CN1051984C - 一种高活性碱金属氢化物作用下卤代烃的还原脱卤反应 - Google Patents
一种高活性碱金属氢化物作用下卤代烃的还原脱卤反应 Download PDFInfo
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- 229910000102 alkali metal hydride Inorganic materials 0.000 title claims abstract description 19
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- 238000005695 dehalogenation reaction Methods 0.000 title claims abstract description 19
- 230000000694 effects Effects 0.000 title claims description 13
- 230000009471 action Effects 0.000 title claims description 9
- 230000009467 reduction Effects 0.000 title claims description 9
- 150000005826 halohydrocarbons Chemical class 0.000 title claims 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000002829 reductive effect Effects 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- -1 Aryl halogenated hydrocarbon Chemical class 0.000 claims abstract 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 11
- 150000004678 hydrides Chemical class 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 238000006298 dechlorination reaction Methods 0.000 claims description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 6
- 239000012312 sodium hydride Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims 1
- 150000003818 basic metals Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- 229910052987 metal hydride Inorganic materials 0.000 claims 1
- 150000004681 metal hydrides Chemical class 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 150000003071 polychlorinated biphenyls Chemical group 0.000 abstract description 9
- 150000008282 halocarbons Chemical class 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000000010 aprotic solvent Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- XOMKZKJEJBZBJJ-UHFFFAOYSA-N 1,2-dichloro-3-phenylbenzene Chemical compound ClC1=CC=CC(C=2C=CC=CC=2)=C1Cl XOMKZKJEJBZBJJ-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 150000004074 biphenyls Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910000103 lithium hydride Inorganic materials 0.000 description 2
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 2
- 229910000105 potassium hydride Inorganic materials 0.000 description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
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- 238000006042 reductive dechlorination reaction Methods 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种温和条件下，卤代烃，尤其是多氯联苯的还原脱卤反应，其特征是采用络合催化法合成的纳米尺寸的活性碱金属氢化物为还原剂，在合成碱金属氢化物的溶液中，原位进行还原脱卤反应。反应在常压、低温(40～80℃)，非质子溶剂中进行。不仅芳基卤代烃、多卤代烃，而且烷基卤代烃也可有效地被还原脱卤。
Description
本发明涉及一种有机化学反应，即提供了一种采用高活性碱金属氢化物作为还原剂的卤代烃能在常压、低温下进行还原脱卤反应的方法。
多氯联苯具有良好的化学稳定性、热稳定性及绝缘性，曾在工业上得到广泛应用。例如电力工业中作为变压器和电容器内的绝缘介质或化学食品工业中加热的热载体等等。六十年代末发现其对人类健康的危害性后，世界上很多国家已经禁止使用这种化合物。我国对此也有有关的明文规定。但是，已生产的多氯联苯的贮存、处理已成为国际上污染物处理的一个重要问题。目前唯一的大规模处理PCB5的方法是直接燃烧法，需要在几秒钟内升温到1300℃～1600℃的高温燃烧，否则生成二恶咽，其毒性远大于多氯联苯。对于含PCB5用燃烧法也不可避免地造成巨大的浪费。
文献及专利中也曾报道了各种用化学方法处理PCB5的过程，目前均处于实验室阶段。Micheal Wilwerding(USP 5,152,844，1992)，用路易氏酸催化剂(AlCl3，FeCl3)在非水介质中，在阳离子(NaOH)300℃以上，使PCB5脱氯，需用大量催化剂及其他试剂，脱氯结果：氯含量小于1ppm；Perry D.Anderson等(USP 5,118,429，1992)采用高锰酸钾、浓硫酸氧化法，对PCB5的破坏效率为99.95％。J.A.Hawari等(USP 4,950,833，1990)，用碱金属及氨盐在隋性气氛及40～60℃下脱氯，其所用碱金属与氨盐的量为PCB5中氯含量的5～10倍；John R.Seiman(US 4,910,353，1990)，用工业氢化钠60～100℃使PCB5从10000ppm降到＜2ppm，在这一过程中，必需加入砜或亚砜。氢化钠与砚的量都必需是PCB5中氯含量的10～100倍，否则脱氯不能完全。中国专利93111152.8提供了一种用NaH脱卤的方法，反应可在常压、低温(20～100℃)下进行，活性较高。
本发明的目的在于提供一种在活性更高的碱金属氢化物作用下，卤代烃的脱卤反应方法。
本发明提供了一种高活性碱金属氢化物作用下卤代烃的还原脱卤反应，采用了利用络合催化法制备的高活性的碱金属氢化物为还原剂，所谓络合催化法是碱金属在多环芳烃化合物存在下，以醚类为溶剂，用过渡金属化合物作为催化剂实现的碱金属氢化反应，其特征在于：碱金属氢化物合成后采用″一锅煮″的方法，即氢化物不与合成反应液分离，直接原位地将卤代烃加入合成釜中进行脱卤，脱卤反应可在常压下进行，反应温度-40℃～100℃，反应中氢化物/卤素摩尔比为0.5～20，在非质子有机溶剂下进行。最佳反应温度范围在40℃～80℃。反应中氢化物/卤素摩尔比最佳范围在1.35～5。
本发明所提供的方法，由于使用新鲜生成的纳米尺寸的高活性氢化物，不经过分离、洗涤、干燥，减少了操作过程中失活的可能性，也减少了小颗粒氢化物聚集失活的可能性，使氢化物表现出特别高的活性。在所使用的碱金属氢化物中，NaH的脱卤效果最佳。这种方法适用于芳基卤化物、多卤化物及烷基卤化物的脱卤反应。当本发明用于多氯联苯的还原脱氯时，NaH对多氯联苯中氯的比例略高于化学计算量，即可高效快速脱氯，氢化物与氯的比为0.5～10，以2.1～10为最佳，最佳温度在40℃～55℃，最佳溶剂为THF。反应液中氯含量可以从几万ppm降到＜0.1ppm，脱氯程度＞99.999％。这种方法可以用于多卤联苯及其他多卤芳烃的杀虫剂、除莠剂等。这是一种有效的处理环境污染物——芳基多卤化物的方法。
下面通过实施例详述本发明。
实例一
活性碱金属氢化物的合成方法：在150ml反应瓶中，置入100mmol碱金属(K，Na或Li，切成小块)和0.64g(5mmol)萘，将反应瓶抽空，充氮三次后，在惰性气体保护下，加入40ml四氢呋喃和2mmol(约0.23ml)TiCl4，经抽空，充氢三次后，在40℃，常压氢气中反应，至反应液不再吸氢为止。
实例二：
在实例一合成的氢化钠反应液中，直接加入含多氯联苯(主要是五氯联苯)的变压器油，多氯联苯在溶液中的浓度为50,000ppm，在50℃，NaH/Cl＝2.1～2.6的条件下，反应4小时后，经色质联用检测，测不到残余的多氯联苯及其他氯代物，反应脱氯程度达＞99.999％。
实例三
按实例一的方法合成氢化锂、氢化钾，按实例二的方法脱氯，反应液中的起始PCB5浓度为50,000ppm时，氢化锂、氢化钾的脱氯效果分别为70.0％和78.6％。
实例四
在15mlTHF中，加入按中国专利93111152.8的方法合成的粉末状活性氢化钠及PCB5，PCB5在溶液中的浓度为10,000ppm，NaH.Cl＝2，50℃，4小时，脱氯程度为99.0％。
实例五
实例一合成的NaH反应液中，加入各种卤代物，脱卤效果见表1。
表1
反应物 NaH/Cl 温度℃ 转化率％ 产物
1.35 50 30.4
100％
5 50 60.0
100％
1.35 50 81.0
100％
2.0 50 100
100％
2.0 67 100
100％ 2.0 67 100
100％
1.35 50 55.6
100％ 1.35 50 100
100％1，4-二氯丁烷 1.35 67 100 氯丁烷20％丁烷70-80％反应时间4小时 溶剂THF
Claims (6)
1.一种高活性碱金属氢化物作用下卤代烃的还原脱卤反应，采用了利用络合催化法制备的高活性的碱金属氢化物为还原剂，所谓络合催化法是碱金属在多环芳烃化合物存在下，以醚类为溶剂，用过渡金属化合物作为催化剂，实现的碱金属氢化反应，其特征在于：碱金属氢化物合成后采用″一锅煮″的方法，即氢化物不与合成反应液分离，直接原位地将卤代烃加入合成釜中进行脱卤，脱卤反应在常压下进行，反应温度40～80℃，反应中氢化物/卤素摩尔比为0.5～20，在非质子有机溶剂下进行。
2.按权利要求1所述高活性碱金属氢化物作用下卤代烃的还原脱卤反应，其特征在于：反应中氢化物/卤素摩尔比为1.35～5。
3.按权利要求1所述高活性碱金属氢化物作用下卤代烃的还原脱卤反应，其特征在于：碱金属氢化物为NaH。
4.按权利要求1所述高活性碱金属氢化物作用下卤代烃的还原脱卤反应，其特征在于：卤代烃芳基卤化物、多卤化物及烷基卤化物。
5.按权利要求1所述高活性碱金属氢化物作用下卤代烃的还原脱卤反应，其特征在于：当用于多氯联苯的还原脱氯时，氢化钠与氯的比为0.5～10，温度在45℃～55℃，溶剂为THF。
6.按权利要求5所述高活性碱金属氢化物作用下卤代烃的还原脱卤反应，其特征在于：氢化钠与氯的比为2.1～10。
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| Application Number | Priority Date | Filing Date | Title |
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| CN95110017A CN1051984C (zh) | 1995-01-24 | 1995-01-24 | 一种高活性碱金属氢化物作用下卤代烃的还原脱卤反应 |
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| CN95110017A CN1051984C (zh) | 1995-01-24 | 1995-01-24 | 一种高活性碱金属氢化物作用下卤代烃的还原脱卤反应 |
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| CN1182730A CN1182730A (zh) | 1998-05-27 |
| CN1051984C true CN1051984C (zh) | 2000-05-03 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8486025B2 (en) | 2006-05-11 | 2013-07-16 | Ronald J. Solar | Systems and methods for treating a vessel using focused force |
| US9050437B2 (en) | 2004-03-04 | 2015-06-09 | YMED, Inc. | Positioning device for ostial lesions |
| US9504473B2 (en) | 2004-03-04 | 2016-11-29 | Y Med Inc. | Vessel treatment devices |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822107B (zh) * | 2018-06-08 | 2020-07-31 | 福建师范大学福清分校 | 一种镍催化多卤代苝二酰亚胺类芳烃脱卤还原的方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4950833A (en) * | 1989-09-28 | 1990-08-21 | Her Majesty The Queen In Right Of Canada, As Represented By The National Research Council Of Canada | Process for the reductive dehalogenation of polyhaloaromatics |
| US5152844A (en) * | 1987-10-13 | 1992-10-06 | Michael Wilwerding | Degradation of polychlorinated biphenyls |
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- 1995-01-24 CN CN95110017A patent/CN1051984C/zh not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5152844A (en) * | 1987-10-13 | 1992-10-06 | Michael Wilwerding | Degradation of polychlorinated biphenyls |
| US4950833A (en) * | 1989-09-28 | 1990-08-21 | Her Majesty The Queen In Right Of Canada, As Represented By The National Research Council Of Canada | Process for the reductive dehalogenation of polyhaloaromatics |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9050437B2 (en) | 2004-03-04 | 2015-06-09 | YMED, Inc. | Positioning device for ostial lesions |
| US9504473B2 (en) | 2004-03-04 | 2016-11-29 | Y Med Inc. | Vessel treatment devices |
| US8486025B2 (en) | 2006-05-11 | 2013-07-16 | Ronald J. Solar | Systems and methods for treating a vessel using focused force |
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| Publication number | Publication date |
|---|---|
| CN1182730A (zh) | 1998-05-27 |
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