Norbornene, acidity

Linear correlations between pK and the Hammett substituent constant a, and between chemical shifts of the carbonyl carbon atom and a, for the four isomeric norbornene acids of gross structure (42) are explained by a perturbation effect between the electric dipoles of the carboxy-group and R (R= H, Cl, NO2, or OMe). The preparation of C-enriched samples of 1-substituted butanes and adamantylmethyl derivatives (label at C-1 and the exocyclic carbon atom respectively) has enabled direct comparison of vicinal coupling constants. The uniformly smaller... 

A-Hydroxy-5-norbornene-2,3-dicarboxylic acid imide [21715-90-2] M 179.2, m 165-166", 166-169", pKesi-6 Dissolve in CHCI3, filter, evaporate and recrystallise from EtOAc. IR (nujol) 1695, 1710 and 1770 (C=0), and 3100 (OH) cm. 0-Acetyl derivative has m 113-114° (from EtOH) with IR bands at 1730, 1770 and 1815 cm only, and the 0-benzoyl derivative has m 143-144° (from propan-2-ol or C6H6). [Bauer and Miarka J Org Chem 24 1293 1959 Fujino et al. Chem Pharm Bull Jpn 22 1857 1974],... 

Boron trifluoride-acetic acid complex Harshaw Chemical Co., Allied Chemical Co. 1,5-Cyclooctadiene A, MCB Sulfur dichloride MCB Boron trifluoride etherate EK, MCB Mercuric acetate MCB Norbornene MCB Calcium carbide MCB Pinacol EK, MCB... 

Optically active norbornene derivatives [26] have been prepared by cycloaddition of hexachlorocyclopentadiene with /-menthylacrylate and /-menthylallyl-ether (Equation 2.9). Low levels of enantiomeric excess have been obtained in the thermal processes, whereas Lewis acid catalyzed reactions (BF3, BBr3, AICI3, SnCU, DCM, 40-80 °C) gave better results. 

As the mechanism, a radical and a cationic pathway are conceivable (Eq. 31). The stereochemical results with rac- or mcjo-1,2-diphenyl succinic acid, both yield only trans-stilbene [321], and the formation of a tricyclic lactone 51 in the decarboxylation of norbornene dicarboxylic acid 50 (Eq. 32) [309] support a cation (path b, Eq. 31) rather than a biradical as intermediate (path a). 

Phosphonoformic acid (85) decarboxylated in acid solution, and it was proposed that the uncatalysed reaction involved a simple decarboxylation of the zwitterion. The acid-catalysed reaction showed some kinetic similarity to that of mesitoic acid and an elimination of carbon dioxide as trihydroxymethylcarbonium ion was preferred. Participation of the trans vicinal phosphonyl group in the solvolysis of the halides (86) and (87) has been deduced from rate measurements. In the norbornene derivatives, the relative rates of loss of chloride from (87a) and (87b) were 5 x 10 1. 

The violent polymerisation of acryl acid caused a violent fire on a boat that was transporting it. The investigation showed that this acid contained ethylidene norbornene, which is a very oxidisable compound that forms a peroxide in air, which caused the acid polymerisation. 

The stereoselectivity of epoxidation with peroxycarboxylic acids has been well studied. Addition of oxygen occurs preferentially from the less hindered side of the molecule. Norbornene, for example, gives a 96 4 exo endo ratio.76 In molecules where two potential modes of approach are not very different, a mixture of products is formed. 

Scheme 20 Reductive hydroacylation of norbornene employing mixed carboxylic anhydrides derived from pivalic acid...

Table 4 Reaction of an or/Ao-substitutcd aryl iodide with an arylboronic acid in the presence of K2C03, Pd(OAc)2 and norbornene.3...

The irreproducibility (98,100) of the Pesci decarboxylations [Eqs. (84) and (86)] (97,99) has further implications since the decarboxylation products were claimed to undergo novel nucleophilic displacements of mercury (96,97,99). Some reported nucleophilic demercurations of an authentic mercurial (96) could not be repeated (98). A Pesci type hemidecarboxylation of 5-norbornene-2,3-dicarboxylic acid has been reported by Takahashi (101), but this has also been found to be irreproduci-ble (101a). 

Similar to the addition of secondary phosphine-borane complexes to alkynes described in Scheme 6.137, the same hydrophosphination agents can also be added to alkenes under broadly similar reaction conditions, leading to alkylarylphosphines (Scheme 6.138) [274], Again, the expected anti-Markovnikov addition products were obtained exclusively. In some cases, the additions also proceeded at room temperature, but required much longer reaction times (2 days). Treatment of the phosphine-borane complexes with a chiral alkene such as (-)-/ -pinene led to chiral cyclohexene derivatives through a radical-initiated ring-opening mechanism. In related work, Ackerman and coworkers described microwave-assisted Lewis acid-mediated inter-molecular hydroamination reactions of norbornene [275]. 

The side products of the reaction between benzoylnitromethane 279 and dipolarophiles (norbornene, styrene, and phenylacetylene) in the presence of l,4-diazabicyclo[2.2.2]octane (DABCO) were identified as furazan derivatives (Scheme 72). The evidence reported indicates that benzoylnitromethane gives the dibenzoylfuroxan as a key intermediate, which is the dimerization product of the nitrile oxide. The furoxan then undergoes addition to the dipolarophile, hydrolysis, and ring rearrangement to the final products (furazans and benzoic acid) <2006EJ03016>. 

Miura reported a 1,4-shift of rhodium in the reaction of norbornene with arylboronic acids (Scheme 3) where rhodium moves from an alkyl sp2-carbon to an aryl sp2-carbon, and the arylrhodium species further reacts with another molecule of norbornene.30 Polyalkylated phenyls are obtained in good yields. Cesium fluoride facilitates the transmetallation, generating the phenylrhodium complex which then coordinates to the -face of norbornene. 

Alkylation of norbornene with acrylic acid derivatives occurs with ruthenium catalysts like [RuCl2(C6H6)]2/Zn in protic solvent.31 (,E)-o -2-norbonylacrylates are obtained with high regio- and stereoselectivity in good yields. 

Treatment of the ketone (287) with pTsOH in benzene at 60 °C provided the norbornen-7-one derivative (288)98), following interesting acid-catalyzed rearrangement. 

Norbornene-ethene copolymer, 16 113 Norbornene-ethylene copolymers, 20 433 physical properties of, 20 420-422 Norbornenodiazetine derivatives, 13 306 Nordel IP (metallocene), 7 637 Nordihydroguaiaretic acid, antioxidant useful in cosmetics, 7 830t Nordstrandite, 2 421, 425 activation, 2 394 classification, 2 422 decomposition sequence, 2 392 from gelatinous boehmite, 2 427 structural properties of, 2 423t NO-reduction reactions, TWC catalyst, 10 49... 

Nonadienoic acid, 4-methyl-, trans, ethyl ester, 53, 116 Nonan-5-ol, 52, 22 D-NORANDROST-5-EN-36-0L-16-CARBOXYLIC ACIDS, 52, 53 Norbornene, with ethyl tri-... 

The living character of the ring opening metathesis polymerization described earlier in this review enables a simple preparation of functionalized norbornene-based monoliths. Adding one more in situ derivatization step that involves functional norborn-2-ene and 7-oxanorborn-2-ene monomers that react with the surface-bound initiator, the pores were provided with a number of typical functional groups such as carboxylic acid, tertiary amine, and cyclodextrin [58,59]. 

Scheme 40 Anodic decarboxylation of a norbornene carboxylic acid.

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