From racemic compounds through metastable to stable racemic conglomerates: crystallization features of chiral halogen and cyano monosubstituted phenyl glycerol ethers

All ortho-substituted Cl, Br, I, and CN phenyl glycerol ethers crystallize as racemic conglomerates, whereas meta- and para-derivatives constitute racemic compounds in the solid state. Only meta-halogen-substituted phenyl glycerol ethers, alongside the thermodynamically preferential heterochiral racemic compound phase, reveal the simultaneous existence of a conglomerate phase; the last state is metastable and turns into a stable racemic compound just in the crystalline phase.

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(S)-3-(2-Chlorophenoxy)-propane-1,2-diolC9H11ClO3Ee = 99.8% [chiral HPLC][α]D20=-14.0 (c 1.0, hexane/EtOH 4:1),[α]D20=+4.0 (с 1.0, EtOH),[α]D20=+8.9 (c 0.7, CHCl3),Initial source of chirality: (S)-3-chloropropane-1,2-diolAbsolute configuration: (S)

(S)-3-(2-Bromophenoxy)-propane-1,2-diolC9H11BrO3Ee = 99.5% [chiral HPLC][α]D20=-13.8 (c 1.0, hexane/EtOH 4:1),[α]D20=+9.0 (c 1.0, CHCl3),Initial source of chirality: (S)-3-chloropropane-1,2-diolAbsolute configuration: (S)

(S)-3-(2-Iodophenoxy)-propane-1,2-diolC9H11IO3Ee = 99.9% [chiral HPLC][α]D20=-16.3 (c 1.0, hexane/EtOH 4:1),Initial source of chirality: (S)-3-chloropropane-1,2-diolAbsolute configuration: (S)

(S)-3-(3-Chlorophenoxy)-propane-1,2-diolC9H11ClO3Ee = 99.9% [chiral HPLC][α]D20=+15.2 (c 0.8, MeOH),[α]D20=+13.0 (c 0.5, EtOH),Initial source of chirality: (S)-3-chloropropane-1,2-diolAbsolute configuration: (S)

(S)-3-(3-Bromophenoxy)-propane-1,2-diolC9H11BrO3Ee = 99.9% [chiral HPLC][α]D20=+10.0 (c 1.0, EtOH),Initial source of chirality: (S)-3-chloropropane-1,2-diolAbsolute configuration: (S)

(S)-3-(3-Iodophenoxy)-propane-1,2-diolC9H11IO3Ee = 97.2% [chiral HPLC][α]D20=+11.5 (c 0.5, EtOH),Initial source of chirality: (S)-3-chloropropane-1,2-diolAbsolute configuration: (S)

(S)-3-(3-Cyanophenoxy)-propane-1,2-diolC10H11NO3Ee = 99.9% [chiral HPLC][α]D20=+19.1 (c 0.75, EtOH),Initial source of chirality: (S)-3-chloropropane-1,2-diolAbsolute configuration: (S)

(S)-3-(4-Cyanophenoxy)-propane-1,2-diolC10H11NO3Ee = 92.6% [chiral HPLC][α]D20=+14.4 (c 0.7, EtOH),Initial source of chirality: (S)-3-chloropropane-1,2-diolAbsolute configuration: (S)

(S)-3-(4-Chlorophenoxy)-propane-1,2-diolC9H11ClO3Ee = 99.2% [chiral HPLC][α]D20=+13.0 (c 0.5, EtOH),[α]D20=+9.8 (c 0.7, MeOH),Initial source of chirality: (S)-3-chloropropane-1,2-diolAbsolute configuration: (S)

(S)-3-(4-Bromophenoxy)-propane-1,2-diolC9H11BrO3Ee = 92.2% [chiral HPLC][α]D20=+9.1 (c 0.6, EtOH),Initial source of chirality: (S)-3-chloropropane-1,2-diolAbsolute configuration: (S)

(S)-3-(4-Iodophenoxy)-propane-1,2-diolC9H11IO3Ee = 99.5% [chiral HPLC][α]D20=+9.0 (c 0.8, EtOH),Initial source of chirality: (S)-3-chloropropane-1,2-diolAbsolute configuration: (S)