Regioselective N-Addition/Substitution Reaction of α-Alkylidene Pyrazolinones with Propargyl Sulfonium Salts to Construct Allylthio-Containing Pyrazolones.
Shen, Shou-Jie; Du, Xiao-Li; Xu, Xiao-Li; Zhao, Ming-Gang; Liang, Jin-Yan; The Journal of organic chemistry 84 (2019) 12520–12531; doi:10.1021/acs.joc.9b02029

data_4033968
_publ_section_title
;
 Regioselective N-Addition/Substitution Reaction of \a-Alkylidene
 Pyrazolinones with Propargyl Sulfonium Salts to Construct
 Allylthio-Containing Pyrazolones.
;
_journal_issue                   19
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12520
_journal_page_last               12531
_journal_paper_doi               10.1021/acs.joc.9b02029
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C26 H21 Br N2 O'
_chemical_formula_sum            'C26 H21 Br N2 O'
_chemical_formula_weight         457.36
_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   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-06-30
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 95.463(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   7.0382(2)
_cell_length_b                   12.4284(4)
_cell_length_c                   25.3081(8)
_cell_measurement_reflns_used    6585
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.4950
_cell_measurement_theta_min      3.3290
_cell_volume                     2203.73(12)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
olex2.solve (L.J. Bourhis, O.V. Dolomanov, R.J. Gildea, J.A.K. Howard,
H. Puschmann, in preparation, 2011)
;
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0251
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.9987
_diffrn_measured_fraction_theta_max 0.9037
_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    -11.00  83.00   1.00   33.62    --   15.68  77.00-120.00   94
  2  \w    -52.00  42.00   1.00   33.62    --   15.68 -77.00 -30.00   94
  3  \w     -1.00  83.00   1.00   33.62    --   15.68  57.00 120.00   84
  4  \w    -54.00  35.00   1.00   33.62    --   15.68 -37.00 -30.00   89
  5  \w    -44.00  50.00   1.00   33.62    --  -17.25  77.00 -30.00   94
  6  \w    -25.00  22.00   1.00   33.62    --  -17.25 -99.00 120.00   47
  7  \w    -52.00  25.00   1.00   33.62    --   15.68 -77.00 150.00   77
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0048226000
_diffrn_orient_matrix_UB_12      -0.0034834000
_diffrn_orient_matrix_UB_13      -0.0278142000
_diffrn_orient_matrix_UB_21      -0.0977459000
_diffrn_orient_matrix_UB_22      -0.0146430000
_diffrn_orient_matrix_UB_23      -0.0034603000
_diffrn_orient_matrix_UB_31      -0.0256728000
_diffrn_orient_matrix_UB_32      0.0550901000
_diffrn_orient_matrix_UB_33      -0.0026534000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0293
_diffrn_reflns_av_unetI/netI     0.0326
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            28457
_diffrn_reflns_theta_full        29.34
_diffrn_reflns_theta_max         29.34
_diffrn_reflns_theta_min         2.91
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.885
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76853
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.378
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             936
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.874
_refine_diff_density_min         -1.139
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         5479
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0900
_refine_ls_R_factor_gt           0.0494
_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^)+(0.0207P)^2^+2.4740P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0866
_refine_ls_wR_factor_ref         0.0991
_reflns_number_gt                3603
_reflns_number_total             5479
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo9b02029_si_003.cif
_cod_data_source_block           190627-1-ssj
_cod_database_code               4033968
_reflns_odcompleteness_completeness 99.87
_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.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C13(H13), C14(H14), C15(H15),
 C16(H16), C17(H17), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26)
2.c X=CH2 refined with riding coordinates:
 C8(H8A,H8B), C20(H20A,H20B)
;
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.240
_oxdiff_exptl_absorpt_empirical_full_min 0.834