Bicyclic Derivatives of the Potent Dual Aromatase–Steroid Sulfatase Inhibitor 2‐Bromo‐4‐{[(4‐cyanophenyl)(4H‐1,2,4‐triazol‐4‐yl)amino]methyl}phenylsulfamate: Synthesis,SAR, Crystal Structure,and in vitro and in vivo Activities

The design and synthesis of a series of bicyclic ring containing dual aromatase–sulfatase inhibitors (DASIs) based on the aromatase inhibitor (AI) 4‐[(4‐bromobenzyl)(4H‐1,2,4‐triazol‐4‐yl)amino]benzonitrile are reported. Biological evaluation with JEG‐3 cells revealed structure–activity relationships. The X‐ray crystal structure of sulfamate 23 was determined, and selected compounds were docked into the aromatase and steroid sulfatase (STS) crystal structures. In the sulfamate‐containing series, compounds containing a naphthalene ring are both the most potent AI ( 39 , IC_{50 AROM}=0.25 nM ) and the best STS inhibitor ( 31 , IC_{50 STS}=26 nM ). The most promising DASI is 39 (IC_{50 AROM}=0.25 nM , IC_{50 STS}=205 nM ), and this was evaluated orally in vivo at 10 mg kg^?1, showing potent inhibition of aromatase (93 %) and STS (93 %) after 3 h. Potent aromatase and STS inhibition can thus be achieved with a DASI containing a bicyclic ring system; development of such a DASI could provide an attractive new option for the treatment of hormone‐dependent breast cancer.     

Structure and antimicrobial activity relationship of quaternary N‐alkyl chitosan derivatives against some plant pathogens

In the present work, quaternary chitosans as water‐soluble compounds were prepared based on three‐step process. Schiff bases were firstly synthesized by the reaction between the amino groups of chitosan with aliphatic aldehydes followed by a reduction with sodium borohydride (NaBH₄) to form N‐(alkyl) chitosans. N,N,N‐(dimethyl alkyl) chitosans were then obtained by a reaction of chitosan containing N‐butyl, N‐pentyl, N‐hexyl, N‐heptyl, and N‐octyl substituents with methyl iodide. The compounds were characterized using IR and NMR spectroscopy. Subsequent experiments were conducted to test their antimicrobial activities against the most economic plant pathogenic bacteria of crown gall disease Agrobacterium tumefaciens, soft mold disease Erwinia carotovora, fungi of grey mold Botrytis cinerea, root rot disease Fusarium oxysporum, and damping off disease Pythium debaryanum. Quaternary chitosans enhanced the antibacterial activity and N,N,N‐(dimethyl pentyl) chitosan was the most active one with Minimum Inhibitory Concentration (MIC) of 750 and 1225 mg/L against A. tumefaciens and E. carotovora, respectively. All quaternized chitosans gave stronger antifungal activities than chitosan where N,N,N‐(dimethyl pentyl) chitosan and N,N,N‐(dimethyl octyl) chitosan were significantly the highest in mycelial growth inhibiation against B. cinerea (EC₅₀ = 908 and 383 mg/L, respectively), F. oxysporum (EC₅₀ = 871 and 812 mg/L, respectively), and P. debaryanum (EC₅₀ = 624 and 440 mg/L, respectively). In addition, spore germination of B. cinerea and F. oxysporum was significantly affected with the compounds at the tested concentrations and the inhibition activity was increased with an increase in the chain length of the alkyl substituent. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis,characterization, and cure reaction of methacrylate‐based multifunctional monomers for dental composites

The synthesis of 2,2‐bis[(4‐(2‐hydroxy‐3‐methacryloxyethoxy)phenyl]propane (BHEP) and (1‐methacryloxy‐3‐ethoxymethacryloxy‐2‐hydroxy)propane (MEHP) for use as the monomer phase in dental composites are reported. The monomers were prepared by the reaction of 2‐hydroxyethyl methacrylate (HEMA) with diglycidyl‐ether of bisphenol A (DGEBA) and with glycidyl methacrylate (GMA), respectively. The progress of the reaction was followed by measuring the disappearance of the epoxide group peak using FTIR and the structure of the monomers was characterized by ¹H‐NMR. BHEP and MEHP have lower viscosity because of the presence of long aliphatic spacer on both sides of the aromatic ring in BHEP and the absence of aromatic rings and the presence of only one hydroxyl group in each molecule of MEHP. Thermal curing of the monomers was conducted in a DSC using benzoyl peroxide as an initiator. Photopolymerization of the monomers was also conducted with the visible light using camphorquinone and N,N‐dimethylaminoethyl methacrylate as the photoinitiating system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Surface Activity Properties and Aggregation Behaviors of Partially Fluorinated Gemini Surfactants in Aqueous Solution

The surface activity and aggregation behavior of partially fluorinated gemini surfactant N,N′‐bis(3‐perfluorohexyl‐2‐hydroxypropyl)‐N,N′‐dipropanesulfonylhexylenediamine (N‐6‐Sul) was studied by surface tension, resonance light scattering and fluorescence spectra measurements. The critical micelle concentration (CMC) values obtained by the three methods are in good agreement. The surface activity parameters such as the effectiveness of surface tension reduction (Π_cmc), the maximum surface excess concentration (Γ_max) and the minimum surface area per molecule (A_min) were obtained through surface tension curves. The effects of pH, inorganic salts and temperature on the surface activity were also investigated. The morphology and size of the aggregates of N‐6‐Sul were examined by transmission electron microscopy (TEM). The results show that the partially fluorinated gemini surfactant N‐6‐Sul has many advantages such as high surface activity, low CMC value, great salt tolerance and temperature resistance.     

Synthesis of N‐aryl azetidine‐2,4‐diones and polymalonamides prepared from selective ring‐opening reactions

Improved high‐yield synthesis of N‐aryl azetidine‐2,4‐dione has been achieved. The azetidine‐2,4‐dione undergoes ring‐opening reactions with aliphatic primary amines to form malonamide linkages. More importantly, this compound exhibits a high reactivity toward primary aliphatic amine group over alcohols or secondary amines. This selective end‐group functionalization is useful for preparing useful polymer intermediates. In this study polymalonamides were synthesized by fast addition reaction of aliphatic diamine and azetidine‐2,4‐dione. In the meantime, further application for structure‐controlled reaction also has been demonstrated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3591–3599, 2007     

On the reaction of (S)-trifluoroacetoxysuccinic anhydride with amines to produce hydroxysuccinamic (malamic) acid derivatives

L-Malic acid ( 2 ) reacts with trifluoroacetic anhydride under anhydrous conditions to give (S)-trifluoroacetoxy-succinic acid anhydride ( 3 ). The anhydride 3 undergoes regioselective ring opening with an excess of anilines or primary aliphatic amines leading to N-substituted-(S)-3-hydroxy-succinamic acids ( 4a – g ). Structural elucidation of the reaction products 4a – g was based on analytical and spectroscopic data and on an X-ray structure analysis of 4b . Secondary aliphatic amines react with 3 by condensation and subsequent elimination to furnish N,N′-disubstituted fumaric acid amides 5a , b . Some N-substituted-2-hydroxysuccinamic acids ( 7a , b ) were also prepared for spectral comparison with the 3-hydroxy compounds.     

Copper‐Catalyzed Trifluoromethylation of Aliphatic N‐Arylhydrazones: A Concise Synthetic Entry to 2‐Trifluoromethylindoles from Simple Aldehydes

The copper‐catalyzed C(sp²) H trifluoromethylation of N,N‐disubstituted hydrazones using the Togni reagent is demonstrated to proceed efficiently for aliphatic aldehyde‐derived substrates. The success of the reactions relied on the choice of the N,N‐diphenylamino group as the terminal hydrazone amino group where N,N‐dialkylamino groups were preferred for (hetero)aromatic aldehyde‐derived substrates. In addition, the trifluoromethylated N‐arylhydrazones are shown to be ideal substrates for Fischer indole synthesis allowing a straightforward, three‐step access to 2‐trifluoromethylindole derivatives from simple aldehydes.

     

Comparative Investigation of Hoveyda–Grubbs Catalysts bearing Modified N‐Heterocyclic Carbene Ligands

This paper reports the structural modification of Hoveyda–Grubbs complexes through the introduction of either an N‐alkyl‐N′‐mesityl heterocyclic carbene, an N‐alkyl‐N′‐(2,6‐diisopropylphenyl) heterocyclic carbene, or an N‐alkyl‐N′‐alkyl heterocyclic carbene. The effect of the modified N‐heterocyclic carbene (NHC) ligand was investigated in representative ring‐opening metathesis polymerization (ROMP), ring‐closing metathesis (RCM) and cross metathesis (CM) reactions. A pronounced influence on both catalyst activity and selectivity was found to be exerted by the NHC amino substituents, which emphasizes that a rigorously selected steric environment is critical in olefin metathesis catalyst design.     

Controllable ring‐opening polymerization of trimethylene carbonate catalyzed by aliphatic tertiary amines in the presence of benzyl alcohol or F127

With the increased awareness of avoiding residue metals, the field of organocatalysts is attracting more attention. Aliphatic tertiary amines, such as triethylamine (TEA), N, N, N, N‐tetramethylethylenediamine (TMEDA) and 1,1,4,7,7‐pentamethyldiethylenetriamine (PMDTA), have low boiling points which allow their easy elimination after a chemical reaction. Here, we used these aliphatic tertiary amines to catalyze ring‐opening polymerizations (ROPs) of trimethylene carbonate (TMC). In the presence of benzyl alcohol, the catalytic activities of the tertiary amines were in the order of TEA < TMEDA < PMDTA. Correlation between the molecular weight of polycarbonates and monomer conversions was linear, suggesting the polymerization was controlled. The polymerization pathway was presumed to follow an alcohol‐activated mechanism according to the end‐group fidelity determined using ¹H NMR spectroscopy. The ROP of TMC was also successfully initiated by PEO₉₉‐PPO₆₅‐PEO₉₉ (F127) under the catalysis of the tertiary amines, producing well‐defined PTMC_n‐F127‐PTMC_n copolymers with narrow dispersity ( ca 1.2) and with thermosensitive properties in aqueous solution. Furthermore, copolymerizations of TMC with acryloyl‐containing cyclic carbonate were catalyzed by the tertiary amines in the presence of F127. No crosslinking reactions were detected. Our results demonstrate that the aliphatic tertiary amines have the potential to catalyze TMC homo‐ or copolymerization featuring controllable structure and composition under mild conditions. Copyright © 2012 Society of Chemical Industry     

Synthesis and Structure–Activity Relationship Studies of Derivatives of the Dual Aromatase–Sulfatase Inhibitor 4‐{[(4‐Cyanophenyl)(4H‐1,2,4‐triazol‐4‐yl)amino]methyl}phenyl sulfamate

4‐{[(4‐Cyanophenyl)(4H‐1,2,4‐triazol‐4‐yl)amino]methyl}phenyl sulfamate and its ortho‐halogenated (F, Cl, Br) derivatives are first‐generation dual aromatase and sulfatase inhibitors (DASIs). Structure–activity relationship studies were performed on these compounds, and various modifications were made to their structures involving relocation of the halogen atom, introduction of more halogen atoms, replacement of the halogen with another group, replacement of the methylene linker with a difluoromethylene linker, replacement of the para‐cyanophenyl ring with other ring structures, and replacement of the triazolyl group with an imidazolyl group. The most potent in vitro DASI discovered is an imidazole derivative with IC₅₀ values against aromatase and steroid sulfatase in a JEG‐3 cell preparation of 0.2 and 2.5 nM , respectively. The parent phenol of this compound inhibits aromatase with an IC₅₀ value of 0.028 nM in the same assay.     

Polymerization of 4‐(4′‐N‐1,8‐naphthalimidophenyl)‐1,2,4‐triazolidine‐3,5‐dione with diisocyanates

4‐(4′‐Aminophenyl)‐1,2,4‐triazolidine‐3,5‐dione ( 1 ) was reacted with 1,8‐naphthalic anhydride ( 2 ) in a mixture of acetic acid and pyridine (3 : 2) under refluxing temperature and gave 4‐(4′‐N‐1,8‐naphthalimidophenyl)‐1,2,4‐triazolidine‐3,5‐dione ( NIPTD ) ( 3 ) in high yield and purity. The compound NIPTD was reacted with excess n‐propylisocyanate in N,N‐dimethylacetamide solution and gave 1‐(n‐propylamidocarbonyl)‐4‐[4′‐(1,8‐naphthalimidophenyl)]‐1,2,4‐triazolidine‐3,5‐dione ( 4 ) and 1,2‐bis(n‐propylamidocarbonyl)‐4‐[4′‐(1,8‐naphthalimidophenyl)]‐1,2,4‐ triazolidine‐3,5‐dione ( 5 ) as model compounds. Solution polycondensation reactions of monomer 3 with hexamethylene diisocyanate ( HMDI ), isophorone diisocyanate ( IPDI ), and tolylene‐2,4‐diisocyanate ( TDI ) were performed under microwave irradiation and conventional solution polymerization techniques in different solvents and in the presence of different catalysts, which led to the formation of novel aliphatic‐aromatic polyureas. The polycondensation proceeded rapidly, compared with conventional solution polycondensation, and was almost completed within 8 min. These novel polyureas have inherent viscosities in a range of 0.06–0.20 dL g^?1 in conc. H₂SO₄ or DMF at 25°C. Some structural characterization and physical properties of these novel polymers are reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2861–2869, 2003     

Synthesis and characterization of biodegradable block copolymer pluronic‐b‐poly(L‐lysine)

This study presented the investigations on the synthesis of a novel biodegradable block copolymer of pluronic‐b‐poly(L ‐lysine) (pluronic‐b‐PLL), which combined the characteristics of aliphatic polyester and poly(amino acids). The synthesis work started with end‐capping of pluronic with N‐t‐butoxycarbonyl‐L ‐phenylalanine using dicyclohexylcarbodiimide in the presence of 4‐dimethylaminopyridine, followed by a deprotection process to obtain the amino‐terminated pluronic; the new primary amino group in the modified pluronic initiated ring‐opening polymerization of amino acid N‐carboxyanhydride, which afforded the pluronic‐b‐poly(N^ε‐(Z)‐L ‐lysine) block copolymer. Finally, removal of the side‐chain N^ε‐(carbonybenzoxy) end protecting groups yields the block copolymer of pluronic‐b‐PLL. The products were characterized by ¹H‐NMR, FTIR, DSC, and GPC. The block copolymer micelle containing the anticancer drug paclitaxel was prepared by the double emulsion method. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Iron‐Catalyzed Oxidative Mono‐ and Bis‐Phosphonation of N,N‐Dialkylanilines

The dehydrogenative α‐phosphonation of substituted N,N‐dialkylanilines by dialkyl H‐phosphonates was achieved under mild conditions by using environmentally benign iron(II) chloride as catalyst and tert‐butyl hydroperoxide as oxidant. The reaction proceeded in the presence of electron‐donating (methoxy, methyl, benzyl) and electron‐withdrawing ring‐substitutents (bromo, carbonyl, carboxyl, m‐nitro) in moderate to good yields. The X‐ray crystal structure of N‐(5,5‐dimethyl‐2‐oxo‐2λ⁵‐[1,3,2]dioxaphosphinan‐2‐yl‐methyl)‐N‐methyl‐p‐toluidine was determined. Bis‐(4‐(dimethylamino)phenyl)methane and bis‐4,4′‐(dimethylamino)benzophenone underwent bisphosphonation selectively by respective monophosphonation at the remote dimethylamino groups. Furthermore, the use of excess dialkyl H‐phosphonate and oxidant allowed us to functionalize both methyl groups of N(CH₃)₂ in N,N‐dimethyl‐p‐toluidine and N,N‐dimethylaminomesidine, respectively, to obtain α,α′‐bisphosphonatoamines in high yield.     

N,N‐diethyl dithiocarbamato group induced photografting of methyl methacrylate onto polyurethane

The N,N‐diethyl dithiocarbamato group present in a variety of compounds acts as an initiator in the photopolymerization processes. The photolability of this group is due to the cleavage of the C S bond by UV irradiation. N,N‐Diethyl dithiocarbamato‐(1,2)‐propane diol with a pendent N,N‐diethyl dithiocarbamato group was prepared from 3‐chloro‐(1,2)‐propane diol and sodium diethyl dithiocarbamate. A polyurethane macrophotoinitiator was then synthesized by a two‐step process, where N,N‐diethyl dithiocarbamato‐(1,2)‐propane diol was used as the chain extender. Other components used included 4,4′‐diphenylmethane diisocyanate and poly(propylene glycol) (molecular weight = 1000). The polyurethane thus synthesized had pendent N,N‐diethyl dithiocarbamato groups. This polyurethane macrophotoinitiator was then used to polymerize methyl methacrylate in a photochemical reactor (Compact‐LP‐MP 88) at 254 nm. The resulting graft copolymer, polyurethane‐g‐poly(methyl methacrylate), was freed from the homopolymer by a standard procedure. The graft copolymer was characterized by Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, thermogravimetric analysis, differential scanning calorimetry, solution viscometry, and scanning electron microscopy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Physical properties of aliphatic polycarbonates made from CO2 and epoxides

A homologous series of aliphatic polycarbonates with different side‐chain lengths was synthesized by ring‐opening polymerization of terminal epoxides with CO₂ using zinc adipionate as catalyst [patented process of Empower Materials (formerly PAC Polymers Inc.)]. Additionally, a polycarbonate was made having a cyclohexane unit in its backbone, together with a terpolymer having both cyclohexane and propylene units. After characterization of thermal properties the aliphatic polycarbonates were found to be completely amorphous. Polycarbonates derived from long‐chain epoxides showed a glass‐transition temperature (T_g) below room temperature, whereas polycarbonates derived from cyclohexene oxide showed a T_g of 105°C, the highest yet reported for this class of polymers. The initial decomposition temperature of the polymers in air and nitrogen atmospheres was found to be less than 300°C. The mechanical properties and the dynamic mechanical relaxation behavior of the polymers were also reported. The effect of the chemical structure on the physical properties of aliphatic polycarbonates was discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1163–1176, 2003     

The effect of benzenesulfonamide plasticizers on the glass transition temperature of an amorphous aliphatic polyamide

The plasticizing effect of benzenesulfonamides (BSAs) on an amorphous aliphatic polyamide (AAPA) has been studied using dynamic mechanical analysis of copper‐supported spin‐coated mixtures. It follows that N‐(n‐butyl)BSA (BBSA), an amorphous liquid hydrogen bonding BSA, is fully miscible with AAPA because their mixtures are characterized by a single glass transition (T_g) throughout the compositional range. The T_g–composition dependence, however, is not linear because experimental results suggest a 20 K fall in T_g occurring around 0.65 BBSA units per amide unit, which coincides with the system shifting from a polymer‐like to a liquid‐like glass‐forming material. When considering a crystallizable hydrogen‐bonding plasticizer such as ethylBSA (EBSA), AAPA/EBSA mixtures become fully crystalline at a 1.3 EBSA unit per amide group. Nevertheless, melting point depression together with the single T_g observed throughout the compositional range on quenched (and therefore amorphous) samples confirms the miscibility of AAPA chains with the plasticizer. N,N‐DialkylBSAs, which lack the sulfonamide proton and therefore the possibility of hydrogen bonding with amide groups, quickly phase separate from AAPA, the glass transition of the latter staying mainly unaffected apart from a small (9 K) decrease at 10–15 mol% plasticizer. © 2001 Society of Chemical Industry     

Synthesis and properties of new aromatic poly(ester‐imide)s derived from 4‐p‐biphenyl‐2,6‐bis(4‐trimellitimidophenyl) pyridine and various dihydroxy compounds

A novel class of wholly aromatic poly(ester‐imide)s, having a biphenylene pendant group, with inherent viscosities of 0.32–0.49 dL g^?1 was prepared by the diphenylchlorophosphate‐activated direct polyesterification of the preformed imide‐ring‐containing diacid, 4‐p‐biphenyl‐2,6‐bis(4‐trimellitimidophenyl)pyridine (1) with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. A reference diacid, 2,6‐bis(trimellitimido)pyridine (2) without a biphenylene pendant group and two phenylene rings in the backbone, was also synthesized for comparison purposes. At first, with due attention to structural similarity and to compare the characterization data, a model compound (3) was synthesized by the reaction of compound 1 with two mole equivalents of phenol. Moreover, the optimum condition of polymerization reactions was obtained via a study of the model compound synthesis. All of the resulting polymers were characterized by Fourier transform infrared and ¹H NMR spectroscopy and elemental analysis. The ultraviolet λ_max values of the poly(ester‐imide)s were also determined. All of the resulting polymers exhibited excellent solubility in common organic solvents, such as pyridine, chloroform, tetrahydrofuran, and m‐cresol, as well as in polar organic solvents, such as N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, and dimethyl sulfoxide. The crystalline nature of the polymers obtained was evaluated by means of wide‐angle X‐ray diffraction. The resulting poly(ester‐imide)s showed nearly an amorphous nature, except poly(ester‐imide) derived from 4,4′‐dihydroxy biphenyl. The glass transition temperatures (T_g) of the polymers determined by differential scanning calorimetry thermograms were in the range 298–342 °C. The 10% weight loss temperatures (T_10%) from thermogravimetric analysis curves were found to be in the range 433–471 °C in nitrogen. Films of the polymers were also prepared by casting the solutions. Copyright © 2006 Society of Chemical Industry     

Synthesis and characterization of novel core‐shell magnetic nanogels based on 2‐acrylamido‐2‐methylpropane sulfonic acid in aqueous media

Ultrafine well‐dispersed Fe₃O₄ magnetic nanoparticles were directly prepared in aqueous solution using controlled coprecipitation method. The synthesis of Fe₃O₄/poly (2‐acrylamido‐2‐methylpropane sulfonic acid) (PAMPS), Fe₃O₄/poly (acrylamide‐co‐2‐acrylamido‐2‐methylpropane sulfonic acid) poly(AM‐co‐AMPS) and Fe₃O₄/poly (acrylic acid‐co‐2‐acrylamido‐2‐methylpropane sulfonic acid) poly(AA‐co‐AMPS) ‐core/shell nanogels are reported. The nanogels were prepared via crosslinking copolymerization of 2‐acrylamido‐2‐methylpropane sulfonic acid, acrylamide and acrylic acid monomers in the presence of Fe₃O₄ nanoparticles, N,N′‐methylenebisacrylamide (MBA) as a crosslinker, N,N,N′,N′‐tetramethylethylenediamine (TEMED) and potassium peroxydisulfate (KPS) as redox initiator system. The results of FTIR and ¹H‐NMR spectra indicated that the compositions of the prepared nanogels are consistent with the designed structure. X‐ray powder diffraction (XRD) and transmission electron microscope (TEM) measurements were used to determine the size of both magnetite and stabilized polymer coated magnetite nanoparticles. The data showed that the mean particle size of synthesized magnetite (Fe₃O₄) nanoparticles was about 10 nm. The diameter of the stabilized polymer coated Fe₃O₄ nanogels ranged from 50 to 250 nm based on polymer type. TEM micrographs proved that nanogels possess the spherical morphology before and after swelling. These nanogels exhibited pH‐induced phase transition due to protonation of AMPS copolymer chains. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Selective Removal of N‐Boc Protecting Group from Aromatic Amines Using Silica Gel‐Supported Sodium Hydrogen Sulfate and HY‐Zeolite as Heterogeneous Catalysts[1]

Silica gel‐supported sodium hydrogen sulfate and HY‐zeolite were found to be efficient catalysts for the selective removal of the N‐Boc protecting group from aromatic amines keeping intact the aliphatic N‐Boc amines. HY‐zeolite was used as a reusable catalyst.     

Block and Random Living,Ring‐Opening Metathesis Copolymerization of Functionally Differentiated Carbazole‐Containing Norbornene Monomers

The synthesis of novel diblock polymers containing both a potential charge transport and a non‐linear optic block has been accomplished. The synthesis exploits the living, ring‐opening metathesis block copolymerization of two norbornene type monomers, one of which contains an unsubstituted N‐carbazolyl ring while the other has a bromo substituent at the 3‐position of the carbazole ring. Conversion of the bromo functionality to a 2,2‐dicyanovinyl group introduces the non‐linear optic property. The first monomer was prepared by the previously reported efficient cation radical Diels–Alder cycloaddition of N‐trans‐1‐propenylcarbazole to 1,3‐cyclopentadiene, while the second was obtained by N‐bromosuccinimide bromination of the first monomer. For purposes of comparison, the corresponding random copolymer was also synthesized.