二乙酸碘苯

二乙酸碘苯
	IUPAC名; Phenyl-λ3-iodanediyl diacetate
別名	I,I-二乙酰氧基碘苯; PIDA
識別
CAS號	3240-34-4
PubChem	76724
ChemSpider	69182
SMILES	CC(=O)OI(C1=CC=CC=C1)OC(=O)C;
InChI	1S/C10H11IO4/c1-8(12)14-11(15-9(2)13)10-6-4-3-5-7-10/h3-7H,1-2H3;
InChIKey	ZBIKORITPGTTGI-UHFFFAOYSA-N
性質
化學式	C10H11IO4
摩爾質量	322.1 g·mol−1
外觀	白色粉末
熔點	163-165 °C（436-438 K）
溶解性（水）	反應
溶解性	可溶於乙酸、乙腈和二氯甲烷
結構
晶體結構	正交晶系
空間群	Pnn2
晶格常數	a = 15.693(3) Å, b = 8.477(2) Å, c = 8.762(2) Å
分子構型	T形分子構型（英語：T-shaped molecular geometry）
相關物質
相關化學品	二(三氟乙酸)碘苯
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

二乙酸碘苯（PIDA）是化學式C
6H
5I(OCOCH
3)
2的超價碘化合物（英語：Hypervalent iodine），在有機化學中用作氧化劑。

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製備

二乙酸碘苯最早是由康拉德·威爾格羅德（英語：Conrad Willgerodt）於1892年^[1]通過碘苯和乙酸與過氧乙酸的混合物反應而成的：^[2]^[3]

C₆H₅I + CH₃CO₃H + CH₃CO₂H → C₆H₅I(O₂CCH₃)₂ + H₂O

PIDA也可以由亞碘酰苯（英語：iodosobenzene）和冰醋酸反應而成：^[3]

C₆H₅IO + 2 CH₃CO₂H → C₆H₅I(O₂CCH₃)₂ + H₂O

二乙酸碘苯最近的合成方式是直接由碘、乙酸和苯再加上作為氧化劑的過硼酸鈉^[4]或過二硫酸鉀^[5]一起反應而成：^[6]

C₆H₆ + I₂ + 2 CH₃CO₂H + K₂S₂O₈ → C₆H₅I(O₂CCH₃)₂ + KI + H₂SO₄ + KHSO₄

結構

PIDA分子是超價分子，它的碘原子形成了三個共價鍵。^[7]這個分子呈T形分子構型（英語：T-shaped molecular geometry），其中苯基佔據水平位置，而乙酰氧基佔據軸向位置，C-I-O鍵角低於90°。^[8]二乙酸碘苯的晶體結構是正交晶系，空間群 Pnn2。^[8]^[9]

反應

PIDA可通過乙酰氧基的取代反應製備結構相似的試劑。舉個例子，它在三氟乙酸中加熱反應，可以得到二(三氟乙酸)碘苯（PIFA）：^[10]^[6]

產物PIFA則可以使酰胺在弱酸性環境^[11]，而不是以前需要的強鹼性環境下發生霍夫曼降解反應。^[12]^[13]N-保護的天冬酰胺可以用PIDA脫羰，這可用於合成β-氨基-L-丙氨酸衍生物。^[14]

PIDA也可用於Suárez氧化反應中，這個反應可以把醇光解成環醚。^[15]^[16]^[17]這個反應被用於數個全合成中，如(−)-majucin、(−)-Jiadifenoxolane A^[18]和cephanolide A的全合成。^[19]

參考資料

[1]
Willgerodt, C. Zur Kenntniss aromatischer Jodidchloride, des Jodoso- und Jodobenzols. Chem. Ber. 1892, 25 (2): 3494–3502 [2022-08-24]. doi:10.1002/cber.189202502221. （原始內容存檔於2022-05-24）（德語）.
[2]
(1963) "Iodosobenzene Diacetate". Org. Synth. 43: 62; Coll. Vol. 5: 660.
[3]
Moriarty, Robert M.; Chany, Calvin J.; Kosmeder, Jerome W.; Du Bois, Justin. (Diacetoxyiodo)benzene. Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons. 2001. ISBN 9780470842898. doi:10.1002/047084289x.rd005m.pub2.
[4]
Hossain, Md. Delwar; Kitamura, Tsugio. Unexpected, Drastic Effect of Triflic Acid on Oxidative Diacetoxylation of Iodoarenes by Sodium Perborate. A Facile and Efficient One-Pot Synthesis of (Diacetoxyiodo)arenes. J. Org. Chem. 2005, 70 (17): 6984–6986. PMID 16095332. doi:10.1021/jo050927n.
[5]
Hossain, Md. Delwar; Kitamura, Tsugio. New and Direct Approach to Hypervalent Iodine Compounds from Arenes and Iodine. Straightforward Synthesis of (Diacetoxyiodo)arenes and Diaryliodonium Salts Using Potassium μ-Peroxo-hexaoxodisulfate. Bull. Chem. Soc. Jpn. 2007, 80 (11): 2213–2219. doi:10.1246/bcsj.80.2213.
[6]
Dohi, Toshifumi; Kita, Yasuyuki. Oxidizing Agents. Kaiho, Tatsuo (編). Iodine Chemistry and Applications. John Wiley & Sons. 2015: 277–302. ISBN 9781118878651.
[7]
Dohi, Toshifumi; Kita, Yasuyuki. Hypervalent Iodine. Kaiho, Tatsuo (編). Iodine Chemistry and Applications. John Wiley & Sons. 2015: 103–158. ISBN 9781118878651.
[8]
Lee, Chow-Kong; Mak, Thomas C. W.; Li, Wai-Kee; Kirner, John F. Iodobenzene diacetate. Acta Crystallogr. B. 1977, 33 (5): 1620–1622. doi:10.1107/S0567740877006694 .
[9]
Alcock, Nathaniel W.; Countryman, Rachel M.; Esperås, Steinar; Sawyer, Jeffery F. Secondary bonding. Part 5. The crystal and molecular structures of phenyliodine(III) diacetate and bis(dichloroacetate). J. Chem. Soc., Dalton Trans. 1979, 1979 (5): 854–860. doi:10.1039/DT9790000854.
[10]
(1988) "Hofmann Rearrangement Under Mildly Acidic Conditions Using [I,I-Bis(Trifluoroacetoxy)Iodobenzene: Cyclobutylamine Hydrochloride from Cyclobutanecarboxamide]". Org. Synth. 66; Coll. Vol. 8: 132.
[11]
Aubé, Jeffrey; Fehl, Charlie; Liu, Ruzhang; McLeod, Michael C.; Motiwala, Hashim F. 6.15 Hofmann, Curtius, Schmidt, Lossen, and Related Reactions. Heteroatom Manipulations. Comprehensive Organic Synthesis II 6. 2014: 598–635. ISBN 9780080977430. doi:10.1016/B978-0-08-097742-3.00623-6.
[12]
Wallis, Everett S.; Lane, John F. The Hofmann Reaction. Org. React. 1946, 3 (7): 267–306. doi:10.1002/0471264180.or003.07.
[13]
Surrey, Alexander R. Hofmann Reaction. Name Reactions in Organic Chemistry 2nd. Academic Press. 1961: 134–136. ISBN 9781483258683.
[14]
Zhang, Lin-hua; Kauffman, Goss S.; Pesti, Jaan A.; Yin, Jianguo. Rearrangement of N_α-Protected L-Asparagines with Iodosobenzene Diacetate. A Practical Route to β-Amino-L-alanine Derivatives. J. Org. Chem. 1997, 62 (20): 6918–6920. doi:10.1021/jo9702756.
[15]
Concepción, José I.; Francisco, Cosme G.; Hernández, Rosendo; Salazar, José A.; Suárez, Ernesto. Intramolecular hydrogen abstraction. Iodosobenzene diacetate, an efficient and convenient reagent for alkoxy radical generation. Tetrahedron Letters. 1984, 25 (18): 1953–1956. doi:10.1016/S0040-4039(01)90085-1.
[16]
Courtneidge, John L.; Lusztyk, Janusz; Pagé, Daniel. Alkoxyl radicals from alcohols. Spectroscopic detection of intermediate alkyl and acyl hypoiodites in the Suárez and Beebe reactions. Tetrahedron Letters. 1994, 35 (7): 1003–1006. doi:10.1016/S0040-4039(00)79950-3.
[17]
Dorta, R. L.; Francisco, C.G.; Freire, R.; Suárez, E. Intramolecular hydrogen abstraction. The use of organoselenium reagents for the generation of alkoxy radicals. Tetrahedron Letters. 1988, 29 (42): 5429–5432. doi:10.1016/S0040-4039(00)82887-7.
[18]
Condakes, Matthew L.; Hung, Kevin; Harwood, Stephen J.; Maimone, Thomas J. Total Syntheses of (−)-Majucin and (−)-Jiadifenoxolane A, Complex Majucin-Type Illicium Sesquiterpenes. Journal of the American Chemical Society. 2017, 139 (49): 17783–17786. doi:10.1021/jacs.7b11493.
[19]
Qing, Zhineng; Mao, Peng; Wang, Tie; Zhai, Hongbin. Asymmetric Total Syntheses of Cephalotane-Type Diterpenoids Cephanolides A–D. Journal of the American Chemical Society. 2022, 144 (23): 10640–10646. doi:10.1021/jacs.2c03978.

[1] [1]
Willgerodt, C. Zur Kenntniss aromatischer Jodidchloride, des Jodoso- und Jodobenzols. Chem. Ber. 1892, 25 (2): 3494–3502 [2022-08-24]. doi:10.1002/cber.189202502221. （原始內容存檔於2022-05-24）（德語）.

[2] [2]
(1963) "Iodosobenzene Diacetate". Org. Synth. 43: 62; Coll. Vol. 5: 660.

[e-EROS-3] [3]
Moriarty, Robert M.; Chany, Calvin J.; Kosmeder, Jerome W.; Du Bois, Justin. (Diacetoxyiodo)benzene. Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons. 2001. ISBN 9780470842898. doi:10.1002/047084289x.rd005m.pub2.

[4] [4]
Hossain, Md. Delwar; Kitamura, Tsugio. Unexpected, Drastic Effect of Triflic Acid on Oxidative Diacetoxylation of Iodoarenes by Sodium Perborate. A Facile and Efficient One-Pot Synthesis of (Diacetoxyiodo)arenes. J. Org. Chem. 2005, 70 (17): 6984–6986. PMID 16095332. doi:10.1021/jo050927n.

[5] [5]
Hossain, Md. Delwar; Kitamura, Tsugio. New and Direct Approach to Hypervalent Iodine Compounds from Arenes and Iodine. Straightforward Synthesis of (Diacetoxyiodo)arenes and Diaryliodonium Salts Using Potassium μ-Peroxo-hexaoxodisulfate. Bull. Chem. Soc. Jpn. 2007, 80 (11): 2213–2219. doi:10.1246/bcsj.80.2213.

[Tatsuo-ch16-6] [6]
Dohi, Toshifumi; Kita, Yasuyuki. Oxidizing Agents. Kaiho, Tatsuo (編). Iodine Chemistry and Applications. John Wiley & Sons. 2015: 277–302. ISBN 9781118878651.

[Tatsuo-ch7-7] [7]
Dohi, Toshifumi; Kita, Yasuyuki. Hypervalent Iodine. Kaiho, Tatsuo (編). Iodine Chemistry and Applications. John Wiley & Sons. 2015: 103–158. ISBN 9781118878651.

[Lee-8] [8]
Lee, Chow-Kong; Mak, Thomas C. W.; Li, Wai-Kee; Kirner, John F. Iodobenzene diacetate. Acta Crystallogr. B. 1977, 33 (5): 1620–1622. doi:10.1107/S0567740877006694 .

[Alcock-9] [9]
Alcock, Nathaniel W.; Countryman, Rachel M.; Esperås, Steinar; Sawyer, Jeffery F. Secondary bonding. Part 5. The crystal and molecular structures of phenyliodine(III) diacetate and bis(dichloroacetate). J. Chem. Soc., Dalton Trans. 1979, 1979 (5): 854–860. doi:10.1039/DT9790000854.

[10] [10]
(1988) "Hofmann Rearrangement Under Mildly Acidic Conditions Using [I,I-Bis(Trifluoroacetoxy)Iodobenzene: Cyclobutylamine Hydrochloride from Cyclobutanecarboxamide]". Org. Synth. 66; Coll. Vol. 8: 132.

[11] [11]
Aubé, Jeffrey; Fehl, Charlie; Liu, Ruzhang; McLeod, Michael C.; Motiwala, Hashim F. 6.15 Hofmann, Curtius, Schmidt, Lossen, and Related Reactions. Heteroatom Manipulations. Comprehensive Organic Synthesis II 6. 2014: 598–635. ISBN 9780080977430. doi:10.1016/B978-0-08-097742-3.00623-6.

[12] [12]
Wallis, Everett S.; Lane, John F. The Hofmann Reaction. Org. React. 1946, 3 (7): 267–306. doi:10.1002/0471264180.or003.07.

[13] [13]
Surrey, Alexander R. Hofmann Reaction. Name Reactions in Organic Chemistry 2nd. Academic Press. 1961: 134–136. ISBN 9781483258683.

[14] [14]
Zhang, Lin-hua; Kauffman, Goss S.; Pesti, Jaan A.; Yin, Jianguo. Rearrangement of N_α-Protected L-Asparagines with Iodosobenzene Diacetate. A Practical Route to β-Amino-L-alanine Derivatives. J. Org. Chem. 1997, 62 (20): 6918–6920. doi:10.1021/jo9702756.

[15] [15]
Concepción, José I.; Francisco, Cosme G.; Hernández, Rosendo; Salazar, José A.; Suárez, Ernesto. Intramolecular hydrogen abstraction. Iodosobenzene diacetate, an efficient and convenient reagent for alkoxy radical generation. Tetrahedron Letters. 1984, 25 (18): 1953–1956. doi:10.1016/S0040-4039(01)90085-1.

[16] [16]
Courtneidge, John L.; Lusztyk, Janusz; Pagé, Daniel. Alkoxyl radicals from alcohols. Spectroscopic detection of intermediate alkyl and acyl hypoiodites in the Suárez and Beebe reactions. Tetrahedron Letters. 1994, 35 (7): 1003–1006. doi:10.1016/S0040-4039(00)79950-3.

[17] [17]
Dorta, R. L.; Francisco, C.G.; Freire, R.; Suárez, E. Intramolecular hydrogen abstraction. The use of organoselenium reagents for the generation of alkoxy radicals. Tetrahedron Letters. 1988, 29 (42): 5429–5432. doi:10.1016/S0040-4039(00)82887-7.

[18] [18]
Condakes, Matthew L.; Hung, Kevin; Harwood, Stephen J.; Maimone, Thomas J. Total Syntheses of (−)-Majucin and (−)-Jiadifenoxolane A, Complex Majucin-Type Illicium Sesquiterpenes. Journal of the American Chemical Society. 2017, 139 (49): 17783–17786. doi:10.1021/jacs.7b11493.

[19] [19]
Qing, Zhineng; Mao, Peng; Wang, Tie; Zhai, Hongbin. Asymmetric Total Syntheses of Cephalotane-Type Diterpenoids Cephanolides A–D. Journal of the American Chemical Society. 2022, 144 (23): 10640–10646. doi:10.1021/jacs.2c03978.

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