JP2004002466A - Method for purification of 1, 1, 1, 5, 5, 5-hexafluoro acetylacetone dihydrate - Google Patents
Method for purification of 1, 1, 1, 5, 5, 5-hexafluoro acetylacetone dihydrate Download PDFInfo
- Publication number
- JP2004002466A JP2004002466A JP2003286394A JP2003286394A JP2004002466A JP 2004002466 A JP2004002466 A JP 2004002466A JP 2003286394 A JP2003286394 A JP 2003286394A JP 2003286394 A JP2003286394 A JP 2003286394A JP 2004002466 A JP2004002466 A JP 2004002466A
- Authority
- JP
- Japan
- Prior art keywords
- dihydrate
- hexafluoroacetylacetone
- solvent
- hexafluoroacetylacetone dihydrate
- organic solvent
- 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.)
- Abandoned
Links
- BZMWYBPDQWRVHE-UHFFFAOYSA-N 1,1,1,5,5,5-hexafluoropentane-2,2,4,4-tetrol Chemical compound FC(F)(F)C(O)(O)CC(O)(O)C(F)(F)F BZMWYBPDQWRVHE-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000000746 purification Methods 0.000 title claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 239000012535 impurity Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- -1 alicyclic hydrocarbon Chemical class 0.000 claims abstract description 9
- 150000004683 dihydrates Chemical class 0.000 claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 4
- 238000005507 spraying Methods 0.000 claims abstract 2
- FHUDAMLDXFJHJE-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-one Chemical compound CC(=O)C(F)(F)F FHUDAMLDXFJHJE-UHFFFAOYSA-N 0.000 claims description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000010410 layer Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 7
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 7
- 239000007810 chemical reaction solvent Substances 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 1
- IDBYQQQHBYGLEQ-UHFFFAOYSA-N 1,1,2,2,3,3,4-heptafluorocyclopentane Chemical compound FC1CC(F)(F)C(F)(F)C1(F)F IDBYQQQHBYGLEQ-UHFFFAOYSA-N 0.000 description 1
- XXZOEDQFGXTEAD-UHFFFAOYSA-N 1,2-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1C(F)(F)F XXZOEDQFGXTEAD-UHFFFAOYSA-N 0.000 description 1
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 1
- PDCBZHHORLHNCZ-UHFFFAOYSA-N 1,4-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(C(F)(F)F)C=C1 PDCBZHHORLHNCZ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229940095564 anhydrous calcium sulfate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VMVNZNXAVJHNDJ-UHFFFAOYSA-N methyl 2,2,2-trifluoroacetate Chemical compound COC(=O)C(F)(F)F VMVNZNXAVJHNDJ-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- IQHNYSGEKCLZAD-UHFFFAOYSA-N pentane-2,4-dione;dihydrate Chemical compound O.O.CC(=O)CC(C)=O IQHNYSGEKCLZAD-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
医薬、農薬などの中間体や電子部品の製造に使用される低沸点キレート化合物の原料として有用な１，１，１，５，５，５−ヘキサフルオロアセチルアセトンの製造方法に関し、より詳しくはその高純度品の製造方法に関する。 The present invention relates to a method for producing 1,1,1,5,5,5-hexafluoroacetylacetone, which is useful as a raw material of a low-boiling-point chelate compound used in the production of intermediates such as pharmaceuticals and agricultural chemicals and electronic components. The present invention relates to a method for producing a pure product.
１，１，１，５，５，５−ヘキサフルオロアセチルアセトンの製造方法としては、下式に示す方法が知られている。 As a method for producing 1,1,1,5,5,5-hexafluoroacetylacetone, a method represented by the following formula is known.
一般に、生成物の純度を高めるためには各種の方法が製造工程の途中で採られるが、１，１，１，５，５，５−ヘキサフルオロアセチルアセトンの製造方法においてもそのような方法が知られている。J.Amer.Chem.Soc.,69,1819(1947)には、中間体として得られる１，１，１，５，５，５−ヘキサフルオロアセチルアセトンナトリウム塩を銅キレート化合物とし、それを再結晶した後硫化水素で銅を取り除いて無水の１，１，１，５，５，５−ヘキサフルオロアセチルアセトンを得ている。非特許文献１には、反応液に希硫酸を加えエーテルで抽出した有機層を蒸留し３６〜９０℃の留分を採取することが記載され、その中の８５〜９０℃の留分は１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物であることが記載されている。非特許文献２には、エーテルで抽出した有機層を濃縮して１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物を析出させる方法が記載されている。
一般に、医・農薬や電子部品の製造原料としては他の用途に比べて非常に高純度の製品が求められ、１，１，１，５，５，５−ヘキサフルオロアセチルアセトンにおいても例外ではない。 Generally, as a raw material for manufacturing medical / agricultural chemicals and electronic parts, products with extremely high purity compared to other uses are required, and 1,1,1,5,5,5-hexafluoroacetylacetone is no exception.
本発明者らは、１，１，１−トリフルオロアセトンとトリフルオロ酢酸エチルを反応させて１，１，１，５，５，５−ヘキサフルオロアセチルアセトンを製造する方法において、中間体として得られる１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物を特定の溶媒で洗浄することにより、あるいは特定の溶媒から再結晶することで１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物に含まれる不純物の含有量を低減させ、ひいては１，１，１，５，５，５−ヘキサフルオロアセチルアセトンの純度を向上させることを見いだし、本発明を完成させた。 The present inventors obtain 1,1,1,5,5,5-hexafluoroacetylacetone as an intermediate in a method for producing 1,1,1,5,5,5-hexafluoroacetylacetone by reacting 1,1,1-trifluoroacetone with ethyl trifluoroacetate. By washing 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate with a specific solvent or recrystallizing from a specific solvent, 1,1,1,5,5,5 Completed the present invention by finding that the content of impurities contained in 5-hexafluoroacetylacetone dihydrate was reduced, and thus the purity of 1,1,1,5,5,5-hexafluoroacetylacetone was improved. I let it.
すなわち、本発明は、不純物を含む１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物を該二水和物に対して難溶性の有機溶剤と接触させて不純物を除くことを特徴とする１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物の精製方法（第１の方法）である。 That is, the present invention removes impurities by contacting 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate containing impurities with an organic solvent which is hardly soluble in the dihydrate. A method for purifying 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate (first method), characterized in that:
また、本発明は、不純物を含む１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物の溶液から１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物の結晶を析出させることからなる１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物の精製方法（第２の方法）である。 Further, the present invention provides a method for preparing 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate from a solution of 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate containing impurities. This is a method (second method) for purifying 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate by precipitating crystals of a hydrate.
本発明の精製方法を適用する１，１，１，５，５，５−ヘキサフルオロアセチルアセトンはどの様な方法によって製造されたものであってもよい。以下に例示するがこれらに限られない。 １ ， 1,1,1,5,5,5-Hexafluoroacetylacetone to which the purification method of the present invention is applied may be produced by any method. The following are examples, but the present invention is not limited to these.
反応容器に、反応溶媒と塩基を仕込み、そこへ１，１，１-トリフルオロアセトンとトリフルオロ酢酸エステルと溶媒を攪拌等することで均一化させて反応温度より低い所定の温度で徐々に添加し、その後必要に応じて反応器の温度を高め反応の完結を速めると１，１，１，５，５，５−ヘキサフルオロアセチルアセトンの塩が生成する。 In a reaction vessel, a reaction solvent and a base are charged, and 1,1,1-trifluoroacetone, trifluoroacetate and the solvent are homogenized by stirring or the like, and gradually added at a predetermined temperature lower than the reaction temperature. Then, if necessary, if the temperature of the reactor is increased to accelerate the completion of the reaction, a salt of 1,1,1,5,5,5-hexafluoroacetylacetone is formed.
この製造方法において、反応器は通常、ガラス、フッ素樹脂またはこれらの材質でライニングし容器が用いられる。反応溶媒としては、エーテル類が用いられ沸点が２０〜８０℃程度のものが好ましく、例えば、ジエチルエーテル、ジブチルエーテル、ｔ-ブチルメチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン（ＴＨＦ）等が用いられる。塩基としては、通常無機塩基であり、例えば、アルカリ金属またはアルカリ土類金属のアルコキシド、水素化物、金属単体が用いられ、具体的には、ナトリウムメトキシド、ナトリウムエトキシド、水素化ナトリウム、金属ナトリウム、カリウムメトキシド、カリウムエトキシド、水素化カリウム、金属カリウム、水素化リチウム等が用いられる。 トリフルオロ酢酸エステルのエステル部位は脱離基として働くので特に限定されないが、工業的に入手の容易なメチルトリフルオロアセテート、エチルトリフルオロアセテートなどを使用すればよい。１，１，１-トリフルオロアセトンとトリフルオロ酢酸エステルの溶媒としては反応溶媒と同一である必要はないが、反応溶媒として使用されるエーテル類から選べばよい。また、操作性を考慮して前記方法では１，１，１-トリフルオロアセトンとトリフルオロ酢酸エステルは溶媒とともに添加したが、反応の点からは必ずしも混合して添加する必要はなく、また溶媒は必ずしも必要ではない。添加する際には通常は冷却して温度の上昇を防ぐのが好ましい。反応温度は、０〜９０℃程度であり、２０〜７０℃程度が好ましい。０℃未満では反応の進行が遅く、９０℃を超えると１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物の収量が減ずるので好ましくない。 に お い て In this production method, the reactor is usually lined with glass, fluororesin or a material of these materials, and a container is used. As the reaction solvent, ethers are used and those having a boiling point of about 20 to 80 ° C. are preferable. For example, diethyl ether, dibutyl ether, t-butyl methyl ether, diisopropyl ether, tetrahydrofuran (THF) and the like are used. The base is usually an inorganic base, for example, an alkoxide of an alkali metal or an alkaline earth metal, a hydride, a simple metal is used.Specifically, sodium methoxide, sodium ethoxide, sodium hydride, sodium metal , Potassium methoxide, potassium ethoxide, potassium hydride, potassium metal, lithium hydride and the like are used. The ester portion of trifluoroacetic acid ester is not particularly limited since it functions as a leaving group, but industrially easily available methyl trifluoroacetate, ethyl trifluoroacetate and the like may be used. The solvent for 1,1,1-trifluoroacetone and trifluoroacetic acid ester does not need to be the same as the reaction solvent, but may be selected from ethers used as the reaction solvent. Also, in the above method, 1,1,1-trifluoroacetone and trifluoroacetate were added together with the solvent in consideration of the operability, but from the viewpoint of the reaction, it is not always necessary to add them in a mixed state. It is not necessary. When adding, it is usually preferable to cool to prevent the temperature from rising. The reaction temperature is about 0 to 90 ° C, preferably about 20 to 70 ° C. If the temperature is lower than 0 ° C., the reaction proceeds slowly. If the temperature exceeds 90 ° C., the yield of 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate decreases, which is not preferable.
反応が完結した後、反応溶媒を除くと粗の１，１，１，５，５，５-ヘキサフルオロアセチルアセトンの塩が得られる。反応溶媒の除去は、加熱または／および減圧することで行われる。これを前記と同様の反応容器へ移し、水を加え、次いで酸、例えば、硫酸、塩酸、硝酸等を加えて塩を分解し、その後反応液に溶媒を加えて有機層を二層分離し、得られた有機層から溶媒を除去すると不純物を含んだ粗の１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物が固体として得られる。 後 After completion of the reaction, removing the reaction solvent gives a crude salt of 1,1,1,5,5,5-hexafluoroacetylacetone. The removal of the reaction solvent is performed by heating or / and reducing the pressure. Transfer this to the same reaction vessel as above, add water, then add acid, for example, sulfuric acid, hydrochloric acid, nitric acid, etc. to decompose the salt, then add a solvent to the reaction solution to separate the organic layer into two layers, When the solvent is removed from the obtained organic layer, crude 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate containing impurities is obtained as a solid.
本発明の精製方法は、不純物を含む粗の１，１，１，５，５，５-ヘキサフルオロアセチルアセトン・二水和物に溶媒を接触させること（第１の方法）、または、不純物を含む１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物の溶液から１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物の結晶を析出させること（第２の方法）で行なう。 In the purification method of the present invention, a solvent is brought into contact with crude 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate containing impurities (first method), or impurities are contained. Precipitating crystals of 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate from a solution of 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate ( Second method).
第１の方法においては、１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物と溶媒の接触方法は特に限られないが、有機溶媒中に１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物を分散させ、その後濾過・分離する方法、濾過装置においてフィルター上に保持された１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物に有機溶媒を洗浄液として散布する方法などを例示できる。これらの処理の後は通常乾燥させるが、１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・無水物の製造原料とする場合は必ずしも乾燥は必要としない。 In the first method, the method of contacting 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate with a solvent is not particularly limited, but 1,1,1,5,5 For dispersing 1,5,5-hexafluoroacetylacetone dihydrate, followed by filtration and separation; 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate held on a filter in a filtration device A method in which an organic solvent is sprayed on the hydrate as a washing liquid can be exemplified. After these treatments, drying is usually performed. However, drying is not necessarily required when the raw material is used as a production raw material of 1,1,1,5,5,5-hexafluoroacetylacetone / anhydride.
第２の方法においては、１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物は一旦有機溶媒に溶解して溶液を調製し、そこへ溶質難溶性の有機溶媒を添加し、析出した１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物を濾過・分離する方法、または前記溶液の温度を下げることで溶解度を低下させる方法を採ることができる。 In the second method, 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate is once dissolved in an organic solvent to prepare a solution, and a solute-insoluble organic solvent is added thereto. Then, a method of filtering and separating the precipitated 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate, or a method of lowering the solubility by lowering the temperature of the solution can be adopted. .
この様な処理を行う温度は特に限定されず、０〜９０℃程度であり、２０〜６０℃程度が好ましい。通常特に加熱や冷却を必要としない温度で行うのが操作性がよく好ましい。 温度 The temperature at which such treatment is performed is not particularly limited, and is about 0 to 90 ° C, preferably about 20 to 60 ° C. Usually, it is preferable to perform the heating at a temperature that does not particularly require heating or cooling because of good operability.
本発明で用いる１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物の難溶性溶媒としては、炭化水素系溶媒や塩素を含まないフッ素系溶媒が使用できる。 難 As the hardly soluble solvent of 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate used in the present invention, a hydrocarbon solvent or a fluorine solvent containing no chlorine can be used.
これらの溶媒は使用状態で液体であることは当然であり、沸点は特に限定されないが１００℃程度以下であるのが好ましい。具体的には、炭化水素系溶媒としては、脂肪族炭化水素：ｎ−ペンタン、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタン、ｎ−ノナン、ｎ−デカンなどまたはこれらの常温（２５℃）付近で液体の異性体、芳香族炭化水素：ベンゼン、トルエン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン、エチルベンゼン、メシチレンなど、脂環式炭化水素：シクロペンタン、シクロヘキサン、メチルシクロペンタン、メチルシクロヘキサン、テトラリン、デカリン、並びにこれらの炭化水素系溶媒の混合物であるリグロイン、石油エーテルなどの工業用ガソリンなどが挙げられる。また、フッ素系溶媒としては、１，２-ビス（トリフルオロメチル）ベンゼン、１，３-ビス（トリフルオロメチル）ベンゼン、１，４-ビス（トリフルオロメチル）ベンゼン、１，１，１，３，３−ペンタフルオロプロパン、１，１，１，３，３−ペンタフルオロブタン、ヘプタフルオロシクロペンタン、フロリナートTMとして知られるパーフルオロ環状エーテルなどが挙げられる。これらの溶媒は二種以上を併用することができる。 It is natural that these solvents are liquid in a used state, and the boiling point is not particularly limited, but is preferably about 100 ° C. or less. Specifically, examples of the hydrocarbon-based solvent include aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane, or a temperature near normal temperature (25 ° C.). And liquid isomers, aromatic hydrocarbons: benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, mesitylene, etc., alicyclic hydrocarbons: cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, Examples include tetralin, decalin, and industrial gasoline such as ligroin and petroleum ether which are mixtures of these hydrocarbon solvents. Examples of the fluorinated solvent include 1,2-bis (trifluoromethyl) benzene, 1,3-bis (trifluoromethyl) benzene, 1,4-bis (trifluoromethyl) benzene, 1,1,1,1 Examples thereof include 3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, heptafluorocyclopentane, and a perfluorocyclic ether known as Fluorinate ™ . Two or more of these solvents can be used in combination.
第１の方法において、これらの１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物難溶性の溶媒に少量の比較的溶解度の大きい溶媒を混合して使用することもできる。難溶性の溶媒１００重量部に対し比較的溶解度の大きな溶媒は３０重量部以下で使用する。そのような溶媒としては、当然限定されないが、反応溶媒として前記したエーテル類やアルコール類：メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノールなどが使用できる。 In the first method, a small amount of a solvent having a relatively high solubility may be mixed with these 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate poorly soluble solvents. . A solvent having a relatively high solubility is used in an amount of 30 parts by weight or less based on 100 parts by weight of the hardly soluble solvent. Such a solvent is not limited, but the above-mentioned ethers and alcohols such as methanol, ethanol, n-propanol, isopropanol and n-butanol can be used as the reaction solvent.
また、第２の方法において、１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物の溶液を調製する溶媒に難溶性の溶媒を添加して溶解度を調節することも可能であり、温度差を利用する析出法をとる場合に、特に有効である。 In the second method, it is also possible to adjust the solubility by adding a poorly soluble solvent to a solvent for preparing a solution of 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate. This is particularly effective when a precipitation method utilizing a temperature difference is employed.
本発明の方法で精製した１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物は、公知の方法で脱水して、無水物とすることができる。例えば、J.Inorganic and Nuclear Chemistry,1956,Vol.2,pp.11-31では、１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物を３倍容量の９８％硫酸に攪拌して分散させ、一晩経た後に再度硫酸を変えて同じ操作を繰り返し、上層を形成した無水物をサイホンで取りだし、それを蒸留することで７０．０〜７０．２℃の留分として無水物を９８％の収率で得ている。 １ ， The 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate purified by the method of the present invention can be dehydrated by a known method to obtain an anhydride. For example, in J. Inorganic and Nuclear Chemistry, 1956, Vol. 2, pp. 11-31, 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate is mixed with three times the volume of 98% sulfuric acid. After stirring overnight, the same operation was repeated with the sulfuric acid being changed again, and the anhydride formed in the upper layer was taken out with a siphon and distilled to obtain a fraction at 70.0 to 70.2 ° C. The anhydride is obtained in 98% yield.
J.Amer.Chem.Soc.,78,2790(1956)では、無水硫酸カルシウム（石膏）と１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物を混合し、加熱し、その際の留出液について再度同じ脱水処理をして沸点６８℃（７３６ｍｍＨｇ）の無水物を得ている。 In J. Amer. Chem. Soc., 78, 2790 (1956), anhydrous calcium sulfate (gypsum) and 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate are mixed and heated. The distillate at that time was subjected to the same dehydration treatment again to obtain an anhydride having a boiling point of 68 ° C. (736 mmHg).
また、エーテル中で五酸化リンと加熱することにより脱水する方法も知られている。 方法 Also, a method of dehydrating by heating with phosphorus pentoxide in ether is known.
本発明の精製方法によると、特定の溶媒と接触させ、または特定の溶媒からなら溶液から固体として析出させるという簡便な操作で、高純度の１，１，１，５，５，５−ヘキサフルオロアセチルアセトン・二水和物が得られ、それから容易に高純度の１，１，１，５，５，５−ヘキサフルオロアセチルアセトンを得ることができる。 According to the purification method of the present invention, high-purity 1,1,1,5,5,5-hexafluoro is obtained by a simple operation of contacting with a specific solvent or, if the specific solvent is used, precipitating it as a solid from a solution. Acetylacetone dihydrate is obtained, from which high purity 1,1,1,5,5,5-hexafluoroacetylacetone can be easily obtained.
以下に実施例をもって本発明を説明するが、本発明の実施態様はこれらに限られない。 The present invention will be described below with reference to examples, but embodiments of the present invention are not limited thereto.
〔実施例１〕
１，１，１，５，５，５-ヘキサフルオロアセチルアセトン・二水和物の製造温度計、滴下ロート及び還流冷却器を備えた５００ｍｌ三口フラスコにナトリウムメトキシド３４．６．ｇ（０．６４ｍｏｌ）及びｔ-ブチルメチルエーテル２４０ｍｌを入れた。１，１，１-トリフルオロアセトン７１．７ｇ（０．６４ｍｏｌ）、エチルトリフルオロアセテート９０．９ｇ（０．６４ｍｏｌ）、ｔ-ブチルメチルエーテル１２０ｍｌを混合し、マグミキサーで撹拌しながら内温３０℃以下で３０分間かけて滴下し、滴下終了後内温４０℃で４時間反応させた。反応終了後、ｔ-ブチルメチルエーテルをエバポレーターにより留去して濃縮し、粗の１，１，１，５，５，５-ヘキサフルオロアセチルアセトンのナトリウム塩を得た。これを、温度計及び還流冷却器を備えた５００ｍｌ三口フラスコに移し、水１２０ｍｌを加えた後、マグミキサーで撹拌しながら２０℃以下で２４％硫酸水溶液１６０ｇを加え、続いて内温６０℃で６時間反応させた。室温まで冷却した後、反応液を２００ｍｌのｔ-ブチルメチルエーテルで抽出し、二層分離した残りの水層を１００ｍｌのｔ-ブチルメチルエーテルで再度抽出した。得られた有機層を合わせて、エバポレーターにてｔ-ブチルメチルエーテルを留去し、粗の１，１，１，５，５，５-ヘキサフルオロアセチルアセトン・二水和物１１８．８ｇを得た。
[Example 1]
Production of 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate Sodium methoxide 34.6. Was placed in a 500 ml three-necked flask equipped with a thermometer, a dropping funnel and a reflux condenser. g (0.64 mol) and 240 ml of t-butyl methyl ether. 71.7 g (0.64 mol) of 1,1,1-trifluoroacetone, 90.9 g (0.64 mol) of ethyl trifluoroacetate, and 120 ml of t-butyl methyl ether were mixed, and the mixture was stirred at an internal temperature of 30 with a mag mixer. The mixture was added dropwise at 30 ° C. or lower over 30 minutes, and after completion of the addition, the reaction was carried out at an internal temperature of 40 ° C. for 4 hours. After completion of the reaction, t-butyl methyl ether was distilled off with an evaporator and concentrated to obtain a crude sodium salt of 1,1,1,5,5,5-hexafluoroacetylacetone. This was transferred to a 500 ml three-necked flask equipped with a thermometer and a reflux condenser. After adding 120 ml of water, 160 g of a 24% sulfuric acid aqueous solution was added at 20 ° C. or lower while stirring with a mag mixer, and then at an internal temperature of 60 ° C. The reaction was performed for 6 hours. After cooling to room temperature, the reaction solution was extracted with 200 ml of t-butyl methyl ether, and the remaining aqueous layer separated into two layers was extracted again with 100 ml of t-butyl methyl ether. The obtained organic layers were combined, and t-butyl methyl ether was distilled off using an evaporator to obtain 118.8 g of crude 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate. .
１，１，１，５，５，５-ヘキサフルオロアセチルアセトンの製造で得られた粗の１，１，１，５，５，５-ヘキサフルオロアセチルアセトン・二水和物６．０ｇに、トルエン１２ｍｌを加え、室温でマグミキサーにより１時間撹拌した後、濾過、乾燥して１，１，１，５，５，５-ヘキサフルオロアセチルアセトン・二水和物５．３ｇを得た。次に、２０ｍｌナス型フラスコに得られた１，１，１，５，５，５-ヘキサフルオロアセチルアセトン・二水和物５．３ｇ及び９８％硫酸２０ｇを加え栓をし、室温でマグミキサーにより４時間撹拌した。１時間静定した後、二層分離して、４．０ｇの１，１，１，５，５，５-ヘキサフルオロアセチルアセトンを得た。これをガスクロマトグラフ（ＧＬＣ：検出器：ＦＩＤ、カラム：ＤＢ-１０．２５ｍｍ×６０ｍ）にて分析すると９９．９％の１，１，１，５，５，５-ヘキサフルオロアセチルアセトンであった。 To 6.0 g of crude 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate obtained in the production of 1,1,1,5,5,5-hexafluoroacetylacetone was added 12 ml of toluene. After stirring at room temperature for 1 hour with a mug mixer, the mixture was filtered and dried to obtain 5.3 g of 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate. Next, 5.3 g of 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate and 20 g of 98% sulfuric acid obtained in a 20 ml eggplant-shaped flask were added and stoppered. Stir for 4 hours. After settling for 1 hour, the mixture was separated into two layers to obtain 4.0 g of 1,1,1,5,5,5-hexafluoroacetylacetone. When this was analyzed by gas chromatography (GLC: detector: FID, column: DB-10.25 mm × 60 m), it was 99.9% of 1,1,1,5,5,5-hexafluoroacetylacetone.
〔実施例２−１〜８〕
１，１，１，５，５，５-ヘキサフルオロアセチルアセトンの製造実施例１で得られた粗の１，１，１，５，５，５-ヘキサフルオロアセチルアセトン・二水和物６．０ｇに、表１に示す各種溶媒を加え、室温でマグミキサーにより１時間撹拌した後、濾過、乾燥して１，１，１，５，５，５-ヘキサフルオロアセチルアセトン・二水和物を得た。次に、２０ｍｌナス型フラスコに得られた１，１，１，５，５，５-ヘキサフルオロアセチルアセトン・二水和物及び９８％硫酸２０ｇを加え栓をし、室温でマグミキサーにより４時間撹拌した。１時間静定した後、二層分離して、１，１，１，５，５，５-ヘキサフルオロアセチルアセトンを得た。これを実施例１と同じ分析を実施した。結果を表１に示す。
[Examples 2-1 to 8]
Production of 1,1,1,5,5,5-hexafluoroacetylacetone To 6.0 g of crude 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate obtained in Example 1 was added. Then, various solvents shown in Table 1 were added, and the mixture was stirred at room temperature for 1 hour with a mag mixer, filtered and dried to obtain 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate. Next, 20 g of 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate and 98% of sulfuric acid obtained in a 20 ml eggplant-shaped flask were added, and the mixture was stoppered. The mixture was stirred at room temperature for 4 hours with a mag mixer. did. After settling for 1 hour, two layers were separated to obtain 1,1,1,5,5,5-hexafluoroacetylacetone. This was subjected to the same analysis as in Example 1. Table 1 shows the results.
〔実施例３〕
１，１，１，５，５，５-ヘキサフルオロアセチルアセトン・二水和物の製造温度計、滴下ロート及び還流冷却器を備えた３００ｍｌ三口フラスコにナトリウムメトキシド８．６７ｇ（０．１６ｍｏｌ）及びジブチルエーテル６０ｍｌを入れた。１，１，１-トリフルオロアセトン１８．０ｇ（０．１６ｍｏｌ）、エチルトリフルオロアセテート２２．８ｇ（０．１６ｍｏｌ）、ジブチルエーテル３０ｍｌを混合し、マグミキサーで撹拌しながら内温３０℃以下で３０分間かけて滴下し、滴下終了後内温４０℃で４時間反応させた。反応終了後、ジブチルエーテルをエバポレーターにより留去して濃縮し、粗の１，１，１，５，５，５-ヘキサフルオロアセチルアセトンのナトリウム塩を得た。これを、温度計及び還流冷却器を備えた３００ｍｌ三口フラスコに移し、水３０ｍｌを加えた後、マグミキサーで撹拌しながら２０℃以下で２４％硫酸４０ｇを加え、続いて内温６０℃で６時間反応させた。室温まで冷却した後、反応液を５０ｍｌのＴＨＦで抽出し、二層分離した残りの水層を４０ｍｌのＴＨＦで再度抽出した。得られた有機層を合わせて、エバポレーターにてＴＨＦを留去し、粗の１，１，１，５，５，５-ヘキサフルオロアセチルアセトン・二水和物を得た。これに、トルエン７０ｍｌを加え、室温でマグミキサーにより１時間撹拌した後、濾過、乾燥して１，１，１，５，５，５-ヘキサフルオロアセチルアセトン・二水和物２７．３ｇを得た。
[Example 3]
Production of 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate 8.67 g (0.16 mol) of sodium methoxide and 300 ml of a three-necked flask equipped with a thermometer, a dropping funnel and a reflux condenser were added. 60 ml of dibutyl ether were charged. 18.0 g (0.16 mol) of 1,1,1-trifluoroacetone, 22.8 g (0.16 mol) of ethyl trifluoroacetate and 30 ml of dibutyl ether were mixed, and the mixture was stirred at an internal temperature of 30 ° C. or lower with a mag mixer. The solution was added dropwise over 30 minutes, and after completion of the addition, the reaction was carried out at an internal temperature of 40 ° C. for 4 hours. After completion of the reaction, dibutyl ether was distilled off by an evaporator and concentrated to obtain a crude sodium salt of 1,1,1,5,5,5-hexafluoroacetylacetone. This was transferred to a 300 ml three-necked flask equipped with a thermometer and a reflux condenser, and after adding 30 ml of water, 40 g of 24% sulfuric acid was added at 20 ° C. or lower while stirring with a mag mixer. Allowed to react for hours. After cooling to room temperature, the reaction solution was extracted with 50 ml of THF, and the remaining aqueous layer separated into two layers was extracted again with 40 ml of THF. The obtained organic layers were combined, and THF was distilled off using an evaporator to obtain crude 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate. To this, 70 ml of toluene was added, and the mixture was stirred at room temperature for 1 hour with a mug mixer, then filtered and dried to obtain 27.3 g of 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate. .
１，１，１，５，５，５-ヘキサフルオロアセチルアセトンの製造温度計、攪拌機、ガラス球を充填した還流冷却器を備えた１００ｍｌガラス反応器に窒素ガスを通じながら、得られた１，１，１，５，５，５-ヘキサフルオロアセチルアセトン・二水和物２７．３ｇ及び９８％硫酸５５ｇを加え、マグミキサーで撹拌しながら徐々に８０℃まで加熱した。約７０℃の留分を収集して２１．０ｇを得、これを実施例１と同じ条件でＧＬＣ分析すると９９．９％の１，１，１，５，５，５-ヘキサフルオロアセチルアセトンであった。 Production of 1,1,1,5,5,5-hexafluoroacetylacetone While nitrogen gas was passed through a 100 ml glass reactor equipped with a thermometer, a stirrer, and a reflux condenser filled with glass balls, the obtained 1,1,1 was obtained. 27.3 g of 1,5,5,5-hexafluoroacetylacetone dihydrate and 55 g of 98% sulfuric acid were added, and the mixture was gradually heated to 80 ° C. while stirring with a mag mixer. A fraction at about 70 ° C. was collected to obtain 21.0 g, which was analyzed by GLC under the same conditions as in Example 1 to find 99.9% of 1,1,1,5,5,5-hexafluoroacetylacetone. Was.
〔比較例１〕
１，１，１，５，５，５-ヘキサフルオロアセチルアセトン・二水和物の製造温度計、滴下ロート及び還流冷却器を備えた３００ｍｌ三口フラスコにナトリウムメトキシド８．６７ｇ（０．１６ｍｏｌ）及びジブチルエーテル６０ｍｌを入れた。１，１，１-トリフルオロアセトン１８．０ｇ（０．１６ｍｏｌ）、エチルトリフルオロアセテート２２．８ｇ（０．１６ｍｏｌ）、ジブチルエーテル３０ｍｌを混合し、マグミキサーで撹拌しながら内温３０℃以下で３０分間かけて滴下し、滴下終了後内温４０℃で４時間反応させた。反応終了後、ジブチルエーテルをエバポレーターにより留去して濃縮し、粗の１，１，１，５，５，５-ヘキサフルオロアセチルアセトンのナトリウム塩を得た。これを、温度計及び還流冷却器を備えた３００ｍｌ三口フラスコに移し、水３０ｍｌを加えた後、マグミキサーで撹拌しながら２０℃以下で２４％硫酸４０ｇを加え、続いて内温６０℃で６時間反応させた。室温まで冷却した後、反応液を５０ｍｌのＴＨＦで抽出し、二層分離した残りの水層を４０ｍｌのＴＨＦで再度抽出した。得られた有機層を合わせて、エバポレーターにてＴＨＦを留去し、粗の１，１，１，５，５，５-ヘキサフルオロアセチルアセトン・二水和物２９．１ｇを得た。
[Comparative Example 1]
Production of 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate 8.67 g (0.16 mol) of sodium methoxide and 300 ml of a three-necked flask equipped with a thermometer, a dropping funnel and a reflux condenser were added. 60 ml of dibutyl ether were charged. 18.0 g (0.16 mol) of 1,1,1-trifluoroacetone, 22.8 g (0.16 mol) of ethyl trifluoroacetate and 30 ml of dibutyl ether were mixed, and the mixture was stirred at an internal temperature of 30 ° C. or lower with a mag mixer. The solution was added dropwise over 30 minutes, and after completion of the addition, the reaction was carried out at an internal temperature of 40 ° C. for 4 hours. After completion of the reaction, dibutyl ether was distilled off by an evaporator and concentrated to obtain a crude sodium salt of 1,1,1,5,5,5-hexafluoroacetylacetone. This was transferred to a 300 ml three-necked flask equipped with a thermometer and a reflux condenser, and after adding 30 ml of water, 40 g of 24% sulfuric acid was added at 20 ° C. or lower while stirring with a mag mixer. Allowed to react for hours. After cooling to room temperature, the reaction solution was extracted with 50 ml of THF, and the remaining aqueous layer separated into two layers was extracted again with 40 ml of THF. The obtained organic layers were combined, and THF was distilled off with an evaporator to obtain 29.1 g of crude 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate.
１，１，１，５，５，５-ヘキサフルオロアセチルアセトンの製造実施例３と同じ反応装置を用い、反応器に得られた粗の１，１，１，５，５，５-ヘキサフルオロアセチルアセトン・二水和物２９．１ｇ及び９８％硫酸５８ｇを加え、マグミキサーで撹拌しながら徐々に８０℃まで加熱し、７０℃の留分２１．３ｇを得た。これを実施例１と同じ条件でＧＬＣ分析分析すると９３．５％の１，１，１，５，５，５-ヘキサフルオロアセチルアセトンであった。 Production of 1,1,1,5,5,5-hexafluoroacetylacetone Using the same reactor as in Example 3, crude 1,1,1,5,5,5-hexafluoroacetylacetone obtained in the reactor 29.1 g of dihydrate and 58 g of 98% sulfuric acid were added, and the mixture was gradually heated to 80 ° C. while stirring with a mag mixer to obtain 21.3 g of a 70 ° C. fraction. GLC analysis of this under the same conditions as in Example 1 revealed 93.5% of 1,1,1,5,5,5-hexafluoroacetylacetone.
Claims (3)
1,1,1,5,5,5-hexafluoroacetylacetone dihydrate containing impurities is obtained by reacting 1,1,1-trifluoroacetone with an ester of trifluoroacetic acid. The 1,1,1,5,5,5-hexafluoroacetylacetone dihydrate according to claim 1 or 2, which is 1,1,5,5,5-hexafluoroacetylacetone dihydrate. A method for purifying the Japanese product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003286394A JP2004002466A (en) | 2003-08-05 | 2003-08-05 | Method for purification of 1, 1, 1, 5, 5, 5-hexafluoro acetylacetone dihydrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003286394A JP2004002466A (en) | 2003-08-05 | 2003-08-05 | Method for purification of 1, 1, 1, 5, 5, 5-hexafluoro acetylacetone dihydrate |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000000526A Division JP3480825B2 (en) | 2000-01-05 | 2000-01-05 | Purification method of 1,1,1,5,5,5-hexafluoroacetylacetone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004002466A true JP2004002466A (en) | 2004-01-08 |
Family
ID=30438784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003286394A Abandoned JP2004002466A (en) | 2003-08-05 | 2003-08-05 | Method for purification of 1, 1, 1, 5, 5, 5-hexafluoro acetylacetone dihydrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2004002466A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9409843B2 (en) | 2013-04-11 | 2016-08-09 | Central Glass Company, Limited | Method for producing 1,1,1,5,5,5-hexafluoroacetylacetone |
| JP7478270B2 (en) | 2022-08-15 | 2024-05-02 | 中國石油化學工業開發股▲分▼有限公司 | Method for purifying 1,2,4,5-cyclohexanetetracarboxylic acid |
-
2003
- 2003-08-05 JP JP2003286394A patent/JP2004002466A/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9409843B2 (en) | 2013-04-11 | 2016-08-09 | Central Glass Company, Limited | Method for producing 1,1,1,5,5,5-hexafluoroacetylacetone |
| JP7478270B2 (en) | 2022-08-15 | 2024-05-02 | 中國石油化學工業開發股▲分▼有限公司 | Method for purifying 1,2,4,5-cyclohexanetetracarboxylic acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110637002B (en) | Production method of hexafluoro-1,3-butadiene | |
| JP3480825B2 (en) | Purification method of 1,1,1,5,5,5-hexafluoroacetylacetone | |
| JP4722327B2 (en) | Method for producing acetylenic diol compound | |
| JP7359141B2 (en) | Method for producing hexafluoro-1,3-butadiene | |
| CN104487423B (en) | Crystal and its manufacturing method containing unsaturated carboxylic acid amide compound | |
| JP2004002466A (en) | Method for purification of 1, 1, 1, 5, 5, 5-hexafluoro acetylacetone dihydrate | |
| WO2003093212A1 (en) | High-purity (fluoroalkyl)benzene derivative and process for producing the same | |
| JPS6219546A (en) | Purification of n-borneol | |
| CN107406356A (en) | The manufacture method of fluor alkaline, the separation of amidine alkali, recovery method and the application method for reclaiming amidine alkali | |
| JP2004137201A (en) | Purification method of fluorenylidene diallyl phenol | |
| US10093599B2 (en) | Method for manufacturing fluorinated hydrocarbon | |
| JPS5839135B2 (en) | Manufacturing method of polyfluoroalcohols | |
| US6384286B1 (en) | Process for purifying 1,1,1,5,5,5-hexafluoroacetylacetone | |
| JP6074670B2 (en) | Process for producing arene compounds containing perfluoroalkenyloxy groups | |
| JP2750761B2 (en) | Separation method of substituted aromatic isomers using inclusion complex | |
| JP4022929B2 (en) | Method for producing 3,5-bis (trifluoromethyl) nitrobenzene | |
| WO2007063939A1 (en) | Method for producing tetrafluorocyclobutenone | |
| JP4269212B2 (en) | Purification method of fluorine-containing chlorosulfonylalkyl vinyl ether | |
| JP5612977B2 (en) | Process for producing 6-bromo-N-methyl-2-naphthamide | |
| JP2004203816A (en) | Method for manufacturing 2,2,2-trifluoroethanol of high purity | |
| JP3036661B2 (en) | Method for producing 2-chlorocyclododecadienone oxime | |
| CN118063341A (en) | Synthesis method of pitobutinib intermediate | |
| JP5585291B2 (en) | Method for producing hexafluoroacetone monohydrate | |
| JP2004035452A (en) | Method for producing alicyclic monoolefin methanol | |
| JP2006001925A (en) | Method for producing 3,4,5-trifluorobenzyl alcohol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Effective date: 20060209 Free format text: JAPANESE INTERMEDIATE CODE: A621 |
|
| RD01 | Notification of change of attorney |
Effective date: 20060424 Free format text: JAPANESE INTERMEDIATE CODE: A7421 |
|
| A762 | Written abandonment of application |
Effective date: 20060714 Free format text: JAPANESE INTERMEDIATE CODE: A762 |