CN113683480B - 一种4-乙基苄氯的制备方法 - Google Patents
一种4-乙基苄氯的制备方法 Download PDFInfo
- Publication number
- CN113683480B CN113683480B CN202110997783.5A CN202110997783A CN113683480B CN 113683480 B CN113683480 B CN 113683480B CN 202110997783 A CN202110997783 A CN 202110997783A CN 113683480 B CN113683480 B CN 113683480B
- Authority
- CN
- China
- Prior art keywords
- ethylbenzyl chloride
- reduced pressure
- ethylbenzyl
- pentafluorophenyl
- borane
- 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
- DUBCVXSYZVTCOC-UHFFFAOYSA-N 1-(chloromethyl)-4-ethylbenzene Chemical compound CCC1=CC=C(CCl)C=C1 DUBCVXSYZVTCOC-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229950000688 phenothiazine Drugs 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical group CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 8
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000002841 Lewis acid Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 150000007517 lewis acids Chemical class 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 abstract 1
- -1 4-ethylbenzyl chloride benzene ring Chemical group 0.000 description 5
- 150000001241 acetals Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- UAYWVJHJZHQCIE-UHFFFAOYSA-L Zinc iodide Inorganic materials I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IYRCFBNKBGBMIT-UHFFFAOYSA-N 1-(chloromethyl)-2-ethylbenzene Chemical compound CCC1=CC=CC=C1CCl IYRCFBNKBGBMIT-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 238000007265 chloromethylation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- YSLBFFIVJGJBSA-UHFFFAOYSA-N (4-ethylphenyl)methanol Chemical compound CCC1=CC=C(CO)C=C1 YSLBFFIVJGJBSA-UHFFFAOYSA-N 0.000 description 1
- LQNFAYOQWHMKDM-UHFFFAOYSA-N 1-(dichloromethyl)-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C(Cl)Cl LQNFAYOQWHMKDM-UHFFFAOYSA-N 0.000 description 1
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000012022 methylating agents Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/32—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by introduction of halogenated alkyl groups into ring compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种4‑乙基苄氯的制备方法，属于有机合成技术领域。以乙苯为原料与乙缩醛、氯磺酸和路易斯酸催化作用下氯甲基化得到4‑乙基苄氯。该方法催化剂可回收套用，且异构体少，相对更容易分离，收率高，所得到产品的含量＞99％，具备潜在的工业化放大前景。
Description
技术领域
本发明涉及一种4-乙基苄氯的制备方法，属于有机合成技术领域。
背景技术
4-乙基苄氯，CAS：1467-05-6，英文名：4-ethylbenzylchloride，氯甲基取代的芳族化合物因其易于转化为有希望的关键中间体、各种精细或特殊化学品，聚合物和药品。由于4-乙基苄氯苯环上含有活泼的氯甲基，可以容易的转化为不同基团。4-乙基苄氯作为乙苯甲基化试剂等有机合成的中间体，在医药、染料、合成香料及农药等领域有着广泛的应用前景。
迄今为止，已经报道了很多种合成乙烯基环己烷的方法，例如采用4-乙基苄醇与三氯氧磷氯化合成，收率73％，由于原料价格贵，不具备放大生产要求[Canadian Journalof Chemistry,1981,vol.59,p.2314-2327]。其反应路线如下：
采用乙苯与甲缩醛为原料，与氯磺酸和路易斯酸碘化锌氯甲基化反应，收率77-87％[Journal ofChemical Research,2019,vol.43,#1-2,p.34-38]和[SyntheticCommunications,2019,vol.49,#7,p.925-932]。该方法中，碘化锌不可套用，对设备具有腐蚀性，用量较大，其反应路线如下：
采用甲醛或多聚甲醛与乙苯在氯化锌存在下50℃水中进行氯甲基化反应[Journal ofthe Chilean Chemical Society,2010,vol.55,#1,p.97-102]，该方法采用大量酸，废水大，异构体多，对设备腐蚀性大，收率低，不利于工业化生产。其反应路线如下：
综上现有合成路线中，存在着不适应工业化生产等问题，因些有必要对4-乙基苄氯进行合成工艺进行深入研究，提供更优、原料易得、安全稳定的反应路线，符合绿色化学，以满足日益增长的市场需求。
发明内容
为了克服上述技术缺陷，以乙苯为原料与乙缩醛、氯磺酸和路易斯酸三(五氟苯基)硼烷催化作用下氯甲基化得到4-乙基苄氯。该方法催化剂可回收套用，且异构体少，相对更容易分离，收率高，所得到产品的含量＞99％，具备潜在的工业化放大前景。
本发明所述一种4-乙基苄氯的制备方法，其特征在于，包括如下步骤：
将催化剂与氯磺酸溶于有机溶剂中，依次加入乙缩醛和乙苯，反应结束，加入阻聚剂先减压蒸馏得到粗品，再减压精馏得到4-乙基苄氯。
进一步地，在上述技术方案中，所述有机溶剂选自二氯甲烷、氯仿或1,2-二氯乙烷。
进一步地，在上述技术方案中，催化剂选自三(五氟苯基)硼烷。
进一步地，在上述技术方案中，所述乙苯、乙缩醛、催化剂和氯磺酸摩尔比例1：1.05-1.1：0.02-0.03：1.15-1.20。
进一步地，在上述技术方案中，反应温度为-5～0℃，反应时间1-2小时。
进一步地，在上述技术方案中，所述阻聚剂选自对叔丁基邻苯二酚或吩噻嗪。
进一步地，在上述技术方案中，加入量为原料重量的0.05-1.0％。
进一步地，在上述技术方案中，所述减压精馏选自100-125℃，7毫米汞柱下，回流比15：1。
发明有益效果
与以往的合成方法相比，本发明具有如下有益效果：
1)本发明合成路线简单，异构体少，大大方便了工业化放大生产。
2)本发明路易斯酸催化剂可回收套用。催化剂回收原理：由于产品易溶于正庚烷，而催化剂三(五氟苯基)硼烷在正庚烷中溶解度很低，因此后处理加入正庚烷，过滤，滤饼既是三(五氟苯基)硼烷。
具体实施例
下面通过具体实例对本发明进行进一步说明。这些实施例应理解为仅用于说明本发明而不用于限制本发明的保护范围。在阅读了本发明记载的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等效变化和修改同样落入本发明权利要求所限定的范围。
4-乙基苄氯的合成
实施例1
在氮气流保护的条件下，向反应瓶内依次加入10.3g(0.02eq)的三(五氟苯基)硼烷、67g(1.15eq)氯磺酸和400mL二氯甲烷，降温至-5℃，缓慢滴加乙缩醛57.3(1.1eq)，滴加结束后反应30分钟，在-5～0℃缓慢滴加53g(0.5mol,1eq)乙苯的二氯甲烷溶液，滴加结束后反应1小时，GC检测原料剩余2％，4-乙基苄氯与2-乙基苄氯比例为94％：6％。加入150g水淬灭，分层，水相用二氯甲烷100mL萃取，合并有机相，用8％碳酸氢钠100mL洗涤一次，有机相用硫酸钠干燥，过滤，滤液减压浓缩蒸除大部分溶剂，加入正庚烷替换，过滤，滤饼为回收的三(五氟苯基)硼烷，滤饼烘干得到三(五氟苯基)硼烷9.5g，回收的三(五氟苯基)硼烷收率92％，滤液加入2.7g对叔丁基邻苯二酚减压蒸馏至不流液，80-100℃减压7毫米汞柱蒸馏，前馏约蒸出5g，100-120℃减压蒸馏得到主馏份。GC检测4-乙基苄氯与2-乙基苄氯比例为98％:2％，主馏份1％对叔丁基邻苯二酚，在100-125℃减压精馏(回流比15:1)得到66.3g4-乙基苄氯。收率85.7％，GC 99.4％，2-乙基氯苄0.08％。1HNMR(400MHz,CDCl3)7.41-7.39(m,2H),7.30-7.28(m,2H),4.67(s,2H),2.75-2.72(m,2H),1.42-1.35(m,3H)
公斤级放大
实施例2
在氮气流保护的条件下，向反应瓶内依次加入0.205Kg的三(五氟苯基)硼烷、2.80Kg氯磺酸和20L二氯甲烷，降温至-5℃，滴加乙缩醛2.35kg，滴加结束后反应30分钟，在-5～0℃缓慢滴加2.12Kg乙苯的二氯甲烷溶液，滴加结束后反应1小时，GC检测原料剩余1.7％，加入15Kg水淬灭，分层，水相用二氯甲烷5L萃取，合并有机相，用8％碳酸氢钠8Kg洗涤一次，有机相用硫酸钠干燥，过滤，滤液减压浓缩蒸除大部分二氯甲烷，加入10L正庚烷替换，浓缩至剩余6L，降温至5～10℃，过滤，滤饼为回收的三(五氟苯基)硼烷，滤饼烘干得到三(五氟苯基)硼烷0.197Kg，收率96％。40-50℃滤液加入85g吩噻嗪减压浓缩至不流液，80-100℃减压7毫米汞柱蒸馏，前馏约蒸出185g，100-120℃减压蒸馏得到主馏份。GC检测，比例约为98:2，主馏份加入50g吩噻嗪，在100-111℃减压精馏(回流比15:1)，先蒸出前馏(主要含有2-乙基氯苄)，随后蒸出主馏分2.67Kg。收率86.3％，GC99.2％2-乙基氯苄0.12％。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明披露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。
Claims (3)
1.一种4-乙基苄氯的制备方法，其特征在于，包括如下步骤：
将催化剂三(五氟苯基)硼烷与氯磺酸溶于有机溶剂中，依次加入二乙氧基甲烷和乙苯，反应结束，后处理加入正庚烷，过滤，滤饼即是三(五氟苯基)硼烷；滤液加入阻聚剂先减压蒸馏得到粗品，再减压精馏得到4-乙基苄氯；所述乙苯、二乙氧基甲烷、催化剂和氯磺酸摩尔比为1：1.05-1.1：0.02-0.03：1.15-1.20；所述阻聚剂选自对叔丁基邻苯二酚或吩噻嗪；所述减压精馏选自100-125℃，7毫米汞柱下，回流比15：1。
2.根据权利要求1所述4-乙基苄氯的制备方法，其特征在于：所述有机溶剂选自二氯甲烷、氯仿或1,2-二氯乙烷。
3.根据权利要求1所述4-乙基苄氯的制备方法，其特征在于：反应温度为-5～0℃，反应时间1-2小时。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110997783.5A CN113683480B (zh) | 2021-08-28 | 2021-08-28 | 一种4-乙基苄氯的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110997783.5A CN113683480B (zh) | 2021-08-28 | 2021-08-28 | 一种4-乙基苄氯的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113683480A CN113683480A (zh) | 2021-11-23 |
| CN113683480B true CN113683480B (zh) | 2024-02-27 |
Family
ID=78583545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110997783.5A Active CN113683480B (zh) | 2021-08-28 | 2021-08-28 | 一种4-乙基苄氯的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113683480B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114213289B (zh) * | 2021-12-30 | 2023-09-22 | 山东三牧新材料科技有限公司 | 一种2,4-二(苯磺酰基)苯酚的制备方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2271379A1 (en) * | 1996-11-22 | 1998-05-28 | David W. Owens | Halogen exchange reactions and uses thereof |
| CN1330656A (zh) * | 1998-12-19 | 2002-01-09 | 巴塞尔聚烯烃股份有限公司 | 单有机硼烷或二有机硼烷的制备方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1569912B1 (en) * | 2002-12-03 | 2015-04-29 | Pharmacyclics, Inc. | 2-(2-hydroxybiphenyl-3-yl)-1h-benzoimidazole-5-carboxamidine derivatives as factor viia inhibitors |
-
2021
- 2021-08-28 CN CN202110997783.5A patent/CN113683480B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2271379A1 (en) * | 1996-11-22 | 1998-05-28 | David W. Owens | Halogen exchange reactions and uses thereof |
| CN1330656A (zh) * | 1998-12-19 | 2002-01-09 | 巴塞尔聚烯烃股份有限公司 | 单有机硼烷或二有机硼烷的制备方法 |
Non-Patent Citations (3)
| Title |
|---|
| An efficient and convenient chloromethylation of some aromatic compounds catalyzed by zinc iodide;Jian Tang et al.,;《Journal of Chemical Research》;第43卷;第34-38页 * |
| Anion Exchange Resins Prepared from Polystyrene Crosslinked Via a Friedel-Crafts Reaction;SOFIA BELFER et al.,;《Journal of Applied Polymer Science》;第24卷;第2147-2157 页 * |
| 含吲哚侧基聚苯乙烯的合成及其后修饰;张苏韬 等;《高分子学报》;第51卷(第10期);第1147-1151页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113683480A (zh) | 2021-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20020062380A (ko) | 연속 증류를 이용하여 수소첨가에 의해 제조된트리메틸올프로판을 정제하는 방법 | |
| CN112739675B (zh) | 回收高品质3-甲基-丁-3-烯-1-醇的方法 | |
| CN113683480A (zh) | 一种4-乙基苄氯的制备方法 | |
| CN114276229B (zh) | 一种麝香t釜残回收利用的方法 | |
| US4067905A (en) | Preparation of 2-amino-n-butanol | |
| CN105461525B (zh) | 1,3,5‑三醛基均苯三酚的制备及制备过程三氟乙酸的回用方法 | |
| EP0209157A2 (en) | Process for the production of alkyl trifluoroacetates | |
| CN116410162B (zh) | 一种副产物作溶剂的呋喃酚生产工艺 | |
| CN116284031B (zh) | 一种r-光甘草定的制备方法 | |
| EP3941894B1 (en) | Process to recover 3-methyl-but-3-en-1-ol | |
| CN116693389A (zh) | 一种合成番茄潜叶蛾性信息素(3e,8z)-3,8-十四碳二烯乙酸酯的方法 | |
| CN103992261A (zh) | 2-溴咔唑工业化制备工艺 | |
| US5847216A (en) | Preparation of selegiline | |
| CN109232465B (zh) | 一种噁草酮结晶母液催化法制备噁草酮酚的方法 | |
| US4658032A (en) | Process for producing 2,3,5-collidine and/or 2,3,5,6-tetramethylpyridine | |
| KR100403143B1 (ko) | 1-브로모에틸 아세테이트의 제조방법 | |
| FR2602766A1 (fr) | Composes dichlorotrifluoromethylnitrotoluenes et procede de preparation d'aminotrifluoromethyltoluenes a partir de ces composes | |
| US3021375A (en) | Process for the preparation of 2, 4-bis-(chloromethyl)-toluene | |
| CN120424008A (zh) | 一种1-甲基-3-(三氟甲基)-4-(氯甲基)-5-(二氟甲氧基)-1h-吡唑的制备方法 | |
| CN109369357B (zh) | 一种催化氧化羰基化制备对称二芳基酮的方法 | |
| JP3209447B2 (ja) | アセタールの製造方法 | |
| JPH01175948A (ja) | ３，５‐ジクロロフェノールの製造方法 | |
| CN121735751A (zh) | 一种低成本高选择性合成邻香兰素的制备工艺 | |
| EP4039730A1 (en) | Process for modifying an aromatic polyether backbone and a modified polyether obtained by this process | |
| Christe et al. | Aromatic Fluorine Compounds. IV. 1 The Introduction of More than One Fluorine Atom into the Same Ring by a Novel Method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A preparation method of 4-ethylbenzyl chloride Granted publication date: 20240227 Pledgee: Shandong Jiaxiang Rural Commercial Bank Co.,Ltd. Pledgor: Shandong Sanmu New Material Technology Co.,Ltd. Registration number: Y2024980033695 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |