TWI343911B - Process for producing r-2-(4-hydroxyphenoxy)propanoic acid or a salt thereof and its use in making herbicidal products - Google Patents
Process for producing r-2-(4-hydroxyphenoxy)propanoic acid or a salt thereof and its use in making herbicidal products Download PDFInfo
- Publication number
- TWI343911B TWI343911B TW093126006A TW93126006A TWI343911B TW I343911 B TWI343911 B TW I343911B TW 093126006 A TW093126006 A TW 093126006A TW 93126006 A TW93126006 A TW 93126006A TW I343911 B TWI343911 B TW I343911B
- Authority
- TW
- Taiwan
- Prior art keywords
- acid
- salt
- propionic acid
- reducing agent
- mild
- Prior art date
Links
- 150000003839 salts Chemical class 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 16
- AQIHDXGKQHFBNW-ZCFIWIBFSA-N (2r)-2-(4-hydroxyphenoxy)propanoic acid Chemical compound OC(=O)[C@@H](C)OC1=CC=C(O)C=C1 AQIHDXGKQHFBNW-ZCFIWIBFSA-N 0.000 title claims description 3
- 230000002363 herbicidal effect Effects 0.000 title description 2
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 21
- 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 claims description 11
- 235000019260 propionic acid Nutrition 0.000 claims description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- -1 fluazifop-P-buty 1 Substances 0.000 claims description 4
- 241000894007 species Species 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005614 Quizalofop-P-ethyl Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- OSUHJPCHFDQAIT-GFCCVEGCSA-N quizalofop-P-ethyl Chemical group C1=CC(O[C@H](C)C(=O)OCC)=CC=C1OC1=CN=C(C=C(Cl)C=C2)C2=N1 OSUHJPCHFDQAIT-GFCCVEGCSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 2
- 125000003106 haloaryl group Chemical group 0.000 claims 2
- YRTWBGRFODFTKA-UHFFFAOYSA-N 2-acetyloxy-2-oxoacetic acid Chemical compound CC(=O)OC(=O)C(O)=O YRTWBGRFODFTKA-UHFFFAOYSA-N 0.000 claims 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims 1
- 235000017491 Bambusa tulda Nutrition 0.000 claims 1
- 244000025254 Cannabis sativa Species 0.000 claims 1
- 244000020518 Carthamus tinctorius Species 0.000 claims 1
- 235000003255 Carthamus tinctorius Nutrition 0.000 claims 1
- 239000005498 Clodinafop Substances 0.000 claims 1
- 240000006927 Foeniculum vulgare Species 0.000 claims 1
- 235000004204 Foeniculum vulgare Nutrition 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims 1
- 206010036790 Productive cough Diseases 0.000 claims 1
- 125000005577 anthracene group Chemical group 0.000 claims 1
- 239000011425 bamboo Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000003776 cleavage reaction Methods 0.000 claims 1
- YUIKUTLBPMDDNQ-MRVPVSSYSA-N clodinafop Chemical compound C1=CC(O[C@H](C)C(O)=O)=CC=C1OC1=NC=C(Cl)C=C1F YUIKUTLBPMDDNQ-MRVPVSSYSA-N 0.000 claims 1
- 230000032050 esterification Effects 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 claims 1
- PQKBPHSEKWERTG-LLVKDONJSA-N ethyl (2r)-2-[4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy]propanoate Chemical group C1=CC(O[C@H](C)C(=O)OCC)=CC=C1OC1=NC2=CC=C(Cl)C=C2O1 PQKBPHSEKWERTG-LLVKDONJSA-N 0.000 claims 1
- MFSWTRQUCLNFOM-SECBINFHSA-N haloxyfop-P-methyl Chemical group C1=CC(O[C@H](C)C(=O)OC)=CC=C1OC1=NC=C(C(F)(F)F)C=C1Cl MFSWTRQUCLNFOM-SECBINFHSA-N 0.000 claims 1
- 125000005553 heteroaryloxy group Chemical group 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 230000007017 scission Effects 0.000 claims 1
- 210000003802 sputum Anatomy 0.000 claims 1
- 208000024794 sputum Diseases 0.000 claims 1
- RVEZZJVBDQCTEF-UHFFFAOYSA-N sulfenic acid Chemical compound SO RVEZZJVBDQCTEF-UHFFFAOYSA-N 0.000 claims 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 claims 1
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 20
- 150000002148 esters Chemical class 0.000 abstract description 4
- GXEMMZPHKGLVPF-SECBINFHSA-N (2R)-2-hydroxy-2-phenoxypropanoic acid Chemical compound O[C@](C(=O)O)(C)OC1=CC=CC=C1 GXEMMZPHKGLVPF-SECBINFHSA-N 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 5
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- AQIHDXGKQHFBNW-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)propanoic acid Chemical compound OC(=O)C(C)OC1=CC=C(O)C=C1 AQIHDXGKQHFBNW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- AQIHDXGKQHFBNW-LURJTMIESA-N (2s)-2-(4-hydroxyphenoxy)propanoic acid Chemical compound OC(=O)[C@H](C)OC1=CC=C(O)C=C1 AQIHDXGKQHFBNW-LURJTMIESA-N 0.000 description 1
- MONMFXREYOKQTI-REOHCLBHSA-N (2s)-2-bromopropanoic acid Chemical compound C[C@H](Br)C(O)=O MONMFXREYOKQTI-REOHCLBHSA-N 0.000 description 1
- AQIHDXGKQHFBNW-UHFFFAOYSA-M 2-(4-hydroxyphenoxy)propanoate Chemical compound [O-]C(=O)C(C)OC1=CC=C(O)C=C1 AQIHDXGKQHFBNW-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- LONQTZORWVBHMK-UHFFFAOYSA-N [N].NN Chemical compound [N].NN LONQTZORWVBHMK-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000006286 aqueous extract Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- CFQGDIWRTHFZMQ-UHFFFAOYSA-N argon helium Chemical compound [He].[Ar] CFQGDIWRTHFZMQ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 150000002429 hydrazines Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Pyridine Compounds (AREA)
Description
1343911 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種旋光純的R-羥基苯氧基丙酸或其鹽 或酯的製造方法及其在以工業規模製造除草產品方面的用 途〇 【先前技術】 旋光純的R-2-(4 -經基苯氧基）丙酸（3)可經由氫醒（2)與 S-2-函代丙酸（1)(其中X是氣或溴，且較佳是氣）於鹼存 在下的反應製得。
(4) 與自氫礙和S-2-鹵代丙酸製造旋光純的r_2-(4-經基苯 氡基）丙酸有關的問題已有所討論，且相關的先前技術係在 EP352 1 68中回顧。特疋5之，氩酷得到雙酸（4)的過烧基 化反應和氫醌得到高度著色副產物的氧化反應是二個嚴重 的問題。在EP352 1 68中所提供的解決方法是進行複雜的 純化程序。 對於工業規模，希望的是有個簡單的方法來製備基本 上不含過烷基化反應產物、不受高度著色副產物污染而因 1343911 此毋需任何複雜或叩貝純化程序的經基笨氧基）丙 酸。申請人已驚訝地發現到，在R_2_(4_羥基笨氧基）丙酸 製造中使用溫和還原劑得以分離出符合上述標準的產物。 【發明内容】 因此提供的是一種經由氫醌或其鹽與s_2·鹵代丙酸或 其鹽於溫和還原劑存在下的反應來製造旋光純的尺_2_(4_羥 基笨氧基）丙酸或其鹽或酯的方法。 S-2-齒代丙酸是S-2-溴丙酸或s_2_氣丙酸，較佳為s· 2 -氣丙酸。 在一較佳具體實例中，係將過量的氫醌回收以供循環。 較佳的是，由該反應所製得R_2_(4_羥基苯氧基）丙酸 的分離係經由酸化，例如用礦物酸，尤其是鹽酸者，以及 過遽來進行。 若必要或有需要，可藉習知技術將R_2_(4_羥基苯氧基） 丙酸轉化成其鹽或酯。 對於反應較佳的溶劑是水或水混溶性溶劑，例如，醇 戒乙醇，單獨或與水摻混者。 較佳的鹼是鹼金屬氫氧化物，尤其是氫氧化鈉。 較佳而言，反應係於10_100〇(：:的溫度進行更佳係在 3〇-70°C 進行。 ’、 反應可在大氣壓力或高達丨巴的過壓下進行。 有利的是在與氫醌的反應中使用不足的S-2-鹵代丙 釀’如其鹽，通常是〇.25_〇.75莫耳/莫耳，而較佳為Ο.〗·" 1343911 莫耳/莫耳。較佳的鹽是鹼金屬鹽，更佳為鈉鹽。 適當而言’係使用對氫醌為過量化學計算量的鹼。較 佳而言，該鹼係以對氩醌為15至2 5莫耳/莫耳之間使用， 更佳係以1.6-2.0莫耳/莫耳使用。 溫和還原劑較佳係存在於整個反應方法中。其可以固 體或以溶液添加到方法中。在方法期間可進行遞增的添 力σ 0 適當而言’溫和還原劑是中性或荷電低氧化態硫物種， 例如二氧化硫、亞硫酸鹽、亞硫酸氫鹽、連二亞硫酸鹽、 焦亞硫酸鼠鹽、次續酸、亞項酸，如曱胖亞績酸，或是低 氧化態磷物種，例如亞磷酸鹽或次磷酸鹽，或是肼、肼的 衍生物，或是抗壞血酸。 較佳的溫和還原劑是鹼金屬亞硫酸鹽或亞硫酸氫鹽， 例如亞硫酸鈉、亞硫酸氫鈉、亞硫酸鉀或亞硫酸氫鉀。 一種較佳的溫和還原劑是亞硫酸氫鈉。 所用溫和還原劑的量是在佔氫酸量的〇.〇1至1〇重量 %之間，且較佳係在〇 1%至5%之間，而最佳係在〇 5%至 2%之間。 本方法較佳係基本上藉由使用惰性氣層如氮而於氧不 存在下進行。 若需要，可採用本方法經由用R-2-鹵代丙酸取代S-2-鹵代丙酸作為起始物來製造S_2_(4_羥基苯氧基）丙酸。 R-2-(4-羥基苯氧基）丙酸係用於製造數種市售除草劑， 例如快伏草（quizalofop-P-ethyl )、甲基合氣氟 1343911 然後用氫氧化鈉（687克，47%溶液）、亞硫酸氫鈉 (4.02克）與水（1013克）的溶液萃取該氫醌的ΜίΒΚ；萃 取液’同時維持惰性氣氛（氮氣）。將氫醌的水性萃取液 裝到反應燒瓶中，接著裝入新鮮氮醌（172.2克）、47%氫 氧化納溶液（1 1 1‘9克）及亞硫酸氫鈉（1.72克），全都 在ll氣層下進行。將溶液加熱到65DC，並於此溫度下添加 S-2-氣丙酸鈉鹽的水溶液（544.4克，32 5%為自由酸，丨.63 莫耳）°將反應混合物保持在65。<：歷時4小時。添加700 克水並將溫度調整到45°C以下。添加磷酸（120克）將pH 調整到約1 1，然後添加98%硫酸（25〇克）將pH降到 6.5-7.5 ’在這些添加過程令將溫度控制在55QC。如上述經 由用ΜιΒΚ萃取除去未反應的氫醌，然後用98%硫酸將剩 餘水相調整到pH 2±〇.2，並用二份250毫升的MiBK萃取 以萃取出R-2-(4-羥基苯氧基）丙酸。將二萃取液合併，然 後用氫氧化钟（155.5克85%濃度物質）與亞硫酸氫鈉（2.15 克）於水（280克）中的溶液洗滌。 用32%鹽酸將r_2_(4_羥基苯氧基）丙酸鉀鹽的水溶液 酸化到pH 1，並將溫度調整到2(rc。然後將淤漿過濾， 並用水洗務固體產物（一次用260克洗，然後二次用230 克洗）。在洗滌之後，將產物乾燥後稱重和分析。 重量 :188 克 濃度 ：99.4% 雙酸 ：0.3% 產率 ：63% I3439u 顏色吸收度：650nm 為 0.023，420nm 為 0.197 下表提供經由本發明方法及未使用亞硫酸氫鈉的相同 克法所得產物的吸收度數據。 _ 觀察到的顏色 650nm 的 ε 420nm 的 ε 無任何亞硫酸氫鈉 埜對照組 淺掠色 0.153 1.614 對氫醌添加 ^°/。亞硫酸氫鈉 白色 0.061 0.243
【圖式簡單說明】 無 【主要元件符號說明】 i «»>
11
Claims (1)
- 丄34別丄—、申請專利範固 100年1月C日修正替換頁 卜種製造R-2-(4,基苯氧基)丙酸或其鹽的方法，1 係經由氫醇或其鹽與H齒代丙酸或其鹽於溫和還原劑存 在下的反應。 2.根據申請專利範圍第1項之方法，其中該S-2峭代丙 •酸是S-2-氣丙酸。 /.根據中請專利範圍第1或2項之方法，其中係將過量 的氫回收以供徜環。 4 ’根據申α月專利範圍帛丄或2項之方法，其中該溫和還鲁 原劑是中性或荷電低氧化態硫物種、低氧化態磷物種、胼、 餅的竹生物或抗壞血酸。 5.根據申請專利範圍第4項之方法，其中該溫和還原劑 是二氧化硫、亞硫酸鹽、亞硫酸氫鹽、連二亞硫酸鹽、焦 亞硫酸氫鹽、次磺酸、亞磺酸、亞磷酸鹽、次磷酸鹽、肼、 餅的衍生物或抗壞血酸。 6 ·根據申請專利範圍第5項之方法，其中該溫和還原劑 是驗金屬亞硫酸鹽或亞硫酸氫鹽。 鲁 7.—種製備快伏草（quizalofop-P-ethyl)、甲基合氣氟 (haloxyfop-P-methyl )、伏寄普（fluazifop-P-buty 1)、炔 草酸（clodinafop) 、丁基赛伏草（cyha丨ofop-butyl)及芬 殺草（fenoxaprop-P-ethyl )的方法，其係經由a)使氫酷或 其鹽與S-2-鹵代丙酸或其鹽於溫和還原劑存在下反應來製 備R-2-(4-羥基笨氧基）丙酸，b)使R-2-(4-羥基苯氧基）丙醆 與適當的鹵芳基或鹵雜芳基部分反應以得到R-2-((4-芳氧 12 1343911 ____ 100年1月 <日修正替換頁 基或雜芳氧基）苯氧基）丙酸，以及c)將得自步驟b)之酸酯化 以得到快伏草、曱基合氣氟、伏寄普、炔草酸、丁基賽伏 草及芬殺草。 •十一、圖式： (無）13
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| US8071804B2 (en) * | 2007-10-24 | 2011-12-06 | Dow Agrosciences Llc | Process for the manufacture of R-(+)-2-(4-(4-cyano-2-fluorophenoxy)phenoxy)propionic acid esters |
| CN102391104A (zh) * | 2011-09-16 | 2012-03-28 | 南通嘉禾化工有限公司 | 一种（r）-（+）-2-对羟基苯氧基丙酸的合成及其分离工艺 |
| CN102584691A (zh) * | 2012-01-12 | 2012-07-18 | 南京红太阳生物化学有限责任公司 | 一种合成炔草酯的新方法 |
| DE102016221270B4 (de) * | 2015-11-30 | 2019-03-21 | Ford Global Technologies, Llc | Mobile Transportvorrichtung, Fahrzeug und Verfahren zum Bewegen einer mobilen Transportvorrichtung |
| CN111187155B (zh) * | 2020-03-25 | 2022-04-05 | 江苏三吉利化工股份有限公司 | 一种气相催化合成r-(+)-2-(4-羟基苯氧基)丙酸的方法 |
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| JPS5616475A (en) * | 1979-07-19 | 1981-02-17 | Nissan Chem Ind Ltd | Quinoxaline derivative and herbicide containing the same as effective component |
| US4505743A (en) * | 1981-12-31 | 1985-03-19 | Ciba-Geigy Corporation | α-[4-(3-Fluoro-5'-halopyridyl-2'-oxy)-phenoxy]-propionic acid derivatives having herbicidal activity |
| DE3240805A1 (de) * | 1982-11-05 | 1984-05-10 | Hoechst Ag, 6230 Frankfurt | Verfahren zur herstellung von hydroxy-phenoxy-alkancarbonsaeuren |
| US4505753A (en) * | 1983-06-30 | 1985-03-19 | Research One Limited Partnership | Cementitious composite material |
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| JPH0610154B2 (ja) * | 1984-12-28 | 1994-02-09 | 日産化学工業株式会社 | 光学活性２−（４−ヒドロキシフエノキシ）プロピオン酸の製法 |
| FR2634481B1 (fr) * | 1988-07-20 | 1990-09-14 | Rhone Poulenc Chimie | Procede de purification de l'acide d-hydroxyphenoxypropionique |
| JP2514072B2 (ja) * | 1988-07-20 | 1996-07-10 | ダイセル化学工業株式会社 | 光学活性２−（４−ヒドロキシフェノキシ）プロピオン酸の製法 |
| JPH02268134A (ja) * | 1989-04-11 | 1990-11-01 | Tosoh Corp | 光学活性２―（４―ヒドロキシフェノキシ）プロピオン酸の製造法 |
| JPH08134018A (ja) * | 1994-11-04 | 1996-05-28 | Nippon Green Consultant Kk | ３−（２−ヒドロキシフェノキシ）プロピオン酸誘導体の製造方法 |
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| US20060270851A1 (en) | 2006-11-30 |
| JP4965256B2 (ja) | 2012-07-04 |
| JP2007507478A (ja) | 2007-03-29 |
| CA2535039A1 (en) | 2005-05-12 |
| ATE353868T1 (de) | 2007-03-15 |
| US7268249B2 (en) | 2007-09-11 |
| PT1670743E (pt) | 2007-03-30 |
| CN1852884A (zh) | 2006-10-25 |
| WO2005042460A1 (en) | 2005-05-12 |
| BRPI0414925B1 (pt) | 2014-02-18 |
| DE602004004810T2 (de) | 2007-12-06 |
| ZA200601145B (en) | 2007-05-30 |
| GB0322917D0 (en) | 2003-11-05 |
| CN100422129C (zh) | 2008-10-01 |
| EP1670743A1 (en) | 2006-06-21 |
| IL173524A (en) | 2010-11-30 |
| KR101102822B1 (ko) | 2012-01-05 |
| EA200600496A1 (ru) | 2006-10-27 |
| DK1670743T3 (da) | 2007-05-29 |
| ES2282897T3 (es) | 2007-10-16 |
| EA009241B1 (ru) | 2007-12-28 |
| PL1670743T3 (pl) | 2007-06-29 |
| JP2011236244A (ja) | 2011-11-24 |
| KR20060094954A (ko) | 2006-08-30 |
| IL173524A0 (en) | 2006-07-05 |
| BRPI0414925A (pt) | 2006-11-07 |
| EP1670743B1 (en) | 2007-02-14 |
| TW200512185A (en) | 2005-04-01 |
| DE602004004810D1 (de) | 2007-03-29 |
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