CN109232642A - A kind of synthetic method of benzyl thiophosphate - Google Patents
A kind of synthetic method of benzyl thiophosphate Download PDFInfo
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- CN109232642A CN109232642A CN201811043293.6A CN201811043293A CN109232642A CN 109232642 A CN109232642 A CN 109232642A CN 201811043293 A CN201811043293 A CN 201811043293A CN 109232642 A CN109232642 A CN 109232642A
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- benzyl
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- synthetic method
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1653—Esters of thiophosphoric acids with arylalkanols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/17—Esters of thiophosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
Abstract
The present invention provides a kind of synthetic methods of benzyl thiophosphate.This method is that alkylating reagent is stirred to react 6~24 hours, a step prepares benzyl phosphorothioate compound with sulphur powder, phosphite ester under conditions of no catalyst at 70~100 DEG C using benzyl alcohol cheap and easy to get, from a wealth of sources, stablizing low toxicity.This method reaction condition is simple, and raw material is easily obtained, and is without the use of excessive alkali, is not necessarily to solvent, only needs single step reaction, easily operated.The gram-grade preparation of product can also easily be amplified, be carried out to this method, have certain research and prospects for commercial application.
Description
Technical field
The invention belongs to compound synthesis technical fields, and in particular to a kind of synthetic method of benzyl thiophosphate.
Background technique
Benzyl thiophosphate is a kind of organophosphorus fungicide, have systemic action, due to its efficiently, low toxicity, to human eye
And skin many advantages, such as having no stimulation, it is widely used in rice blast, sclerotium oryzicola, banded sclerotial blight, the water such as withered fringe disease
The prevention and treatment of rice disease.
The synthetic method of benzyl thiophosphate is mainly diphosphite and sulphur powder in excess base (ammonia in industrial production
Water, sodium carbonate, sodium hydroxide etc.) promote lower generation thiophosphoric acid diester, it is then reacted with chlorine bromine benzyl, and then be expected
Benzyl thiophosphate product；Also there is the document report using water phase ammonia process one-step synthesis dibenzylsulfide for phosphoric acid diisopropyl ester
Road.There are still following disadvantages for the prior art.1) due to needing that large excess of alkali is added in reaction system, lead to reaction
Byproduct is more, and environmental hazard is big；2) chemical structure of kitazine class pesticide activity molecule is stablized under acid and neutrallty condition,
Hydrolysis is easy to happen under alkaline condition.Dosage, the concentration of alkali in strict control reaction are needed using existing synthesis technology
And the conditions such as reaction temperature, the hydrolysis of product is avoided with this.But in the actual production process, still it can be observed that producing
The more apparent hydrolysis of product, leads to yield reduction and impurity increases；3) existing synthesis technology generally use comparison it is active,
The halogenated hydrocarbons being more toxic is as reaction raw materials, and by-product is more and harm is serious.Therefore, still urgently develop benzyl thiophosphate
Class pesticide activity molecule green, efficient synthetic method.
In recent years, also there is the report of improved method.Such as Wu reports Ga (OTf)3It is catalyzed lower benzylalcohol and thiophosphoric acid two
The Direct Dehydration of ester reacts；The thiophosphoric acid two that this method is limited using commercial source, high poison, stench, corrosivity are strong
Ethyl ester, and using expensive rare-earth metal catalyst, in addition it is worth noting that, diethyl thiophosphate still needs to anti-by multistep
It should be prepared.Kumaraswamy seminar reports the idol that cuprous iodide is catalyzed lower benzyl sulfohydrazide and diethyl phosphite
Connection reaction；Hong etc. reports the new synthetic method of the thiophosphate using sulfinic acid as sulphur source, and above-mentioned reaction is with organic sulfur
Reagent is as reaction raw materials.Disadvantage mentioned above greatlys restrict the practical application of these methods.
Summary of the invention
In order to overcome the problems in above-mentioned technology, the present invention is using benzene first from a wealth of sources, cheap and easy to get, stablizing low toxicity
A step dehydration occurs under conditions of no catalyst and generates benzyl thiophosphate, the synthesis for alcohol, sulphur powder and phosphite ester
Method is green and efficient.
To achieve the above object, the invention adopts the following technical scheme:
A kind of synthetic method of benzyl thiophosphate, uses benzyl alcohol, sulphur powder and phosphite ester for raw material, is in reaction temperature
Under conditions of 70~100 DEG C, carries out a step dehydration and generate benzyl thiophosphate, the reaction time is 6~24 hours, reaction
Formula are as follows:
Wherein: R is alkyl.
Further, the reaction temperature is 80~90 DEG C.
Further, the reaction carries out in a nitrogen atmosphere.
Further, the reaction carries out in air atmosphere.
Further, the reaction time is 12~18h.
Further, the benzyl alcohol: sulphur powder: the molar feed ratio of phosphite ester is 1~1.2:1~1.2:1~1.2.
Further, the benzyl alcohol: sulphur powder: the molar feed ratio of phosphite ester is 1.2:1.2:1.0.
Compared with prior art, the beneficial effects of the present invention are:
1, raw material benzyl alcohol, sulphur powder, the phosphite ester that compared with prior art, this method uses are cheap and easy to get, from a wealth of sources, steady
Fixed low toxicity, environmentally protective, realization alkylating reagent benzyl alcohol, sulphur powder and phosphorous acid under no catalyst, alkali-free, condition of no solvent
One step dehydration of ester generates benzyl phosphorothioate compound.
2, this method can easily be amplified to gram-grade preparation, requirement to reaction condition is lower, with known method phase
Than with the obvious advantage, it is with a wide range of applications.
Specific embodiment
Following embodiment is technical solution in order to better illustrate the present invention, rather than limits guarantor of the invention with this
Protect range.
Embodiment 1
Benzyl alcohol, sulphur powder and diethyl phosphite prepare benzyl diethyl thiophosphate (kitazine)
Sequentially added into tubular reactor sulphur powder (76.8mg, 2.4mmol, 1.2equiv.), benzyl alcohol (259.2mg,
2.4mmol, 1.2equiv.) and diethyl phosphite (276.0mg, 2.0mmol, 1.0equiv.), tube sealing after nitrogen protection sets
18h is stirred to react at 80 DEG C.It after TLC monitors fully reacting, is cooled to room temperature, product purifies (solvent with pillar layer separation
Petrol ether/ethyl acetate=4/1), separation yield 65%.Reaction equation is as follows:
The nuclear-magnetism of product characterizes:1H NMR(500MHz,CDCl3)δ7.38–7.29(m,4H),7.28–7.24(m,1H),
4.16-4.07 (m, 2H), 4.06-3.97 (m, 4H), 1.28 (t, J=7.2Hz, 6H)；13C NMR(125MHz,CDCl3)δ
137.51 (d, J=5.3Hz), 128.91,128.66,127.63,63.53 (d, J=5.8Hz), 34.97 (d, J=3.9Hz),
15.95 (d, J=7.4Hz)；31P NMR(202MHz,CDCl3)δ26.79。
Embodiment 2
Benzyl alcohol, sulphur powder and diethyl phosphite prepare benzyl diethyl thiophosphate (kitazine)
Sequentially added into tubular reactor sulphur powder (64.0mg, 2.0mmol, 1.0equiv.), benzyl alcohol (216.0mg,
2.0mmol, 1.0equiv.) and diethyl phosphite (276.0mg, 2.0mmol, 1.0equiv.), tube sealing be placed at 80 DEG C and stir
Mix reaction 18h.It after TLC monitors fully reacting, is cooled to room temperature, product purifies (solvent petroleum ether/acetic acid with pillar layer separation
Ethyl ester=4/1), separation yield 56%.Reaction equation is as follows:
The nuclear-magnetism of product characterizes:1H NMR(500MHz,CDCl3)δ7.38–7.29(m,4H),7.28–7.24(m,1H),
4.16-4.07 (m, 2H), 4.06-3.97 (m, 4H), 1.28 (t, J=7.2Hz, 6H)；13C NMR(125MHz,CDCl3)δ
137.51 (d, J=5.3Hz), 128.91,128.66,127.63,63.53 (d, J=5.8Hz), 34.97 (d, J=3.9Hz),
15.95 (d, J=7.4Hz)；31P NMR(202MHz,CDCl3)δ26.79。
Embodiment 3
Benzyl alcohol, sulphur powder and diethyl phosphite prepare benzyl diethyl thiophosphate (kitazine)
Sequentially added into tubular reactor sulphur powder (76.8mg, 2.4mmol, 1.2equiv.), benzyl alcohol (216.0mg,
2.0mmol, 1.0equiv.) and diethyl phosphite (331.2mg, 2.4mmol, 1.2equiv.), tube sealing be placed at 80 DEG C and stir
Mix reaction 18h.It after TLC monitors fully reacting, is cooled to room temperature, product purifies (solvent petroleum ether/acetic acid with pillar layer separation
Ethyl ester=4/1), separation yield 62%.Reaction equation is as follows:
The nuclear-magnetism of product characterizes:1H NMR(500MHz,CDCl3)δ7.38–7.29(m,4H),7.28–7.24(m,1H),
4.16-4.07 (m, 2H), 4.06-3.97 (m, 4H), 1.28 (t, J=7.2Hz, 6H)；13C NMR(125MHz,CDCl3)δ
137.51 (d, J=5.3Hz), 128.91,128.66,127.63,63.53 (d, J=5.8Hz), 34.97 (d, J=3.9Hz),
15.95 (d, J=7.4Hz)；31P NMR(202MHz,CDCl3)δ26.79。
Embodiment 4
Benzyl alcohol, sulphur powder and diethyl phosphite prepare benzyl diethyl thiophosphate (kitazine)
Sequentially added into tubular reactor sulphur powder (384mg, 12.0mmol, 1.2equiv.), benzyl alcohol (1296mg,
12.0mmol, 1.2equiv.) and diethyl phosphite (1380mg, 10.0mmol, 1.0equiv.), tube sealing be placed at 80 DEG C
It is stirred to react for 24 hours.It after TLC monitors fully reacting, is cooled to room temperature, product purifies (solvent petroleum ether/second with pillar layer separation
Acetoacetic ester=4/1), separation yield 61%.Reaction equation is as follows:
The nuclear-magnetism of product characterizes:1H NMR(500MHz,CDCl3)δ7.38–7.29(m,4H),7.28–7.24(m,1H),
4.16-4.07 (m, 2H), 4.06-3.97 (m, 4H), 1.28 (t, J=7.2Hz, 6H)；13C NMR(125MHz,CDCl3)δ
137.51 (d, J=5.3Hz), 128.91,128.66,127.63,63.53 (d, J=5.8Hz), 34.97 (d, J=3.9Hz),
15.95 (d, J=7.4Hz)；31P NMR(202MHz,CDCl3)δ26.79。
Embodiment 5
Benzyl alcohol, sulphur powder and diisopropyl phosphite prepare dibenzylsulfide for diisopropyl phosphate (different rice blast net)
Sequentially added into tubular reactor sulphur powder (76.8mg, 2.4mmol, 1.2equiv.), benzyl alcohol (259.2mg,
2.4mmol, 1.2equiv.) and diisopropyl phosphite (332.0mg, 2.0mmol, 1.0equiv.), tube sealing be placed in 100 DEG C
Under be stirred to react 18h.TLC monitor fully reacting after, be cooled to room temperature, product with pillar layer separation purify (solvent petroleum ether/
Ethyl acetate=4/1), separation yield 60%.Reaction equation is as follows:
The nuclear-magnetism of product characterizes:1H NMR(600MHz,CDCl3) δ 7.36-7.32 (m, 2H), 7.30 (dd, J=10.2,
4.8Hz, 2H), 7.26-7.22 (m, 1H), 4.79-4.54 (m, 2H), 4.04 (d, J=13.2Hz, 2H), 1.31 (d, J=
6.0Hz, 6H), 1.26 (d, J=6.0Hz, 6H)；13C NMR(151MHz,CDCl3)δ129.03,128.74,127.65,72.76
(d, J=6.4Hz), 35.30 (d, J=3.9Hz), 23.92 (d, J=4.3Hz), 23.61 (d, J=5.8Hz)；31P NMR
(243MHz,CDCl3)δ24.77。
Embodiment 6
Benzyl alcohol, sulphur powder and diisopropyl phosphite prepare dibenzylsulfide for diisopropyl phosphate (different rice blast net)
Sequentially added into tubular reactor sulphur powder (384mg, 12.0mmol, 1.2equiv.), benzyl alcohol (1296mg,
12.0mmol, 1.2equiv.) and diisopropyl phosphite (1660mg, 10.0mmol, 1.0equiv.), tube sealing be placed in 100 DEG C
Under be stirred to react for 24 hours.TLC monitor fully reacting after, be cooled to room temperature, product with pillar layer separation purify (solvent petroleum ether/
Ethyl acetate=4/1), separation yield 56%.Reaction equation is as follows:
The nuclear-magnetism of product characterizes:1H NMR(600MHz,CDCl3) δ 7.36-7.32 (m, 2H), 7.30 (dd, J=10.2,
4.8Hz, 2H), 7.26-7.22 (m, 1H), 4.79-4.54 (m, 2H), 4.04 (d, J=13.2Hz, 2H), 1.31 (d, J=
6.0Hz, 6H), 1.26 (d, J=6.0Hz, 6H)；13C NMR(151MHz,CDCl3)δ129.03,128.74,127.65,72.76
(d, J=6.4Hz), 35.30 (d, J=3.9Hz), 23.92 (d, J=4.3Hz), 23.61 (d, J=5.8Hz)；31P NMR
(243MHz,CDCl3)δ24.77。
Embodiment 7
Benzyl alcohol, sulphur powder and dimethylphosphite prepare dibenzylsulfide for dimethyl phosphate
Sequentially added into tubular reactor sulphur powder (76.8mg, 2.4mmol, 1.2equiv.), benzyl alcohol (259.2mg,
2.4mmol, 1.2equiv.) and dimethylphosphite (220.0mg, 2.0mmol, 1.0equiv.), tube sealing be placed at 80 DEG C and stir
Mix reaction 18h.It after TLC monitors fully reacting, is cooled to room temperature, product purifies (solvent petroleum ether/acetic acid with pillar layer separation
Ethyl ester=4/1), separation yield 63%.Reaction equation is as follows:
The nuclear-magnetism of product characterizes:1H NMR(600MHz,CDCl3) δ 7.28-7.37 (m, 5H), 4.03 (d, J=14.4Hz,
2H),3.64–3.72(m,6H)；13C NMR(151MHz,CDCl3) δ 137.2 (d, J=5.4Hz), 128.7,128.5,127.5,
53.5 (d, J=6.0Hz), 34.7 (d, J=3.6Hz)；31P NMR(202MHz,CDCl3)δ30.55。
Embodiment 8
Benzyl alcohol, sulphur powder and diethyl phosphite prepare benzyl diethyl thiophosphate (kitazine)
Sequentially added into tubular reactor sulphur powder (76.8mg, 2.4mmol, 1.2equiv.), benzyl alcohol (259.2mg,
2.4mmol, 1.2equiv.) and diethyl phosphite (276.0mg, 2.0mmol, 1.0equiv.), tube sealing after nitrogen protection sets
18h is stirred to react at 70 DEG C.It after TLC monitors fully reacting, is cooled to room temperature, product purifies (solvent with pillar layer separation
Petrol ether/ethyl acetate=4/1), separation yield 16%.Reaction equation is as follows:
The nuclear-magnetism of product characterizes:1H NMR(500MHz,CDCl3)δ7.38–7.29(m,4H),7.28–7.24(m,1H),
4.16-4.07 (m, 2H), 4.06-3.97 (m, 4H), 1.28 (t, J=7.2Hz, 6H)；13C NMR(125MHz,CDCl3)δ
137.51 (d, J=5.3Hz), 128.91,128.66,127.63,63.53 (d, J=5.8Hz), 34.97 (d, J=3.9Hz),
15.95 (d, J=7.4Hz)；31P NMR(202MHz,CDCl3)δ26.79。
Embodiment 9
Benzyl alcohol, sulphur powder and diethyl phosphite prepare benzyl diethyl thiophosphate (kitazine)
Sequentially added into tubular reactor sulphur powder (76.8mg, 2.4mmol, 1.2equiv.), benzyl alcohol (259.2mg,
2.4mmol, 1.2equiv.) and diethyl phosphite (276.0mg, 2.0mmol, 1.0equiv.), tube sealing after nitrogen protection sets
18h is stirred to react at 90 DEG C.It after TLC monitors fully reacting, is cooled to room temperature, product purifies (solvent with pillar layer separation
Petrol ether/ethyl acetate=4/1), separation yield 60%.Reaction equation is as follows:
The nuclear-magnetism of product characterizes:1H NMR(500MHz,CDCl3)δ7.38–7.29(m,4H),7.28–7.24(m,1H),
4.16-4.07 (m, 2H), 4.06-3.97 (m, 4H), 1.28 (t, J=7.2Hz, 6H)；13C NMR(125MHz,CDCl3)δ
137.51 (d, J=5.3Hz), 128.91,128.66,127.63,63.53 (d, J=5.8Hz), 34.97 (d, J=3.9Hz),
(15.95 d, J=7.4Hz)；31P NMR(202MHz,CDCl3)δ26.79。
Embodiment 10
Benzyl alcohol, sulphur powder and diethyl phosphite prepare benzyl diethyl thiophosphate (kitazine)
Sequentially added into tubular reactor sulphur powder (76.8mg, 2.4mmol, 1.2equiv.), benzyl alcohol (259.2mg,
2.4mmol, 1.2equiv.) and diethyl phosphite (276.0mg, 2.0mmol, 1.0equiv.), tube sealing after nitrogen protection sets
12h is stirred to react at 80 DEG C.It after TLC monitors fully reacting, is cooled to room temperature, product purifies (solvent with pillar layer separation
Petrol ether/ethyl acetate=4/1), separation yield 60%.Reaction equation is as follows:
The nuclear-magnetism of product characterizes:1H NMR(500MHz,CDCl3)δ7.38–7.29(m,4H),7.28–7.24(m,1H),
4.16-4.07 (m, 2H), 4.06-3.97 (m, 4H), 1.28 (t, J=7.2Hz, 6H)；13C NMR(125MHz,CDCl3)δ
137.51 (d, J=5.3Hz), 128.91,128.66,127.63,63.53 (d, J=5.8Hz), 34.97 (d, J=3.9Hz),
15.95 (d, J=7.4Hz)；31P NMR(202MHz,CDCl3)δ26.79。
Embodiment 11
Benzyl alcohol, sulphur powder and diethyl phosphite prepare benzyl diethyl thiophosphate (kitazine)
Sequentially added into tubular reactor sulphur powder (70.4mg, 2.2mmol, 1.1equiv.), benzyl alcohol (237.6mg,
2.2mmol, 1.1equiv.) and diethyl phosphite (276.0mg, 2.0mmol, 1.0equiv.), tube sealing after nitrogen protection sets
18h is stirred to react at 80 DEG C.It after TLC monitors fully reacting, is cooled to room temperature, product purifies (solvent with pillar layer separation
Petrol ether/ethyl acetate=4/1), separation yield 62%.Reaction equation is as follows:
The nuclear-magnetism of product characterizes:1H NMR(500MHz,CDCl3)δ7.38–7.29(m,4H),7.28–7.24(m,1H),
4.16-4.07 (m, 2H), 4.06-3.97 (m, 4H), 1.28 (t, J=7.2Hz, 6H)；13C NMR(125MHz,CDCl3)δ
137.51 (d, J=5.3Hz), 128.91,128.66,127.63,63.53 (d, J=5.8Hz), 34.97 (d, J=3.9Hz),
15.95 (d, J=7.4Hz)；31P NMR(202MHz,CDCl3)δ26.79。
The embodiment of the above is only used to explain the present invention, the scope of the present invention is not limited, for this technology
It, certainly can be according to technology contents disclosed in this specification, by way of replacing or changing for the technical staff in field
Other embodiments are made easily, therefore all changes and improvements etc. done in the principle of the present invention and process conditions, it should all wrap
It includes in scope of the present invention patent.
Claims (7)
1. a kind of synthetic method of benzyl thiophosphate, it is characterised in that: use benzyl alcohol, sulphur powder and phosphite ester for original
Material carries out a step dehydration and generates benzyl thiophosphate, reaction time under conditions of reaction temperature is 70~100 DEG C
It is 6~24 hours, reaction equation are as follows:
Wherein: R is alkyl.
2. a kind of synthetic method of benzyl thiophosphate according to claim 1, it is characterised in that: the reaction temperature
It is 80~90 DEG C.
3. a kind of synthetic method of benzyl thiophosphate according to claim 1, it is characterised in that: the reaction is in nitrogen
It is carried out under gas atmosphere.
4. a kind of synthetic method of benzyl thiophosphate according to claim 1, it is characterised in that: the reaction is in sky
It is carried out under gas atmosphere.
5. a kind of synthetic method of benzyl thiophosphate according to claim 1, it is characterised in that: the reaction time
For 12~18h.
6. a kind of synthetic method of benzyl thiophosphate according to claim 1, it is characterised in that: the benzyl alcohol:
Sulphur powder: the molar feed ratio of phosphite ester is 1~1.2:1~1.2:1~1.2.
7. a kind of synthetic method of benzyl thiophosphate according to claim 1, it is characterised in that: the benzyl alcohol:
Sulphur powder: the molar feed ratio of phosphite ester is 1.2:1.2:1.0.
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| CN111662322A (en) * | 2020-07-20 | 2020-09-15 | 温州大学 | Efficient green preparation method of sulfo-organic phosphonic acid derivative |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111662322A (en) * | 2020-07-20 | 2020-09-15 | 温州大学 | Efficient green preparation method of sulfo-organic phosphonic acid derivative |
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