The sulfonation of aromatic and heteroaromatic polycyclic compounds

Katritzky, Alan R.; Kim, Myong Sang; Fedoseyenko, Dmytro; Widyan, Khalid; Siskin, Mike; Francisco, Manuel

doi:10.1016/j.tet.2008.11.023

Cited by 36 publications

(43 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[10]). A four-proton multiplet was observed at δ 8.14-8.23 ppm [9]. The 13 C NMR spectrum of compound IIa, recorded by us, also differed from that given in [9].…”

mentioning

confidence: 60%

“…The isomer ratio in the product mixtures was determined by 1 Katritzky et al [9] reported on the sulfonation of phenanthrene with sulfuric anhydride in nitrobenzene at 25°C which gave 81% of a compound which was assigned the structure of phenanthrene-2-sulfonic acid IIa. We reproduced the synthesis described in [9] and obtained a mixture of 1-, 2-, 3-, and 9-sulfonic acids in an overall yield of 77% at a ratio of 2 : 1 : 10 : 5.6.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

“…We reproduced the synthesis described in [9] and obtained a mixture of 1-, 2-, 3-, and 9-sulfonic acids in an overall yield of 77% at a ratio of 2 : 1 : 10 : 5.6. The 1 H NMR spectrum of the phenanthrene sulfonation product (in DMSO-d 6 ) was given in [9] without assignment of signals and analysis of their fine structure, and the downfield signal (m, 1H) was located at δ 9.15-9.18 ppm in that spectrum. According to our data, phenanthrene-2-sulfonic acid (IIa) in DMSO-d 6 is characterized by a downfield multiplet at δ 8.75-8.84 ppm (m, 2H) due to 4-H and 5-H, while the 1-H proton characteristically resonates at δ 8.24 ppm as a broadened singlet (cf.…”

mentioning

confidence: 99%

See 3 more Smart Citations

Optimization of the synthesis of phenanthrene-2- and -3-sulfonyl chlorides

2012

View full text Add to dashboard Cite

Sulfonation of phenanthrene with sulfuric acid, followed by neutralization with sodium hydroxide, gave a mixture of isomeric sodium phenanthrenesulfonates in an overall yield of 83%. Sodium phenanthrene-2-, -3-, and -9-sulfonates were isolated in 17, 43, and 4% yield, respectively. Sulfonation of phenanthrene with ClSO 3 H or SO 3 did not improve the yields of phenanthrene-2-and -3-sulfonic acids. Treatment of sodium phenanthrene-2-and -3-sulfonates with PCl 5 -POCl 3 or SOCl 2 -DMF afforded the corresponding sulfonyl chlorides in 89 and 87 or 69 and 70% yield, respectively. Pure phenanthrene-2-and -3-sulfonyl chlorides were also synthesized in 27 and 51% yield by reaction of a mixture of 2-and 3-sulfonates with PCl 5 -POCl 3 .Phenanthrene-2-and 3-sulfonyl chlorides are initial compounds in the synthesis of a number of sulfurcontaining phenanthrenes [1, 2] and their subsequent transformation into substituted 9,10-phenanthrenequinones exhibiting photochemical activity. For example, 9,10-phenanthrenequinone was used as a component of light-sensitive materials [3]. However, the series of available photoactive derivatives of 9,10-phenanthrenequinone [4] is limited due to the lack of convenient procedures for their synthesis. Phenanthrene-2-and 3-sulfonyl chlorides can be obtained from the corresponding sulfonic acids. The yield of phenanthrene-3-sulfonyl chloride from potassium phenanthrene-3-sulfonate was 6% calculated on the initial phenanthrene [2].The present work was aimed at optimizing the synthesis of phenanthrene-2-and 3-sulfonyl chlorides via sulfonation of phenanthrene as intermediate step.Sulfonation of phenanthrene (I) can give rise to four mono-and twelve disulfonic acids [5]. Salts of these acids are capable of forming supersaturated aqueous solutions, which hinders separation of isomeric products by fractional crystallization.Fieser [6] developed a procedure for the sulfonation of phenanthrene in sulfuric acid with predominant formation of monosulfo derivatives. Following this procedure, the 2-isomer was isolated as barium phenanthrene-2-sulfonate in 17-21% yield, and potassium phenanthrene-3-sulfonate was isolated in 24-26% yield. The same compounds were later isolated in slightly lower yields, 16 and 21%, respectively [7]. According to Ioffe [8], the yields of barium phenanthrene-2-sulfonate and potassium phenanthrene-3-sulfonate were 29 and 32%, respectively; raising the temperature to 135°C increased the yield of 2-sulfonic acid [8].The formation of disulfonic acids is the main side process complicating the synthesis of phenanthrene monosulfonic acids by sulfonation of phenanthrene. Therefore, we performed sulfonation of phenanthrene with sulfuric acid under conditions favoring formation of monosulfonic acids, i.e., the reaction was carried out at 135°C and was terminated after 25-30 min when the residual amount of phenanthrene was about 2%. Sulfuric acid was added under vigorous stirring to molten phenanthrene to a molar ratio of 1.6 : 1. The residual amount of phenanthrene was controlled by the s...

show abstract

“…[10]). A four-proton multiplet was observed at δ 8.14-8.23 ppm [9]. The 13 C NMR spectrum of compound IIa, recorded by us, also differed from that given in [9].…”

mentioning

confidence: 60%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 2 more Smart Citations

Optimization of the synthesis of phenanthrene-2- and -3-sulfonyl chlorides

2012

View full text Add to dashboard Cite

show abstract

“…This result is consistent with the specific surface area calculated by the BET method since the PC200 shows the highest BET value and when this material is sulfonated achieves the larger conversion rate. The electrophilic sulfonation of aromatic rings is a reversible reaction (Katritzky et al, 2009). Therefore, all sulfonated aromatic materials including graphitic domains of carbon, could lose the sulfonic groups by hydrolysis.…”

Section: Fischer Esterification Of Acetic Acid With Ethanolmentioning

confidence: 99%

Application of sulfonated nanoporous carbons as acid catalysts for Fischer esterification reactions

Tamborini

Militello

Balach

et al. 2019

Arabian Journal of Chemistry

View full text Add to dashboard Cite

Heterogeneous acid catalysts were prepared by sulfonation of nanoporous carbons (NPCs). The NPCs were produced by pyrolysis of resorcinol-formaldehyde nanoporous resins (NPRs). The NPRs were synthesized as wet gels by condensation of resorcinol and formaldehyde in a sol-gel polycondensation using Na 2 CO 3 as catalyst. A cationic polyelectrolyte (poly(diallyl dimethyl ammonium chloride)) was used as pore stabilizer, allowing to dry the gels in air without any special procedures. Five NPRs with different properties were synthesized by varying the monomer to catalyst ratio (Resorcinol/Na 2 CO 3 , R/C). The morphological and textural characterizations of the NPCs were performed by scanning electron microscopy and nitrogen adsorption-desorption isotherms. The results indicate that using a molar ratio of R/C = 200, a nanoporous carbon NPC with large surface area (695 m 2 /g) is obtained. This NPC was sulfonated by reaction with three different sulfonating agents: (i) concentrated sulfuric acid; (ii) fuming sulfuric acid and (iii) chlorosulfonic acid in order to obtain a novel Fischer esterification catalyst. The amount of acid groups attached to the NPC surface was determined by titration using a modified Boehm method. The catalytic activity, for Fischer esterification reaction of different sulfonated NPCs, was compared with sulfonated NPRs, sulfonated commercial porous carbons and polymeric acid catalyst (cationic ion exchange resins, sulfonated fluoropolymers). The modification of NPCs with concentrated sulfuric

show abstract

Analysis of complex drugs by comprehensive two-dimensional gas chromatography and high-resolution mass spectrometry: detailed chemical description of the active pharmaceutical ingredient sodium bituminosulfonate and its process intermediates

et al. 2022

View full text Add to dashboard Cite

The European pharmacopeia provides analytical methods for the chemical characterization of active pharmaceutical ingredients (APIs). However, the complexity of some APIs exceeds the limitations of the currently prevailing physicochemical methods. Sodium bituminosulfonate (SBS) is described by the collection of key parameters of generalizing criteria such as dry matter, sulfur and sodium content, and neutrality, but techniques to unravel the complexity on a molecular level are lacking. We present a study based on online derivatization with tetramethylammonium hydroxide in combination with comprehensive two-dimensional gas chromatography coupled to an electron ionization high-resolution time-of-flight mass spectrometer (GC × GC-HR-ToF–MS) for the chemical description of SBS as well as its process intermediates. The application of GC × GC allowed the comprehensive description of the chemical components in the API and the process intermediates for the first time. Furthermore, it was possible to classify peaks regarding their elemental and structural composition based on accurate mass information, elution behavior, and mass fragmentation pattern. This work demonstrates not only the general applicability, advantages but also limitations of GC × GC for the characterization of APIs for complex drugs. Graphical Abstract

show abstract

The sulfonation of aromatic and heteroaromatic polycyclic compounds

Cited by 36 publications

References 32 publications

Optimization of the synthesis of phenanthrene-2- and -3-sulfonyl chlorides

Optimization of the synthesis of phenanthrene-2- and -3-sulfonyl chlorides

Application of sulfonated nanoporous carbons as acid catalysts for Fischer esterification reactions

Analysis of complex drugs by comprehensive two-dimensional gas chromatography and high-resolution mass spectrometry: detailed chemical description of the active pharmaceutical ingredient sodium bituminosulfonate and its process intermediates

Contact Info

Product

Resources

About