JP2007176839A - メルカプトアルキルホスホニウム化合物の製造法 - Google Patents
メルカプトアルキルホスホニウム化合物の製造法 Download PDFInfo
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- JP2007176839A JP2007176839A JP2005375535A JP2005375535A JP2007176839A JP 2007176839 A JP2007176839 A JP 2007176839A JP 2005375535 A JP2005375535 A JP 2005375535A JP 2005375535 A JP2005375535 A JP 2005375535A JP 2007176839 A JP2007176839 A JP 2007176839A
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- Prior art keywords
- compound
- mercaptoalkylphosphonium
- preparing
- halogenoalkylphosphonium
- thiourea
- 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.)
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title abstract description 13
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical class NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000003573 thiols Chemical class 0.000 claims description 6
- -1 mercaptobutyltriphenylphosphonium compound Chemical class 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract 1
- 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 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- BJDNCJGRAMGIRU-UHFFFAOYSA-M 4-bromobutyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCBr)C1=CC=CC=C1 BJDNCJGRAMGIRU-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HILSVOIVEJVFOZ-UHFFFAOYSA-N triphenyl(4-sulfanylbutyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCS)C1=CC=CC=C1 HILSVOIVEJVFOZ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 3
- DMAYBPBPEUFIHJ-UHFFFAOYSA-N 4-bromobut-1-ene Chemical compound BrCCC=C DMAYBPBPEUFIHJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MXDAUBREDOXDIP-UHFFFAOYSA-N 4-diethylphosphanylbutane-1-thiol Chemical compound CCP(CC)CCCCS MXDAUBREDOXDIP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZAHUZZUGJRPGKW-UHFFFAOYSA-M 3-bromopropyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCBr)C1=CC=CC=C1 ZAHUZZUGJRPGKW-UHFFFAOYSA-M 0.000 description 1
- YLEXRTHICRYWDL-UHFFFAOYSA-N 4-bromobutyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCBr)C1=CC=CC=C1 YLEXRTHICRYWDL-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- CYDUSHQGTMJRHO-UHFFFAOYSA-N but-3-enyl(diethyl)phosphane Chemical compound CCP(CC)CCC=C CYDUSHQGTMJRHO-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- INJBDKCHQWVDGT-UHFFFAOYSA-N chloro(diethyl)phosphane Chemical compound CCP(Cl)CC INJBDKCHQWVDGT-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
【解決手段】ハロゲノアルキルホスホニウム化合物とチオ尿素を反応させてイソチウロニウム塩を合成し、次いでアルカリ分解することにより、容易に単離可能でかつ高収率でメルカプトアルキルホスホニウム化合物が製造できる。
【選択図】なし
Description
Archives of Biochemistry and Biophysics、Vol.322、P.60(1995)
以下、本発明を実施例により、更に具体的に説明する。しかしながら、本発明はこれら実施例のみに限定されるものではない。
トリフェニルホスフィン20g、1,4−ジブロモブタン16.5gをトルエン50ml中に溶解し16時間還流を行った。その後濾過して得られた固体をトルエンで洗浄し、乾燥して32.1gの(4−ブロモブチル)トリフェニルホスホニウムブロミドを得た。トリフェニルホスフィンおよび1,4−ジブロモブタンに対する収率はいずれも88%であった。
(1)で得た(4−ブロモブチル)トリフェニルホスホニウムブロミド11.0g、チオ尿素1.75gを250mlのエタノールに溶解し、約8時間還流を行った。この溶液から約170mlのエタノールを留去し、更に0℃に冷却、放置した後に濾過して得られた固体をクロロホルムで充分に洗浄、乾燥し、イソチウロニウム塩を得た。このイソチウロニウム塩のすべてを充分に脱気したイオン交換水230ml中に溶解し、この中に1.6%水酸化ナトリウム水溶液50mlを、窒素雰囲気下で滴下した。その後、窒素雰囲気下で60℃、2時間攪拌した後室温まで冷却し、この中に5.6%HBr水溶液20mlを添加した。この水相に120mlのクロロホルムを加えて抽出する操作を4回繰り返し、すべてのクロロホルム相を一緒にし、脱溶媒して白色結晶6.0gを得た。この白色結晶の1H−NMR測定およびLC−MS測定を行ったところ、(4−メルカプトブチル)トリフェニルホスホニウムブロミドが98%の純度であった。ブロモブチルトリフェニルホスホニウムに対する収率は59%であった。したがってトリフェニルホスフィンおよび1,4−ジブロモブタンに対する収率は52%であった。
Claims (2)
- ハロゲノアルキルホスホニウム化合物とチオ尿素を反応させてイソチウロニウム塩を生成させ、次いでこのイソチウロニウム塩からチオールを生成することを特徴とするメルカプトアルキルホスホニウム化合物の製造法。
- メルカプトアルキルホスホニウム化合物がメルカプトブチルトリフェニルホスホニウム化合物である請求項1記載のメルカプトアルキルホスホニウム化合物の製造法。
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JP2005375535A JP4495670B2 (ja) | 2005-12-27 | 2005-12-27 | メルカプトアルキルホスホニウム化合物の製造法 |
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JP2005375535A JP4495670B2 (ja) | 2005-12-27 | 2005-12-27 | メルカプトアルキルホスホニウム化合物の製造法 |
Publications (2)
Publication Number | Publication Date |
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JP2007176839A true JP2007176839A (ja) | 2007-07-12 |
JP4495670B2 JP4495670B2 (ja) | 2010-07-07 |
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JP2005375535A Expired - Fee Related JP4495670B2 (ja) | 2005-12-27 | 2005-12-27 | メルカプトアルキルホスホニウム化合物の製造法 |
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JP (1) | JP4495670B2 (ja) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5291814A (en) * | 1976-01-26 | 1977-08-02 | Ciba Geigy Ag | Polyfluoroalkylthioalcohol and ester * their preparation and use |
JP2001302684A (ja) * | 1991-07-15 | 2001-10-31 | La Jolla Pharmaceut Co | 5’−修飾オリゴヌクレオチド |
JP2003128668A (ja) * | 2001-10-22 | 2003-05-08 | Mitsui Chemicals Inc | 新規なポリチオール |
JP2003206287A (ja) * | 2002-01-10 | 2003-07-22 | Mitsui Chemicals Inc | 2,5−ビス(メルカプトメチル)−1,4−ジチアン類の製造方法 |
-
2005
- 2005-12-27 JP JP2005375535A patent/JP4495670B2/ja not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5291814A (en) * | 1976-01-26 | 1977-08-02 | Ciba Geigy Ag | Polyfluoroalkylthioalcohol and ester * their preparation and use |
JP2001302684A (ja) * | 1991-07-15 | 2001-10-31 | La Jolla Pharmaceut Co | 5’−修飾オリゴヌクレオチド |
JP2003128668A (ja) * | 2001-10-22 | 2003-05-08 | Mitsui Chemicals Inc | 新規なポリチオール |
JP2003206287A (ja) * | 2002-01-10 | 2003-07-22 | Mitsui Chemicals Inc | 2,5−ビス(メルカプトメチル)−1,4−ジチアン類の製造方法 |
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