7314-84-3Relevant academic research and scientific papers
The Hydrogen-Bond Basicity pKHB Scale of Peroxides and Ethers
Berthelot, Michel,Besseau, Francois,Laurence, Christian
, p. 925 - 931 (1998)
Using 4-fluorophenol as a reference hydrogen-bond donor, equilibrium constants, Kf, for the formation of 1:1 hydrogen-bonded complexes have been obtained by FTIR spectrometry for 39 ethers of widely different structure (cyclic and acyclic ethers, crown ethers, glymes, acetals, orthoesters, and disiloxane) and 3 peroxides, in CCl4 at 298 K. The pkHB scale of monoethers extends from 1.44 for 2,3-diadamant-2-yloxirane to -0.53 for hexamethyldisiloxane. The main effects explaining the variation of the hydrogen-bond basicity of sp3 oxygen atoms are (i) the electron-withdrawing field-inductive effect [e.g. in (CF3)2CHOMe], (ii) the electron-withdrawing resonance effect (e.g. in EtOCH=CH2) (iii) the steric effect (e.g. in tBu2O), (iv) the lone-pair-lone-pair repulsion (e.g. in cyclic peroxides), and (v) the cyclization giving the basicity order: oxetane > tetrahydrofuran > tetrahydropyran > oxirane. A spectroscopic scale of hydrogen-bond basicity is constructed from, the infrared frequency shift Δv(OH) of methanol hydrogen-bonded to peroxides and ethers. The thermodynamic pKHB scale does not correlate with the Δv(OH) scale because of (i) statistical effects in polyethers and peroxides (ii) secondary hydrogen-bond acceptor sites (e.g. in benzyl ether), (iii) variations of the s character of oxygen lone pairs either by conjugation or cyclization, (iv) steric effects, (v) lone-pair-lone-pair repulsions, and (vi) anomeric effects. The v(OH...O) band shape reveals two stereoisomeric complexes, the most stable being tetrahedral at the ether oxygen atom.
Antiplasmodial activity of alkyl-substituted 1,2-dioxetanes against Plasmodium falciparum
Silva, Adriana F.,Oliveira, Vani X.,Silva, Leandro S.,Pinheiro, Ana A.S.,Ciscato, Luiz F.M.L.
, p. 5007 - 5008 (2016)
This article reports the in vitro antiplasmodial activity of two endoperoxides of the class 1,2-dioxetanes against Plasmodium falciparum: bis(adamantyl)-1,2-dioxetane and 3,3,4,4-tetramethyl-1,2-dioxetane. The results reveal that bis(adamantyl)-1,2-dioxetane displays substantial antiplasmodial activity, at least two orders of magnitude higher than that of artemisinin, while 3,3,4,4-tetramethyl-1,2-dioxetane is less active.
Cyclic 1, 2-dioxocyclobutane force response group and synthesis method and application thereof
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Paragraph 0032-0036, (2020/10/20)
The invention discloses a cyclic 1, 2-dioxocyclobutane force response group and a synthesis method and application thereof. The cyclic 1, 2-dioxocyclobutane force response group is shown in the formula I in the specification. The method for preparing the 1, 2-dioxocyclobutane force response group is simple and efficient; the mechanical force induced chemiluminescence linear self-repairing polyolefin film prepared by utilizing ring-opening metathesis polymerization (ROMP) has excellent self-repairing performance (the spontaneous stress recovery rate reaches 95.0 percent); in addition, the filmcan also emit chemiluminescence after strain is applied, covalent bond breakage can be researched sensitively in time and space, and thus a bridge between microscopic molecular horizontal bond breakage and macroscopic material self-repairing performance is built, and a new method is provided for sensitively detecting polymer material damage in real time.
Semipinacol and protoadamantane-adamantane rearrangements of 5,6-dibromoadamantan-2-one and -2-ol
Wang, Xiaofang,Dong, Yuxiang,Ezell, Edward L.,Garrison, Jered C.,Wood, James K.,Hagen, James P.,Vennerstrom, Jonathan L.
, p. 2972 - 2976 (2017/04/26)
A number of new polybrominated adamantanes were formed by rearrangements and bromination of 2,2,6,6-tetrabromoadamantane under Friedel-Crafts conditions. Protoadamantane-4,10-dione, 10-acetoxyprotoadamantan-4-one, 1,2,6-triacetoxyadamantane and 5,6-diacetoxyadamantan-2-one were formed by successive semipinacol and protoadamantane-adamantane rearrangements of 5,6-dibromoadamantan-2-one and 5,6-dibromoadamantan-2-ol. This work may open up new pathways for the synthesis of 1,2,6-trisubstituted adamantanes.
Adamantane-2-spiro-3'-diazirine in reactions with protic and aprotic acids
Isaev, S. D.,Zhalnina, G. G.,Murzinova, Z. N.,Lastovenko, S. I.,Yurchenko, A. G.
, p. 126 - 131 (2007/10/02)
During the action of strong protic acids on adamantane-2-spiro-3'-diazirine addition of the proton is accompanied by the elimination of a molecule of nitrogen and the formation of the intermediate 2-adamantyl cation.In the presence of nucleophiles the latter is converted into the corresponding 2-substituted derivatives of adamantane.Lewis acids promote isomerization of the cyclic diazirine to the linear diazo compound, and the main reaction product is adamantanone azine.Trifluoroacetic acid and bromine react by both mechanisms simultaneously. (In the latter case Br+ plays the role of the proton in the first stage.)
SYNTHESIS OF 1-SUBSTITUTED DERIVATIVES OF PENTACYCLO2,6.03,10.05,9>UNDECANE (SYMMETRICAL TRISHOMOCUBANE)
Aleksandrov, A. M.,Sorochinskii, A. E.,Petrenko, A. E.,Kukhar', V. P.
, p. 681 - 686 (2007/10/02)
During the action of boron tribromide on adamantanone and pentacyclo2,6.03,10.05,9>undecane-4-one the carbonyl group is substituted by a dibromomethylene group.Protoadamantan-4-one is converted into 1,2-dibromoadam
PHOTOOXYDATIONS PAR TRANSFERT D'ELECTRON. PHOTOOXIGENATIONS SENSIBILISEES PAR LE DICYANO-9,10 ANTHRACENE. FORMATION DE O2. ET (1)O2.
Santamaria, J.,Ouchabane, R.
, p. 5559 - 5566 (2007/10/02)
Photooxidation of electron-rich compounds (donor) sensitized by 9,10-dicyanoanthracene (DCA, acceptor) gives evidence for the effect of solvent polarity on the photochemical reaction mechanism.The chemical outcome can be connected with the fluorescence data.The formation of O2. and (1)O2 proceeds from a charge transfer complex between the donor and the acceptor upon excitation.
