CN100422129C - 光学纯2-(4-羟基苯氧基)-丙酸化合物的制备方法 - Google Patents
光学纯2-(4-羟基苯氧基)-丙酸化合物的制备方法 Download PDFInfo
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- AQIHDXGKQHFBNW-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)propanoic acid Chemical class OC(=O)C(C)OC1=CC=C(O)C=C1 AQIHDXGKQHFBNW-UHFFFAOYSA-N 0.000 title description 2
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 43
- 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 claims description 17
- 230000002829 reductive effect Effects 0.000 claims description 14
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 13
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 244000025254 Cannabis sativa Species 0.000 claims description 7
- 239000005502 Cyhalofop-butyl Substances 0.000 claims description 7
- TYIYMOAHACZAMQ-CQSZACIVSA-N Cyhalofop-butyl Chemical group C1=CC(O[C@H](C)C(=O)OCCCC)=CC=C1OC1=CC=C(C#N)C=C1F TYIYMOAHACZAMQ-CQSZACIVSA-N 0.000 claims description 7
- 239000005614 Quizalofop-P-ethyl Substances 0.000 claims description 7
- 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 7
- 150000001345 alkine derivatives Chemical class 0.000 claims description 6
- YUVKUEAFAVKILW-UHFFFAOYSA-N 2-(4-{[5-(trifluoromethyl)pyridin-2-yl]oxy}phenoxy)propanoic acid Chemical compound C1=CC(OC(C)C(O)=O)=CC=C1OC1=CC=C(C(F)(F)F)C=N1 YUVKUEAFAVKILW-UHFFFAOYSA-N 0.000 claims description 5
- MPPOHAUSNPTFAJ-UHFFFAOYSA-N 2-[4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy]propanoic acid Chemical compound C1=CC(OC(C)C(O)=O)=CC=C1OC1=NC2=CC=C(Cl)C=C2O1 MPPOHAUSNPTFAJ-UHFFFAOYSA-N 0.000 claims description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 5
- MFSWTRQUCLNFOM-UHFFFAOYSA-N methyl 2-(4-{[3-chloro-5-(trifluoromethyl)pyridin-2-yl]oxy}phenoxy)propanoate Chemical group C1=CC(OC(C)C(=O)OC)=CC=C1OC1=NC=C(C(F)(F)F)C=C1Cl MFSWTRQUCLNFOM-UHFFFAOYSA-N 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 125000003106 haloaryl group Chemical group 0.000 claims description 3
- 125000005216 haloheteroaryl group Chemical group 0.000 claims description 3
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 3
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 3
- 235000019252 potassium sulphite Nutrition 0.000 claims description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 125000005553 heteroaryloxy group Chemical group 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 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 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 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
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- -1 2-(4-hydroxyphenoxy)-phenylpropionic acid compound Chemical class 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RVEZZJVBDQCTEF-UHFFFAOYSA-N sulfenic acid Chemical compound SO RVEZZJVBDQCTEF-UHFFFAOYSA-N 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
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005498 Clodinafop Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 208000034809 Product contamination Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000006286 aqueous extract Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 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 description 1
- 230000000295 complement effect Effects 0.000 description 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 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- VAIZTNZGPYBOGF-CYBMUJFWSA-N fluazifop-P-butyl Chemical group C1=CC(O[C@H](C)C(=O)OCCCC)=CC=C1OC1=CC=C(C(F)(F)F)C=N1 VAIZTNZGPYBOGF-CYBMUJFWSA-N 0.000 description 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 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- BACHBFVBHLGWSL-JTQLQIEISA-N rac-diclofop methyl Natural products C1=CC(O[C@@H](C)C(=O)OC)=CC=C1OC1=CC=C(Cl)C=C1Cl BACHBFVBHLGWSL-JTQLQIEISA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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)
Abstract
一种在温和还原剂存在下，通过对苯二酚或其盐与S-卤代丙酸或其盐反应以制备光学纯R-羟基苯氧基丙酸或其盐或酯的方法。
Description
本发明涉及光学纯R-羟基苯氧基丙酸或其盐或酯的制备方法以及其在以工业规模制备除草产品中的应用。
光学纯R-2-(4-羟基苯氧基)丙酸(3)可通过对苯二酚(2)与S-2-卤代丙酸(1)在碱存在下反应而制备，其中X是氯、溴且优选是氯。
在EP352168中已经讨论了与从对苯二酚和S-2-卤代丙酸制备光学纯R-2-(4-羟基苯氧基)丙酸相关的问题并综述了相关现有技术。特别地，两个严重的问题是对苯二酚过度-烷基化生成二-酸(4)和对苯二酚氧化生成深色副产物。EP352168中提供的解决方案是进行复杂的纯化过程。
在工业规模上，基本上不含过度-烷基化产物的制备R-2-(4-羟基苯氧基)-丙酸的简单方法是合意的，其没有被深色副产物污染并因此不需要复杂或昂贵的纯化过程。本申请人令人惊奇地发现在制备R-2-(4-羟基苯氧基)丙酸中应用温和还原剂可使得所分离的产物达到上述标准。
因此提供了一种在温和还原剂存在下，通过对苯二酚或其盐与S-2-卤代丙酸或其盐反应以制备R-2-(4-羟基苯氧基)丙酸的方法。
S-2-卤代丙酸是S-2-溴代丙酸或S-2-氯代丙酸，优选S-2-氯代丙酸。
在一个优选的实施方案中，回收过量的对苯二酚循环利用。
优选地，通过酸化如使用矿酸特别是盐酸和过滤分离通过该反应所产生的R-2-(4-羟基苯氧基)丙酸。
如果必要或需要，可通过常规技术将R-2-(4-羟基苯氧基)丙酸转化为其盐或酯。
该反应的优选溶剂是水或水混溶性溶剂如甲醇或乙醇，单独使用或与水混合使用。
优选的碱是碱金属氢氧化物特别是氢氧化钠。
优选地，该反应在10-100℃的温度下进行，更优选30-70℃。
该反应可以在大气压或至多过量1巴的压力下进行。
与对苯二酚反应时，使用不足量的S-2-卤代丙酸(为其盐)是有利的，通常为0.25-0.75mol/mol且优选0.3-0.6mol/mol。优选的盐是碱金属盐，更优选钠盐。
合适地，使用基于对苯二酚超过化学计量的碱。优选地，所用的碱基于对苯二酚为1.5-2.5mol/mol且更优选为1.6-2.0mol/mol。
温和还原剂优选存在于整个过程。其可以作为固体或作为溶液加入方法中。在该过程中可进行增量添加。
合适地，温和还原剂是中性或带电荷的低氧化态硫物质，比如二氧化硫、亚硫酸盐、亚硫酸氢盐(bisulphite)、连二亚硫盐(hydrosulphite)、偏酸式亚硫酸盐、次磺酸(sulphenic acid)、亚磺酸(sulphinic acid)例如甲脒亚磺酸或低氧化态磷物质比如亚磷酸盐或次磷酸盐，或肼，肼衍生物或抗坏血酸。
优选的温和还原剂是碱金属亚硫酸盐或酸式亚硫酸盐比如亚硫酸钠、亚硫酸氢钠、亚硫酸钾或亚硫酸氢钾。
优选的温和还原剂是亚硫酸氢钠。
所用的温和还原剂的量为基于对苯二酚量的0.01％至10％重量且优选0.1％至5％且最优选0.5％至2％。
该方法优选通过采用惰性气体氛例如氮气在基本没有氧存在下进行。
如果需要，通过使用R-2-卤代丙酸替代S-2-卤代丙酸作为起始原料，可以采用该方法来制备S-2-(4-羟基苯氧基)丙酸。
R-2-(4-羟基苯氧基)丙酸被用于制造若干商业除草剂比如精喹禾灵(quizalofop-P-ethyl)、精氟吡甲禾灵(haloxyfop-P-methyl)、精吡氟禾草灵(fluazifop-P-butyl)、炔草酯(clodinafop)、氰氟草酯(cyhalofop-butyl)和精噁唑禾草灵(fenoxaprop-P-ethyl)。
因此，本发明另一方面提供了一种制备精喹禾灵、精氟吡甲禾灵、精吡氟氯禾草灵、炔草酯、氰氟草酯或精噁唑禾草灵的方法：a)在温和还原剂存在下，通过对苯二酚或其盐与S-2-卤代丙酸或其盐反应制备R-2-(4-羟基苯氧基)丙酸，b)使R-2-(4-羟基苯氧基)丙酸与适当卤代-芳基或卤代-杂芳基部分反应以生成R-2-((4-芳氧基或杂芳氧基)苯氧基)丙酸以及c)酯化由步骤b)得到的酸以生成精喹禾灵、精氟吡甲禾灵、精吡氟禾草灵、炔草酯、氰氟草酯或精噁唑禾草灵。
适当的卤代-芳基或卤代-杂芳基部分是精喹禾灵的2-卤代-6-氯-喹喔啉；精氟吡甲禾灵的2-卤代-3-氯-5-三氟甲基吡啶；精吡氟禾草灵的2-卤代-5-三氟甲基吡啶；炔草酯的2-卤代-5-氯-3-氟吡啶；氰氟草酯的4-卤代-3-氟苄腈以及精噁唑禾草灵的2-卤代-6-氯-苯并噁唑。
本领域技术人员公知R-2-(4-羟基苯氧基)-丙酸转化为步骤b)的酸和步骤c)的酯的方法，例如参见Advanced Organic Chemistry，Jerry March，John Wiley & Sons，1992，p393。
现将参照下面的实施例进一步举例说明本发明。
通过HPLC确定产品质量并如下确定颜色。将大约10克的R-2-(4-羟基苯氧基)丙酸悬浮于10ml水中，使用氢氧化钾溶液调节至pH 7，之后另外使用水补足至100ml。于420和650nm处测量溶液的吸光度并表示为消光系数(ε，1摩尔溶液和1cm光程长度的吸光度)。
实施例1
在亚硫酸氢钠存在下制备R-2-(4-羟基苯氧基)丙酸，并循环使用对苯二酚
步骤1
将对苯二酚(574g，5.22mol)装入反应瓶中，之后加入亚硫酸氢钠(5.74g)和水(1014g)，建立氮气氛围。搅拌该混合物并加热至50℃，加入47％的氢氧化钠水溶液(799.5g，9.39mol)。将该溶液加热至65℃，加入S-2-氯丙酸钠盐的水溶液(544.4g，32.5％以游离酸计，1.63mol)。该反应混合物于65℃维持4小时。之后，总反应物重为2937.6g并含有8.60％的R-2-(4-羟基苯氧基)丙酸，相当于252.54产物或85％收率。加入700g水并将温度调至低于45℃。加入磷酸(120g)调节pH至约11，然后加入98％硫酸(250g)使得pH降低至6.5-7.5，添加过程中将温度控制于55℃。然后连续使用四份638ml甲基异丁基酮(MiBK)萃取该溶液，得到对苯二酚的MiBK溶液，备于下一循环使用。
步骤2
然后维持惰性气体(氮气)，使用氢氧化钠(687g 47％溶液)、亚硫酸氢钠(4.02g)和水(1013g)的溶液萃取对苯二酚的MiBK萃取物。将对苯二酚的含水萃取物装入反应瓶中，随后加入新鲜的对苯二酚(172.2g)、47％氢氧化钠溶液(111.9g)和亚硫酸氢钠(1.72g)，均在氮气氛围下进行。将该溶液加热至65℃并在此温度加入S-2-氯丙酸钠盐的水溶液(544.4g，32.5％以游离酸计，1.63mol)。该反应混合物于65℃维持4小时。加入700g水并将温度调至低于45℃。加入磷酸(120g)调节pH至约11，然后加入98％硫酸(250g)使得pH降低至6.5-7.5，添加过程中将温度控制于55℃。如上通过使用MiBK萃取除去未反应的对苯二酚，然后使用98％硫酸调节残留水相至pH 2±0.2，使用两份250ml的MiBK萃取以提取R-2-(4-羟基苯氧基)丙酸。合并两份萃取物并使用氢氧化钾(155.5g的85％强度)和亚硫酸氢钠(2.15g)在水(280g)中的溶液洗涤。
用32％盐酸酸化R-2-(4-羟基苯氧基)丙酸钾盐的水溶液至pH 1并将温度调至20℃。过滤该淤浆并使用水洗涤(一次洗涤260g，然后两次洗涤230g)固体产物。洗涤后，干燥产物、称重并分析。
重量188g
纯度99.4％
二酸0.3％
收率63％
颜色吸光度于650nm处为0.023，于420nm处为0.197
下表给出了通过本发明方法和未使用亚硫酸氢钠的相同方法所获得产品的吸光度数据
| 反应 | 观察到颜色 | ε/650nm | ε/420nm |
| 未用亚硫酸氢钠的对照 | 浅褐色 | 0.153 | 1.614 |
| 基于对苯二酚加入5％亚硫酸氢钠 | 白色 | 0.061 | 0.243 |
Claims (5)
1. 一种在温和还原剂存在下通过对苯二酚或其盐与S-2-卤代丙酸或其盐反应制备R-2-(4-羟基苯氧基)丙酸或其盐的方法，其中所述温和还原剂选自亚硫酸钠、亚硫酸氢钠、亚硫酸钾或亚硫酸氢钾。
2. 根据权利要求1的方法，其中S-2-卤代丙酸是S-2-氯代丙酸。
3. 根据权利要求1或2的方法，其中回收过量的对苯二酚循环利用。
4. 根据权利要求1或2的方法，其中所述温和还原剂是亚硫酸氢钠。
5. 一种制备精喹禾灵、精氟吡甲禾灵、精吡氟禾草灵、炔草酯、氰氟草酯或精噁唑禾草灵的方法，该方法包括：a)在选自亚硫酸钠、亚硫酸氢钠、亚硫酸钾或亚硫酸氢钾的温和还原剂存在下，通过对苯二酚或其盐与S-2-卤代丙酸或其盐反应制备R-2-(4-羟基苯氧基)丙酸，b)使R-2-(4-羟基苯氧基)丙酸与适当卤代-芳基或卤代-杂芳基部分反应以得到R-2-((4-芳氧基或杂芳氧基)苯氧基)丙酸以及c)酯化由步骤b)得到的酸以生成精喹禾灵、精氟吡甲禾灵、精吡氟禾草灵、炔草酯、氰氟草酯或精噁唑禾草灵。
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| BRPI0818376A2 (pt) * | 2007-10-24 | 2015-04-14 | Dow Agrosciences Llc | Processo aperfeiçoado para a fabricação dos ésteres do ácido (r)-(+)-2-(4-(4-ciano-2-fluorofenóxi) fenóxi propiônico |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR763374A (fr) * | 1933-01-23 | 1934-04-30 | Manuf De Prod Chim Purs | Procédé pour la préparation des antipodes optiques de corps doués de pouvoir rotatoire |
| 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 |
| US4532346A (en) * | 1982-11-05 | 1985-07-30 | Hoechst Aktiengesellschaft | Process for the preparation of hydroxyphenoxy-alkanecarboxylic acids |
| US4625053A (en) * | 1984-12-28 | 1986-11-25 | Nissan Chemical Industries Ltd. | Process for preparing optically active 2-(4-hydroxy-phenoxy) propionic acid compounds |
| US4981998A (en) * | 1988-07-20 | 1991-01-01 | Rhone-Poulenc Chimie | Process for the preparation and purification of D-hydroxyphenoxypropionic acid |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5616475A (en) * | 1979-07-19 | 1981-02-17 | Nissan Chem Ind Ltd | Quinoxaline derivative and herbicide containing the same as effective component |
| US4505753A (en) * | 1983-06-30 | 1985-03-19 | Research One Limited Partnership | Cementitious composite material |
| JPS60123443A (ja) * | 1983-12-07 | 1985-07-02 | Nissan Chem Ind Ltd | ２−（４−ヒドロキシフェノキシ）アルカン酸の製造方法 |
| 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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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR763374A (fr) * | 1933-01-23 | 1934-04-30 | Manuf De Prod Chim Purs | Procédé pour la préparation des antipodes optiques de corps doués de pouvoir rotatoire |
| 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 |
| US4532346A (en) * | 1982-11-05 | 1985-07-30 | Hoechst Aktiengesellschaft | Process for the preparation of hydroxyphenoxy-alkanecarboxylic acids |
| US4625053A (en) * | 1984-12-28 | 1986-11-25 | Nissan Chemical Industries Ltd. | Process for preparing optically active 2-(4-hydroxy-phenoxy) propionic acid compounds |
| US4981998A (en) * | 1988-07-20 | 1991-01-01 | Rhone-Poulenc Chimie | Process for the preparation and purification of D-hydroxyphenoxypropionic acid |
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