CN103554175A - Reagent preparation method - Google Patents
Reagent preparation method Download PDFInfo
- Publication number
- CN103554175A CN103554175A CN201310502915.8A CN201310502915A CN103554175A CN 103554175 A CN103554175 A CN 103554175A CN 201310502915 A CN201310502915 A CN 201310502915A CN 103554175 A CN103554175 A CN 103554175A
- Authority
- CN
- China
- Prior art keywords
- reaction flask
- product
- reaction
- phosphorous acid
- acid diester
- 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.)
- Pending
Links
Abstract
The invention discloses a reagent preparation method, and belongs to the field of organic synthesis. The reagent preparation method comprises the following steps: adding a preset amount of N-chlorosuccinimide to a reaction flask; replacing air in the reaction flask with inert gas, and cooling the reaction flask to a preset temperature; dropwise adding phosphorous acid diester to the reaction flask; when ending the reaction, diluting by using a preset amount of anhydrous solvent, and filtering an diluted product; and concentrating the product, thus obtaining diester chlorophosphate. The reagent preparation method has the advantages that no solvent is used in an ester chlorophosphate reaction process, the reaction can be completely carried out, the reaction time is short, and liquid waste is not generated; under normal circumstances, the obtained product has enough high purity and meets the requirements of common organic synthesis, and if the purity is unsatisfactory, the product can be further distilled.
Description
Technical field
The present invention relates to organic synthesis field, particularly a kind of preparation method of reagent thereof.
Background technology
Chlorine di(2-ethylhexyl)phosphate hydrocarbyl carbonate is synthetic organo phosphorous compounds, the particularly reagent of phosphoric acid mixed ester compound.Chlorine di(2-ethylhexyl)phosphate hydrocarbyl carbonate is as standby in chlorine, phosgene reaction legal system by phosphorous acid ester and gas chlorine source, needs to remove dissolved gases and acid in product with dry air and lead carbonate after reaction.Produce the solid waste of contaminate environment.In prior art, use nitrogen-chloro-succimide or TCCA (Trichloroisocyanuric acid) as chlorine source.
In realizing process of the present invention, contriver finds that prior art at least exists following problem:
The preparation method of prior art uses acetonitrile or toluene to make solvent, produces unnecessary liquid debris; Reaction process needs heating, long reaction time; This preparation method is only applicable to the less product of carbon atoms number in alkyl, with carbon atom number in product alkyl, increases, and the productive rate of product declines, and not exclusively, product is difficult to purifying in reaction.
Summary of the invention
For solve with nitrogen-chloro-succimide or TCCA (Trichloroisocyanuric acid) as chlorine source the reaction in organic solvent carry out incomplete or substantially nonreactive problem, the invention provides a kind of preparation method of reagent thereof.Described technical scheme is as follows:
The N-neoprene imide that adds predetermined amount in reaction flask;
By air displacement in described reaction flask, be rare gas element, and be cooled to preset temp;
In described reaction flask, drip phosphorous acid diester;
When described reaction finishes, with the dilution of predetermined amount anhydrous solvent, and product is filtered;
Described product is carried out to concentration, obtain chlorine phosphodiester.
The beneficial effect that technical scheme provided by the invention is brought is:
In the preparation process of chlorine phosphoric acid ester, do not use any solvent, can make reaction carry out completely, the reaction times is short, and can output liquid debris.Generally products therefrom has sufficiently high purity, meets the needs of general organic synthesis, as can be further distilled purity is dissatisfied.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below embodiment of the present invention is described further in detail.
The embodiment of the present invention provides a kind of preparation method of reagent thereof, embodiment, and details are as follows:
The N-neoprene imide that adds predetermined amount in dry reaction flask; By air displacement in described reaction flask, be rare gas element, and be cooled to preset temp; In described reaction flask, drip phosphorous acid diester, while stir, drip phosphorous acid diester, dropwise rear continuation and stir certain hour to reacting complete; When institute's reaction flask reaction finishes, with the dilution of predetermined amount anhydrous solvent, and product is filtered; Again with a small amount of anhydrous solvent washing several times, filtrate and for the first time filtrate merge precipitation after filtration; Filtrate after merging obtains chlorine phosphodiester after concentrating.Wherein, the N-neoprene imide of predetermined amount, preset temp, predetermined amount anhydrous solvent the present embodiment is not specifically limited, and can be set by research staff.
Preferably, N-neoprene imide is replaced with to TCCA (Trichloroisocyanuric acid).
In the reaction process of the chlorine phosphoric acid ester that the embodiment of the present invention provides, do not use any solvent, can make reaction carry out completely, the reaction times is short, and can output liquid debris.Generally products therefrom has sufficiently high purity, meets the needs of general organic synthesis, as can be further distilled purity is dissatisfied.
Embodiment mono-
The embodiment of the present invention only be take two (2-ethyl) the own ester synthetic methods of chlorine phosphoric acid and is described as example, and details are as follows:
Concrete, in 50 milliliters of dry twoport flasks, add 36 mmoles, the N-neoprene imide of 4.807 grams;
Add magnetic stick, a bottleneck connects vacuum argon gas pipeline, and side bottleneck is installed turned welt rubber plug, and atmosphere in bottle is replaced as to argon gas;
Device is put into ice bath, open magnetic and stir.With syringe, by plug, be added dropwise to continuously 30 mmoles, 9.193 grams of two (2-ethyl) own esters of phosphorous acid;
Stir and after 2 hours, product liquid is filtered out.
Preferably, be to improve productive rate, can be with a small amount of anhydrous hexane solid 2 times, remove desolventizing with filtrate is for the first time concentrated after merging.Product is for being colourless oil liquid, productive rate 97%.Nuclear-magnetism characterizes: hydrogen spectrum (300 megahertzes, deuterochloroform): chemical shift δ 0.85-0.95 (multiplet, 12 hydrogen), 1.20-1.49 (multiplet, 16 hydrogen), 1.56-1.69 (multiplet, 2 hydrogen), 4.02-4.19 (multiplet, 4 hydrogen).Carbon spectrum (75.4 megahertzes, deuterochloroform): chemical shift δ 10.9 (bimodal, 5J=2.3Hz, CH3), 14.0 (CH3), 22.9 (CH2), 23.2 (CH2), 28.9 (bimodal, 4J=2.3Hz, CH2), 29.9 (CH2), 39.9 is (bimodal, 3J=8.6Hz, CH), 71.8 is (bimodal, 2J=8.0Hz, CH2).
High resolution mass spectrum-ESI (m/z): [M+H]+C16H35C103P, calculated value 341.20123, experimental value 341.20195.
Characterization data shows that products therefrom is two (2-ethyl) the own esters of chlorine phosphoric acid.
With diisopropyl phosphite, replace two (2-ethyl) the own esters of phosphorous acid, with aforesaid method, can prepare diisopropyl chlorophosphate.
Preferably, N-neoprene imide is replaced with to TCCA (Trichloroisocyanuric acid).That is to say, in 50 milliliters of dry twoport flasks, add 12 mmoles, the TCCA (Trichloroisocyanuric acid) of 2.788 grams, adds magnetic stick, and a bottleneck connects vacuum argon gas pipeline, and side bottleneck is installed turned welt rubber plug, and atmosphere in bottle is replaced as to argon gas.Device is put into ice bath, open magnetic and stir.With syringe, by plug, drip continuously 30 mmoles, 9.193 grams of two (2-ethyl) own esters of phosphorous acid.Stir and after 2 hours, product liquid is filtered out.
Preferably, be to improve productive rate, can be with a small amount of anhydrous hexane solid 2 times, remove desolventizing with filtrate is for the first time concentrated after merging.
The method that the embodiment of the present invention provides, is not used any solvent in reaction process, can make reaction carry out completely, and the reaction times is short, and can output liquid debris, does not need distillation can obtain pure product.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (6)
1. a preparation method of reagent thereof, is characterized in that, described method comprises:
The N-neoprene imide that adds predetermined amount in reaction flask;
By air displacement in described reaction flask, be rare gas element, and be cooled to preset temp;
In described reaction flask, drip phosphorous acid diester;
When described reaction finishes, with the dilution of predetermined amount anhydrous solvent, and product is filtered;
Described product is carried out to concentration, obtain chlorine phosphodiester.
2. method according to claim 1, is characterized in that, described reaction flask is dry.
3. method according to claim 1, is characterized in that, to dripping phosphorous acid diester in described reaction flask, comprises:
In described reaction flask, drip while stirring phosphorous acid diester, after dropwising, continue to stir, until reaction finishes.
4. method according to claim 1, is characterized in that, described product is carried out to concentration, and after obtaining chlorine phosphodiester, described method also comprises:
Described chlorine phosphodiester product is distilled.
5. method according to claim 1, is characterized in that, the mole number of described predetermined amount N-neoprene imide is higher than described phosphorous acid diester.
6. method according to claim 1, is characterized in that, described method also comprises:
Described N-neoprene imide is replaced with to TCCA (Trichloroisocyanuric acid).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310502915.8A CN103554175A (en) | 2013-10-15 | 2013-10-15 | Reagent preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310502915.8A CN103554175A (en) | 2013-10-15 | 2013-10-15 | Reagent preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103554175A true CN103554175A (en) | 2014-02-05 |
Family
ID=50008570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310502915.8A Pending CN103554175A (en) | 2013-10-15 | 2013-10-15 | Reagent preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103554175A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106518907A (en) * | 2015-09-15 | 2017-03-22 | 江苏海阔生物医药有限公司 | Method for preparation of dialkyl chlorophosphate reagent from H acid |
| CN106518909A (en) * | 2015-09-15 | 2017-03-22 | 江苏海阔生物医药有限公司 | Method for preparing chlorophosphate dialkyl ester reagent from cyclopentadiene-acrolein |
| CN106518912A (en) * | 2015-09-15 | 2017-03-22 | 江苏海阔生物医药有限公司 | Preparation method for manufacturing dialkyl chlorophosphate reagent from benzylamine-propanal |
| CN106518908A (en) * | 2015-09-15 | 2017-03-22 | 江苏海阔生物医药有限公司 | Method of preparing dialkyl chlorophosphate reagent from morpholine-normal propionaldehyde |
| CN106518911A (en) * | 2015-09-15 | 2017-03-22 | 江苏海阔生物医药有限公司 | Method of preparing dialkyl chlorophosphate reagent from polyvinyl alcohol |
| CN106518913A (en) * | 2015-09-15 | 2017-03-22 | 江苏海阔生物医药有限公司 | Preparation method for producing dialkyl chlorophosphate reagent from polyethylene glycol |
| CN106518914A (en) * | 2015-09-15 | 2017-03-22 | 江苏海阔生物医药有限公司 | Preparation method for producing dialkyl chlorophosphate reagent from nicotinic acid |
| CN106518910A (en) * | 2015-09-15 | 2017-03-22 | 江苏海阔生物医药有限公司 | Method for preparing dialkyl chlorophosphate reagent through trimethylpyridine-phosphamide |
-
2013
- 2013-10-15 CN CN201310502915.8A patent/CN103554175A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| J.ACHARYA,ET AL.: "Trichloroisocyanuric acid: an efficient reagent for the synthesis of dialkyl chlorophosphates from dialkyl phosphites", 《TETRAHEDRON LETTERS》 * |
| 倪颖等: "Neat法室温合成氯膦酸二辛基酯", 《化学工程师》 * |
| 陈志卫等: "合成磷酰氯二烷基酯的新方法", 《合成化学》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106518907A (en) * | 2015-09-15 | 2017-03-22 | 江苏海阔生物医药有限公司 | Method for preparation of dialkyl chlorophosphate reagent from H acid |
| CN106518909A (en) * | 2015-09-15 | 2017-03-22 | 江苏海阔生物医药有限公司 | Method for preparing chlorophosphate dialkyl ester reagent from cyclopentadiene-acrolein |
| CN106518912A (en) * | 2015-09-15 | 2017-03-22 | 江苏海阔生物医药有限公司 | Preparation method for manufacturing dialkyl chlorophosphate reagent from benzylamine-propanal |
| CN106518908A (en) * | 2015-09-15 | 2017-03-22 | 江苏海阔生物医药有限公司 | Method of preparing dialkyl chlorophosphate reagent from morpholine-normal propionaldehyde |
| CN106518911A (en) * | 2015-09-15 | 2017-03-22 | 江苏海阔生物医药有限公司 | Method of preparing dialkyl chlorophosphate reagent from polyvinyl alcohol |
| CN106518913A (en) * | 2015-09-15 | 2017-03-22 | 江苏海阔生物医药有限公司 | Preparation method for producing dialkyl chlorophosphate reagent from polyethylene glycol |
| CN106518914A (en) * | 2015-09-15 | 2017-03-22 | 江苏海阔生物医药有限公司 | Preparation method for producing dialkyl chlorophosphate reagent from nicotinic acid |
| CN106518910A (en) * | 2015-09-15 | 2017-03-22 | 江苏海阔生物医药有限公司 | Method for preparing dialkyl chlorophosphate reagent through trimethylpyridine-phosphamide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103554175A (en) | Reagent preparation method | |
| JP2014015343A (en) | Method for producing lithium dihalogenophosphate | |
| CN108423651B (en) | Method for preparing lithium difluorophosphate | |
| CN110551151A (en) | preparation method of phosphate or phosphite ester, electrolyte and secondary battery | |
| CN108910919A (en) | A kind of preparation method of the double oxalic acid lithium phosphates of electron level difluoro | |
| CN101792390A (en) | Preparation method of bisphenol monocarboxylic ester compound antioxidant | |
| EP2351762A1 (en) | NOVEL PYRIMIDINE DERIVATIVE AND METHOD FOR PRODUCING HMG-CoA REDUCTASE INHIBITOR INTERMEDIATE | |
| Saga et al. | The PMe3-catalyzed addition of enantiomerically pure (−)-MenthylO (Ph) P (O) H to electron-deficient alkenes: an efficient way for the preparation of P-stereogenic compounds | |
| CN104080791B (en) | The method separated and use (the fluoro-3-of the chloro-2-of 4-substituted-phenyl) borate | |
| US20110201837A1 (en) | Method for producing 6-chlorodibenzo[d,f] [1,3,2]dioxaphosphepin | |
| CN103275116A (en) | Preparation method of tri-hexafluoroisopropyl phosphate | |
| CN103910759A (en) | Preparation method of (carbethoxyethylidene)triphenylphosphorane | |
| CN101302234B (en) | Synthetic method of 2,2'-methano-bis (4,6-ditertbutyl phenol) phosphate | |
| CN103012461B (en) | Preparation method of biotin key intermediate 1, 2-bi(trimethylsilanolate) cyclohexene | |
| CN101613358A (en) | The preparation method of cephalothin acid | |
| CN111925388B (en) | Preparation method of titanium tetraisopropoxide | |
| EP3383878A1 (en) | Process for isolating a (thio)phosphoric acid derivative | |
| CN102675369A (en) | New method for preparing fosaprepitant intermediate | |
| CN107445856B (en) | Synthesis process of N-isopropyl acrylamide | |
| CN110845524A (en) | Method for preparing specific lithium salt by using organic acyloxy silane | |
| CN103788129B (en) | A kind of preparation method of trialkylphosphine oxide | |
| CN104004017B (en) | Diphenylphosphine cumyl phenolic ester and synthetic method thereof | |
| CN104017022B (en) | Method for preparing phosphite antioxidant | |
| CN106518913A (en) | Preparation method for producing dialkyl chlorophosphate reagent from polyethylene glycol | |
| CN101704847B (en) | Method for catalyzing and synthesizing 2, 2'-methylene-bis (4, 6 - di-tert-butyl-phenol) by DMAP |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140205 |