CN103819512A - Synthetic method of diphosphine ligand - Google Patents
Synthetic method of diphosphine ligand Download PDFInfo
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- CN103819512A CN103819512A CN201410046432.6A CN201410046432A CN103819512A CN 103819512 A CN103819512 A CN 103819512A CN 201410046432 A CN201410046432 A CN 201410046432A CN 103819512 A CN103819512 A CN 103819512A
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 15
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000003446 ligand Substances 0.000 title claims abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 107
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 -isopropyl alachlor Chemical compound 0.000 claims abstract description 11
- 239000012280 lithium aluminium hydride Substances 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 238000010792 warming Methods 0.000 claims abstract description 11
- 238000001953 recrystallisation Methods 0.000 claims abstract description 10
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 25
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 25
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 230000002363 herbicidal effect Effects 0.000 abstract description 4
- 239000004009 herbicide Substances 0.000 abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000012827 research and development Methods 0.000 abstract description 3
- CRTMHFYHYMQVSB-UHFFFAOYSA-N CC=1C=C(C=C(C1)C)[P](C1=CC(=CC(=C1)C)C)=O Chemical compound CC=1C=C(C=C(C1)C)[P](C1=CC(=CC(=C1)C)C)=O CRTMHFYHYMQVSB-UHFFFAOYSA-N 0.000 abstract 1
- 238000004440 column chromatography Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 238000010791 quenching Methods 0.000 abstract 1
- 230000000171 quenching effect Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 20
- 241000196324 Embryophyta Species 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000013517 stratification Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 2
- 206010003694 Atrophy Diseases 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 241001582888 Lobus Species 0.000 description 1
- 231100000987 absorbed dose Toxicity 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000037444 atrophy Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 241001233957 eudicotyledons Species 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
The invention discloses a synthetic method of diphosphine ligand, and relates to the technical field of the synthetic technology of hydrogenation catalyst diphosphine ligand of agricultural herbicide S-isopropyl alachlor. The method comprises the following steps: lithium aluminium hydride is dissolved in diethyl ether and stirred under the protection of nitrogen, after the diethyl ether is cooled down, a diethyl ether solution of bis (3,5-dimethyl phenyl) phosphorus oxide is dropwise added into the diethyl ether, then a warming and reflux reaction is performed, after the reaction, hydrochloric acid is dropwise added into the diethyl ether, so as to perform a quenching reaction, after a diethyl ether layer is dried, an acetic acid solution of (R)-N,N-dimethyl-1-((s)-2-(diphenyl phosphorus base) ferrocenyl) ethylamine is added into the diethyl ether layer, then diethyl ether is removed, the temperature is raised to 70 to 80 DEG C till the reaction is finished, acetic acid is removed, then a mixed solvent of ethyl alcohol and methyl alcohol is added, and then the diphosphine ligand is obtained after recrystallization is performed. The synthetic method optimizes the subsequent processing technology, simplifies the operation steps, adopts a method of mixed solvent recrystallization to replace a column chromatography through research and development, and ensures that the cost is reduced, the productivity is improved, and the product content and yield are improved.
Description
Technical field
The present invention relates to the synthesis technology field of the hydrogenation catalyst biphosphine ligand of agricultural herbicide S-sec.-propyl alachlor.
Background technology
1-[(1R)-1-[bis-(3,5-3,5-dimethylphenyl) phosphino-] ethyl]-2-(diphenylphosphine)-(2S) ferrocene is the hydrogenation catalyst biphosphine ligand of synthetic agricultural herbicide S-sec.-propyl alachlor.S-sec.-propyl alachlor is selective herbicide, by the synthetic growth that suppresses cell of impede protein matter.The hypocotyl that is monocotyledonous coleoptile, dicotyledons by the young shoot of plant absorbs upwards conduction, seed and root liquid Assimilation and conductivity, but absorbed dose is less, and the speed of disturbing by making noise is slow.After emerging, mainly upwards conduct by root absorption, suppress the growth of young shoot and root.Susceptible weeds is before germination is unearthed afterwards or be just unearthed and be poisoned to death immediately, and show as coleoptile hard-pressed bale and vegetative point, slightly chap, the thin and bending of radicle, need not root, and vegetative point gradually browning look, black rots.If soil moisture content is good, weeds were killed in the young shoot phase.If soil moisture is few, after weeds are unearthed, along with rainfall soil humidity increases, weeds absorb sec.-propyl alachlor, the distortion of gramineous grass lobus cardiacus, atrophy, and after other leaf shrinkages, whole strain is withered.The whole strain of broadleaf weeds leaf shrinkage flavescence is withered.On farm crop without impact.
The producer of at present domestic a small amount of production all after reaction finishes precipitation obtain sticky solid thing, then adopt the method for note chromatography to obtain diphosphine ligand, cause production capacity very little, and the product content obtaining only has 94% left and right, the hydrogenation effect of S-sec.-propyl alachlor is had to impact.And yield is lower, only has 74% left and right.In this method, note chromatography complicated operation, production capacity is little, and solvent loss is large, causes cost very high.Be unfavorable for utilization and extention.
Summary of the invention
The object of the invention is to provide a kind of 1-[(1R)-1-[bis-(3,5-3,5-dimethylphenyl) phosphino-] ethyl]-2-(diphenylphosphine)-(2S) synthetic method of ferrocene, optimize aftertreatment technology, step simplifies the operation, by research and development, adopt the method for mixed solvent recrystallization to substitute note chromatography again, make cost, production capacity increases, and has improved content and the yield of product.
Technical solution of the present invention is: under nitrogen protection, lithium aluminum hydride is dissolved in ether and is stirred, after cooling, drip wherein two (3, 5-3,5-dimethylphenyl) diethyl ether solution of phosphorus oxide, dropping finishes rear temperature rising reflux reaction, after reaction finishes, drip hydrochloric acid cancellation reaction, ether layer adds (R)-N through super-dry, N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] in the acetic acid solution of ethamine, then remove ether, be warming up to 70～80 ℃ to reaction finish after, remove acetic acid, add again the mixed solvent of ethanol and methyl alcohol, recrystallization obtains 1-[(1R)-1-[bis-(3, 5-3,5-dimethylphenyl) phosphino-] ethyl]-2-(diphenylphosphine)-(2S) ferrocene.
Synthetic method of the present invention has been optimized aftertreatment technology, and the step that simplifies the operation, again by research and development, adopts the method for mixed solvent recrystallization to substitute note chromatography, makes cost, and production capacity increases, and has improved content and the yield of product.Make average yield be increased to 84.7%.Reduce energy consumption, deducted the use of ethyl acetate and sherwood oil equal solvent, reduced production cost, greatly improved the core competitiveness of product, and alleviated environmental protection pressure.
In order to react thoroughly, without excessive or without residue, (R)-N of the present invention, N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] molar ratio of ethamine and two (3,5-3,5-dimethylphenyl) phosphorus oxide is 1 ︰ 3～5.
The molar ratio of described two (3,5-3,5-dimethylphenyl) phosphorus oxide and lithium aluminum hydride is 1 ︰ 1.5～2.5.
Described (R)-N, N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] molar ratio of ethamine and ethanol is 1 ︰ 9000～13000.
The volume ratio of described methyl alcohol and ethanol is 1 ︰ 0.5～1.5.
The diethyl ether solution of described two (3,5-3,5-dimethylphenyl) phosphorus oxide is two (3,5-3,5-dimethylphenyl) phosphorus oxide and the ether composition of 116～161g ︰ 1500ml by feed ratio.
Described (R)-N, N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] acetic acid solution of ethamine is (R)-N of 50～65g ︰ 750ml by feed ratio, N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] ethamine and acetic acid composition.
In order to reduce the generation of side reaction, improve yield, the reaction of two (3,5-3,5-dimethylphenyl) phosphorus oxide and lithium aluminum hydride is to carry out under the mixed degree of reaction system is the condition of-5～5 ℃.
Described two (3,5-3,5-dimethylphenyl) sub-phosphorus and (R)-N, N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] reaction of ethamine is to carry out under the mixed degree of reaction system is the condition of 70～80 ℃.This condition has improved speed of reaction, as temperature of reaction exceedes 80 ℃, can affect the ee value of product.
Embodiment
Embodiment 1
The diethyl ether solution of preparation two (3,5-3,5-dimethylphenyl) phosphorus oxide: 23.1g (0.0842mol) two (3,5-3,5-dimethylphenyl) phosphorus oxide and 300ml ether are mixed, form.
In the A of 500ml bottle, stirring is housed, thermometer, addition funnel, reflux exchanger, under nitrogen protection, add 6.7g (0.1748mol) lithium aluminum hydride, 100ml ether stirs, be cooled to 0～5 ℃, drip above make two (3, 5-3,5-dimethylphenyl) diethyl ether solution of phosphorus oxide, by make above two (3, 5-3,5-dimethylphenyl) diethyl ether solution of phosphorus oxide all drips and finishes rear stirring 1h, temperature is controlled at 0～5 ℃, after finishing, insulation is warming up to 25 ℃ of reaction 3h, after reaction finishes, add hydrochloric acid cancellation reaction, stratification, get upper solution.
Stirring, thermometer, reflux exchanger, dropping pipe are housed in the B of 500ml bottle; under nitrogen protection; add 10g (0.0227mol) (R)-N; N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] ethamine, 150ml acetic acid stirs; form (R)-N; N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] acetic acid solution of ethamine, stand-by.
Upper solution in A bottle is added dropwise in B bottle by dripping pipe through drying installation, after dropping finishes, heats up and remove ether, after de-ether finishes, be warming up to 80 ℃ of reaction 3h, after reaction finishes, decompression removes acetic acid, obtain orange sticky solid, add the mixing solutions of ethanol and methyl alcohol to carry out recrystallization, obtain 12.4g1-[(1R)-1-[bis-(3,5-3,5-dimethylphenyl) phosphino-] ethyl]-2-(diphenylphosphine)-(2S) ferrocene, content 100%, yield 85.62%.
Embodiment 2
The diethyl ether solution of preparation two (3,5-3,5-dimethylphenyl) phosphorus oxide: 121.9g (0.4725mol) two (3,5-3,5-dimethylphenyl) phosphorus oxide and 1500ml ether are mixed, form.
In the A of 2000ml bottle, stirring, thermometer, addition funnel, reflux exchanger are housed; under nitrogen protection, add 42.48g (1.12mol) lithium aluminum hydride, 400ml ether to stir, be cooled to-5～0 ℃; drip two (3; 5-3,5-dimethylphenyl) diethyl ether solution of phosphorus oxide, all drip and finish rear stirring 1h, temperature is controlled at 0～5 ℃; after finishing, insulation is warming up to 29 ℃ of reaction 3h; after reaction finishes, add hydrochloric acid cancellation reaction, stratification.
Stirring, thermometer, reflux exchanger, dropping pipe are housed in the B of 2000ml bottle; under nitrogen protection; add 50g (0.1135mol) (R)-N; N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] ethamine, 750ml acetic acid stirs; form (R)-N; N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] acetic acid solution of ethamine, stand-by.
Upper solution in A bottle is added dropwise in B bottle by dripping pipe through drying installation, after dropping finishes, heats up and remove ether, after de-ether finishes, be warming up to 75 ℃ of reaction 3h, after reaction finishes, decompression removes acetic acid, obtain orange sticky solid, add the mixing solutions of ethanol and methyl alcohol to carry out recrystallization, obtain 57.4g1-[(1R)-1-[bis-(3,5-3,5-dimethylphenyl) phosphino-] ethyl]-2-(diphenylphosphine)-(2S) ferrocene, content 99.8%, yield 79.18%.
Embodiment 3
The diethyl ether solution of preparation two (3,5-3,5-dimethylphenyl) phosphorus oxide: 160.9g (0.6238mol) two (3,5-3,5-dimethylphenyl) phosphorus oxide and 1500ml ether are mixed, form.
In the A of 2000ml bottle, stirring, thermometer, addition funnel, reflux exchanger are housed; under nitrogen protection, add 42.5g (1.12mol) lithium aluminum hydride, 400ml ether to stir, be cooled to 0～5 ℃; drip two (3; 5-3,5-dimethylphenyl) diethyl ether solution of phosphorus oxide, all drip and finish rear stirring 1h, temperature is controlled at-5～0 ℃; after finishing, insulation is warming up to 30 ℃ of reaction 3h; after reaction finishes, add hydrochloric acid cancellation reaction, stratification.
At 2000ml(B bottle) be equipped with in the reaction flask of stirring, thermometer, reflux exchanger, dropping pipe and nitrogen protection; add 60g (0.1362mol) (R)-N; N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] ethamine, 750ml acetic acid stirs; form (R)-N; N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] acetic acid solution of ethamine, stand-by.
Upper solution in A bottle is added dropwise in B bottle by dripping pipe through drying installation, after dropping finishes, heats up and remove ether, after de-ether finishes, be warming up to 70 ℃ of reaction 3h, after reaction finishes, decompression removes acetic acid, obtain orange sticky solid, add the mixing solutions of ethanol and methyl alcohol to carry out recrystallization, obtain 74.6g1-[(1R)-1-[bis-(3,5-3,5-dimethylphenyl) phosphino-] ethyl]-2-(diphenylphosphine)-(2S) ferrocene, content 100%, yield 85.98%.
Embodiment 4
The diethyl ether solution of preparation two (3,5-3,5-dimethylphenyl) phosphorus oxide: 146.3g (0.5671mol) two (3,5-3,5-dimethylphenyl) phosphorus oxide and 1500ml ether are mixed, form.
In the A of 2000ml bottle, stirring, thermometer, addition funnel, reflux exchanger are housed; under nitrogen protection, add 42.5g (1.12mol) lithium aluminum hydride, 400ml ether to stir, be cooled to-5～0 ℃; drip two (3; 5-3,5-dimethylphenyl) diethyl ether solution of phosphorus oxide, all drip and finish rear stirring 1h, temperature is controlled at-5～0 ℃; after finishing, insulation is warming up to 30 ℃ of reaction 3h; after reaction finishes, add hydrochloric acid cancellation reaction, stratification.
Stirring, thermometer, reflux exchanger, dropping pipe are housed in the B of 2000ml bottle; under nitrogen protection; add 65g (0.1476mol) (R)-N; N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] ethamine, 750ml acetic acid; stir; form (R)-N, N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] acetic acid solution of ethamine, stand-by.
Upper solution in A bottle is added dropwise in B bottle by dripping pipe through drying installation, after dropping finishes, heats up and remove ether.After de-ether finishes, be warming up to 75 ℃ of reaction 3h.
After reaction finishes, decompression removes acetic acid, obtains orange sticky solid, add the mixing solutions of ethanol and methyl alcohol to carry out recrystallization, obtain 82.9g1-[(1R)-1-[bis-(3,5-3,5-dimethylphenyl) phosphino-] ethyl]-2-(diphenylphosphine)-(2S) ferrocene, content 100%, yield 88.17%.
Reaction formula of the present invention is as follows:
Claims (9)
1. the synthetic method of a biphosphine ligand, it is characterized in that under nitrogen protection, lithium aluminum hydride is dissolved in ether and is stirred, after cooling, drip wherein two (3, 5-3,5-dimethylphenyl) diethyl ether solution of phosphorus oxide, dropping finishes rear temperature rising reflux reaction, after reaction finishes, drip hydrochloric acid cancellation reaction, ether layer adds (R)-N through super-dry, N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] in the acetic acid solution of ethamine, then remove ether, be warming up to 70～80 ℃ to reaction finish after, remove acetic acid, add again the mixed solvent of ethanol and methyl alcohol, recrystallization obtains 1-[(1R)-1-[bis-(3, 5-3,5-dimethylphenyl) phosphino-] ethyl]-2-(diphenylphosphine)-(2S) ferrocene.
2. synthetic method according to claim 1, is characterized in that described (R)-N, N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] molar ratio of ethamine and two (3,5-3,5-dimethylphenyl) phosphorus oxide is 1 ︰ 3～5.
3. synthetic method according to claim 1, is characterized in that the molar ratio of described two (3,5-3,5-dimethylphenyl) phosphorus oxide and lithium aluminum hydride is 1 ︰ 1.5～2.5.
4. synthetic method according to claim 1, is characterized in that described (R)-N, N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] molar ratio of ethamine and ethanol is 1 ︰ 9000～13000.
5. synthetic method according to claim 1, the reaction that it is characterized in that two (3,5-3,5-dimethylphenyl) phosphorus oxide and lithium aluminum hydride is to carry out under the mixed degree of reaction system is the condition of-5～5 ℃.
6. synthetic method according to claim 1, it is characterized in that described two (3,5-3,5-dimethylphenyl) sub-phosphorus and (R)-N, N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] reaction of ethamine is to carry out under the mixed degree of reaction system is the condition of 70～80 ℃.
7. according to the synthetic method described in claim 1 or 2 or 3 or 4, the diethyl ether solution that it is characterized in that described two (3,5-3,5-dimethylphenyl) phosphorus oxide is two (3,5-3,5-dimethylphenyl) phosphorus oxide and the ether composition of 116～161g ︰ 1500ml by feed ratio.
8. according to the synthetic method described in claim 1 or 2 or 3 or 4, it is characterized in that described (R)-N, N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] acetic acid solution of ethamine is (R)-N of 50～65g ︰ 750ml by feed ratio, N-dimethyl-1-[(S)-2-(diphenylphosphine base) ferrocenyl] ethamine and acetic acid composition.
9. synthetic method according to claim 1, the volume ratio that it is characterized in that methyl alcohol and ethanol is 1 ︰ 0.5～1.5.
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| CN201410046432.6A CN103819512A (en) | 2014-02-10 | 2014-02-10 | Synthetic method of diphosphine ligand |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111138310A (en) * | 2019-12-23 | 2020-05-12 | 江苏长青农化股份有限公司 | Preparation method of (S) -metolachlor and catalyst used in preparation process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5583241A (en) * | 1993-10-01 | 1996-12-10 | Ciba-Geigy Corporation | Fluoroalkyl-substituted ferrocenyl diphosphines as ligands for homogeneous catalysts |
| CN101857612A (en) * | 2010-06-11 | 2010-10-13 | 南京工业大学 | Chiral diphosphine ligand, iridium composite catalyst thereof, preparation method and application of chiral diphosphine ligand in asymmetric hydrogenation synthesis of -metolachlor |
-
2014
- 2014-02-10 CN CN201410046432.6A patent/CN103819512A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5583241A (en) * | 1993-10-01 | 1996-12-10 | Ciba-Geigy Corporation | Fluoroalkyl-substituted ferrocenyl diphosphines as ligands for homogeneous catalysts |
| CN101857612A (en) * | 2010-06-11 | 2010-10-13 | 南京工业大学 | Chiral diphosphine ligand, iridium composite catalyst thereof, preparation method and application of chiral diphosphine ligand in asymmetric hydrogenation synthesis of -metolachlor |
Non-Patent Citations (2)
| Title |
|---|
| ESTEBAN MEJÍA等: "Asymmetric Transfer Hydrogenation of Ketones Catalyzed by Rhenium Complexes with Chiral Ferrocenylphosphane Ligands", 《EUR. J. INORG. CHEM.》 * |
| 李玉峰等: "(R)-1-[(S)-2-(二苯基膦)二茂铁基]乙基二(3,5-二甲基苯基)膦的合成", 《精细化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111138310A (en) * | 2019-12-23 | 2020-05-12 | 江苏长青农化股份有限公司 | Preparation method of (S) -metolachlor and catalyst used in preparation process |
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