亞磷酸二乙酯

亞磷酸二乙酯
	IUPAC名; Diethyl phosphonate; 膦酸二乙酯
別名	diethyl phosphonite; DEP; Phosphonic acid, diethyl ester
識別
CAS號	762-04-9
PubChem	12977
ChemSpider	12437
SMILES	CCOP(OCC)=O;
InChI	1S/C4H11O3P/c1-3-6-8(5)7-4-2/h5H,3-4H2,1-2H3;
InChIKey	SULWMEGSVQCTSK-UHFFFAOYSA-N
Beilstein	4-01-00-01329
性質
化學式	C4H11O3P
摩爾質量	138.1 g·mol−1
外觀	無色液體
密度	1.072 g/cm3
沸點	50-51 °C（2 mm Hg）
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

亞磷酸二乙酯是一種有機磷化合物，化學式為(C₂H₅O)₂P(O)H。它得益於P-H鍵的高反應性，是其他有機磷化合物的合成中的常用試劑。亞磷酸二乙酯是無色液體，^[1]分子構型為四面體形。

合成和性質

亞磷酸二乙酯有可能最先於1850年代，由三氯化磷與乙醇反應而成，但之後才有意製備。它的生成反應如下：^[2]

PCl₃ + 3 C₂H₅OH → (C₂H₅O)₂P(O)H + 2 HCl + C₂H₅Cl

在類似條件和鹼的存在下，這個反應會生成亞磷酸三乙酯：^[3]

PCl₃ + 3 EtOH + 3 R₃N → P(OEt)₃ + 3 R₃NH + 3 Cl⁻

亞磷酸二乙酯的許多類似物都能製備。^[4]^[5]雖然化合物名為磷酸酯，但它與亞磷酸相似，絕大部分是膦酸酯（C₂H₅O)₂P(O)H），可很多反應可以視為磷(III)互變異構體的反應。^[6]

(C₂H₅O)₂P^III(OH) ⇌ (C₂H₅O)₂P^V(O)H, K = 15 x 10⁶（25 °C，水中）^[7]

反應

水解和醇解

亞磷酸二乙酯水解後生成亞磷酸。這個反應能用氯化氫催化。:^[2]

亞磷酸二乙酯可以與醇產生酯交換反應。如果醇的沸點高，則這個轉換反應可以通過去除醇而加速：^[8]

(C₂H₅O)₂P(O)H + 2 ROH → (RO)₂P(O)H + 2 C₂H₅OH

同樣，胺可以取代乙氧基：^[9]

(C₂H₅O)₂P(O)H + RNH₂ → (C₂H₅O)(RN(H)P(O)H + C₂H₅OH

P-烷基化

亞磷酸二乙酯可以與三級丁酸鉀進行去質子化，因此可以作烷基化（米夏埃利斯-貝克爾反應（英語：Michaelis–Becker reaction））：^[10]

(C₂H₅O)₂P(O)H + KO^tBu → (C₂H₅O)₂P(O)K + HO^tBu

(C₂H₅O)₂P(O)K + RBr → (C₂H₅O)₂P(O)R + KBr

鹵代芳烴的轉化反應可以用鈀催化劑催化。^[1]C-P偶聯過程與布赫瓦爾德-哈特維希偶聯反應類似。

亞磷酸二乙酯與格氏試劑的反應由去質子化和乙氧基的取代反應組成。^[11]^[12]這個反應可以生成二級氧化膦（如二甲基氧化膦（英語：dimethylphosphine oxide）），如下：

(C₂H₅O)₂P(O)H + CH₃MgBr → (C₂H₅O)₂P(O)MgBr + CH₄

(C₂H₅O)₂P(O)MgBr + 2 CH₃MgBr → (CH₃)₂P(O)MgBr + 2 MgBr(OC₂H₅)

(CH₃)₂P(O)MgBr + H₂O → (CH₃)₂P(O)H + MgBr(OH)

氫膦酰化反應

亞磷酸二乙酯可以通過氫膦酰化反應（英語：hydrophosphonylation）與不飽和基團加成。例如，它與醛加成，方法與阿布拉莫夫反應（英語：Abramov reaction）相似：

(C₂H₅O)₂P(O)H + RCHO → (C₂H₅O)₂P(O)CH(OH)R

它也能通過普多維克反應（英語：Pudovik reaction）或卡巴奇尼克-菲爾茨反應與亞胺反應，^[13] 生成氨基膦酸酯（英語：aminophosphonate）。

參見

參考

^ ^1.0 ^1.1 Green, Kenneth. Encyclopedia of Reagents for Organic Synthesis. 2001. ISBN 0471936235. doi:10.1002/047084289X.rd211.
^ ^2.0 ^2.1 Malowan, J. E. Inorganic Syntheses 4. 1953: 58–60. ISBN 9780470132357. doi:10.1002/9780470132357.ch19.
^ Ford-Moore, A. H.; Perry, B. J. Triethyl Phosphite. Org. Synth. 1951, 31: 111. doi:10.15227/orgsyn.031.0111.
^ Pedrosa, Leandro. Esterification of Phosphorus Trichloride with Alcohols; Diisopropyl phosphonate. ChemSpider Synthetic Pages (Royal Society of Chemistry). March 20, 2011. SyntheticPage 488 [July 10, 2017]. doi:10.1039/SP488 .
^ Fakhraian, H.; Mirzaei, A. Reconsideration of the Base-Free Batch-Wise Esterification of Phosphorus Trichloride with Alcohols. Org. Process Res. Dev. 2004, 8 (3): 401–404. doi:10.1021/op049958v.
^ Doak, G. O.; Freedman, Leon D. The Structure and Properties of the Dialkyl Phosphonates. Chem. Rev. 1961, 61 (1): 31–44. doi:10.1021/cr60209a002.
^ Guthrie, J. Peter. Tautomerization Equilibria for Phosphorous Acid and its Ethyl Esters, Free Energies of Formation of Phosphorous and Phosphonic Acids and their Ethyl Esters, and p Ka Values for Ionization of the P—H Bond in Phosphonic Acid and Phosphonic Esters. Canadian Journal of Chemistry. 1979, 57 (2): 236–239. doi:10.1139/v79-039 .
^ Malowan, John E. Inorganic Syntheses 4. 1953: 61–62. ISBN 9780470132357. doi:10.1002/9780470132357.ch20.
^ John M. Read, Yu-Pu Wang, Rick L. Danheiser. Synthesis of Phosphoryl Ynamides by Copper-Catalyzed Alkynylation of Phosphoramidates. Preparation of Diethyl Benzyl(oct-1-yn-1-yl)phosphoramidate. Org. Synth. 2015, 92: 156. doi:10.15227/orgsyn.092.0156 .
^ (1988) "6-Diethylphosphonomethyl-2,2-dimethyl-1,3-dioxen-4-one (Phosphonic acid, [(2,2-dimethyl-4-oxo-4H-1,3-dioxin-6-yl)methyl-, diethyl ester)]". Org. Synth. 66; Coll. Vol. 8: 192.
^ Hays, Hugh R. Reaction of diethyl phosphonate with methyl and ethyl Grignard reagents. J. Org. Chem. 1968, 33 (10): 3690–3694. doi:10.1021/jo01274a003.
^ (2007) "Synthesis of Electron-Deficient Secondary Phosphine Oxides and Secondary Phosphines: Bis[3,5-bis(trifluoromethyl)phenylphosphine Oxide and Bis[3,5-bis(trifluoromethyl)phenyl]phosphine]". Org. Synth. 84.
^ Keglevich, György; Bálint, Erika. The Kabachnik–Fields Reaction: Mechanism and Synthetic Use. Molecules. 1 November 2012, 17 (11): 12821–12835. PMC 6268146 . PMID 23117425. doi:10.3390/molecules171112821 .

[eEROS-1] 1.0 ^1.1 Green, Kenneth. Encyclopedia of Reagents for Organic Synthesis. 2001. ISBN 0471936235. doi:10.1002/047084289X.rd211.

[Malowan-2] 2.0 ^2.1 Malowan, J. E. Inorganic Syntheses 4. 1953: 58–60. ISBN 9780470132357. doi:10.1002/9780470132357.ch19.

[3] Ford-Moore, A. H.; Perry, B. J. Triethyl Phosphite. Org. Synth. 1951, 31: 111. doi:10.15227/orgsyn.031.0111.

[4] Pedrosa, Leandro. Esterification of Phosphorus Trichloride with Alcohols; Diisopropyl phosphonate. ChemSpider Synthetic Pages (Royal Society of Chemistry). March 20, 2011. SyntheticPage 488 [July 10, 2017]. doi:10.1039/SP488 .

[5] Fakhraian, H.; Mirzaei, A. Reconsideration of the Base-Free Batch-Wise Esterification of Phosphorus Trichloride with Alcohols. Org. Process Res. Dev. 2004, 8 (3): 401–404. doi:10.1021/op049958v.

[6] Doak, G. O.; Freedman, Leon D. The Structure and Properties of the Dialkyl Phosphonates. Chem. Rev. 1961, 61 (1): 31–44. doi:10.1021/cr60209a002.

[7] Guthrie, J. Peter. Tautomerization Equilibria for Phosphorous Acid and its Ethyl Esters, Free Energies of Formation of Phosphorous and Phosphonic Acids and their Ethyl Esters, and p Ka Values for Ionization of the P—H Bond in Phosphonic Acid and Phosphonic Esters. Canadian Journal of Chemistry. 1979, 57 (2): 236–239. doi:10.1139/v79-039 .

[8] Malowan, John E. Inorganic Syntheses 4. 1953: 61–62. ISBN 9780470132357. doi:10.1002/9780470132357.ch20.

[9] John M. Read, Yu-Pu Wang, Rick L. Danheiser. Synthesis of Phosphoryl Ynamides by Copper-Catalyzed Alkynylation of Phosphoramidates. Preparation of Diethyl Benzyl(oct-1-yn-1-yl)phosphoramidate. Org. Synth. 2015, 92: 156. doi:10.15227/orgsyn.092.0156 .

[10] (1988) "6-Diethylphosphonomethyl-2,2-dimethyl-1,3-dioxen-4-one (Phosphonic acid, [(2,2-dimethyl-4-oxo-4H-1,3-dioxin-6-yl)methyl-, diethyl ester)]". Org. Synth. 66; Coll. Vol. 8: 192.

[11] Hays, Hugh R. Reaction of diethyl phosphonate with methyl and ethyl Grignard reagents. J. Org. Chem. 1968, 33 (10): 3690–3694. doi:10.1021/jo01274a003.

[12] (2007) "Synthesis of Electron-Deficient Secondary Phosphine Oxides and Secondary Phosphines: Bis[3,5-bis(trifluoromethyl)phenylphosphine Oxide and Bis[3,5-bis(trifluoromethyl)phenyl]phosphine]". Org. Synth. 84.

[13] Keglevich, György; Bálint, Erika. The Kabachnik–Fields Reaction: Mechanism and Synthetic Use. Molecules. 1 November 2012, 17 (11): 12821–12835. PMC 6268146 . PMID 23117425. doi:10.3390/molecules171112821 .

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