JPS63290890A - Production of quaternary phosphonium salt of inorganic acid - Google Patents
Production of quaternary phosphonium salt of inorganic acidInfo
- Publication number
- JPS63290890A JPS63290890A JP12542887A JP12542887A JPS63290890A JP S63290890 A JPS63290890 A JP S63290890A JP 12542887 A JP12542887 A JP 12542887A JP 12542887 A JP12542887 A JP 12542887A JP S63290890 A JPS63290890 A JP S63290890A
- Authority
- JP
- Japan
- Prior art keywords
- inorganic acid
- quaternary phosphonium
- carbonate
- reaction
- 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.)
- Granted
Links
- 150000007522 mineralic acids Chemical class 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 150000004714 phosphonium salts Chemical group 0.000 title description 3
- -1 HCl) Chemical class 0.000 claims abstract description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 7
- CYMQRGKQAOPOAQ-UHFFFAOYSA-N diphosphanium;carbonate Chemical group [PH4+].[PH4+].[O-]C([O-])=O CYMQRGKQAOPOAQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 20
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 14
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 7
- 150000004650 carbonic acid diesters Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 abstract description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 abstract description 8
- 150000003003 phosphines Chemical class 0.000 abstract description 8
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 150000005690 diesters Chemical class 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical group O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 description 5
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical group [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 3
- RAQHAAHPMZUHGU-UHFFFAOYSA-N (1-methylcyclohexa-2,4-dien-1-yl)phosphanium;carbonate Chemical compound [O-]C([O-])=O.CC1([PH3+])CC=CC=C1.CC1([PH3+])CC=CC=C1 RAQHAAHPMZUHGU-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical group [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- JJNUGGOQMWVCKE-UHFFFAOYSA-L triethyl(methyl)phosphanium;carbonate Chemical compound [O-]C([O-])=O.CC[P+](C)(CC)CC.CC[P+](C)(CC)CC JJNUGGOQMWVCKE-UHFFFAOYSA-L 0.000 description 2
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 2
- MNSMKQPDHKCWNW-UHFFFAOYSA-N tritylphosphanium;carbonate Chemical compound [O-]C([O-])=O.C=1C=CC=CC=1C(C=1C=CC=CC=1)([PH3+])C1=CC=CC=C1.C=1C=CC=CC=1C(C=1C=CC=CC=1)([PH3+])C1=CC=CC=C1 MNSMKQPDHKCWNW-UHFFFAOYSA-N 0.000 description 2
- ZKWQSBFSGZJNFP-UHFFFAOYSA-N 1,2-bis(dimethylphosphino)ethane Chemical compound CP(C)CCP(C)C ZKWQSBFSGZJNFP-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- RKUQEIQYCLUZNZ-UHFFFAOYSA-N 1-phenylphosphepane Chemical compound C1CCCCCP1C1=CC=CC=C1 RKUQEIQYCLUZNZ-UHFFFAOYSA-N 0.000 description 1
- TVQBEEQDPWQLFD-UHFFFAOYSA-N CC[PH4] Chemical compound CC[PH4] TVQBEEQDPWQLFD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- 229910004713 HPF6 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 229910004814 HzPO4 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- GEKAWPIATFUQJW-UHFFFAOYSA-N bis(ethenyl)-phenylphosphane Chemical compound C=CP(C=C)C1=CC=CC=C1 GEKAWPIATFUQJW-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- WXMZPPIDLJRXNK-UHFFFAOYSA-N butyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CCCC)C1=CC=CC=C1 WXMZPPIDLJRXNK-UHFFFAOYSA-N 0.000 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- LOEIOOSCALHKOG-UHFFFAOYSA-N dibutyl(methyl)phosphane Chemical compound CCCCP(C)CCCC LOEIOOSCALHKOG-UHFFFAOYSA-N 0.000 description 1
- HZHUAESPXGNNFV-UHFFFAOYSA-N diethyl(methyl)phosphane Chemical compound CCP(C)CC HZHUAESPXGNNFV-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- OSRKWUXYLYWDOH-UHFFFAOYSA-N phenyl(dipropyl)phosphane Chemical compound CCCP(CCC)C1=CC=CC=C1 OSRKWUXYLYWDOH-UHFFFAOYSA-N 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- IFXORIIYQORRMJ-UHFFFAOYSA-N tribenzylphosphane Chemical compound C=1C=CC=CC=1CP(CC=1C=CC=CC=1)CC1=CC=CC=C1 IFXORIIYQORRMJ-UHFFFAOYSA-N 0.000 description 1
- YWBQOYHVWPWZJO-UHFFFAOYSA-L tributyl(methyl)phosphanium;carbonate Chemical compound [O-]C([O-])=O.CCCC[P+](C)(CCCC)CCCC.CCCC[P+](C)(CCCC)CCCC YWBQOYHVWPWZJO-UHFFFAOYSA-L 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- IWPNEBZUNGZQQQ-UHFFFAOYSA-N tripentylphosphane Chemical compound CCCCCP(CCCCC)CCCCC IWPNEBZUNGZQQQ-UHFFFAOYSA-N 0.000 description 1
- SHTYTGKCJZIXLD-UHFFFAOYSA-N tritylphosphanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C=1C=CC=CC=1C(C=1C=CC=CC=1)([PH3+])C1=CC=CC=C1 SHTYTGKCJZIXLD-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ホスフィン類を炭酸ジエステルと反応させる
ことにより、対応する四級ホスホニウム炭酸塩とし、さ
らにこれに無機酸を混合して脱炭酸することにより、四
級ホスホニウム無機酸塩を製造する方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention involves reacting phosphines with a carbonic acid diester to form the corresponding quaternary phosphonium carbonate, which is further mixed with an inorganic acid and decarboxylated. In particular, it relates to a method for producing a quaternary phosphonium inorganic acid salt.
本発明の方法で得られる四級ホスホニウム無機酸塩は、
相関移動触媒などの各種触媒、水系及び有機系の電解液
のための電解質、各種の添加物、薬品として幅広い分野
で使用される有用な有機化合物である。The quaternary phosphonium inorganic acid salt obtained by the method of the present invention is
It is a useful organic compound that is used in a wide range of fields as various catalysts such as phase transfer catalysts, electrolytes for aqueous and organic electrolytes, various additives, and chemicals.
四級ホスホニウム塩の合成方法としては一般にホスフィ
ン類をアルキルハライド、ジアルキル硫酸などで加熱下
で四級化する方法が採用されている。又、陰イオン種を
種々に変化させた四級ホスホニウム塩を製造する場合に
は、通常四級ホスホニウムハライド（塩化物、臭化物、
ヨウ化物）の陰イオン交換による方法が採用されている
。例えば、下記に示すような反応式に従って、四級アン
モニウム臭化物を四級ホスホニウム水酸化物に転換した
のち（反応１ａ）無機酸によって中和処理する方法（反
応１ｂ）、四級ホスホニウム臭化物を無機酸と反応させ
、対応する無機酸塩が不溶な溶媒を選定することにより
析出分離する方法（反応２）、四級ホスホニウム臭化物
と無機酸のアルカリ金属塩とを反応させ、無機酸塩を析
出または抽出により得る方法（反応３）、さらには四級
ホスホニウム臭化物と無機酸の銀塩を反応させて臭化銀
を析出させてろ液から目的物を得る方法（反応４）など
を例示することができる。As a method for synthesizing quaternary phosphonium salts, a method is generally employed in which phosphines are quaternized with an alkyl halide, dialkyl sulfate, etc. under heating. In addition, when producing quaternary phosphonium salts with various anion species, quaternary phosphonium halides (chloride, bromide,
A method based on anion exchange of iodide) has been adopted. For example, according to the reaction formula shown below, quaternary ammonium bromide is converted to quaternary phosphonium hydroxide (reaction 1a) and then neutralized with an inorganic acid (reaction 1b). (Reaction 2) A method in which quaternary phosphonium bromide is reacted with an alkali metal salt of an inorganic acid to precipitate or extract the inorganic acid salt by selecting a solvent in which the corresponding inorganic acid salt is insoluble. (Reaction 3), and a method (Reaction 4) in which a quaternary phosphonium bromide and a silver salt of an inorganic acid are reacted to precipitate silver bromide to obtain the desired product from the filtrate (Reaction 4).
Ｒ４Ｐ６ＤＢｒｅ−→Ｒ４ＰΦｏｎｅ （
反応１ａ）Ｒ，Ｐ４１１ＯＨｅ＋ＨΦＡｅ →Ｒ４，Ｐ
’Ａｅ＋ Ｈ２Ｏ（反応１ｂ）Ｒ，ＰｅＢｒｅ＋ Ｈｅ
ＡｅＲ４ＰｅＡｅＬ ＋ ＨＢｒ （反応２）Ｒａ、
Ｐ’Ｂｒｅ＋ＮａｅＡｅ→Ｒ＊ＰｅＡｅ＋ＮａＢｒ
（反応３）ＲｉＰ’Ｂｒｅ＋ Ａｇ＠ＡｅＲｔＰΦＡｅ
＋ ＡｇＢｒ ｌ （反応４）反応１ａによる四級ホス
ホニウム水酸化物の製造法としては、適当な溶媒に溶か
した四級ホスホニウム臭化物を四級ホスホニウム水酸化
物型のイオン交換樹脂と反応させる方法、四級ホスホニ
ウム臭化物を液状媒体中でアルカリ金属水酸化物と反応
させる方法、電気化学的方法により臭素イオンをＢｒｚ
として分離し、水酸化物を得る方法、さらには銀化合物
を用いる方法などが知られている。R4P6DBre-→R4PΦone (
Reaction 1a) R,P411OHe+HΦAe →R4,P
'Ae+ H2O (reaction 1b) R, PeBre+ He
AeR4PeAeL + HBr (reaction 2) Ra,
P'Bre+NaeAe→R*PeAe+NaBr
(Reaction 3) RiP'Bre+ Ag@AeRtPΦAe
+AgBr l (Reaction 4) Methods for producing quaternary phosphonium hydroxide by reaction 1a include a method in which quaternary phosphonium bromide dissolved in a suitable solvent is reacted with a quaternary phosphonium hydroxide type ion exchange resin; A method in which phosphonium bromide is reacted with an alkali metal hydroxide in a liquid medium, and bromide ion is converted to Brz by an electrochemical method.
Methods of separating silver as a hydroxide to obtain hydroxides, and methods of using silver compounds are known.
しかしながら、反応１ａによるいずれの方法も四級ホス
ホニウム水酸化物の製法として高価な方法であり、又一
般に四級ホスホニウム水酸化物中の臭素イオンを完全に
除くことは困難であるので、反応１ｂによる中和生成物
の純度に問題を生ずることが多い。また、反応２および
３の方法においては、目的とする四級ホスホニウム無機
酸塩中の臭素イオンの除去はかなり困難であり、高純度
の四級ホスホニウム無機酸塩を得る製造法としては不適
当である。反応４に基づく方法は定量的な反応を行わせ
る方法としては好ましいものと考えられるが、原料とな
る無機酸の銀塩がきわめて高価であり、工業的に採用で
きる方法とは言い難い。However, any method using Reaction 1a is an expensive method for producing quaternary phosphonium hydroxide, and it is generally difficult to completely remove bromine ions from quaternary phosphonium hydroxide, so Reaction 1b is used. Problems often arise with the purity of the neutralized product. In addition, in the methods of Reactions 2 and 3, it is quite difficult to remove the bromine ion from the target quaternary phosphonium inorganic acid salt, and it is not suitable as a production method for obtaining a high-purity quaternary phosphonium inorganic acid salt. be. Although the method based on Reaction 4 is considered to be preferable as a method for carrying out a quantitative reaction, the silver salt of an inorganic acid used as a raw material is extremely expensive, and it is difficult to say that it is a method that can be adopted industrially.
以上、四級ホスホニウム臭化物を一例として述べたが、
他のハライド、硫酸塩などを用いた場合も同様であり、
一般に効率的かつ高純度で種々の陰イオン交換した塩を
作る方法は知られていない。The quaternary phosphonium bromide was described above as an example, but
The same is true when using other halides, sulfates, etc.
Generally, there is no known method for producing various anion-exchanged salts efficiently and with high purity.
本発明者らは、従来の方法に較べて効率的な生産が可能
となり、かつ目的生成物の純度を高める工業的製法に関
する新しい技術を確立し、本発明に到達したものである
。The present inventors have established a new technology for an industrial manufacturing method that enables more efficient production than conventional methods and improves the purity of the desired product, and has thus arrived at the present invention.
すなわち、本発明は、四級ホスホニウムの無機酸塩を製
造する方法において、
（ａ） ホスフィン類を炭酸ジエステルと反応させる
ことにより、対応する四級ホスホニウム炭酸塩を製造す
る工程
（ｂ） さらに、生成してくる四級ホスホニウム炭酸
塩を無機酸と混合して炭酸ガスを系外に除去せしめて対
応する無機酸塩を製造する工程の２段階の工程を経るこ
とを特徴とする四級ホスホニウム無機酸塩の製造方法を
提案するものである。That is, the present invention provides a method for producing an inorganic acid salt of a quaternary phosphonium, including (a) a step of producing a corresponding quaternary phosphonium carbonate by reacting a phosphine with a carbonic acid diester; The quaternary phosphonium inorganic acid is characterized in that it undergoes a two-step process of mixing the resulting quaternary phosphonium carbonate with an inorganic acid and removing carbon dioxide from the system to produce the corresponding inorganic acid salt. This paper proposes a method for producing salt.
本発明の原料となるホスフィン類としては、トリメチル
ホスフィン、ジエチルメチルホスフィン、トリエチルホ
スフィン、トリーｎ−プロピルホスフィン、トリーｎ−
ブチルホスフィン、トリーｎ−ペンチルホスフィン、ト
リーミーブチルホスフィン、ジ−ｎ−ブチルメチルホス
フィン、トリシクロヘキシルホスフィン、１．２−ビス
（ジメチルホスフィノ）エタンなどの飽和脂肪族ホスフ
ィン類、トリアリールホスフィンなどの不飽和脂肪族ホ
スフィン類、トリフェニルホスフィン、トリベンジルホ
スフィン、ジ−ミープロピルフェニルホスフィン、ジビ
ニルフェニルホスフィン、ｎ−ブチル−ジフェニルホス
フィンなどの芳香族ホスフィン類、１−エチルホスホラ
ン、■−フェニルホスホラン、１−フェニルホスファン
、１−フェニルホスフェパンなどの脂環式ホスフィン類
などを挙げることができる。Examples of phosphines used as raw materials for the present invention include trimethylphosphine, diethylmethylphosphine, triethylphosphine, tri-n-propylphosphine, and tri-n-propylphosphine.
Saturated aliphatic phosphine such as butylphosphine, tri-n-pentylphosphine, tri-butylphosphine, di-n-butylmethylphosphine, tricyclohexylphosphine, 1,2-bis(dimethylphosphino)ethane, triarylphosphine, etc. Unsaturated aliphatic phosphine, aromatic phosphine such as triphenylphosphine, tribenzylphosphine, di-propylphenylphosphine, divinylphenylphosphine, n-butyl-diphenylphosphine, 1-ethylphosphorane, ■-phenylphosphorane , 1-phenylphosphane, 1-phenylphosphepane, and other alicyclic phosphines.
炭酸ジエステルとしては炭酸ジメチル、炭酸エチルメチ
ル、炭酸ジエチル、炭酸ジプロピルなどを挙げることが
できるが、炭酸ジメチルなどのようにアルキル基の炭素
数が少ない方が四級化反応が速やかに進行し好ましい。Examples of diester carbonates include dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, dipropyl carbonate, etc., but it is preferred that the alkyl group has fewer carbon atoms, such as dimethyl carbonate, because the quaternization reaction proceeds more quickly.
無機酸としては、特に制約はないが、炭酸に比較し強酸
なものほど陰イオンへの交換は速く完結する。又、炭酸
に較べて弱い酸でも平衡を少しずつずらせながら行うこ
とで時間をかければ陰イオン交換は達成される。これら
の無機酸の具体的な例として、肝、 ＩＩＣｌ 、 １
ＩＢｒ、旧、 ＨＮＯ３，ＨｚＳＯ＊。There are no particular restrictions on the inorganic acid, but the stronger the acid compared to carbonic acid, the faster the exchange into anions will be completed. Furthermore, anion exchange can be achieved even with an acid weaker than carbonic acid if it is carried out while gradually shifting the equilibrium and takes time. Specific examples of these inorganic acids include liver, IICl, 1
IBr, old, HNO3, HzSO*.
ＨｚＰＯ４，ＨＪＯｚ、 ）（Ｃ１０４，ＨＢＦ４．
ＨＰＦ６． Ｈ５ｂＦｈ。HzPO4,HJOz, )(C104,HBF4.
HPF6. H5bFh.
＋１ＡＳＦ＆Ｉ ｌｌ０３Ｏ２Ｃｅ 、 ＨＯ５ＱｚＰ
、 Ｈ２ＣｒＯａ＋ ＨｚＳｚＯｂ＋１１Ｍｎ０４＋
ＨＲｅＯｎ＋ ＨｚＳｅＯ，ｔｌｓｃＮなどを挙げるこ
とができる。+1ASF&I ll03O2Ce, HO5QzP
, H2CrOa+ HzSzOb+11Mn04+
Examples include HReOn+ HzSeO, tlscN, and the like.
第１工程である四級化反応はホスフィン類と炭酸ジエス
テルとのモル比で０．２〜５、より好ましくは０．３〜
３とし、溶媒の存在下又は非存在下、反応温度２０〜２
００℃、より好ましくは３０〜１６０℃で実施される。In the first step, the quaternization reaction, the molar ratio of phosphines and diester carbonate is 0.2 to 5, more preferably 0.3 to 5.
3, in the presence or absence of a solvent, at a reaction temperature of 20 to 2
It is carried out at 00°C, more preferably at 30-160°C.
通常ホスフィン類が四級化物に充分転化したところで、
未反応のホスフィン類もしくは炭酸ジエステルを溶媒を
用いた場合には溶媒とともに留去したのち、あるいは必
要に応じて適当な有機溶媒で再結晶して、第２工程に送
られる。Usually, once the phosphines have been sufficiently converted to quaternized products,
If a solvent is used, unreacted phosphines or diester carbonate are distilled off together with the solvent, or if necessary, recrystallized from a suitable organic solvent and sent to the second step.
第２工程では、四級ホスホニウム炭酸塩に通常量論値に
相当する無機酸を溶媒存在下又は非存在下に滴下し、発
生する炭酸ガスを減圧下又は不活性ガスを反応系に吹き
込むことで除去する。この際、起る反応は炭酸ジメチル
を原料とした場合、次式で表わされる。In the second step, a stoichiometric amount of an inorganic acid is added dropwise to the quaternary phosphonium carbonate in the presence or absence of a solvent, and the generated carbon dioxide is removed under reduced pressure or by blowing an inert gas into the reaction system. Remove. At this time, the reaction that occurs is expressed by the following formula when dimethyl carbonate is used as the raw material.
（第１工程） Ｒ＋ＲＪ３Ｐ ＋ ＭｅｚＣＯｚ−Ｒ
＋ＲｚＲ３ＭｅＰ”Ｃ−ＯＭｅ＋ ＭｅＯＨ＋ ＧＯ，
ｊ
（式中、Ｒ＋ＲＪｘはホスフィンの炭化水素残基、Ｘは
無機酸の共役塩基を示す。）
反応後、副生アルコール及び溶媒を留去したのち得られ
る固体が目的の四級ホスホニウム無機酸塩である。必要
に応じて適当な溶媒により再結晶などで高純度なものを
得ることができる。(First step) R+RJ3P + MezCOz-R
+RzR3MeP"C-OMe+ MeOH+ GO,
j (In the formula, R + RJx represents the hydrocarbon residue of phosphine, and X represents the conjugate base of the inorganic acid.) After the reaction, the by-product alcohol and solvent are distilled off, and the solid obtained is the target quaternary phosphonium inorganic acid salt. It is. If necessary, a highly pure product can be obtained by recrystallization using an appropriate solvent.
又、炭酸イオンを完全に除くために量論値より少し過剰
な無機酸を使用した場合には、過剰の無機酸を再結晶な
どの処理によって除くことができる。Further, when an inorganic acid is used in an amount slightly in excess of the stoichiometric value in order to completely remove carbonate ions, the excess inorganic acid can be removed by a treatment such as recrystallization.
本発明の方法によれば、効率的に各種の四級ホスホニウ
ム無機酸塩を製造することが可能であるが、同時に目的
とする塩を高純度で得ることができる点も本発明の大き
な特徴である。According to the method of the present invention, it is possible to efficiently produce various quaternary phosphonium inorganic acid salts, and at the same time, a major feature of the present invention is that the desired salt can be obtained with high purity. be.
以下、実施例により本発明をさらに具体的に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例−１ （第１工程） 攪拌式オートクレーブに炭酸ジメチル９．０ ｇ 。Example-1 (1st step) 9.0 g of dimethyl carbonate in a stirred autoclave.
トリーｎ−ブチルホスフィン１８．５ ｇを充てんし、
反応温度１１５℃、反応圧力５．０ ｋｇ／ ｃｎ！
Ｇで１５時間反応した。反応後オートクレーブを冷却し
、反応液を取り出してガスクロマトグラフで分析したと
ころ、トリーｎ−ブチルホスフィンの転化率は７２．８
％であり、未反応物及び溶媒を留去したのちの固体収量
は１７．５ ｇであった（理論収率６３．６％）、元素
分析並びに’＋（−ＮＭＲなどからこの固体はトリーｎ
−ブチルメチルホスホニウム炭酸塩であることが確認さ
れた。Filled with 18.5 g of tri-n-butylphosphine,
Reaction temperature: 115℃, reaction pressure: 5.0 kg/cn!
G for 15 hours. After the reaction, the autoclave was cooled and the reaction solution was taken out and analyzed by gas chromatography, and the conversion rate of tri-n-butylphosphine was 72.8.
%, and the solid yield after distilling off unreacted substances and the solvent was 17.5 g (theoretical yield 63.6%). Elemental analysis and '+(-NMR) revealed that this solid was tri-n.
-Butylmethylphosphonium carbonate was confirmed.
（第２工程）
トリーｎ−ブチルメチルホスホニウム炭酸塩１０、０
ｇを水１０．０ ｇに溶解させ、４２％ＨＢＦ。(Second step) tri-n-butylmethylphosphonium carbonate 10,0
g was dissolved in 10.0 g of water, 42% HBF.
水溶液７．９ｇを徐々に添加、添加と同時に激しく炭酸
ガスが発生した。より完全に炭酸ガスを除去するために
４０℃／２０１■Ｈｇで２時間脱気、イオンクロマトグ
ラフィーにより炭酸イオンが２０ｐｐｍ以下であること
を確認後、水を留去した。残渣を水−ＭｅＯＨの混合溶
媒から再結晶するとト’） −ｎ −ブチルメチルホス
ホニウムテトラフルオロボレート１０．１ｇ（論理収率
９２．４％、トリーｎ−ブチルホスフィンに対し５８．
８％収率）を得た。7.9 g of the aqueous solution was gradually added, and carbon dioxide gas was violently generated at the same time as the addition. In order to remove carbon dioxide gas more completely, the mixture was degassed at 40° C./201 μHg for 2 hours, and after confirming by ion chromatography that the carbonate ion content was 20 ppm or less, water was distilled off. The residue was recrystallized from a mixed solvent of water and MeOH to give 10.1 g of -n-butylmethylphosphonium tetrafluoroborate (theoretical yield 92.4%, 58.1 g based on tri-n-butylphosphine).
8% yield) was obtained.
実施例−２
（第１工程）
原料として炭酸ジメチル９．０ｇ、トリエチルホスフィ
ン１１．８ｇ、メタノール１０．０ ｇを使用した以外
は実施例−１第１工程と同様の反応を行ったところ１７
．２ ｇの固体を得た（理論収率の７８．９％）元素分
析、’Ｈ−ＮＭＲなどからこの固体はトリエチルメチル
ホスホニウム炭酸塩であることが確認された。Example 2 (1st step) The same reaction as in the 1st step of Example 1 was carried out except that 9.0 g of dimethyl carbonate, 11.8 g of triethylphosphine, and 10.0 g of methanol were used as raw materials.17
．． 2 g of a solid was obtained (78.9% of theoretical yield), and elemental analysis, 'H-NMR, etc. confirmed that this solid was triethylmethylphosphonium carbonate.
（第２工程）
トリエチルメチルホスホニウム炭酸塩１０．０ ｇ、４
２％１ＩＢＦ４水溶液１１．３ｇ及び水１０．０ ｇを
使用した以外は実施例−１第２工程と同様の操作を行っ
たところトリエチルメチルホスホニウムテトラフルオロ
ボレート１０．８ｇ（理論収率の１５．３％、トリエチ
ルホスフィンに対し７５．２％収率）を得た。(Second step) Triethylmethylphosphonium carbonate 10.0 g, 4
The same operation as in the second step of Example 1 was performed except that 11.3 g of a 2% 1IBF4 aqueous solution and 10.0 g of water were used, resulting in 10.8 g of triethylmethylphosphonium tetrafluoroborate (theoretical yield of 15.3 g). %, yield of 75.2% based on triethylphosphine).
実施例−３
（第１工程）
原料として炭酸ジメチル９．０ｇ、１−フェニルホスフ
ァン１７．８ｇ、溶媒としてメタノール１０．０ｇを使
用した以外は実施例−１第１工程と同様の反応を行った
ところ、１９．１ ｇの固体を得た（理論収率の７１．
３％）。元素分析、’ＩＩ−ＮＭＲなどからこの固体は
１−メチルフェニルホスファニウム炭酸塩であることが
確認された。Example 3 (1st step) The same reaction as in the 1st step of Example 1 was carried out except that 9.0 g of dimethyl carbonate, 17.8 g of 1-phenylphosphane was used as the raw material, and 10.0 g of methanol was used as the solvent. As a result, 19.1 g of solid was obtained (theoretical yield was 71.9 g).
3%). Elemental analysis, 'II-NMR, etc. confirmed that this solid was 1-methylphenylphosphanium carbonate.
（第２工程） １−メチルフェニルホスファニウム炭ａ塩ｔｏ、。(Second process) 1-Methylphenylphosphanium carbonate to.
ｇと６０％過塩素酸６．９ｇ及び水１０．０ ｇを使用
した以外は実施例−５と同様の操作を行ったところ過塩
素酸メチルフェニルホスファニウム１０．９ｇ （ｉ論
収率の９４．８％、■−フェニルホスファンに対し６７
．６％収率）を得た。The same operation as in Example 5 was performed except that 6.9 g of 60% perchloric acid and 10.0 g of water were used. As a result, 10.9 g of methylphenylphosphanium perchlorate (the theoretical yield of 94.8%, ■-67 for phenylphosphane
．． 6% yield) was obtained.
実施例−４
（第１工程）
原料として炭酸ジメチル９．０ｇ、トリフェニルホスフ
ィン２６．２ｇ、溶媒としてメタノール１０．０ｇを使
用した以外は実施例−１第１工程と同様の反応を行った
ところ２１．３ ｇの固体を得た（論理収率６０．５％
）。元素分析、’Ｈ−ＮＭＲなどからこの固体はトリフ
ェニルメチルホスホニウム炭酸塩であることが確認され
た。Example 4 (1st step) The same reaction as in the 1st step of Example 1 was carried out except that 9.0 g of dimethyl carbonate, 26.2 g of triphenylphosphine and 10.0 g of methanol were used as the solvent as raw materials. Obtained 21.3 g of solid (60.5% theoretical yield)
). Elemental analysis, 'H-NMR, etc. confirmed that this solid was triphenylmethylphosphonium carbonate.
（第２工程）
トリフェニルメチルホスホニウム炭酸塩１０．０ｇと６
０％過塩素酸６．２ｇ及びエタノール１００ｇを使用し
た以外は実施例−５と同様の操作を行ったところ過塩素
酸トリフェニルメチルホスホニウム１０．３ｇ（論理収
率の９２．８％、トリフェニルホスフィンに対し５６．
１％収率）を得た。(Second step) Triphenylmethylphosphonium carbonate 10.0g and 6
The same operation as in Example 5 was performed except that 6.2 g of 0% perchloric acid and 100 g of ethanol were used. As a result, 10.3 g of triphenylmethylphosphonium perchlorate (92.8% of the theoretical yield, triphenyl 56 for phosphine.
1% yield) was obtained.
Claims (1)
る四級ホスホニウム炭酸塩を製造する工程 （ｂ）生成した四級ホスホニウム炭酸塩を無機酸と混合
して炭酸ガスを系外に除去せしめて対応する無機酸塩を
製造する工程 の２段階の工程を経ることを特徴とする四級ホスホニウ
ム無機酸塩の製造方法。[Scope of Claims] A method for producing a quaternary phosphonium inorganic acid salt, comprising: (a) a step of producing a corresponding quaternary phosphonium carbonate by reacting a phosphine with a carbonic acid diester; (b) a produced quaternary phosphonium carbonate; 1. A method for producing a quaternary phosphonium inorganic acid salt, which comprises a two-step process of mixing a quaternary phosphonium inorganic acid salt with an inorganic acid and removing carbon dioxide from the system to produce a corresponding inorganic acid salt.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12542887A JPH0826053B2 (en) | 1987-05-22 | 1987-05-22 | Method for producing quaternary phosphonium inorganic acid salt |
| US07/192,524 US4892944A (en) | 1987-05-13 | 1988-05-11 | Process for producing quaternary salts |
| DE8888107735T DE3868138D1 (en) | 1987-05-13 | 1988-05-13 | METHOD FOR PRODUCING QUATERNAUS SALTS. |
| EP88107735A EP0291074B1 (en) | 1987-05-13 | 1988-05-13 | Process for producing quaternary salts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12542887A JPH0826053B2 (en) | 1987-05-22 | 1987-05-22 | Method for producing quaternary phosphonium inorganic acid salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63290890A true JPS63290890A (en) | 1988-11-28 |
| JPH0826053B2 JPH0826053B2 (en) | 1996-03-13 |
Family
ID=14909855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12542887A Expired - Fee Related JPH0826053B2 (en) | 1987-05-13 | 1987-05-22 | Method for producing quaternary phosphonium inorganic acid salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0826053B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2004056917A1 (en) * | 2002-12-19 | 2006-04-20 | 日本化学工業株式会社 | Antistatic agent for resin, antistatic resin composition and antistatic resin molded product |
| JP2007518772A (en) * | 2004-01-26 | 2007-07-12 | ビーエーエスエフ アクチェンゲゼルシャフト | Method for producing ionic liquid |
-
1987
- 1987-05-22 JP JP12542887A patent/JPH0826053B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2004056917A1 (en) * | 2002-12-19 | 2006-04-20 | 日本化学工業株式会社 | Antistatic agent for resin, antistatic resin composition and antistatic resin molded product |
| JP2007518772A (en) * | 2004-01-26 | 2007-07-12 | ビーエーエスエフ アクチェンゲゼルシャフト | Method for producing ionic liquid |
| KR101222321B1 (en) * | 2004-01-26 | 2013-01-16 | 바스프 에스이 | Method for producing ionic liquids |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0826053B2 (en) | 1996-03-13 |
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