CN113444021A - 邻胺基芳香酸的异羟肟酸重排法制备 - Google Patents
邻胺基芳香酸的异羟肟酸重排法制备 Download PDFInfo
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
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- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005052 trichlorosilane Substances 0.000 claims description 2
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- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
- C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
- C07C259/10—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及有机功能新材料化学品领域，首次披露了若干邻胺基芳香酸的异羟肟酸前体重排法制备的新工艺技术。这些物质是已知的染料和颜料以及医药农药相关领域里用途广泛的关键精细化学品。
Description
【技术领域】
本发明涉及有机功能新材料化学品领域，首次披露了若干邻胺基芳香酸的异羟肟酸前体重排法制备的新工艺技术。这些物质是已知的染料和颜料以及医药农药相关领域里用途广泛的关键精细化学品。
【背景技术】
以邻胺基苯甲酸为代表的若干邻胺基芳香酸及其酯化物在染料，颜料，医药，农药，香料，以及环境监控测试等领域应用十分广泛。当前工业上沿用的生产工艺是苯酐酰胺化产物的碱促降解反应，该方法工艺特质决定了大量产生高盐和高浓度工业废水，COD值高达50000以上，环保压力巨大。因此其制备工艺技术和革新，在安全可靠，环保节能，和低成本经济竞争力等要素的强力驱动下，是业界从业研发和工程技术人员孜孜不倦持续追求的突破目标。
【发明内容】
本项申请现已首次意外地发现，如下反应式(I)所示，结构通式A描述的芳香异羟肟酸(hydroxamic acid)前体或中间体化合物在适当反应条件conditions下发生重排反应(re-arrangement)，以“一步法”和/或“一锅煮”的方式直接生成结构通式B描述的邻胺基芳香酸或其酯化物，展现了新工艺技术优异的简单性，高效性，温和性，环保性，和低成本经济性。
其中X是O或NH；定义R0是含有1-24个碳原子的直链或支链的烷基，或含有4-24个碳原子的取代或未取代的(杂)芳基，R1-R5分别独立的是氢，羟基，羧基，醛基，卤素，OR0基，NHR0基，N(R0)2基，C(O)R0基；相邻的任意两个R1-R5基之间可以形成3-8元环结构。
结构通式A描述的芳香异羟肟酸是未见文献报道的新化学物质，我们因此也对这类化合物结构宣称权利。
conditions是溶剂，温度，压力，和/或添加剂中任意之一或任意二者或二者以上的联合应用。
本工艺所涉及的反应“溶剂”选自含有1-24个碳的取代或非取代的芳香烃，直链或支链的脂肪烃，(亚)砜，酰胺，醚，酯，酮，腈，羧酸，水，胺，离子液，超临界二氧化碳，或上述任意二者或二者以上类型溶剂组成的混合溶剂；优先的溶剂是二甲基亚砜，二甲基砜，苯甲基亚砜，苯甲基砜，环丁亚砜，环丁砜，三氯硅烷，二氯甲烷，二氯乙烷，氯仿，四氯化碳，苯，甲苯，二甲苯，三甲苯，四甲苯，乙腈，乙苯，二乙苯，氯苯，二氯苯，苯甲醚，硝基苯，庚烷，己烷，石油醚，二氧六环，四氢呋喃，甲基叔丁基醚，乙二醇二甲醚，双缩乙二醇二甲醚，三缩乙二醇二甲醚，丙二醇甲醚醋酸酯，三乙胺，三丁胺，二甲基异丙胺，吡啶，N，N-四甲基乙二胺，N-烷基吗啉，N-烷基吡咯，N，N-二甲基甲酰胺，甲酰吗啉，N，N-二乙基甲酰胺，N-甲基吡咯烷酮，或上述任意二者或二者以上溶剂组成的混合溶剂。该反应也可以仅选用少量甚至不选用任何常规的“溶剂”，而采用原料固相加热和/或研磨，和/或超声波和/或微波辐照促进，的方式进行。
本工艺所涉及的反应“温度”选自-70摄氏度至200摄氏度之间，优先的是选自-30摄氏度至180摄氏度之间，更优先的是选自-20摄氏度至150摄氏度之间。
本工艺所涉及的反应“压力”选自0.001至200个标准大气压之间，优先的是选自0.1至100个标准大气压之间，更优先的是选自0.1至20个标准大气压之间。
本工艺所涉及的反应“添加剂”涵盖反应促进剂，增效剂，催化剂，和/或功能助剂，其是路易斯酸或路易斯碱型(Lewis acids/bases)单质或化合物，优选的是有机(叔)胺，碱金属，碱土金属，主族金属，或过渡金属的氟化物，氯化物，溴化物，碘化物，氧化物，氢氧化物，硫化物，烷氧化物，烷基或芳基金属化合物；或碱金属，碱土金属，主族金属，或过渡金属的碳酸盐，碳酸氢盐，亚硫酸盐，硫酸氢盐，磺酸盐，或羧酸盐；或碱金属，碱土金属，或过渡金属的一元或多元有机磷，有机胺，羟基，酮羰基，酯羰基，或羧酸配体的配合物；或四烷基卤化铵，四烷基氢氧化铵，或离子液体(Ionic Liquids)；或无机质子酸，有机羧酸，有机磺酸，杂多酸，分子筛，沸石，硅藻土，蒙拓土，高岭土；或硼，硅，磷元素的氟化物，氯化物，溴化物，碘化物，氧化物，氢氧化物，硫化物，烷氧化物；或满足上述定义“添加剂”中任意二者或二者以上的混合物或其联合使用。以反应原材料摩尔当量为基准，所述“添加剂”的使用量可以是催化量，等当量，或过当量。
反应原料A可以经由化合物C和羟胺NH2OH或其化学等价物(其化学等价物包括但不限于其酸盐例如盐酸羟胺，硫酸羟胺，硝酸羟胺，磷酸羟胺，或其羟胺酯)反应制备。细节在实施例中详细披露。因此，如通式(II)所示，自C-A-B是制备目标化合物的“一锅煮”式工艺路线。Q是O，NH，N-OR0。
在实施例中我们将进一步说明。
【具体实施方式】
实施例一：异羟肟酸苯甲酸的合成
在氮气保护下，将7.0克盐酸羟胺和150毫升水加入到250毫升三口瓶中，随后冰浴下滴加4.1克氢氧化钠溶于20毫升水配置的溶液，滴加完成后室温搅拌20分钟。随后室温下加入14.8克邻苯二甲酸酐并继续搅拌2小时。最终加入浓盐酸调节pH至4，过滤、冰水洗涤、干燥得目标产物异羟肟酸苯甲酸17.8克，产率98％。1H NMR(400MHz，DMSO-d6)：δ＝12.7(s，br，1H)，10.8(s，br，1H)，9.02(s，br，1H)，7.78(dd，J＝7.4，1.4Hz，1H)，7.57(td，J＝7.4，1.4Hz，1H)，7.52(td，J＝7.4，1.4Hz，1H)，7.38(dd，J＝7.4，1.4Hz，1H).13C NMR(100MHz，DMSO-d6)：δ＝168.2，166.3，136.5，131.8，131.6，130.0，129.9，128.8。
实施例二：邻胺基苯甲酸的合成
在氮气保护下将10.0克异羟肟酸苯甲酸和150毫升水加入到250毫升三口瓶中，随后室温下滴加2.3克氢氧化钠溶于10毫升水配置的溶液，滴加完成后升温至60摄氏度搅拌2小时。最终反应体系室温下加入浓盐酸调节pH至中性，过滤、冰水洗涤、干燥得目标产物邻氨基苯甲酸7.2克，产率95％。
实施例三：邻胺基苯甲酸的合成
在氮气保护下，将7.8克盐酸羟胺和150毫升水加入到250毫升三口瓶中，随后冰浴下滴加4.6克氢氧化钠溶于20毫升水配置的溶液，滴加完成后室温搅拌20分钟。室温下加入16.4克邻苯二甲酸酐并继续搅拌2小时。随后继续加入4.6克氢氧化钠溶于20毫升水配置的溶液并加热至60摄氏度搅拌2小时。最终反应体系加入浓盐酸调节pH至中性，过滤、冰水洗涤、干燥得目标产物邻氨基苯甲酸14.8克，产率97％。
实施例三：邻胺基苯甲酸的合成
在氮气保护下，将9.4克盐酸羟胺和150毫升水加入到250毫升三口瓶中，随后冰浴下滴加11.0克氢氧化钠溶于40毫升水配置的溶液，滴加完成后室温搅拌25分钟。室温下加入19.8克邻苯二甲酸酐并继续搅拌2小时，随后将反应体系加热至60摄氏度搅拌2小时。最终反应体系加入浓盐酸调节pH至中性，过滤、冰水洗涤、干燥得目标产物邻氨基苯甲酸17.6克，产率95％。
需要强调的是，上述实施例仅仅为示例性而非限定性说明，基于本项申请披露，任何从业技术人员所通常可能采用的反应条件或参数等调整或变动均不会偏离本发明的要旨，本专利的保护范围应以相关的权利书记载条目为准。
Claims (8)
1.结构式A描述的异羟肟酸芳香酸化合物：
其中X是O或NH；定义R0是含有1-24个碳原子的直链或支链的烷基，或含有4-24个碳原子的取代或未取代的(杂)芳基，R1-R5分别独立的是氢，羟基，羧基，醛基，卤素，OR0基，NHR0基，N(R0)2基，C(O)R0基，C(O)OR0基，C(O)NHR0；相邻的任意两个R1-R5基之间可以形成3-8元环结构。
2.反应式(I)所示的工艺过程，结构通式A描述的异羟肟酸芳香酸前体或中间体化合物在适当反应条件conditions下发生重排反应而直接生成结构通式B描述的邻胺基芳香酸或其酯化物：
其中X和R1-R5的定义与权利要求1相同；conditions是溶剂，温度，压力，和/或添加剂中任意之一或任意二者或二者以上的联合应用；优选的，conditions中的添加剂含有碱性化合物。
3.反应式(II)所示的工艺过程，化合物C和羟胺NH2OH或其化学等价物缩合制备异羟肟酸芳香酸中间体A，继而A在适当反应条件conditions下发生重排反应生成结构通式B描述的邻胺基芳香酸或其酯化物，该工艺可以分布实施，也可以以“一锅煮”方式连续实施：
Q是O，NH，N-OR0；
X和R1-R5以及conditions的定义与权利要求1和2中相同。
4.根据权利要求2-3描述的制备方法，所述反应“溶剂”选自含有1-24个碳的取代或非取代的芳香烃，直链或支链的脂肪烃，(亚)砜，酰胺，醚，酯，酮，腈，羧酸，水，胺，离子液，超临界二氧化碳，或上述任意二者或二者以上类型溶剂组成的混合溶剂；优先的溶剂是二甲基亚砜，二甲基砜，苯甲基亚砜，苯甲基砜，环丁亚砜，环丁砜，三氯硅烷，二氯甲烷，二氯乙烷，氯仿，四氯化碳，苯，甲苯，二甲苯，三甲苯，四甲苯，乙腈，乙苯，二乙苯，氯苯，二氯苯，苯甲醚，硝基苯，庚烷，己烷，石油醚，二氧六环，四氢呋喃，甲基叔丁基醚，乙二醇二甲醚，双缩乙二醇二甲醚，三缩乙二醇二甲醚，丙二醇甲醚醋酸酯，三乙胺，三丁胺，二甲基异丙胺，吡啶，N，N-四甲基乙二胺，N-烷基吗啉，N-烷基吡咯，N，N-二甲基甲酰胺，甲酰吗啉，N，N-二乙基甲酰胺，N-甲基吡咯烷酮，或上述任意二者或二者以上溶剂组成的混合溶剂。该反应也可以仅选用少量甚至不选用任何常规的“溶剂”，而采用原料固相加热和/或研磨，和/或超声波和/或微波辐照促进，的方式进行。
5.根据权利要求2-3描述的制备方法，所述反应“温度”选自-70摄氏度至200摄氏度之间；优先的是选自-30摄氏度至180摄氏度之间；更优先的是选自-20摄氏度至150摄氏度之间。
6.根据权利要求2-3描述的制备方法，所述反应“压力”选自0.001至200个标准大气压之间；优先的是选自0.1至100个标准大气压之间；更优先的是选自0.1至20个标准大气压之间。
7.根据权利要求2-3描述的制备方法，所述反应“添加剂”涵盖反应促进剂，增效剂，催化剂，和/或功能助剂，其是路易斯酸或路易斯碱型(Lewis acids/bases)单质或化合物；优选的是有机(叔)胺，碱金属，碱土金属，主族金属，或过渡金属的氟化物，氯化物，溴化物，碘化物，氧化物，氢氧化物，硫化物，烷氧化物，烷基或芳基金属化合物；或碱金属，碱土金属，主族金属，或过渡金属的碳酸盐，碳酸氢盐，亚硫酸盐，硫酸氢盐，磺酸盐，或羧酸盐；或碱金属，碱土金属，或过渡金属的一元或多元有机磷，有机胺，羟基，酮羰基，酯羰基，或羧酸配体的配合物；或四烷基卤化铵，四烷基氢氧化铵，或离子液体(Ionic Liquids)；或无机质子酸，有机羧酸，有机磺酸，杂多酸，分子筛，沸石，硅藻土，蒙拓土，高岭土；或硼，硅，磷元素的氟化物，氯化物，溴化物，碘化物，氧化物，氢氧化物，硫化物，烷氧化物；或满足上述定义“添加剂”中任意二者或二者以上的混合物或其联合使用。以反应原材料摩尔当量为基准，所述“添加剂”的使用量可以是催化量，等当量，或过当量。
8.根据权利要求1描述的化合物以及2-3描述的制备方法，自邻苯二甲酸酐(苯酐)和盐酸羟胺或其化学等价物缩合制备异羟肟酸苯甲酸中间体，该中间体在适当反应条件conditions下发生重排反应生成邻胺基芳香酸：
其中conditions的定义与权利要求2-3以及4-7中相同。
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