CN107216286B - 5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法 - Google Patents
5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法 Download PDFInfo
- Publication number
- CN107216286B CN107216286B CN201710502061.1A CN201710502061A CN107216286B CN 107216286 B CN107216286 B CN 107216286B CN 201710502061 A CN201710502061 A CN 201710502061A CN 107216286 B CN107216286 B CN 107216286B
- Authority
- CN
- China
- Prior art keywords
- dimethyl
- bromomethyl
- pyridinedicarboxylate
- methyl
- reaction
- 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.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000005893 bromination reaction Methods 0.000 claims abstract description 14
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims abstract description 11
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000007858 starting material Substances 0.000 claims abstract description 5
- MKOJTLPEGLTEFM-UHFFFAOYSA-N dimethyl 5-methylpyridine-2,3-dicarboxylate Chemical compound COC(=O)C1=CC(C)=CN=C1C(=O)OC MKOJTLPEGLTEFM-UHFFFAOYSA-N 0.000 claims description 14
- ZGSOVUCMPRAGQI-UHFFFAOYSA-N dimethyl 5-(bromomethyl)pyridine-2,3-dicarboxylate Chemical compound COC(=O)C1=CC(CBr)=CN=C1C(=O)OC ZGSOVUCMPRAGQI-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical group CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 22
- 230000031709 bromination Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- 125000000950 dibromo group Chemical group Br* 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 108010000700 Acetolactate synthase Proteins 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- NUPJIGQFXCQJBK-UHFFFAOYSA-N 2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)-5-(methoxymethyl)nicotinic acid Chemical compound OC(=O)C1=CC(COC)=CN=C1C1=NC(C)(C(C)C)C(=O)N1 NUPJIGQFXCQJBK-UHFFFAOYSA-N 0.000 description 3
- 239000005566 Imazamox Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- ISULOVLSEOKTOW-UHFFFAOYSA-N dimethyl 5-(dibromomethyl)pyridine-2,3-dicarboxylate Chemical compound COC(=O)C1=CC(C(Br)Br)=CN=C1C(=O)OC ISULOVLSEOKTOW-UHFFFAOYSA-N 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 102100027324 2-hydroxyacyl-CoA lyase 1 Human genes 0.000 description 1
- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical compound O=C1CNC=N1 CAAMSDWKXXPUJR-UHFFFAOYSA-N 0.000 description 1
- 230000006820 DNA synthesis Effects 0.000 description 1
- 101001009252 Homo sapiens 2-hydroxyacyl-CoA lyase 1 Proteins 0.000 description 1
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 1
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000005693 branched-chain amino acids Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- XIZXOWDZJGWPGN-UHFFFAOYSA-N dimethyl 5-(tribromomethyl)pyridine-2,3-dicarboxylate Chemical group C(=O)(C1=NC=C(C(Br)(Br)Br)C=C1C(=O)OC)OC XIZXOWDZJGWPGN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229960000310 isoleucine Drugs 0.000 description 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- 229960003136 leucine Drugs 0.000 description 1
- 230000011278 mitosis Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000005080 plant death Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229960004295 valine Drugs 0.000 description 1
Classifications
-
- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
-
- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明公开了一种5‑溴甲基‑2,3‑吡啶二甲酸二甲酯的制备方法，它是以5‑甲基‑2,3‑吡啶二甲酸二甲酯为起始原料，在偶氮二异丁腈的存在下、在有机溶剂中经溴化反应制得；所述溴化反应是在溴酸钠的存在下与氢溴酸进行的。本发明的方法采用氢溴酸作为溴化试剂，同时采用溴酸钠与偶氮二异丁腈共同作为引发剂，这样能够大大减少副产物的生产，单次反应副产物只有1%左右，循环反应副产物也只有2%左右，从而可以通过循环套用获得90%以上的收率。
Description
技术领域
本发明属于除草剂中间体制备技术领域，具体涉及一种5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法。
背景技术
甲氧咪草烟是由美国氰胺（现为BASF）公司开发的咪唑啉酮类除草剂，属于乙酰乳酸合成酶（ALS）或乙酸羟酸合成酶（AHAs）的抑制剂，通过叶片吸收、传导并积累于分生组织，抑制AHAS的活性，导致支链氨基酸-撷氨酸、亮氨酸与异亮氨酸生物合成停止，干扰DNA合成及细胞有丝***与植物生长，最终造成植株死亡。甲氧咪草烟在中国发展前景良好，市场空间巨大，未来发展将保持逐步上升态势。
5-溴甲基-2,3-吡啶二甲酸二甲酯则是制备甲氧咪草烟的关键中间体。
美国专利文献US5288866A公开了一种5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法，它是以5-甲基-2,3-吡啶二甲酸二甲酯为起始原料，在偶氮二异丁腈的存在下、在四氯化碳溶剂中、经N-溴代丁二酰亚胺溴化制得；该方法的不足在于：目标产物只有57%，尤其是（二溴）副产物高达23%，导致收率较低，即使通过循环套用最高收率也不会超过75%。
世界专利文献WO2010055042A1公开了一种5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法，它是以5-甲基-2,3-吡啶二甲酸二甲酯为起始原料，在偶氮二异丁腈的存在下、在二氯乙烷溶剂中、经液溴溴化制得；该方法的不足在于：副产物更多，除了二溴副产物，还有三溴副产物，因此，其转化率只有50%，表明其收率更低。
发明内容
本发明的目的在于克服现有技术的上述不足，提供一种副产物较少、目标产物收率较高的5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法。
实现本发明上述目的的技术方案是：一种5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法，它是以5-甲基-2,3-吡啶二甲酸二甲酯为起始原料，在偶氮二异丁腈的存在下、在有机溶剂中经溴化反应制得；所述溴化反应是在溴酸钠的存在下与氢溴酸进行的。
所述5-甲基-2,3-吡啶二甲酸二甲酯与所述氢溴酸的摩尔比为1∶1～1∶3，优选为1∶2。
所述5-甲基-2,3-吡啶二甲酸二甲酯与所述溴酸钠的摩尔比为1∶0.1～1∶1，优选为1∶0.4。
所述5-甲基-2,3-吡啶二甲酸二甲酯与所述偶氮二异丁腈的摩尔比为1∶0.05～1∶0.5，优选为1∶0.1。
所述有机溶剂为二氯乙烷、乙腈、二甲基甲酰胺（DMF）、四氢呋喃或者甲苯，优选为二氯乙烷。
所述溴化反应温度为回流反应温度。
所述溴化反应时间为1～5h，优选为2h。
本发明具有的积极效果：（1）本发明的方法采用氢溴酸作为溴化试剂，同时采用溴酸钠与偶氮二异丁腈共同作为引发剂，这样能够大大减少副产物的生产，单次反应副产物只有1%左右，循环反应副产物也只有2%左右，从而可以通过循环套用获得90%以上的收率。（2）本发明的方法还避免使用剧毒液溴，原料易得、工艺简便、副反应少、操作安全，适合工业化大生产。
具体实施方式
（实施例1）
本实施例的5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法如下：
向反应瓶中加入50g的5-甲基-2,3-吡啶二甲酸二甲酯（0.24mol）、128g的二氯乙烷、14.5g的溴酸钠（0.096mol）、3.92g的偶氮二异丁腈（0.024mol）以及130g的水，加热至回流，滴加97g的浓度为40wt%的氢溴酸（0.48mol），约2h滴完，滴完继续保温回流反应2h。
反应结束后，将反应液冷却至室温（15～25℃，下同），用30wt%氢氧化钠水溶液将反应液pH值调至6.0±0.2，搅拌后静置分层，将有机层水洗后减压脱除溶剂，得到68g红棕色液体。
HPCL显示该单次反应后的红棕色液体含65.8%的目标产物，31.3%的5-甲基-2,3-吡啶二甲酸二甲酯，0.9%的5-二溴甲基-2,3-吡啶二甲酸二甲酯。
分离出红棕色液体中没有反应的原料循环套用，继续进行溴化反应，约3次溴化后总收率达95.2%，5-二溴甲基-2,3-吡啶二甲酸二甲酯含量为1.8%。
（实施例2～实施例6）
各实施例的制备方法与实施例1基本相同，不同之处见表1。
表1
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | |
| 5-甲基-2,3-吡啶二甲酸二甲酯 | 50g，0.24mol | 50g，0.24mol | 50g，0.24mol | 50g，0.24mol | 50g，0.24mol | 100g，0.48mol |
| 40wt%氢溴酸 | 97g，0.48mol | 48.5g，0.24mol | 145.5g，0.72mol | 97g，0.48mol | 97g，0.48mol | 194g，0.96mol |
| 溴酸钠 | 14.5g，0.096mol | 14.5g，0.096mol | 14.5g，0.096mol | 3.63g，0.024mol | 36.3g，0.240mol | 29.0g，0.192mol |
| 单次反应目标产物 | 65.8% | 65.5% | 66.1% | 65.2% | 65.3% | 65.7% |
| 单次反应剩余原料 | 31.3% | 31.5% | 31.5% | 31.1% | 31.3% | 31.2% |
| 单次反应二溴副产物 | 0.9% | 1.1% | 0.7% | 1.3% | 1.2% | 1.0% |
| 循环反应二溴副产物 | 1.8% | 2.1% | 1.6% | 2.3% | 2.2% | 1.8% |
| 循环反应总收率 | 95.2% | 94.8% | 95.6% | 94.3% | 94.6% | 95.3% |
（对比例1～对比例4）
各对比例的制备方法与实施例1基本相同，不同之处见表2。
表2
| 实施例1 | 对比例1 | 对比例2 | 对比例3 | 对比例4 | |
| 5-甲基-2,3-吡啶二甲酸二甲酯 | 50g，0.24mol | 50g，0.24mol | 50g，0.24mol | 50g，0.24mol | 50g，0.24mol |
| 40wt%氢溴酸 | 97g，0.48mol | 97g，0.48mol | 97g，0.48mol | / | / |
| 溴酸钠 | 14.5g，0.096mol | / | 18.1g，0.12mol | / | / |
| 偶氮二异丁腈 | 3.92g，0.024mol | 19.7g，0.12mol | / | 19.7g，0.12mol | 19.7g，0.12mol |
| N-溴代丁二酰亚胺 | / | / | / | 85.4g，0.48mol | / |
| 液溴 | / | / | / | / | 38.4g，0.24mol |
| 单次反应目标产物 | 65.8% | 57.6% | 55.5% | 59.2% | 47.6% |
| 单次反应剩余原料 | 31.3% | 32.6% | 30.7% | 15.4% | 16.8% |
| 单次反应二溴副产物 | 0.9% | 7.5% | 11.5% | 22.7% | 27.3% |
| 单次反应三溴副产物 | / | / | / | / | 5.9% |
| 循环反应二溴副产物 | 1.8% | 12.3% | 18.5% | 25.4% | 29.5% |
| 循环反应三溴副产物 | / | / | / | / | 7.3% |
| 总收率 | 95.2% | 83.8% | 77.3% | 71.3% | 59.8% |
表1和表2中的目标产物即为5-溴甲基-2,3-吡啶二甲酸二甲酯，原料即为5-甲基-2,3-吡啶二甲酸二甲酯，二溴副产物即为5-二溴甲基-2,3-吡啶二甲酸二甲酯，三溴副产物即为5-三溴甲基-2,3-吡啶二甲酸二甲酯。
Claims (8)
1.一种5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法，它是以5-甲基-2,3-吡啶二甲酸二甲酯为起始原料，在偶氮二异丁腈的存在下、在有机溶剂中经溴化反应制得；其特征在于：所述溴化反应是在溴酸钠的存在下与氢溴酸进行的；
所述5-甲基-2,3-吡啶二甲酸二甲酯与所述氢溴酸的摩尔比为1∶1～1∶3；
所述5-甲基-2,3-吡啶二甲酸二甲酯与所述溴酸钠的摩尔比为1∶0.1～1∶1。
2.根据权利要求1所述的5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法，其特征在于：所述5-甲基-2,3-吡啶二甲酸二甲酯与所述氢溴酸的摩尔比为1∶2。
3.根据权利要求1所述的5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法，其特征在于：所述5-甲基-2,3-吡啶二甲酸二甲酯与所述溴酸钠的摩尔比为1∶0.4。
4.根据权利要求1所述的5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法，其特征在于：所述5-甲基-2,3-吡啶二甲酸二甲酯与所述偶氮二异丁腈的摩尔比为1∶0.05～1∶0.5。
5.根据权利要求4所述的5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法，其特征在于：所述5-甲基-2,3-吡啶二甲酸二甲酯与所述偶氮二异丁腈的摩尔比为1∶0.1。
6.根据权利要求1所述的5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法，其特征在于：所述有机溶剂为二氯乙烷、乙腈、二甲基甲酰胺、四氢呋喃或者甲苯。
7.根据权利要求1所述的5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法，其特征在于：所述溴化反应温度为回流反应温度。
8.根据权利要求1所述的5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法，其特征在于：所述溴化反应时间为1～5h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710502061.1A CN107216286B (zh) | 2017-06-27 | 2017-06-27 | 5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710502061.1A CN107216286B (zh) | 2017-06-27 | 2017-06-27 | 5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107216286A CN107216286A (zh) | 2017-09-29 |
| CN107216286B true CN107216286B (zh) | 2020-03-31 |
Family
ID=59951373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710502061.1A Active CN107216286B (zh) | 2017-06-27 | 2017-06-27 | 5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107216286B (zh) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818627A (zh) * | 2018-08-09 | 2020-02-21 | 北京颖泰嘉和生物科技股份有限公司 | 5-甲氧甲基-2,3-吡啶二甲酸二酯的制备方法 |
| CN113004197A (zh) * | 2019-12-19 | 2021-06-22 | 北京颖泰嘉和生物科技股份有限公司 | 5-甲基-2,3-吡啶二甲酸二酯的回收方法 |
| CN113024455A (zh) * | 2019-12-25 | 2021-06-25 | 北京颖泰嘉和生物科技股份有限公司 | 5-甲氧基甲基-2,3-吡啶二甲酸二甲酯的制备方法 |
| CN113968814A (zh) * | 2020-07-22 | 2022-01-25 | 帕潘纳(北京)科技有限公司 | 一种制备5-溴甲基-2,3-吡啶羧酸二甲酯的方法 |
| CN114933561A (zh) * | 2022-05-09 | 2022-08-23 | 沈阳万菱生物技术有限公司 | 一种5-取代-2,3-吡啶二羧酸酯化合物及其季铵盐的制备方法 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0434965A2 (en) * | 1989-12-27 | 1991-07-03 | American Cyanamid Company | Alkyl esters of 5-heterocyclic-pyridine-2,3-dicarboxylic acids and 5-heterocyclic 2-(2-imidazolin-2-yl) pyridines and methods for preparation thereof |
| CN1265639A (zh) * | 1997-07-30 | 2000-09-06 | 巴斯福股份公司 | 取代苄基溴的制备方法 |
| WO2010055042A1 (en) * | 2008-11-13 | 2010-05-20 | Basf Se | 2-[(1-cyanopropyl)carbamoyl]-5-methoxymethyl nicotinic acids and the use thereof in manufacturing herbicidal imidazolinones |
| CN102245575A (zh) * | 2008-12-08 | 2011-11-16 | 巴斯夫欧洲公司 | 制备取代的5-甲氧基甲基吡啶-2，3-二甲酸衍生物的方法 |
| CN105777623A (zh) * | 2016-02-29 | 2016-07-20 | 北京颖泰嘉和生物科技股份有限公司 | 一种吡啶侧链甲基季铵盐类化合物的制备方法 |
-
2017
- 2017-06-27 CN CN201710502061.1A patent/CN107216286B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0434965A2 (en) * | 1989-12-27 | 1991-07-03 | American Cyanamid Company | Alkyl esters of 5-heterocyclic-pyridine-2,3-dicarboxylic acids and 5-heterocyclic 2-(2-imidazolin-2-yl) pyridines and methods for preparation thereof |
| CN1265639A (zh) * | 1997-07-30 | 2000-09-06 | 巴斯福股份公司 | 取代苄基溴的制备方法 |
| WO2010055042A1 (en) * | 2008-11-13 | 2010-05-20 | Basf Se | 2-[(1-cyanopropyl)carbamoyl]-5-methoxymethyl nicotinic acids and the use thereof in manufacturing herbicidal imidazolinones |
| CN102245575A (zh) * | 2008-12-08 | 2011-11-16 | 巴斯夫欧洲公司 | 制备取代的5-甲氧基甲基吡啶-2，3-二甲酸衍生物的方法 |
| CN105777623A (zh) * | 2016-02-29 | 2016-07-20 | 北京颖泰嘉和生物科技股份有限公司 | 一种吡啶侧链甲基季铵盐类化合物的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107216286A (zh) | 2017-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107216286B (zh) | 5-溴甲基-2,3-吡啶二甲酸二甲酯的制备方法 | |
| CN104478797A (zh) | 烟酰胺类杀菌剂啶酰菌胺的制备方法 | |
| JP6201595B2 (ja) | ２−ヒドロキシメチル−２，３−ジヒドロ−チエノ［３，４−ｂ］［１，４］ジオキシンの製造方法 | |
| CN109293565B (zh) | 一种氟吡菌酰胺的制备方法 | |
| CN104725303A (zh) | 一种2-氯-n-(4′-氯联苯-2-基)烟酰胺的合成方法 | |
| CN112500311B (zh) | 一种o-3-氯-2-丙烯基羟胺游离碱的制备工艺 | |
| CN106117143B (zh) | 一种吡唑醚菌酯的制备方法 | |
| CN117820214A (zh) | 制备甲氧基甲基吡啶二甲酸酯的方法 | |
| CN103896855B (zh) | 一种4-(1-溴代乙基)-5-氟-6-氯嘧啶的合成方法 | |
| CN108203384B (zh) | 一种制备邻硝基苄溴的方法 | |
| CN103254058B (zh) | 一种2,3,3,3-四氟丙酸的合成方法 | |
| CN109503418B (zh) | 一种甲基肼的制备工艺 | |
| CN104610136A (zh) | 一种2-氯-5-氯甲基吡啶的合成方法 | |
| CN103613535A (zh) | 一种5-（甲氧基甲基）-2,3-吡啶二甲酸二甲酯的合成方法 | |
| CN103724167B (zh) | 一种高收率的全氟甲基乙烯基醚(pmve)的绿色合成方法 | |
| CN108558686B (zh) | 一种盐酸安非他酮的制备方法 | |
| CN109232569B (zh) | 一种敌草快阴离子盐的绿色制备方法 | |
| CN108358835B (zh) | 一种2,3,5-三氯吡啶的制备方法 | |
| CN104140356B (zh) | 一种新型绿色三氟氯乙烯的制备方法 | |
| CN111170846A (zh) | 一种制备3,3-二甲基-2-氧-丁酸的方法 | |
| CN102659571B (zh) | 一种除草剂中间体2, 4-二氯苯氧乙酸钠的连续化制备方法 | |
| CN106146294B (zh) | 一种全氟甲基乙烯基醚及其中间体的生产方法 | |
| CN109438356B (zh) | 一种咪鲜胺原药的纯化方法 | |
| CN111574439A (zh) | 一种制备2-氨基-3氯-5-三氟甲基吡啶的方法 | |
| CN100522932C (zh) | 2-溴甲基-2-苯基-4-(4-氯苯基)-丁腈的制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240528 Address after: 434020 No. 98 Nongji Road, Jingzhou Development Zone, Jingzhou City, Hubei Province Patentee after: Hubei Wojia Biological Agriculture Co.,Ltd. Country or region after: China Address before: 213022 No. 1218, Changjiang North Road, Weitang chemical industry zone, Xinbei District, Changzhou City, Jiangsu Province Patentee before: JIANGSU AGROCHEM LABORATORY Co.,Ltd. Country or region before: China Patentee before: NANJING GAOHENG BIOTECHNOLOGY CO.,LTD. |