CN102424692B - 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
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- CN102424692B CN102424692B CN2011104224296A CN201110422429A CN102424692B CN 102424692 B CN102424692 B CN 102424692B CN 2011104224296 A CN2011104224296 A CN 2011104224296A CN 201110422429 A CN201110422429 A CN 201110422429A CN 102424692 B CN102424692 B CN 102424692B
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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 (6)
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 passes through exsiccant ozone generation oxidizing reaction in organic solvent; Remove organic solvent, cut is collected in rectification under vacuum, obtains 2-chloro-2-oxygen-1; 3,2-dioxaphospholane, steps A) described in the temperature of reaction of in organic solvent system, reacting be-20-20 ℃; Reaction times is 1-6h, step B) described in 2-chloro-1,3; The 2-dioxaphospholane is 1 with the mol ratio of described ozone: 2-4, and the temperature of reaction of described oxidizing reaction is-5～40 ℃, the flow of described ozone is 200-500ml/min.
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 aromatic 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 organic solvent is toluene or YLENE.
5.
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.
6.
2-chloro-2-oxygen-1,3 according to claim 1, the preparation method of 2-dioxaphospholane is characterized in that described ozone is the ozone by the ozonizer preparation
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