CN104804039A - Synthesis method for organic phosphorus based flame retardant metabolite - Google Patents
Synthesis method for organic phosphorus based flame retardant metabolite Download PDFInfo
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- CN104804039A CN104804039A CN201510160051.5A CN201510160051A CN104804039A CN 104804039 A CN104804039 A CN 104804039A CN 201510160051 A CN201510160051 A CN 201510160051A CN 104804039 A CN104804039 A CN 104804039A
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Abstract
The invention relates to a synthesis method for an organic phosphorus based flame retardant metabolite. Through the improvement of a synthesis route, the product purity is greatly improved; all reaction raw materials, such as chlorine oxytrichloride, triethylamine and ROH, involved in the synthesis method are cheap and highly available; the synthesis principles of all intermediate compounds are simple; the reaction conditions are controllable; the yield is stable; the product purity is high.
Description
Technical field
The present invention relates to a kind of synthetic method of organic phosphorus flame retardant metabolite.Comprise meta-bolites di(2-ethylhexyl)phosphate (butoxyethyl group) ester (DBEP) of synthesis tricresyl phosphate (butoxyethyl group) ester (TBEP); The meta-bolites Dichloroethyl phosphoric acid ester (BCEP) of trichloroethyl phosphate (TCEP); Meta-bolites di(2-ethylhexyl)phosphate (the chloro-2-propyl group of the 1-) ester (BCPP) of tricresyl phosphate (1-chloro-2-propyl group) ester (TCPP); Triphenylphosphate (TPhP) meta-bolites diphenyl phosphate (DPhP); The meta-bolites xylenylphosphate (DCP) etc. of Tritolyl Phosphate (TCP).
Background technology
Due to bioconcentration and the potential toxicity thereof of Poly Brominated Diphenyl Ethers, the agent of current Poly Brominated Diphenyl Ethers fire-retardant is worldwide forbidden gradually, thus organic phosphoric acid flame retardant is widely applied, and this fire retardant is extensively present in surrounding medium.Schindler in 2009 etc. have detected the metabolite of organic phosphorus flame retardant first in German urine sample, and confirm the structure of meta-bolites.The biological toxicity of further research organic phosphorus flame retardant metabolite, needs a large amount of highly purified metabolite standard substance.The method of current this compounds of conventional synthesis is by organic phosphorus flame retardant direct hydrolysis, reacts as follows:
The shortcoming of this reaction is the more difficult control of hydrolysis degree, and products therefrom is complicated, respectively with one, two and three hydroxyls, because this compounds lacks uv-absorbing, makes to adopt each meta-bolites of the more difficult purifying of conventional post chromatography method.Organic phosphorus flame retardant meta-bolites standard specimen on sale in the market is all prepared by HPLC method, therefore, prepares organic phosphorus flame retardant meta-bolites in a large number by this synthetic method is more difficult.
Summary of the invention
The object of the invention is to the difficulty overcoming purifying in existing synthetic method, provide a kind of synthetic method of new organic phosphorus flame retardant metabolite, the relatively large synthesis of the method energy obtains the target compound of purifying.
For achieving the above object, the present invention adopts following reaction mechanism:
According to above-mentioned reaction mechanism, the present invention adopts following technical scheme:
A synthetic method for organic phosphorus flame retardant metabolite, is characterized in that the concrete steps of the method are:
A. phosphorus oxychloride is dissolved in methylene dichloride, at-60 ~ 0 DEG C of temperature, is added dropwise to triethylamine and ROH; At room temperature stirring reaction 30 ~ 150min, removing methylene dichloride, obtain compound 2, its structural formula is:
, described ROH is butyl glycol ether, ethylene chlorhydrin, 1-chloro-2-propanol, phenol, p-cresol or meta-cresol; The molar ratio range of described phosphorus oxychloride: triethylamine: ROH remains on 1:2:2 ~ 1.5:2:2;
B. step a gained compound 2 is dissolved in tetrahydrofuran (THF), remains on-10
0c ~ 10
0c, be hydrolyzed reaction in the aqueous solution of 1 mol/L NaOH, stirring reaction 40 ~ 150min, adjust ph to 1 ~ 4; Be extracted with ethyl acetate, remove organic solvent, separation and purification, obtains organic phosphorus flame retardant metabolite, its structural formula:
.
The proton nmr spectra of di(2-ethylhexyl)phosphate (butoxyethyl group) ester (DBEP)
1h NMR (CDCl
3, 500MHz), δ 0.892-0.921 (t,
j=14.5Hz, 6H), 1.318-1.393 (m,
j=37.5Hz, 4H), 1.535-1.578 (m,
j=21.5Hz, 4H), 3.458-3.489 (td,
j 1 =2Hz,
j 2 =2.5Hz,
j 3 =2Hz, 4H), 3.608-3.644 (m,
j=18Hz, 4H), 4.134-4.217 (td,
j 1 =2Hz,
j 2 =3Hz,
j 3 =4.5Hz, 4H), 10.98 (s, 1H).
The proton nmr spectra of Dichloroethyl phosphoric acid ester (BCEP)
1h NMR (CDCl
3,500MHz), δ 3.730-3.750 (t,
j 1 =5Hz,
j 2 =5Hz, 4H), 4.295-4.306 (d,
j=32.5Hz, 4H), 10.086 (s, 1H).
The proton nmr spectra of di(2-ethylhexyl)phosphate (the chloro-2-propyl group of 1-) ester (BCPP)
1h NMR (CDCl
3, 500MHz), δ 1.18 (s, 6H) 3.59 (d,
j=6Hz, 4H), 3.71 (s,
2h), 9.97 (s, 1H).
The proton nmr spectra of diphenyl phosphate (DPhP)
1h NMR (CDCl
3,500MHz), δ 7.155-7.184 (t,
j 1 =7.5Hz,
j 2 =7Hz, 6H), 7.279-7.31 (t,
j 1 =7.5Hz,
j 2 =8Hz, 4H), 9.764 (s, 1H).
The proton nmr spectra of phosphoric acid m-xylene ester DmCP
1h NMR (CDCl
3,500MHz), δ 2.281 (s, 6H), 6.964 (s, 6H), 7.145 (s, 2H), 10.04 (s, 1H).
The proton nmr spectra of phosphoric acid p-Xylol ester DpCP
1h NMR (CDCl
3,500MHz), δ 2.3 (s, 6H), 7.025-7.082 (m, 8H), 9.79 (s, 1H).
Organic phosphorus flame retardant metabolite preparation method of the present invention, compared with the conventional method, has the following advantages:
1. production cost is low.Compared with existing method, the synthesis material price that the present invention utilizes is comparatively cheap.
2. be easy to purifying.Original synthetic method product is complicated, and purifying difficulty is large.Utilize the method for the invention, control by equivalence ratio the number replacing molecule, its product purity is higher, and purifying is easy.
3. productive rate is high.Through experimental study, the productive rate of product is up to 80 more than %.
4. experimental implementation is easy.It is many that existing method obtains by product, utilizes HPLC to carry out purifying, and post-treating method operation is comparatively complicated, and preparation amount is little.Utilize the method for the invention, operate all comparatively easy, purifying only needs to adopt conventional column chromatography method purifying.
Embodiment
Concrete steps are as follows:
(1) in the there-necked flask of 250ml, add (1.53 g, 10 mmol) phosphorus oxychloride join methylene dichloride (100 ml) and be placed in the low temperature instrument of-60 ~ 0 DEG C; Triethylamine (2.02g g, 20 mmol) and compound (1) (10 mmol) are dissolved in methylene dichloride (30 ml).Slowly be added drop-wise in there-necked flask by constant pressure funnel; At room temperature stir 30 ~ 150 min after dripping, after question response is complete, vacuum rotary steam, to remove methylene dichloride, obtains compound (2).
(2) above-mentioned product is dissolved in tetrahydrofuran (THF) (10ml); Be placed in the system of-10 ~ 10 DEG C, and drip 1 mol/L aqueous sodium hydroxide solution 10ml gradually, vigorous stirring 30 min under this system after dropping terminates, after reaction terminates, add hydrochloric acid adjust pH to acid, be then extracted with ethyl acetate, aqueous layer with ethyl acetate washed three times.After terminating, organic layer is revolved steaming, chromatography, with organic phosphorus flame retardant metabolite that must be purer.
Claims (1)
1. a synthetic method for organic phosphorus flame retardant metabolite, is characterized in that the concrete steps of the method are:
A. phosphorus oxychloride is dissolved in methylene dichloride, at-60 ~ 0 DEG C of temperature, is added dropwise to triethylamine and ROH; At room temperature stirring reaction 30 ~ 150min, removing methylene dichloride, obtain compound 2, its structural formula is:
, described ROH is butyl glycol ether, ethylene chlorhydrin, 1-chloro-2-propanol, phenol, p-cresol or meta-cresol; The molar ratio range of described phosphorus oxychloride: triethylamine: ROH remains on 1:2:2 ~ 1.5:2:2;
B. step a gained compound 2 is dissolved in tetrahydrofuran (THF), remains on-10
0c ~ 10
0c, be hydrolyzed reaction in the aqueous solution of 1 mol/L NaOH, stirring reaction 40 ~ 150min, adjust ph to 1 ~ 4; Be extracted with ethyl acetate, remove organic solvent, separation and purification, obtains organic phosphorus flame retardant metabolite, its structural formula:
.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317822A (en) * | 2016-08-18 | 2017-01-11 | 刘世超 | Infrared signal attenuation-reducing engineering plastic for televisions |
| CN106588978A (en) * | 2016-12-03 | 2017-04-26 | 苏州大学 | Phosphate ester fire retardant based on biomass and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012025840A (en) * | 2010-07-22 | 2012-02-09 | Marubishi Oil Chem Co Ltd | Fire retarding agent containing cyclic amine salt, and fire-retardant resin composition |
-
2015
- 2015-04-07 CN CN201510160051.5A patent/CN104804039A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012025840A (en) * | 2010-07-22 | 2012-02-09 | Marubishi Oil Chem Co Ltd | Fire retarding agent containing cyclic amine salt, and fire-retardant resin composition |
Non-Patent Citations (2)
| Title |
|---|
| DANIEL DEROUET等: ""Chemical modification of 1,4-polydienes by di(alkyl or aryl)phosphates"", 《EUROPEAN POLYMER JOURNAL》, vol. 37, 22 May 2001 (2001-05-22) * |
| NICO SANTSCHI等: ""Reactivity of an electrophilic hypervalent iodine trifluoromethylation reagent with hydrogen phosphates—A mechanistic study"", 《JOURNAL OF FLUORINE CHEMISTRY》, vol. 135, 3 September 2011 (2011-09-03) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317822A (en) * | 2016-08-18 | 2017-01-11 | 刘世超 | Infrared signal attenuation-reducing engineering plastic for televisions |
| CN106588978A (en) * | 2016-12-03 | 2017-04-26 | 苏州大学 | Phosphate ester fire retardant based on biomass and preparation method thereof |
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