Diels-Alder Reactions of Furan By: Robert B. Login rloginconsulting.com

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1 Diels-Alder eactios of Fura By: obert B. Logi rlogicosultig.com eversible DA eactios: DA reversible reactios of furas ad maleimides are a type of click reactio that ca proceed at some lower temperature oly to be reversed at a higher temperature. This DA reactio ca be applied to a variety of applicatios for example reversible hair fixatives. Lets review several of these fura-maleimide approaches: (The oldest referece for this reactio is Crave, James M. "Cross-liked thermally reversible polymers produced from codesatio polymers with pedat fura groups cross-liked with maleimides." U.S. Patet o. 3,435, Mar ) (1)

2 (2) (3) (4) (5)

3 (6) above ad others (7-18) The above is just a sample of the extesive literature cocerig reversible DA reactios. Ca this reversible DA reactio have hair care applicatios. As a reversible cross-likig mechaism, it would ehace fixative properties but this would be reversible with the heat of a curlig iro. For example, a Gafquat type copolymer with oe of these previously discussed suitable reversible DA reactios would fit this idea. All of the above refereces have thigs i commo, the Diels-Alder compoets are either termial or pedat to the polymer chai. I have foud oly oe referece where the Diels-Alder compoet is i the polymer backboe. This seems like a obvious idea so why oly the oe referece? For example: Polyesters Polyamides etc. dimethyl fura-2,5-dicarboxylate ' ' Scheme 1

4 Apparetly the above scheme does't work because the carboxylic esters reduce the electro desity i the fura rig makig it a less attractive DA diee. DA dieeophiles ca be ehaced i reactivity with trasitio metal derivatives. Could such ehaced dieeophiles work with the above scheme 1 fura dicarboxylates? Ca the dicarboxylates be moved further away from the fura rig or ca the 3,4 fura dicarboxylates react because the carboxylates are attached to carbos away from the fura rig oxyge? Actually 3,4-fura reacts very well with dieeophiles.(19-20) As the followig shows, the hydroxyl derivatives work as DA diees. PFS as show, is DA reactive.(21-22) Maleic Ahydride ad Bezee derivatives: PFS ca be employed i other DA reactios with strog dieeophiles like maleic ahydride. For example:

5 A B C A D=C diester A E base/ 2 F Scheme 2 Possible aromatic derivatives. 7-xaorborees are readily coverted to aromtic derivatives with acidic catalysis. Might acetylee work by itself to go more readily to the bezee derivative sice may refereces show that eve relatively ureactive ethylee reacts with furas uder the right coditios ad will form the bezee derivative. Polymers E ad F above should be water soluble i their carboxylate form. I would expect them to also be readily hydrolytically degradable because of the locatio of the carboxylate vs. the ester backboe. This could be a way to degradable PET plastics by puttig eough of these repeat uits i the PET backboe to do the job. Whe exposed to sea water for example, they would hydrolyze the ahydrides ad cause polymer hydrolysis by achimeric assistace.(23-26)

6 This suggests aother possible sythesis: Scheme 3: Alcohol groups would iitially eed to be protected. D is a moomeric bis imide. E is the adduct of acrylates. I this case, the alcohols are protected with removable groups which whe removed allow the esters or amides to form. If treated with acidic reagets, the resultig oxaorborees ca be trasformed ito bezee rigs. Compoud B would therefore be a very versatile reactat. Further ideas as i scheme 4 seems related to the Picer DA reactio. Scheme 4 etc. polymer furo[3,4-c]fura-4,6-dioe A B C D E F G

7 3,4 fura dicarboxylic acid is a kow compoud that ca be coverted to the ahydride. I'm suggestig that the DA reactio with maleic ahydride iitiates a chai reactio to form the above polymer. MW would be cotrolled by the amout of maleic ahydride or other suitable dieeophile used to start the reactio. This proposed DA reactio is some what similar to Picer DA's, for example: (27-28) As ca be see i the above scheme, that my scheme 3 proposal might have a more complicated stereochemistry tha I have proposed but the idea is the same. The 3,4 fura dicarboxylic ahydride could also be coverted to the aromatic tetracarboxylic diahydride, a valuable polyimide compoet. Scheme 5 r this is a simpler approach to aliphatic bis-ahydrides vs. the followig scheme?

8 All that would have to be doe is the hydrogeatio of the scheme 5 illustrated double bod. ther approaches to polymers are possible. ' ' ' ' Scheme 6: The above polyimide ca be post coverted to the aromatic derivative, a ew method of sythesizig polyimide plastics. I coclusio, derivatives of xabicyclo[2.2.1]heptae are a sigificat area of orgaic chemistry; therefore, I would thik that fura, a readily available M from biomass should ispire ew possibilities.(29-30) The followig idea is based o chemistry that Prof. Wolisky ad I developed i the 1960's.(31-32) It is based o the reactio of the i-situ formatio of a diee from a usaturated carboyl compoud ad isopropeyl acetate catalyzed by acid.

9 Ac Ac Ac Ad Etc Etc Scheme 7 The i-situ formed diee attached to the maleimide dieeophile results i a polymer that sice the acetoxy cyclohexee ca with heat lose acetic acid resultig i a cyclohexadiee that ca also react to form a bicyclooctae cross-lik. These DA reactios should be reversible formig healable polymers. Scheme 8 is oe suggested outlie sythesis of the startig M. Wittig eactio X.. X Scheme 8 Ac Ac Ac Scheme 9 Alterative polymerizatio with the usaturated ketoe.

10 efereces: 1.Gheeim, aa, Catalia Perez-Berume, ad Alessadro Gadii. "Diels Alder reactios with ovel polymeric diees ad dieophiles: sythesis of reversibly cross-liked elastomers."macromolecules, (2002): Liu, Yig-Lig, Chia-Yu sieh, ad Yi-We Che. "Thermally reversible cross-liked polyamides ad thermo -resposive gels by meas of Diels Alder reactio."polymer, 47.8 (2006): Tasdele, Mehmet Atilla. "Diels Alder click reactios: recet applicatios i polymer ad material sciece."polymer Chemistry, 2.10 (2011): Gadii, Alessadro, Armado JD Silvestre, ad Dora Coelho. "eversible click chemistry at the service of macromolecular materials."polymer Chemistry, 2.8 (2011): Yu, She, et al. "Bio Ispired igh Performace ad ecyclable Cross Liked Polymers." Advaced Materials, (2013): García-Astrai, C., et al. "Gree chemistry for the sythesis of methacrylate-based hydrogels crossliked through Diels Alder reactio."europea Polymer Joural, (2013): Bai, a, George P. Simo, ad Kei Saito. "Ivestigatio of the thermal self-healig mechaism i a cross-liked epoxy system."sc Advaces, 3.43 (2013): Du, Pegfei, et al. "Sythesis ad characterizatio of liear self-healig polyurethae based o thermally reversible Diels Alder reactio."sc Advaces, 3.35 (2013): Berg, Gayla J., et al. "A dual-cure, solid-state photoresist combiig a thermoreversible Diels Alder etwork ad a chai growth acrylate etwork."macromolecules, (2014): García-Astrai, C., et al. "Diels Alder click chemistry for the cross-likig of furfuryl-gelati-polyetheramie hydrogels."sc Advaces, 4.67 (2014): Du, Pegfei, et al. "Diels Alder based crossliked self healig polyurethae/urea from polymeric methylee dipheyl diisocyaate."joural of Applied Polymer Sciece, (2014). 12. ivero, Guadalupe, et al. "e-pot thermo-remedable shape memory polyurethaes."macromolecules,47.6 (2014): Che, Shegli, et al. "A Sigle Molecular Diels Alder Crossliker for Achievig ecyclable Cross Liked Polymers."Macromolecular rapid commuicatios, (2015): oy, abaru, Berd Bruchma, ad Jea-Marie Leh. "DYAMES: dyamic polymers as self-healig materials."chemical Society eviews, (2015): Li, Jihui, et al. "Thermally reversible ad self healig ovolac epoxy resis based o Diels Alder chemistry."joural of Applied Polymer Sciece, (2015). 15. Pramaik, abedu B., ad ikhil K. Sigha. "Amphiphilic fuctioal block copolymers bearig a reactive furfuryl group via AFT polymerizatio; reversible core cross-liked micelles via a Diels Alder click reactio."sc

11 Advaces, 6.3 (2016): Kuag, Xiao, et al. "Triple-shape memory epoxy based o Diels Alder adduct molecular switch."polymer, 84 (2016): Buoerba, Atoio, et al. "A Comprehesive Depictio of the Fura Maleimide Couplig via Kietic ad Thermodyamic Ivestigatios of the Diels Alder eactio of Poly (styree co 2 viylfura) with Maleimides."ChemistrySelect, 2.4 (2017): Polgar, Lorezo Massimo, et al. "Thermoreversible Cross-Likig of Fura-Cotaiig Ethylee/Viyl Acetate ubber with Bismaleimide."Polymers, 9.3 (2017): Weis, C. D. "Diee ad etrodiee eactios of Electroegatively 3, 4-Disubstituted Furas."The Joural of rgaic Chemistry, (1962): Vogel, Pierre. "Combiatorial Diels-Alder approach to the sythesis of ati-tumor athracyclies ad aalogues."curret rgaic Chemistry, 2.LGSA-ATICLE (1998): Zeg, Chao, et al. "Bio-based fura polymers with self-healig ability."macromolecules, 46.5 (2013): Gadii, Alessadro. "Furas as offsprig of sugars ad polysaccharides ad progeitors of a family of remarkable polymers: a review of recet progress."polymer Chemistry, 1.3 (2010): Koehle, Maura, et al. "Productio of p Methylstyree ad p Diviylbezee from Furaic Compouds."ChemSusChem, 10.1 (2017): Patet, ya E., et al. "Kietic regime chage i the tadem dehydrative aromatizatio of fura Diels Alder products."acs Catalysis, 5.4 (2015): Padwa, Albert, et al. "Diels Alder eactio of 2-Amio-Substituted Furas as a Method for Preparig Substituted Ailies."The Joural of rgaic Chemistry, (1997): Mahmoud, Eyas, et al. "Diels Alder ad Dehydratio eactios of Biomass-Derived Fura ad Acrylic Acid for the Sythesis of Bezoic Acid."ACS Catalysis,5.11 (2015): Lautes, Mark, ad Eric Fillio. "A expediet route for the stereoselective costructio of bridged polyheterocyclic rig systems usig the tadem picer Diels Alder reactio."the Joural of orgaic chemistry, (1997): Daishefsky, S., ad T. Kitahra. "Diels-Alder route to cis-fused. DELTA. 1-3-octaloes."The Joural of rgaic Chemistry, 40.4 (1975): Vogel, Pierre, et al. "Derivatives of 7-oxabicyclo [2.2. 1] heptae i ature ad as useful sythetic itermediates."tetrahedro, (1999): Puerto Galvis, Carlos E., Leoor Y. Vargas Médez, ad Vladimir V. Kouzetsov. "Catharidi Based Small Molecules as Potetial Therapeutic Agets."Chemical biology & drug desig, 82.5 (2013): Wolisky, Joseph, ad obert B. Logi. "ovel route to bicyclo [2.2. 2] octeetetracarboxylic acid diahydrides."the Joural of rgaic Chemistry, 37.1 (1972):

12 32. Wolisky, Joseph, ad obert B. Logi. "Diels-Alder reactio of acetoxy-1, 3-diees with dimethyl acetyleedicarboxylate ad chloromaleic ahydride. Sythesis of bezee derivatives."the Joural of rgaic Chemistry, (1970): Thak you for readig these proposals. Dr. obert B. Logi rlogicosultig.com