CN104402812A - 一种合成吡啶甲酸的方法 - Google Patents
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- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 title abstract description 26
- 238000010189 synthetic method Methods 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- 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 1
- -1 alkyl pyridine Chemical compound 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- OLVNACLFTOTCQZ-UHFFFAOYSA-N methane pyridine Chemical compound C.N1=CC=CC=C1.N1=CC=CC=C1 OLVNACLFTOTCQZ-UHFFFAOYSA-N 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 18
- 229940081066 picolinic acid Drugs 0.000 abstract description 12
- 239000007787 solid Substances 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 4
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 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
- C07D213/803—Processes of preparation
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明公开了一种合成吡啶甲酸的方法，其处理方法为：将烷基吡啶在固定床上加热至300-450℃，经过3小时的持续加热全部变为蒸汽。把甲烷吡啶蒸汽与氨气，水蒸气，氧气充分反应，在容器中静置半小时。再向气体中加入四氯化钛进行催化，等待2小时后得吡啶甲腈。在得到的吡啶甲腈中加入1.2g无离子水然后开始搅拌，升温到40-70℃，加入氢氧化那，搅拌，升温到80-95℃，保温4-12小时。结束反应，降温至30-60℃，过滤，用无离子水洗涤，烘干得得10g的固体粉末。产率：83.3％。避免了传统方法中造成环境污染的问题，大大提高了产率，而且可以在常温常压或者低压下反应。
Description
技术领域
本发明属于有机化学合成领域，涉及到一种吡啶甲酸的合成方法。
背景技术
吡啶甲酸的分子式为：C5H5NO2。在结构上同为喊有lewis酸和lewis碱性官能团，是典型的杂环类两性化合物。吡啶甲酸系列广泛应用于医药，化工，食品及生活中，具有不可替代的作用与价值。因此国内外的学者和专家对吡啶甲酸合成进行了大量的研究。吡啶甲酸包括a，B，7三种异构体：皮考啉酸、烟酸和异烟酸。传统合成吡啶甲酸的方法是：气相催化氧化法。它在于高温下烷基吡啶汽化，与空气和水蒸气混合，经过催化剂床直接氧化成吡啶甲酸。这种方法催化剂对原料的纯度要求高，容易产生焦油和有毒气体，造成环境污染。
发明内容
为了解决现有技术中存在的容易产生环境污染的问题，本发明提供了一种合成吡啶甲酸方法，用该方法合成吡啶甲酸，避免了传统方法中造成环境污染的问题，大大提高了产率，而且可以在常温常压或者低压下反应。
达到上述目的，本发明吡啶甲酸的合成路线为：
本发明涉及的吡啶甲酸的合成过程包括以下步骤：
(1)将12g的烷基吡啶在固定床上加热至300-450℃，经过3小时的持续加热全部变为蒸汽；
(2)把甲烷吡啶蒸汽与氨气，水蒸气，氧气充分反应，在容器中静置半小时；
(3)再向气体中加入5mol的四氯化钛进行催化，等待2小时后得到0.85g的吡啶甲腈；
(4)在得到的吡啶甲腈中加入1.2g无离子水然后开始搅拌，升温到40-70℃，一次性加入0.08g氢氧化那，搅拌，升温到80-95℃，保温4-12小时。结束反应，降温至30-60℃，过滤，用0.4g的无离子水洗涤，烘干得10g的固体粉末。产率：83.3％。
具体实施方案：
将12g的烷基吡啶在固定床上加热至300-450℃，经过3小时的持续加热全部变为蒸汽.把甲烷吡啶蒸汽与氨气，水蒸气，氧气充分反应，在容器中静置半小时,再向气体中加入5mol的四氯化钛进行催化，等待2小时后得到0.85g的吡啶甲腈.在得到的吡啶甲腈中加入1.2g无离子水然后开始搅拌，升温到40-70℃，一次性加入0.08g氢氧化那，搅拌，升温到80-95℃，保温4-12小时。结束反应，降温至30-60℃，过滤，用0.4g的无离子水洗涤，得10g的固体粉末。产率：83.3％；
实例1
将12g的烷基吡啶在固定床上加热至300℃，经过3小时的持续加热全部变为蒸汽.把甲烷吡啶蒸汽与氨气，水蒸气，氧气充分反应，在容器中静置半小时,再向气体中加入5mol的四氯化钛进行催化，等待2小时后得到0.85g的吡啶甲腈.在得到的吡啶甲腈中加入1.2g无离子水然后开始搅拌，升温到40℃，一次性加入0.08g氢氧化那，搅拌，升温到80℃，保温4小时。结束反应，降温至30℃，过滤，用0.4g的无离子水洗涤，得9.5g的固体粉末。产率：79.1％。
实例2
将12g的烷基吡啶在固定床上加热至350℃，经过3小时的持续加热全部变为蒸汽.把甲烷吡啶蒸汽与氨气，水蒸气，氧气充分反应，在容器中静置半小时,再向气体中加入5mol的四氯化钛进行催化，等待2小时后得到0.85g的吡啶甲腈.在得到的吡啶甲腈中加入1.2g无离子水然后开始搅拌，升温到70℃，一次性加入0.08g氢氧化那，搅拌，升温到85℃，保温6小时。结束反应，降温至30℃，过滤，用0.4g的无离子水洗涤，得9.8g的固体粉末。产率：81.7％。
实例3
将12g的烷基吡啶在固定床上加热至450℃，经过3小时的持续加热全部变为蒸汽.把甲烷吡啶蒸汽与氨气，水蒸气，氧气充分反应，在容器中静置半小时,再向气体中加入5mol的四氯化钛进行催化，等待2小时后得到0.85g的吡啶甲腈.在得到的吡啶甲腈中加入1.2g无离子水然后开始搅拌，升温到40℃，一次性加入0.08g氢氧化那，搅拌，升温到80℃，保温12小时。结束反应，降温至60℃，过滤，用0.4g的无离子水洗涤，得9.9g的固体粉末。产率：82.5％。
Claims (1)
1.一种合成吡啶甲酸的方法，其特征在于：
(1)将12g的烷基吡啶在固定床上加热至300-450℃，经过3小时的持续加热全部变为蒸汽；
(2)把甲烷吡啶蒸汽与氨气，水蒸气，氧气充分反应，在容器中静置半小时；
(3)再向气体中加入5mol的四氯化钛进行催化，等待2小时后得到0.85g的吡啶甲腈；
(4)在得到的吡啶甲腈中加入1.2g无离子水然后开始搅拌，升温到40-70℃，一次性加入0.08g氢氧化那，搅拌，升温到80-95℃，保温4-12小时。结束反应，降温至30-60℃，过滤，用0.4g的无离子水洗涤，烘干得10g的固体粉末。
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