The synthesis of some N-hydroxyimides

Ames, D. E.; Grey, T. F.

doi:10.1039/jr9550000631

Cited by 57 publications

(25 citation statements)

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“…Because the phthalic protecting group can easily be removed, PI‐ORs are the main precursors of organic O ‐substituted hydroxylamines (Scheme , direction A ), valuable intermediates in the synthesis of biologically active compounds . In reactions with various reducing agents, PI‐ORs can undergo a wide spectrum of transformations and participate in processes that lead to the selective cleavage of either the CO pi‐bond (NaBH 4 as the reducing agent, direction B ), the C―O bond (H 2 /Pd as the reducing agent, direction C ), or the N―O bond (TiCl 3, Bu 3 SnH, or Ph 3 SnH as the reducing agent, directions D‐E ). The reactions with R 3 SnH in the presence of the radical initiator AIBN are believed to proceed via attack of R 3 Sn• radical at the carbonyl oxygen followed by a β‐scission to form an oxygen‐centered free radical.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical behavior of N‐oxyphthalimides: Cascades initiating self‐sustaining catalytic reductive N―O bond cleavage

Syroeshkin

Krylov

Hughes

et al. 2017

J of Physical Organic Chem

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N-oxyphthalimides are stable and easily accessible compounds that can produce oxygen radicals upon 1-electron reduction. We present a systematic study of electrochemical properties of N-oxyphthalimide derivatives (PI-ORs) in DMF by cyclic voltammetry. In all cases, electron transfer to the substrate leads to decomposition of the intermediate radical anion via the N-O bond cleavage. In the case of benzyloxyphthalimide or its derivatives containing electrondonating substituents, reductive electron transfer induces the chain decomposition of the substrate to phthalimide (PI) radical-anion and the corresponding carbonyl compound. The PI radical-anion product is a powerful reductant that can transfer an electron to the reactant PI-OR, thus establishing a catalytic cycle for reductive N-O scission. This self-catalytic process is reflected in a considerable decrease in the reduction current for the substrate (<1e -/molecule). By contrast, reductive fragmentations of benzyl derivatives containing electronwithdrawing substituents in the aromatic ring or at the benzylic position, as well as tosyl and alkyl derivatives, occur via a 1-electron mechanism. A sequence of N-O and C-C scissions was engineered to support the intermediacy of O-centered radicals in these processes.

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Section: Introductionmentioning

confidence: 99%

Electrochemical behavior of N‐oxyphthalimides: Cascades initiating self‐sustaining catalytic reductive N―O bond cleavage

Syroeshkin

Krylov

Hughes

et al. 2017

J of Physical Organic Chem

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“…The sensitivities of the resists are not enough compared with the known chemical amplification resists (2,13). The pK a values of W-hydroxysuo cinimides are reported to be as high as 6 to 7 due to the strongly acidic JV-hydroxy functionality (14) and are higher than those values of the imino protons of succinimides and phenolic protons which are known to be about 10. However, the high deprotection temperatures of the t-Bu protected HOMI copolymer, namely P(t-BuOMI/St), rendered rather low sensitivity as a resists material compared with t-BOC protected polymers.…”

Section: Lithographic Evaluation Of P(t-buomi / St)mentioning

confidence: 91%

Synthesis and Polymerizations of N-(tert-Butoxy)maleimide and Application of Its Polymers as a Chemical Amplification Resist

Ahn

Koo

1993

ACS Symposium Series

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N-(tert-Butoxy)maleimide, t-BuOMI was synthesized as a new kind of a protected acid-labile monomer. Its radical copolymerizations were performed and the thermal deprotection behavior of its copolymers were investigated. t-BuOMI was readily copolymerized with styrene derivatives (X-St) to give copolymers, P(t-BuOMI/X-St) in high conversions. The t-BuOMI units of the tert-butyl (t-Bu) protected copolymers were converted into the N-hydroxymaleimide (HOMI) units by heating at about 280 °C releasing 2-methylpropene and the facile deprotection of the side-chain t-Bu groups resulted in a large polarity change in the polymer structure. The deprotected copolymers, P(HOMI/X-St) have very high glass transition temperatures higher than about 250 °C and showed solubilities in aqueous base solutions whereas the protected polymers are soluble only in organic solvents. Acidolytic deprotection of P(t-BuOMI/St) was observed at 130 °C or lower temperatures in the presence of catalytic acids. Resist solutions of P(t-BuOMI/St) containing triphenylsulfonium salts as a photoacid generator were prepared and the films were imagewise exposed to 260 nm light by a contact mode. The films were post-exposure baked at 130 °C and were followed by development with 2.38 wt% TMAH solution to obtain positive tone images.The design and synthesis of protected polymers having acid-labile groups are considered to be of challenging research for obtaining imageable polymers which can serve high sensitivity resist materials for fabricating microelectronic devices (i). Adequately protected polymers bring a remarkable change in polarity, thereof considerable differentiation in solubilities, when the side-chain protecting groups of polymers are deprotected by thermolysis or acidolysis. Those protected polymers are best suited for the application as chemically amplified resists to achieve high sensitivity (2).A typical acid-labile protecting group is terf-butoxycarbonyl (t-BOC) group which is known to be readily deprotected in the presence of catalytic acids. Poly[p-(r-butoxycarbonyloxy)styrene] has been investigated in detail as a prototype t-BOC protected polymer and successfully applied in the manufacture of VLSI devices (3,4). In this case, the acid-labile t-BOC group is utilized to

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“…Table 2 reports the principal absorbing bands of this product compared with those of JH,, NHS and Nacetoxy NHS [6] . After 18 h of reaction at room temperature the ester derivative was purified on TLC in ethyl acetate/hexane, 80 : 20 (RF = 0.830), extracted with chloroform and evaporated to dryness.…”

Section: N-hydroxysuccinimide Ester Preparationmentioning

confidence: 99%

A simple and sensitive radioimmunoassay of insect Juvenile hormone using an iodinated tracer

et al. 1976

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The synthesis of some N-hydroxyimides

Cited by 57 publications

References 0 publications

Electrochemical behavior of N‐oxyphthalimides: Cascades initiating self‐sustaining catalytic reductive N―O bond cleavage

Electrochemical behavior of N‐oxyphthalimides: Cascades initiating self‐sustaining catalytic reductive N―O bond cleavage

Synthesis and Polymerizations of N-(tert-Butoxy)maleimide and Application of Its Polymers as a Chemical Amplification Resist

A simple and sensitive radioimmunoassay of insect Juvenile hormone using an iodinated tracer

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