JP2002371088A - Sulfonic acid amine salt and method for producing the same - Google Patents
Sulfonic acid amine salt and method for producing the sameInfo
- Publication number
- JP2002371088A JP2002371088A JP2002087549A JP2002087549A JP2002371088A JP 2002371088 A JP2002371088 A JP 2002371088A JP 2002087549 A JP2002087549 A JP 2002087549A JP 2002087549 A JP2002087549 A JP 2002087549A JP 2002371088 A JP2002371088 A JP 2002371088A
- Authority
- JP
- Japan
- Prior art keywords
- sulfonic acid
- reaction
- lower alkyl
- alkyl group
- salt
- 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
- -1 Sulfonic acid amine salt Chemical class 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 150000003998 acyclic ketones Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 239000003054 catalyst Substances 0.000 abstract description 16
- 239000002244 precipitate Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 150000001993 dienes Chemical class 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 150000003460 sulfonic acids Chemical class 0.000 abstract 2
- 238000000151 deposition Methods 0.000 abstract 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 12
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 10
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 10
- 150000004714 phosphonium salts Chemical class 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 8
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 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 6
- 239000003513 alkali Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- HXVJDHROZFWXHT-UHFFFAOYSA-N 2-diphenylphosphanylbenzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 HXVJDHROZFWXHT-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 238000006471 dimerization reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 3
- YHYGSIBXYYKYFB-VOTSOKGWSA-N (2e)-octa-2,7-dien-1-ol Chemical compound OC\C=C\CCCC=C YHYGSIBXYYKYFB-VOTSOKGWSA-N 0.000 description 2
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- ZBMZOFSLQIPSPW-UHFFFAOYSA-N 3-bis(3-sulfophenyl)phosphanylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S(O)(=O)=O)C=2C=C(C=CC=2)S(O)(=O)=O)=C1 ZBMZOFSLQIPSPW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- RHLVCLIPMVJYKS-UHFFFAOYSA-N 3-octanone Chemical compound CCCCCC(=O)CC RHLVCLIPMVJYKS-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- PCELKVAQHUEQKH-UHFFFAOYSA-N octa-1,7-dien-3-ol Chemical compound C=CC(O)CCCC=C PCELKVAQHUEQKH-UHFFFAOYSA-N 0.000 description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NTUROZDXWLPVHB-UHFFFAOYSA-M sodium;3-diphenylphosphanylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NTUROZDXWLPVHB-UHFFFAOYSA-M 0.000 description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- PJKUVJSPRYXAFR-UHFFFAOYSA-N 2-[phenyl-(2-sulfophenyl)phosphanyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1P(C=1C(=CC=CC=1)S(O)(=O)=O)C1=CC=CC=C1 PJKUVJSPRYXAFR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- VXBOQUXGRAKYGH-UHFFFAOYSA-N bis(2-methylphenyl)-phenylphosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1 VXBOQUXGRAKYGH-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- VZZJVOCVAZHETD-UHFFFAOYSA-N diethylphosphane Chemical compound CCPCC VZZJVOCVAZHETD-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- RDOHPVPONNHSPH-UHFFFAOYSA-N octa-2,7-dienyl acetate Chemical compound CC(=O)OCC=CCCCC=C RDOHPVPONNHSPH-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- FTBRHZVBDSDPAX-UHFFFAOYSA-N tris(2,3,4,5-tetramethylphenyl)phosphane Chemical compound CC1=C(C)C(C)=CC(P(C=2C(=C(C)C(C)=C(C)C=2)C)C=2C(=C(C)C(C)=C(C)C=2)C)=C1C FTBRHZVBDSDPAX-UHFFFAOYSA-N 0.000 description 1
- GHXAMMRRGBIANW-UHFFFAOYSA-N tris(2,3,4-trimethylphenyl)phosphane Chemical compound CC1=C(C)C(C)=CC=C1P(C=1C(=C(C)C(C)=CC=1)C)C1=CC=C(C)C(C)=C1C GHXAMMRRGBIANW-UHFFFAOYSA-N 0.000 description 1
- GIIXTFIYICRGMZ-UHFFFAOYSA-N tris(2,3-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(P(C=2C(=C(C)C=CC=2)C)C=2C(=C(C)C=CC=2)C)=C1C GIIXTFIYICRGMZ-UHFFFAOYSA-N 0.000 description 1
- RLRSSUBSVSBAJD-UHFFFAOYSA-N tris(2-ethylphenyl)phosphane Chemical compound CCC1=CC=CC=C1P(C=1C(=CC=CC=1)CC)C1=CC=CC=C1CC RLRSSUBSVSBAJD-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- BWRYYJRIGUZFAT-UHFFFAOYSA-N tris(2-propylphenyl)phosphane Chemical compound CCCC1=CC=CC=C1P(C=1C(=CC=CC=1)CCC)C1=CC=CC=C1CCC BWRYYJRIGUZFAT-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、スルホン酸アミン
塩およびその製造方法に関する。本発明により提供され
るスルホン酸アミン塩は、共役ジエンと活性水素化合物
とのテロメリゼーション反応を促進する触媒の構成成分
である水溶性ホスホニウム塩の原料として有用である。
テロメリゼーション反応により得られる２，７−オクタ
ジエン−１−オール、１，７−オクタジエン−３−オー
ル、１−アセトキシ−２，７−オクタジエンなどのアル
カジエニル化合物は、種々の高分子化合物、医薬、農薬
などの原料などとして用いられる。TECHNICAL FIELD The present invention relates to an amine sulfonate and a method for producing the same. The sulfonic acid amine salt provided by the present invention is useful as a raw material for a water-soluble phosphonium salt that is a component of a catalyst that promotes a telomerization reaction between a conjugated diene and an active hydrogen compound.
Alkadienyl compounds such as 2,7-octadien-1-ol, 1,7-octadien-3-ol, 1-acetoxy-2,7-octadiene obtained by telomerization reaction are various polymer compounds, medicines, It is used as a raw material for pesticides.
【０００２】[0002]
【従来の技術】ケムテック（ＣＨＥＭＴＥＣＨ）１９８
７年９月号５７０頁および同１９９５年１月号３３頁に
記載されているように、ホスフィンのスルホン酸塩は貴
金属触媒反応の触媒原料として有用であることが知られ
ている。2. Description of the Related Art Chemtech 198
As described in September, 1995, p. 570 and January, 1995, p. 33, sulfonate of phosphine is known to be useful as a catalyst raw material for precious metal catalysis.
【０００３】ホスフィンのスルホン酸塩として、ジフェ
ニルホスフィノベンゼン−３−モノスルホン酸のアルカ
リ金属塩が知られており（特開昭５８−１３１９９４号
公報参照） 、該スルホン酸塩から誘導されるホスホニ
ウム塩とパラジウム化合物からなるテロメリゼーション
触媒が報告されている（特開昭６４−８５９８８号公報
および特開平７−２０６９１３号公報参照）。As a sulfonate of phosphine, an alkali metal salt of diphenylphosphinobenzene-3-monosulfonic acid is known (see JP-A-58-131994), and phosphonium derived from the sulfonate is known. A telomerization catalyst comprising a salt and a palladium compound has been reported (see JP-A-64-85988 and JP-A-7-206913).
【０００４】また、ホスフィンのスルホン酸塩として、
ジフェニルホスフィノベンゼンスルホン酸の高級アミン
塩が知られている。ジフェニルホスフィノベンゼンスル
ホン酸の高級アミン塩は、その界面活性作用を利用し
て、ブタジエンのテロメリゼーション反応に用いられて
おり［アプライド キャタリシス Ａ：ジェネラル（Ａ
ｐｐｌｉｅｄ Ｃａｔａｌｙｓｉｓ Ａ：Ｇｅｎｅｒａ
ｌ）、１３１巻１６７頁（１９９５年）参照］ 、また
有機溶媒に可溶性である性質を利用して、ヒドロホルミ
ル化反応に用いられている（米国特許第４７１６２５０
号明細書参照）。しかしながら、ジフェニルホスフィノ
ベンゼンスルホン酸の高級アミン塩は水に不溶であり、
かかる高級アミン塩を構成成分とする触媒をブタジエン
と水とのテロメリゼーション反応に用いた場合には、そ
の触媒活性は十分には発現されない。Further, as a sulfonate of phosphine,
Higher amine salts of diphenylphosphinobenzenesulfonic acid are known. Higher amine salts of diphenylphosphinobenzenesulfonic acid have been used in the telomerization reaction of butadiene by utilizing their surface-active action [Applied Catalysis A: General (A
applied Catalysis A: Genera
l), 131, 167 (1995)], and utilizing the property of being soluble in an organic solvent, in a hydroformylation reaction (US Pat. No. 4,716,250).
No.). However, higher amine salts of diphenylphosphinobenzenesulfonic acid are insoluble in water,
When a catalyst containing such a higher amine salt as a component is used in the telomerization reaction between butadiene and water, its catalytic activity is not sufficiently exhibited.
【０００５】ホスフィンのスルホン酸塩として、（スル
ホフェニル）ジフェニルホスフィン、ジ（スルホフェニ
ル）フェニルホスフィンまたはトリ（スルホフェニル）
ホスフィンの第四級アンモニウム塩が知られており、こ
れらのうち実際にはリン（３価）を６０％含有するトリ
（３−スルホフェニル）ホスフィンのテトラエチルアン
モニウム塩がブタジエンのテロメリゼーション反応に用
いられている（特公昭５４−６２７０号公報参照） 。
かかるトリ−（３−スルホフェニル）−ホスフィンのテ
トラエチルアンモニウム塩は、不純物としてリン（５
価）を含有していることが推定される。このような不純
物を含有したホスフィンから調製されたホスホニウム塩
をテロメリゼーション触媒の構成成分とする場合、テロ
メリゼーション反応系中で不純物が蓄積したり、該反応
系の反応基質の溶解度が変化するなど、反応に悪影響を
及ぼす可能性がある。As a sulfonate of phosphine, (sulfophenyl) diphenylphosphine, di (sulfophenyl) phenylphosphine or tri (sulfophenyl)
The quaternary ammonium salts of phosphine are known. Of these, the tetraethylammonium salt of tri (3-sulfophenyl) phosphine containing 60% of phosphorus (trivalent) is used for the telomerization reaction of butadiene. (See Japanese Patent Publication No. 54-6270).
Such a tetraethylammonium salt of tri- (3-sulfophenyl) -phosphine has phosphorus (5
Value). When a phosphonium salt prepared from phosphine containing such impurities is used as a component of the telomerization catalyst, impurities accumulate in the telomerization reaction system or the solubility of the reaction substrate in the reaction system changes. May adversely affect the reaction.
【０００６】[0006]
【発明が解決しようとする課題】本発明者らは、ジフェ
ニルホスフィノベンゼン−３−モノスルホン酸のアルカ
リ金属塩から誘導されるホスホニウム塩とパラジウム化
合物からなるテロメリゼーション触媒を用いて、ブタジ
エンと水との二量化反応を長期間連続して行ったとこ
ろ、反応系中に沈澱物が析出する場合があることを見出
し、かかる沈澱物の析出が配管の詰まりや反応器の伝熱
効率の低下を引き起こすことを認めた。DISCLOSURE OF THE INVENTION The present inventors have developed butadiene using a telomerization catalyst comprising a phosphonium salt derived from an alkali metal salt of diphenylphosphinobenzene-3-monosulfonic acid and a palladium compound. When the dimerization reaction with water was performed continuously for a long period of time, it was found that precipitates might be precipitated in the reaction system, and such precipitation caused clogging of pipes and reduction in heat transfer efficiency of the reactor. Admitted to cause.
【０００７】本発明者らは沈澱物発生の原因究明に努め
た結果、ブタジエンと水との二量化反応を長期間連続し
て行う際には、反応液中においてホスホニウム塩の成分
として含まれるアルカリ金属イオンの濃度が予想外に上
がること、かかるアルカリ金属イオンが反応促進剤であ
る重炭酸イオンまたは炭酸イオンと反応して重炭酸アル
カリ塩および／または炭酸アルカリ塩となること、これ
らのアルカリ塩が沈殿物として析出することを解明し
た。本来、ブタジエンと水との二量化反応の条件下で
は、重炭酸アルカリ塩および炭酸アルカリ塩は溶解状態
を保つことから、上記の現象は極めて意外であった。As a result of the present inventors' efforts to investigate the cause of the generation of precipitates, when the dimerization reaction of butadiene and water is continuously performed for a long period of time, the alkali contained as a component of the phosphonium salt in the reaction solution is considered. That the concentration of metal ions rises unexpectedly, that such alkali metal ions react with bicarbonate ions or carbonate ions as reaction accelerators to form alkali bicarbonate and / or alkali carbonate, and that these alkali salts It was elucidated that it would precipitate as a precipitate. Originally, the above-mentioned phenomenon was extremely surprising since alkali bicarbonate and alkali carbonate keep a dissolved state under the conditions of the dimerization reaction between butadiene and water.
【０００８】本発明の目的は、ブタジエンと水との二量
化反応を長期間連続して工業的規模で行う際にも、反応
系中に沈殿物が全く析出しないテロメリゼーション触媒
の原料となるスルホン酸塩を高純度で提供することにあ
る。本発明の他の目的は、上記のスルホン酸塩を製造す
る方法を提供することにある。An object of the present invention is to provide a raw material for a telomerization catalyst in which no precipitate is deposited in a reaction system even when a dimerization reaction of butadiene and water is continuously performed on an industrial scale for a long period of time. It is to provide a sulfonate with high purity. Another object of the present invention is to provide a method for producing the above sulfonate.
【０００９】[0009]
【課題を解決するための手段】本発明によれば、上記の
目的は、一般式（Ｉ）According to the present invention, the above objects have been achieved by the general formula (I)
【００１０】[0010]
【化４】 Embedded image
【００１１】（式中、Ｒ1 およびＲ2 はそれぞれ低級ア
ルキル基で置換されていてもよいフェニル基を表し、Ｒ
3 は低級アルキル基で置換されていてもよいフェニレン
基を表し、Ｒ4 、Ｒ5 およびＲ6 はそれぞれ低級アルキ
ル基を表す。）で示されるスルホン酸アミン塩［以下、
これをスルホン酸アミン塩（Ｉ）と称する］を提供する
ことによって達成され、かつ一般式（ＩＩ）Wherein R 1 and R 2 each represent a phenyl group which may be substituted with a lower alkyl group;
3 represents a phenylene group which may be substituted with a lower alkyl group, and R 4 , R 5 and R 6 each represent a lower alkyl group. ) Sulfonic acid amine salt [hereinafter, referred to as
This is referred to as sulfonic acid amine salt (I)] and has the general formula (II)
【００１２】[0012]
【化５】 Embedded image
【００１３】（式中、Ｒ1 、Ｒ2 およびＲ3 は前記定義
のとおりである。）で示されるスルホン酸［以下、これ
をスルホン酸（ＩＩ）と称する］と一般式（ＩＩＩ）(Wherein R 1 , R 2 and R 3 are as defined above) [hereinafter referred to as sulfonic acid (II)] and a general formula (III)
【００１４】[0014]
【化６】 Embedded image
【００１５】（式中、Ｒ4 、Ｒ5 およびＲ6 は前記定義
のとおりである。）で示されるアミン［以下、これをア
ミン（ＩＩＩ）と称する］とを炭素数６〜９の非環式ケ
トン中で反応させることを特徴とするスルホン酸アミン
塩（Ｉ）の製造方法を提供することによって達成され
る。(Wherein R 4 , R 5 and R 6 are as defined above) [hereinafter referred to as amine (III)]. This is achieved by providing a method for producing an amine sulfonate (I), which is characterized by reacting in a formula ketone.
【００１６】[0016]
【発明の実施の形態】スルホン酸アミン塩（Ｉ）は文献
未載の新規化合物であり、水溶性であるため、テロメリ
ゼーション触媒の調製系への溶解度が極めて高い。BEST MODE FOR CARRYING OUT THE INVENTION Amine sulfonate (I) is a novel compound not described in any literature and is water-soluble, so that its solubility in a preparation system for a telomerization catalyst is extremely high.
【００１７】上記一般式中、Ｒ1 およびＲ2 が表すフェ
ニル基が有する低級アルキル基、Ｒ 3 が表すフェニレン
基が有する低級アルキル基並びにＲ4 、Ｒ5 およびＲ6
が表す低級アルキル基としては、それらが形成するスル
ホン酸アミン塩（Ｉ）が水溶性であればよく、例えばメ
チル基、エチル基、プロピル基、ブチル基などの炭素数
１〜４のアルキル基が好ましく、メチル基およびエチル
基がより好ましい。In the above general formula, R1 And RTwo Fe
A lower alkyl group possessed by a nyl group, R Three Represents phenylene
A lower alkyl group of the group and RFour , RFive And R6
Are lower alkyl groups represented by
It is sufficient that the amine sulfonate (I) is water-soluble.
Carbon number of tyl group, ethyl group, propyl group, butyl group, etc.
1-4 alkyl groups are preferred, methyl and ethyl
Groups are more preferred.
【００１８】上記のスルホン酸（ＩＩ）とアミン（ＩＩ
Ｉ）との反応は炭素数６〜９の非環式ケトン中で行われ
る。ここで、溶媒として用いられる非環式ケトンとして
は、例えば４−メチル−２−ペンタノン、５−メチル−
３−ヘプタノン、２−オクタノン、３−オクタノン、５
−ノナノンなどが挙げられる。これらの非環式ケトンは
単独で、また２種以上の混合物として使用される。これ
らの中でも４−メチル−２−ペンタノンを使用すること
が望ましい。溶媒の使用量は、スルホン酸（ＩＩ）が溶
解する量であればよいが、多すぎる場合には経済的に効
率が悪いため、スルホン酸（ＩＩ）１ｇに対して２〜１
０ｍlの容量であるのが好ましく、３〜６ｍlの容量であ
るのがより好ましい。The above sulfonic acid (II) and amine (II)
The reaction with I) is carried out in an acyclic ketone having 6 to 9 carbon atoms. Here, as the acyclic ketone used as the solvent, for example, 4-methyl-2-pentanone, 5-methyl-pentanone
3-heptanone, 2-octanone, 3-octanone, 5
-Nonanone and the like. These acyclic ketones are used alone or as a mixture of two or more. Among these, it is desirable to use 4-methyl-2-pentanone. The amount of the solvent used may be any amount that dissolves the sulfonic acid (II), but if it is too large, it is economically inefficient.
The volume is preferably 0 ml, more preferably 3 to 6 ml.
【００１９】上記の反応において、アミン（ＩＩＩ）の
使用量は、スルホン酸（ＩＩ）に対して１．０〜１０．
０モル倍であるのが好ましく、１．０〜２．０モル倍で
あるのがより好ましい。なお、生成物であるスルホン酸
アミン塩（Ｉ）中の不純物の１つであるホスフィンオキ
シドの生成を抑制するために、反応は全工程にわたっ
て、窒素、アルゴンまたはこれらの混合ガスなどの不活
性気体の雰囲気下で、酸素を排除して行うのが望まし
い。反応温度は０〜６０℃の範囲の温度であるのが好ま
しく、１０〜３０℃の範囲の温度であるのがより好まし
い。また、反応時間は反応が長すぎても特に問題はない
が、効率の点から０．２５〜３時間の範囲であるのが好
ましい。In the above reaction, the amount of the amine (III) to be used is 1.0 to 10.3 based on the sulfonic acid (II).
It is preferably 0 mole times, more preferably 1.0 to 2.0 mole times. In order to suppress the formation of phosphine oxide, which is one of the impurities in the product sulfonate amine salt (I), the reaction was carried out in all steps in an inert gas such as nitrogen, argon, or a mixed gas thereof. It is preferable to remove oxygen in an atmosphere of the above. The reaction temperature is preferably in the range of 0 to 60C, more preferably in the range of 10 to 30C. The reaction time is not particularly limited even if the reaction is too long, but is preferably in the range of 0.25 to 3 hours from the viewpoint of efficiency.
【００２０】このようにして得られるスルホン酸アミン
塩（Ｉ）の反応混合物からの分離は、例えば、次の方法
により行うことができる。反応混合物から必要に応じて
溶媒を減圧下に留去した後、得られた残渣を酢酸エチ
ル、ヘキサンなどの溶媒で洗浄することによりスルホン
酸アミン塩（Ｉ）の結晶を取得する。また、スルホン酸
アミン塩（Ｉ）の溶媒への溶解度が低い場合には、溶媒
を留去することなく濾過によりスルホン酸アミン塩
（Ｉ）の結晶を取得する。得られたスルホン酸アミン塩
（Ｉ）はそのままテロメリゼーション触媒の調製に供す
ることが可能であり、また必要に応じて再結晶などの方
法により精製した後、テロメリゼーション触媒の調製に
供してもよい。The thus obtained sulfonic acid amine salt (I) can be separated from the reaction mixture by, for example, the following method. The solvent is distilled off from the reaction mixture under reduced pressure as necessary, and the obtained residue is washed with a solvent such as ethyl acetate or hexane to obtain a crystal of amine sulfonate (I). When the solubility of the amine sulfonate (I) in the solvent is low, crystals of the amine sulfonate (I) are obtained by filtration without distilling off the solvent. The obtained sulfonic acid amine salt (I) can be used as it is for the preparation of a telomerization catalyst, and if necessary, purified by a method such as recrystallization, and then used for the preparation of a telomerization catalyst. Is also good.
【００２１】本発明における反応により、スルホン酸ア
ミン塩（Ｉ）への不純物の混入量を低減させることがで
き、高純度のスルホン酸アミン塩（Ｉ）が得られる。By the reaction in the present invention, the amount of impurities mixed into the sulfonic acid amine salt (I) can be reduced, and a high-purity amine sulfonic acid salt (I) can be obtained.
【００２２】スルホン酸（ＩＩ）は、対応する一般式
（ＩＶ）The sulfonic acid (II) has the corresponding general formula (IV)
【００２３】[0023]
【化７】 Embedded image
【００２４】（式中、Ｒ1 、Ｒ2 およびＲ3 はそれぞれ
前記定義のとおりである。）で示されるリン化合物［以
下、これをリン化合物（ＩＶ）と称する］から公知の方
法により得ることができる。純度のより高いスルホン酸
アミン塩（Ｉ）を得るためには、純度の高いリン化合物
（ＩＶ）を使用することが望ましい。また、リン化合物
（ＩＶ）を発煙硫酸でスルホン化する方法によれば、短
工程でかつ容易にスルホン酸（ＩＩ）が得られるが、か
かる方法では、一般にジスルホン体、酸化体などの不純
物の混入量が多くなるため、スルホン酸（ＩＩ）を一旦
アルカリ金属塩に変換し、上記の不純物を除いた後に、
該アルカリ金属塩を酸処理などによりスルホン酸（Ｉ
Ｉ）に変換する方法を採用するのが望ましい。(Wherein R 1 , R 2 and R 3 are as defined above) [hereinafter referred to as phosphorus compound (IV)] by a known method. Can be. In order to obtain a sulfonic acid amine salt (I) with a higher purity, it is desirable to use a phosphorus compound (IV) with a higher purity. Further, according to the method of sulfonating the phosphorus compound (IV) with fuming sulfuric acid, the sulfonic acid (II) can be easily obtained in a short step, but in such a method, generally, impurities such as a disulfone compound and an oxidized compound are mixed. Since the amount increases, the sulfonic acid (II) is once converted into an alkali metal salt, and after removing the above impurities,
The alkali metal salt is treated with sulfonic acid (I
It is desirable to adopt a method of converting to I).
【００２５】リン化合物（ＩＶ）としては、例えばトリ
フェニルホスフィン、トリ（トリル）ホスフィン、トリ
（エチルフェニル）ホスフィン、トリ（プロピルフェニ
ル）ホスフィン、トリルジフェニルホスフィン、ジ（ト
リル）フェニルホスフィン、ジ（エチルフェニル）フェ
ニルホスフィン、トリ（ジメチルフェニル）ホスフィ
ン、トリス（トリメチルフェニル）ホスフィン、トリス
（テトラメチルフェニル）ホスフィンなどが挙げられ
る。Examples of the phosphorus compound (IV) include triphenylphosphine, tri (tolyl) phosphine, tri (ethylphenyl) phosphine, tri (propylphenyl) phosphine, tolylphenylphenylphosphine, di (tolyl) phenylphosphine, and di (ethyl) phosphine. Phenyl) phenylphosphine, tri (dimethylphenyl) phosphine, tris (trimethylphenyl) phosphine, tris (tetramethylphenyl) phosphine and the like.
【００２６】スルホン酸アミン塩（Ｉ）から、テロメリ
ゼーション反応触媒の構成成分であるホスホニウム塩が
得られる。例えば、スルホン酸アミン塩（Ｉ）を、炭酸
ガス雰囲気下または加圧下に、パラジウム、水、２，７
−オクタジエン−１−オールなどのアルケニル化合物お
よびジオキサン、テトラヒドロフラン、スルホランなど
の溶媒と攪拌することによりホスホニウム塩を得る。From the sulfonate amine salt (I), a phosphonium salt which is a component of the telomerization reaction catalyst is obtained. For example, a sulfonic acid amine salt (I) is converted into palladium, water,
A phosphonium salt is obtained by stirring with an alkenyl compound such as -octadien-1-ol and a solvent such as dioxane, tetrahydrofuran and sulfolane.
【００２７】[0027]
【実施例】以下、本発明を実施例により具体的に説明す
るが、本発明は実施例により制限されるものではない。EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to the examples.
【００２８】実施例１ トリエチルアンモニウム ３−（ジフェニルホスフィ
ノ）ベンゼンスルホナートの合成Example 1 Synthesis of triethylammonium 3- (diphenylphosphino) benzenesulfonate
【００２９】１．ナトリウム ３−（ジフェニルホスフ
ィノ）ベンゼンスルホナートの合成温度計、攪拌装置、
滴下ロートおよび窒素ガスラインを備えた内容量３００
ｍｌの三つ口フラスコに濃硫酸１１０ｇ（１．１２モ
ル）およびトリフェニルホスフィン６０ｇ（０．２３モ
ル）を仕込み、系内を窒素ガスで置換した。内容物を攪
拌しながら、該内容物に滴下ロートから発煙硫酸（三酸
化硫黄の含有量：２５重量％、三酸化硫黄のモル数：
０．６９モル）２２０ｇを、内温２５℃を保ちながら１
時間かけて滴下した。滴下終了後、内温２５℃で１２時
間攪拌を継続した。得られた反応混合物を窒素雰囲気中
で氷水1．８ｋｇに滴下して反応混合物を加水分解し、
希釈した。得られた水溶液に、室温で４−メチル−２−
ペンタノン１．５リットルを加えてよく混合し、静置し
た後、４−メチル−２−ペンタノン層を分液した。得ら
れた４−メチル−２−ペンタノン層に、窒素雰囲気下で
５重量％の水酸化ナトリウム水溶液１２０ｍｌを、内温
２５℃を保ちながら滴下して中和した。反応混合液から
水層を取り出し、この水層を４−メチル−２−ペンタノ
ン１００ｍｌで洗浄し、水層を分液により取得して、８
０℃で８０ｍｌまで濃縮した後、放冷し、結晶を析出さ
せた。析出した結晶を濾過により取得し、６０℃、５ｍ
ｍＨｇで２時間減圧乾燥することにより、ナトリウム
３−（ジフェニルホスフィノ）ベンゼンスルホナート・
二水和物３５ｇを白色結晶として得た。1. Sodium 3- (diphenylphosphino) benzenesulfonate synthesis thermometer, stirrer,
300 with drip funnel and nitrogen gas line
110 g (1.12 mol) of concentrated sulfuric acid and 60 g (0.23 mol) of triphenylphosphine were charged into a 3-ml three-necked flask, and the system was purged with nitrogen gas. While stirring the contents, fuming sulfuric acid (content of sulfur trioxide: 25% by weight, mol number of sulfur trioxide:
0.69 mol) 220 g was added to 1
It was dropped over time. After completion of the dropwise addition, stirring was continued at an internal temperature of 25 ° C. for 12 hours. The reaction mixture obtained was added dropwise to 1.8 kg of ice water in a nitrogen atmosphere to hydrolyze the reaction mixture,
Diluted. At room temperature, 4-methyl-2-
After 1.5 liters of pentanone was added, mixed well, and allowed to stand, the 4-methyl-2-pentanone layer was separated. Under a nitrogen atmosphere, 120 ml of a 5% by weight aqueous solution of sodium hydroxide was added dropwise to the obtained 4-methyl-2-pentanone layer while maintaining the internal temperature at 25 ° C. to neutralize. The aqueous layer was taken out of the reaction mixture, washed with 100 ml of 4-methyl-2-pentanone, and the aqueous layer was obtained by liquid separation.
After concentrating to 80 ml at 0 ° C., the mixture was allowed to cool to precipitate crystals. The precipitated crystals were obtained by filtration, and were
By drying under reduced pressure at mHg for 2 hours, sodium
3- (diphenylphosphino) benzenesulfonate
35 g of dihydrate were obtained as white crystals.
【００３０】２．トリエチルアンモニウム ３−（ジフ
ェニルホスフィノ）ベンゼンスルホナートの合成 温度計、攪拌装置、滴下ロートおよび窒素ガスラインを
備えた内容量３００ｍｌの三つ口フラスコにナトリウム
３−（ジフェニルホスフィノ）ベンゼンスルホナート
・二水和物３０ｇ（７５ミリモル）および水７５ｍｌを
仕込み、系内を窒素ガスで置換した。内容物を攪拌しな
がら、該内容物に滴下ロートから５０重量％硫酸３８ｍ
ｌを、内温２５℃を保ちながら滴下した。滴下終了後、
内温２５℃で１時間攪拌を継続した。得られた反応混合
物を窒素雰囲気中で４−メチル−２−ペンタノン１３０
ｍｌと混合し、静置した後、４−メチル−２−ペンタノ
ン層を分液した。得られた４−メチル−２−ペンタノン
層に、窒素雰囲気下でトリエチルアミン８．３ｇ（８２
ミリモル）を、内温２５℃を保ちながら滴下して中和し
た。反応混合液を３０ｍｍＨｇ、４０℃で７０ｍｌまで
濃縮し、固体を析出させた。固体を濾過により取得し、
減圧乾燥することにより収量３１．６ｇ（収率９５％）
で白色粉末を得た。この白色粉末を高速液体クロマトグ
ラフィー［溶離液：０．０１モル／リットルのリン酸水
溶液／メタノール＝３５／６５（容量）、カラム：Ｌ−
ｃｏｌｕｍｎ ＯＤＳ（４．６×１５０ｍｍ、財団法人
化学物質評価研究機構） ］で分析したところ、ホスフ
ィンオキシド含量は０．８モル％であった。また 1Ｈ−
ＮＭＲスペクトル分析および31Ｐ−ＮＭＲスペクトル分
析の結果と原子吸光によるＮａ含量の分析結果は以下の
とおりであり、得られた白色粉末は構造式（Ｖ）で示さ
れるトリエチルアンモニウム ３−（ジフェニルホスフ
ィノ）ベンゼンスルホナートであると決定した。また、
ヨードメトリー分析の結果によれば、純度は９８．５％
であった。2. Synthesis of triethylammonium 3- (diphenylphosphino) benzenesulfonate Sodium 3- (diphenylphosphino) benzenesulfonate was placed in a 300 ml three-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a nitrogen gas line. 30 g (75 mmol) of dihydrate and 75 ml of water were charged, and the system was purged with nitrogen gas. While stirring the contents, 50% by weight sulfuric acid 38 m
1 was added dropwise while maintaining the internal temperature at 25 ° C. After dropping,
Stirring was continued at an internal temperature of 25 ° C. for 1 hour. The obtained reaction mixture was treated with 4-methyl-2-pentanone 130 in a nitrogen atmosphere.
After the mixture was allowed to stand still, the 4-methyl-2-pentanone layer was separated. 8.3 g of triethylamine (82 g) was added to the obtained 4-methyl-2-pentanone layer under a nitrogen atmosphere.
(Mmol) was neutralized dropwise while maintaining the internal temperature at 25 ° C. The reaction mixture was concentrated to 30 ml at 30 mmHg and 40 ° C. to precipitate a solid. Obtaining the solid by filtration;
Drying under reduced pressure yields 31.6 g (95% yield).
Yielded a white powder. This white powder was subjected to high performance liquid chromatography [eluent: 0.01 mol / liter phosphoric acid aqueous solution / methanol = 35/65 (volume), column: L-
column ODS (4.6 × 150 mm, Japan Chemicals Evaluation and Research Organization)], the phosphine oxide content was 0.8 mol%. The 1 H-
The results of the NMR spectrum analysis and the 31 P-NMR spectrum analysis and the analysis results of the Na content by atomic absorption are as follows, and the obtained white powder was triethylammonium 3- (diphenylphosphino) represented by the structural formula (V). ) It was determined to be benzenesulfonate. Also,
According to the results of the iodometric analysis, the purity was 98.5%.
Met.
【００３１】[0031]
【化８】 Embedded image
【００３２】1Ｈ−ＮＭＲ（２７０ＭＨｚ、ＣＤ３ Ｏ
Ｄ、ＴＭＳ基準、ｐｐｍ）δ：１．２７（ｔ，Ｊ＝７Ｈ
ｚ，９Ｈ）、３．１６（ｑ，６Ｈ）、７．２５−７．８
４（ｍ，１４Ｈ）31 Ｐ−ＮＭＲ（Ｄ2 Ｏ、８５％リン酸基準、ｐｐｍ）
δ：−５．２ 原子吸光：Ｎａ不検出 1 H-NMR (270 MHz, CD 3 O
D, TMS standard, ppm) δ: 1.27 (t, J = 7H)
z, 9H), 3.16 (q, 6H), 7.25-7.8.
4 (m, 14H) 31 P-NMR (D 2 O, based on 85% phosphoric acid, ppm)
δ: -5.2 Atomic absorption: Na not detected
【００３３】実施例２ トリエチルアンモニウム ３−（ジフェニルホスフィ
ノ）ベンゼンスルホナートの合成 温度計、攪拌装置、滴下ロートおよび窒素ガスラインを
備えた内容量３００ｍｌの三つ口フラスコに濃硫酸１１
０ｇ（１．１２モル）およびトリフェニルホスフィン６
０ｇ（０．２３モル）を仕込み、系内を窒素ガスで置換
した。内容物を攪拌しながら、該内容物に滴下ロートか
ら発煙硫酸（三酸化硫黄の含有量：２５重量％、三酸化
硫黄のモル数：０．６９モル）２２０ｇを、内温２５℃
を保ちながら１時間かけて滴下した。滴下終了後、内温
２５℃で１２時間攪拌を継続した。得られた反応混合物
を窒素雰囲気中で氷水1．８ｋｇに滴下して反応混合物
を加水分解し、希釈した。得られた水溶液に、室温で４
−メチル−２−ペンタノン１．５リットルを加えてよく
混合し、静置した後、４−メチル−２−ペンタノン層を
分液した。得られた４−メチル−２−ペンタノン層に、
窒素雰囲気下でトリエチルアミン３０ｍｌを、内温２５
℃を保ちながら滴下して中和した。得られた反応液を約
２５０ｇまで濃縮し、２００ｍｌの水で抽出した後、減
圧にて水を留去し、白色の固体を４７ｇ得た。分析の結
果、この白色固体はトリエチルアンモニウム３−（ジフ
ェニルホスフィノ）ベンゼンスルホナート（ホスフィン
オキシドの含有量５モル％）であった。また、純度は９
０％であった。Example 2 Synthesis of triethylammonium 3- (diphenylphosphino) benzenesulfonate Concentrated sulfuric acid was placed in a 300 ml three-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a nitrogen gas line.
0 g (1.12 mol) and triphenylphosphine 6
0 g (0.23 mol) was charged, and the system was replaced with nitrogen gas. While stirring the contents, 220 g of fuming sulfuric acid (sulfur trioxide content: 25% by weight, mole number of sulfur trioxide: 0.69 mol) was dropped from the dropping funnel into the contents at an internal temperature of 25 ° C
Was added dropwise over 1 hour. After completion of the dropwise addition, stirring was continued at an internal temperature of 25 ° C. for 12 hours. The obtained reaction mixture was added dropwise to 1.8 kg of ice water in a nitrogen atmosphere to hydrolyze and dilute the reaction mixture. The resulting aqueous solution was added at room temperature for 4 hours.
1.5 liter of -methyl-2-pentanone was added, mixed well, and allowed to stand. Then, the 4-methyl-2-pentanone layer was separated. In the obtained 4-methyl-2-pentanone layer,
Under a nitrogen atmosphere, 30 ml of triethylamine was added at an internal temperature of 25.
The solution was neutralized by dropping while maintaining the temperature. The obtained reaction solution was concentrated to about 250 g, extracted with 200 ml of water, and then water was distilled off under reduced pressure to obtain 47 g of a white solid. As a result of the analysis, this white solid was triethylammonium 3- (diphenylphosphino) benzenesulfonate (phosphine oxide content: 5 mol%). The purity is 9
It was 0%.
【００３４】参考例１ 実施例１で得られたトリエチルアンモニウム ３−（ジ
フェニルホスフィノ）ベンゼンスルホナートを原料とし
て次の方法によりホスホニウム塩を含有する触媒液を調
製した。すなわち、攪拌装置を備えた１００ｍｌ容ステ
ンレス製オートクレーブに、酢酸パラジウム０．０６８
ｇ（０．３０４ミリモル）、実施例１で得られたトリエ
チルアンモニウム ３−（ジフェニルホスフィノ）ベン
ゼンスルホナート２．７ｇ（６．０８ミリモル）、水１
６ｇ、２，７−オクタジエン−１−オール４．２８ｇ
（３４ミリモル）、トリエチルアミン５．５１ｇ（５
４．６ミリモル）およびスルホラン１７．１ｇを仕込
み、炭酸ガスで系内を置換した後、０．６９ＭＰａ（７
ｋｇ／ｃｍ２ ）（ゲージ圧）の圧力をかけ、８０℃に
昇温した。そのまま１３時間加熱攪拌を続けた後、冷却
して触媒液とした。この触媒液を高速液体クロマトグラ
フィーで分析し、トリエチルアンモニウム ３−（ジフ
ェニルホスフィノ）ベンゼンスルホナートが系中で全て
ホスホニウム塩に変換されていることを確認した。Reference Example 1 Using the triethylammonium 3- (diphenylphosphino) benzenesulfonate obtained in Example 1 as a raw material, a catalyst solution containing a phosphonium salt was prepared by the following method. That is, 0.068 palladium acetate was placed in a 100 ml stainless steel autoclave equipped with a stirrer.
g (0.304 mmol), 2.7 g (6.08 mmol) of triethylammonium 3- (diphenylphosphino) benzenesulfonate obtained in Example 1, water 1
6 g, 4.28 g of 2,7-octadien-1-ol
(34 mmol), 5.51 g of triethylamine (5
4.6 mmol) and 17.1 g of sulfolane were charged, and the inside of the system was replaced with carbon dioxide gas.
kg / cm 2 ) (gauge pressure), and the temperature was raised to 80 ° C. After continuing heating and stirring for 13 hours as it was, it was cooled to obtain a catalyst liquid. The catalyst solution was analyzed by high performance liquid chromatography, and it was confirmed that all of triethylammonium 3- (diphenylphosphino) benzenesulfonate was converted to a phosphonium salt in the system.
【００３５】次に、ブタジエンと水とのテロメリゼーシ
ョン反応を次の方法により行った。すなわち、系内に
１，３−ブタジエン、水、スルホラン、トリエチルアミ
ンおよび上記で得られた触媒液を下記の組成になるよう
に連続的に供給し、二酸化炭素で加圧して反応圧力１．
３７ＭＰａ（１４ｋｇ／ｃｍ２ ）（ゲージ圧）、反応
温度７２℃、滞留時間１時間で反応を行った。Next, a telomerization reaction between butadiene and water was carried out by the following method. That is, 1,3-butadiene, water, sulfolane, triethylamine and the catalyst solution obtained above were continuously supplied into the system so as to have the following composition, and the reaction pressure was increased by pressurizing with carbon dioxide.
The reaction was carried out at 37 MPa (14 kg / cm 2 ) (gauge pressure), at a reaction temperature of 72 ° C., and for a residence time of 1 hour.
【００３６】 １，３−ブタジエン： ６重量％ 水 ： ２４重量％ スルホラン ： ４０重量％ トリエチルアミン ： ７重量％ パラジウム ：２００ｐｐｍ ホスホニウム塩 ：パラジウムに対して２０モル倍1,3-butadiene: 6% by weight Water: 24% by weight Sulfolane: 40% by weight Triethylamine: 7% by weight Palladium: 200 ppm Phosphonium salt: 20-fold molar amount to palladium
【００３７】上記の反応を３ヶ月間連続して行ったが、
無機塩等の固体の析出は認められなかった。The above reaction was carried out continuously for three months.
No precipitation of a solid such as an inorganic salt was observed.
【００３８】[0038]
【発明の効果】本発明により、共役ジエンと活性水素化
合物とのテロメリゼーション反応を長期間連続して工業
的規模で行う際にも、反応系中に沈殿物が全く析出しな
いテロメリゼーション触媒の原料となるスルホン酸塩が
高純度で提供され、また該スルホン酸塩の製造方法が提
供される。Industrial Applicability According to the present invention, a telomerization catalyst in which no precipitate is deposited in a reaction system even when a telomerization reaction between a conjugated diene and an active hydrogen compound is continuously performed on an industrial scale for a long period of time. And a method for producing the sulfonate.
Claims (2)
置換されていてもよいフェニル基を表し、Ｒ3 は低級ア
ルキル基で置換されていてもよいフェニレン基を表し、
Ｒ4 、Ｒ5 およびＲ6 はそれぞれ低級アルキル基を表
す。）で示されるスルホン酸アミン塩。1. A compound of the general formula (I) (Wherein, R 1 and R 2 each represent a phenyl group optionally substituted with a lower alkyl group, R 3 represents a phenylene group optionally substituted with a lower alkyl group,
R 4 , R 5 and R 6 each represent a lower alkyl group. ) Amine sulfonate salt represented by the formula:
置換されていてもよいフェニル基を表し、Ｒ3 は低級ア
ルキル基で置換されていてもよいフェニレン基を表
す。）で示されるスルホン酸と一般式（ＩＩＩ） 【化３】 （式中、Ｒ4 、Ｒ5 およびＲ6 はそれぞれ低級アルキル
基を表す。）で示されるアミンとを炭素数６〜９の非環
式ケトン中で反応させることを特徴とする請求項１記載
のスルホン酸アミン塩の製造方法。2. A compound of the general formula (II) (Wherein, R 1 and R 2 each represent a phenyl group optionally substituted with a lower alkyl group, and R 3 represents a phenylene group optionally substituted with a lower alkyl group.) And the general formula (III) (Wherein, R 4 , R 5 and R 6 each represent a lower alkyl group) in an acyclic ketone having 6 to 9 carbon atoms. A method for producing an amine salt of sulfonic acid.
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