CN106957333A - A kind of preparation method of bis-alkoxy Thiophosphonate - Google Patents
A kind of preparation method of bis-alkoxy Thiophosphonate Download PDFInfo
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- CN106957333A CN106957333A CN201710191557.1A CN201710191557A CN106957333A CN 106957333 A CN106957333 A CN 106957333A CN 201710191557 A CN201710191557 A CN 201710191557A CN 106957333 A CN106957333 A CN 106957333A
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- alkoxy
- thiophosphonate
- bis
- preparation
- sulfonyl chloride
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 150000001879 copper Chemical class 0.000 claims abstract description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 11
- 238000004440 column chromatography Methods 0.000 claims description 7
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical group O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 3
- -1 aryl sulphur Chemical compound 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 4
- 229910021529 ammonia Inorganic materials 0.000 claims 2
- 235000015177 dried meat Nutrition 0.000 claims 2
- 150000001263 acyl chlorides Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 125000001500 prolyl group Chemical group [H]N1C([H])(C(=O)[*])C([H])([H])C([H])([H])C1([H])[H] 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000005311 nuclear magnetism Effects 0.000 description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- MFYLRNKOXORIPK-UHFFFAOYSA-N (3-nitrophenyl)-phenylmethanone Chemical class [O-][N+](=O)C1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 MFYLRNKOXORIPK-UHFFFAOYSA-N 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- GYOBZOBUOMDRRN-UHFFFAOYSA-N 2-methoxybenzenesulfonyl chloride Chemical compound COC1=CC=CC=C1S(Cl)(=O)=O GYOBZOBUOMDRRN-UHFFFAOYSA-N 0.000 description 1
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical class CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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 Table
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention belongs to technical field of organic synthesis, specifically disclose a kind of preparation method of bis-alkoxy Thiophosphonate, including aryl sulfonyl chloride and dialkyl phosphite are added in organic solvent, copper salt catalyst and L proline parts are added, 10~20h is reacted at 80~100 DEG C；After reaction terminates, concentration of reaction solution obtains bis-alkoxy Thiophosphonate after isolating and purifying.The present invention, without alkaline environment, only under the mantoquita and part of catalytic amount, produces product using aryl sulfonyl chloride and dialkyl phosphite cheap and easy to get as raw material；Inventive substrate is applied widely, and technique is simple, easy to operate, and substrate spectrum is wide, with preferably yield, is adapted to popularization and application, and the product of preparation can be used for the various fields such as medicine, agricultural chemicals.
Description
Technical field
The invention belongs to technical field of organic synthesis, more particularly to a kind of preparation method of bis-alkoxy Thiophosphonate.
Background technology
Bis-alkoxy Thiophosphonate is class intermediate important in organic synthesis, in medicine, agricultural chemicals and pigment etc.
With important application value.The method that several synthesis bis-alkoxy Thiophosphonate has been disclosed in prior art, but these
Method has problems with：Raw material taste is big, severe reaction conditions, base amount are big etc..
Wherein, a CN 104292255 describes " a kind of preparation method of S- arylthios phosphate ", disclose with
Aryl sulfonyl chloride and phosphite ester are raw material, under the catalysis of mantoquita, and 12~24h are reacted at 60~150 DEG C, and target product is made.
This method reaction temperature is high, and the compound prepared in embodiment is required to more than 120 DEG C, and the reaction time is long, needs 24h.Cause
This, finding a kind of gentle method synthesis bis-alkoxy Thiophosphonate turns into problem urgently to be resolved hurrily in organic synthesis.
The content of the invention
The present invention provides a kind of preparation method of bis-alkoxy Thiophosphonate, with aryl sulfonyl chloride and phosphorous acid dialkyl
Ester is raw material, makees in mantoquita catalysis and L-PROLINE under part, 10~20h is reacted at 80~100 DEG C, bis-alkoxy sulphur is made
For phosphonate ester.
Technical scheme is as follows：
A kind of preparation method of bis-alkoxy Thiophosphonate, it is characterised in that comprise the following steps：
(1) aryl sulfonyl chloride and dialkyl phosphite are added in organic solvent, add copper salt catalyst and L-
Proline part, reacts 10~20h at 80~100 DEG C；
(2) after reaction terminates, concentration of reaction solution obtains bis-alkoxy Thiophosphonate after isolating and purifying.
Preferably, the mol ratio of described aryl sulfonyl chloride and dialkyl phosphite is 1:2-1:4.
Preferably, the aryl sulfonyl chloride described in every mole adds 2-10L organic solvents.
Preferably, the substitution of described aryl sulfonyl chloride has one kind in alkoxy, alkyl, halogen or nitro.
Preferably, described organic solvent is tetrahydrofuran.
Preferably, described copper salt catalyst is Copper dichloride dihydrate.
Preferably, the mole percent of described copper salt catalyst is 5-10%.
Preferably, the mole percent of described L-PROLINE part is 10-20%.
Preferably, when step (2) is isolated and purified, the reactant being concentrated to give is with ethyl acetate/petroleum ether=1/3-1/10
(V/V) column chromatography for separation is carried out for solvent.
Compared with prior art, beneficial effects of the present invention are as follows：
First, the preparation method of a kind of bis-alkoxy Thiophosphonate of the invention, with aryl sulfonyl chloride cheap and easy to get and
Dialkyl phosphite is raw material, and without alkaline environment, only under the mantoquita and part of catalytic amount, idol can occur in the solution
Connection reaction, prepares bis-alkoxy phosphonothiolic acid esters compound；
2nd, preparation method of the invention, wide application range of substrates, to a variety of groups such as alkoxy, alkyl, halogen, nitro
Substituted aryl sulfonyl chloride, with preferable applicability；And the preparation method technique of the present invention is simple, easy to operate, substrate model
Enclose wide, with preferably yield, be adapted to popularization and application, the product of preparation can be used for the various fields such as medicine, agricultural chemicals.
Brief description of the drawings
Fig. 1 is the O of embodiment 1, O- diethyl-S- (4- aminomethyl phenyls) Thiophosphonate1H NMR hydrogen spectrograms；
Fig. 2 is the O of embodiment 2, O- diethyl-S- (4- methoxyphenyls) Thiophosphonate1H NMR hydrogen spectrograms；
Fig. 3 is the O of embodiment 3, O- diethyl-S- (3- nitrobenzophenones) Thiophosphonate1H NMR hydrogen spectrograms.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this hair
It is bright, rather than limit protection scope of the present invention.Those skilled in the art are according to changing that the present invention makes in actual applications
Enter and adjust, still fall within protection scope of the present invention.
A kind of preparation method of bis-alkoxy Thiophosphonate of the present invention, specifically includes following steps：
(1) aryl sulfonyl chloride and dialkyl phosphite are added in tetrahydrofuran, add Copper dichloride dihydrate and urge
Agent and L-PROLINE part, react 10~20h at 80~100 DEG C；
(2) after reaction terminates, concentration of reaction solution obtains bis-alkoxy Thiophosphonate after isolating and purifying.
Reaction expression of the present invention is as follows：
Wherein, R1For methyl, ethyl, isopropyl one or more；R2 is unsubstituted or with substituent phenyl,
The substituent is one kind in alkoxy, nitro, alkyl or halogen.
Embodiment 1
The preparation method of O, O- diethyl-S- (4- aminomethyl phenyls) Thiophosphonate, comprises the following steps：
2.0mmol diethyl phosphite and 0.5mmol p-methyl benzene sulfonic chlorides are weighed in reaction bulb, 5% is added
Copper dichloride dihydrate is as catalyst, and 10% L-PROLINE is added at 1.0mL tetrahydrofurans, 80 DEG C and reacted as part
12h.After reaction solution is concentrated under reduced pressure, with ethyl acetate/petroleum ether=1:3 (v/v) are solvent column chromatography for separation, obtain 98mg targets
Compound.
The target product yield of the present embodiment 1 is 75%.
As shown in figure 1, nuclear-magnetism sign is carried out to target product, it is as follows：1H NMR(500MHz,CDCl3):δ 7.44 (d, J=
7.0Hz, 2H), 7.15 (d, J=8.0Hz, 2H), 4.25-4.12 (m, 4H), 2.34 (s, 3H), 1.31 (t, J=7.0Hz, 3H)
Embodiment 2
The preparation method of O, O- diethyl-S- (4- methoxyphenyls) Thiophosphonate, comprises the following steps：
2.0mmol diethyl phosphite and 0.5mmol are weighed to Methoxybenzenesulfonyl chloride in reaction bulb, add 5%
Copper dichloride dihydrate as catalyst, 10% L-PROLINE is added at 1.0mL tetrahydrofurans, 80 DEG C and reacted as part
12h.After reaction solution is concentrated under reduced pressure, with ethyl acetate/petroleum ether=1:3 (v/v) are solvent column chromatography for separation, obtain 94mg targets
Compound.
The target product yield of the present embodiment 2 is 68%.
As shown in Fig. 2 nuclear-magnetism sign is carried out to target product, it is as follows：1H NMR(500MHz,CDCl3):δ7.48-7.46
(m, 2H), 6.88 (d, J=9.0Hz, 2H), 4.24-4.12 (m, 4H), 3.80 (s, 3H), 1.31 (t, J=7.0Hz, 6H)
Embodiment 3
The preparation method of O, O- diethyl-S- (3- nitrobenzophenones) Thiophosphonate, comprises the following steps：
2.0mmol diethyl phosphite and 0.5mmol3- nitrobenzene sulfonyl chlorides are weighed in reaction bulb, 5% is added
Copper dichloride dihydrate is as catalyst, and 10% L-PROLINE is added at 1.0mL tetrahydrofurans, 80 DEG C and reacted as part
12h.After reaction solution is concentrated under reduced pressure, with ethyl acetate/petroleum ether=1:3 (v/v) are solvent column chromatography for separation, obtain 101mg mesh
Mark compound.
The target product yield of the present embodiment is 69%.
As shown in figure 3, nuclear-magnetism sign is carried out to target product, it is as follows：1H NMR(500MHz,CDCl3):δ8.45-8.44
(m, 1H), 8.23 (d, J=8.0Hz, 1H), 7.94 (d, J=8.0Hz, 1H), 7.57 (t, J=8.0Hz, 1H), 4.31-4.19
(m, 4H), 1.36 (t, J=7.0Hz, 6H)
Embodiment 4
The preparation method of O, O- diethyl-S- (2,4,6- trimethylphenyl) Thiophosphonate, comprises the following steps：
2.0mmol diethyl phosphite and 0.5mmol2 is weighed, 4,6- trimethylbenzene chlorides are added in reaction bulb
5% Copper dichloride dihydrate is as catalyst, and 10% L-PROLINE is added anti-at 1.0mL tetrahydrofurans, 80 DEG C as part
Answer 12h.After reaction solution is concentrated under reduced pressure, with ethyl acetate/petroleum ether=1:3 (v/v) are solvent column chromatography for separation, obtain 93mg mesh
Mark compound.
The target product yield of the present embodiment 4 is 64%.
Nuclear-magnetism sign is carried out to target product, it is as follows：1H NMR(500MHz,CDCl3):δ6.94(s,2H),4.17-4.05
(m, 4H), 2.53 (s, 6H), 2.25 (d, J=2.0Hz, 3H), 1.28 (t, J=7.0Hz, 6H)
Embodiment 5
The preparation method of O, O- dimethyl-S- (4- chlorphenyls) Thiophosphonate, comprises the following steps：
2.0mmol dimethylphosphite and 0.5mmol parachloroben-zenesulfonyl chlorides are weighed in reaction bulb, the two of addition 5%
Hydrated copper chloride is as catalyst, and 10% L-PROLINE adds at 1.0mL tetrahydrofurans, 80 DEG C as part and reacts 12h.
After reaction solution is concentrated under reduced pressure, with ethyl acetate/petroleum ether=1:3 (v/v) are solvent column chromatography for separation, obtain 76mg target chemical combination
Thing.
The target product yield of the present embodiment 5 is 60%.
Nuclear-magnetism sign is carried out to target product, it is as follows：1H NMR(500MHz,CDCl3):δ 7.50 (d, J=7.0Hz, 2H),
(s, the 3H) of 7.33 (d, J=8.5Hz, 2H), 3.84 (s, 3H), 3.81
Present invention disclosed above preferred embodiment is only intended to help and illustrates the present invention.Preferred embodiment is not detailed
All details of narration, it is only described embodiment that the invention is not limited yet.Obviously, according to the content of this specification,
It can make many modifications and variations.This specification is chosen and specifically describes these embodiments, is to preferably explain the present invention
Principle and practical application so that skilled artisan can be best understood by and utilize the present invention.The present invention is only
Limited by claims and its four corner and equivalent.
Claims (9)
1. a kind of preparation method of bis-alkoxy Thiophosphonate, it is characterised in that comprise the following steps：
(1) aryl sulfonyl chloride and dialkyl phosphite are added in organic solvent, add copper salt catalyst and L- dried meat ammonia
Sour part, reacts 10~20h at 80~100 DEG C；
(2) after reaction terminates, concentration of reaction solution obtains bis-alkoxy Thiophosphonate after isolating and purifying.
2. the preparation method of bis-alkoxy Thiophosphonate according to claim 1, it is characterised in that described aryl sulphur
The mol ratio of acyl chlorides and dialkyl phosphite is 1:2-1:4.
3. the preparation method of bis-alkoxy Thiophosphonate according to claim 1, it is characterised in that described in every mole
Aryl sulfonyl chloride adds 2-10L organic solvents.
4. the preparation method of bis-alkoxy Thiophosphonate according to claim 1, it is characterised in that described aryl sulphur
Acyl chlorides substitution has one kind in alkoxy, alkyl, halogen or nitro.
5. the preparation method of bis-alkoxy Thiophosphonate according to claim 1, it is characterised in that described is organic molten
Agent is tetrahydrofuran.
6. the preparation method of bis-alkoxy Thiophosphonate according to claim 1, it is characterised in that described mantoquita is urged
Agent is Copper dichloride dihydrate.
7. the preparation method of bis-alkoxy Thiophosphonate according to claim 1, it is characterised in that described mantoquita is urged
The mole percent of agent is 5-10%.
8. the preparation method of bis-alkoxy Thiophosphonate according to claim 1, it is characterised in that described L- dried meat ammonia
The mole percent of sour part is 10-20%.
9. the preparation method of bis-alkoxy Thiophosphonate according to claim 1, it is characterised in that step (2) is separated
During purifying, the reactant being concentrated to give is that solvent carries out column chromatography point with ethyl acetate/petroleum ether=1/3-1/10 (V/V)
From.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573376A (en) * | 2017-09-07 | 2018-01-12 | 上海应用技术大学 | A kind of preparation method of alkyl sulfide (selenium) for phosphonate ester |
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|---|---|---|---|---|
| CN104292255A (en) * | 2014-01-06 | 2015-01-21 | 郑州大学 | Preparation method of S-aryl phosphorothioate |
| CN106478728A (en) * | 2016-10-17 | 2017-03-08 | 上海应用技术大学 | A kind of 10 virtues（Alkane）The preparation method of miscellaneous luxuriant and rich with fragrance 10 oxides of sulfenyl 9 oxa- 10 phosphine |
-
2017
- 2017-03-28 CN CN201710191557.1A patent/CN106957333B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104292255A (en) * | 2014-01-06 | 2015-01-21 | 郑州大学 | Preparation method of S-aryl phosphorothioate |
| CN106478728A (en) * | 2016-10-17 | 2017-03-08 | 上海应用技术大学 | A kind of 10 virtues（Alkane）The preparation method of miscellaneous luxuriant and rich with fragrance 10 oxides of sulfenyl 9 oxa- 10 phosphine |
Non-Patent Citations (3)
| Title |
|---|
| DUNGAI WANG ET AL: "Metal and base-free reductive coupling reaction of P(O)–H with aryl/alkyl sulfonyl chlorides: a novel protocol for the construction of P–S–Cbonds", 《ORG. BIOMOL. CHEM.》 * |
| HE, WEI ET AL: "Direct synthesis of thiophosphates by reaction of diphenylphosphine oxide with sulfonyl chlorides", 《TETRAHEDRON》 * |
| 白洁: "铜催化芳基磺酰氯与亚磷酸酯还原偶联反应合成S_芳基硫代磷酸酯", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573376A (en) * | 2017-09-07 | 2018-01-12 | 上海应用技术大学 | A kind of preparation method of alkyl sulfide (selenium) for phosphonate ester |
| CN107573376B (en) * | 2017-09-07 | 2019-09-27 | 上海应用技术大学 | A kind of preparation method of alkyl sulfide (selenium) for phosphonate ester |
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