CN109824725A - A kind of preparation method of 4- phosphate -2H- chromene derivative - Google Patents
A kind of preparation method of 4- phosphate -2H- chromene derivative Download PDFInfo
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- CN109824725A CN109824725A CN201910179347.XA CN201910179347A CN109824725A CN 109824725 A CN109824725 A CN 109824725A CN 201910179347 A CN201910179347 A CN 201910179347A CN 109824725 A CN109824725 A CN 109824725A
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- chromene derivative
- chromene
- ethyl acetate
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- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000010452 phosphate Substances 0.000 claims abstract description 12
- 150000008371 chromenes Chemical class 0.000 claims abstract description 10
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical group OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000000746 purification Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000010898 silica gel chromatography Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 4
- 239000000243 solution Substances 0.000 claims 2
- 239000012267 brine Substances 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000035484 reaction time Effects 0.000 abstract description 4
- 235000021317 phosphate Nutrition 0.000 abstract 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 3
- -1 ester compound Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HDFFVHSMHLDSLO-UHFFFAOYSA-N Dibenzyl phosphate Chemical compound C=1C=CC=CC=1COP(=O)(O)OCC1=CC=CC=C1 HDFFVHSMHLDSLO-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QZHPTGXQGDFGEN-UHFFFAOYSA-N chromene Chemical compound C1=CC=C2C=C[CH]OC2=C1 QZHPTGXQGDFGEN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Abstract
The invention discloses a kind of 4- phosphates -2HThe preparation method of chromene derivative, the method is using adjacent propargyl alcohol phenol as raw material, it is sufficiently dissolved in organic solvent is added under room temperature, it is then added and contains P (O)-OH class compound, it is reacted 3-6 hours at 80 DEG C, after reaction, reaction product obtains 4- phosphate -2 through silica gel column chromatography separating purificationHChromene derivative.The present invention has the characteristics that raw material is simple and easy to get, reaction condition is mild, easy to operate, the reaction time is short, pollution is few, is a kind of chemical synthesis process of preferable popularization and application foreground.
Description
Technical field
The invention belongs to technical field of organic synthesis, are related to a kind of 4- phosphate -2HThe preparation method of chromene derivative.
Background technique
Organophosphorus ester compound is a kind of very important organic compound and organic intermediate in organic synthesis
Building block, such compound have good catalytic activity, optical activity and bioactivity, so that it is in biology, optical activity material
The fields such as material and medicine have a wide range of applications.Meanwhile organic phosphorus compound is in life entity and indispensable, such as human body
Interior ADP, ATP, RNA and organic phospholipid bilayer etc..But it is difficult to find pure natural organophosphorus ester in nature
Class compound, and P elements are present in nature in the form of inorganic salts mostly, current known organophosphorus ester
Class compound is synthesized by chemical means mostly.
In addition, 2HChromene framework compound is a kind of very important compound, has certain pharmacological properties, is mesh
The important intermediate of preceding synthesis many native compounds and pharmaceutical activity molecule, while also having certain health-care effect.Therefore, right
2HThe functional group of chromene framework compound is combined to have very important application prospect and theoretical direction, by organic synthesis
The concern of family.Although 4- function dough 2 of building at presentHThe method of chromene derivative has very much, but for constructing 4- phosphoric acid
Ester -2HUp to the present the document of chromene derivative has not yet to see report.
Based on organophosphorus ester compound and 2HChromene analog derivative is in organic synthesis, pharmaceutical chemistry and material science
The extensive use in equal fields, develop a kind of atom economy, efficiently, the synthetic strategy of green be built into 4- phosphate -2HChromene
Derivative is particularly important.
Summary of the invention
That it is an object of the invention to provide a kind of reagents is cheap and easy to get, reaction condition is mild, technological operation is simple, reaction when
Between short, the few 4- phosphate -2 of pollutionHThe preparation method of chromene derivative.
A kind of 4- phosphate -2 of the inventionHThe preparation method of chromene derivative, with adjacent propargyl alcohol phenol () it is raw material,
It is sufficiently dissolved in organic solvent is added under room temperature, is then added and contains P (O)-OH class compound, it is small that 3-6 is reacted at 80 DEG C
When, after reaction, reaction product through silica gel column chromatography separating purification obtain as formula () shown in 4- phosphate -2HChromene spreads out
Biology；
(),(),
Wherein formula () or formula () in R1~R4Respectively stand alone as H, CH3, X(F, Cl, Br), OCH3In any one；R5With
R6Respectively stand alone as aryl, alkoxy, aryloxy group, any one in alkyl；Ar1With Ar2It is the virtue that different substituents replace
Base.
The reaction equation of the reaction is as follows:
,
Wherein, the quality of the organic solvent is 10-30 times of adjacent propargyl alcohol oxybenzene compound quality, the organic solvent
For any one in 1,2- dichloroethanes, 1,2- methylene chloride, tetrahydrofuran, dioxane, acetonitrile, nitromethane.
In the present invention, recommending the ratio between the adjacent propargyl alcohol phenol, amount of substance containing P (O)-OH class compound is 1:
1.5 ~ 2.5, preferably 1:2.0.
In reaction process of the present invention with TCL track the extent of reaction time, recommend the reaction time be 4-8 hours, preferably 8
Hour.
The reaction temperature that the method is controlled in the present invention is 60 ~ 80 DEG C, preferably 80 DEG C.
Heretofore described method carries out in accordance with the following steps: by adjacent propargyl alcohol phenol () be dissolved at room temperature
In organic solvent, then plus contains P (O)-OH class compound, 3 ~ 6 hours, after reaction, reaction product point are reacted at 80 DEG C
4- phosphate -2 is obtained from purifyingHChromene derivative.
Following steps can be used in heretofore described isolating and purifying: unsaturated carbonate hydracid sodium solution is added in reaction solution,
Ethyl acetate is added, rear stratification is sufficiently stirred；The aqueous layer with ethyl acetate extraction separated, by the extract of ethyl acetate
It is dry with saturated common salt water washing, anhydrous sodium sulfate respectively after merging with the organic layer separated；Ethyl acetate solvent is evaporated off, thereafter
4- phosphate -2 is obtained through silica gel column chromatography separating purificationHChromene derivative.
Compared with prior art, the present invention its advantages are embodied in: 1, providing the new synthetic strategy of one kind to construct；2,
Reaction of the invention is not necessarily to catalyst, mild condition；3, the method for the present invention is easy to operate, substrate applicability is also wide, can obtain not
With substituent group 4- phosphate -2HChromene derivative；4, raw material of the present invention is simple and easy to get, and the reaction time is short, pollution is few.
Specific embodiment
Embodiment 1: diphenyl-(2,2- diphenyl -2HChromene -4- base)-phosphinate preparation
,
Representative implementation process: at room temperature, adjacent propargyl alcohol phenol is successively added into reaction flask- 1 (300 mg, 1
Mmol) and 5 ml dry 1,2- dichloroethanes, and then diphenylphosphoric acid (436 mg, 2 mmol) is added in reaction flask,
Then reaction is placed at 80 DEG C and is reacted 3 hours.After reaction unsaturated carbonate is added in reaction solution by TLC tracking extent of reaction
Hydrogen sodium solution, adds ethyl acetate, and rear stratification is sufficiently stirred；The aqueous layer with ethyl acetate extraction separated, by acetic acid second
The extract of ester is dry with saturated common salt water washing, anhydrous sodium sulfate respectively after merging with the organic layer separated；Acetic acid second is evaporated off
Ester solvent, after through silica gel column chromatography separating purification obtain diphenyl-(2,2- diphenyl -2HChromene -4- base)-phosphinate
410 mg, reaction yield 82%.1H NMR (400 MHz, CDCl3): δ 6.13 (d, J = 1.2 Hz, 1 H), 6.90
– 6.93 (m, 3 H), 7.09 – 7.21 (m, 11 H), 7.43 – 7.53 (m, 5 H), 7.55 – 7.61 (m,
2 H), 7.90 – 7.95 (m, 4 H). 13C NMR (100 MHz, CDCl3): δ 83.9, 111.9, 112.0,
116.7, 118.3, 118.4, 121.1, 121.8, 126.9, 127.5, 127.9, 128.7, 128.9, 129.8,
130.7, 131.1, 131.7, 131.8, 132.6, 132.7, 142.2, 142.3, 144.4, 153.6. 31P NMR
(160 MHz, CDCl3): δ 31.3. HRMS (ESI, m/z): calcd for C33H25O3P: [M+H]+ =
501.1614; found: 501.1616。
Embodiment 2: dibenzyl-(2,2- diphenyl -2HChromene -4- base) phosphate preparation
,
At room temperature, adjacent propargyl alcohol phenol is successively added into reaction flaskThe dry 1,2- of -2 (300 mg, 1 mmol) and 5 ml
Phosphate dibenzyl ester (556 mg, 2 mmol) is then added in reaction flask, then reaction is placed at 80 DEG C by dichloroethanes
Reaction 3 hours, TLC track extent of reaction.Purification procedures obtain diphenyl-(2,2- diphenyl -2 with embodiment 1HColor
Alkene -4- base) 476 mg of phosphate, reaction yield 85%.1H NMR (400 MHz, CDCl3): δ 5.11 (s, 2 H),
5.13 (s, 2 H), 6.06 (s, 1 H), 6.82 (t, J = 7.6 Hz, 1 H), 6.92 (d, J = 8.0 Hz,
1 H), 7.15 – 7.29 (m, 17 H), 7.35 – 7.37 (m, 5 H). 13C NMR (100 MHz, CDCl3): δ
70.1, 83.8, 111.6, 111.7, 116.5, 117.8, 117.9, 121.0, 121.9, 126.9, 127.6,
128.0, 128.1, 128.6, 128.7, 130.7, 135.1, 135.2, 141.8, 141.9, 144.5, 153.4.31P NMR (160 MHz, CDCl3): δ -6.1. HRMS (ESI, m/z): calcd for C35H29O5P: [M+H]+ =
561.1825; found: 561.1825。
Embodiment 3: diphenyl-(2,2- bis- (p-methylphenyl) -2HChromene -4- base)-phosphinate preparation
,
At room temperature, adjacent propargyl alcohol phenol is successively added into reaction flaskThe dry 1,2- of -3 (328 mg, 1 mmol) and 5 ml
Diphenylphosphoric acid (436 mg, 2 mmol) is then added in reaction flask, then reaction is placed at 80 DEG C by dichloroethanes
Reaction 4 hours, TLC track extent of reaction.Purification procedures are with embodiment 1, and obtaining diphenyl-, (2,2- bis- (to methylbenzene
Base) -2HChromene -4- base) 423 mg of-phosphinate, reaction yield 80%.1H NMR (400 MHz, CDCl3): δ 2.26
(s, 6 H), 6.10 (d, J = 1.2 Hz, 1 H), 6.86 – 6.90 (m, 2 H), 6.95 – 7.00 (m, 8
H), 7.14 – 7.18 (m, 1 H), 7.41 – 7.49 (m, 5 H), 7.55 – 7.59 (m, 2 H), 7.89 –
7.94 (m, 4 H). 13C NMR (100 MHz, CDCl3): δ 20.9, 83.8, 112.2, 112.3, 116.6,
118.3, 118.4, 120.9, 121.7, 126.8, 128.5, 128.6, 128.8, 129.9, 130.5, 131.2,
131.6, 131.7, 132.5, 132.6, 137.0, 141.6, 142.0, 142.1, 153.6. 31P NMR (160
MHz, CDCl3): δ 31.0. HRMS (ESI, m/z): calcd for C35H29O3P: [M+H]+ = 529.1927;
found: 529.1925。
Embodiment 4: diphenyl-(2,2- bis- (p-methoxyphenyl) -2HChromene -4- base)-phosphinate preparation
,
At room temperature, adjacent propargyl alcohol phenol is successively added into reaction flaskThe dry 1,2- of -4 (360 mg, 1 mmol) and 5 ml
Diphenylphosphoric acid (436 mg, 2 mmol) is then added in reaction flask, then reaction is placed at 80 DEG C by dichloroethanes
Reaction 3 hours, TLC track extent of reaction.Purification procedures are with embodiment 1, and obtaining diphenyl-, (2,2- bis- (to methoxyl group
Phenyl) -2HChromene -4- base) 364 mg of-phosphinate, reaction yield 65%.1H NMR (400 MHz, CDCl3): δ
3.74 (s, 6 H), 6.08 (d, J = 1.2 Hz, 1 H), 6.68 (d, J = 8.8 Hz, 4 H), 6.86 –
6.92 (m, 2 H), 7.01 (d, J = 8.8 Hz, 4 H), 7.15 – 7.19 (m, 1 H), 7.42 – 7.50
(m, 5 H), 7.56 – 7.60 (m, 2 H), 7.89 – 7.94 (m, 4 H). 13C NMR (100 MHz,
CDCl3): δ 55.1, 83.5, 112.4, 112.5, 113.1, 116.6, 118.3, 118.4, 120.9, 121.7,
128.2, 128.6, 128.8, 129.9, 130.5, 131.2, 131.6, 131.7, 132.5, 132.6, 136.8,
142.0, 142.1, 153.6, 158.7. 31P NMR (160 MHz, CDCl3): δ 31.1. HRMS (ESI, m/z):
calcd for C35H29O5P: [M+H]+ = 561.1825; found: 561.1824。
Claims (4)
1. a kind of 4- phosphate -2HThe synthetic method of chromene derivative, it is characterised in that: the method is with adjacent propargyl alcohol
Phenol () it is raw material, in organic solvent dissolution is added under room temperature, then it is added and contains P (O)-OH class compound, at 80 DEG C
Reaction 3-6 hours, after reaction, reaction product through silica gel column chromatography separating purification obtain as formula () shown in 4- phosphate-
2HChromene derivative；
(),(),
Wherein formula () and formula () in R1~R4Respectively stand alone as H, CH3, X(F, Cl, Br), OCH3In any one；R5With
R6Respectively stand alone as aryl, alkoxy, aryloxy group, any one in alkyl；Ar1With Ar2It is the virtue that different substituents replace
Base.
2. a kind of 4- phosphate -2 as described in claim 1HThe synthetic method of chromene derivative, it is characterised in that: the original
Expect the mass ratio of the material that feeds intake, adjacent propargyl alcohol phenol: being 1:1.5 ~ 2.5 containing P (O)-OH class compound.
3. a kind of 4- phosphate -2 as described in claim 1HThe synthetic method of chromene derivative, it is characterised in that: described
Organic solvent is 1,2- dichloroethanes, 1,2- methylene chloride, tetrahydrofuran, dioxane, acetonitrile, any one in nitromethane
Kind.
4. a kind of 4- phosphate -2 as described in claim 1HThe synthetic method of chromene derivative, it is characterised in that: described point
Method from purifying are as follows: unsaturated carbonate hydracid sodium solution is added in reaction solution, adds ethyl acetate, stands and divides after being sufficiently stirred
Layer；The aqueous layer with ethyl acetate extraction separated, respectively with saturation after the extract of ethyl acetate is merged with the organic layer separated
Brine It, anhydrous sodium sulfate are dry；Ethyl acetate solvent is evaporated off, after through silica gel column chromatography separating purification obtain 4- phosphoric acid
Ester -2HChromene derivative.
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| CN110526940A (en) * | 2019-08-19 | 2019-12-03 | 江西科技师范大学 | A kind of preparation method of 4- (2H- chromene)-thio phosphine (phosphorus) acid esters |
| CN110804069A (en) * | 2019-11-19 | 2020-02-18 | 江西科技师范大学 | Preparation method of thio-phosphine (phosphate) ester substituted allene compound |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110526940A (en) * | 2019-08-19 | 2019-12-03 | 江西科技师范大学 | A kind of preparation method of 4- (2H- chromene)-thio phosphine (phosphorus) acid esters |
| CN110804069A (en) * | 2019-11-19 | 2020-02-18 | 江西科技师范大学 | Preparation method of thio-phosphine (phosphate) ester substituted allene compound |
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