CN104710441B - 吡啶五甲酸二钾化合物及其制备方法 - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- -1 Pyridine pentacarbonic acid dipotassium compound Chemical class 0.000 title abstract description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 35
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- SGJONSOGICNYNJ-UHFFFAOYSA-N formic acid;potassium Chemical class [K].[K].OC=O SGJONSOGICNYNJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- 238000013517 stratification Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract 2
- 238000007254 oxidation reaction Methods 0.000 abstract 2
- 150000001412 amines Chemical class 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 239000012464 large buffer Substances 0.000 abstract 1
- 239000006179 pH buffering agent Substances 0.000 abstract 1
- 239000012286 potassium permanganate Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- XGFJCRNRWOXGQM-UHFFFAOYSA-N hot-2 Chemical compound CCSC1=CC(OC)=C(CCNO)C=C1OC XGFJCRNRWOXGQM-UHFFFAOYSA-N 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- GANDVAJEIJXBQJ-UHFFFAOYSA-M potassium;hydron;2-hydroxy-2-oxoacetate Chemical compound [K+].OC(=O)C(O)=O.OC(=O)C([O-])=O GANDVAJEIJXBQJ-UHFFFAOYSA-M 0.000 description 2
- VPQOOVGPOPRJDE-UHFFFAOYSA-N 2,4,6-trimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid Chemical compound CC1C(C(O)=O)=C(C)NC(C)=C1C(O)=O VPQOOVGPOPRJDE-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
-
- 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
Abstract
本发明涉及一种吡啶‑2，3，4，5，6‑五甲酸二钾化合物及其制备方法，其特征在于，该化合物的结构如下式所示：制备方法为：乙酰乙酸乙酯和乙醛在有机胺催化作用下发生化学反应，之后，再与氨反应得到2，4，6‑三甲基‑1，4‑二氢吡啶‑3，5‑二甲酸二乙酯；经硝酸氧化得到2，4，6‑三甲基吡啶‑3，5‑二甲酸二乙酯；再经KOH水解得到2，4，6‑三甲基吡啶‑3，5‑二甲酸二钾；最后经KMnO4氧化得到吡啶‑2，3，4，5，6‑五甲酸二钾；该化合物可用作pH缓冲剂，在pH值2.3时有较大的缓冲能力；本发明制备工艺简单、能耗低、原料易得、有较好的推广应用前景。
Description
技术领域
本发明涉及一种吡啶-2，3，4，5，6-五甲酸二钾化合物及其制备方法。该化合物可用作pH缓冲剂，配制标准pH缓冲溶液，其pH值在2.3左右，具有较大的缓冲容量。
背景技术
常用的标准pH缓冲溶液有：邻苯二甲酸氢钾溶液，磷酸二氢钾和磷酸氢二钠混合盐溶液，硼砂溶液，四草酸钾等。不同的缓冲溶液的适用范围是不同的，一般在其最大缓冲能力的pH附近使用。例如，0.05mol/L的邻苯二甲酸氢钾溶液pH＝4.00，磷酸二氢钾和磷酸氢二钠混合盐溶液中二者浓度都是0.025mol/L时pH＝6.86，四草酸钾浓度为0.05mol/L时pH＝1.68。虽然用现有的缓冲剂可以配得pH值2.3左右缓冲溶液，但都存在缓冲容量很小、稳定性差等不足。本发明公开了一种吡啶-2，3，4，5，6-五甲酸二钾化合物，其在pH值2.3左右缓冲容量大，稳定性好，能克服现有缓冲剂化合物的不足，有较好的推广应用前景。
发明内容
本发明的目的之一在于提出一种吡啶-2，3，4，5，6-五甲酸二钾化合物，其用作pH缓冲剂，配制的溶液在pH值2.3左右缓冲容量大、稳定性好。
为实现上述发明目的，采用如下技术方案：吡啶-2，3，4，5，6-五甲酸二钾化合物，其特征在于，这该化合物的结构如下式所示：
本发明的另一目的在于提出吡啶-2，3，4，5，6-五甲酸二钾的合成方法，其工艺简单、设备投资少、便于控制、易于规模化生产，且原料廉价易得，成本低廉，其技术方案如下：
在反应器中加入130g(1.0mol)乙酰乙酸乙酯，加入适量的催化剂，搅拌下在4-8小时内滴加40％乙醛55g-110g(0.5-1mol)，室温下继续搅拌48小时，分出上层水相，下层有机相加入等体积的乙醇，通氨气饱和，静置密封放置72小时，有浅黄色晶体2，4，6-三甲基-1，4-二氢吡啶-3，5-二甲酸二乙酯析出，抽滤，滤液蒸出一半量的酒精，冷却后又析出黄色固体2，4，6-三甲基-1，4-二氢吡啶-3，5-二甲酸二乙酯。
在另一反应器中搅拌下依次加入135g水，39g 98％硫酸和38g 60％硝酸，加热至微沸，加入100g 2，4，6-三甲基-1，4-二氢吡啶-3，5-二甲酸二乙酯，继续保温沸腾10min，用50％液碱调下层水相pH值7-12 范围，停止搅拌，静置分层，分出上层有机相，将其转入另一反应釜中，搅拌下加入3倍体积的乙醇，加入30g的固体KOH，加热使其溶解后，继续回流1h，蒸馏出乙醇，加100g水，加热到90℃，搅拌下分10批加入50g研细的KMnO4，到溶液颜色不褪后，保温反应10min，滴加甲醛使颜色褪除，趁热过滤除去MnO2，滤液冷却后，搅拌下滴加浓HCl，调pH值到2.0，析出大量的无色晶体，过滤得到吡啶-2，3，4，5，6-五甲酸二钾。
如上所述适量的催化剂为乙二胺、二乙胺或苯胺，其用量为乙酰乙酸乙酯质量的0.2-1.0％。
合成原理如下：
本发明的化合物为无色三水合吡啶-2，3，4，5，6-五甲酸二钾单斜晶体，100℃转化为一结晶水粉状固体，熔点：272-274℃。
吡啶-2，3，4，5，6-五甲酸二钾部分晶体学数据见下表1：
表1吡啶-2，3，4，5，6-五甲酸二钾部分晶胞参数及空间群
与现有技术相比，本发明的有益效果在于：
1、本发明的物质含有多个羧基，有丰富的络合基团，又能与吡啶环的氮原子生成多向络合体系，基团的络合能力有强有弱，释放与络合形成较强的互补平衡。
2、在pH值2.3左右，缓冲容量大，稳定性好。
本发明的技术特点在于：工艺简单，能耗低，原料廉价易得，有较好的推广应用前景。
附图说明
为了进一步说明产品的结构和性能特给出如下附图。
1、吡啶-2，3，4，5，6-五甲酸二钾晶胞，详见说明书附图1
2、吡啶-2，3，4，5，6-五甲酸二钾晶胞堆积图，详见说明书附图2
3、吡啶-2，3，4，5，6-五甲酸二钾红外光谱图，详见说明书附图3
4、吡啶-2，3，4，5，6-五甲酸二钾热重分析图，详见说明书附图4
具体实施方式
以下结合具体实施例对本发明的技术方案作进一步说明。
实施例1在反应器中加入130g(1.0mol)乙酰乙酸乙酯，加入催化剂乙二胺0.3g，搅拌下在4小时内滴加40％乙醛55g(0.5mol)，室温下继续搅拌48小时，分出上层水相，下层有机相加入等体积的乙醇，通氨气饱和，静置密封放置72小时，有浅黄色晶体2，4，6-三甲基-1，4-二氢吡啶-3，5-二甲酸二乙酯析出，抽滤，滤液蒸出一半量的酒精，冷却后又析出黄色固体2，4，6-三甲基-1，4-二氢吡啶-3，5-二甲酸二乙酯，产率33％。
在另一反应器中搅拌下依次加入135g水，39g 98％硫酸和38g 60％硝酸，加热至微沸，加入100g 2，4，6-三甲基-1，4-二氢吡啶-3，5-二甲酸二乙酯，继续保温沸腾10min，用50％液碱调下层水相pH值7-12范围，停止搅拌，静置分层，分出上层有机相，将其转入另一反应釜中，搅拌下加入3倍体积的乙醇，加入30g的固体KOH，加热使其溶解后，继续回流1h，蒸馏出乙醇，加100g水，加热到90℃，搅拌下分10批加入50g研细的KMnO4，到溶液颜色不褪后，保温反应10min，滴加甲醛使颜色褪除，趁热过滤除去MnO2，滤液冷却后，搅拌下滴加浓HCl，调pH值到2.0，析出大量的无色晶体，过滤得到吡啶-2，3，4，5，6-五甲酸二钾，产率64％。
实施例2：在反应器中加入130g(1.0mol)乙酰乙酸乙酯，加入催化剂二乙胺0.6g，搅拌下在6小时内滴加40％乙醛77g(0.7mol)，室温下继续搅拌60小时，分出上层水相，下层有机相加入等体积的 乙醇，通氨气饱和，静置密封放置96小时，有浅黄色晶体2，4，6-三甲基-1，4-二氢吡啶-3，5-二甲酸二乙酯析出，抽滤，滤液蒸出一半量的酒精，冷却后又析出黄色固体2，4，6-三甲基-1，4-二氢吡啶-3，5-二甲酸二乙酯，产率57％。
在另一反应器中搅拌下依次加入135g水，39g 98％硫酸和38g 60％硝酸，加热至微沸，加入100g 2，4，6-三甲基-1，4-二氢吡啶-3，5-二甲酸二乙酯，继续保温沸腾10min，用50％液碱调下层水相pH值7-12范围，停止搅拌，静置分层，分出上层有机相，将其转入另一反应釜中，搅拌下加入3倍体积的乙醇，加入30g的固体KOH，加热使其溶解后，继续回流1h，蒸馏出乙醇，加100g水，加热到90℃，搅拌下分10批加入50g研细的KMnO4，到溶液颜色不褪后，保温反应10min，滴加甲醛使颜色褪除，趁热过滤除去MnO2，滤液冷却后，搅拌下滴加浓HCl，调pH值到2.0，析出大量的无色晶体，过滤得到吡啶-2，3，4，5，6-五甲酸二钾，产率64％。
实例3在反应器中加入130g(1.0mol)乙酰乙酸乙酯，加入催化剂苯胺1.2g，搅拌下在8小时内滴加40％乙醛110g(1mol)，室温下继续搅拌72小时，分出上层水相，下层有机相加入等体积的乙醇，通氨气饱和，静置密封放置120小时，有浅黄色晶体2，4，6-三甲基-1，4-二氢吡啶-3，5-二甲酸二乙酯析出，抽滤，滤液蒸出一半量的酒精，冷却后又析出黄色固体2，4，6-三甲基-1，4-二氢吡啶-3，5-二甲酸二乙酯，产率50％。
在另一反应器中搅拌下依次加入135g水，39g 98％硫酸和38g 60％硝酸，加热至微沸，加入100g 2，4，6-三甲基-1，4-二氢吡啶-3，5-二甲酸二乙酯，继续保温沸腾10min，用50％液碱调下层水相pH值7-12范围，停止搅拌，静置分层，分出上层有机相，将其转入另一反应釜中，搅拌下加入3倍体积的乙醇，加入30g的固体KOH，加热使其溶解后，继续回流1h，蒸馏出乙醇，加100g水，加热到90℃，搅拌下分10批加入50g研细的KMnO4，到溶液颜色不褪后，保温反应10min，滴加甲醛使颜色褪除，趁热过滤除去MnO2，滤液冷却后，搅拌下滴加浓HCl，调pH值到2.0，析出大量的无色晶体，过滤得到吡啶-2，3，4，5，6-五甲酸二钾。
本案发明人将上述合成的吡啶-2，3，4，5，6-五甲酸二钾用于配制缓冲溶液，并与相同浓度、相同量的邻苯二甲酸氢钾进行对比。吡啶-2，3，4，5，6-五甲酸二钾、邻苯二甲酸氢钾的浓度均为0.025mol/L，用量为40.0mL，加入0.01mol/L KOH或0.02mol/L HCl测试缓冲溶液pH变化值与所加酸碱量的关系，列出了部分实验结果如表2、表3所示：
表2吡啶-2，3，4，5，6-五甲酸二钾对碱的缓冲能力数据
表3吡啶-2，3，4，5，6-五甲酸二钾对酸的缓冲能力数据
Claims (3)
1.一种吡啶-2，3，4，5，6-五甲酸二钾化合物，其特征在于，该化合物的结构如下式所示：
2.如权利要求1所述吡啶-2，3，4，5，6-五甲酸二钾化合物的制备方法，其特征在于，该方法为：
在反应器中加入130g(1.0mol)乙酰乙酸乙酯，加入适量的催化剂，搅拌下在4-8小时内滴加40％乙醛55g-110g(0.5-1mol)，室温下继续搅拌48-72小时，分出上层水相，下层有机相加入等体积的乙醇，通氨气饱和，静置密封放置72-120小时，有浅黄色晶体2，4，6-三甲基-1，4-二氢吡啶-3，5-二甲酸二乙酯析出，抽滤，滤液蒸出一半量的酒精，冷却后又析出黄色固体2，4，6-三甲基-1，4-二氢吡啶-3，5-二甲酸二乙酯；在另一反应器中搅拌下依次加入135g水，39g 98％硫酸和38g 60％硝酸，加热至微沸，加入100g 2，4，6-三甲基-1，4-二氢吡啶-3，5-二甲酸二乙酯，继续保温沸腾10min，用50％液碱调下层水相pH值7-12范围，停止搅拌，静置分层，分出上层有机相，将其转入另一反应釜中，搅拌下加入3倍体积的乙醇，加入30g的固体KOH，加热使其溶解后，继续回流1h，蒸馏出乙醇，加100g水，加热到90℃，搅拌下分10批加入50g研细的KMnO4，到溶液颜色不褪后，保温反应10min，滴加甲醛使颜色褪除，趁热过滤除去MnO2，滤液冷却后，搅拌下滴加浓HCl，调pH值到2.0，析出大量的无色晶体，过滤得到吡啶-2，3，4，5，6-五甲酸二钾。
3.如权利要求2所述吡啶-2，3，4，5，6-五甲酸二钾化合物的制备方法，其特征在于：所述的催化剂为乙二胺、二乙胺、苯胺，其用量为乙酰乙酸乙酯质量的0.2％-1.0％。
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