CN105315159A - Resolution method for compounds - Google Patents
Resolution method for compounds Download PDFInfo
- Publication number
- CN105315159A CN105315159A CN201410415353.8A CN201410415353A CN105315159A CN 105315159 A CN105315159 A CN 105315159A CN 201410415353 A CN201410415353 A CN 201410415353A CN 105315159 A CN105315159 A CN 105315159A
- Authority
- CN
- China
- Prior art keywords
- formula
- splitting according
- splitting
- rac
- nitroolefin
- Prior art date
- 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.)
- Granted
Links
- 0 *C(C(N=O)=CI)O Chemical compound *C(C(N=O)=CI)O 0.000 description 2
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a resolution method for compounds. According to the resolution method provided by the invention, the operation is simple and convenient, and a (S)-3 chiral compound can be obtained through simple and effective resolution without specially using intermediates with optical isomerism to carry out reaction, so that a novel choice is provided for the chiral resolution of related compounds.
Description
Technical field
The present invention relates to a kind of method for splitting of compound.
Background technology
Chirality factor biology, chemistry and other multi-field in all there is extremely important influence power.Along with organic chemistry and biochemical development, the Chiral properties of compound has started to be subject to increasing attention.Numerous research shows, different optical isomers may have distinct physiologically active, transporting mechanism, metabolic rate and toxicity, is also not quite similar in absorption, distribution and excretion.
Chiral separation (Chiralresolution), also known as optical resolution (Opticalresolution) or racemate resolution, in stereochemistry, becomes the method for two different mirror image isomerism things in order to separation of racemic compound.Normally used method for splitting has crystallization Split Method, chemical resolution method, enzymolysis process and column chromatography etc., wherein, chemical resolution method often uses a pure optical activity isomer participation reaction, forms diastereomer, then diastereomer backward reaction is sloughed pure optical activity isomer.But also not all compound can both find applicable optical activity isomer to participate in reaction, if can find a kind of method not using specific light active isomer just can split compound, will provide new thinking and selection for chiral separation method.
Summary of the invention
The object of the present invention is to provide a kind of chiral separation method of compound.
Particularly, the invention provides (S) as follows-3 method for splitting of compound, reaction path is as follows:
racemic modification;
R1 is selected from phenyl ring, substituted benzene ring or five yuan or hexa-member heterocycle, and R2 is selected from C1-C4 alkyl, and R3 is selected from H or C1-C4 alkyl.
Further, the substituting group of described substituted-phenyl is selected from halogen or nitro, and substituting group quantity is 1 ~ 3.
Further, described halogen is selected from F, Cl or Br.
Further, substituting group quantity is 1 or 2.
Further, described C1-C4 alkyl is selected from methyl or ethyl.
Further, concrete operation step is as follows:
Get Rac-3 and add aldehyde 4, dimethyl dried meat ammonia alcohol silicon ether IIa and Glacial acetic acid, reaction is at room temperature carried out, and with TLC monitoring to reacting end, concentrated and silica gel column chromatography (PE/EA=10:1) is successively separated and obtains MBH product (S)-3 and chirality tetrahydropyrans alcohol product 5.
Further, the preparation method of Rac-3 is:
Wherein, the concrete operation step of Rac-3 preparation method is as follows:
Nitroolefin 1 and carbonyl compound 2 are under DMAP exists, and make solvent with MeCN, stirring at room temperature obtains MBH adduct rac-3.
MBH and Belize-Harry Hillman reaction.
Further, nitroolefin shown in formula 1: carbonyl compound shown in formula 2: DMAP: aldehyde shown in formula 4: catalyzer: Glacial acetic acid=0.5-1.0mmol:1.0mmol:0.05-0.2mmol:1.0-2.0mmol:0.1-0.3mmol: 0.1-0.2mmol.
Preferably, nitroolefin shown in formula 1: carbonyl compound shown in formula 2: DMAP: aldehyde shown in formula 4: catalyzer: Glacial acetic acid=0.5mmol:1.0mmol:0.05mmol:1.0mmol:0.1mmol:0.1mmol.
Method for splitting of the present invention, easy and simple to handle, without the need to using the intermediate possessing optical siomerism to react especially, just can split simply and effectively and obtain (S)-3 chipal compounds, the chiral separation for related compound provides new selection.
Below by way of embodiment, the present invention is described in further detail, but do not limit the present invention, those skilled in the art can make various change and distortion according to the present invention, only otherwise depart from spirit of the present invention, all should belong to the scope of claims of the present invention.
Embodiment
Embodiment 1 method for splitting of the present invention
Nitroolefin 1 (0.5mmol) and the activated carbonyl compound 2 (1.0mmol) of tool are under the existence of DMAP (6.1mg, 0.05mmol), and make solvent with MeCN, stirring at room temperature 30min obtains MBH adduct rac-3.Then one kettle way adds aldehyde 4 (1.0mmol), dimethyl dried meat ammonia alcohol silicon ether IIa (32.5mg, 0.1mmol) and Glacial acetic acid (6.0mg, 0.1mmol).Reaction is at room temperature carried out, and monitors reaction process with TLC.Concentrated and silica gel column chromatography (PE/EA=10:1) is successively separated and obtains MBH product (S)-3 and chirality tetrahydropyrans alcohol product 5.
The each particular compound split is as follows:
hydrogen is composed
1hNMR (400MHz, CDCl
3): δ=7.38-7.29 (m, 3H), 7.19 (d, J=7.6Hz, 2H), 5.35 (d, J=4.8Hz, 1H), 5.18 (dd, J=9.6Hz, J=6.0Hz, 1H), 5.07 (d, J=5.6Hz, 1H), 4.26-4.20 (m, 2H), 4.03 (brs, 1H), 3.16 (t, J=11.6Hz, 1H), 1.97-1.94 (m, 1H), (1.24 t, J=7.2Hz, 3H), 0.86 (d, J=6.4Hz, 3H) ppm; Carbon is composed
13cNMR (100MHz, CDCl
3): δ=167.95,137.63,129.11,128.07,128.00,98.15,89.72,69.35,62.29,48.19,39.32,15.50,13.85ppm; ESIHRMS: calculated value C
15h
19nO
6+ Na332.1110, measured value 332.1112.
mL/min), UV254nm, t
minor=13.97min, t
major=17.28min. optically-active: [α]
d 20+ 108.4 (c=0.21inCH
2cl
2).
hydrogen is composed
1hNMR (400MHz, CDCl
3): δ=7.41 (d, J=7.6Hz, 1H), 7.31-7.19 (m, 3H), 5.30 (brs, 2H), 5.10 (d, J=4.8Hz, 1H), 4.34 (brs, 1H), 4.30-4.23 (m, 2H), 2.12-2.05 (m, 1H), (1.25 t, J=6.8Hz, 3H), 0.88 (d, J=6.4Hz, 3H) ppm; Carbon is composed
13cNMR (100MHz, CDCl
3): δ=167.89,130.43,130.26,129.13,128.32,127.67,127.40,98.39,95.33,83.64,69.98,68.89,62.38,15.08,13.88ppm; ESIHRMS:calcd.ForC
15h
18clNO
6+ Na366.0720, measured value 366.0716.
(S)-3b: spectral data is consistent with racemic product 3b.Yield: 39% (55.7mg). high performance liquid phase CelluCoat post measures ee value 98% (5%2-propanol/n-hexane, 1mL/min), UV220nm, t
minor=13.24min, t
major=14.23min. optically-active: [α]
d 20+ 86.2 (c=0.11inCH
2cl
2).
hydrogen is composed
1hNMR (400MHz, CDCl
3): δ=7.31-7.29 (m, 2H), 7.20 (s, 1H), 7.10-7.08 (m, 1H), 5.34 (dd, J=7.6Hz, J=4.4Hz, 1H), 5.13 (dd, J=10.4Hz, J=6.0Hz, 1H), 5.04 (d, J=5.6Hz, 1H), 4.28-4.21 (m, 2H), 3.46 (d, J=4.0Hz, 1H), 3.21-3.15 (m, 1H), 1.95-1.85 (m, 1H), (1.26 t, J=7.2Hz, 3H), 0.87 (d, J=6.4Hz, 3H) ppm; Carbon is composed
13cNMR (100MHz, CDCl
3): δ=167.64,139.71,135.02,130.40,128.41,128.09,126.32,97.82,88.98,69.60,62.34,47.65,39.49,15.36,13.87ppm; High resolution mass spectrum ESIHRMS: calculated value C
15h
18clNO
6+ Na366.0720, measured value 366.0723.
2-propanol/n-hexane, 1mL/min), UV220nm, t
minor=10.13min, t
major=19.33min. optically-active: [α]
d 20+ 97.6 (c=0.15inCH
2cl
2).
-86.2 (c=0.15inCH
2cl
2); Hydrogen is composed
1hNMR (400MHz, CDCl
3): δ=7.35 (d, J=8.0Hz, 2H), 7.14 (d, J=7.6Hz, 2H), 5.33 (d, J=6.8Hz, 1H), 5.13 (dd, J=10.0Hz, J=6.0Hz, 1H), 5.06 (d, J=5.6Hz, 1H), 4.26-4.20 (m, 2H), 4.06 (brs, 1H), 3.15 (t, J=11.2Hz, 1H), 1.95-1.89 (m, 1H), (1.24 t, J=7.2Hz, 3H), 0.85 (d, J=6.4Hz, 3H) ppm; Carbon is composed
13cNMR (100MHz, CDCl
3): δ=166.80,135.12,132.96,128.34,128.31,96.94,88.37,68.25,61.35,46.58,38.26,14.41,12.82ppm; High resolution mass spectrum ESIHRMS: calculated value C
15h
18clNO
6+ Na366.0720, measured value 366.0723.
(S)-3d: spectral data is consistent with racemic product 3d. yield: 38% (54.3mg). high performance liquid phase AD-H post measures ee value 98% (10%2-propanol/n-hexane, 1mL/min), UV220nm, t
minor=16.01min, t
major=30.78min. optically-active: [α]
d 20+ 82.4 (c=0.12inCH
2cl
2).
-65.4 (c=0.08inCH
2cl
2); Hydrogen is composed
1hNMR (400MHz, CDCl
3): δ=7.44 (s, 1H), 7.31-7.21 (m, 2H), 5.28 (brs, 2H), 5.07 (d, J=4.4Hz, 1H), 4.32-4.23 (m, 2H), 4.09 (brs, 1H), 3.92-3.80 (m, 1H), 2.05 (brs, 1H), 1.25 (t, J=7.2Hz, 3H), 0.87 (d, J=6.4Hz, 3H) ppm; Carbon is composed
13cNMR (100MHz, CDCl
3): δ=167.68,134.37,130.25,130.08,128.07,127.74,127.67,98.19,95.18,83.25,69.86,69.01,62.44,14.99,13.88ppm; High resolution mass spectrum ESIHRMS:calcd.ForC
15h
17cl
2nO
6+ Na400.0331, measured value 400.0328.
optically-active: [α]
d 20+ 76.9 (c=0.21inCH
2cl
2).
-107.4 (c=0.10inCH
2cl
2); Hydrogen is composed
1hNMR (400MHz, CDCl
3): δ=7.45 (d, J=8.4Hz, 1H), 7.37 (s, 1H), 7.24-7.23 (m, 1H), 7.14 (d, J=7.6Hz, 1H), 5.32 (d, J=7.2Hz, 1H), 5.15 (dd, J=9.6Hz, J=5.6Hz, 1H), 5.07 (d, J=5.6Hz, 1H), 4.44 (brs, 1H), 4.25-4.20 (m, 2H), 3.14 (t, J=11.2Hz, 1H), 1.97-1.89 (m, 1H), 1.24 (t, J=7.2Hz, 3H), 0.87 (d, J=6.4Hz, 3H) ppm; Carbon is composed
13cNMR (100MHz, CDCl
3): δ=166.91,139.13,130.29,129.95,129.64,125.83,122.14,96.99,88.27,68.11,61.41,46.89,38.22,14.52,12.82ppm; High resolution mass spectrum ESIHRMS: calculated value C
15h
18brNO
6+ Na410.0215, measured value 410.0211.
(S)-3f: spectral data is consistent with racemic product 3f. yield: 41% (67.7mg). high performance liquid phase AD-H post measures ee value 90% (15%2-propanol/n-hexane, 1mL/min), UV220nm, t
minor=9.80min, t
major=18.88min. optically-active: [α]
d 20+ 65.8 (c=0.16inCH
2cl
2).
-82.4 (c=0.20inCH
2cl
2); Hydrogen is composed
1hNMR (400MHz, CDCl
3): δ=7.50 (d, J=7.6Hz, 2H), 7.08 (d, J=7.6Hz, 2H), 5.33 (d, J=4.0Hz, 1H), 5.12 (dd, J=9.6Hz, J=6.0Hz, 1H), 5.05 (d, J=5.2Hz, 1H), 4.25-4.21 (m, 2H), 4.08 (brs, 1H), 3.14 (t, J=11.2Hz, 1H), 1.95-1.88 (m, 1H), (1.24 t, J=7.2Hz, 3H), 0.85 (d, J=6.4Hz, 3H) ppm; Carbon is composed
13cNMR (100MHz, CDCl
3): δ=166.80,135.66,131.29,128.65,121.05,96.91,88.26,68.27,61.36,46.65,38.23,14.40,12.82ppm; High resolution mass spectrum ESIHRMS: calculated value C
15h
18brNO
6+ Na410.0215, measured value 410.0217.
min, t
major=32.45min. optically-active: [α]
d 20+ 87.2 (c=0.16inCH
2cl
2).
-93.2 (c=0.19inCH
2cl
2); Hydrogen is composed
1hNMR (400MHz, CDCl
3): δ=7.19-7.16 (m, 2H), 7.08-7.04 (m, 2H), 5.35-5.33 (m, 1H), 5.13 (dd, J=9.6Hz, J=6.0Hz, 1H), 5.06 (d, J=5.6Hz, 1H), 4.29-4.17 (m, 3H), 3.15 (t, J=11.2Hz, 1H), 1.96-1.90 (m, 1H), 1.24 (t, J=7.2Hz, 3H), 0.85 (d, J=6.4Hz, 3H) ppm; Carbon is composed
13cNMR (100MHz, CDCl
3): δ=167.93,162.36 (d, J
cF=246Hz), 133.38 (d, J
cF=3Hz), 129.59 (d, J
cF=8Hz), 116.14 (d, J
cF=21Hz), 98.08,89.76,69.19,62.38,47.57,39.35,15.49,13.84ppm; High resolution mass spectrum ESIHRMS: calculated value C
15h
18fNO
6+ Na350.1016, measured value 350.1011.
(S)-3h: spectral data is consistent with racemic product 3h. yield: 36% (48.5mg). high performance liquid phase AD-H post measures ee value 99% (15%2-propanol/n-hexane, 1mL/min), UV220nm, t
minor=12.73min, t
major=24.56min. optically-active: [α]
d 20+ 75.4 (c=0.20inCH
2cl
2).
hydrogen is composed
1hNMR (400MHz, CDCl
3): δ=7.89 (d, J=8.0Hz, 1H), 7.67 (t, J=7.6Hz, 1H), 7.51-7.47 (m, 2H), 5.35-5.21 (m, 2H), 5.12 (d, J=5.2Hz, 1H), 4.32-4.18 (m, 3H), 4.03 (brs, 1H), 2.08 (brs, 1H), 1.25 (t, J=7.2Hz, 3H), 0.85 (d, J=6.4Hz, 3H) ppm; Carbon is composed
13cNMR (100MHz, CDCl
3): δ=167.62,133.51,133.05,128.91,128.08,125.19,124.96,97.91,95.17,88.35,83.98,69.70,62.52,13.85,13.43ppm; High resolution mass spectrum ESIHRMS: calculated value C
15h
18n
2o
8+ H355.1141, measured value 355.1145.
t
major=34.45min. optically-active: [α]
d 20+ 91.6 (c=0.16inCH
2cl
2).
-102.6 (c=0.11inCH
2cl
2); Hydrogen is composed
1hNMR (400MHz, CDCl
3): δ=8.25 (d, J=8.4Hz, 2H), 7.42 (d, J=8.4Hz, 2H), 5.35 (dd, J=6.8Hz, J=4.4Hz, 1H), 5.18 (dd, J=10.0Hz, J=6.0Hz, 1H), 5.10 (d, J=5.6Hz, 1H), 4.31-4.19 (m, 2H), 3.80 (d, J=3.6Hz, 1H), 3.34 (t, J=11.2Hz, 1H), 2.01-1.95 (m, 1H), 1.26 (t, J=7.2Hz, 3H), 0.86 (d, J=6.4Hz, 3H) ppm; Carbon is composed
13cNMR (100MHz, CDCl
3): δ=167.58,147.73,145.19,129.08,124.39,97.64,88.44,69.45,62.51,47.80,39.45,15.31,13.86ppm; High resolution mass spectrum ESIHRMS: calculated value C
15h
18n
2o
8+ Na377.0961, measured value 377.0958.
min, t
major=24.45min. optically-active: [α]
d 20+ 65.8 (c=0.22inCH
2cl
2).
Claims (9)
1. (S)-3 method for splitting of compound as follows, is characterized in that: reaction path is as follows:
racemic modification;
R1 is selected from phenyl ring, substituted benzene ring or five yuan or hexa-member heterocycle, and R2 is selected from C1-C4 alkyl, and R3 is selected from H or C1-C4 alkyl.
2. method for splitting according to claim 1, is characterized in that: the substituting group of described substituted-phenyl is selected from halogen or nitro, and substituting group quantity is 1 ~ 3.
3. method for splitting according to claim 2, is characterized in that: described halogen is selected from F, Cl or Br.
4. method for splitting according to claim 2, is characterized in that: substituting group quantity is 1 or 2.
5. method for splitting according to claim 1, is characterized in that: described C1-C4 alkyl is selected from methyl or ethyl.
6. method for splitting according to claim 1, is characterized in that: concrete operation step is as follows:
Get Rac-3 and add aldehyde 4, dimethyl dried meat ammonia alcohol silicon ether IIa and Glacial acetic acid, reaction is at room temperature carried out, with TLC monitoring to reacting end, concentrated and through silica gel column chromatography, petrol ether/ethyl acetate=10:1 wash-out is separated and obtains MBH product (S)-3 and chirality tetrahydropyrans alcohol product 5.
7. method for splitting according to claim 1, is characterized in that: the preparation method of Rac-3 is:
Nitroolefin 1 and carbonyl compound 2 are under DMAP exists, and make solvent with MeCN, stirring at room temperature obtains MBH adduct Rac-3.
8. method for splitting according to claim 7, is characterized in that: nitroolefin shown in formula 1: carbonyl compound shown in formula 2: DMAP: aldehyde shown in formula 4: catalyzer: Glacial acetic acid=0.5-1.0mmol:1.0mmol:0.05-0.2mmol:1.0-2.0mmol:0.1-0.3mmol: 0.1-0.2mmol.
9. method for splitting according to claim 8, is characterized in that: nitroolefin shown in formula 1: carbonyl compound shown in formula 2: DMAP: aldehyde shown in formula 4: catalyzer: Glacial acetic acid=0.5mmol:1.0mmol:0.05mmol:1.0mmol:0.1mmol:0.1mmol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410415353.8A CN105315159B (en) | 2014-06-26 | 2014-08-21 | A kind of method for splitting of compound |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410298812 | 2014-06-26 | ||
| CN2014102988129 | 2014-06-26 | ||
| CN201410415353.8A CN105315159B (en) | 2014-06-26 | 2014-08-21 | A kind of method for splitting of compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105315159A true CN105315159A (en) | 2016-02-10 |
| CN105315159B CN105315159B (en) | 2017-12-15 |
Family
ID=55243562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410415353.8A Expired - Fee Related CN105315159B (en) | 2014-06-26 | 2014-08-21 | A kind of method for splitting of compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105315159B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315248A (en) * | 2014-06-26 | 2016-02-10 | 成都中医药大学 | Tetrahydropyranol series chiral compound, synthesis method therefor and use of tetrahydropyranol series chiral compound |
-
2014
- 2014-08-21 CN CN201410415353.8A patent/CN105315159B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315248A (en) * | 2014-06-26 | 2016-02-10 | 成都中医药大学 | Tetrahydropyranol series chiral compound, synthesis method therefor and use of tetrahydropyranol series chiral compound |
Non-Patent Citations (4)
| Title |
|---|
| BIN TAN, ET AL.: "Organocatalytic Asymmetric Tandem Michael-Henry Reactions: A Highly Stereoselective Synthesis of Multifunctionalized Cyclohexanes with Two Quaternary Stereocenters", 《ORG. LETT.》 * |
| HAYATO ISHIKAWA等: "Asymmetric One-Pot Four-Component Coupling Reaction: Synthesis of Substituted Tetrahydropyrans Catalyzed by Diphenylprolinol Silyl Ether", 《ANGEW. CHEM.》 * |
| XIANG LI, ET AL.: "Organocatalytic tandem Morita–Baylis–Hillman–Michael reaction for asymmetric synthesis of a drug-like oxa-spirocyclic indanone scaffold", 《CHEM. COMMUN.》 * |
| XIN XIE, ET AL.: "Asymmetric synthesis of a structurally and stereochemically complex spirooxindole pyran scaffold through an organocatalytic multicomponent cascade reaction", 《CHEM. COMMUN.》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105315159B (en) | 2017-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9139859B2 (en) | Method for preparing (R)-praziquantel | |
| CN101613341B (en) | Synthetic method of key intermediate of rosuvastatin calcium side chain | |
| Wardrop et al. | π-Face selective azaspirocyclization of ω-(methoxyphenyl)-N-methoxyalkylamides | |
| CN107129462B (en) | Total synthesis of natural product (+/-) -achillea base G and resolution method of enantiomer | |
| Nascimento et al. | Stereoselective synthesis of 8, 9-licarinediols | |
| Liu et al. | Copper-catalysed enantioselective intramolecular etherification of propargylic esters: synthetic approach to chiral isochromans | |
| Dzieszkowski et al. | NHC-catalyzed enantioselective C2-functionalization of 3-hydroxychromenones via α, β-unsaturated acyl azoliums | |
| CN101274915B (en) | Method for synthesizing isoxazole | |
| CN113135840B (en) | Synthetic method of conjugated alkenyl amidine compound | |
| CN103012241B (en) | Polysubstitution indole, synthesis method for same and synthesis application of polysubstitution indole to indomethacin | |
| CN105837494A (en) | Difluoroalky lindolone derivative and preparation method thereof | |
| CN111072605B (en) | Preparation method of fluoroalkyl-substituted benzofuran derivative or indole derivative | |
| CN105646327A (en) | 2-perfluoroalkyl indole derivative and synthesis method thereof | |
| CN102249976A (en) | Preparation method of optically pure (-)-clausenamide compound | |
| CN105315159A (en) | Resolution method for compounds | |
| CN106588807A (en) | Olefin compound containing gem-difluoro-methylene and preparing method thereof | |
| CN108164461B (en) | Total synthesis of natural product (+/-) -ylacrine and resolution method of enantiomer | |
| Maezaki et al. | 1, 5-Benzodithiepan-3-one 1, 5-dioxide: A novel chiral auxiliary for asymmetric desymmetrization of meso-1, 2-diols | |
| CN102344431A (en) | Method for preparing nebivolol hydrochloride | |
| CN114014802B (en) | Method for synthesizing enamide by dehydrogenation coupling of palladium catalyst | |
| EP3196189A1 (en) | Method for producing 2-amino-substituted benzaldehyde compound | |
| Forsyth et al. | Total synthesis of (+)-didemnenones A and B. Absolute configurations of the didemnenones | |
| CN103965059A (en) | Method for preparation of (1R,2S)-2-(3,4-difluorophenyl)cyclopropylamine | |
| CN108299369B (en) | Coumarin-4-sulfonic acid ester derivative and preparation method thereof | |
| Snetkov et al. | Methyl 3-(Bromomethyl) but-3-enoate and Methyl 3-[(Tributylstannyl) methyl] but-3-enoate in Azomethine Allylation Reactions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171215 Termination date: 20200821 |