906486A CN 105906486 A CN105906486 A CN 105906486A CN 201610251703 A CN201610251703 A CN 201610251703A CN 105906486 A CN105906486 A CN 105906486A
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- China
- Prior art keywords
- methoxyphenyl
- product
- phenol
- ethyl
- benzyloxy
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- 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.)
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- HGQQRAXOBYWKDV-UHFFFAOYSA-N 2-[2-(3-methoxyphenyl)ethyl]phenol Chemical compound COC1=CC=CC(CCC=2C(=CC=CC=2)O)=C1 HGQQRAXOBYWKDV-UHFFFAOYSA-N 0.000 title claims abstract description 11
- FFYNAVGJSYHHFO-UHFFFAOYSA-N sarpogrelate Chemical compound COC1=CC=CC(CCC=2C(=CC=CC=2)OCC(CN(C)C)OC(=O)CCC(O)=O)=C1 FFYNAVGJSYHHFO-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229950005789 sarpogrelate Drugs 0.000 title claims abstract description 10
- 238000010189 synthetic method Methods 0.000 title claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims abstract description 8
- PBEJTRAJWCNHRS-UHFFFAOYSA-N 2-phenylmethoxybenzaldehyde Chemical compound O=CC1=CC=CC=C1OCC1=CC=CC=C1 PBEJTRAJWCNHRS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003208 petroleum Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000004519 grease Substances 0.000 claims description 4
- YMHAQZODPXEMNF-UHFFFAOYSA-N 1-methoxy-3-[2-(2-phenylmethoxyphenyl)ethenyl]benzene Chemical compound COC1=CC=CC(C=CC=2C(=CC=CC=2)OCC=2C=CC=CC=2)=C1 YMHAQZODPXEMNF-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- -1 Methoxyphenyl Chemical group 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 5
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 abstract 2
- YUKILTJWFRTXGB-UHFFFAOYSA-N 1-chloro-3-methoxybenzene Chemical compound COC1=CC=CC(Cl)=C1 YUKILTJWFRTXGB-UHFFFAOYSA-N 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 abstract 1
- 229960004889 salicylic acid Drugs 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 240000000203 Salix gracilistyla Species 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000002785 anti-thrombosis Effects 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/1414—Esters of phosphorous acids with arylalkanols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/20—Preparation of ethers by reactions not forming ether-oxygen bonds by hydrogenation of carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthetic method of a sarpogrelate intermediate 2-[2-(3-methoxyphenyl)ethyl]phenol and relates to the technical field of organic synthesis. In the method, with m-methoxyl chlorobenzene, which is easy to obtain and is low in cost, as a raw material, the method includes the steps of: 1) performing condensation to the raw material with triethyl phosphite; and 2) performing condensation with o-phenylmethoxyl benzaldehyde (which is prepared from salicylic acid and chlorobenzene), performing hydrogenation to alkylate a double bond, and crystallizing a product with petroleum ether to prepare a white crystal target product. The method simplifies process steps, reduces loss ratio and is 99.5% in product purity. The 2-[2-(3-methoxyphenyl)ethyl]phenol is used for preparing sarpogrelate hydrochloride, wherein single impurity is less than 0.1% in content and the product purity reaches more than 99.8%.
Description
Technical field:
The present invention relates to technical field of organic synthesis, be specifically related to a kind of Sarpogrelate intermediate 2-[2-(3-first
Phenyl) ethyl] synthetic method of phenol.
Background technology:
2-[2-(3-methoxyphenyl) ethyl] phenol is the key intermediate of antithrombotic sarpogrelate hydrochloride,
Owing to this intermediate fusing point is relatively low, current art is for the husky lattice of lower step synthesis with the grease of this intermediate
Thunder ester, causes final products impurity height, colour-difference, purification difficult, and cost remains high.Report
Synthetic route have that step is various, severe reaction conditions, three wastes growing amount is big and yield is low shortcoming,
It is unfavorable for industrialized production.
Summary of the invention:
The technical problem to be solved is to provide that a kind of technique is simple, low cost and yield high
The synthetic method of Sarpogrelate intermediate 2-[2-(3-methoxyphenyl) ethyl] phenol.
The technical problem to be solved uses following technical scheme to realize:
The synthetic method of Sarpogrelate intermediate 2-[2-(3-methoxyphenyl) ethyl] phenol, including walking as follows
Rapid:
(1) synthesis of 1-benzyloxy-2-[2-(3-methoxyphenyl) vinyl] benzene: to 100g meta-methoxy chlorobenzene
Middle addition 300ml NSC 5284, mixture is warming up to back flow reaction 1.5h, and reaction is reduced pressure back after terminating
Receive NSC 5284, then in residual liquid, add 136g neighbour's benzyloxy benzaldehyde and 400ml dehydrated alcohol,
Back flow reaction 8h, adds frozen water, stirring, is filtrated to get 390g 1-benzyloxy-2-[2-(3-after recovered solvent
Methoxyphenyl) vinyl] benzene wet product；
(2) synthesis of 2-[2-(3-methoxyphenyl) ethyl] phenol: the product wet product of upper step gained is added 500
In ml 80% methanol, and add 6g 5% palladium carbon and make catalyst, then be passed through hydrogen 15atm, be hydrogenated to system
Till not inhaling hydrogen, it is filtered to remove palladium carbon, recovered under reduced pressure methanol, then cools down, be layered, obtain lower floor and produce
Thing oil reservoir, adds 200ml petroleum ether in grease, stirs 2h in-2～0 DEG C, is filtrated to get crystallization and produces
Product, obtain 115g product then at 20～25 DEG C of vacuum dryings, and HPLC detection purity is 99.6%.
The invention has the beneficial effects as follows: the present invention uses the meta-methoxy chlorobenzene being easy to get inexpensive to be raw material, with
NSC 5284 is condensed, then with adjacent benzyloxy benzaldehyde (being prepared by bigcatkin willow vinegar and chlorobenzene) condensation,
Repeated hydrogenation makes double bond alkylation, and crystallizes with petroleum ether, obtains the target product of white crystalline, simplifies
Processing step, reduce loss rate, product purity reaches 99.5%, by this quality 2-[2-(3-methoxyphenyl) second
Base] phenol prepares sarpogrelate hydrochloride, and single impurity is both less than 0.1%, and product purity reaches more than 99.8%.
Detailed description of the invention:
For the technological means making the present invention realize, creation characteristic, reach purpose and effect and be readily apparent from
Solve, below in conjunction with specific embodiment, the present invention is expanded on further.
Embodiment 1
(1) synthesis of 1-benzyloxy-2-[2-(3-methoxyphenyl) vinyl] benzene: to 100g meta-methoxy chlorobenzene
Middle addition 300ml NSC 5284, mixture is warming up to back flow reaction 1.5h, and reaction is reduced pressure back after terminating
Receive NSC 5284, then in residual liquid, add 136g neighbour's benzyloxy benzaldehyde and 400ml dehydrated alcohol,
Back flow reaction 8h, adds frozen water, stirring, is filtrated to get 390g 1-benzyloxy-2-[2-(3-after recovered solvent
Methoxyphenyl) vinyl] benzene wet product；
(2) synthesis of 2-[2-(3-methoxyphenyl) ethyl] phenol: the product wet product of upper step gained is added 500
In ml 80% methanol, and add 6g 5% palladium carbon and make catalyst, then be passed through hydrogen 15atm, be hydrogenated to system
Till not inhaling hydrogen, it is filtered to remove palladium carbon, recovered under reduced pressure methanol, then cools down, be layered, obtain lower floor and produce
Thing oil reservoir, adds 200ml petroleum ether in grease, stirs 2h in-2～0 DEG C, is filtrated to get crystallization and produces
Product, obtain 115g product then at 20～25 DEG C of vacuum dryings, and HPLC detection purity is 99.6%.
The ultimate principle of the present invention and principal character and advantages of the present invention have more than been shown and described.One's own profession
Skilled person will appreciate that of industry, the present invention is not restricted to the described embodiments, above-described embodiment and explanation
The principle that the present invention is simply described described in book, without departing from the spirit and scope of the present invention,
The present invention also has various changes and modifications, and these changes and improvements both fall within claimed invention model
In enclosing.Claimed scope is defined by appending claims and equivalent thereof.
Claims (1)
1. the synthetic method of Sarpogrelate intermediate 2-[2-(3-methoxyphenyl) ethyl] phenol, its feature exists
In, comprise the steps:
(1) synthesis of 1-benzyloxy-2-[2-(3-methoxyphenyl) vinyl] benzene: to 100g meta-methoxy chlorobenzene
Middle addition 300ml NSC 5284, mixture is warming up to back flow reaction 1.5h, and reaction is reduced pressure back after terminating
Receive NSC 5284, then in residual liquid, add 136g neighbour's benzyloxy benzaldehyde and 400ml dehydrated alcohol,
Back flow reaction 8h, adds frozen water, stirring, is filtrated to get 390g 1-benzyloxy-2-[2-(3-after recovered solvent
Methoxyphenyl) vinyl] benzene wet product；
(2) synthesis of 2-[2-(3-methoxyphenyl) ethyl] phenol: the product wet product of upper step gained is added 500
In ml 80% methanol, and add 6g 5% palladium carbon and make catalyst, then be passed through hydrogen 15atm, be hydrogenated to system
Till not inhaling hydrogen, it is filtered to remove palladium carbon, recovered under reduced pressure methanol, then cools down, be layered, obtain lower floor and produce
Thing oil reservoir, adds 200ml petroleum ether in grease, stirs 2h in-2～0 DEG C, is filtrated to get crystallization and produces
Product, obtain 115g product then at 20～25 DEG C of vacuum dryings, and HPLC detection purity is 99.6%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610251703.0A CN105906486B (en) | 2016-04-20 | 2016-04-20 | The synthetic method of Sarpogrelate intermediate 2 [2 (3 methoxyphenyl) ethyl] phenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610251703.0A CN105906486B (en) | 2016-04-20 | 2016-04-20 | The synthetic method of Sarpogrelate intermediate 2 [2 (3 methoxyphenyl) ethyl] phenol |
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| Publication Number | Publication Date |
|---|---|
| CN105906486A true CN105906486A (en) | 2016-08-31 |
| CN105906486B CN105906486B (en) | 2018-04-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610251703.0A Active CN105906486B (en) | 2016-04-20 | 2016-04-20 | The synthetic method of Sarpogrelate intermediate 2 [2 (3 methoxyphenyl) ethyl] phenol |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107324979A (en) * | 2017-08-16 | 2017-11-07 | 北京奥得赛化学股份有限公司 | A kind of preparation method of sarpogrelate hydrochloride intermediate |
| CN109824527A (en) * | 2019-03-18 | 2019-05-31 | 安徽峆一药业股份有限公司 | A kind of synthetic method of sarpogrelate hydrochloride |
| CN114394905A (en) * | 2019-03-18 | 2022-04-26 | 安徽峆一药业股份有限公司 | Synthetic method of sarpogrelate hydrochloride intermediate 2- (3-dimethylamino-2-hydroxy) propoxybenzaldehyde |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439828A (en) * | 2015-12-30 | 2016-03-30 | 苏州诚和医药化学有限公司 | Method for synthesizing 1-benzyloxy-2-[2-(3-methoxyphenyl) vinyl]benzene |
-
2016
- 2016-04-20 CN CN201610251703.0A patent/CN105906486B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439828A (en) * | 2015-12-30 | 2016-03-30 | 苏州诚和医药化学有限公司 | Method for synthesizing 1-benzyloxy-2-[2-(3-methoxyphenyl) vinyl]benzene |
Non-Patent Citations (3)
| Title |
|---|
| GUO HUA CHEN等: "A practical synthesis of sarpogrelate hydrochloride and in vitro platelet aggregation inhibitory activities of its analogues", 《CHINESE CHEMICAL LETTERS》 * |
| 王世盛等: "白藜芦醇的化学合成研究", 《中国药物化学杂质》 * |
| 王生等: "盐酸沙格雷酯的合成", 《中国医药工业杂志》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107324979A (en) * | 2017-08-16 | 2017-11-07 | 北京奥得赛化学股份有限公司 | A kind of preparation method of sarpogrelate hydrochloride intermediate |
| CN109824527A (en) * | 2019-03-18 | 2019-05-31 | 安徽峆一药业股份有限公司 | A kind of synthetic method of sarpogrelate hydrochloride |
| CN114394905A (en) * | 2019-03-18 | 2022-04-26 | 安徽峆一药业股份有限公司 | Synthetic method of sarpogrelate hydrochloride intermediate 2- (3-dimethylamino-2-hydroxy) propoxybenzaldehyde |
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| Publication number | Publication date |
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| CN105906486B (en) | 2018-04-20 |
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Address after: 239300 Yang Cun Industrial Zone, Chuzhou, Anhui, Tianchang Applicant after: Anhui He pharmaceutical Limited by Share Ltd Address before: 239300 Yang Cun Industrial Zone, Chuzhou, Anhui, Tianchang Applicant before: Anhui Heryi Chemicals Co., Ltd. |
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