JP5678762B2 - ジフルオロ酢酸クロライドの精製方法 - Google Patents
ジフルオロ酢酸クロライドの精製方法 Download PDFInfo
- Publication number
- JP5678762B2 JP5678762B2 JP2011070387A JP2011070387A JP5678762B2 JP 5678762 B2 JP5678762 B2 JP 5678762B2 JP 2011070387 A JP2011070387 A JP 2011070387A JP 2011070387 A JP2011070387 A JP 2011070387A JP 5678762 B2 JP5678762 B2 JP 5678762B2
- Authority
- JP
- Japan
- Prior art keywords
- difluoroacetic acid
- acid chloride
- reaction
- chloride
- fluoride
- 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
Links
- KURKJXZWCPWPFX-UHFFFAOYSA-N 2,2-difluoroacetyl chloride Chemical compound FC(F)C(Cl)=O KURKJXZWCPWPFX-UHFFFAOYSA-N 0.000 title claims description 38
- 238000000034 method Methods 0.000 title claims description 23
- CRLSHTZUJTXOEL-UHFFFAOYSA-N 2,2-difluoroacetyl fluoride Chemical compound FC(F)C(F)=O CRLSHTZUJTXOEL-UHFFFAOYSA-N 0.000 claims description 34
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 16
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 13
- 239000001110 calcium chloride Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 description 34
- 238000000746 purification Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- VLIDBBNDBSNADN-UHFFFAOYSA-N 1,1-dichloro-2,2-difluoroethane Chemical compound FC(F)C(Cl)Cl VLIDBBNDBSNADN-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VOGSDFLJZPNWHY-UHFFFAOYSA-N 2,2-difluoroethanol Chemical compound OCC(F)F VOGSDFLJZPNWHY-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- JUCMRTZQCZRJDC-UHFFFAOYSA-N acetyl fluoride Chemical compound CC(F)=O JUCMRTZQCZRJDC-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- FBCCMZVIWNDFMO-UHFFFAOYSA-N dichloroacetyl chloride Chemical compound ClC(Cl)C(Cl)=O FBCCMZVIWNDFMO-UHFFFAOYSA-N 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/64—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/38—Acyl halides
- C07C53/46—Acyl halides containing halogen outside the carbonyl halide group
- C07C53/48—Halogenated acetyl halides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
少なくともジフルオロ酢酸フルオライドを含むジフルオロ酢酸クロライド組成物を反応可能な温度において塩化カルシウムと接触させて、ジフルオロ酢酸フルオライドをジフルオロ酢酸クロライドに転換させる工程を含むジフルオロ酢酸クロライドの精製方法。
接触が、ジフルオロ酢酸フルオライド組成物を反応可能な温度の塩化カルシウムに流通させることからなる発明1のジフルオロ酢酸クロライドの精製方法。
反応式が示すように、反応において、ジフルオロ酢酸フルオライドは純分であるジフルオロ酢酸クロライドに変換されるためさらなる精製操作は必要なく、一方、ハロゲン交換で取り除かれたフッ素原子はフッ化カルシウムとして固定されるため、廃棄等の処理は容易である。
内径37mm長さ1000mmのステンレス鋼製反応管に、純正化学株式会社製無水塩化カルシウム(粒径:約2.5〜3.5mm)を150g充填して、窒素を流通させながら反応管をテープヒーターで200℃に加熱した。温度が200℃で安定した後、4.8%のジフルオロ酢酸フルオライド(DFAF)を含む粗ジフルオロ酢酸クロライド(DFAC。純度95.0%)を0.2g/分の速度で流通させると同時に、窒素の供給を停止した。100g流通させた後、反応管出口に接続したドライアイストラップに回収された有機物(98g)をガスクロマトグラフで分析した。その結果、DFAC純度は99.9%であり、DFAFは痕跡量(0.001%未満)であった。
(DFAC調製)
攪拌器を備えた1000ccステンレス鋼製オートクレーブに、塩化リチウム(LiCl。168.7g、4.0mol)を仕込み内部を減圧した。ドライアイス−アセトン浴で内温−40℃に冷却後、少量のモノフルオロメタンを含むDFAF(300g、3.06mol)を攪拌しながら圧入した。その後、浴を外し、室温(約25℃)で1時間攪拌し、次にバンドヒーターを用いて1時間かけて70℃に昇温し4時間そのまま保持した。その時の圧力は0.56MPaG(ゲージ圧)であった。反応終了後、内容物を回収し、フラッシュ蒸留し、ガスクロマトグラフで分析したところ純度98.64%のDFAC(CHF2COCl)であった(回収率96%)。主な不純物は、原料のDFAF中不純物由来のCH3F:0.36%、未反応DFAF:0.15%、ジフルオロ酢酸:(CHF2COOH):0.33%であった。
得られた粗DFACを用いて、実施例1と同様の実験を行った。100g流通させた後、反応管出口に接続したドライアイストラップに回収された有機物(103g)をガスクロマトグラフで分析した。その結果、DFAC純度は99.9%であり、DFAFは痕跡量(0.001%未満)であった。
4.8%のDFAFを含む粗DFAC(純度95.0%)を原料とする以外実施例2と同一の反応を行った。その結果、反応開始4時間後の分析結果では、2,2−ジフルオロエチルアルコール(CHF2CH2OH):99.09%、ジフルオロ酢酸2,2−ジフルオロエチル(CHF2COOCH2CHF2):0.03%、DFAC:検出されず、DFAF検出されず、であったが、16時間後には、CHF2CH2OH:88.09%、CHF2COOCH2CHF2:11.21%、DFAC:検出されず、DFAF:検出されず、であった。
Claims (2)
- 少なくともジフルオロ酢酸フルオライドを含むジフルオロ酢酸クロライド組成物を50℃〜250℃において塩化カルシウムと接触させて、ジフルオロ酢酸フルオライドをジフルオロ酢酸クロライドに転換させる工程を含むジフルオロ酢酸クロライドの精製方法。
- 接触が、ジフルオロ酢酸フルオライド組成物を50℃〜250℃の塩化カルシウムに流通させることからなる請求項1に記載のジフルオロ酢酸クロライドの精製方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011070387A JP5678762B2 (ja) | 2011-03-28 | 2011-03-28 | ジフルオロ酢酸クロライドの精製方法 |
CN201280014782.3A CN103443065B (zh) | 2011-03-28 | 2012-03-28 | 二氟乙酰氯的提纯方法 |
US14/000,754 US8785689B2 (en) | 2011-03-28 | 2012-03-28 | Method for purifying difluoroacetic acid chloride |
PCT/JP2012/058083 WO2012133501A1 (ja) | 2011-03-28 | 2012-03-28 | ジフルオロ酢酸クロライドの精製方法 |
EP12763938.3A EP2676948B1 (en) | 2011-03-28 | 2012-03-28 | Method for purifying difluoroacetic acid chloride |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011070387A JP5678762B2 (ja) | 2011-03-28 | 2011-03-28 | ジフルオロ酢酸クロライドの精製方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2012201667A JP2012201667A (ja) | 2012-10-22 |
JP5678762B2 true JP5678762B2 (ja) | 2015-03-04 |
Family
ID=46931210
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2011070387A Expired - Fee Related JP5678762B2 (ja) | 2011-03-28 | 2011-03-28 | ジフルオロ酢酸クロライドの精製方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US8785689B2 (ja) |
EP (1) | EP2676948B1 (ja) |
JP (1) | JP5678762B2 (ja) |
CN (1) | CN103443065B (ja) |
WO (1) | WO2012133501A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2554534B1 (en) * | 2010-03-29 | 2015-06-10 | Central Glass Company, Limited | Method for producing difluoroacetyl chloride |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3718524A1 (de) * | 1987-06-03 | 1988-12-22 | Basf Ag | Verfahren zur herstellung von fluorsubstituierten carbonsaeurechloriden |
JPH0853388A (ja) * | 1994-06-08 | 1996-02-27 | Asahi Glass Co Ltd | ジフルオロ酢酸ハライドおよびジフルオロ酢酸の製造方法 |
JP3632243B2 (ja) | 1994-07-28 | 2005-03-23 | 旭硝子株式会社 | ジフルオロ酢酸フルオリドおよびジフルオロ酢酸エステルの製造方法 |
US5905169A (en) * | 1995-03-20 | 1999-05-18 | E. I. Du Pont De Nemours And Company | Process for producing polyfluoroacyl compositions |
EP2554534B1 (en) * | 2010-03-29 | 2015-06-10 | Central Glass Company, Limited | Method for producing difluoroacetyl chloride |
-
2011
- 2011-03-28 JP JP2011070387A patent/JP5678762B2/ja not_active Expired - Fee Related
-
2012
- 2012-03-28 CN CN201280014782.3A patent/CN103443065B/zh not_active Expired - Fee Related
- 2012-03-28 WO PCT/JP2012/058083 patent/WO2012133501A1/ja active Application Filing
- 2012-03-28 EP EP12763938.3A patent/EP2676948B1/en not_active Not-in-force
- 2012-03-28 US US14/000,754 patent/US8785689B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
EP2676948B1 (en) | 2018-01-24 |
EP2676948A1 (en) | 2013-12-25 |
US8785689B2 (en) | 2014-07-22 |
EP2676948A4 (en) | 2014-08-20 |
JP2012201667A (ja) | 2012-10-22 |
CN103443065A (zh) | 2013-12-11 |
US20140031588A1 (en) | 2014-01-30 |
WO2012133501A1 (ja) | 2012-10-04 |
CN103443065B (zh) | 2015-09-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3632243B2 (ja) | ジフルオロ酢酸フルオリドおよびジフルオロ酢酸エステルの製造方法 | |
US9115044B2 (en) | Method for producing trans-1-chloro-3,3,3-trifluoropropene | |
JP5678761B2 (ja) | ジフルオロ酢酸クロライドの製造方法 | |
JP3792051B2 (ja) | パーハロゲン化シクロペンテンの製造方法 | |
KR101492352B1 (ko) | 오불화인의 제조 방법 | |
JP3592368B2 (ja) | 2−h−ヘプタフルオルプロパンの製造方法 | |
JP5678762B2 (ja) | ジフルオロ酢酸クロライドの精製方法 | |
JP2009091301A (ja) | シス−1,2,3,3,3−ペンタフルオロプロペンの製造方法 | |
WO2005105668A1 (ja) | 二フッ化カルボニルの製造方法 | |
JP4785532B2 (ja) | ハイドロフルオロカーボンの製造方法、その製品およびその用途 | |
US5629458A (en) | Process for the preparation of 2 2 2 trifluoroethanol | |
JP4433203B2 (ja) | オクタフルオロシクロペンテンの製造方法 | |
CN113272268A (zh) | 环丁烷的制造方法 | |
JPH0688919B2 (ja) | 含水素フルオロクロロアルカンの製造方法 | |
RU2807184C2 (ru) | Способ получения циклобутана | |
RU2807184C9 (ru) | Способ получения циклобутана | |
JP2005008543A (ja) | ヨウ化トリフルオロメタンの製造方法およびその装置 | |
JP2009091300A (ja) | シス−1,2,3,3,3−ペンタフルオロプロペンの製造方法 | |
JP2000159700A (ja) | ビスジフルオロメチルベンゼンの製造方法 | |
JP2012006866A (ja) | ジフルオロ酢酸クロライドの製造方法 | |
CN115803308A (zh) | 1-氯-2,3,3-三氟丙烯的制造方法 | |
JP3556853B2 (ja) | 3,3−ジクロロ−1,1,1−トリフルオロアセトンの製造方法 | |
JP2018108961A (ja) | 2,2,2,1−テトラフルオロエチルジクロロメチルエーテルの製造方法 | |
JPH1087525A (ja) | ペンタフルオロエタンの精製 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20131220 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20141118 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20141119 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20141209 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20141222 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5678762 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |