CN102424692A - Preparation method for 2-chloro-2-oxo-1,3,2-dioxaphospholane - Google Patents
Preparation method for 2-chloro-2-oxo-1,3,2-dioxaphospholane Download PDFInfo
- Publication number
- CN102424692A CN102424692A CN2011104224296A CN201110422429A CN102424692A CN 102424692 A CN102424692 A CN 102424692A CN 2011104224296 A CN2011104224296 A CN 2011104224296A CN 201110422429 A CN201110422429 A CN 201110422429A CN 102424692 A CN102424692 A CN 102424692A
- Authority
- CN
- China
- Prior art keywords
- chloro
- dioxaphospholane
- preparation
- organic solvent
- oxygen
- 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
Abstract
The invention relates to a preparation method for 2-chloro-2-oxo-1,3,2-dioxaphospholane, and belongs to the technical field of phosphorus-containing organic compound intermediate preparation. The method comprises the following steps: A) preparation of 2-chloro-1,3,2-dioxaphospholane: ethylene glycol reacts with phosphorus trichloride in an organic solvent system to generate 2-chloro-1,3,2-dioxaphospholane; B) preparation of 2-chloro-2-oxo-1,3,2-dioxaphospholane: the 2-chloro-1,3,2-dioxaphospholane is subjected to an oxidizing reaction in an organic solvent with dried ozone, then the organic solvent is removed, and the fraction is collected by vacuum rectification to obtain the 2-chloro-2-oxo-1,3,2-dioxaphospholane. The method has the following advantages that: the ozone is adopted during the preparation process of the target product 2-chloro-2-oxo-1,3,2-dioxaphospholane so as to substantially improve the oxidation capacity, such that the yield is 59-80%, and the method has the value of the industrialized enlarged production, wherein the resulting 2-chloro-1,3,2-dioxaphospholane from the step A) is subjected to the step B) to obtain the target product 2-chloro-2-oxo-1,3,2-dioxaphospholane.
Description
Technical field
The invention belongs to the preparing technical field of organic phosphorus compound midbody, be specifically related to a kind of 2-chloro-2-oxygen-1,3, the preparation method of 2-dioxaphospholane
Background technology
Chloro-2-oxygen-1,3, the English name of 2-dioxaphospholane is: 2-chloro-1,3,2-dioxaphospholane; English another name is: 2-oxide; 2-chloro-1,3,2-dioxaphospholane 2-oxide; Molecular formula is: C
2
H
4
CLO
3
P; Molecular weight is: 142.4781.2-chloro-2-oxygen-1,3,2-dioxaphospholane are the catalyzer of synthetic phosphorous heavy metal complex; It is the important source material of important intermediate, stereospecific reaction reagent and biomaterial etc. of the P contained compound of synthetic biologically active; It is the important source material of Yelkin TTS PC, LPC and GPC of important intermediate, especially biologically active of the phosphatide cpd of synthetic biologically active.
Preparation 2-chloro-2-oxygen-1,3 in the prior art, the method for 2-dioxaphospholane mainly contains following three kinds:
1) preparation method that in anhydrous organic solvent, reacts of terepthaloyl moietie and POCl3 (see Annales Pharmaceutiques Francaises, 38 (1), 65-74; 1980).
this method is owing to be difficult to control the terminal point of reaction when reaction; Therefore in the existence of the simultaneous side reaction of reaction; Mainly show as title product continuation and phosphorus oxychloride reaction generation polymerization macromolecule compound that reaction obtains, and be difficult to obtain target compound.
) reaction of terepthaloyl moietie and phosphorus trichloride obtains intermediate product, and the preparation method with oxygen reaction in toluene or other solvents (sees Nippon Kagaku kaishi, (12), 2335-7; 1985) and see " chemical research " 2004 the 3rd phases (2-chloro-2-oxygen-1,3,2-dioxaphospholane synthetic).
are though this method has been avoided product polymeric problem; But 2-chloro-1,3, oxidizing reaction takes place in 2-dioxa phosphorus pentamethylene and exsiccant oxygen in benzene or toluene solvant; Because of the oxidation capacity of oxygen more weak; In the gas-liquid two-phase reaction system, be difficult to complete reaction, cause yield low, be merely about 28%.
) preparation method under the heavy metal catalyst condition of terepthaloyl moietie and phosphoric acid (see Advan.Org.Chem, 3,75-157; 1963)
But though used precious metal silver to make catalyzer in the fairly simple reaction process of this method, cause cost, so can not satisfy need of industrial production than higher
Summary of the invention
task of the present invention is to the 2-chloro-2-oxygen-1 in the prior art; 3; The defective that the synthetic route of 2-dioxaphospholane and technology exist; Particularly easy polymeric unstable of terepthaloyl moietie and phosphorus oxychloride reaction product and terepthaloyl moietie and phosphorus trichloride prepare under the heavy metal catalyst condition with defectives such as the reaction yield of oxygen reaction is low and terepthaloyl moietie and phosphoric acid and are not suitable for the drawback of industrial amplification production and provide a kind of and help to improve oxidation capacity and use and improve yield to satisfy the 2-chloro-2-oxygen-1 that industrial amplification production requires; 3, the preparation method of 2-dioxaphospholane.
Task of the present invention is accomplished like this, a kind of 2-chloro-2-oxygen-1,3, and the preparation method of 2-dioxaphospholane may further comprise the steps:
A) preparation 2-chloro-1,3, the 2-dioxaphospholane:
Terepthaloyl moietie and phosphorus trichloride are reacted in organic solvent system, obtain 2-chloro-1,3, the 2-dioxaphospholane;
B) preparation 2-chloro-2-oxygen-1,3, the 2-dioxaphospholane:
with 2-chloro-1,3, the 2-dioxaphospholane through exsiccant ozone generation oxidizing reaction, is removed organic solvent in organic solvent, and cut is collected in rectification under vacuum, obtains 2-chloro-2-oxygen-1,3, the 2-dioxaphospholane.
in a concrete embodiment of the present invention, steps A) described in terepthaloyl moietie, the mol ratio of phosphorus trichloride be 1:1 ~ 5.
in another concrete embodiment of the present invention, steps A) described in organic solvent be halohydrocarbon organic solvent or fragrant same clan organic solvent.
in another concrete embodiment of the present invention, described halohydrocarbon organic solvent is chloroform or ethylene dichloride; Described aromatic hydrocarbon based organic solvent is toluene or YLENE.
in another concrete embodiment of the present invention, steps A) described in the temperature of reaction of in organic solvent system, reacting be-20-20 ℃, the reaction times is 1-6h.
also have among the concrete embodiment step B of the present invention) described in 2-chloro-1,3, the 2-dioxaphospholane is 1 with the mol ratio of described ozone: 2-4.
more of the present invention and among concrete embodiment, step B) described in the temperature of reaction of oxidizing reaction be-5~40 ℃.
in of the present invention and then concrete embodiment, step B) described in the organic solvent of removing be under reduced pressure, to remove organic solvent.
of the present invention again more and among concrete embodiment, step B) described in the flow of ozone be 200-500ml/min.
in again of the present invention and then concrete embodiment, described ozone is the ozone by the ozonizer preparation.
technical scheme provided by the invention is because with steps A) the 2-chloro-1 that obtains; 3, the 2-dioxaphospholane is through step B) preparation title product 2-chloro-2-oxygen-1,3; Adopted ozone in the process of 2-dioxaphospholane; Thereby improved oxidation capacity unexpectedly, made yield reach 59-80%, thereby possessed the value of industrial amplification production.
Embodiment
Embodiment below
only is the applicant's a preferred example; Thereby can not be interpreted as restriction to the present invention program; For example; The applicant is in the above to steps A) in organic solvent mentioned that halohydrocarbon makes organic solvent and given an example to belong to the chloroform and the ethylene dichloride of this halohydrocarbon organic solvent category, but do not show that other the organic solvent that belongs to halohydrocarbon of not giving an example can not be suitable for.Based on same reason, aromatic hydrocarbon based organic solvent is not limited to toluene and the YLENE lifted.
Embodiment 1:
A) preparation midbody 2-chloro-1,3, the 2-dioxaphospholane
add the phosphorus trichloride of 0.5mol in the four-hole boiling flask of exsiccant 500ml; The 100ml chloroform cools to-10 ℃, drips the terepthaloyl moietie of 0.5mol and the chloroformic solution of 100ml; Dropwise temperature and be warmed up to room temperature; Kept 3 hours, chloroform is removed in underpressure distillation, collects the fraction of 60 ℃/20mmHg.Obtain 2-chloro-1,3,2-dioxaphospholane 44.0g, yield 69.8%.1H-NMR(ppm)δ:4.45(m,2H,a-CHCH-),4.24(m,2H,E-CHCH-);
B) preparation 2-chloro-2-oxygen-1,3, the 2-dioxaphospholane
add 100ml toluene, the 2-chloro-1,3 that 25.3g (0.2mol) is above-mentioned in the four-hole boiling flask of exsiccant 500ml; The 2-dioxaphospholane under 30 ℃ of conditions, feeds the exsiccant ozone that is produced by producer gas generator at leisure; Flow is about 250ml/min, controlled temperature, and the time is approximately 2 hours; Be warmed up to backflow then, this temperature condition reacted 1 hour down again.Cooling, organic solvent is removed in underpressure distillation, collects the fraction of 90 ℃/1mmHg at last, obtains 2-chloro-2-oxo-1,3,2-dioxaphospholane 22.9g, yield 80.0%.
δ:4.45(m,2H,a-CHCH-),4.56(m,2H,E-CHCH-)。
Embodiment 2:
A) preparation midbody 2-chloro-1,3, the 2-dioxaphospholane
add the phosphorus trichloride of 2.5mol in the four-hole boiling flask of exsiccant 500ml; 200ml ethylene dichloride, controlled temperature are about 15 ℃, drip the terepthaloyl moietie of 0.5mol and the dichloroethane solution of 200ml; Dropwise temperature and be warmed up to room temperature; Kept 3 hours, ethylene dichloride is gone out in underpressure distillation, collects the fraction of 60 ℃/20mmHg.Obtain 2-chloro-1,3,2-dioxaphospholane 40.0g, yield 63.5%;
B) preparation 2-chloro-2-oxygen-1,3, the 2-dioxaphospholane
add 100ml chloroform, the 2-chloro-1,3 that 25.3g (0.2mol) is above-mentioned in the four-hole boiling flask of exsiccant 500ml; The 2-dioxaphospholane cools under 0 ℃ of condition, feeds the exsiccant ozone that is produced by producer gas generator at leisure; Flow is about 450ml/min, controlled temperature, and the time is approximately 5 hours; Be warmed up to backflow then, this temperature condition reacted 1 hour down again.Cooling, organic solvent is removed in underpressure distillation, collects the fraction of 90 ℃/1mmHg at last, obtains 2-chloro-2-oxo-1,3,2-dioxaphospholane 20.3g, yield 70.9%.
Embodiment 3:
A) preparation midbody 2-chloro-1,3, the 2-dioxaphospholane
In the four-hole boiling flask of exsiccant 500ml, add the phosphorus trichloride of 1.0mol, 160ml toluene, controlled temperature are about 0 ℃; Drip the terepthaloyl moietie of 0.5mol and the toluene solution of 160ml, dropwise temperature and be warmed up to room temperature, kept 3 hours; Toluene is gone out in underpressure distillation, collects the fraction of 60 ℃/20mmHg, obtains 2-chloro-1; 3,2-dioxaphospholane 37.2g, yield 59.0%;
B) preparation 2-chloro-2-oxygen-1,3, the 2-dioxaphospholane
add 100ml toluene, the 2-chloro-1,3 that 25.3g (0.2mol) is above-mentioned in the four-hole boiling flask of exsiccant 500ml; 2-dioxaphospholane, temperature are controlled under 20 ℃ of conditions, feed the exsiccant ozone that is produced by producer gas generator at leisure; Flow is about 250ml/min, controlled temperature, and the time is approximately 3 hours; Be warmed up to backflow then, this temperature condition reacted 1 hour down again.Cooling, organic solvent is removed in underpressure distillation, collects the fraction of 90 ℃/1mmHg at last, obtains 2-chloro-2-oxo-1,3,2-dioxaphospholane 21.6g, yield 75.5%.
Embodiment 4:
A) preparation midbody 2-chloro-1,3, the 2-dioxaphospholane
add the phosphorus trichloride of 2.0mol in the four-hole boiling flask of exsiccant 500ml; 120ml YLENE, controlled temperature are about 10 ℃, drip the terepthaloyl moietie of 0.5mol and the xylene solution of 120ml; Dropwise temperature and be warmed up to room temperature; Kept 3 hours, underpressure distillation goes out removal xylene, collects the fraction of 60 ℃/20mmHg.Obtain 2-chloro-1,3,2-dioxaphospholane 42.7g, yield 67.7%;
B) preparation 2-chloro-2-oxygen-1,3, the 2-dioxaphospholane
add 100ml YLENE, the 2-chloro-1,3 that 25.3g (0.2mol) is above-mentioned in the four-hole boiling flask of exsiccant 500ml; The 2-dioxaphospholane cools under-5 ℃ of conditions, feeds the exsiccant ozone that is produced by producer gas generator at leisure; Flow is about 300ml/min, controlled temperature, and the time is approximately 1 hour; Be warmed up to backflow then, this temperature condition reacted 1 hour down again.Cooling, organic solvent is removed in underpressure distillation, collects the fraction of 90 ℃/1mmHg at last, obtains 2-chloro-2-oxo-1,3,2-dioxaphospholane 16.9g, yield 59.1%.
Embodiment 5:
A) preparation midbody 2-chloro-1,3, the 2-dioxaphospholane
add the phosphorus trichloride of 0.5mol in the four-hole boiling flask of exsiccant 500ml; 100ml ethylene dichloride, controlled temperature are about-20 ℃, drip the terepthaloyl moietie of 0.5mol and the dichloroethane solution of 100ml; Dropwise temperature and be warmed up to room temperature; Kept 3 hours, ethylene dichloride is gone out in underpressure distillation, collects the fraction of 60 ℃/20mmHg.Obtain 2-chloro-1,3,2-dioxaphospholane 38.9g, yield 61.7%;
B) preparation 2-chloro-2-oxygen-1,3, the 2-dioxaphospholane
add 100ml chloroform, the 2-chloro-1,3 that 25.3g (0.2mol) is above-mentioned in the four-hole boiling flask of exsiccant 500ml; The 2-dioxaphospholane cools under-5 ℃ of conditions, feeds the exsiccant ozone that is produced by producer gas generator at leisure; Flow is about 200ml/min, controlled temperature, and the time is approximately 6 hours; Be warmed up to backflow then, this temperature condition reacted 1 hour down again.Cooling, organic solvent is removed in underpressure distillation, collects the fraction of 90 ℃/1mmHg at last, obtains 2-chloro-2-oxo-1,3,2-dioxaphospholane 18.2g, yield 63.6%.
Embodiment 6:
A) preparation midbody 2-chloro-1,3, the 2-dioxaphospholane
add the phosphorus trichloride of 2.5mol in the four-hole boiling flask of exsiccant 500ml; 200ml chloroform, controlled temperature are about 20 ℃, drip the terepthaloyl moietie of 0.5mol and the chloroformic solution of 200ml; Dropwise temperature and be warmed up to room temperature; Kept 3 hours, chloroform is gone out in underpressure distillation, collects the fraction of 60 ℃/20mmHg.Obtain 2-chloro-1,3,2-dioxaphospholane 39.6g, yield 62.8%;
B) preparation 2-chloro-2-oxo-1,3, the 2-dioxaphospholane
add 100ml ethylene dichloride, the 2-chloro-1,3 that 25.3g (0.2mol) is above-mentioned in the four-hole boiling flask of exsiccant 500ml; The 2-dioxaphospholane cools under-5 ℃ of conditions, feeds the exsiccant ozone that is produced by producer gas generator at leisure; Flow is about 500ml/min, controlled temperature, and the time is approximately 1.5 hours; Be warmed up to backflow then, this temperature condition reacted 1 hour down again.Cooling, organic solvent is removed in underpressure distillation, collects the fraction of 90 ℃/1mmHg at last, obtains 2-chloro-2-oxo-1,3,2-dioxaphospholane 21.7g, yield 75.8%.
Embodiment 7:
A) preparation midbody 2-chloro-1,3, the 2-dioxaphospholane
add the phosphorus trichloride of 1.5mol in the four-hole boiling flask of exsiccant 500ml; 140ml toluene, controlled temperature are about 15 ℃, drip the terepthaloyl moietie of 0.5mol and the toluene solution of 140ml; Dropwise temperature and be warmed up to room temperature; Kept 3 hours, toluene is gone out in underpressure distillation, collects the fraction of 60 ℃/20mmHg.Obtain 2-chloro-1,3,2-dioxaphospholane 38.8g, yield 61.8%;
B) preparation 2-chloro-2-oxo-1,3, the 2-dioxaphospholane
add 100ml ethylene dichloride, the 2-chloro-1,3 that 25.3g (0.2mol) is above-mentioned in the four-hole boiling flask of exsiccant 500ml; 2-dioxaphospholane, temperature are controlled under 40 ℃ of conditions, feed the exsiccant ozone that is produced by producer gas generator at leisure; Flow is about 400ml/min, controlled temperature, and the time is approximately 2.5 hours; Be warmed up to backflow then, this temperature condition reacted 1 hour down again.Cooling, organic solvent is removed in underpressure distillation, collects the fraction of 90 ℃/1mmHg at last, obtains 2-chloro-2-oxo-1,3,2-dioxaphospholane 19.9g, yield 69.5%.
Embodiment 8:
A) preparation midbody 2-chloro-1,3, the 2-dioxaphospholane
add the phosphorus trichloride of 1mol in the four-hole boiling flask of exsiccant 500ml; 180ml chloroform, controlled temperature are about-15 ℃, drip the terepthaloyl moietie of 0.5mol and the chloroformic solution of 180ml; Dropwise temperature and be warmed up to room temperature; Kept 3 hours, chloroform is gone out in underpressure distillation, collects the fraction of 60 ℃/20mmHg.Obtain 2-chloro-1,3,2-dioxaphospholane 39.2g, yield 62.2%;
B) preparation 2-chloro-2-oxo-1,3, the 2-dioxaphospholane
add 300ml chloroform, the 2-chloro-1,3 that 25.3g (0.2mol) is above-mentioned in the four-hole boiling flask of exsiccant 500ml; 2-dioxaphospholane, temperature are controlled under 40 ℃ of conditions, feed the exsiccant ozone that is produced by producer gas generator at leisure; Flow is about 250ml/min, controlled temperature, and the time is approximately 2 hours; Be warmed up to backflow then, this temperature condition reacted 1 hour down again.Cooling, organic solvent is removed in underpressure distillation, collects the fraction of 90 ℃/1mmHg at last, obtains 2-chloro-2-oxo-1,3,2-dioxaphospholane 21.4g, yield 75.6%
Claims (10)
1.
A kind of 2-chloro-2-oxygen-1,3, the preparation method of 2-dioxaphospholane is characterized in that may further comprise the steps:
A) preparation 2-chloro-1,3, the 2-dioxaphospholane:
Terepthaloyl moietie and phosphorus trichloride are reacted in organic solvent system, obtain 2-chloro-1,3, the 2-dioxaphospholane;
B) preparation 2-chloro-2-oxygen-1,3, the 2-dioxaphospholane:
with 2-chloro-1,3, the 2-dioxaphospholane through exsiccant ozone generation oxidizing reaction, is removed organic solvent in organic solvent, and cut is collected in rectification under vacuum, obtains 2-chloro-2-oxygen-1,3, the 2-dioxaphospholane.
2.
2-chloro-2-oxygen-1,3 according to claim 1, the preparation method of 2-dioxaphospholane is characterized in that steps A) described in terepthaloyl moietie, the mol ratio of phosphorus trichloride be 1:1 ~ 5.
3.
2-chloro-2-oxygen-1,3 according to claim 1, the preparation method of 2-dioxaphospholane is characterized in that steps A) described in organic solvent be halohydrocarbon organic solvent or fragrant same clan organic solvent.
4.
2-chloro-2-oxygen-1,3 according to claim 3, the preparation method of 2-dioxaphospholane is characterized in that described halohydrocarbon organic solvent is chloroform or ethylene dichloride; Described aromatic hydrocarbon based organic solvent is toluene or YLENE.
5.
2-chloro-2-oxygen-1 according to claim 1; 3; The preparation method of 2-dioxaphospholane is characterized in that steps A) described in the temperature of reaction of in organic solvent system, reacting be-20-20 ℃, the reaction times is 1-6h.
6.
2-chloro-2-oxygen-1,3 according to claim 1, the preparation method of 2-dioxaphospholane is characterized in that step B) described in 2-chloro-1,3, the 2-dioxaphospholane is 1 with the mol ratio of described ozone: 2-4.
7.
2-chloro-2-oxygen-1,3 according to claim 1, the preparation method of 2-dioxaphospholane is characterized in that step B) described in the temperature of reaction of oxidizing reaction be-5~40 ℃.
8.
2-chloro-2-oxygen-1,3 according to claim 1, the preparation method of 2-dioxaphospholane is characterized in that step B) described in the organic solvent of removing be under reduced pressure, to remove organic solvent.
9.
2-chloro-2-oxygen-1,3 according to claim 1, the preparation method of 2-dioxaphospholane is characterized in that step B) described in the flow of ozone be 200-500ml/min.
10.
2-chloro-2-oxygen-1,3 according to claim 9, the preparation method of 2-dioxaphospholane is characterized in that described ozone is the ozone by the ozonizer preparation
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2011104224296A CN102424692B (en) | 2011-12-16 | 2011-12-16 | Preparation method for 2-chloro-2-oxo-1,3,2-dioxaphospholane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2011104224296A CN102424692B (en) | 2011-12-16 | 2011-12-16 | Preparation method for 2-chloro-2-oxo-1,3,2-dioxaphospholane |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102424692A true CN102424692A (en) | 2012-04-25 |
CN102424692B CN102424692B (en) | 2012-11-07 |
Family
ID=45958725
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2011104224296A Active CN102424692B (en) | 2011-12-16 | 2011-12-16 | Preparation method for 2-chloro-2-oxo-1,3,2-dioxaphospholane |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102424692B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104212432A (en) * | 2013-06-04 | 2014-12-17 | 中国石油化工股份有限公司 | Negative-positive double-ion surfactant and preparation method thereof |
CN106946936A (en) * | 2016-08-16 | 2017-07-14 | 南京构友生物材料有限公司 | The method that a kind of continuous flow reactor safe and efficient oxygen of 2 chlorine of oxidative synthesis 2 in utilization microchannel closes 1,3,2 dioxaphospholane |
CN107746462A (en) * | 2017-09-20 | 2018-03-02 | 中国科学技术大学 | Thio polyphosphate and its preparation method and application |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1978492A (en) * | 2006-11-24 | 2007-06-13 | 南京大学 | Polycaprolactone-polyethylene glycol block copolymer, and its preparing method and use |
CN101265304A (en) * | 2008-04-18 | 2008-09-17 | 中国药科大学 | Bionic chitosan derivatives, preparation method thereof and lipoid plastid preparation containing the same |
CN101732721A (en) * | 2009-01-15 | 2010-06-16 | 中国科学技术大学 | Biocompatibility nanoparticle and application thereof as drug conveying carrier |
-
2011
- 2011-12-16 CN CN2011104224296A patent/CN102424692B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1978492A (en) * | 2006-11-24 | 2007-06-13 | 南京大学 | Polycaprolactone-polyethylene glycol block copolymer, and its preparing method and use |
CN101265304A (en) * | 2008-04-18 | 2008-09-17 | 中国药科大学 | Bionic chitosan derivatives, preparation method thereof and lipoid plastid preparation containing the same |
CN101732721A (en) * | 2009-01-15 | 2010-06-16 | 中国科学技术大学 | Biocompatibility nanoparticle and application thereof as drug conveying carrier |
Non-Patent Citations (1)
Title |
---|
AIPING ZHU ET.AL.: "Preparation and blood compatibility of phosphorylcholine-bonded O-butyrylchitosan", 《POLYMER INTERNATIONAL》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104212432A (en) * | 2013-06-04 | 2014-12-17 | 中国石油化工股份有限公司 | Negative-positive double-ion surfactant and preparation method thereof |
CN106946936A (en) * | 2016-08-16 | 2017-07-14 | 南京构友生物材料有限公司 | The method that a kind of continuous flow reactor safe and efficient oxygen of 2 chlorine of oxidative synthesis 2 in utilization microchannel closes 1,3,2 dioxaphospholane |
CN106946936B (en) * | 2016-08-16 | 2019-01-25 | 南京构友生物材料有限公司 | A method of 2-chloro-2-oxo-1,3,2-dioxaphospholane is synthesized using microchannel continuous flow reactor |
CN107746462A (en) * | 2017-09-20 | 2018-03-02 | 中国科学技术大学 | Thio polyphosphate and its preparation method and application |
Also Published As
Publication number | Publication date |
---|---|
CN102424692B (en) | 2012-11-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5746035B2 (en) | Slurry process for the synthesis of bisphosphite | |
CN102432638B (en) | Synthesizing method for bis-phosphite ligand | |
CN102424692B (en) | Preparation method for 2-chloro-2-oxo-1,3,2-dioxaphospholane | |
CA2591754A1 (en) | Process for producing aromatic carbonate | |
US10557086B2 (en) | Resveratrol-based flame retardant materials | |
CN101326149B (en) | Process for producing polyglyceryl ether derivative | |
JP5666535B2 (en) | Diarylalkylphosphonates and methods for their preparation | |
KR101616945B1 (en) | Method for Preparing Racemic or Optically Active Glycerophosphoryl choline | |
CN101928299B (en) | Clean process method for preparing high-purity glyphosate from glycine | |
TW201100326A (en) | Method for producing dodeca halogen neopentasilanes | |
CN103664866A (en) | Method for purifying glycolide | |
LU103176B1 (en) | Method for synthesizing phosphite antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite | |
Palacios et al. | Diastereoselective hydrophosphonylation of imines using (R, R)-TADDOL phosphite. Asymmetric synthesis of α-aminophosphonic acid derivatives | |
CN109897064B (en) | Preparation method of 3-indolyl-3- (phosphodiethyl) oxoindole compound | |
CN1247601C (en) | Method for preparing beta-phosphorus-contained nitroxide free radical | |
CN110229187B (en) | Method for preparing alkyl phosphonyl compound from peroxide | |
CN101704802A (en) | Preparation method of epoxy compound | |
CN114249768B (en) | Amino acid-based phosphorus flame retardant, and preparation method and application thereof | |
US20230399349A1 (en) | Method of preparing symmetrical phosphate-based compound | |
JP5652184B2 (en) | Method for producing fluorophosphazene derivative | |
JP4524404B2 (en) | Method for producing epoxy group-containing phosphorus compound | |
CN112778090A (en) | Preparation method of 3, 5-difluorophenol | |
CN101781205A (en) | Method for synthesizing substitutional crylic acid phenyl ester | |
JP2019147747A (en) | Manufacturing method of alkenyl phosphorus compound | |
JP5563552B2 (en) | Slurry method for phosphoromonochloridite synthesis |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C56 | Change in the name or address of the patentee |
Owner name: SUZHOU FUSHILAI PHARMACEUTICAL CO., LTD. Free format text: FORMER NAME: CHANGSHU FUSHILAI MEDICINE CHEMICAL CO., LTD. |
|
CP03 | Change of name, title or address |
Address after: 215522 Jiangsu province Changshu New Material Industrial Park Haiwang Road No. 16 Patentee after: SUZHOU FUSHILAI PHARMACEUTICAL CO., LTD. Address before: Tu South Bridge 215558 Jiangsu province Suzhou city Changshou City East Development Zone in Hong Kong before the canal road Patentee before: Changshu Fushilai Medicine Chemical Co., Ltd. |