CN106279264B - 一种α-烷氧基对氯苄基膦酸酯的制备方法 - Google Patents
一种α-烷氧基对氯苄基膦酸酯的制备方法 Download PDFInfo
- Publication number
- CN106279264B CN106279264B CN201610671261.5A CN201610671261A CN106279264B CN 106279264 B CN106279264 B CN 106279264B CN 201610671261 A CN201610671261 A CN 201610671261A CN 106279264 B CN106279264 B CN 106279264B
- Authority
- CN
- China
- Prior art keywords
- alpha
- phosphonate ester
- alkoxy base
- catalyst
- chemical compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- -1 p-chlorobenzyl phosphonate ester Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 230000002269 spontaneous effect Effects 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 3
- GPLBEXMSGZWIPD-UHFFFAOYSA-N 1-chloro-4-(diethoxymethyl)benzene Chemical compound CCOC(OCC)C1=CC=C(Cl)C=C1 GPLBEXMSGZWIPD-UHFFFAOYSA-N 0.000 description 2
- YRNBYTFFWMWTGG-UHFFFAOYSA-N 1-chloro-4-(dimethoxymethyl)benzene Chemical compound COC(OC)C1=CC=C(Cl)C=C1 YRNBYTFFWMWTGG-UHFFFAOYSA-N 0.000 description 2
- UFNOUKDBUJZYDE-UHFFFAOYSA-N 2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol Chemical compound C1=NC=NN1CC(O)(C=1C=CC(Cl)=CC=1)C(C)C1CC1 UFNOUKDBUJZYDE-UHFFFAOYSA-N 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 2
- 244000105624 Arachis hypogaea Species 0.000 description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 description 2
- 235000018262 Arachis monticola Nutrition 0.000 description 2
- 235000016068 Berberis vulgaris Nutrition 0.000 description 2
- 241000335053 Beta vulgaris Species 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- 239000005757 Cyproconazole Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000016213 coffee Nutrition 0.000 description 2
- 235000013353 coffee beverage Nutrition 0.000 description 2
- JJPBKCZJVYSKGV-UHFFFAOYSA-N diethoxyphosphane Chemical compound CCOPOCC JJPBKCZJVYSKGV-UHFFFAOYSA-N 0.000 description 2
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 235000020232 peanut Nutrition 0.000 description 2
- OILXMJHPFNGGTO-UHFFFAOYSA-N (22E)-(24xi)-24-methylcholesta-5,22-dien-3beta-ol Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)C=CC(C)C(C)C)C1(C)CC2 OILXMJHPFNGGTO-UHFFFAOYSA-N 0.000 description 1
- RQOCXCFLRBRBCS-UHFFFAOYSA-N (22E)-cholesta-5,7,22-trien-3beta-ol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CCC(C)C)CCC33)C)C3=CC=C21 RQOCXCFLRBRBCS-UHFFFAOYSA-N 0.000 description 1
- PEBSGZFMUOMTOZ-UHFFFAOYSA-N (4-chlorophenyl)methylphosphane Chemical compound PCC1=CC=C(Cl)C=C1 PEBSGZFMUOMTOZ-UHFFFAOYSA-N 0.000 description 1
- OQMZNAMGEHIHNN-UHFFFAOYSA-N 7-Dehydrostigmasterol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CC(CC)C(C)C)CCC33)C)C3=CC=C21 OQMZNAMGEHIHNN-UHFFFAOYSA-N 0.000 description 1
- OGBVRMYSNSKIEF-UHFFFAOYSA-N Benzylphosphonic acid Chemical compound OP(O)(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DNVPQKQSNYMLRS-NXVQYWJNSA-N Ergosterol Natural products CC(C)[C@@H](C)C=C[C@H](C)[C@H]1CC[C@H]2C3=CC=C4C[C@@H](O)CC[C@]4(C)[C@@H]3CC[C@]12C DNVPQKQSNYMLRS-NXVQYWJNSA-N 0.000 description 1
- 241000221787 Erysiphe Species 0.000 description 1
- 241000510928 Erysiphe necator Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- 241001533598 Septoria Species 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 241000317942 Venturia <ichneumonid wasp> Species 0.000 description 1
- 241000228452 Venturia inaequalis Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 210000003323 beak Anatomy 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- DNVPQKQSNYMLRS-SOWFXMKYSA-N ergosterol Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H](CC[C@]3([C@H]([C@H](C)/C=C/[C@@H](C)C(C)C)CC[C@H]33)C)C3=CC=C21 DNVPQKQSNYMLRS-SOWFXMKYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 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
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/094—Esters of phosphoric acids with arylalkanols
Landscapes
- 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及一种α‑烷氧基对氯苄基膦酸酯的制备方法,所述的α‑烷氧基对氯苄基膦酸酯由化合物Ⅰ和化合物Ⅱ在催化剂作用下,在‑20~150℃条件下反应0.1~10小时得到;所述化合物Ⅰ的结构式为:所述化合物Ⅱ的结构式为:所述的α‑烷氧基对氯苄基膦酸酯的结构式为:其中,R1是C1‑C4烷基中的任意一种,R2是甲基或乙基;所述的催化剂为酸性催化剂。本发明使用反应方法,操作简单,收率高,符合安全环保要求,适合工业化生产。
Description
技术领域
本发明属于化学化工领域,涉及一种α-烷氧基对氯苄基膦酸酯的制备方法。
背景技术
环丙唑醇是瑞士山道士公司开发的三唑类杀菌剂,是麦角甾醇脱甲基化抑制剂,具有预防和治疗的作用,对禾谷类作物、咖啡、甜菜、果树和葡萄上的白粉菌属、锈菌目、孢霉菌属、喙孢属、壳针孢属、黑星菌属病菌均有效,可防治谷类和咖啡锈病,谷类、果树和葡萄白粉病,花生、甜菜叶斑病,苹果黑星病和花生白腐病,还可以与其它杀菌剂混用。
1-(4-氯苯基)-2-环丙基-1-丙酮是环丙唑醇的关键中间体,而通过α-烷氧基对氯苄基膦酸酯合成1-(4-氯苯基)-2-环丙基-1-丙酮的方法具有工艺简便、操作安全、经济性好、适合规模化开发的优点。
探索合成α-烷氧基对氯苄基膦酸酯的高效合成方法具有重要意义。
发明内容
本发明所要解决的技术问题是提供一种产率高、安全环保的α-烷氧基对氯苄基膦酸酯的制备方法。
为了解决上述技术问题,本发明采用如下技术方案:
本发明的目的是提供一种α-烷氧基对氯苄基膦酸酯的制备方法,所述的α-烷氧基对氯苄基膦酸酯由化合物Ⅰ和化合物Ⅱ在催化剂作用下,在-20~150℃条件下反应0.1~10小时得到;
所述化合物Ⅰ的结构式为:所述化合物Ⅱ的结构式为:所述的α-烷氧基对氯苄基膦酸酯的结构式为:其中,R1是C1-C4烷基中的任意一种,R2是甲基或乙基;
所述的催化剂为酸性催化剂。
优选地,R1是甲基或乙基。
优选地,所述化合物Ⅰ和化合物Ⅱ的投料摩尔比为1.0:1.0~2.0,进一步优选为1.0:1.7~1.9。
优选地,所述的酸性催化剂为质子酸、路易斯酸或其他酸性催化剂。
进一步优选地,所述的质子酸催化剂为选自硫酸、硝酸、磷酸、氯化氢、对甲苯磺酸、苯磺酸、甲磺酸的一种或多种;所述的路易斯酸催化剂为选自TiCl4、BF3、AlCl3、FeCl3、ZnCl2中的一种或多种。
优选地,所述催化剂与化合物Ⅰ的摩尔比为0.01~1.1:1.0。
进一步优选地,所述催化剂与化合物Ⅰ的摩尔比为0.1~0.5:1.0。
优选地,进行所述的反应的温度为90~110℃。
优选地,所述的反应在无溶剂的条件下进行。
优选地,所述α-烷氧基对氯苄基膦酸酯的具体制备方法为:将所述的化合物Ⅰ和所述的化合物Ⅱ在惰性气体的保护下于-20~150℃反应,缓慢加入所述的催化剂,得到的反应混合物自然恢复至0~40℃,充分搅拌10~24小时,滤去固体物,分离出的有机液经水洗、干燥后,蒸馏脱溶得到淡黄色油状液体,即所述的α-烷氧基对氯苄基膦酸酯。
本发明的反应方程式如下:
由于以上技术方案的实施,本发明与现有技术相比具有如下优点:
本发明使用的工艺相对简单,原料易得,操作过程所用试剂和药品成本相对较低,而且反应条件温和,时间短,收率高,同时成本较低,三废较少,目标产品的含量高,很适合工业化生产。
具体实施方式
以下结合具体实施例对本发明做进一步详细说明。应理解,这些实施例是用于说明本发明的基本原理、主要特征和优点,而本发明不受以下实施例的限制。实施例中采用的实施条件可以根据具体要求做进一步调整,未注明的实施条件通常为常规实验中的条件。
实施例1
将18.65g(0.1mol)对氯苯甲醛二甲缩醛和16.56g(0.12mol)亚膦酸二乙酯在惰性气体的保护下冷却到-20℃反应,缓慢加入13.35g AlCl3,得到的反应混合物自然恢复至室温,充分搅拌16小时,滤去固体物,分离出的有机液经水洗、干燥后,蒸馏脱溶得到27.13g淡黄色油状液体,即α-甲氧基对氯苄基膦酸二乙酯,纯度为95.1%,收率88.2%。
实施例2
将21.45g(0.1mol)对氯苯甲醛二乙缩醛和20.70g(0.15mol)亚膦酸二乙酯在惰性气体的保护下冷却到20℃反应,缓慢加入2.94g磷酸,得到的反应混合物自然恢复至室温,充分搅拌12小时,滤去固体物,分离出的有机液经水洗、干燥后,蒸馏脱溶得到27.59g淡黄色油状液体,即α-乙氧基对氯苄基膦酸二乙酯,纯度为94.8%,收率85.3%。
实施例3
将21.45g(0.1mol)对氯苯甲醛二乙缩醛和11.00g(0.1mol)亚膦酸二甲酯在惰性气体的保护下冷却到50℃反应,缓慢加入16.25g FeCl3,得到的反应混合物自然恢复至室温,充分搅拌18小时,滤去固体物,分离出的有机液经水洗、干燥后,蒸馏脱溶得到25.06g淡黄色油状液体,即α-乙氧基对氯苄基膦酸二乙酯,纯度为94.0%,收率84.6%。
实施例4
将18.65g(0.1mol)对氯苯甲醛二甲缩醛和19.80g(0.18mol)亚膦酸二甲酯在惰性气体的保护下冷却到100℃反应,缓慢加入3.44g对甲苯磺酸,得到的反应混合物自然恢复至室温,充分搅拌20小时,滤去固体物,分离出的有机液经水洗、干燥后,蒸馏脱溶得到24.51g淡黄色油状液体,即α-甲氧基对氯苄基膦酸二甲酯,纯度为95.3%,收率88.3%。
上述实施例只是为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围,凡根据本发明精神实质所作的等效变化或者修饰,都应该涵盖在本发明的保护范围之内。
Claims (2)
1. 一种α-烷氧基对氯苄基膦酸酯的制备方法,其特征在于:将化合物Ⅰ和化合物Ⅱ在惰性气体的保护下于-20~100 ℃反应,缓慢加入催化剂,得到的反应混合物自然恢复至0~40℃,充分搅拌10~24小时,滤去固体物,分离出的有机液经水洗、干燥后,蒸馏脱溶得到淡黄色油状液体,即所述的α-烷氧基对氯苄基膦酸酯;
所述化合物Ⅰ的结构式为:,所述化合物Ⅱ的结构式为:,所述的α-烷氧基对氯苄基膦酸酯的结构式为:,其中,R1是甲基或乙基,R2是甲基或乙基;
所述的催化剂为AlCl3、磷酸、FeCl3或对甲苯磺酸;所述的反应在无溶剂的条件下进行;
所述化合物Ⅰ和化合物Ⅱ的投料摩尔比为1.0:1.0~2.0;所述催化剂与化合物Ⅰ的摩尔比为0.1~0.5:1.0。
2.根据权利要求1所述的α-烷氧基对氯苄基膦酸酯的制备方法,其特征在于:进行所述的反应的温度为90~100℃。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610671261.5A CN106279264B (zh) | 2016-08-16 | 2016-08-16 | 一种α-烷氧基对氯苄基膦酸酯的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610671261.5A CN106279264B (zh) | 2016-08-16 | 2016-08-16 | 一种α-烷氧基对氯苄基膦酸酯的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106279264A CN106279264A (zh) | 2017-01-04 |
CN106279264B true CN106279264B (zh) | 2019-05-24 |
Family
ID=57671949
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610671261.5A Active CN106279264B (zh) | 2016-08-16 | 2016-08-16 | 一种α-烷氧基对氯苄基膦酸酯的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106279264B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113121595A (zh) * | 2019-12-30 | 2021-07-16 | 江苏剑牌农化股份有限公司 | 一种α-R烷氧基对氯苄基膦酸单酯 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102942465A (zh) * | 2012-11-22 | 2013-02-27 | 江苏澄扬作物科技有限公司 | 1-(4-氯苯基)-2-环丙基-1-丙酮的制备方法及其中间体 |
-
2016
- 2016-08-16 CN CN201610671261.5A patent/CN106279264B/zh active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102942465A (zh) * | 2012-11-22 | 2013-02-27 | 江苏澄扬作物科技有限公司 | 1-(4-氯苯基)-2-环丙基-1-丙酮的制备方法及其中间体 |
Non-Patent Citations (1)
Title |
---|
Iron-catalyzed cross coupling of P-H/C-O bonds: efficient synthesis ofα-alkoxyphosphorus compounds;Li, Xue et al.;《Dalton Transactions》;20150819;第1877-1880页 |
Also Published As
Publication number | Publication date |
---|---|
CN106279264A (zh) | 2017-01-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3356431B1 (en) | Procatalyst and polymerization process using the same | |
US9447002B2 (en) | 7-acetyleno quinone methide derivatives and their application as vinylic polymerization retarders | |
WO2013087167A3 (en) | A process for the production of bimodal polyethylene in the presence of this catalyst system | |
CN105294490B (zh) | 一种合成肟菌酯的方法 | |
CN102639484A (zh) | 制备二芳基碳酸酯的方法 | |
WO2013087185A3 (en) | A catalyst system and a process for the production of ultra high molecular weight polyethylene in presence of this catalyst system | |
ITMI951445A1 (it) | Procedimento per la produzione di carbammati aromatici | |
US20060205987A1 (en) | Process for preparing alkyl chlorides | |
CN106279264B (zh) | 一种α-烷氧基对氯苄基膦酸酯的制备方法 | |
CN101307069A (zh) | 制备丙烯酰氧基烷基烷氧基硅烷的方法,其提纯方法,在组合物中的稳定化方法及其应用 | |
CN100447133C (zh) | 一种对称四氯吡啶的制备方法 | |
CN110981788B (zh) | 一种含有受阻酚结构的受阻胺光稳定剂的制备方法 | |
CN102432523B (zh) | 一种3-羟基-3-芳基吲哚-2-酮衍生物的合成方法 | |
Huang et al. | Hydrothermal syntheses, characterizations of novel three-dimensional indium phosphite and indium phosphite–phosphate with intersecting 8-membered ring channels:[In3 (H2PO3) 3 (HPO3) 4]·(trans-C6N2H16) and [In6 (HPO3) 8 (H2PO3) 5 (H2PO4)]·(C3N2H12) 2 | |
CN110776464A (zh) | 一种咪唑类化合物n1位烷基化方法 | |
CN109705048B (zh) | 一种戊唑醇的清洁制备方法 | |
EP2878603B1 (en) | Novel neodymium compound and catalyst for diene polymerization containing same | |
US7468174B2 (en) | Method for producing chlorosulfonyl isocyanate | |
CN109111363A (zh) | 一种乙氧基亚甲基丙二酸二乙酯的制备方法 | |
Rad et al. | Synthesis and structural characterisation of lithium, zinc, and aluminium pyrazolate complexes | |
KR102025262B1 (ko) | 촉매의 제조방법 | |
Sprenger et al. | Salts of novel chelatoborate anions:[RFBX (ox)]−(RF= CF3, C2F5; X= F, OMe; ox= oxalato) and [RFB (OMe)(cat)]−(RF= CF3, C2F5; cat= catecholato) | |
RU2797603C1 (ru) | Способ получения 1-бромметил-4-хлорметилбензола | |
CN107298637A (zh) | 一种三氟乙酰丙酮的制备方法 | |
US20100016529A1 (en) | Catalyst precursor for the production of olefins with an odd number of carbons atoms, process for its preparation and production method for such olefins |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |