CN1049492A - 分离两种异构体的方法及其纯化1-苯基-2溴乙烷的应用 - Google Patents
分离两种异构体的方法及其纯化1-苯基-2溴乙烷的应用 Download PDFInfo
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- 238000009833 condensation Methods 0.000 claims abstract description 8
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- 239000007859 condensation product Substances 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 6
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- 229910021536 Zeolite Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- CPOPGNHRAJPRIU-UHFFFAOYSA-N benzene;bromoethane Chemical class CCBr.C1=CC=CC=C1 CPOPGNHRAJPRIU-UHFFFAOYSA-N 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
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- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
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- 239000010457 zeolite Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
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- -1 free radical hydrogen Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- 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
- C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
- C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
- C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
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- 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
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S203/00—Distillation: processes, separatory
- Y10S203/06—Reactor-distillation
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Abstract
本发明涉及分离两种异构体的方法，其特征在于
(i)在弗瑞德—克来福特催化剂的存在下使其中一种
异构体与具有至少一个芳氢的物质选择性地缩合，
(ii)然后将所得的缩合产物与另一种异构体分离。
在1-苯基-2-溴乙烷和1-苯基-1-溴乙烷的混合物
中，在氯化铁的存在下只有后者可与二甲苯缩合生成
苯基二甲苯基乙烷。
Description
本发明涉及一种分离两种异构体的方法及其纯化1-苯基-2-溴乙烷的应用。
1-苯基-2-溴乙烷（C6H5-CH2-CH2Br）或苯乙基溴是有机合成的中间体，它是通过苯乙烯与气态溴化氢的自由基氢溴化反应制备的。
通过向苯乙烯在极性很低的惰性溶剂如四氯化碳中的溶液中同时引入空气和HBr气体，来促进反马科尼科夫（anti-MARKOVNIKOV）型加成反应。但该反应决不是完全选择性的，有马科尼科夫型加成与其竞争：
随着苯乙烯在CCl4中的浓度的增加，该竞争反应的程度增加。另一方面，有金属杂质如铁存在有利于该反应。
由于苯乙基溴和其异构体1-溴-1-苯基乙烷的沸点相差很小，苯乙基溴为217℃，1-溴-1-苯基乙烷为203℃，所以很难通过蒸馏将它们分离开。
先有技术美国专利3 058 892建议在100-150℃下用氧化锌处理苯乙基溴和其异构体的混合物以促使该异构体的选择性分解。建议将反应温度和时间降低到最低程度以避免苯乙基溴的分解。现在已发现另一种与前者完全相反的方法，因为该方法是使1-溴-1-苯基乙烷与另一种物质选择性地缩合以将其变成易于通过蒸馏而分离的重产物。
本发明的另一个优点是在比先有技术低的温度下操作。在研究过程中，本申请人发现了一种选择性地分离许多异构体系的方法。
因此本发明是一种分离下式的两种异构体的方法：
式中A代表可被取代的芳基;X代表卤素;R1代表X1、氢或烷基;R2代表X2、H或烷基;X1和X2代表卤素;R3代表氢或烷基;所述方法的特征在于：
a）在弗瑞德-克来福特催化剂存在下使异构体（Ⅰ）与带有至少一个芳氢的物质缩合，
b）然后将所得的缩合产物与异构体（Ⅱ）分离。
这两种异构体是由例如下式化合物与卤化氢加成而得到的：
A、R1、R2和R3具有上述定义。
比较有利的是A代表由苯、联苯、萘或蒽衍生得到的基团。A可以被卤素、NO2、CN、烷基或烷氧基取代。
比较有利的是X、X1和X2代表氯或溴。
R1、R2和R3也代表可具有至多4个碳原子的烷基。异构体（Ⅰ）和（Ⅱ）比较理想的是例如其中的A为可被取代的苯基，R1和R2为具有至多4个碳原子的烷基，而R3为氢。
将异构体（Ⅰ）与一种具有至少一个芳氢的物质缩合。该物质可以是任何物质，只要它带有足够流动的氢并与异构体（Ⅰ）偶联可消除HX即可。有利地是使用芳烃、具有芳族部分的醚以及酚。在芳烃中，可以提及苯、甲苯、乙苯、异丙苯以及二甲苯混合物。可以提及的醚是苯基甲基醚（C6H5-O-CH3）。使用芳烃、醚的混合物或这些物质的各种组合物将不会超出本发明的范围。
异构体（Ⅰ）和（Ⅱ）可以单独存在或存在于溶剂混合物中。弗瑞德-克来福特催化剂本身是已知的。它指路易斯酸（金属卤化物等）、质子酸和沸石。可以提及的金属卤化物有氯化铁和氯化铝。可以提及的质子酸有含氧酸如硫酸和对甲苯磺酸;可以提及的沸石有除去阳离子的X或Y八面沸石。
作为例子，在苯乙基溴（C6H5-CH2-CH2Br）和1-苯基-1-溴乙烷（C6H5-CHBr-CH3）的混合物中，只有后者可按照下述反应与间二甲苯缩合形成苯基二甲苯基乙烷：
如此形成的苯基二甲苯基乙烷具有很高的沸点（高于300℃），因此不会给蒸馏分离苯乙基溴（沸点217℃）带来任何麻烦。催化剂的用量可以在很宽的范围内变化，例如每千克苯乙基溴可以使用0.5-2克FeCl3。反应温度可在很宽的范围内变化，比较有利的是在异构体和用来进行缩合反应的物质为液态的温度范围内，最好是在50-100℃下进行反应。也选择压力以使该缩合反应能在大气压或不超过几巴的压力下进行。
反应时间为几分钟～2或3小时;该反应时间随反应温度升高而缩短。
如果异构体已在溶剂如芳烃、具有芳族部分的醚或酚中，在该混合物中加入催化剂就足以实现本发明。
在该方法的步骤a即缩合反应后，可以用盐酸水溶液洗涤该反应混合物。然后进行步骤b即分离回收异构体Ⅱ。可以使用任何方式，但最好是蒸馏。
下列实例说明本发明。
实例1
在下列装置中进行反应：
-带有放液口的1升锥形烧瓶，
-带有热电偶的测温套管，
-氮气保护层，
-水回流冷凝器，
-水扩散器（Water bubbler）。
在锥形烧瓶中装入370克粗苯乙基溴（其组成如表Ⅰ所示）以及212克二甲苯异构体的混合物（富有间位异构体的商业产品）。然后加入0.5克无水氯化铁，在氮气吹扫下将反应体系加热至60℃。将气流通入水扩散器中，所形成的氢溴酸在酚酞的存在下用氢氧化钠溶液测定。释出的HBr的量（0.165摩尔）基本上与1-苯基-1-溴乙烷的量（0.153摩尔）一致。
此外，对在反应5小时10分末的取样所进行的色谱分析（见表Ⅰ）表明1-苯基-1-溴乙烷全部消失。
在6小时40分末所进行的同样分析表明实际上反应混合物没有变化。苯乙基溴的含量没有降低，即在这些条件下该产品是稳定的（样品在进行分析以前立即用水+10%HCl洗涤）。
实验结束后，全部反应混合物用10%盐水洗涤然后用水洗涤。将有机相装入顶上装有五塔板的柱的蒸馏烧瓶中，接着使烧瓶中的温度保持在80℃左右在真空下进行共沸干燥操作。干燥结束后，在蒸馏柱上安一个回流头，在逐渐减压下用轻微回流蒸馏烧瓶的内容物。在15毫米汞柱和101-103℃下流出的馏分（见表Ⅰ上的分析）为起始原料中所存在的苯乙基溴含量的90%。蒸馏结束时的底部温度为170℃，没有发现分解。
如此得到的苯乙基溴（无色）的纯度高于98.5%。通过精馏会得到更高的纯度。事实上，鉴于1，2-二溴乙基苯的沸点明显很高，因此很容易将其分离出来。
另一方面，研究表中的结果，发现除1-苯基-1-溴乙烷外还有某些其它物质消失或减少（峰7、12和14）。这些未鉴定的物质可能都有活泼的溴原子，在没有进行所述的处理而蒸馏苯乙基溴时，它可能是不稳定性的因素。1-苯基-1-溴乙烷已与二甲苯缩合形成苯基二甲苯基乙烷。
实例2
在与实例1相同的装置中，处理具有下列组成的混合物：
-72.6%乙苯
-25.8%1-氯-1-苯基乙烷，
-1.6%2-氯-1-苯基乙烷。
用1小时30分钟将该混合物加入含有1.64克无水FeCl3的12.6摩尔70℃的乙苯中。
然后将该反应混合物在70℃下保持3小时。在加料完毕直至实验停止对不同试样所进行的色谱分析表明：
-1-氯-1-苯基乙烷消失得很快，
-2-氯-1-苯基乙烷没有发生反应。
实例3
在与实例1相同的装置中，加入370克粗苯乙基溴（其组成如表Ⅱ所示）以及85克甲苯。然后加入0.12克无水氯化铁，在用氮气吹扫下将反应体系加热至85-125℃。气流通入水扩散器，连续测定所形成的氢溴酸。反应结束时所释出的HBr量为0.451摩尔。
此外，色谱分析（见表Ⅱ）表明1-溴-1-苯基乙烷消失得很快，而1，2-二溴乙基苯（或1，2-二溴-1-苯基乙烷）逐渐消失。相反，在整个处理过程中苯乙基溴的含量没有变化。用与实例1相同的方法处理的反应混合物在蒸馏后苯乙基溴的纯度高于99.5%，与初始用量相比收率为90%。
Claims (5)
1、分离下列二式的两种异构体的方法：
其中A代表可被取代的芳基；X代表卤素；R1代表X1、氢或烷基；R2代表X2、H或烷基；X1和X2代表卤素；R3代表氢或烷基，其特征在于：
a)在弗瑞德-克来福特催化剂的存在下使异构体(Ⅰ)与具有至少一个芳氢的物质缩合，
b)然后将所得的缩合产物与异构体(Ⅱ)分离。
2、根据权利要求1所述的方法，其特征在于A是可被取代的苯基，R1和R2是具有至多4个碳原子的烷基，R3是氢而卤素X、X1和X2是氯或溴。
3、根据权利要求1或2的方法，其特征在于具有芳氢的物质选自芳烃、具有芳族部分的醚以及酚。
4、根据权利要求1至3中任一项的方法，其特征在于弗瑞德-克来福特催化剂是氯化铁。
5、根据权利要求2至4中任一项的方法，其特征在于用于纯化苯乙基溴。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8907800A FR2648130B1 (fr) | 1989-06-13 | 1989-06-13 | Procede de separation de deux isomeres, son application a la purification du phenyl-1 bromo-2 ethane |
| FR8907800 | 1989-06-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1049492A true CN1049492A (zh) | 1991-02-27 |
| CN1024788C CN1024788C (zh) | 1994-06-01 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90104354A Expired - Fee Related CN1024788C (zh) | 1989-06-13 | 1990-06-13 | 分离两种异构体的方法及其纯化1-苯基-2溴乙烷的应用 |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US5181992A (zh) |
| EP (1) | EP0403331B1 (zh) |
| JP (1) | JP2701226B2 (zh) |
| KR (1) | KR920006538B1 (zh) |
| CN (1) | CN1024788C (zh) |
| AT (1) | ATE87291T1 (zh) |
| CA (1) | CA2017650C (zh) |
| DE (1) | DE69001154T2 (zh) |
| DK (1) | DK0403331T3 (zh) |
| ES (1) | ES2054292T3 (zh) |
| FI (1) | FI95240C (zh) |
| FR (1) | FR2648130B1 (zh) |
| IE (1) | IE64625B1 (zh) |
| NO (1) | NO173231C (zh) |
| PT (1) | PT94357B (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2129610C (en) * | 1993-08-06 | 2005-10-18 | Hiroaki Fujishima | Process for preparing 1-bromoalkylbenzene derivatives and intermediates thereof |
| WO1998029373A1 (fr) * | 1996-12-26 | 1998-07-09 | Nippon Zeon Co., Ltd. | φ-BROMOALKYLBENZENES ET PROCEDE DE PREPARATION |
| US6374732B1 (en) * | 2000-06-05 | 2002-04-23 | Frank Perretta | Dampener for use in lithographic presses |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2246762A (en) * | 1934-12-22 | 1941-06-24 | Unichem Chemikalien Handels A | Method for condensation |
| NL89164C (zh) * | 1951-05-10 | 1900-01-01 | ||
| US3058892A (en) * | 1960-11-07 | 1962-10-16 | Du Pont | Separation of beta-bromoethylbenzene from alpha-bromoethylbenzene by distillation |
| US3453339A (en) * | 1967-05-11 | 1969-07-01 | Chevron Res | 1-haloalkyl substituted aromatic hydrocarbons and process for their production |
| US4219652A (en) * | 1975-09-30 | 1980-08-26 | Eli Lilly And Company | N-Methyl and N-phenethyl-cis-decahydroisoquinolines |
| US4321383A (en) * | 1980-11-24 | 1982-03-23 | E. R. Squibb & Sons, Inc. | Heterobicyclo intermediates |
-
1989
- 1989-06-13 FR FR8907800A patent/FR2648130B1/fr not_active Expired - Lifetime
-
1990
- 1990-05-28 CA CA002017650A patent/CA2017650C/fr not_active Expired - Fee Related
- 1990-06-01 EP EP90401490A patent/EP0403331B1/fr not_active Expired - Lifetime
- 1990-06-01 ES ES90401490T patent/ES2054292T3/es not_active Expired - Lifetime
- 1990-06-01 AT AT90401490T patent/ATE87291T1/de not_active IP Right Cessation
- 1990-06-01 DK DK90401490.9T patent/DK0403331T3/da active
- 1990-06-01 DE DE90401490T patent/DE69001154T2/de not_active Expired - Fee Related
- 1990-06-08 KR KR1019900008413A patent/KR920006538B1/ko not_active IP Right Cessation
- 1990-06-12 FI FI902953A patent/FI95240C/fi not_active IP Right Cessation
- 1990-06-12 PT PT94357A patent/PT94357B/pt not_active IP Right Cessation
- 1990-06-12 IE IE211690A patent/IE64625B1/en unknown
- 1990-06-13 CN CN90104354A patent/CN1024788C/zh not_active Expired - Fee Related
- 1990-06-13 US US07/537,926 patent/US5181992A/en not_active Expired - Fee Related
- 1990-06-13 NO NO902627A patent/NO173231C/no not_active IP Right Cessation
- 1990-06-13 JP JP2154975A patent/JP2701226B2/ja not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CA2017650A1 (fr) | 1990-12-13 |
| KR910000584A (ko) | 1991-01-29 |
| CN1024788C (zh) | 1994-06-01 |
| DK0403331T3 (da) | 1993-04-19 |
| NO173231C (no) | 1993-11-17 |
| JPH03101629A (ja) | 1991-04-26 |
| PT94357A (pt) | 1991-02-08 |
| DE69001154D1 (de) | 1993-04-29 |
| JP2701226B2 (ja) | 1998-01-21 |
| US5181992A (en) | 1993-01-26 |
| NO902627L (no) | 1990-12-14 |
| FI95240C (fi) | 1996-01-10 |
| ATE87291T1 (de) | 1993-04-15 |
| EP0403331A1 (fr) | 1990-12-19 |
| PT94357B (pt) | 1997-01-31 |
| FI95240B (fi) | 1995-09-29 |
| KR920006538B1 (ko) | 1992-08-08 |
| EP0403331B1 (fr) | 1993-03-24 |
| IE902116A1 (en) | 1991-01-02 |
| ES2054292T3 (es) | 1994-08-01 |
| FR2648130A1 (fr) | 1990-12-14 |
| FI902953A0 (fi) | 1990-06-12 |
| FR2648130B1 (fr) | 1991-09-06 |
| DE69001154T2 (de) | 1993-10-14 |
| NO902627D0 (no) | 1990-06-13 |
| IE64625B1 (en) | 1995-08-23 |
| NO173231B (no) | 1993-08-09 |
| CA2017650C (fr) | 1995-03-21 |
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