Selenium Dioxide-Mediated Bromination of α,β-Unsaturated Ketones Using <i>N</i>-Bromosuccinimide in the Presence of <i>p</i>-Toluenesulfonic Acid: A Versatile Route for the Synthesis of α'-Bromo-4-arylbut-3-en-2-one and α',α'-Dibromo-4-arylbut-3-en-2-one.
Lipon, Tyrchain Mitre; Marpna, Ibakyntiew D.; Wanniang, Kmendashisha; Shangpliang, O. Risuklang; Laloo, Badaker M.; Nongkhlaw, Rishanlang; Myrboh, Bekington; ACS omega 6 (2021) 27466–27477; doi:10.1021/acsomega.1c04352

data_4519102
_publ_section_title
;
 Selenium Dioxide-Mediated Bromination of \a,\b-Unsaturated Ketones Using
 <i>N</i>-Bromosuccinimide in the Presence of <i>p</i>-Toluenesulfonic
 Acid: A Versatile Route for the Synthesis of
 \a'-Bromo-4-arylbut-3-en-2-one and \a',\a'-Dibromo-4-arylbut-3-en-2-one.
;
_journal_issue                   41
_journal_name_full               'ACS omega'
_journal_page_first              27466
_journal_page_last               27477
_journal_paper_doi               10.1021/acsomega.1c04352
_journal_volume                  6
_journal_year                    2021
_chemical_formula_moiety         '2(C20 H16 Br2 N2 O6)'
_chemical_formula_sum            'C40 H32 Br4 N4 O12'
_chemical_formula_weight         1080.33
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-12-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   11.0125(16)
_cell_length_b                   6.5230(11)
_cell_length_c                   14.3222(12)
_cell_measurement_reflns_used    994
_cell_measurement_temperature    290.69(16)
_cell_measurement_theta_max      28.3400
_cell_measurement_theta_min      4.6880
_cell_volume                     1028.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      290.69(16)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1279
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.911
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w     -2.00  24.00   1.00    3.31    --  -17.90 -99.00 -30.00   26
  2  \w    -47.00  41.00   1.00    3.31    --   20.16 -77.00   0.00   88
  3  \w      2.00  89.00   1.00    3.31    --   20.16  57.00 120.00   87
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0249079000
_diffrn_orient_matrix_UB_12      -0.0431478000
_diffrn_orient_matrix_UB_13      -0.0331017000
_diffrn_orient_matrix_UB_21      0.0579201000
_diffrn_orient_matrix_UB_22      -0.0211420000
_diffrn_orient_matrix_UB_23      0.0094530000
_diffrn_orient_matrix_UB_31      -0.0132364000
_diffrn_orient_matrix_UB_32      -0.0118375000
_diffrn_orient_matrix_UB_33      0.1032098000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0880
_diffrn_reflns_av_unetI/netI     0.1078
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.911
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            3818
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.911
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.847
_diffrn_reflns_theta_min         3.394
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.980
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33773
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.744
_exptl_crystal_description       block
_exptl_crystal_F_000             536
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.23
_refine_diff_density_max         0.491
_refine_diff_density_min         -0.604
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     91
_refine_ls_number_reflns         1329
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.1376
_refine_ls_R_factor_gt           0.0639
_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^)+(0.0394P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1057
_refine_ls_wR_factor_ref         0.1307
_reflns_Friedel_coverage         0.000
_reflns_number_gt                702
_reflns_number_total             1329
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ao1c04352_si_001.cif
_cod_data_source_block           ov_tb-12(4)
_cod_database_code               4519102
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         C10H8BrNO3
_reflns_odcompleteness_completeness 98.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Others
 Fixed Sof: H10A(0.5) H10B(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B)
3.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7), C1(H1), C8(H8), C3(H3), C4(H4)
;
_shelx_res_checksum              84227
_shelx_hkl_checksum              90794
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.194
_oxdiff_exptl_absorpt_empirical_full_min 0.493