Replacement of C−O by P−O in Cyclic Acetals and Ketals

Wang, Feng; Ma, Shuguang; Tao, W. Andy; Cooks, R. Graham

doi:10.1002/(sici)1521-3773(19990201)38:3<386::aid-anie386>3.0.co;2-5

Cited by 22 publications

(31 citation statements)

References 11 publications

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“…This reaction is analogous to reactions of acylium ions RCO ϩ and cyclic acetals or ketals like 1,3-dioxolane (eq 2 in Scheme 1) by the gas-phase transacetalization mechanism initially discovered by Eberlin et al [22][23][24][25][26]. In Eberlin reactions, structures of product ions have been clearly determined by their fragmentation patterns [21,22] and by isotopelabeling experiments [27] and transacetalization mechanisms are well established. Not only have the reactions been studied extensively but these reactions have already found analytical and synthetic applications [28 -32].…”

mentioning

confidence: 78%

“…An earlier study from this laboratory reported the formation of cyclic 1,3,2-dioxaphospholanium ions in the ketalization reactions of phosphonium ions CH 3 P(O)OCH 3 ϩ (93 Th) and CH 3 OP(O)OCH 3 ϩ (109 Th) with 1,3-dioxolane (eq 1 in Scheme 1) [21]. The ketalization reaction involved transacetalization in which the protecting group of 1,3-dioxolane, the oxirane CH 2 CH 2 O moiety, was transferred onto the phosphoryl group, producing the cyclic 1,3,2-dioxaphospholanium ion and releasing the free ketone.…”

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confidence: 99%

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Ketalization of phosphonium ions by 1,4-dioxane: Selective detection of the chemical warfare agent simulant DMMP in mixtures using ion/molecule reactions

Chen

Zheng

Cooks

2003

J. Am. Soc. Mass Spectrom.

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Phosphonium ions CH(3)P(O)OCH(3)(+) (93 Th) and CH(3)OP(O)OCH(3)(+) (109 Th) react with 1,4-dioxane to form unique cyclic ketalization products, 1,3,2-dioxaphospholanium ions. By contrast, a variety of other types of ions having multiple bonds, including the acylium ions CH(3)CO(+) (43 Th), CH(3)OCO(+) (59 Th), (CH(3))(2)NCO(+) (72 Th), and PhCO(+) (105 Th), the iminium ion H(2)C[double bond]NHC(2)H(5)(+) (58 Th) and the carbosulfonium ion H(2)C[double bond]SC(2)H(5)(+) (75 Th) do not react with 1,4-dioxane under the same conditions. The characteristic ketalization reaction can also be observed when CH(3)P(OH)(OCH(3))(2)(+), viz. protonated dimethyl methylphosphonate (DMMP), collides with 1,4-dioxane, as a result of fragmentation to yield the reactive phosphonium ion CH(3)P(O)OCH(3)(+) (93 Th). This novel ion/molecule reaction is highly selective to phosphonium ions and can be applied to identify DMMP selectively in the presence of ketone, ester, and amide compounds using a neutral gain MS/MS scan. This method of DMMP analysis can be applied to aqueous solutions using electrospray ionization; it shows a detection limit in the low ppb range and a linear response over the range 10 to 500 ppb.

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confidence: 78%

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confidence: 99%

Ketalization of phosphonium ions by 1,4-dioxane: Selective detection of the chemical warfare agent simulant DMMP in mixtures using ion/molecule reactions

Chen

Zheng

Cooks

2003

J. Am. Soc. Mass Spectrom.

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“…Benzomorpholine, 3,4-dihydro-2H-1,4-benzoxazine, is a constituent of many naturally occurring substances [46]. An earlier study [51] from this laboratory reported that arenesulfenylium cation PhS ϩ can undergo the Eberlin reaction with 2,2-dimethyl-1,3-dioxolane, a cyclic ketal and form a characteristic four-membered cyclic product, 2-aryl-1,2-oxathietan-2-ium ion (the prototype Eberlin reaction [52][53][54][55] is the gas-phase transacetalization of acylium ions RCO ϩ by cyclic acetals or ketals, as shown in Scheme 7). It is therefore important to seek new simple routes for the synthesis of benzomorpholine.…”

Section: Synthesis Of N-heterocycles Using Arylnitrenium Ionsmentioning

confidence: 99%

Generation of arylnitrenium ions by nitro-reduction and gas-phase synthesis of N-Heterocycles

Chen

Cooks

et al. 2004

J. Am. Soc. Mass Spectrom.

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Nitro-reduction by the vinyl halide radical cation CH2 = CH-X+* (X = Cl or Br) converts nitroaromatics into arylnitrenium ions, significant intermediates in carcinogenesis, and the present study reports on the scope and regioselectivity of this versatile reaction. The reaction is general for different kinds of substituted nitroaromatics; para/meta substitutents have little effect on the reaction while ortho substitutents result in low yields of arylnitrenium ions. The phenylnitrenium ion PhNH+ can be generated by chemical ionization (CI) of nitrobenzene using 1,2-dichloroethane as the reagent gas or by atmospheric pressure chemical ionization (APCI) of 1,2-dichloroethane solution doped with nitrobenzene. The chemical reactivities of the arylnitrenium ions include one-step ion/molecule reactions with nucleophiles ethyl vinyl ether and 1,3-dioxolanes, respectively, involving the direct formation of new CN bonds and synthesis of indole and benzomorpholine derivatives. The indole formation reaction parallels known condensed phase chemistry, while the concise morpholine-forming reaction remains to be sought in solution. The combination of collision-induced dissociation (CID) with novel ion/molecule reactions should provide a selective method for the detection of explosives such as TNT, RDX and HMX in mixtures using mass spectrometry. In addition to the reduction of the nitro group, reduction of methyl phenyl sulfone PhS(O)2Me to the thioanisole radical cation PhSMe+* occurs using the same chemical ionization reagent 1,2-dichloroethane. This probably involves an analogous reduction reaction by the reagent ion CH2 = CH-Cl+*.

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“…This reaction led to an adduct ion [RR′CHCOOR″, OP(OCH 3 ) 2 ] + which loses spontaneously a molecule of ketene (CH 2 CO) or substituted ketene (RR′CCO) 19. Cooks and co‐workers found that phosphonium ions undergo structurally diagnostic transacetylation with 1,3‐dioxolane20a and 1,4‐dioxane20b to generate 1,3,2‐dioxaphospholanium ions.…”

Section: Introductionmentioning

confidence: 99%

Gas‐phase reactivity of the OP(OCH₃)₂⁺ phosphonium ion towards α,β‐unsaturated esters in a quadrupole ion trap

et al. 2005

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Ion-molecule reactions between the O=P(OCH3)2 + phosphonium ions and eight alpha,beta-unsaturated esters (methyl acrylate, ethyl acrylate, methyl crotonate, ethyl crotonate, methyl 3,3-dimethylacrylate, ethyl 3,3-dimethylacrylate, methyl methacrylate and ethyl methacrylate) were performed in a quadrupole ion trap mass spectrometer. The O=P(OCH3)2 + phosphonium ions, formed by electron ionization from neutral trimethyl phosphite, were found to react with alpha,beta-unsaturated esters to give an adduct [RR'C=CR''COOR''', O=P(OCH3)2]+, which lose spontaneously a molecule of trimethyl phosphate (R'''=CH3) or dimethyl ethyl phosphate (R'''=C2H5). An ion corresponding to a protonated trialkyl phosphate is also observed when substituent R''=H. To confirm the experimental results, and to elucidate the mechanism for the formation of the ionic species, a theoretical study using the density functional theory (DFT) approach was carried out. The potential energy surface obtained from B3LYP/6-31G(d,p) calculations for the reaction between O=P(OCH3)2 + and methyl acrylate is described.

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Replacement of C−O by P−O in Cyclic Acetals and Ketals

Cited by 22 publications

References 11 publications

Ketalization of phosphonium ions by 1,4-dioxane: Selective detection of the chemical warfare agent simulant DMMP in mixtures using ion/molecule reactions

Ketalization of phosphonium ions by 1,4-dioxane: Selective detection of the chemical warfare agent simulant DMMP in mixtures using ion/molecule reactions

Generation of arylnitrenium ions by nitro-reduction and gas-phase synthesis of N-Heterocycles

Gas‐phase reactivity of the OP(OCH₃)₂⁺ phosphonium ion towards α,β‐unsaturated esters in a quadrupole ion trap

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Replacement of C−O by P−O in Cyclic Acetals and Ketals

Cited by 22 publications

References 11 publications

Ketalization of phosphonium ions by 1,4-dioxane: Selective detection of the chemical warfare agent simulant DMMP in mixtures using ion/molecule reactions

Ketalization of phosphonium ions by 1,4-dioxane: Selective detection of the chemical warfare agent simulant DMMP in mixtures using ion/molecule reactions

Generation of arylnitrenium ions by nitro-reduction and gas-phase synthesis of N-Heterocycles

Gas‐phase reactivity of the OP(OCH3)2+ phosphonium ion towards α,β‐unsaturated esters in a quadrupole ion trap

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Gas‐phase reactivity of the OP(OCH₃)₂⁺ phosphonium ion towards α,β‐unsaturated esters in a quadrupole ion trap