CN100343245C - 4－氟－1,3－二噁茂烷－2－酮的制备方法 - Google Patents
4－氟－1,3－二噁茂烷－2－酮的制备方法 Download PDFInfo
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- CN100343245C CN100343245C CNB2004800039400A CN200480003940A CN100343245C CN 100343245 C CN100343245 C CN 100343245C CN B2004800039400 A CNB2004800039400 A CN B2004800039400A CN 200480003940 A CN200480003940 A CN 200480003940A CN 100343245 C CN100343245 C CN 100343245C
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- Prior art keywords
- ethylene carbonate
- fluoro
- fluorine
- dioxolane
- ketone
- 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.)
- Expired - Fee Related
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- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 title abstract 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 21
- 239000011737 fluorine Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 230000008676 import Effects 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 2
- 239000011261 inert gas Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000004334 fluoridation Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/42—Halogen atoms or nitro radicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Furan Compounds (AREA)
Abstract
本发明涉及一种制备4-氟-1，3-二噁茂烷-2-酮的方法。根据本发明，将碳酸亚乙酯和作为碳酸亚乙酯的溶剂的3-20重量%的4-氟-1，3-二噁茂烷-2-酮(以碳酸亚乙酯计)混合，并且在15-45℃的温度下将氟或在惰性气体中含有氟的混合物导入到该溶液中。
Description
本发明涉及一种有着较高选择性的制备4-氟-1，3-二噁茂烷-2-酮的方法。4-氟-1，3-二噁茂烷-2-酮可以通过氯代碳酸亚乙酯和氟化钾的化学计量反应而制得。此处反应持续时间为约24小时。JP2000309583中记载了一种通过碳酸亚乙酯和氟反应制备4-氟-1，3-二噁茂烷-2-酮的方法。因为直接氟化反应放热非常强烈，所以需将碳酸亚乙酯溶于有机溶剂中并将氟气或含氟的混合气导入到碳酸亚乙酯中去。这里的反应温度在20-100℃的范围内。直接氟化过程是强烈放热的反应，其中必须要注意，须将反应温度维持在可控范围内。根据JP2000309583，要冷却所导入的气相。
本发明的任务在于提供一种改善了的4-氟-1，3-二噁茂烷-2-酮的制备方法。该方法的特征应在于有着较高选择性和很好的温度控制性。
根据本发明，将碳酸亚乙酯和3-20重量％的4-氟-1，3-二噁茂烷-2-酮(以碳酸亚乙酯的量计)混合。首先将溶液加热到35℃以溶解碳酸亚乙酯。将氟气或在惰性气体中含有氟的混合物导入到反应溶液中去。在一实施方式中，还可以追加入碳酸亚乙酯和作为碳酸亚乙酯的溶剂的4-14重量％的4-氟-1，3-二噁茂烷-2-酮(以碳酸亚乙酯的量计)。氟的用量低于以所存在的碳酸亚乙酯量计的化学计量，以此抑制副产物的生成。氟的用量可为，例如，60-95摩尔％，优选70-95摩尔％(以所存在的碳酸亚乙酯的量计)。在整个反应持续时间期间，冷却反应溶液温度至15-45℃。溶液的温度只在氟化反应开始时很短时间内高于碳酸亚乙酯的熔点(37-39℃)。在超过90％的氟化反应时间里，溶液温度都是低于碳酸亚乙酯熔点的。在一实施方式中，溶液温度为20-35℃。在谨慎地中和所形成的氢氟酸之后，于真空下多次蒸馏提纯过程中所得到的反应溶液。含有碳酸亚乙酯的馏分可作为原料用于本发明方法中。由此即能在生产过程中回收未反应的碳酸亚乙酯。
可以根据已知方法制备本发明方法中所需的初始量的4-氟-1，3-二噁茂烷-2-酮。
现已发现，通过添加入4-氟-1，3-二噁茂烷-2-酮可以降低反应混合物的熔点。由此就能在低于碳酸亚乙酯熔点的温度下，使反应成分相互进行反应。
此外还发现，通过添加4-氟-1，3-二噁茂烷-2-酮，不只可以降低反应混合物的温度，同时还能以此降低反应性。
由此就能显著改善反应的选择性，而这一点就体现在，必须使用较少量的氟并且在反应中转化为产品的氟的利用率获得提高。同样，由此也能抑制副产物的生成。因此如果将氟的用量减半，也能得到符合已知方法的利用率。
本发明方法的另一优点在于，其中并不需要另外的且在合成了4-氟-1，3-二噁茂烷-2-酮之后还要再次加以除去的、独立的惰性溶剂。由此也就简化了对所得反应溶液的提纯过程。
以下实施例用来阐释而非限制本发明。
实施例1
碳酸亚乙酯具有37-39℃的熔点，而4-氟-1，3-二噁茂烷-2-酮的熔点则为约17℃。通过添加4-氟-1，3-二噁茂烷-2-酮到碳酸亚乙酯中，可以降低其熔点。87％的碳酸亚乙酯和13％的4-氟-1，3-二噁茂烷-2-酮组成的混合物的熔点为约20℃。
实施例2
在室温下将2000g的碳酸亚乙酯置于PFA-容器中。补加入616g含有4-氟-1，3-二噁茂烷-2-酮且含有碳酸亚乙酯的溶液。整个的反应溶液含有95.03重量％的碳酸亚乙酯(2483.4g；28.22mol)和4.88重量％的4-氟-1，3-二噁茂烷-2-酮(129.3g；1.22mol)。
将该悬浮液加热到35℃，该过程中预置入的碳酸亚乙酯会完全溶解。
然后经由一个带有PTFE烧结料的浸入管而导入氟/氮气混合物(5∶95体积％)。
总共导入25.23mol的氟(以100％的氟计算)。
在氟化作用开始阶段，溶液温度短时期内会高于碳酸亚乙酯的熔点。在超过90％的氟化时间内，溶液温度低于碳酸亚乙酯的熔点，优选在30-35℃的范围内。
反应结束后，首先加入丙酮来提纯反应溶液。然后在搅拌下用碳酸氢钾中和。利用吸滤装置抽吸所得的悬浮液并再用丙酮洗涤残留物。多次真空蒸馏所得溶液。
相应地得到1839g(17.34mol)4-氟-1，3-二噁茂烷-2-酮。在扣除了原来所含有量的4-氟-1，3-二噁茂烷-2-酮后，以所用的氟的量计算得到4-氟-1，3-二噁茂烷-2-酮的产率为63.9％。
Claims (7)
1.一种通过碳酸亚乙酯和元素氟的反应来制备4-氟-1，3-二噁茂烷-2-酮的方法，其特征在于，在反应容器中将碳酸亚乙酯和作为碳酸亚乙酯的溶剂的以碳酸亚乙酯计3-20重量％的4-氟-1，3-二噁茂烷-2-酮混合，并且于15-45℃的温度下将氟气或在惰性气体中含有氟的混合物导入到溶液中。
2.如权利要求1所述的4-氟-1，3-二噁茂烷-2-酮的制备方法，其特征在于，追加入碳酸亚乙酯和作为碳酸亚乙酯的溶剂的以碳酸亚乙酯计4-14重量％的4-氟-1，3-二噁茂烷-2-酮。
3.如权利要求1-2之一所述的方法，其特征在于，不向反应中加入其它溶剂。
4.如权利要求1所述的方法，其特征在于，在低于碳酸亚乙酯的熔点的温度下进行反应。
5.如权利要求1所述的方法，其特征在于，氟的用量低于以所存在的碳酸亚乙酯量计的化学计量，以此抑制副产物的生成。
6.如权利要求5所述的方法，其特征在于，氟的用量为60-95Mol％，以所存在的碳酸亚乙酯量计。
7.如权利要求1所述的方法，其特征在于，回收未反应的碳酸亚乙酯。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10308149A DE10308149A1 (de) | 2003-02-26 | 2003-02-26 | Verfahren zur Herstellung von 4-Fluor-1, 3-dioxolan-2-on |
| DE10308149.6 | 2003-02-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1747946A CN1747946A (zh) | 2006-03-15 |
| CN100343245C true CN100343245C (zh) | 2007-10-17 |
Family
ID=32841893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800039400A Expired - Fee Related CN100343245C (zh) | 2003-02-26 | 2004-02-13 | 4－氟－1,3－二噁茂烷－2－酮的制备方法 |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US7745648B2 (zh) |
| EP (1) | EP1599459B1 (zh) |
| JP (1) | JP4791952B2 (zh) |
| KR (1) | KR101158121B1 (zh) |
| CN (1) | CN100343245C (zh) |
| AT (1) | ATE374760T1 (zh) |
| CA (1) | CA2517395C (zh) |
| DE (2) | DE10308149A1 (zh) |
| TW (1) | TWI311991B (zh) |
| WO (1) | WO2004076439A1 (zh) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006004878A (ja) * | 2004-06-21 | 2006-01-05 | Sony Corp | 電池 |
| KR100655225B1 (ko) | 2005-01-24 | 2006-12-08 | 울산화학주식회사 | 4-플루오로에틸렌카보네이트의 제조방법 및 장치 |
| ATE530537T1 (de) * | 2007-09-24 | 2011-11-15 | Evonik Degussa Gmbh | VERFAHREN ZUR HERSTELLUNG VON MONOCHLORETHYLENCARBONAT UND ZU DESSEN ANSCHLIEßENDER UMWANDLUNG IN VINYLENCARBONAT |
| EP2271637A1 (en) * | 2008-03-27 | 2011-01-12 | Solvay Fluor GmbH | Process for the removal of hf from hf containing organic carbonates |
| KR20100126562A (ko) * | 2008-03-27 | 2010-12-01 | 솔베이 플루오르 게엠베하 | 특정 흡수제를 이용하여 ｈｆ가 감소된 불소화 유기 카보네이트를 제조하는 방법 |
| TW201012796A (en) * | 2008-09-02 | 2010-04-01 | Solvay Fluor Gmbh | Method for removal of contaminants |
| EP2196464A1 (en) | 2008-12-15 | 2010-06-16 | Solvay Fluor GmbH | Container containing fluorinated organic carbonates |
| TW201105646A (en) * | 2009-05-28 | 2011-02-16 | Solvay Fluor Gmbh | Process for the preparation of 4-fluoro-4-R-5-R'-1,3-dioxolane-2-ones |
| CA2770443A1 (en) * | 2009-08-20 | 2011-02-24 | Alain Lambert | Process for the destillative purification of fluoroethylene carbonate |
| TW201121938A (en) * | 2009-09-28 | 2011-07-01 | Solvay Fluor Gmbh | Manufacture of difluoroethylene carbonate, trifluoroethylene carbonate and tetrafluoroethylene carbonate |
| TW201118065A (en) | 2009-09-28 | 2011-06-01 | Solvay Fluor Gmbh | Continuous preparation of carbonates |
| CN101717389B (zh) * | 2009-10-29 | 2013-01-09 | 江苏华盛精化工股份有限公司 | 氟代碳酸乙烯酯的除酸除水方法 |
| KR20150064748A (ko) | 2012-10-09 | 2015-06-11 | 솔베이(소시에떼아노님) | 플루오르화 유기 카보네이트의 정제 방법 |
| JP2015535845A (ja) * | 2012-10-09 | 2015-12-17 | ソルヴェイ（ソシエテ アノニム） | 精製フルオロ置換有機カーボネートの製造 |
| EP2854147A1 (en) | 2013-09-30 | 2015-04-01 | Solvay SA | Electrolyte compositions comprising fluorinated carbonates |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000309583A (ja) * | 1999-04-28 | 2000-11-07 | Kanto Denka Kogyo Co Ltd | ４−フルオロ−１，３−ジオキソラン−２−オンの製造方法 |
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| JPS62290072A (ja) | 1986-06-09 | 1987-12-16 | Matsushita Electric Ind Co Ltd | 有機電解質二次電池 |
| CA2087390A1 (en) * | 1992-02-12 | 1993-08-13 | Jack E. Richman | Preparation of fluorinated functional compounds |
| JPH07312227A (ja) | 1994-05-17 | 1995-11-28 | Mitsubishi Chem Corp | リチウム二次電池 |
| WO1998015024A1 (en) * | 1996-10-03 | 1998-04-09 | National Research Council Of Canada | Electrolyte comprising fluoro-ethylene carbonate and propylene carbonate, for alkali metal-ion secondary battery |
| JP4431212B2 (ja) | 1999-06-02 | 2010-03-10 | 関東電化工業株式会社 | 含フッ素環状炭酸エステルの製造方法 |
| JP2004161638A (ja) | 2002-11-11 | 2004-06-10 | Mitsubishi Chemicals Corp | フッ素含環状化合物の製造方法 |
-
2003
- 2003-02-26 DE DE10308149A patent/DE10308149A1/de not_active Withdrawn
- 2003-12-19 TW TW092136083A patent/TWI311991B/zh not_active IP Right Cessation
-
2004
- 2004-02-13 KR KR1020057015765A patent/KR101158121B1/ko not_active IP Right Cessation
- 2004-02-13 WO PCT/EP2004/001345 patent/WO2004076439A1/de active IP Right Grant
- 2004-02-13 JP JP2006501829A patent/JP4791952B2/ja not_active Expired - Fee Related
- 2004-02-13 AT AT04710797T patent/ATE374760T1/de active
- 2004-02-13 EP EP04710797A patent/EP1599459B1/de not_active Expired - Lifetime
- 2004-02-13 DE DE502004005133T patent/DE502004005133D1/de not_active Expired - Lifetime
- 2004-02-13 CN CNB2004800039400A patent/CN100343245C/zh not_active Expired - Fee Related
- 2004-02-13 CA CA2517395A patent/CA2517395C/en not_active Expired - Fee Related
-
2005
- 2005-08-25 US US11/210,868 patent/US7745648B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000309583A (ja) * | 1999-04-28 | 2000-11-07 | Kanto Denka Kogyo Co Ltd | ４−フルオロ−１，３−ジオキソラン−２−オンの製造方法 |
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| Title |
|---|
| Electroorganic synthesis under solvent-free conditions.highly regioselective anodic monofluorination of cyclicethers,lactone,and a cyclic carbonate Masaru Hasegawa,et al,Tetrahedron Letters,Vol.43 No.8 2002 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1747946A (zh) | 2006-03-15 |
| KR101158121B1 (ko) | 2012-06-19 |
| DE502004005133D1 (de) | 2007-11-15 |
| CA2517395C (en) | 2011-11-22 |
| US20060036102A1 (en) | 2006-02-16 |
| US7745648B2 (en) | 2010-06-29 |
| ATE374760T1 (de) | 2007-10-15 |
| CA2517395A1 (en) | 2004-09-10 |
| TWI311991B (en) | 2009-07-11 |
| EP1599459B1 (de) | 2007-10-03 |
| EP1599459A1 (de) | 2005-11-30 |
| TW200502229A (en) | 2005-01-16 |
| JP2006519191A (ja) | 2006-08-24 |
| JP4791952B2 (ja) | 2011-10-12 |
| DE10308149A1 (de) | 2004-09-09 |
| WO2004076439A1 (de) | 2004-09-10 |
| KR20050105487A (ko) | 2005-11-04 |
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