CN103819508A - Method for synthesizing di(3,5-dimethyl phenyl)phosphorus oxide - Google Patents
Method for synthesizing di(3,5-dimethyl phenyl)phosphorus oxide Download PDFInfo
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- CN103819508A CN103819508A CN201410046420.3A CN201410046420A CN103819508A CN 103819508 A CN103819508 A CN 103819508A CN 201410046420 A CN201410046420 A CN 201410046420A CN 103819508 A CN103819508 A CN 103819508A
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- phosphorus oxide
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- bromobenzene
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- 238000000034 method Methods 0.000 title abstract description 6
- 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 title abstract 3
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 35
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000012044 organic layer Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- LMFRTSBQRLSJHC-UHFFFAOYSA-N 1-bromo-3,5-dimethylbenzene Chemical compound CC1=CC(C)=CC(Br)=C1 LMFRTSBQRLSJHC-UHFFFAOYSA-N 0.000 claims description 17
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 13
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 13
- 238000010189 synthetic method Methods 0.000 claims description 11
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 239000011630 iodine Substances 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 7
- 230000001143 conditioned effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract description 4
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002363 herbicidal effect Effects 0.000 abstract description 4
- 239000004009 herbicide Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- -1 -isopropyl alachlor Chemical compound 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 3
- 238000004440 column chromatography Methods 0.000 abstract 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 abstract 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 abstract 1
- 241000196324 Embryophyta Species 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- 150000004795 grignard reagents Chemical class 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
- 230000007613 environmental effect Effects 0.000 description 1
- 241001233957 eudicotyledons Species 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing di(3,5-dimethyl phenyl)phosphorus oxide, and relates to the technical field of synthesis processes of a midbody of a hydrogenation catalyst diphosphine ligand of agriculture herbicide S-isopropyl alachlor. The method comprises the following steps: firstly, completely mixing Mg, tetrahydrofuran and iodine, adding a small amount of 3,5-dimentyl bromobenzene, heating to initialize reaction, raising the temperature of the mixing temperature to be 50-60 DEG C, cooling down, adding a great deal of 3,5-dimentyl bromobenzene, heating to ensure reaction of the mixing system at 45-50 DEG C till the reaction is accomplished, further cooling down, dropping diethyl phosphate, stirring to react till the reaction is accomplished, subsequently adjusting the pH value of the system after reaction to be 1 by using hydrochloric acid, further adding methylbenzene to extract and layer, desolventizing an organic layer to obtain white solid, and recrystalizing the white solid by using cyclohexane so as to obtain the di(3,5-dimethyl phenyl)phosphorus oxide. According to the method, operation steps of column chromatography and the like are eliminated, the capacity is increased, the yield is increased, the energy consumption is reduced, and the production cost is lowered.
Description
Technical field
The present invention relates to the intermediate of the hydrogenation catalyst biphosphine ligand of agricultural herbicide S-sec.-propyl alachlor---the synthesis technology field of two (3,5-3,5-dimethylphenyl) phosphorus oxide.
Background technology
Two (3,5-3,5-dimethylphenyl) phosphorus oxide is the intermediate of 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 domestic a small amount of production at present all adopts and in THF, adds Mg, adds iodine to make catalyzer, drips a small amount of 3,5-dimethyl bromobenzene, adds thermal booster reaction, temperature rise, cooling drips 3,5-dimethyl bromobenzene, after reaction finishes, cooling drips diethyl phosphite, drips and finishes stirring reaction, and reaction finishes, adjust pH=1 with hydrochloric acid, add water and chloroform, stir layering, organic layer precipitation obtains yellow dope, obtains two (3,5-3,5-dimethylphenyl) phosphorus oxide by note chromatography.Its average yield only has 54% left and right, and note chromatography complicated operation, and 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 synthetic method of two (3,5-3,5-dimethylphenyl) phosphorus oxide, changes solvent, optimizes aftertreatment technology, and the step that simplifies the operation, again by research and development, adopts the method for solvent recrystallization, makes cost, and production capacity increases, and yield improves.
Technical solution of the present invention is: first Mg, tetrahydrofuran (THF) (THF) and iodine are mixed complete, add on a small quantity 3,5-dimethyl bromobenzene, adds thermal booster reaction, after mixed system temperature rise to 50 ℃～60 ℃, be cooled to 20～30 ℃, then add a large amount of 3,5-dimethyl bromobenzene, after heating finishes conditioned response to the reaction of 45 ℃～50 ℃ of mixed systems, be cooled to again-10～5 ℃, then drip diethyl phosphite, at temperature of reaction system be under the condition of-5～5 ℃ stirring reaction to finishing; Then adopt hydrochloric acid to adjust the pH=1 of system after reaction, then add toluene extracting and demixing, get organic layer precipitation and obtain white solid, obtain two (3,5-3,5-dimethylphenyl) phosphorus oxide with hexanaphthene recrystallization.
The present invention has optimized the synthesis condition of grignard reagent and diethyl phosphite, adds for the first time on a small quantity 3, and 5-dimethyl bromobenzene first react a small amount of grignard reagent of generation at higher temperature with Mg, cause whole reaction as initiator; Add for the second time in a large number 3,5-dimethyl bromobenzene, can make reaction thoroughly, then adopts again toluene to carry out aftertreatment, directly obtains white solid, by hexanaphthene recrystallization, obtains two (3,5-3,5-dimethylphenyl) phosphorus oxide.Save the operation stepss such as note chromatography, increased production capacity, improved yield.Make average yield be increased to 72%.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 addition, in order to react thoroughly, without excessive or without residue, Mg of the present invention and described on a small quantity 3, the molar ratio of 5-dimethyl bromobenzene is 1 ︰ 1.0～1.5.
Described a large amount of 3,5-dimethyl bromobenzene and a small amount of 3, the mass ratio of 5-dimethyl bromobenzene is 4～4.5 ︰ 1.
The feed ratio of Mg and tetrahydrofuran (THF) is 1mol ︰ 300～500ml.
The molar ratio of Mg and iodine is 250 ︰ 1～5.
The molar ratio of Mg and diethyl phosphite is 1 ︰ 0.3～0.5.
The feed ratio of Mg and toluene is 1mol ︰ 300～500ml.
The feed ratio of Mg and hexanaphthene is 1mol ︰ 300～500ml.
The feed ratio of Mg and toluene is 1mol ︰ 250～400ml.
Embodiment
Embodiment 1
At 1000ml, stirring is housed, thermometer, in the reaction flask of reflux exchanger, add 28.8g (1.2mol) Mg, 500mlTHF, 0.1g(0.4mmol) iodine and 63g(0.341mol) 3, 5-dimethyl bromobenzene, intensification initiation reaction, temperature rises to 60 ℃, be cooled to 20～25 ℃, drip 270g(1.46mol) 3, 5-dimethyl bromobenzene, drip and finish, be warming up to 45 ℃ of reaction 4h, after reaction finishes, be cooled to-10～-5 ℃, drip 55.2g(0.4mol) diethyl phosphite, drip and finish, stirring reaction 1h, temperature is controlled at-5～0 ℃, after reaction finishes, adjust pH=1 with hydrochloric acid, add 400ml toluene extracting and demixing, organic layer precipitation obtains white solid, add 300ml hexanaphthene recrystallization to obtain 68g bis-(3, 5-3,5-dimethylphenyl) phosphorus oxide, yield 65.8%.
Embodiment 2
At 1000ml, stirring is housed, thermometer, in the reaction flask of reflux exchanger, add 28.8g (1.2mol) Mg, 450mlTHF, 0.2g(0.8mmol) iodine and 54.6g(0.2951mol) 3, 5-dimethyl bromobenzene, intensification initiation reaction, temperature rises to 55 ℃, be cooled to 25～30 ℃, drip 234g(1.2649mol) 3, 5-dimethyl bromobenzene, drip and finish, be warming up to 50 ℃ of reaction 4h, after reaction finishes, be cooled to-10～-5 ℃, drip 69g(0.5mol) diethyl phosphite, drip and finish, stirring reaction 1h, temperature is controlled at 0～5 ℃, after reaction finishes, adjust pH=1 with hydrochloric acid, add 500ml toluene extracting and demixing, organic layer precipitation obtains white solid, add 350ml hexanaphthene recrystallization to obtain 96.6g bis-(3, 5-3,5-dimethylphenyl) phosphorus oxide, yield 74.9%.
Embodiment 3
At 2000ml, stirring is housed, thermometer, in the reaction flask of reflux exchanger, add 57.6g (2.4mol) Mg, 1000mlTHF, 0.5g(2.0mmol) iodine and 84g(0.454mol) 3, 5-dimethyl bromobenzene, intensification initiation reaction, temperature rises to 55 ℃, be cooled to 25～30 ℃, drip 360g(1.946mol) 3, 5-dimethyl bromobenzene, drip and finish, be warming up to 40 ℃ of reaction 4h, after reaction finishes, be cooled to-5～5 ℃, drip 143.5g(1.04mol) diethyl phosphite, drip and finish, stirring reaction 1h, temperature is controlled at 0～5 ℃, after reaction finishes, adjust pH=1 with hydrochloric acid, add 1200ml toluene extracting and demixing, organic layer precipitation obtains white solid, add 800ml hexanaphthene recrystallization to obtain 196.3g bis-(3, 5-3,5-dimethylphenyl) phosphorus oxide, yield 73.16%.
Embodiment 4
At 2000ml, stirring is housed, thermometer, in the reaction flask of reflux exchanger, add 57.6g (2.4mol) Mg, 900mlTHF, 0.4g(1.6mmol) iodine and 92.4g(0.4994mol) 3, 5-dimethyl bromobenzene, intensification initiation reaction, temperature rises to 50 ℃, be cooled to 25～30 ℃, drip 396g(2.1406mol) 3, 5-dimethyl bromobenzene, drip and finish, be warming up to 55 ℃ of reaction 4h, after reaction finishes, be cooled to-5～0 ℃, drip 92g(0.667mol) diethyl phosphite, drip and finish, stirring reaction 1h, temperature is controlled at 0～5 ℃, after reaction finishes, adjust pH=1 with hydrochloric acid, add 700ml toluene extracting and demixing, organic layer precipitation obtains white solid, add 800ml hexanaphthene recrystallization to obtain 127.5g bis-(3, 5-3,5-dimethylphenyl) phosphorus oxide, yield 74.13%.
Reaction formula of the present invention is as follows:
Claims (9)
1. two (3,5-3,5-dimethylphenyl) synthetic method of phosphorus oxide, it is characterized in that first Mg, tetrahydrofuran (THF) and iodine being mixed complete, add a small amount of 3,5-dimethyl bromobenzene, add thermal booster reaction, after mixed system temperature rise to 50 ℃～60 ℃, be cooled to 20～30 ℃, then add a large amount of 3,5-dimethyl bromobenzene, after heating finishes conditioned response to the reaction of 45 ℃～50 ℃ of mixed systems, be cooled to again-10～5 ℃, then drip diethyl phosphite, at temperature of reaction system be under the condition of-5～5 ℃ stirring reaction to finishing; Then adopt hydrochloric acid to adjust the pH=1 of system after reaction, then add toluene extracting and demixing, get organic layer precipitation and obtain white solid, obtain two (3,5-3,5-dimethylphenyl) phosphorus oxide with hexanaphthene recrystallization.
2. synthetic method according to claim 1, is characterized in that Mg and described a small amount of 3, and the molar ratio of 5-dimethyl bromobenzene is 1 ︰ 1.0～1.5.
3. according to synthetic method described in claim 1 or 2, it is characterized in that described a large amount of 3,5-dimethyl bromobenzene and a small amount of 3, the mass ratio of 5-dimethyl bromobenzene is 4～4.5 ︰ 1.
4. synthetic method according to claim 1, the feed ratio that it is characterized in that Mg and tetrahydrofuran (THF) is 1mol ︰ 300～500ml.
5. synthetic method according to claim 1, the molar ratio that it is characterized in that Mg and iodine is 250 ︰ 1～5.
6. synthetic method according to claim 1, the molar ratio that it is characterized in that Mg and diethyl phosphite is 1 ︰ 0.3～0.5.
7. synthetic method according to claim 1, the feed ratio that it is characterized in that Mg and toluene is 1mol ︰ 300～500ml.
8. synthetic method according to claim 1, the feed ratio that it is characterized in that Mg and hexanaphthene is 1mol ︰ 300～500ml.
9. synthetic method according to claim 1, the feed ratio that it is characterized in that Mg and toluene is 1mol ︰ 250～400ml.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410046420.3A CN103819508A (en) | 2014-02-10 | 2014-02-10 | Method for synthesizing di(3,5-dimethyl phenyl)phosphorus oxide |
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| CN201410046420.3A CN103819508A (en) | 2014-02-10 | 2014-02-10 | Method for synthesizing di(3,5-dimethyl phenyl)phosphorus oxide |
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| CN103819508A true CN103819508A (en) | 2014-05-28 |
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| CN201410046420.3A Pending CN103819508A (en) | 2014-02-10 | 2014-02-10 | Method for synthesizing di(3,5-dimethyl phenyl)phosphorus oxide |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100519569C (en) * | 2001-12-07 | 2009-07-29 | 武田药品工业株式会社 | Process for preparing diphosphine compounds and intermediates useful in the process |
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2014
- 2014-02-10 CN CN201410046420.3A patent/CN103819508A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100519569C (en) * | 2001-12-07 | 2009-07-29 | 武田药品工业株式会社 | Process for preparing diphosphine compounds and intermediates useful in the process |
Non-Patent Citations (2)
| Title |
|---|
| MASAYOSHI JIN等: "Synthesis of Novel C2 andC1 Symmetric CHIRAPHOS Derivatives and Their Application in Palladium-catalyzed Miyaura-Michael Reaction", 《CHEM. LETT.》 * |
| 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）磷的合成", 《精细化工》 * |
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