JPH02237991A - Lithium diphenylphosphinobenzene-m-monosulfonate - Google Patents
Lithium diphenylphosphinobenzene-m-monosulfonateInfo
- Publication number
- JPH02237991A JPH02237991A JP5878789A JP5878789A JPH02237991A JP H02237991 A JPH02237991 A JP H02237991A JP 5878789 A JP5878789 A JP 5878789A JP 5878789 A JP5878789 A JP 5878789A JP H02237991 A JPH02237991 A JP H02237991A
- Authority
- JP
- Japan
- Prior art keywords
- monosulfonate
- lithium
- diphenylphosphinobenzene
- organic carboxylic
- carboxylic acid
- 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.)
- Pending
Links
- JNLITWGBJTYNNO-UHFFFAOYSA-M lithium;3-diphenylphosphanylbenzenesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 JNLITWGBJTYNNO-UHFFFAOYSA-M 0.000 title claims abstract description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 20
- 238000001914 filtration Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 238000001953 recrystallisation Methods 0.000 abstract description 5
- 238000009835 boiling Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 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 13
- 229910052744 lithium Inorganic materials 0.000 description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 235000011054 acetic acid Nutrition 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 238000004811 liquid chromatography Methods 0.000 description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 3
- 229940005605 valeric acid Drugs 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- -1 amine salt Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 2
- 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
- ITPOKAFWZBFZCV-UHFFFAOYSA-N 3-diphenylphosphanylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 ITPOKAFWZBFZCV-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- UEMSXAXBVXSKSZ-UHFFFAOYSA-N lithium;triphenylphosphane Chemical compound [Li].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UEMSXAXBVXSKSZ-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008096 xylene Substances 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、ジフェニルホスフイノベンゼン−ｍ〜モノス
ルホン酸リチウムの精製法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for purifying diphenylphosphinobenzene-m-lithium monosulfonate.
ジフェニルホスフイノベンゼン−ｍ−モノスルホン酸リ
チウムは、種々の触媒反応において金属触媒を安定化さ
せろと共に触媒成分を含水溶媒中に溶解さ仕ることがで
きるので、触媒を含む溶液を触媒の熱劣化をまねき易い
蒸発操作に付することなく、常温でデカンテーションや
抽出により水に難溶性の生成物と触媒を分離することが
できるプロセスを与える点で産業上極めて重要な化合物
である。Lithium diphenylphosphinobenzene-m-monosulfonate can stabilize metal catalysts in various catalytic reactions and dissolve catalyst components in aqueous solvents, so that solutions containing catalysts can be used to prevent thermal degradation of catalysts. It is an extremely important compound industrially in that it provides a process that allows the separation of poorly water-soluble products and catalysts by decantation or extraction at room temperature without subjecting them to evaporation operations that can easily lead to evaporation.
触媒反応に用いられるジフェニルホスフイノベンゼン−
ｍ−モノスルホン酸リチウムは高純度であることが要求
されるので、精製されたジフェニルホスフイノベンゼン
−ｍ−モノスルホン酸リウチムが有用である。Diphenylphosphinobenzene used in catalytic reactions
Since lithium m-monosulfonate is required to be highly pure, purified lithium diphenylphosphinobenzene-m-monosulfonate is useful.
［従来の技術］
特開昭５８− Ｈｌ９９４号公報には、トリフエニルホ
スフィンをスルホン化した後、メチルイソブチルケトン
によって、生成物を有゜機層へ抽出分離し、この有機層
を水酸化リチウム水溶液と接触させることによって生成
物の中和と水層への抽出を行い、得られた生成物を含む
水溶液から水を蒸発乾固することによってジフェニルホ
スフイノベンゼン−ｍ−モノスルホン酸リチウムを製造
する方法が記載されている。[Prior Art] JP-A-58-H1994 discloses that after triphenylphosphine is sulfonated, the product is extracted and separated into an organic layer using methyl isobutyl ketone, and this organic layer is added to an aqueous lithium hydroxide solution. The product is neutralized and extracted into an aqueous layer by contacting with the product, and water is evaporated to dryness from the resulting aqueous solution containing the product to produce lithium diphenylphosphinobenzene-m-monosulfonate. The method is described.
また、特開昭５９− ７３５９４号公報には、トリフエ
ニルホスフィンをスルホン化した後、水不溶性の有機溶
媒に溶かしたアミンを加えるこにとよって、スルホン酸
のアミン塩を有機層へ抽出分離し、次いでこの有機膚を
水酸化リチウム水溶液と接触させてスルホン酸リチウム
塩を水層へ移し、この水層から水を蒸発乾固する方法に
よってジフェニルホスフイノベンゼン−ｍ−モノスルホ
ン酸リチウムを製造する方法が記載されている。Furthermore, JP-A-59-73594 discloses that after sulfonating triphenylphosphine, the amine salt of sulfonic acid is extracted and separated into an organic layer by adding an amine dissolved in a water-insoluble organic solvent. Then, this organic skin is brought into contact with an aqueous lithium hydroxide solution to transfer the lithium sulfonate salt to an aqueous layer, and the water is evaporated to dryness from this aqueous layer, thereby producing lithium diphenylphosphinobenzene-m-monosulfonate. The method is described.
しかしながら、これらの方法では、スルホン化反応液か
ら生成物を抽出するためにどうしても硫酸の混入は避け
難く、このため中和後の水溶液中に硫酸リチウムが生成
物と共に抽出され、ジフェニルホスフイノベンゼン−ｍ
−モノスルホン酸リチウム中に硫酸リチウムが混在する
という問題が生じる。しかもジフェニルホスフイノベン
ゼン−ｍ−モノスルホン酸リチウムは、水への溶解度が
大きくナトリウム塩と同様に水から再結晶することがで
きない。However, in these methods, the contamination of sulfuric acid is unavoidable in order to extract the product from the sulfonation reaction solution, and as a result, lithium sulfate is extracted together with the product into the aqueous solution after neutralization, and diphenylphosphinobenzene- m
- A problem arises in that lithium sulfate is mixed in lithium monosulfonate. Moreover, lithium diphenylphosphinobenzene-m-monosulfonate has a high solubility in water and cannot be recrystallized from water like sodium salt.
一方、特開昭５８− １３１９９４号公報には、ジフェ
ニルホスフイノベンゼンーｍ−モノスルホン酸リチウム
を再結晶する方法が記載されている。同公報では、再結
溶媒として、メチルイソプチルケトン、６ ａ − ｎ
−ブチル、ジフエニルエテルまたはジフエニルエーテル
とトルエン、キシレン、ジフエニルなどの芳香族炭化水
素との混合溶媒があげられているが、上記の溶媒では再
結品の晶折率が低いという問題がある。On the other hand, JP-A-58-131994 describes a method for recrystallizing lithium diphenylphosphinobenzene-m-monosulfonate. In the same publication, methyl isobutyl ketone, 6a-n is used as the reconsolidation solvent.
Although a mixed solvent of -butyl, diphenyl ether, or diphenyl ether and an aromatic hydrocarbon such as toluene, xylene, or diphenyl is mentioned, the problem with the above solvent is that the crystal refractive index of the recrystallized product is low.
［発明が解決しようとする課題］
ジフェニルホスフイノベンゼン−ｍ−モノスルホン酸リ
チウムを貴金属錯体触媒反応に用いろ場合、反応成績、
触媒活性などの点で極めて高い純度のジフェニルホスフ
イノベンゼン−ｍ−モノスルホン酸リチウムか要求され
る。しかしながら、従来公知の製造方法では、高純度の
ジフェニルホスフイノベンゼン−ｍ−モノスルホン酸リ
チウムが得られなく、たとえ再結晶したとｌ７てら収率
が低いために経済的とは言いがたい。[Problem to be solved by the invention] When lithium diphenylphosphinobenzene-m-monosulfonate is used in a noble metal complex catalyzed reaction, the reaction results,
Extremely high purity lithium diphenylphosphinobenzene-m-monosulfonate is required in terms of catalytic activity and the like. However, with the conventionally known production methods, highly pure lithium diphenylphosphinobenzene-m-monosulfonate cannot be obtained, and even if it is recrystallized, the yield is low and it cannot be said to be economical.
本発明の目的は、工業的な触媒反応に適した高純度のジ
フェニルホスフイノベンゼン−ｍ−モノスルホン酸リチ
ウムを得るために、ジフェニルホスフイノベンゼン−ｍ
−モノスルホン酸リチウムを精製する方法を提供するこ
とにある。The purpose of the present invention is to obtain lithium diphenylphosphinobenzene-m-monosulfonate of high purity suitable for industrial catalytic reactions.
- To provide a method for purifying lithium monosulfonate.
［課題を解決するための手段］
本発明者らは、上記の目的を達成するために、ジフェニ
ルホスフイノベンゼン−ｍ−モノスルホン酸リチウムの
Ｍ製法に関して鋭意検討した結果、ジフェニルホスフイ
ノベンゼン−ｍ−モノスルホン酸リチウムを炭素数１〜
８の有機カルボン酸から再結晶操作を行えば、晶折率よ
くジフェニルホスフイノベンゼン−ｍ−モノスルホン酸
リチウムを取得し得ろことを見出だし、本発明を完成す
るに至った。[Means for Solving the Problems] In order to achieve the above-mentioned object, the present inventors have conducted intensive studies on the M method for producing lithium diphenylphosphinobenzene-m-monosulfonate. - Lithium monosulfonate with 1 or more carbon atoms
The inventors have discovered that lithium diphenylphosphinobenzene-m-monosulfonate can be obtained with a good crystal refractive index by performing a recrystallization operation from the organic carboxylic acid No. 8, and have completed the present invention.
本発明において、原料の姐ジフェニルホスフイノベンゼ
ン−ｍ−モノスルホン酸リチウムとしては、公知の方法
で製造されたものが用いられる（特開昭５８− Ｈｌ９
９４号公報参照）。In the present invention, as the raw material lithium diphenylphosphinobenzene-m-monosulfonate, one produced by a known method is used (Japanese Unexamined Patent Publication No. 58-198-H19).
(See Publication No. 94).
本発明において再結晶溶媒として用いられろ炭素数Ｉ〜
８の有機カルボン酸としては、蟻酸、酢酸、プロピオン
酸、酪酸、吉草酸、ヘキサン酸、ヘブタン酸、オクタン
酸などがあげられる。これらの中でも特に、酢酸が好ま
しい。炭素数９以上の有機カルボン酸では、融点が３０
℃以上になるために晶折率が低下するので好ましくない
。The number of carbon atoms used as a recrystallization solvent in the present invention is I~
Examples of the organic carboxylic acids of No. 8 include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, hebutanoic acid, and octanoic acid. Among these, acetic acid is particularly preferred. Organic carboxylic acids with 9 or more carbon atoms have a melting point of 30
℃ or higher, the crystal refractive index decreases, which is not preferable.
再結晶操作は、用いられる有機カルボン酸の沸点におい
て最大の溶解量またはそれに近い量のジフェニルホスフ
イノベンゼン−ｍ−モノスルホン酸リチウムを溶解させ
、不溶物を熱時ｆ過し、得られた母液を室温付近まで冷
却することによって行われる。使用される溶媒の量は溶
媒の種類によるが、例えば酢酸の場合、ジフェニルホス
フイノベンゼン−ｍ−モノスルホン酸リチウム４０ｇに
対し、ｌＯＱｇの酢酸が用いられるのが好ましい。In the recrystallization operation, lithium diphenylphosphinobenzene-m-monosulfonate is dissolved at or close to the maximum dissolution amount at the boiling point of the organic carboxylic acid used, the insoluble matter is filtered under heat, and the resulting mother liquor is This is done by cooling to around room temperature. The amount of solvent used depends on the type of solvent, but for example, in the case of acetic acid, it is preferable to use 10Qg of acetic acid per 40g of lithium diphenylphosphinobenzene-m-monosulfonate.
再結晶によりジフェニルホスフイノベンゼン−ｍ−モノ
スルホン酸リチウムと、有機カルボン酸との１対！（モ
ル比）付加物が析出してくるが、この付加物を、有機カ
ルボン酸の沸点以上の温度で減圧乾燥することにより、
カルボン酸を含まないジフェニルホスフイノベンゼン−
ｍ−モノスルホン酸リチウムが得られる。A pair of lithium diphenylphosphinobenzene-m-monosulfonate and an organic carboxylic acid by recrystallization! (Molar ratio) An adduct precipitates out, but by drying this adduct under reduced pressure at a temperature higher than the boiling point of the organic carboxylic acid,
Carboxylic acid-free diphenylphosphinobenzene
Lithium m-monosulfonate is obtained.
［実施例〕
以下、実施例により本発明を具体的に説明するか、本発
明は何らこれらに制限されるものではない。[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these in any way.
参考例！
（ジフェニルホスフイノベンゼン−ｍ−モノスルホン酸
リチウムの合成）
温度計、撹拌装置、滴下ロ一トおよび窒素ガス出入り口
を備えた内容５００ｍｌの４つロフラスコに系内を窒素
ガスで置換しながらトリフエニルホスフィン８０ｇおよ
び１硫酸３６ｇを仕込み、内温を３０℃以下に保ちなが
ら溶解させた。この混合液に内温を３０℃以下に保ちな
がら、撹拌下にＳＯｓを２０ｖｔ％含む発煙硫酸３２０
ｇを３０分間かけて滴下した。発煙硫酸の滴下終了後、
３０℃で３時間撹拌を続けた。Reference example! (Synthesis of lithium diphenylphosphinobenzene-m-monosulfonate) Triphenyl was added to a 500 ml four-bottle flask equipped with a thermometer, a stirring device, a dropping funnel, and a nitrogen gas inlet/outlet while purging the system with nitrogen gas. 80 g of phosphine and 36 g of 1-sulfuric acid were charged and dissolved while keeping the internal temperature below 30°C. While keeping the internal temperature below 30°C, add fuming sulfuric acid 320 containing 20vt% of SOs to this mixed solution while stirring.
g was added dropwise over 30 minutes. After dropping the fuming sulfuric acid,
Stirring was continued for 3 hours at 30°C.
反応混合液を液体クロマトグラフイーによって、未反応
のトリフエニルホスフインを分析したところ、トリフエ
ニルホスフインの転化率は６０％であった。反応混合液
を冷却しながら氷水約１５００ｍｌを加えることによっ
て約２ａ％の硫酸水溶液とした。When the reaction mixture was analyzed for unreacted triphenylphosphine by liquid chromatography, the conversion rate of triphenylphosphine was 60%. Approximately 1,500 ml of ice water was added to the reaction mixture while cooling it to obtain an approximately 2a% sulfuric acid aqueous solution.
この硫酸水溶液に１回につき７００ｍｌのメチルイソブ
チルケトンを用いて合計２回の抽出操作を施した。メチ
ルイソブチルケトン層に約４１ｔ％の水酸化リチウム水
溶液約９０■ｌを加えることによって系全体を中和した
。静置後の水層をエバボレーターで蒸発させたところ６
２ｇの白色粉末が得られた。This aqueous sulfuric acid solution was subjected to a total of two extraction operations using 700 ml of methyl isobutyl ketone each time. The entire system was neutralized by adding about 90 liters of about 41 t% lithium hydroxide aqueous solution to the methyl isobutyl ketone layer. After standing still, the water layer was evaporated with an evaporator 6
2 g of white powder was obtained.
この白色粉末を、元素分析、液体クロマトグラフイー分
析などで分析したところ、粉末中には、硫酸リチウムが
０．５ｖｔ％、ジフェニルホスフイノベンゼンーｍ−モ
ノスルホン酸リチウムの酸化物が２．０豐ｔ％、ジフエ
ニルホスフイノベンゼン−ｍ −モノスルホン酸リチウ
ムが９５ｗｔ％および対応するジスルホン酸リチウムが
２．５ｗｔ％含まれていろことがわかった。When this white powder was analyzed by elemental analysis and liquid chromatography analysis, it was found that the powder contained 0.5% by volume of lithium sulfate and 2.0% by volume of lithium diphenylphosphinobenzene-m-monosulfonate oxide. 95 wt% of lithium diphenylphosphinobenzene-m-monosulfonate and 2.5 wt% of the corresponding lithium disulfonate.
実施例ｌ
参考例ｌで得られた徂ジフェニルホスフイノベンゼンー
ｍ−モノスルホン酸り背Ｏｇに酢酸１００ｍｌを加え、
富素雰囲気下、加熱還流し該リチウム塩を溶解させた。Example 1 Add 100 ml of acetic acid to Og of diphenylphosphinobenzene-m-monosulfonic acid obtained in Reference Example 1,
The lithium salt was dissolved by heating under reflux under an enriched atmosphere.
溶液中の不溶物を熱時炉遇することにより除いた。得ら
れた酢酸溶液を室温まで冷却した。析出してくる白色結
晶を炉過により捕集した。この白色結晶を’ＨＮＭＲ分
近したところジフェニルホスフイノベンゼン−ｍ−モノ
スルホン酸リチウムと酢酸との■対ｌの付加物であった
。Insoluble matter in the solution was removed by heating in a hot oven. The resulting acetic acid solution was cooled to room temperature. The precipitated white crystals were collected by filtration. When this white crystal was subjected to 'HNMR analysis, it was found to be an adduct of lithium diphenylphosphinobenzene-m-monosulfonate and acetic acid in a ratio of 1 to 1.
この白色結晶を１４０℃、Ｉｇ＋ｓ｝ＩＨの条件下で５
時間減圧乾燥した。その結果、３８ｇのジフェニルホス
フイノベンゼンーｍ−モノスルホン酸リチウムが得られ
た。この白色結晶を、元素分析、液体クロマトグラフイ
ー分析などで分叶したところ、純度１００％のジフエニ
ルホスブイノベンゼンーｍ−モノスルホン酸リチウムで
あることがわかった。This white crystal was heated at 140°C under Ig+s}IH conditions for 5
Dry under reduced pressure for an hour. As a result, 38 g of lithium diphenylphosphinobenzene-m-monosulfonate was obtained. When this white crystal was separated by elemental analysis and liquid chromatography analysis, it was found to be lithium diphenylphosbuinobenzene-m-monosulfonate with 100% purity.
実施例２
参考例！で得られた徂ジフェニルホスフイノベンゼン−
ｍ−モノスルホン酸リチウム４０ｇにプロピオン酸４０
ｈｌを加え、実施例ｌと同様に再結操作を行った。析出
してくる白色結晶を炉過により捕果した。この白色結晶
を’ＨＮＭＲ分析したところジフェニルホスフイノベン
ゼン−ｍ−モノスルホン酸リチウムとプロビオン酸との
１対！の付加物であった。この白色結晶を２００℃、１
ａｍｌｇの条件下で５時間減圧乾燥した。その結果、３
８ｇのジフェニルホスフイノベンゼン−ｍ−モノスルホ
ン酸リチウムが得られた。この白色結晶を、元素分匠、
液体クａマトグラフイー分析などで分析したところ、純
度１００％のジフェニルホスフイノベンゼン−ｍ−モノ
スルホン酸リチウムであることがわかった。Example 2 Reference example! Diphenylphosphinobenzene obtained in
40 g of lithium m-monosulfonate and 40 g of propionic acid
hl was added and the reconsolidation operation was performed in the same manner as in Example 1. The precipitated white crystals were collected by filtration. 'HNMR analysis of this white crystal revealed that it was a pair of lithium diphenylphosphinobenzene-m-monosulfonate and propionic acid! It was an addition of This white crystal was heated at 200℃ for 1
It was dried under reduced pressure for 5 hours under amlg conditions. As a result, 3
8 g of lithium diphenylphosphinobenzene-m-monosulfonate were obtained. This white crystal, element master,
When analyzed by liquid chromatography analysis, etc., it was found to be lithium diphenylphosphinobenzene-m-monosulfonate with 100% purity.
実施Ｎ３
参考例ｌで得られた祖ジフェニルホスフイノベンゼン−
ｍ−モノスルホン酸リチウム４０ｇに吉草酸２００ｍｌ
を加え、実施例ｌと同様に再結操作を行った。析出して
くる白色結晶を炉過により捕集した。この白色結晶を’
ＨＮＭＲ分析したところジフェニルホスフイノベンゼン
−ｍ−モノスルホン酸リチウムと吉草酸とのｌ対ｌの付
加物であった。Implementation N3 Diphenylphosphinobenzene obtained in Reference Example 1
200 ml of valeric acid to 40 g of lithium m-monosulfonate
was added, and the reconsolidation operation was performed in the same manner as in Example 1. The precipitated white crystals were collected by filtration. This white crystal'
HNMR analysis revealed that it was a 1:1 adduct of lithium diphenylphosphinobenzene-m-monosulfonate and valeric acid.
この白色結晶を２２０℃、ｌｍｍｌ！ｇの条件下で５時
間減圧乾燥した。その結果、３８ｇのジフェニルホスフ
イノベンゼン−ｍ−モノスルホン酸リチウムが得られた
。この白色結晶を、元素分析、液体クロマトグラフイー
分計などで分析したところ、純度ＩＯＯ％のジフェニル
ホスフイノベンゼン−ｍ−モノスルホン酸リチウムであ
ることがわかった。Pour this white crystal at 220℃, lmml! It was dried under reduced pressure for 5 hours under the conditions of g. As a result, 38 g of lithium diphenylphosphinobenzene-m-monosulfonate was obtained. When this white crystal was analyzed by elemental analysis, liquid chromatography, etc., it was found to be lithium diphenylphosphinobenzene-m-monosulfonate with a purity of IOO%.
比較例！
参考例！で得られた粗ジフェニルホスフイノベンゼン−
ｍ−モノスルホン酸リチウム４０ｇにメチルイソブチル
ケトン３００ｍｌを加え、実施例ｌと同様に再結操作を
行った。匠出してくる白色結晶を炉過により捕果した。Comparative example! Reference example! Crude diphenylphosphinobenzene obtained in
300 ml of methyl isobutyl ketone was added to 40 g of lithium m-monosulfonate, and the reconsolidation operation was performed in the same manner as in Example 1. The white crystals that emerged were collected by filtration.
この白色結晶を元素分匠、液体クロマトグラフイー分析
などで分匠したところ、純度１００％のジフエニルホス
フイノベンゼンａ−ｍ−モノスルホン酸リチウムである
ことがわかったが、白色結晶として得られたものは１２
ｇで、まだ母液に２６ｇのジフェニルホスフイノベンゼ
ン−ｍ−モノスルホン酸リチウムが析出せずに残ってい
ることがわかった。When this white crystal was analyzed by elemental analysis and liquid chromatography analysis, it was found to be 100% pure diphenylphosphinobenzene am-lithium monosulfonate, but it was obtained as a white crystal. There are 12 things
It was found that 26 g of lithium diphenylphosphinobenzene-m-monosulfonate still remained in the mother liquor without being precipitated.
［発明の効果］
本発明によって、工業的実施に適したジフェニルホスフ
イノベンゼン−ｍ−モノスルホン酸リチウムの精製が可
能となった。[Effects of the Invention] The present invention has made it possible to purify lithium diphenylphosphinobenzene-m-monosulfonate suitable for industrial implementation.
Claims (2)
ン酸リチウムを炭素数１〜８の有機カルボン酸から再結
晶することを特徴とするジフェニルホスフイノベンゼン
−ｍ−モノスルホン酸リチウムの精製方法。(1) A method for purifying lithium diphenylphosphinobenzene-m-monosulfonate, which comprises recrystallizing lithium diphenylphosphinobenzene-m-monosulfonate from an organic carboxylic acid having 1 to 8 carbon atoms.
法。(2) The purification method according to claim 1, wherein the organic carboxylic acid is acetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5878789A JPH02237991A (en) | 1989-03-10 | 1989-03-10 | Lithium diphenylphosphinobenzene-m-monosulfonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5878789A JPH02237991A (en) | 1989-03-10 | 1989-03-10 | Lithium diphenylphosphinobenzene-m-monosulfonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02237991A true JPH02237991A (en) | 1990-09-20 |
Family
ID=13094284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5878789A Pending JPH02237991A (en) | 1989-03-10 | 1989-03-10 | Lithium diphenylphosphinobenzene-m-monosulfonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02237991A (en) |
-
1989
- 1989-03-10 JP JP5878789A patent/JPH02237991A/en active Pending
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