Synthesis of Trifluoroethyl Pyrazolines via Trichloroisocyanuric Acid Promoted Cascade Cyclization/Trifluoromethylation of β,γ-Unsaturated Hydrazones.
Chang, Bingbing; Su, Yingpeng; Huang, Danfeng; Wang, Ke-Hu; Zhang, Weigang; Shi, Ya; Zhang, Xinghu; Hu, Yulai; The Journal of organic chemistry 83 (2018) 4365–4374; doi:10.1021/acs.joc.8b00009

data_4034929
_publ_section_title
;
 Synthesis of Trifluoroethyl Pyrazolines via Trichloroisocyanuric Acid
 Promoted Cascade Cyclization/Trifluoromethylation of \b,\g-Unsaturated
 Hydrazones.
;
_journal_issue                   8
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4365
_journal_page_last               4374
_journal_paper_doi               10.1021/acs.joc.8b00009
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C20 H19 F3 N2 O2'
_chemical_formula_sum            'C20 H19 F3 N2 O2'
_chemical_formula_weight         376.37
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-10-31
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                67.583(9)
_cell_angle_beta                 83.056(10)
_cell_angle_gamma                72.226(11)
_cell_formula_units_Z            2
_cell_length_a                   7.8390(12)
_cell_length_b                   10.1239(10)
_cell_length_c                   13.0356(12)
_cell_measurement_reflns_used    1083
_cell_measurement_temperature    293.18(11)
_cell_measurement_theta_max      26.2520
_cell_measurement_theta_min      4.2110
_cell_volume                     910.7(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293.18(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.958
_diffrn_measured_fraction_theta_max 0.958
_diffrn_measurement_details
;
  1 omega -102.00  -77.00   1.0000   14.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.5055  178.0000   30.0000 25

  2 omega   -1.00   25.00   1.0000   14.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.5055  -99.0000  -30.0000 26

  3 omega  -97.00  -70.00   1.0000   14.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.5055  178.0000 -120.0000 27

  4 omega  -48.00   44.00   1.0000   14.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867    0.0000    0.0000 92

  5 omega   43.00  105.00   1.0000   14.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867 -178.0000 -150.0000 62

  6 omega  -32.00    5.00   1.0000   14.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867   19.0000  -60.0000 37
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0329585000
_diffrn_orient_matrix_UB_12      -0.0543189000
_diffrn_orient_matrix_UB_13      0.0522114000
_diffrn_orient_matrix_UB_21      -0.0796611000
_diffrn_orient_matrix_UB_22      -0.0223927000
_diffrn_orient_matrix_UB_23      0.0093316000
_diffrn_orient_matrix_UB_31      0.0397604000
_diffrn_orient_matrix_UB_32      -0.0528323000
_diffrn_orient_matrix_UB_33      -0.0255338000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_unetI/netI     0.0680
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            4863
_diffrn_reflns_theta_full        26.02
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.29
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.110
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.30310
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.373
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             392
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.337
_refine_diff_density_min         -0.298
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.884
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     246
_refine_ls_number_reflns         4863
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.884
_refine_ls_R_factor_all          0.1230
_refine_ls_R_factor_gt           0.0714
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1237P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1848
_refine_ls_wR_factor_ref         0.2015
_reflns_number_gt                2476
_reflns_number_total             4863
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo8b00009_si_002.cif
_cod_data_source_block           changbb_1030_twin1_hklf4
_cod_original_cell_volume        910.68(19)
_cod_database_code               4034929
_chemical_oxdiff_formula         'C11 H10 N O'
_diffrn_oxdiff_twin_integration_method simultaneous
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6662(16)
 0.3338(16)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Ternary CH refined with riding coordinates:
 C9(H9)
3.b Secondary CH2 refined with riding coordinates:
 C8(H8B,H8A), C10(H10A,H10B), C13(H13A,H13B)
3.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C15(H15), C16(H16), C17(H17), C18(H18),
 C19(H19)
3.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
;
_olex2_submission_special_instructions 'No special instructions were received'