Different paths lead to the same destination: a highly efficient TMSOTf/HFIP catalytic system for large-scale synthesis of fluoroalkyl-containing 4,4′-methylenedianiline (MDA) monomers
Wu, Ziyan; Fang, Guodong; Li, Xindi; Wu, Yuhao; Li, Jinshan; Feng, Yan; Xie, Jialin; Zhou, Xueqing; Wen, Zhenchang; Jia, Chunman; Green Chemistry 27 (2025) 13751–13761; doi:10.1039/D5GC03637B

data_7251022
_publ_section_title
;
 Different paths lead to the same destination: a highly efficient
 TMSOTf/HFIP catalytic system for large-scale synthesis of
 fluoroalkyl-containing 4,4&#x2032;-methylenedianiline (MDA) monomers
;
_journal_issue                   43
_journal_name_full               'Green Chemistry'
_journal_page_first              13751
_journal_page_last               13761
_journal_paper_doi               10.1039/D5GC03637B
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C16 H18 F2 N2'
_chemical_formula_sum            'C16 H18 F2 N2'
_chemical_formula_weight         276.32
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-22
_audit_creation_method
;
Olex2 1.5
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6396)
;
_audit_update_record
;
2025-06-17 deposited with the CCDC.	2025-10-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.2280(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.3495(2)
_cell_length_b                   7.30540(10)
_cell_length_c                   15.1869(2)
_cell_measurement_reflns_used    7193
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.9740
_cell_measurement_theta_min      3.5960
_cell_volume                     1367.96(3)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.00(10)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.956
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0223
_diffrn_reflns_av_unetI/netI     0.0207
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            9633
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         77.355
_diffrn_reflns_theta_min         3.585
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.816
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84303
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.342
_exptl_crystal_description       block
_exptl_crystal_F_000             584
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.257
_refine_diff_density_min         -0.321
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     199
_refine_ls_number_reflns         2780
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.0407
_refine_ls_R_factor_gt           0.0379
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0593P)^2^+0.5424P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1008
_refine_ls_wR_factor_ref         0.1034
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2549
_reflns_number_total             2780
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5gc03637b2.cif
_cod_data_source_block           wzy-1
_cod_depositor_comments
'Adding full bibliography for 7251021--7251022.cif.'
_cod_database_code               7251022
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.923
_shelx_estimated_absorpt_t_min   0.854
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C8(H8), C9(H9)
2.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C11(H11), C12(H12), C3(H3), C14(H14), C5(H5)
2.c Idealised Me refined as rotating group:
 C1(H1C,H1D,H1E), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              40857
_olex2_submission_special_instructions 'No special instructions were received'