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词条 N-Hydroxyphthalimide
释义

  1. Occurrence and production

  2. Properties

  3. Applications and reactions

     Phthalimido-N-oxyl (PINO) 

  4. References

{{DISPLAYTITLE:N-Hydroxyphthalimide}}{{Chembox
| Name = N-Hydroxyphthalimide
| ImageFile = N-Hydroxyphthalimid Struktur.svg
| ImageSize = 200px
| ImageAlt =
| IUPACName = 2-Hydroxyisoindole-1,3-dione
| OtherNames =
| Section1 = {{Chembox Identifiers
| CASNo = 524-38-9
| PubChem = 10665
| ChemSpiderID = 10215
| EINECS = 208-358-1
| SMILES = O=C2N(O)C(C1=CC=CC=C12)=O
| StdInChI = 1S/C8H5NO3/c10-7-5-3-1-2-4-6(5)8(11)9(7)12/h1-4,12H
| StdInChIKey = CFMZSMGAMPBRBE-UHFFFAOYSA-N
| Section2 = {{Chembox Properties
| C=8|H=5|N=1|O=3
| Appearance =
| Density =
| MeltingPt =
| BoilingPt =
| Solubility =
| Section3 = {{Chembox Hazards
| MainHazards =
| FlashPt =
| AutoignitionPt =
}}N-Hydroxyphthalimide is the N-hydroxy derivative of phthalimide. The compound is used, inter alia, as catalyst for oxidation reactions, in particular for the selective oxidation (e. g. alkanes to alcohols) with molecular oxygen under mild conditions.[1][2]

Occurrence and production

The synthesis of N-hydroxyphthalimide from phthaloyl chloride and hydroxylamine hydrochloride in the presence of sodium carbonate in aqueous solution was first reported by Lassar Cohn in 1880 (referred to as "Phthalylhydroxylamin").[3]

The product forms as a red sodium salt under basic conditions, while white N-hydroxyphthalimide precipitates in 55% yield as the solution is acidified. N-hydroxyphthalimide is also produced by reacting hydroxylamine hydrochloride with diethyl phthalate in the presence of sodium acetate,[4] or with phthalic anhydride in the presence of sodium carbonate with heating. In the last case, an overall yield of 76% is produced following purification by recrystallization.[5]

Microwave irradiation of phthalic anhydride and hydroxylamine hydrochloride in pyridine produces N-hydroxyphthalimide in 81% yield.[6] Even in the absenceof a base, phthalic anhydride and hydroxylamine phosphate react to produce N-hydroxyphthalimide in 86% yield when heated to 130 °C.[7]

Properties

N-Hydroxyphthalimide is a colorless to yellow, odorless crystalline powder which is soluble in water and organic solvents such as acetic acid, ethyl acetate and acetonitrile.[8] The compound exists in two different-colored monoclinic crystal forms. In case of the colorless white form, the N-OH group is rotated about 1.19° from the plane of the molecule, while in the yellow form it is much closer to planarity (0.06° rotation).[9]

The color of the synthesized N-hydroxyphthalimide depends on the type of solvent used; the color transition from white to yellow is irreversible.[10] N-hydroxyphthalimide forms strongly colored, mostly yellow or red salts with alkali and heavy metals, ammonia and amines.[11] Hydrolysis of N-hydroxyphthalimide by the addition of strong bases produces phthalic acid monohydroxamic acid by adding water across one of the carbon–nitrogen bonds.[4] N-hydroxyphthalimide ethers, on the other hand, are colorless and provide O-alkylhydroxylamines by alkaline hydrolysis or cleavage through hydrazine hydrate.

The "phthalylhydroxylamine" reported by Cohn was known to have a molecular formula of {{chem|C|8|H|5|N|O|3}} but the exact structure was not known.[3] Three possibilities were discussed and are shown in the Figure below: a mono-oxime of phthalic anhydride ("phthaloxime", I), an expanded ring with two heteroatoms, (2,3-benzoxazine-1,4-dione, II), and N-hydroxyphthalimide (III).[10][12] It was not until the 1950s that Cohn's product was definitely shown to be (III), N-hydroxyphthalimide.[13]

Applications and reactions

Nefkens and Tesser developed a technique for generating active esters from N-hydroxyphthalimide[14] for use in peptide synthesis,[15] an approach later extended to using N-hydroxysuccinimide.[16] The ester linkage is formed between the N-hydroxyphthalimide and a carboxylic acid by elimination of water, the coupling achieved with N,N'-dicyclohexylcarbodiimide (DCC). For peptide synthesis, the N-terminus of the growing peptide is protected with tert-butyloxycarbonyl while its C-terminus (Z-NH-CH(R)-COOH) is coupled to N-hydroxyphthalimide. An ester of the next amino acid in the desired peptide sequence is shaken with activated ester, adding to the chain and displacing the N-hydroxyphthalimide. This reaction is quantitative and nearly instantaneous at 0 °C.[15][21] The resulting ester needs to be hydrolysed before the cycle can be repeated.

The N-hydroxyphthalimide can be removed by shaking with sodium bicarbonate,[15] but the N-hydroxysuccinimide approach shows greater reactivity and convenience, and is generally preferred.[16][17]

Esters of N-hydroxyphthalimide and activated sulfonic acids such as trifluoromethanesulfonic anhydride or p-toluenesulfonyl chloride are used as so-called photoacids, which split off protons during UV irradiation.

The protons generated serve for the targeted local degradation of acid-sensitive photoresists.[18]

N-hydroxyphthalimide can be converted with vinyl acetate in the presence of palladium(II)acetate to the N-vinyloxyphthalimide, which is quantitatively hydrogenated to N-ethoxyphthalimide and after purified by cleavage, yielding O-ethylhydroxylamine.[19]

A variety of different functional groups can be oxidized with the aminoxyl radical (phthalimide-N-oxyl, PINO)[20] formed by the abstraction of a hydrogen atom from N-hydroxyphthalimide under gentle conditions (similar to the piperidine derivative 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO)):[1]

Using molecular oxygen alkanes can be oxidized to form alcohols, secondary alcohols to ketones, acetals to esters and alkenes to epoxides.[21][22][23] Amides can be converted into carbonyl compounds with N-hydroxyphthalimide and cobalt(II)salts under mild conditions.[24]

Efficient oxidation reactions of precursors of important basic chemicals are of particular technical interest. For example, ε-caprolactam can be prepared using NHPI from the so-called KA oil ("ketone-alcohol" oil, a mixture of cyclohexanol and cyclohexanone) which is obtained during the oxidation of cyclohexane. The reaction proceeds via cyclohexanol hydroperoxide which reacts with ammonia to give peroxydicyclohexylamine followed by a rearrangement in the presence of catalytic amounts of lithium chloride.[22][25]

The use of N-hydroxyphthalimide as a catalyst in the oxidation of KA oil avoids the formation of the undesirable by-product ammonium sulfate which is produced by the conventional ε-caprolactam synthesis (Beckmann rearrangement of cyclohexanone oxime with sulfuric acid).

Alkanes are converted into nitroalkanes in the presence of nitrogen dioxide.[26]

Cyclohexane is converted at 70 °C with nitrogen dioxide/air into a mixture of nitrocyclohexane (70%), cyclohexyl nitrate (7%) and cyclohexanol (5%).

Furthermore, applications of N-hydroxyphthalimide as oxidizing agents in photographic developers[27] and as charge control agents in toners[28] have been described in the patent literature.

Phthalimido-N-oxyl (PINO)

The radical derived by removal of an H-atom from N-hydroxyphthalimide is called N-phthalimido-N-oxyl, acronym being PINO. It is a powerful H-atom abstracting agent.[29]

References

1. ^1 {{cite journal|first1 = Francesco|last1 = Recupero|first2 = Carlo|last2 = Punta|journal = Chem. Rev.|title = Free Radical Functionalization of Organic Compounds Catalyzed by N-Hydroxyphthalimide|volume = 107|issue = 9|year = 2007|pages = 3800–3842|doi = 10.1021/cr040170k}}
2. ^{{cite journal|first1 = Lucio|last1 = Melone|first2 = Carlo|last2 = Punta|journal = Beilstein J. Org. Chem.|title = Metal-free aerobic oxidations mediated by N-hydroxyphthalimide. A concise review|volume = 9|year = 2013|pages = 1296–1310|doi = 10.3762/bjoc.9.146|doi-access = free}}
3. ^1 {{cite journal|first1 = Lassar|last1 = Cohn|journal = Justus Liebigs Ann. Chem.|title = Phthalylhydroxylamin: Ueberführung der Phthalsäure in Salicylsäure|trans-title=N-hydroxyphthalimide: Conversion of phthalic acid into salicylic acid|language = German|volume = 205|issue = 3|year = 1880|pages = 295–314|doi = 10.1002/jlac.18802050304}}
4. ^1 {{cite journal|first1 = Ludwig|last1 = Bauer|first2 = Stanley V.|last2 = Miarka|journal = J. Am. Chem. Soc.|title = The Chemistry of N-Hydroxyphthalimide|volume = 79|issue = 8|year = 1957|pages = 1983–1985|doi = 10.1021/ja01565a061}}
5. ^{{cite journal|first1 = H.|last1 = Gross|first2 = I.|last2 = Keitel|journal = J. Prakt. Chem.|title = Zur Darstellung von N-Hydroxyphthalimid und N-Hydroxysuccinimid|language = German|trans-title=On the preparation of N-hydroxyphthalimide and N-hydroxysuccinimide|volume = 311|issue = 4|year = 1969|pages = 692–693|doi = 10.1002/prac.19693110424}}
6. ^{{cite journal|title = Microwave‐assisted Synthesis of N‐Hydroxyphthalimide Derivatives|first1 = Kazuhiro|last1 = Sugamoto|first2 = Yoh‐ichi|last2 = Matsushita|first3 = Yu‐hei|last3 = Kameda|first4 = Masahiko|last4 = Suzuki|first5 = Takanao|last5 = Matsui|pages = 67-70|year = 2005|doi = 10.1081/SCC-200046498|journal = Synth. Commun.|volume = 35|issue = 1}}
7. ^{{cite patent|country = EP|number = 1085013|status = application|type = A1|title = Verfahren zur Herstellung cyclischer N-Hydroxy-dicarboximide (Process for the preparation of cyclic N-hydroxydicarboximides)|pubdate = 2001-03-21|fdate = 2000-08-31|pridate = 1999-09-07|inventor = Elke Fritz-Langhals|assignee = Consortium für elektrochemische Industrie GmbH}}
8. ^{{cite encyclopedia|first1 = Cristian|last1 = Gambarotti|first2 = Carlo|last2 = Punta|first3 = Francesco|last3 = Recupero|first4 = Maria|last4 = Zlotorzynska|first5 = Glenn|last5 = Sammis|encyclopedia = Encyclopedia of Reagents for Organic Synthesis|title = N-Hydrophthalimide|year = 2013|doi = 10.1002/047084289X.rn00598.pub2}}
9. ^{{cite journal|first1 = Hendrik|last1 = Reichelt|first2 = Chester A.|last2 = Faunce|first3 = Henrich H.|last3 = Paradies|journal = J. Phys. Chem. A|title = Elusive forms and structures of N-hydroxyphthalimide: The colorless and yellow crystal forms of N-hydroxyphthalimide|volume = 111|issue = 13|year = 2007|pages = 2587–2601|doi = 10.1021/jp068599y}}
10. ^1 {{cite journal|first1 = D. E.|last1 = Ames|first2 = T. F.|last2 = Grey|journal = J. Chem. Soc.|title = N-Hydroxy-imides. Part II. Derivatives of homophthalic and phthalic acid|year = 1955|pages = 3518–3521|doi = 10.1039/JR9550003518}}
11. ^{{cite book|first1 = Andrea|last1 = Porcheddu|first2 = Giampaolo|last2 = Giacomelli|editor1-first = Zvi|editor1-last = Rappaport|editor2-first = Joel F.|editor2-last = Lieberman|chapter = Synthesis of oximes and hydroxamic acids|title = The Chemistry of Hydroxylamines, Oximes, and Hydroxamic Acids, Part 1|publisher = Wiley|location = Chichester|year = 2009|pages = 224−226|isbn = 978-0-470-51261-6}}
12. ^{{cite journal|first1 = Oscar L.|last1 = Bradly|first2 = Leslie C.|last2 = Baker|first3 = Richard F.|last3 = Goldstein|first4 = Samuel|last4 = Harris|journal = J. Chem. Soc.|title = LXVIII.—The isomerism of the oximes. Part XXXIII. The oximes of opianic acid and of phthalic anhydride|year = 1928|pages = 529–539|doi = 10.1039/JR9280000529}}
13. ^{{cite journal|first1 = Charles D.|last1 = Hurd|first2 = Charles M.|last2 = Buess|first3 = Ludwig|last3 = Bauer|journal = J. Org. Chem.|title = Succino- and phthalo-hydroxamic acids|volume = 19|issue = 7|year = 1954|pages = 1140–1149|doi = 10.1021/jo01372a021}}
14. ^{{cite journal|journal = Recl. Trav. Chim. Pays-Bas|year = 1962|volume = 81|issue = 8|pages = 683–690|title = Synthesis and reactions of esters of N-hydroxyphthalimide and N-protected amino acids|first1 = G. H. L.|last1 = Nefkens|first2 = G. I.|last2 = Tesser|first3 = R. J. F.|last3 = Nivard|doi = 10.1002/recl.19620810807}}
15. ^1 2 {{cite journal|title = A Novel Activated Ester in Peptide Synthesis|first1 = G. H. L.|last1 = Nefkens|first2 = G. I.|last2 = Tesser|journal = J. Am. Chem. Soc.|year = 1961|volume = 83|issue = 5|page = 1263|doi = 10.1021/ja01466a068}}
16. ^1 {{cite journal|title = The Use of Esters of N-Hydroxysuccinimide in Peptide Synthesis|first1 = George W.|last1 = Anderson|first2 = Joan E.|last2 = Zimmerman|first3 = Francis M.|last3 = Callahan|journal = J. Am. Chem. Soc.|year = 1964|volume = 86|issue = 9|pages = 1839–1842|doi = 10.1021/ja01063a037}}
17. ^1 {{cite book|title = Principles of Peptide Synthesis|first = Miklos|last = Bodanszky|edition = 2nd|isbn = 9783642780561|url = https://books.google.com/books?id=nvHvCAAAQBAJ&pg=PA34|chapter = Activation and Coupling|pages = 9-61|publisher = Springer-Verlag|year = 1993|doi = 10.1007/978-3-642-78056-1_2}}
18. ^{{Cite patent|Country = EP|number =0919867 |Code=B1 |Title =Chemisch verstärkter Resist für die Elektronenstrahllithografie |V-Datum =2003-05-21 |A-Datum =1998-11-17 |inventor =K. Elian, E. Günther, R. Leuschner |Anmelder =Infineon Technologies AG |DB =Google}}
19. ^{{Cite patent|Country = WO|number =1995025090 |Title =Cyclic N-alkenyloxyimides and a method for the preparation of cyclic N-alkenyloxyimides, the corresponding cyclic N-alkoxyimides and O-alkoxyamines |V-Datum =1995-9-21 |A-Datum =1995-3-14 |inventor =D.M.C. Callant, A.M.C.F. Castelijns, J.G. De Vries |Anmelder =DSM N.V. |DB =Google}}
20. ^{{citation|surname1=S. Coseri|periodical=Catal. Rev. Sci. Eng.|title=Phthalimide‐N‐oxyl (PINO) Radical, a Powerful Catalytic Agent: Its Generation and Versatility Towards Various Organic Substrates|volume=51|issue=2|pages=218–292|date= 2009 |doi=10.1080/01614940902743841}}
21. ^{{citation|surname1=Y. Ishii, K. Nakayama, M. Takeno, S. Sakaguchi, T. Iwahama, Y. Nishiyama|periodical=J. Org. Chem.|title=Novel Catalysis by N-Hydroxyphthalimide in the Oxidation of Organic Substrates by Molecular Oxygen|volume=60|issue=13|pages=3934–3935|date= 1995 |doi=10.1021/jo00118a002}}
22. ^1 {{cite web|title=Discovery of a carbon radical producing catalyst and its application to organic synthesis|trans-title=|periodical=TCIMAIL, number 116|publisher=Tokyo Chemical Industry Co. Ltd.|url=http://www.tcichemicals.com/de/de/support-download/tcimail/backnumber/article/116drE.pdf|deadurl=|format=|accessdate=2016-08-11|archiveurl=|archivedate=|last=|date=April 2003|year=|month=|day= |pages=|quote=}}
23. ^{{citation|surname1=B.B. Wentzel, M.P.J. Donners, P.L. Alsters, M.C. Feiters, R.J.M. Nolte|periodical=Tetrahedron|title=N-Hydroxyphthalimide/cobalt(II) catalyzed low temperature benzylic oxidation using molecular oxygen|volume=56|pages=7797–7803|date= 2000 |doi=10.1016/S0040-4020(00)00679-7}}
24. ^{{citation|surname1=F. Minisci, C. Punta, F. Recupero, F. Fontana, G.F. Pedulli|periodical=J. Org. Chem.|title=Aerobic Oxidation of N-Alkylamides Catalyzed by N-Hydroxyphthalimide under Mild Conditions. Polar and Enthalpic Effects|volume=67|issue=8|pages=2671–2676|date= 2002 |doi=10.1021/jo16398e}}
25. ^{{citation|surname1=O. Fukuda, S. Sakaguchi, Y. Ishii|periodical=Tetrahedron Lett.|title=A new strategy for catalytic Baeyer-Villiger oxidation of KA-oil with molecular oxygen using N-hydroxyphthalimide|volume=42|issue=20|pages=3479–3481|date= 2001 |doi=10.1016/S0040-4039(01)00469-5}}
26. ^{{citation|surname1=S. Sakaguchi, Y. Nishiwaki, T. Kitamura, Y. Ishii|periodical=Angew. Chem., Int. Edit.|title=Efficient catalytic alkane nitration with NO2 under air assisted by N-hydroxyphthalmide|volume=40|issue=1|pages=222–224|date= 2001 |doi=10.1002/1521-3773(20010105)40:1<222::AID-ANIE222>3.0.CO;2-W}}
27. ^{{cite patent|Title=|country=EP|number=0664479|status=application|title=Method of processing silver halide photographic lightsensitive material|pubdate=1994-7-26|fdate=1994-12-06|pridate=1993-12-6|invent1=W. Ishikawa|invent2=T. Sampei|assign1=Konica Corp.|class=|url=}}
28. ^{{cite patent|country=US|number=5332637|status=|title=Electrostatographic dry toner and developer compositions with hydroxyphthalimide|gdate=1994-7-26|fdate=1993-8-31|pridate=1993-8-31|invent1=J.C. Wilson|invent2=S.M. Bonser|invent3=H.W. Osterhoudt|assign1=Eastman Kodak Co.|assign2=|class=|url=}}
29. ^{{cite journal|authors=Recupero, F.; Punta, C.|title=Free Radical Functionalization of Organic Compounds Catalyzed by N-Hydroxyphthalimide|journal=Chemical Reviews|year=2007|volume=107|pages=3800-3842|doi= 10.1021/cr040170k}}
{{DEFAULTSORT:Hydroxyphthalimide, N-}}

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