定义Definition
脱羧反应是羧酸(或其盐)失去一分子二氧化碳、羧基被氢或其他基团取代的反应。β-酮酸和丙二酸类加热即易脱羧。
Decarboxylation is the loss of carbon dioxide from a carboxylic acid (or salt), the carboxyl group being replaced by hydrogen or another group. β-Keto acids and malonic acids decarboxylate readily on heating.
β-酮酸的脱羧β-Keto acid decarboxylation
β-酮酸经六元环状过渡态,羧基 H 转移给酮羰基氧,同时 C–C 断裂放出 CO₂,生成烯醇,互变异构为酮。这是乙酰乙酸乙酯合成法、丙二酸酯合成法的最后一步。
β-Keto acids lose CO₂ through a six-membered cyclic TS in which the carboxyl H moves to the ketone oxygen as C–C breaks, giving an enol that tautomerises to the ketone — the final step of the acetoacetic and malonic ester syntheses.
其他脱羧Other decarboxylations
碱石灰与羧酸钠共热得烷烃(如乙酸钠 + NaOH → CH₄,中学实验室制甲烷);电解脱羧偶联(柯尔贝电解);巴顿脱羧;现代光氧化还原脱羧偶联以羧酸为自由基前体。
Heating sodium carboxylates with soda lime gives alkanes (sodium acetate + NaOH → CH₄, the school preparation of methane); Kolbe electrolysis couples radicals; Barton decarboxylation; modern photoredox decarboxylative couplings use acids as radical precursors.
生物学意义Biological significance
丙酮酸脱羧(乙醇发酵,需焦磷酸硫胺素)、氨基酸脱羧生成神经递质(多巴 → 多巴胺、组氨酸 → 组胺、谷氨酸 → GABA,需磷酸吡哆醛)、三羧酸循环中的氧化脱羧都是关键代谢步骤。
Pyruvate decarboxylation (ethanol fermentation, thiamine pyrophosphate), amino-acid decarboxylations to neurotransmitters (DOPA → dopamine, histidine → histamine, glutamate → GABA, pyridoxal phosphate) and oxidative decarboxylations in the citric-acid cycle are key metabolic steps.
反应Reactions
β-酮酸、丙二酸:100–150 °C;羧酸盐与碱石灰:强热
β-Keto and malonic acids: 100–150 °C; carboxylates with soda lime: strong heating
形成六元环状过渡态(β-酮酸)。
Six-membered cyclic TS (β-keto acids).
C–C 断裂放出 CO₂ 得烯醇。
C–C cleavage releases CO₂ and an enol.
烯醇互变为酮。
The enol tautomerises to the ketone.
丙二酸脱羧得乙酸。
Malonic acid to acetic acid.
反应机理图Mechanism
红色弯箭头表示一对电子的移动方向:从电子来源(孤对电子或化学键)指向电子去向。Red curly arrows show where an electron pair moves: from its source (lone pair or bond) to its destination.
β-酮酸经六元环过渡态失去 CO₂
A β-keto acid loses CO₂ through a six-membered transition state
烯醇 + CO₂
Enol + CO₂
丙酮
Acetone
年表Timeline
- 1849
柯尔贝电解脱羧
Kolbe electrolysis
- 1985
巴顿脱羧
Barton decarboxylation