CN1059207C - 糖精羧酸和羧酸酯的制备 - Google Patents
糖精羧酸和羧酸酯的制备 Download PDFInfo
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- CN1059207C CN1059207C CN95195020A CN95195020A CN1059207C CN 1059207 C CN1059207 C CN 1059207C CN 95195020 A CN95195020 A CN 95195020A CN 95195020 A CN95195020 A CN 95195020A CN 1059207 C CN1059207 C CN 1059207C
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- Prior art keywords
- alkyl
- hydrogen
- methyl
- formula
- asccharin
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 32
- 230000002363 herbicidal effect Effects 0.000 title claims description 8
- 229940081974 saccharin Drugs 0.000 title abstract 2
- 235000019204 saccharin Nutrition 0.000 title abstract 2
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 title abstract 2
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 title description 12
- 150000002148 esters Chemical class 0.000 title description 5
- -1 saccharin carboxylic acids Chemical class 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 20
- 239000000460 chlorine Substances 0.000 claims abstract description 17
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 8
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 7
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims abstract description 6
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 35
- 238000002360 preparation method Methods 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 19
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 230000012010 growth Effects 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 238000006473 carboxylation reaction Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 5
- 150000003818 basic metals Chemical class 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 238000005810 carbonylation reaction Methods 0.000 claims description 4
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 150000003672 ureas Chemical class 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract description 5
- 125000001424 substituent group Chemical group 0.000 abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 3
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 abstract 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- CEJDLTNRMCYNBU-UHFFFAOYSA-N 4-chloro-1,1,3-trioxo-1,2-benzothiazole-5-carboxylic acid Chemical compound OC(=O)C1=CC=C2S(=O)(=O)NC(=O)C2=C1Cl CEJDLTNRMCYNBU-UHFFFAOYSA-N 0.000 abstract 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract 1
- 229940054334 silver cation Drugs 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- 241000196324 Embryophyta Species 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000009333 weeding Methods 0.000 description 7
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical compound C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 235000019439 ethyl acetate Nutrition 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- CGKASBWNGYDCQW-UHFFFAOYSA-N 1,2-benzothiazole-5-carboxylic acid Chemical compound OC(=O)C1=CC=C2SN=CC2=C1 CGKASBWNGYDCQW-UHFFFAOYSA-N 0.000 description 4
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
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- 239000013543 active substance Substances 0.000 description 4
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- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
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- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 238000009331 sowing Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
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- 241000335053 Beta vulgaris Species 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
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- 150000001263 acyl chlorides Chemical class 0.000 description 3
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
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- C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
- C07D275/06—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to the ring sulfur atom
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/08—Formation or introduction of functional groups containing oxygen of carboxyl groups or salts, halides or anhydrides thereof
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- Hydrogenated Pyridines (AREA)
Abstract
式Ⅰ的糖精羧酸和羧酸酯可通过如下方法制备:
其中取代基具有如下定义:
L和M是氢,烷基,烷氧基,烷硫基,氯,氰基,烷基磺酰基,硝基或三氟甲基;
Z是氢,烷基,环烷基,烷基,芳基或芳烷基;
R是H或C1-C6烷基,
使式Ⅱ的溴代或碘代糖精衍生物
其中L,M和Z定义如上,或如果Z≠H,式Ⅲ化合物
在加压条件下,钯,镍,钴或铑过渡金属和碱存在下与一氧化碳和水或C1-C6醇反应。
Description
本发明涉及式I的糖精羧酸和糖精羧酸酯的制备其中取代基具有如下定义:L和M是氢,烷基,烷氧基,烷硫基,氯,氰基,烷基磺酰基,硝基或三氟甲基;Z是氢,烷基,环烷基,芳基或芳烷基;R是H或C1-C6烷基。
本发明还涉及具有除草活性的精选的糖精衍生物Ia和其中OR基团被其它基团替代的用作制备糖精衍生物中间体的化合物。这些二级产物是平行的德国申请的主题。
本发明还涉及使用化合物Ia’控制不希望的植物的生长的方法。
根据现有技术,例如DE-A 36 07 343,在苯环上含有羧基取代基的糖精衍生物可按照下列反应式获得:这些羧基官能基通过氧化甲基被引入,且氧化的环同时关闭(也可参见1936年德国Reichs专利(DRP)671 788)此方法的缺点在于存在多个可氧化官能基,不能保证选择性氧化。另外,整个反应过程的步骤数目很多,因此,不可避免地导致产率下降。
美国专利5,034,534描述了一种通过在钯络合物和至少一种烷基膦配体存在下羰基化氯代的芳香磺酰胺制备糖精衍生物的方法。从此文献看不出可向糖精结构的苯环中引入羧基官能基的内容。
本发明的目的是在避免剧烈的氧化方法,如使用高锰酸钾的条件下,得到在苯环上具有羧基官能基的式I糖精衍生物。
我们发现此目的是通过下面制备式I糖精衍生物的方法完成的。它包括使式II的溴代或碘代糖精衍生物其中L,M和Z定义如上,或如果Z≠H,则为式III化合物在加压条件下,钯,镍,钴或铑过渡金属催化剂和碱存在下与一氧化碳和水或C1-C6醇反应,制备式I的糖精衍生物。
式I中的烷基优选低分子量烷基,例如,具有1-6个碳原子。同样适用于烷氧基或烷硫基和烷基磺酰基。环烷基是例如C3-C8环烷基,如环戊基,环己基或环丙基。芳基是例如可含有惰性取代基的苯基。芳烷基是例如,可含有惰性取代基的苯基-C1-C4-烷基,如苄基或苯乙基。反应式为:
过渡金属催化使用羰基化试剂将芳香卤化物转化为相应的羰基或羧基化合物在现有技术中是已知的,例如,从US 2,640,071;US 3,988,358;US4,845,273;Urata等在有机化学杂志(J.Org.Chem.)56(1991),4320ff;Pri-Bar,Buchman在有机化学杂志53(1988),624ff;;US 4,990,657,GB-A2,261,662和M.Foa等在有机金属化学杂志(J.Organometallic Chem.)285(1985),293ff.中可知道。
但是本发明的方法中使用特定的起始物II和III是令人惊奇的。特别是,按照本发明的方法以起始物中存在官能基为基础的成功是无法预料的。另外,也没有想到起始物III可按照本发明经过此路线通过消除伯胺ZNH2直接得到羧化的糖精衍生物I。
催化剂镍,钴,铑且特别优选钯,它们可以金属形式或常用盐的形式,如卤化物,例如PdCl2,RhCl3·3H2O,乙酸盐例如Pd(OAc)2,氰化物等以已知化合价的形式存在。还可以与叔膦,金属烷基羰基,金属羰基的金属配位化合物,例如,Co2(CO)8,Ni(CO)4,与叔膦的金属羰基配位化合物,例如(PPh3)2Ni(CO)2,或过渡金属盐与叔膦的配位化合物的形式存在。上述情况中,优选钯作为催化剂。这里的膦配体的性质可在较大范围内变化。例如,可以下式代表:其中n是1,2,3或4,且基团R1到R4是低分子量烷基,例如,C1-C6-烷基,芳基或C1-C4-烷基-芳基,例如苄基,苯乙基或芳氧基。芳基是,例如萘基,蒽基,且优选未取代或取代的苯基,只需考虑取代基对羧化反应的惰性,否则它可在较大范围内变化且包括所有惰性C-有机基团如C1-C6-烷基,例如甲基,羧基如COOH,COOM(M是,例如碱金属,碱土金属或铵盐),或通过氧键合的C-有机基团,如C1-C6-烷氧基。
可按已知方法制备膦络合物,例如在开始列举的文献中。例如,常用的商业上可得到的金属盐如PdCl2或Pd(OCOCH3)2用作起始物,并加入膦,例如P(C6H5)3,P(正-C4H9)3,PCH3(C6H5)2或1,2-双(二苯基膦)乙烷。下面是可列举的催化剂的例子:1,3-双(二异丙基膦)丙烷,三-对-茴香基膦,三-邻-甲苯基膦,1,2-双(二苯基膦)丁烷,三苯基亚磷酸酯。
催化剂也可键合到聚合的载体上。这类催化剂的制备描述于,特别是,美国专利5,034,534或美国专利4,426,318。
膦的使用量,基于过渡金属,一般为0-20,优选0.1-10mol当量,特别优选1-5mol当量。
过渡金属的用量无特别限制,但考虑到经济原因,优选使用较小量,例如,基于起始物II或III,使用0.1-10mol%,优选1-5mol%。
基于起始物II或III,与一氧化碳或至少等摩尔量的水反应,用于制备糖精羧酸。即,R=H。优选使用至少等摩尔的醇用于制备酯,即,R=OC1-C6-烷基,例如,OCH3,OC2H5,O-正-C3H7,O-异-C3H7,O-正-C4H9,O-异-C4H9,O-叔-C4H9,O-正-C5H11,O-正-C6H13。反应组分水或C1-C6-烷基-OH同时也可用作溶剂,即,对最大使用量无特别限制。
但是,根据起始物和所使用的催化剂的性质,使用其它惰性溶剂或用于羧化的碱代替反应组分作为溶剂也是优选的。在这种情况下,反应组分水或醇的使用量一般为1-10,优选1-5mol当量,基于II或III。
用于羧化反应的惰性溶剂是常规溶剂如烃,例如,甲苯,二甲苯,己烷,戊烷,环己烷,醚如甲基叔丁基醚,四氢呋喃,二噁烷,二甲氧基乙烷,取代的酰胺如二甲基甲酰胺,过取代的脲如四-C1-C4-烷基脲,或腈如苄腈或乙腈。
在优选的制备方案中,一个反应组分,特别是碱是过量使用的,以便不再另加入溶剂。
适于此反应的碱是所有在反应中可结合碘化氢或释放溴化氢的惰性碱。这里可列举的例子包括叔胺如三乙胺,环胺如N-甲基哌啶或N,N’-二甲基哌嗪,吡啶,酰胺如N,N-二甲基甲酰胺,碱金属或碱土金属氢氧化物,碳酸盐或碳酸氢盐,和四烷基取代的脲衍生物如四-C1-C4-烷基脲,例如四甲基脲。
对碱的用量无特别限制,一般使用1-10,优选1-5mol。如果碱同时用作溶剂,其原则是使用比例使反应组分溶解,为了节省花费,使用最小体积的反应容器并保证反应组分之间最大限度的接触,没有必要过量很多。
在反应过程中,调节一氧化碳的压力,使其对于II或III总是过量的。优选一氧化碳在室温的压力为1-250巴,特别优选5-150巴。
通常,在20-250℃,优选30-150℃连续或分批进行羰基化反应。在分批进行时,将一氧化碳连续适量地加入反应混合物以保持稳定的压力。
可用常规方法,例如,通过蒸馏将产物从所得反应混合物中分离出来。
用于反应的起始物II和III是已知的或可用已知方法制备。它们既可通过高锰酸盐氧化碘代的2-甲基苯磺酰胺制备,也可通过Sandmeyer反应从氨基糖精制备。氨基糖精可用已知方法从还原硝基糖精制备,它们在下列文献中有报道(Kastle,美国化学杂志(Amer.Chem.Journal)11(1889),184或DRP 551423(1930))或按照已知方法从合适的硝基苯衍生物(Liebigs纪要(Ann.)669(1963),85)或苯磺酰胺合成。
它们可按照实施例1-12类似的制备方法得到。
糖精衍生物I用于制备作物保护剂,特别是用于制备如描述于平行的德国申请DE-A 44 27 995中的式E结构的除草剂。其中取代基具有如下含义:L和M是氢,C1-C4-烷基,C1-C4-烷氧基,C1-C4烷硫基,氯,氰基,甲磺酰基,硝基或三氟甲基;Z是氢,C1-C4烷基,C3-C8环烷基,C3-C6链烯基,C3-C5炔基,C1-C4酰基或苄基或未取代或被卤素或C1-C4烷基取代的苯基;Q是基团CO-J,J是2位链连的环己烷-1,3-二酮环,具有式A1结构其中既可以Ra到Rf是氢或甲基,也可以是,Ra,Rb,Rc,Re和Rf是氢,Rd是2-乙基硫代丙基,四氢吡喃-3-基、四氢吡喃-4-基、四氢硫代吡喃-3-基或1-甲基硫代环丙基,或,如果Ra,Rd,Re是氢且Rf是甲基,Rb和Rc形成三员环,则得到式A3的2位链连的双环[4.1.0]-庚烷环。
反应流程的第一步,酰化是按照已知方法进行,例如,在辅助的碱存在下,将式A2的酰氯加到式A2或A3的环己烷-1,3-二酮的溶液或悬浮液中。在此情况下优选使用等摩尔量的反应剂和辅助碱。合适的辅助碱是叔烷基胺,吡啶或碱金属碳酸盐,而溶剂可使用,例如,二氯甲烷,乙醚,甲苯或乙酸乙酯。在加入酰氯的过程中,优选将反应混合物冷却至0-10℃,然后在25-50℃搅拌,直到反应完成。分离纯化(working up)可将反应混合物倒入水中,用二氯甲烷萃取。干燥有机相和除去溶剂后,粗品烯醇酯不需纯化即可进行重排。例如,在EP-A 186 118或US4,780,127中可找到环己烷-1,3-二酮的苯甲酰基烯醇酯的制备实施例。
烯醇酯重排成式E的化合物适合在20-40℃于溶剂中,在辅助碱存在下,且在氰基化合物作为催化剂的帮助下进行。可使用的溶剂有例如乙腈,二氯甲烷,1,2-二氯乙烷,乙酸乙酯或甲苯。优选的溶剂是乙腈。合适的辅助碱是四烷基胺,吡啶或碱金属碳酸盐,它的用量从等摩尔到最多4倍量的过量。优选的辅助碱为加倍用量的三乙胺。合适的催化剂是氰化钾或丙酮氰醇,使用量为1-50mol%,基于烯醇酯计。优选使用用量为10mol%的丙酮氰醇。如在EP-A 186 118或US 4,780,127中可找到环己烷-1,3-二酮的氰化物催化的烯醇酯的重排的实施例。
为了分离纯化(working up)可将反应混合物酸化,例如,用稀释的无机酸如5%浓度盐酸或硫酸并使用二氯甲烷或乙酸乙酯萃取。为了纯化,将萃取物用冷却的5-10%浓度的碱金属碳酸盐溶液萃取,将最后的产物转入水相。酸化水溶液沉淀出式E产物,或再用二氯甲烷萃取,干燥并除去溶剂得到式E产物。
作为起始产物的式A2和A3的1,3-二酮是已知的或可用已知方法制备(参见EP-A 71 707,EP-A 142 741,EP-A 243 313,US 4249 937和WO 92/13821)。环己烷-1,3-二酮和双甲酮是商业可得的化合物。
也可使用类似的方法,用吡唑-4-基基团代替环己烷-1,3-二酮环制备糖精衍生物E。在这种情况下,使用起始产物A4此类型的除草活性二级产物在平行的德国申请DE-A 44 27 997中有描述。
式I的糖精羧酸或酯不仅可作为中间体制备具有除草活性的二级产物,它本身还具有很好的除草活性。因此,可使用化合物Ia’作为除草剂或使用化合物Ia’控制不希望的植物生长的方法是本发明的另一个方面特征。其中取代基具有如下含义:L和M是氢,C1-C4烷基,C1-C4烷氧基,C1-C4烷硫基,氯,氰基,甲磺酰基,硝基或三氟甲基;Z是氢,C1-C4烷基,C3-C8环烷基,苄基或苯基,它们中苯环可以是未取代或被C1-C4烷基取代;R是H或C1-C6烷基。
本发明还涉及新的式Ia的具有除草活性的糖精羧酸或羧酸酯其中取代基具有如下含义:L和M是氢,C1-C4烷基,C1-C4烷氧基,C1-C4烷硫基,氯,氰基,甲磺酰基,硝基或三氟甲基;Z是氢,C1-C4烷基,C3-C8环烷基,苄基或苯基,它们中苯环可以是未取代或被C1-C4烷基取代;R是H或C1-C6烷基,条件是如果L和M是氢,Z不是甲基,苯基,氢或碱金属或银正离子,且不包括5-羧基-7-甲基糖精和5-羧基-4-氯糖精。
优选式Ia的羧酸(R=H)在苯环上还具有一或两个取代基,例如具有L=C1-C4烷基,例如甲基,氯,甲硫基,甲磺酰基或C1-C4烷氧基如甲氧基且M=氢或C1-C4烷基或烷氧基,例如甲基或甲氧基。
化合物Ia或Ia’可以其农业可用盐的形式存在,盐的性质一般关系不大。一般地,对I或Ia’的除草作用无不利的影响的那些碱的盐都适用。
合适的盐为碱金属盐,优选钠盐和钾盐,碱土金属盐,优选钙盐或镁盐,和过渡金属盐,优选银,铜,锌和铁盐,以及铵盐,它可带有1-3个C1-C4烷基或羟基-C1-C4烷基取代基和/或苯基或苄基取代基,优选二异丙基铵,四甲基铵,四丁基铵,三甲基苄基铵和三甲基-(2-羟乙基)铵盐,鏻盐,锍盐,优选三(C1-C4)烷基锍盐,和氧化锍盐,优选三(C1-C4)烷基氧化锍盐。
化合物Ia或Ia’或含有它们的除草组合物和它们环境可允许的盐,例如,碱金属盐,碱土金属盐或氨和胺或含有它们的除草组合物可用于有效控制作物如小麦,稻米,玉米,大豆和棉花中的阔叶杂草和牧草(grass)杂草而对作物无明显伤害。此效果在较低用量就可以达到。
考虑到各种应用方法,化合物Ia,Ia’或含有它们的组合物可用于一系列作物用于除去不希望的植物。合适的作物的例子如下:洋葱,凤梨,落花生,天门冬属officinalis,甜菜(Beta vulgaris spp.altissima),Beta vulgaris spp.rapa,芸苔属(Brassica napus var.napus),大头菜,芜菁(Brassica rapa var.silvestris),茶,红花,美国山核桃,柠檬,甜橙,小果咖啡(中果咖啡,大果咖啡),黄瓜,狗芽菜,野胡罗卜,油棕,欧洲草莓,大豆,陆地棉(树棉,草棉,Gossypiumvitifolium),向日葵,橡胶树,大麦,啤酒花,甘薯,胡桃,兵豆,亚麻,番茄(Lycopersicon lycopersicum),苹果类,木薯,紫苜蓿,芭蕉属,烟草(黄花烟草),油橄榄,稻,金甲豆,菜豆,欧洲云杉,松属,Pisumsativum,欧洲甜樱桃,桃,西洋梨,茶蔗子(Ribes sylvestre),蓖麻,甘蔗属officinarum,黑麦,马铃薯,栽培种高粱(高粱野生种之一),可可,红三叶草,普通小麦,硬粒小麦,蚕豆,葡萄和玉米。
而且,化合物Ia和Ia’还可用于对Ia或Ia’或其它除草剂已具有较大耐受性的作物,这些作物的耐受性是通过育种和/或基因工程的方法获得的。
可在苗前或苗后使用除草组合物或活性化合物。如果一些作物对活性化合物是低耐受性的,如果可能可使用借助喷雾设备喷雾除草组合物的施药技术,该技术使得敏感的作物的叶子不受影响,而活性化合物达到生长在下面的不希望的植物的叶子或未覆盖的土壤表面(苗后直接施用,备用(post-directed,lay-by))。
化合物Ia,Ia’或含有它们的除草组合物可通过喷雾,弥雾,喷粉,撒播或泼浇的方法使用,例如以直接可喷雾的含水溶液,粉剂,悬浮液,甚至高浓度水剂,油剂或其它悬浮剂或分散剂,乳剂,油分散剂,糊剂,喷粉组合物,撒播组合物或颗粒剂的形式施用。施用形式依赖于使用的目的;如果可能在每种情况下要确保本发明的活性化合物最细地分散。
适用于制备直接可喷雾溶液,乳液,糊剂或油分散剂的惰性助剂主要有:中到高沸点的矿物油馏分如煤油或柴油,还包括煤焦油和植物或动物来源的油,脂肪的,环状的和芳香烃,例如,石蜡,四氢萘,烷基化萘或其衍生物,烷基化苯和其衍生物,醇如甲醇,乙醇,丙醇,丁醇和环己醇,酮如环己酮,或强极性溶剂,例如,胺如N-甲基吡咯烷酮,或水。
可从乳液浓缩物,悬浮剂,糊剂,可湿润粉剂或水可分散的颗粒剂加入水制备含水的使用形式。为了制备乳液,糊剂或油分散剂,可将物质直接在水中匀化,或依靠湿润剂,粘合剂,分散剂或乳化剂使其溶于油或溶剂中。但是,也可通过含有活性物质,湿润剂,粘合剂,分散剂或乳化剂的浓缩物和可用的溶剂或适于稀释的油和水制备。
合适的表面活性剂是芳族磺酸的碱金属,碱土金属或铵盐,例如木素磺酸,苯酚磺酸,萘磺酸和二丁基萘磺酸的这些盐,以及脂肪酸,烷基-和烷基芳基磺酸酯的这些盐,烷基-,月桂基醚和脂肪醇磺酸酯,还包括硫酸化的十六-,十七-和十八烷醇的盐以及脂肪醇乙二醇醚,磺化的萘及其衍生物与甲醛的浓缩产物,萘或萘磺酸与苯酚和甲醛的浓缩物,聚氧化乙烯辛基苯酚醚,羟乙基化的异辛基-,辛基-或壬基苯酚,烷基苯酚或三丁基苯基聚乙二醇醚,烷基芳基聚醚醇,异十三烷醇,脂肪醇-环氧乙烷浓缩物,羟乙基化蓖麻油,聚氧化乙烯或聚氧化丙烯烷基醚,月桂醇聚乙二醇醚乙酸酯,山梨醇酯,木素-亚硫酸盐废液或甲基纤维素。
可通过混合或一起研磨活性物质和固体载体制备粉剂,撒播和喷粉组合物。
可将活性化合物连接到固体载体上制备颗粒剂,例如包衣的,浸沾的和均匀的颗粒。固体载体是矿物泥土如硅酸,硅胶,硅酸盐,滑石,高岭土,石灰石,石灰,白垩,胶灰粘土,黄土,粘土,白云石,硅藻土,硫酸钙和硫酸镁,氧化镁,磨细的合成材料,肥料如硫酸铵,磷酸铵,硝酸铵,尿素和植物产物如谷粉,树皮粉,木粉和坚果壳粉,纤维素粉或其它固体载体。
一般地,该制剂含有0.01-95%重量比,优选0.5-90%重量比的活性化合物。这里所使用的活性化合物是90%-100%纯度的,优选95%-100%(依据NMR谱)纯度的化合物。
本发明的化合物I可被制成,例如,如下的组合物:
I、将20重量份的化合物No.1.002溶于下述混合物中,该混合物由80重量份的烷基化苯,10重量份8-10mol环氧乙烷与1mol油酸N-单乙醇酰胺的加成产物,5重量份十二烷基苯磺酸钙盐和5重量份40mol环氧乙烷与1mol蓖麻油的加成产物组成。将上述溶液倒入并细分散于100,000重量份的水中,得到含有0.02%重量活性化合物的水分散液。
II、将20重量份的化合物No.1.002溶于下述混合物中,该混合物由40重量份环己酮、30重量份异丁醇、20重量份7mol环氧乙烷与1mol异辛基苯酚的加成产物和10重量份40mol环氧乙烷与1mol蓖麻油的加成产物。将上述溶液倒入并细分散于100,000重量份的水中,得到含有0.02%重量活性化合物的水分散液。
III、将20重量份的活性化合物No.1.002溶于下述混合物中,该混合物由25重量份环己酮,65重量份沸点210-280℃的矿物油馏分和10重量份的40mol环氧乙烷与1mol蓖麻油的加成产物组成。将上述溶液倒入并细分散于100,000重量份的水中,得到含有0.02%重量活性化合物的水分散液。
IV、将20重量份的活性化合物No.1.002与3重量份二异丁基萘α-磺酸钠盐,17重量份从亚硫酸盐废液中得到的木质素磺酸钠盐和60重量份的硅胶粉末充分混合并在锤磨机中研磨。将上述混合物均匀分散于20,000重量份的水中,得到含有0.1%重量活性化合物的喷雾混合物。
V、将3重量份的活性化合物No.1.002与97重量份细分散高岭土混合。以上述方式获得含有3%重量活性化合物的粉剂组合物。
VI、将20重量份的活性化合物No.1.002与2重量份十二烷基苯磺酸钙盐、8重量份脂肪醇聚乙二醇醚,2重量份苯酚/尿素/甲醛缩合物钠盐和68重量份矿物石蜡油混合。获得稳定的油分散液。
为了扩大作用范围和获得协同效应,式Ia或Ia’的糖精衍生物可与许多其它除草剂的典型代表或生长调节活性化合物配组混合并一起施用。例如,合适的混合物组分是二嗪,4H-3,1-苯并噁嗪衍生物,苯并噻二嗪酮,2,6-二硝基苯胺,N-苯基氨基甲酸酯,硫代氨基甲酸酯,卤代羧酸,三嗪,酰胺,尿素,二苯基醚,三嗪酮,尿嘧啶,苯并呋喃衍生物,在2-位带有如羧基或碳酰亚氨基团的环己烷-1,3-二酮衍生物,喹啉羧酸衍生物,咪唑啉酮,磺酰胺,磺酰脲,芳氧或杂芳氧苯氧丙酸及其盐,酯和酰胺等等。
另外,可使用化合物Ia或Ia’本身或与其它除草剂结合使用,还可加入作物保护剂,例如控制鼠疫或植物真菌和细菌的药剂。另外,还可与用于消除营养和微量元素缺乏的无机盐溶液混合使用。还可加入对植物无害的油和油浓缩物。
根据控制目的,使用年限,目的植物和生长阶段,活性化合物的施用率为0.001-3.0,优选0.01-1.0kg/ha的活性物质(a.s.)。制备实施例A)制备起始物1、2-甲基-6-乙酰氨基苯甲酸
将90.6g(0.6mol)的6-甲基邻氨基苯甲酸加入到24.8g(0.62mol)NaOH在500ml水的溶液中,然后滴加入乙酸酐63.4g(0.62mol)。搅拌1小时后,将混合物在冷却下用浓盐酸酸化至pH3,抽滤所得沉淀,用水洗涤,并在50℃减压干燥。产量:107g(0.55mol)=理论值的92%,m.p.:189-190℃2、2-甲基-3-硝基-6-乙酰氨基苯甲酸
先在-5℃取出271ml的98%的硝酸,并向其中分批加入制备例1制备的2-甲基-6-乙酰氨基苯甲酸106g(0.55mol)。在10℃搅拌1小时后,将反应混合物倒入540g冰和270ml水的混合物中,抽滤所得沉淀,用水洗涤,并在50℃减压干燥。产量:75.6g(0.317mol)=理论值的58%,m.p.:190-191℃经过相对长的静置,从滤液中沉淀出3-位硝化的异构体:产量:21.3g(0.089mol)=理论值的16%,m.p.:180-182℃3、2-甲基-3-硝基-6-氨基苯甲酸
先取450ml的2N的NaOH,并向其中加入2-甲基-3-硝基-6-乙酰氨基苯甲酸75.6g(0.317mol)。将反应混合物加热到95℃并在此温度搅拌1小时。冷却到10℃后,加入425ml的2N的HCl进行酸化,抽滤所得沉淀,用水洗涤,并在50℃减压干燥。产量:50.7g(0.258mol)=理论值的82%,m.p.:183-184℃4、2-甲基-3-硝基-6-氨基苯甲酸甲酯
将49.7g(0.253mol)2-甲基-3-硝基-6-氨基苯甲酸溶于380ml丙酮并加入43g(0.51mol)碳酸氢钠。将混合物加热至沸直到生成的二氧化碳全部排除。向如此生成的2-甲基-3-硝基-6-氨基苯甲酸钠盐的悬浮液中用2小时在丙酮的沸点滴加入硫酸二甲酯35.3g(0.28mol),然后将混合物回流3小时之后冷却。将反应混合物倒入1.8升水中,用二氯甲烷萃取。干燥后,有机相浓缩,所得固体用于下一步反应已足够纯(NMR)。产量:50g(0.238mol)=理论值的94%,m.p.:92-94℃5、2-甲氧羰基-3-甲基-4-硝基苯磺酰氯
在加热条件下,将58.5g(0.278mol)2-甲基-3-硝基-6-氨基苯甲酸甲酯溶于280ml冰醋酸,将此溶液在15-20℃倒入85ml浓盐酸。在5-10℃滴加入19.3g(0.28mol)的亚硝酸钠在60ml水中的溶液,然后将混合物在5℃搅拌30分钟。然后将此重氮盐溶液滴加入一溶液中,此溶液为374g SO2在750ml冰醋酸中的溶液,且其含有14gCuCl2(溶于30ml水中)。当氮气出完后,将混合物再搅拌15分钟,然后倒入1.4升冰水中。用1.2升二氯甲烷提取分离磺酰氯。干燥后浓缩有机相,得到73g(0.25mol)(=理论值的90%)的油,依据NMR(在CDCl3中)是纯的2-甲氧羰基-3-甲基-4-硝基苯磺酰氯。6、4-甲基-5-硝基糖精
首先取104ml 25%的氨水溶液,加入100ml水,然后在10℃,滴加入48.7g(0.166mol)2-甲氧羰基-3-甲基-4-硝基苯磺酰氯在70ml四氢呋喃中的溶液。在25℃搅拌3小时后,将混合物在旋转蒸发器中浓缩,除去水和四氢呋喃。剩余物用乙酸乙酯搅拌,抽滤并用乙酸乙酯洗涤。减压干燥后,得到34g(0.131mol)=理论值的79%的白色固体,m.p.312℃(分解)。7、2,4-二甲基-5-硝基糖精
将50ml水倒入50ml 40%的甲胺溶液中,在10℃向其中滴加入24.3g(83mmol)2-甲氧羰基-3-甲基-4-硝基苯磺酰氯在35mlTHF中的溶液。在25℃搅拌1小时后,用旋转蒸发器除去所有挥发性组分,用乙酸乙酯萃取剩余物,有机相用水洗涤,干燥并浓缩。剩余物放置相对长的时间后仍为结晶。产量:10.3g(40mmol=理论值的48%),m.p.:125-126℃,用乙酸乙酯重结晶后,m.p.:144-145℃。9、4-甲基-5-氨基-1,1,3-三氧-2,3-二氢-1λ6苯并[d]异噻唑(Beilstein nomenclature)
将33.6g(0.13mol)4-甲基-5-硝基-1,1,3-三氧-2,3-二氢-1λ6苯并[d]异噻唑溶于1.2升水中并加热到45℃,向其中加入5g Pd/C(10%在活性炭上)。在充分搅拌下通入氢气(无压氢化)。在4.5小时内吸收了9升氢气。冷却至25℃,滤除催化剂,并将滤液浓缩至200ml(使用旋转蒸发器),然后酸化至pH1。抽滤所得沉淀,用水洗涤,并在50℃减压干燥。得到23.4g(0.11mol=理论值的85%)的白色固体,m.p.:272-273℃。10、4-甲基-5-碘代-1,1,3-三氧-2,3-二氢-1λ6苯并[d]异噻唑(Beilstein nomenclature)
取205ml冰醋酸,160ml水和40ml浓盐酸的混合物,在15-20℃搅拌下加入4-甲基-5-氨基-1,1,3-三氧-2,3-二氢-1λ6苯并[d]异噻唑23.4g(0.11mol)。在5-10℃向所得悬浮液中滴加入亚硝酸钠7.9g(0.115mol)并在5℃搅拌30分钟。将悬浮液形式的重氮盐分批滴加入19.1g(0.115mol)碘化钾在170ml水中的溶液,溶液升温至50℃,形成氮气。冷却至室温,抽滤分离所得沉淀产物,用水洗涤,并在50℃减压干燥。得到32.5g(0.1mol=理论值的91%)的固体,m.p.:257-258℃。燃烧分析得出碘含量为38.5%(理论值39.3%)。
按照实施例9描述的类似方法,将实施例8的3-甲基-4-硝基-2-(N’-甲基)羧氨基-N-甲基苯磺酰胺在无压力条件下氢化。以93%的产率得到上述结构的苯胺衍生物,m.p.217-218℃。12、3-甲基-4-碘代-2-(N’-甲基)羧氨基-N-甲基苯磺酰胺
按照实施例10描述的类似方法重氮化上述化合物,并与KI反应转化为上式结构的碘苯衍生物。产率:理论值的95%,m.p.:60-62℃。B)制备终产物I13、4-甲基-1,1,3-三氧-2,3-二氢-1λ6苯并[d]异噻唑-5-羧酸
将6.4g(0.02mol)4-甲基-5-碘代-1,1,3-三氧-2,3-二氢-1λ6苯并[d]异噻唑溶于70ml四甲基脲中,并加入30ml水,用0.7g二氯化双(三苯基膦)合钯处理。将混合物在300ml高压釜中加热到100℃并在100bar一氧化碳压力下搅拌36小时。
为了分离纯化,将混合物过滤,在高真空下蒸馏除去水和四甲基脲。剩余物用甲基-叔丁基醚(MTBE)溶解,用NaHCO3溶液萃取,用HCl酸化后,再用MTBE萃取。浓缩后得到2.8g(4-甲基-1,1,3-三氧-2,3-二氢-1λ6苯并[d]异噻唑-5-羧酸)(理论值的58%)。1H NMR(DMSO,400.1MHz):2.85(3H,s);8.05(1H,d);8.2(1H,d);13C NMR(DMSO,100.6MHz):167.4(CO);161.3(CO);141.6(quart.C);139.7(quart.C);138.7(quart.C);135.6(CH);125.4(quart.C);118.5(CH);15.4(CH3)。14、4-N-二甲基-1,1,3-三氧-2,3-二氢-1λ6苯并[d]异噻唑-5-羧酸
先取7.3g(0.02mol)3-甲基-4-碘代-2-(N’-甲基)羧氨基-N-甲基苯磺酰胺放入300ml高压釜中,再加入0.69g二氯化双(三苯基膦)合钯,30ml水和70ml四甲基脲。将混合物在加热到100℃并在100bar一氧化碳压力下搅拌36小时。
按照实施例13的方法分离纯化后,得到4.1g标题化合物(0.014mol=理论值的72%)1H NMR(DMSO,400.1MHz):2.9(3H,s);3.15(3H,s);8.2(2H,2d);14.0(1H,s)。13C NMR(DMSO,100.6MHz):167.3(CO);158.6(CO);139.7(quart.C);139.1(quart.C);138.9(quart.C);135.5(CH);124.6(quart.C);119.0(CH);22.9(CH3);15.6(CH3)。
可按照类似的方法得到表1中的糖精羧酸。表1中提到的取代基与前述取代基相比,各个取代基的组合是独立的,是特别优选的取代基定义。表1
C)使化合物I反应得到除草活性的二级产物15、2,4-二甲基糖精-5-酰氯
No. | L | M | Z |
1.001 | CH3 | H | H |
1.002 | CH3 | H | CH3 |
1.003 | CH3 | H | CH3 |
1.004 | Cl | H | CH3 |
No. | L | M | Z |
1.005 | SCH3 | H | H |
1.006 | SO2CH3 | CH3 | C2H5 |
1.007 | H | H | CH3 |
1.008 | H | CH3 | H |
1.009 | Cl | OCH3 | H |
1.010 | OCH3 | CH3 | CH3 |
1.011 | CH3 | CH3 | H |
1.012 | Cl | CH3 | CH3 |
1.013 | CH3 | H | CH2-C6H5 |
1.014 | CH3 | H | C6H5 |
将3.8g(14.9mmol)4,N-二甲基-1,1,3-三氧-2,3-二氢-1λ6苯并[d]异噻唑-5-羧酸悬浮于100ml甲苯中,将混合物加热到80℃并滴加入3.5g(29.8mmol)亚硫酰氯。回流2小时后,趁热倾出溶液,将反应混合物用旋转蒸发器浓缩。产率:理论值的74%,m.p.:149-150℃。16、环己二酮的酰化
向1.23g(10.9mmol)环己烷-1,3-二酮在50ml二氯甲烷中的悬浮液中倒入1.21g(12mmol)三乙胺,然后在25℃滴加入3g(10.9mmol)4,N-二甲基-1,1,3-三氧-2,3-二氢-1λ6苯并[d]异噻唑-5-酰氯在60ml二氯甲烷中的溶液。将混合物在40℃搅拌7小时。冷却后,倒入60ml水,用分液漏斗分出二氯甲烷相并用硫酸镁干燥。除去溶剂后得到伴生(accompanying)结构的烯醇酯无定形剩余物,不需纯化可直接用于下一步的重排。17、重排成最终产物E
将2.5g(7.2mmol)上述烯醇酯溶于80ml乙腈中,先用3.5ml三乙胺再用0.33g(4mmol)丙酮氰醇处理,搅拌16小时。然后向反应混合物中加入24.5g 5%d HCl,并用100ml二氯甲烷萃取。将有机相用5%碳酸钾溶液萃取,使产物转移至水相。用浓盐酸酸化碱水溶液,沉淀出胶状固体,用二异丙基醚研制得到结晶。用石油醚洗涤,在减压下干燥。产量:0.88g(理论值的35%)
表2
表3 表4
表5
No. | Ra-Rf | L | M | Z |
2.001 | H | CH3 | H | H |
2.002 | H | CH3 | H | CH3 |
2.003 | Rc=Rd=CH3Ra,Rb,Re,Rf=H | CH3 | H | CH3 |
2.004 | H | Cl | H | CH3 |
2.005 | H | SCH3 | H | H |
No. | Ra-Rf | L | M | Z |
2.006 | H | SO2CH3 | CH3 | C2H5 |
2.007 | H | H | H | CH3 |
2.008 | H | H | CH3 | H |
2.009 | Rc=Rd=CH3Ra,Rb,Re,Rf=H | Cl | OCH3 | H |
2.010 | Rc=Rd=CH3Ra,Rb,Re,Rf=H | OCH3 | CH3 | CH3 |
2.011 | Ra=CH3Rb-Rf=H | CH3 | CH3 | H |
2.012 | Rc=Rd=CH3Ra,Rb,Re,Rf=H | Cl | CH3 | CH3 |
2.013 | Rc=Rd=CH3Ra,Rb,Re,Rf=H | CH3 | H | CH2-C6H5 |
2.014 | Rc=Rd=CH3Ra,Rb,Ra,Rf=H | CH3 | H | C6H5 |
No. | Q | L | M | Z | M.p.[℃] |
4.001 | 4-COOK | H | H | H | |
4.002 | 6-COOCH3 | H | H | NH4 -盐 | 278-280 |
4.003 | 6-COOCH3 | H | H | CH3 | 185-187 |
4.004 | 4-COOCH3 | H | H | CH3 | 173-174 |
4.005 | 6-COOCH3 | H | H | H | >200 |
4.006 | 6-COOC2H5 | H | H | CH3 | 123-124 |
4.007 | 5-COOCH3 | H | 6-CH3 | CH3 | 215-216 |
4.008 | 6-COOCH3 | H | H | 苯基 | 183-185 |
No. | O-位 | L | M | Z | M.p.[℃] |
5.001 | 5 | 4-CH3 | H | CH3 | 206-207 |
5.002 | 6 | H | H | CH3 | >200 |
5.003 | 6 | H | H | H | >200 |
5.004 | 7 | H | H | CH3 | 227-229 |
表明除草活性的化合物Ia和Ia’的实施例
可用温室试验显示式Ia和Ia’的糖精羧酸或其酯的除草效果:
所使用的容器是装满含有约3.0%的腐殖土的沙壤土的塑料花盆。试验植物的种子按物种分别播种。
在苗前处理时,播种后,使用细分散的喷嘴直接施用活性化合物在水中的悬浮液或乳液。向容器中适当浇水以促进发芽和生长,然后用透明塑料防护罩盖上,直到植物长出根。如果活性化合物对植物生长无不利的影响。,覆盖可使试验植物均匀生长。
在苗后处理时,先使试验植物生长,根据生长的形态,对高度为3-15cm的植物施用活性化合物在水中的悬浮液或乳液。在此试验中,试验植物既可以在同一容器中播种和生长,也可以先在其它容器中播种生长,然后在处理前几天移种到试验容器中。苗后处理的施用率为3.0kg/ha,a.s.
在10-25℃或20-35℃保持植物物种特定。试验时间持续2-4周。在此期间照顾植物,并测定它们对个别处理的反应。
等级范围为0-100。100时指植物没有出现或至少在上述土地范围内植物完全被破坏。;0是指没有破坏或正常生长。
用于温室试验的植物由下列种属组成:
植物学名称 | 一般名称 |
稗 | 稗草 |
小米 | 狐尾粟 |
按照施用率3.0kg/ha a.s,苗后使用实施例1.002的化合物可非常有效地控制不希望的植物的生长。
Claims (11)
2、权利要求1的方法,其中使用羰基化反应的钯催化剂。
3、权利要求1的方法,其中羧化反应在钯催化剂存在下进行,此钯催化剂含有叔膦的膦配体。
4、权利要求1的方法,其中使用的碱是叔胺或四烷基取代的脲衍生物。
5、权利要求1的方法,其中碱是四甲基脲。
6、权利要求1或5的方法,其中碱同时用作溶剂。
7、权利要求1的方法,其中反应组分水或醇同时用作溶剂。
8、权利要求1的方法,其中羧化反应在20-200℃进行。
10、除草组合物,含有权利要求9的式Ia的化合物和惰性载体。
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US6605751B1 (en) * | 1997-11-14 | 2003-08-12 | Acrymed | Silver-containing compositions, devices and methods for making |
DE59900096D1 (de) * | 1998-03-25 | 2001-06-28 | Basf Ag | Verfahren zur Herstellung von Saccharincarbonsäurehalogeniden |
AU2742401A (en) * | 1999-12-30 | 2001-07-16 | Acrymed | Methods and compositions for improved delivery devices |
CN1678277B (zh) | 2002-07-29 | 2010-05-05 | 艾克里麦德公司 | 治疗皮肤病的方法和组合物 |
EP2789235B1 (en) | 2004-07-30 | 2015-12-23 | Avent, Inc. | Method of preparing silver nanoparticles |
WO2006015317A2 (en) | 2004-07-30 | 2006-02-09 | Acrymed, Inc. | Antimicrobial devices and compositions |
US8361553B2 (en) | 2004-07-30 | 2013-01-29 | Kimberly-Clark Worldwide, Inc. | Methods and compositions for metal nanoparticle treated surfaces |
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US8293965B2 (en) * | 2006-04-28 | 2012-10-23 | Kimberly-Clark Worldwide, Inc. | Antimicrobial site dressings |
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US5034534A (en) * | 1988-07-15 | 1991-07-23 | E. I. Du Pont De Nemours And Company | Process for producing saccharin, saccharin analogues or their salts |
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DE671788C (de) * | 1935-04-20 | 1939-02-15 | I G Farbenindustrie Akt Ges | Verfahren zur Herstellung von Diazoaminoverbindungen |
FR2525593A1 (fr) * | 1982-04-23 | 1983-10-28 | Rhone Poulenc Agrochimie | Derives d'acides phenoxybenzoiques, leur preparation et leur utilisation pour le desherbage des cultures |
DE3430805A1 (de) * | 1984-03-08 | 1985-09-19 | Bayer Ag, 5090 Leverkusen | Mikrobizide mittel |
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EP0308371A1 (de) * | 1987-09-18 | 1989-03-22 | Ciba-Geigy Ag | 4-Azasaccharine, 4-Aza-dihydro-oder-tetrahydrosaccharine und Verfahren zu deren Herstellung |
EP0323869A1 (en) * | 1988-01-06 | 1989-07-12 | Shell Internationale Researchmaatschappij B.V. | Saccharin derivatives |
US5160363A (en) * | 1988-05-12 | 1992-11-03 | E. I. Du Pont De Nemours And Company | Herbicidal sulfonamides |
US5236917A (en) * | 1989-05-04 | 1993-08-17 | Sterling Winthrop Inc. | Saccharin derivatives useful as proteolytic enzyme inhibitors and compositions and method of use thereof |
SG48298A1 (en) * | 1989-05-04 | 1998-04-17 | Sterling Winthorp Inc | Saccharin deriatives useful as proteolytic enzymeinhibitors and preparation of |
AU642537B2 (en) * | 1990-11-01 | 1993-10-21 | Sanofi | 2-saccharinylmethyl aryl carboxylates useful as proteolytic enzyme inhibitors and compositions and method of use thereof |
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US3673200A (en) * | 1970-01-02 | 1972-06-27 | Monsanto Co | 3(2-sec-butyl-4,6-dimitrophenoxy)-1,2-benzisothiozole 1,1-dioxide |
US4410353A (en) * | 1981-07-17 | 1983-10-18 | Rhone-Poulenc Agrochimie | Herbicidal N-sulfonyl 5-[substituted phenoxy]-2-substituted benzamides |
US5034534A (en) * | 1988-07-15 | 1991-07-23 | E. I. Du Pont De Nemours And Company | Process for producing saccharin, saccharin analogues or their salts |
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AU688562B2 (en) | 1998-03-12 |
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CN1159189A (zh) | 1997-09-10 |
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ATE205840T1 (de) | 2001-10-15 |
CA2197120A1 (en) | 1996-02-22 |
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