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(((4-Methoxyphenyl)Amino)Methyl)-N,N-Dimethylaniline and 2-Methoxy-5-((Phenylamino)Methyl)Phenol

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(((4-Methoxyphenyl)Amino)Methyl)-N,N-Dimethylaniline and 2-Methoxy-5-((Phenylamino)Methyl)Phenol molbank Communication 4-(((4-Methoxyphenyl)amino)methyl)-N,N-dimethylaniline and 2-Methoxy-5-((phenylamino)methyl)phenol Peter A. Ajibade * and Fartisincha P. Andrew School of Chemistry and Physics, University of KwaZulu-Natal, Private Bag X01, Pietermaritzburg 3209, South Africa; [email protected] * Correspondence: [email protected] Abstract: Molecular structures of 4-(((4-methoxyphenyl)amino)methyl)-N,N-dimethylaniline and 2-methoxy-5-((phenylamino)methyl)phenol synthesized via Schiff bases reduction route are reported. The compounds consist of asymmetric units of C16H20N2O(1) and C14H15NO2 (2) in orthorhombic and monoclinic crystal systems, respectively. Compound 1 consist of intermolecular C11—H11···N2 hydrogen bonding with C11···N21 = 3.463(4) Å. The hydroxyl group in 2 is also involved in inter- molecular O2—H2···O2 and O2—H2···O21 hydrogen bonding with O2···O11 = 2.8885(15) Å and O1···O21 = 2.9277(5) Å. The molecular structures of the compounds are stabilized by secondary intermolecular interactions of C1—H1B···O11 and C5—H···(C41, C51, C61, C71) for 1 and H···C, C—H···O and N—H···C for 2. The reported compounds are important starting material for the synthesis of many compounds such as azo dyes and dithiocarbamate. Keywords: secondary amines; crystal structure; sodium borohydride; supramolecular structure Citation: Ajibade, P.A.; Andrew, F.P. 1. Introduction 4-(((4-Methoxyphenyl)amino) N-alkylation of primary amines and ammonia, reduction of nitriles and amides in methyl)-N,N-dimethylaniline and the presence of catalyst such as LiAlH4 and NaBH4, tin, or iron have been used for the 2-Methoxy-5-((phenylamino)methyl) preparation of secondary amines [1–5]. NaBH4 is a powerful reducing agent that has been phenol. Molbank 2021, 2021, M1274. used for the reduction of different functional groups [6] due to its selectivity; it also does https://doi.org/10.3390/M1274 not affect reducible substituents such as nitro and chloride during the reduction process [7]. Secondary amines are important starting materials for the preparation of compounds Academic Editor: R. Alan Aitken such as dithiocarbamates and dyes, among others, and form the constituents of many Received: 18 July 2021 pharmaceuticals such as antidepressants (clomipramine, desipramine) psychedelic and Accepted: 23 August 2021 opiate analgesics (phenethylamines, codeine, heroin, morphine), and agrochemicals, among Published: 31 August 2021 others [8–17]. Related secondary amines to the title compounds that have been reported include 2-[(4-chlorophenyl)aminomethyl]-6-methoxyphenol [18], 2-[(4-methoxyanilino) Publisher’s Note: MDPI stays neutral methyl]phenol [19], 2-(anilinomethyl)phenol [20]. Herein we report the synthesis and with regard to jurisdictional claims in crystal structures of 4-(((4-methoxyphenyl)amino)methyl)-N,N-dimethylaniline (1) and published maps and institutional affil- 2-methoxy-5-((phenylamino)methyl)phenol (2). iations. 2. Results and Discussion 2.1. Synthesis of the Compounds The compounds were synthesized by condensation of the primary amines with the Copyright: © 2021 by the authors. corresponding aldehydes in methanol and sequential reduction of the resulting Schiff Licensee MDPI, Basel, Switzerland. bases with sodium borohydride in methanol and dichloromethane at room temperature This article is an open access article (Scheme1). distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/). Molbank 2021, 2021, M1274. https://doi.org/10.3390/M1274 https://www.mdpi.com/journal/molbank Molbank 2021, 2021, x FOR PEER REVIEW 2 of 6 Molbank 2021,, 2021,, M1274x FOR PEER REVIEW 2 of 6 (Compound 1) Yield = 78% (Compound 2) Yield = 80% (Compound 1) Yield = 78% (Compound 2) Yield = 80% Scheme 1. Synthetic routes for the preparation of secondary amines (1,2). Scheme 1. Synthetic routes for the preparationpreparation of secondary amines ((11,,22).). 2.2. Molecular Structures of the Compounds 2.2. Molecular Structures of the Compounds The molecular structures of 1 and 2 are presented in Figure 1. The crystal data and structureThe molecular refinement structures are presented of 1 andin Table 2 are 1 presentedpresented while the inpacking FigureFigure diagrams1 1.. TheThe crystalcrystal are presented datadata andand instructure Figure refinement2.refinement The molecular areare presentedpresented structures in in Tableof Table both1 while1 compounds while the the packing packing consist diagrams diagramsof a monomeric are are presented presented unit inin theinFigure Figure asymmetric2. The 2. The molecular molecular unit. structures structuresCompound of both of both compounds1 compoundsconsist consistof consistN,N of a -of monomericdimethylaniline a monomeric unit unit inand the in methoxyphenylaminotheasymmetric asymmetric unit. unit. Compound Compound moieties1 consistwhile 1 consist 2of consistN of,N N,N-dimethylaniline-dimethylaniline of phenylamino and and and methoxyphenylamino phenol methoxyphenyla- moieties. The phenylminomoieties moieties rings while in while2bothconsist compounds2 consist of phenylamino of liephenylamino in distinct and phenolplanes and phenol with moieties. dihedralmoieties. The angles phenyl The phenyl of rings 73.89° rings in for both in 1 ◦ 1 ◦ 2 andbothcompounds 86.61° compounds for lie 2 between in lie distinct in distinct the planes planes planes with(Figure with dihedral dihedral3). Compound angles angles of 1 of 73.89is 73.89°involvedfor for in1and and intermolecular 86.61 86.61° forfor 2 between the planes (Figure3 3).) . Compound 11 isis involvedinvolved inin intermolecularintermolecular C11—H11C11—H11···N21 ···N2 C11—H11···N2 hydrogen bonding1 (C11···N2 = 3.463(4) Å ); symmetry operation1 of 1/2+x,- hydrogen bonding (C11···N21 = 3.463(4) Å); symmetry operation of1 1/2 + x, − y, + z. y,+z.hydrogen The hydroxylbonding (C11···N2group of 2 = is3.463(4) involved Å); in symmetry intermolecular operation hydrogen of 1/2+x,-y,+z. bonding Thearising hy- droxylThe hydroxyl group of group 2 is ofinvolved2 is involved in intermolecular in intermolecular hydrogen hydrogen bonding bonding arising arising from O2— from1 from O2—H2···O2 (methoxy oxygen of the neighboring molecule) and O21—H2···O2 ··· ···1 H2···O2O2—H2 (methoxyO2 (methoxy oxygen oxygen of the of ne theighboring neighboring molecule) molecule) and O2—H2···O2 and1 O2—H2 (hydroxylO2 (hydroxyl oxy-1 (hydroxyl oxygen of the neighboring molecule), with1 O2···O1 = 2.8885(15) Å and1 O1···O2 ··· 1 ···1 genoxygen of the of theneighboring neighboring molecule), molecule), with with1 O2···O1 O2 O1 = 2.8885(15)= 2.8885(15) Å and Å and O1···O2 O1 O2 = 2.9277(5)= 2.9277(5) Å; = 2.9277(5) Å ; symmetry operation1 of 1-x,−1/2+y,1-z. The molecular structures of 1 and 2 Å; symmetry operation1 of 1 − x, − 1/2 + y,1 − z. The molecular structures of 1 and 2 symmetry operation of 1-x,−1/2+y,1-z. The molecular structures of 1 and 2 (Figure 3) are1 (Figure 3) are held together by secondary intermolecular interactions of C1—H1B···O11 (Figure3) are held together by secondary intermolecular interactions of C1—H1B1 ···O1 andheld C5 together—H···(C4 by1, C5secondary1, C61, C7 1intermol) for 1 andecular H···C, interactions C—H···O andof C1—H1B···O1 N—H···C for 2 and(Table C5— 2). and C5—H···(C41, C51, C61, C71) for 1 and H···C, C—H···O and N—H···C for 2 (Table2). TheH···(C4 values1, C5 of1, C6the1, shortC71) for contact 1 and len H···C,gths C—H···O are less than and theN—H···C sum of for their 2 (Table Vander 2). WaalThe values radii The values of the short contact lengths are less than the sum of their Vander Waal radii [21]. [21]of the. All short bond contact lengths lengths and angles are less are thanin the the expected sum of ranges their Vander of similar Waal compounds radii [21]. thatAll bondhave All bond lengths and angles are in the expected ranges of similar compounds that have beenlengths reported and angles [18,19,20] are in. the expected ranges of similar compounds that have been reported [18–20].been reported [18–20]. (1) (2) (A) (B) FigureFigure 1. 1. MolecularMolecular structures structures of of 11 andand 22 displacementdisplacement ellipsoid drawn drawn at 50% probability. Figure 1. Molecular structures of (A,B) displacement ellipsoid drawn at 50% probability. Molbank 2021, 2021, M1274 3 of 6 Table 1. Crystal data and refinement details. 1 2 Formula C16H20N2OC14H15NO2 −3 Dcalc/g cm 1.230 1.330 −1 µ(MoKα)/mm 0.077 0.089 Formula Weight 256.34 229.27 Colour colourless colourless Shape block Plank Size/mm3 0.78 × 0.34 × 0.32 0.38 × 0.21 × 0.14 Crystal System orthorhombic monoclinic Space Group Pca21 P21 a/Å 6.590(1) 9.9964(2) b/Å 7.278(1) 5.65940(10) c/Å 28.870(4) 10.6027(2) ◦ α/ 90 90 ◦ β/ 90 107.3100(10) ◦ γ/ 90 90 V/Å3 1384.6(3) 572.666(19) Z/Z’ 4/1 2/1 Wavelength/Å 0.71073 0.71073 ◦ Qmin/ 1.411 2.012 ◦ Qmax/ 25.969 28.390 Measured Refl. 8346 11733 Independent Refl. 2612 2860 Reflections Used 2521 2767 Rint 0.0268 0.0190 Parameters 176 156 Largest Peak 0.289 0.252 Deepest Hole −0.200 −0.177 GooF 1.189 1.047 wR2 (all data) 0.1507 0.0766 wR2 0.1483 0.0756 R (all data) 0.0433 0.0290 Molbank 2021, 2021, x FOR PEER REVIEW 1 3 of 6 R1 0.0418 0.0279 (1) (2) Figure 2. Unit cell packings of 1 and 2 viewed along b-axisb-axis with hydrogen bonds shown as dash lines.lines. Table 1. Crystal data and refinement details. 1 2 Formula C16H20N2O C14H15NO2 Dcalc/g cm−3 1.230 1.330 μ(MoKα)/mm−1 0.077 0.089 Formula Weight 256.34 229.27 Colour colourless colourless Shape block Plank Size/mm3 0.78 × 0.34 × 0.32 0.38 × 0.21 × 0.14 Crystal System orthorhombic monoclinic Space Group Pca21 P21 a/Å 6.590(1) 9.9964(2) b/Å 7.278(1) 5.65940(10) c/Å 28.870(4) 10.6027(2) α/° 90 90 β/° 90 107.3100(10) γ/° 90 90 V/Å 3 1384.6(3) 572.666(19) Z/Z’ 4/1 2/1 Wavelength/Å 0.71073 0.71073 Θmin/° 1.411 2.012 Θmax/° 25.969 28.390 Measured Refl.
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