Direct radical trifluoromethylthiolation and thiocyanation of aryl alkynoate esters: mild and facile synthesis of 3-trifluoromethylthiolated and 3-thiocyanated coumarins
Zeng, Yao-Fu; Tan, Dong-Hang; Chen, Yunyun; Lv, Wen-Xin; Liu, Xu-Ge; Li, Qingjiang; Wang, Honggen; Organic Chemistry Frontiers 2 (2015) 1511–; doi:10.1039/C5QO00271K

data_1553186
_publ_section_title
;
 Direct radical trifluoromethylthiolation and thiocyanation of aryl
 alkynoate esters: mild and facile synthesis of 3-trifluoromethylthiolated
 and 3-thiocyanated coumarins
;
_journal_issue                   11
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              1511
_journal_paper_doi               10.1039/C5QO00271K
_journal_volume                  2
_journal_year                    2015
_chemical_formula_moiety         'C16 H8 Br F3 O2 S'
_chemical_formula_sum            'C16 H8 Br F3 O2 S'
_chemical_formula_weight         401.19
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-06-18
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-06-27 deposited with the CCDC.
2015-09-16 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 91.2584(11)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   12.9202(2)
_cell_length_b                   7.94120(10)
_cell_length_c                   14.2105(2)
_cell_measurement_reflns_used    5049
_cell_measurement_temperature    103(2)
_cell_measurement_theta_max      71.6510
_cell_measurement_theta_min      3.0850
_cell_volume                     1457.67(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      103(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.2417
_diffrn_detector_type            Onyx
_diffrn_measured_fraction_theta_full 0.958
_diffrn_measured_fraction_theta_max 0.958
_diffrn_measurement_details
;
  1 omega    8.00   89.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       42.2034   77.0000   60.0000 81

  2 omega   72.00  178.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000  150.0000 106

  3 omega  113.00  177.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000 -120.0000 64

  4 omega   99.00  129.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000 -180.0000 30

  5 omega   69.00   95.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000 -180.0000 26

  6 omega   72.00  175.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000 -150.0000 103

  7 omega   10.00  107.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       42.2034   77.0000 -180.0000 97

  8 omega -124.00  -69.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -95.0000   77.0000  -30.0000 55

  9 omega -122.00  -55.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -95.0000   77.0000   90.0000 67
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Onyx, Nova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1098704000
_diffrn_orient_matrix_UB_12      -0.0495336000
_diffrn_orient_matrix_UB_13      0.0297811000
_diffrn_orient_matrix_UB_21      0.0461074000
_diffrn_orient_matrix_UB_22      -0.1382148000
_diffrn_orient_matrix_UB_23      0.0645398000
_diffrn_orient_matrix_UB_31      0.0068527000
_diffrn_orient_matrix_UB_32      0.1267170000
_diffrn_orient_matrix_UB_33      0.0818240000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0280
_diffrn_reflns_av_unetI/netI     0.0273
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            5748
_diffrn_reflns_theta_full        71.65
_diffrn_reflns_theta_max         71.65
_diffrn_reflns_theta_min         4.68
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'Nova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.575
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.29482
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.828
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             792
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.182
_refine_diff_density_min         -0.748
_refine_diff_density_rms         0.115
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.099
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     208
_refine_ls_number_reflns         2725
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.099
_refine_ls_R_factor_all          0.0402
_refine_ls_R_factor_gt           0.0390
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0773P)^2^+0.6099P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1079
_refine_ls_wR_factor_ref         0.1093
_reflns_number_gt                2623
_reflns_number_total             2725
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c5qo00271k2.cif
_cod_data_source_block           zyf_150615
_cod_database_code               1553186
_reflns_odcompleteness_completeness 98.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C11(H11), C13(H13), C14(H14), C15(H15), C17(H17), C18(H18), C19(H19), C22(H22)
;
_olex2_submission_special_instructions 'No special instructions were received'