CN107573374A - A kind of preparation method of alkenyl sulphur (selenium) for phosphine (phosphorus) acid esters - Google Patents
A kind of preparation method of alkenyl sulphur (selenium) for phosphine (phosphorus) acid esters Download PDFInfo
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- CN107573374A CN107573374A CN201710800344.4A CN201710800344A CN107573374A CN 107573374 A CN107573374 A CN 107573374A CN 201710800344 A CN201710800344 A CN 201710800344A CN 107573374 A CN107573374 A CN 107573374A
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- selenium
- phosphine
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Abstract
The present invention relates to a kind of alkenyl sulphur (selenium) for the preparation method of phosphine (phosphorus) acid esters, comprise the following steps：1) aryl Terminal Acetylenes, P (O) S H (P (O) Se H) reagent are mixed in toluene solution, then add BFEE, after reacting 10~60min at a temperature of 50~100 DEG C, be cooled to room temperature, obtain reaction solution；2) reaction solution obtained by step 1) is concentrated with organic solvent, isolated and purified, that is, obtain alkenyl sulphur (selenium) for phosphine (phosphorus) acid esters；The present invention compared with the existing technology, avoids the use of metallic catalyst, has the characteristics that preparation technology is simple and convenient to operate, substrate expansibility is good, yield is outstanding, and be swift in response, substrate strong adaptability；In addition, the target product alkenyl sulphur (selenium) being prepared can be applied to the fields such as organic synthesis, medical science, photoelectric material for phosphine (phosphorus) acid esters.
Description
[technical field]
The invention belongs to technical field of organic synthesis, preparation of specifically a kind of alkenyl sulphur (selenium) for phosphine (phosphorus) acid esters
Method.
[background technology]
S- arylthio phosphates containing P-S-C (sp2) bond structure, in terms of medicine can be used as medicine intermediate,
Insecticide, bactericide, curing accelerator, antistatic additive, a kind of anticholinesterase.In terms of functional material, as surface
Activating agent, photoelectric material, phosphonium flame retardant.Equally, the compound containing Se elements has in life regulation, photoelectric material etc.
Important application.Therefore, efficiently synthesize alkenyl sulphur (selenium) substituted phosphate turns into study hotspot.However, how quickly and easily
Alkenyl sulphur (selenium) is synthesized for phosphine (phosphorus) acid esters, is not had been reported that but.
[content of the invention]
A kind of system of alkenyl sulphur (selenium) for phosphine (phosphorus) acid esters is provided present invention aim to solve above-mentioned deficiency
Preparation Method, the use of metallic catalyst is avoided, with preparation technology is simple and convenient to operate, substrate expansibility is good, yield is excellent
The features such as elegant.
A kind of alkenyl sulphur (selenium) is designed to achieve the above object for the preparation method of phosphine (phosphorus) acid esters, is comprised the following steps：
1) aryl Terminal Acetylenes, P (O)-S-H (P (O)-Se-H) reagent are mixed in toluene solution, then add BFEE,
After reacting 10~60min at a temperature of 50~100 DEG C, room temperature is cooled to, obtains reaction solution；2) by reaction solution obtained by step 1) with organic
Solvent concentration, isolate and purify, that is, obtain alkenyl sulphur (selenium) for phosphine (phosphorus) acid esters.
Further, in step 1), the aryl Terminal Acetylenes, P (O)-S-H (P (O)-Se-H) reagent, BFEE
Mol ratio is (1~2)：1：(1~2).
Further, in step 1), aryl Terminal Acetylenes, P (O)-S-H (P (O)-Se-H) reagent are weighed in test tube, adds first
Benzene, test tube is sealed, then with microsyringe by BFEE injecting tube, then stirring reaction.
Further, in step 1), P (O)-S-H (P (O)-Se-H) reagent is sulphur (selenium) for phosphoric acid or sulphur (selenium) generation
Phosphinic acids.
Further, in step 1), P (O)-S-H (P (O)-Se-H) reagent is diphenyl phosphonothiolic acid, O, O- bis-
Ethyl S- hydrogen D2EHDTPA, O- ethyl S- hydrogen phenylphosphonothioic acid, diphenyl seleno phosphonic acids, O, in O- diphenyl D2EHDTPAs
It is any.
Further, in step 1), the aryl Terminal Acetylenes is phenylacetylene.
Further, in step 1), the dosage of the toluene is：Every mM of aryl end acetylene compound 2~6mL first
Benzene.
Further, in step 1), the content of the BFEE is 48~98%.
Further, in step 2), after isolating and purifying, column chromatography for separation is carried out to concentrate, with ethyl acetate and oil
For the mixture of ether as solvent, its volume ratio is ethyl acetate/petroleum ether=1/1~1/10.
The present invention is compared with the existing technology, there is provided and one kind efficiently prepares method of the alkenyl sulphur (selenium) for phosphine (phosphorus) acid esters,
It is anti-in the presence of BFEE by the way that aryl Terminal Acetylenes, P (O)-S-H (P (O)-Se-H) reagent are put in toluene solution
Should, room temperature is cooled to, obtains reaction solution, then the reaction solution is directly concentrated, isolated and purified, that is, alkenyl sulphur (selenium) is obtained for phosphine
(phosphorus) acid esters, this method avoid the use of metallic catalyst, there is preparation technology to be simple and convenient to operate, substrate expansibility
Well, the features such as yield is outstanding, and be swift in response, substrate strong adaptability；In addition, target product alkenyl sulphur (selenium) generation being prepared
Phosphine (phosphorus) acid esters can be applied to the fields such as organic synthesis, medical science, photoelectric material.
[embodiment]
The invention provides a kind of alkenyl sulphur (selenium) for the preparation method of phosphine (phosphorus) acid esters, comprise the following steps：1) by virtue
Cardinal extremity alkynes, P (O)-S-H (P (O)-Se-H) reagent are mixed in toluene solution, BFEE are then added, 50~100
After reacting 10~60min at a temperature of DEG C, room temperature is cooled to, obtains reaction solution；2) it is reaction solution organic solvent obtained by step 1) is dense
Contract, isolate and purify, that is, obtain alkenyl sulphur (selenium) for phosphine (phosphorus) acid esters.Gained target product alkenyl sulphur (selenium) can for phosphine (phosphorus) acid esters
Applied to fields such as organic synthesis, medical science, photoelectric materials.
In step 1), aryl Terminal Acetylenes, P (O)-S-H (P (O)-Se-H) reagent, BFEE mol ratio for (1~
2)：1：(1~2), by the mol ratio, aryl Terminal Acetylenes, P (O)-S-H (P (O)-Se-H) reagent are weighed in test tube, add toluene,
Test tube is sealed, then with microsyringe by BFEE injecting tube, then stirring reaction.P(O)-S-H(P(O)-
Se-H) reagent be sulphur (selenium) for phosphoric acid or sulphur (selenium) generation phosphonic acids, specifically, P (O)-S-H (P (O)-Se-H) reagent is hexichol
Base phosphonothiolic acid, O, O- diethyl S- hydrogen D2EHDTPA, O- ethyl S- hydrogen phenylphosphonothioic acid, diphenyl seleno phosphonic acids, O, O-
Any of diphenyl D2EHDTPA.Aryl Terminal Acetylenes is phenylacetylene, and the dosage of toluene is：Every mM of aryl Terminal Acetylenes class chemical combination
Thing 2~6mL toluene, the content of BFEE is 48~98%.In step 2), after isolating and purifying, concentrate is carried out
Column chromatography for separation, using the mixture of ethyl acetate and petroleum ether as solvent, its volume ratio is ethyl acetate/petroleum ether=1/
1~1/10.
For alkenyl sulphur (selenium) of the present invention for the preparation method of phosphine (phosphorus) acid esters, the reaction expression being related to is as follows：
X:S8Or Se
Wherein, Ar is aryl, R1、R2For aryl, aryloxy group, alkoxy.
The present invention is made with reference to specific embodiment further explained below：
Embodiment 1
The preparation method of S- (1- phenyl vinyls) diphenyl Thiophosphonate, comprises the following steps：Weigh 0.3mmol bis-
Phenylphosphonothioic acid, 0.36mmol phenylacetylenes add toluene in test tube, seal test tube, then with microsyringe by 0.3mmol
In BFEE injecting tube, reaction 30min is stirred under the conditions of 90 DEG C, room temperature is cooled to, obtains reaction solution.Gained
Reaction solution is concentrated under reduced pressure, and with ethyl acetate/petroleum ether=1/3 (v/v) for solvent, carries out column chromatography for separation to concentrate, obtains
99.8mg target products.
The target product yield of the present embodiment is 99%.Nuclear-magnetism sign is carried out to target product, it is as follows：
1H NMR(500MHz,CDCl3):δ 7.88-7.83 (m, 4H), 7.47 (t, J=7.1Hz, 2H), 7.41-7.38 (m,
6H), 7.24-7.15 (m, 3H), 5.91 (d, J=2.7Hz, 1H), 5.85 (d, J=2.4Hz, 1H)13C NMR(125MHz,
CDCl3):δ 139.5,135.4 (d, J=246.7Hz), 132.4 (d, J=107.8Hz), 132.2 (d, J=2.9Hz), 131.6
(d, J=10.2Hz), 128.4 (d, J=13.1Hz), 128.2,128.0,127.0,125. (d, J=6.2Hz)31P NMR
(202MHz,CDCl3):δ39.63.
Embodiment 2
The preparation method of O, O- diethyl S- (1- phenyl vinyls) thiophosphate, comprises the following steps：Weigh
0.3mmol O, O- diethyl S- hydrogen D2EHDTPA, 0.36mmol phenylacetylenes add toluene in test tube, seal test tube, then use
Microsyringe in 0.3mmol BFEE injecting tubes, will be stirred reaction 30min, cooling under the conditions of 90 DEG C
To room temperature, reaction solution is obtained.Gained reaction solution is concentrated under reduced pressure, with ethyl acetate/petroleum ether=1/3 (v/v) for solvent, to concentration
Thing carries out column chromatography for separation, obtains 80mg target products.
The target product yield of the present embodiment is 98%.Nuclear-magnetism sign is carried out to target product, it is as follows：
1H NMR(500MHz,CDCl3):δ 7.59 (d, J=6.6Hz, 2H), 7.37-7.31 (m, 3H), 5.96 (d, J=
4.0Hz, 1H), 5.90 (d, J=4.1Hz, 1H), 4.18-4.10 (m, 2H), 4.06-3.98 (m, 2H), 1.22 (t, J=
7.1Hz,6H)；13C NMR(125MHz,CDCl3):δ 139.5 (d, J=3.2Hz), 136.0 (d, J=8.6Hz), 128.6,
128.1,127.1,125.0 (d, J=5.6Hz), 63.8 (d, J=5.9Hz), 15.8 (d, J=7.4Hz)；31P NMR
(202MHz,CDCl3):21.25.
Embodiment 3
The preparation method of O- ethyls-S- (1- phenyl vinyls) phenylphosphonothioic acid ester, comprises the following steps：Weigh
0.3mmol O- ethyl S- hydrogen phenylphosphonothioic acid, 0.36mmol phenylacetylenes add toluene in test tube, seal test tube, then use
Microsyringe in 0.3mmol BFEE injecting tubes, will be stirred reaction 30min, cooling under the conditions of 90 DEG C
To room temperature, reaction solution is obtained.Gained reaction solution is concentrated under reduced pressure, with ethyl acetate/petroleum ether=1/3 (v/v) for solvent, to concentration
Thing carries out column chromatography for separation, obtains 89.4mg target products.
The target product yield of the present embodiment is 98%.Nuclear-magnetism sign is carried out to target product, it is as follows：
1H NMR(500MHz,CDCl3):δ 7.74-7.70 (m, 2H), 7.47 (t, J=6.8Hz, 1H), 7.40-7.33 (m,
4H), 7.21 (d, J=6.2Hz, 3H), 5.82 (d, J=3.7Hz, 1H), 5.63 (d, J=3.8Hz, 1H), 4.32-4.24 (m,
1H), 4.14-4.06 (m, 1H), 1.25 (t, J=7.1Hz, 3H)；13C NMR(125MHz,CDCl3):δ139.3,136.2(d,J
=6.8Hz), 132.3 (d, J=3.4Hz), 131.5 (d, J=150.1Hz), 131.4 (d, J=10.5Hz), 128.3,
(128.1,128.0,127.1,125.8 d, J=5.5Hz), 62.3 (d, J=6.8Hz), 16.0 (d, J=7.1Hz)；31P NMR
(202MHz,CDCl3):39.77.
Embodiment 4
The preparation method of Se- (1- phenyl vinyls) diphenyl seleno phosphonate ester ester, comprises the following steps：Weigh
0.3mmol diphenyl selenos phosphonic acids, 0.36mmol phenylacetylenes add toluene in test tube, seal test tube, then use microsyringe
Reaction 30min in 0.3mmol BFEE injecting tubes, will be stirred under the conditions of 90 DEG C, room temperature is cooled to, obtains instead
Answer liquid.Gained reaction solution is concentrated under reduced pressure, and with ethyl acetate/petroleum ether=1/4 (v/v) for solvent, post layer is carried out to concentrate
Analysis separation, obtains 112mg target products.
The target product yield of the present embodiment is 98%.Nuclear-magnetism sign is carried out to target product, it is as follows：
1H NMR(500MHz,CDCl3):δ7.87-7.83(m,Hz,4H),7.50-7.47(m,2H),7.43-7.39(m,
4H), 7.33-7.31 (m, 2H), 7.19-7.18 (m, 3H), 6.01 (d, J=2.3Hz, 1H), 5.92 (d, J=2.4Hz, 1H)；13C NMR(125MHz,CDCl3):δ 140.6,134.4 (d, J=6.5Hz), 133.5 (d, J=97.4Hz), 132.2 (d, J=
3.2Hz), 131.4 (d, J=10.5Hz), 128.4 (d, J=13.0Hz), 128.1,128.0,127.5,126.3 (d, J=
5.6Hz).31P NMR(202MHz,CDCl3):39.44.
Embodiment 5
The preparation method of O, O- diphenyl S- (1- phenyl vinyls) thiophosphate, comprises the following steps：Weigh
0.3mmolO, O- diphenyl D2EHDTPA, 0.36mmol phenylacetylenes in test tube, add toluene, seal test tube, then with it is micro enter
Sample device in 0.3mmol BFEE injecting tubes, will be stirred reaction 30min under the conditions of 90 DEG C, be cooled to room temperature,
Obtain reaction solution.Gained reaction solution is concentrated under reduced pressure, and with ethyl acetate/petroleum ether=1/4 (v/v) for solvent, concentrate is carried out
Column chromatography for separation, obtain 92.7mg target products.
The target product yield of the present embodiment is 84%.Nuclear-magnetism sign is carried out to target product, it is as follows：
1H NMR(500MHz,CDCl3):δ7.50-7.49(m,2H),7.31-7.27(M,7H),7.19-7.13(m,6H),
6.02 (d, J=4.4Hz, 1H), 5.89 (d, J=4.6Hz, 1H)13C NMR(125MHz,CDCl3):13C NMR(126MHz,
Chloroform-d) δ 150.2 (d, J=8.3Hz), 138.7,135.0 (d, J=8.9Hz), 129.6,128.8,128.2,
127.2,126.2 (d, J=9.5Hz), 125.4,120.3 (d, J=5.2Hz)；31P NMR(202MHz,CDCl3):14.77。
The present invention is simultaneously not limited to the embodiments described above limitation, other any Spirit Essences and principle without departing from the present invention
Lower made change, modification, replacement, combination, simplification, should be equivalent substitute mode, be included in the protection model of the present invention
Within enclosing.
Claims (9)
1. a kind of alkenyl sulphur (selenium) is for the preparation method of phosphine (phosphorus) acid esters, it is characterised in that comprises the following steps：
1) aryl Terminal Acetylenes, P (O)-S-H (P (O)-Se-H) reagent are mixed in toluene solution, then add boron trifluoride second
Ether, after reacting 10~60min at a temperature of 50~100 DEG C, room temperature is cooled to, obtains reaction solution；
2) reaction solution obtained by step 1) is concentrated with organic solvent, isolated and purified, that is, obtain alkenyl sulphur (selenium) for phosphine (phosphorus) acid esters.
2. the method as described in claim 1, it is characterised in that：In step 1), the aryl Terminal Acetylenes, P (O)-S-H (P (O)-
Se-H) reagent, the mol ratio of BFEE are (1~2)：1：(1~2).
3. method as claimed in claim 2, it is characterised in that：In step 1), weigh aryl Terminal Acetylenes, P (O)-S-H (P (O)-
Se-H) reagent is in test tube, adds toluene, seals test tube, then with microsyringe by BFEE injecting tube, so
Stirring reaction afterwards.
4. method as claimed in claim 3, it is characterised in that：In step 1), P (O)-S-H (P (O)-Se-H) reagent is
Sulphur (selenium) is for phosphoric acid or sulphur (selenium) generation phosphonic acids.
5. method as claimed in claim 3, it is characterised in that：In step 1), P (O)-S-H (P (O)-Se-H) reagent is
Diphenyl phosphonothiolic acid, O, O- diethyl S- hydrogen D2EHDTPA, O- ethyl S- hydrogen phenylphosphonothioic acid, diphenyl seleno phosphonic acids,
Any of O, O- diphenyl D2EHDTPA.
6. the method as described in claim 4 or 5, it is characterised in that：In step 1), the aryl Terminal Acetylenes is phenylacetylene.
7. method as claimed in claim 6, it is characterised in that：In step 1), the dosage of the toluene is：Every mM of aryl
Hold acetylene compound 2~6mL toluene.
8. method as claimed in claim 7, it is characterised in that：In step 1), the content of the BFEE for 48~
98%.
9. method as claimed in claim 8, it is characterised in that：In step 2), after isolating and purifying, column chromatography is carried out to concentrate
Separation, using the mixture of ethyl acetate and petroleum ether as solvent, its volume ratio is ethyl acetate/petroleum ether=1/1~1/
10。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129512A (en) * | 2018-02-07 | 2018-06-08 | 上海应用技术大学 | A kind of allyl sulfide generation or the preparation method of phosphoroselenoate and phosphonate ester |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3077431A (en) * | 1960-01-14 | 1963-02-12 | Monsanto Chemicals | Phosphinothioates |
| CN106188136A (en) * | 2016-07-13 | 2016-12-07 | 上海应用技术学院 | A kind of diphenyl sulfur (selenium) is for the environment-friendly preparation method thereof of phosphonate ester |
-
2017
- 2017-09-07 CN CN201710800344.4A patent/CN107573374A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3077431A (en) * | 1960-01-14 | 1963-02-12 | Monsanto Chemicals | Phosphinothioates |
| CN106188136A (en) * | 2016-07-13 | 2016-12-07 | 上海应用技术学院 | A kind of diphenyl sulfur (selenium) is for the environment-friendly preparation method thereof of phosphonate ester |
Non-Patent Citations (1)
| Title |
|---|
| GAZIEVA, N.I. ET AL.: "-", 《ZH. OBSHCH. KHIM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129512A (en) * | 2018-02-07 | 2018-06-08 | 上海应用技术大学 | A kind of allyl sulfide generation or the preparation method of phosphoroselenoate and phosphonate ester |
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Application publication date: 20180112 |