- A Practical and Cost-Effective Method for the Synthesis of Bicyclo[22.2]octane-1,4-dicarboxylic Acid
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A short and efficient synthesis of bicyclo[2.2.2]octane-1,4-dicarboxylic acid involving the formation of a semicarbazone is developed, and a reproducible protocol for the reduction of this semicarbazone is described. The use of microwaves significantly shortens the duration of the sequence to the diacid compared to the previously described synthetic method. In addition, by shifting from the use of large amounts of Raney nickel to a solid-phase process, both the safety and cost are improved notably.
- Le Marquer, Nicolas,Laurent, Mathieu Yves,Martel, Arnaud
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- SYNTHESIS OF BICYCLO[2.2.2]OCTANE DERIVATIVES
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Provided is a process for the preparation of certain 1,4-bicyclo[2.2.2]octane derivatives. The new synthetic procedure involves treating 1,4-dimethylene cyclohexane with an oxidizing agent in the presence of a transition metal catalyst to afford an oxo-substituted bicyclo[2.2.2]octane species. This intermediate structure can then be further derivatized. The processes of this disclosure thus affords a novel and simplified means for the commercial production of a wide variety of bicyclo[2.2.2]octane derivatives.
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Paragraph 0088-0089
(2019/05/02)
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- Bicyclo [2.2.2] octane - 1, 4 - dicarboxylic acid mono methyl ester synthesis method
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The invention relates to a synthetic method of an organic compound. The synthetic method of bicyclo-[2.2.2]octane-1,4-dicarboxylic acid monomethyl easter is as follows: firstly, adopting sodium hydride, DMSS and 1,2-dibromoethane to synthesize the intermediate I; secondly, adopting the intermediate I, sodium acetate, ammourea hydrochloride and alcohol to synthesize semicarbazon; thirdly, adopting potassium hydroxide, diethylene glycol and semicarbazon to synthesize target diacid; fourthly, adopting target diacid, thionyl chloride and methanol to synthesize target diester; and fifthly, adopting target diester, potassium hydroxide and 95% of methanol water solution to synthesize the target product monoester. The invention has reasonable synthetic process route, mild process conditions, environment friendly, easy operation, low raw material cost, high product yield and excellent purity, and is applicable to industrial production and satisfies the application requirement of each industry.
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Paragraph 0007; 0024; 0026; 0027; 0032; 0033
(2017/07/07)
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- Tuning Singlet Fission in π-Bridge-π Chromophores
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We have designed a series of pentacene dimers separated by homoconjugated or nonconjugated bridges that exhibit fast and efficient intramolecular singlet exciton fission (iSF). These materials are distinctive among reported iSF compounds because they exist in the unexplored regime of close spatial proximity but weak electronic coupling between the singlet exciton and triplet pair states. Using transient absorption spectroscopy to investigate photophysics in these molecules, we find that homoconjugated dimers display desirable excited-state dynamics, with significantly reduced recombination rates as compared to conjugated dimers with similar singlet fission rates. In addition, unlike conjugated dimers, the time constants for singlet fission are relatively insensitive to the interplanar angle between chromophores, since rotation about σ bonds negligibly affects the orbital overlap within the π-bonding network. In the nonconjugated dimer, where the iSF occurs with a time constant >10 ns, comparable to the fluorescence lifetime, we used electron spin resonance spectroscopy to unequivocally establish the formation of triplet-triplet multiexcitons and uncoupled triplet excitons through singlet fission. Together, these studies enable us to articulate the role of the conjugation motif in iSF.
- Kumarasamy, Elango,Sanders, Samuel N.,Tayebjee, Murad J. Y.,Asadpoordarvish, Amir,Hele, Timothy J. H.,Fuemmeler, Eric G.,Pun, Andrew B.,Yablon, Lauren M.,Low, Jonathan Z.,Paley, Daniel W.,Dean, Jacob C.,Choi, Bonnie,Scholes, Gregory D.,Steigerwald, Michael L.,Ananth, Nandini,McCamey, Dane R.,Sfeir, Matthew Y.,Campos, Luis M.
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p. 12488 - 12494
(2017/09/23)
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- New ultrahigh affinity host-guest complexes of cucurbit[7]uril with bicyclo[2.2.2]octane and adamantane guests: Thermodynamic analysis and evaluation of M2 affinity calculations
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A dicationic ferrocene derivative has previously been shown to bind cucurbit[7]uril (CB[7]) in water with ultrahigh affinity (ΔGo= -21 kcal/mol). Here, we describe new compounds that bind aqueous CB[7] equally well, validating our prior suggestion that they, too, would be ultrahigh affinity CB[7] guests. The present guests, which are based upon either a bicyclo[2.2.2]octane or adamantane core, have no metal atoms, so these results also confirm that the remarkably high affinities of the ferrocene-based guest need not be attributed to metal-specific interactions. Because we used the M2 method to compute the affinities of several of the new host-guest systems prior to synthesizing them, the present results also provide for the first blinded evaluation of this computational method. The blinded calculations agree reasonably well with experiment and successfully reproduce the observation that the new adamantane-based guests achieve extremely high affinities, despite the fact that they position a cationic substituent at only one electronegative portal of the CB[7] host. However, there are also significant deviations from experiment, and these lead to the correction of a procedural error and an instructive evaluation of the sensitivity of the calculations to physically reasonable variations in molecular energy parameters. The new experimental and computational results presented here bear on the physical mechanisms of molecular recognition, the accuracy of the M2 method, and the usefulness of host-guest systems as test-beds for computational methods.
- Moghaddam, Sarvin,Yang, Cheng,Rekharsky, Mikhail,Ko, Young Ho,Kim, Kimoon,Inoue, Yoshihisa,Gilson, Michael K.
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supporting information; scheme or table
p. 3570 - 3581
(2011/05/04)
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- Unique gas and hydrocarbon adsorption in a highly porous metal-organic framework made of extended aliphatic ligands
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High and unique gas and hydrocarbon adsorption in a highly stable guest-free microporous metal-organic framework constructed on rigid aliphatic ligands, H2bodc and ted, is reported in this work. The Royal Society of Chemistry.
- Li, Kunhao,Lee, Jeongyong,Olson, David H.,Emge, Thomas J.,Bi, Wenhua,Eibling, Matthew J.,Li, Jing
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supporting information; experimental part
p. 6123 - 6125
(2009/05/06)
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- PEPTIDASE INHIBITORS
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The present invention relates to a series of novel compounds having the formula (I) wherein: X is NR3 or O; n is 1 or 2; A is a bicyclic carbocycle and R1 and R1 are as described herein. The compounds are useful as DPP-IV inhibitors, such as for the treatment of diabetes.
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Page/Page column 41
(2010/10/19)
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- PEPTIDASE INHIBITORS
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The present invention relates to a series of novel compounds having the formula: [INSERT FORMULA I] wherein A is a bicyclic carbocycle and R?1? and R?2? are independently [INSERT MOLECULE FROM CLAIM 1] The compounds are useful as DPP-IV inhibitors and for treating diabetes.
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Page/Page column 33-34
(2010/10/19)
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- Decarboxylation of Bridgehead Carboxylic Acids by the Barton Procedure
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Reductive decarboxylation of a series of bicyclic and polycyclic acids in which the carboxyl group is attached to the bridgehead position has been investigated.Conversion of the acids into thiohydroxamic esters occurs via reaction of the derived acid chlorides with N-hydroxypyridine-2-thione.Decomposition of the esters proceeds smoothly in boiling benzene in the presence of 1-butyl mercaptan to give the reduced product in high yield.The procedure appears to be generally applicable, and is unaffected by functional groups such as esters and acetals.
- Della, Ernest W.,Tsanaktsidis, John
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p. 2061 - 2066
(2007/10/02)
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- SYNTHESIS OF 1,4-DISUBSTITUTED BICYCLOOCTANES BY THE DIELS-ALDER REACTION
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Methods were developed for the synthesis of 1,4-diethoxy-, 1,4-dicyano-, and 1,4-diphenyl-1,3-cyclohexadienes.Their adducts with maleic anhydride, acrylonitrile, acrolein, nitroethylene, fumaronitrile, and α-acetoacrylonitrile were converted into the corresponding substituted bicyclooctanes.The configuration of the diene synthesis products was studied by IR and PMR spectroscopy.
- Geivandov, R.Kh.,Kovshev, E.I.
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p. 461 - 470
(2007/10/02)
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- Potential antitumor agents. 18. Bisquaternary ammonium heterocycles
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It was earlier proposed that a close approach to overall planarity was a structural prerequisite for antileukemic activity (L1210) in bisquaternary ammonium heterocycles. The preparation of L1210 active 3,3' [bicyclo[2.2.2] octane 1,4 dicarbonylbis (imino p phenylenecarbonylimino)] bis (1 alkylpyridinium) salts, containing a nonplanar bridged ring system, negates this view. A replacement proposal is that a relatively rigid molecular framework is necessary to maintain the spacing and positioning of the quaternary functions, thereby ensuring correct site selection. Replacement of a terephthaloyl drug component by a bicyclo [2.2.2] octane 1,4 dicarbonyl residue lowers DNA binding. A terephthaloyl unit confers necessary molecular rigidity, greater DNA binding, and higher L1210 activity.
- Cain,Atwell
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p. 1417 - 1419
(2007/10/08)
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