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_4033967
_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         'C27 H24 N2 O S'
_chemical_formula_sum            'C27 H24 N2 O S'
_chemical_formula_weight         424.54
_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     iterative
_audit_creation_date             2019-05-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.443(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.3362(3)
_cell_length_b                   12.5626(4)
_cell_length_c                   24.8378(10)
_cell_measurement_reflns_used    6184
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.4100
_cell_measurement_theta_min      3.2760
_cell_volume                     2274.64(15)
_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    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     35.00  88.00   1.00   19.54    --   15.84 178.00 150.00   53
  2  \w    -53.00  35.00   1.00   19.54    --   15.84 -37.00 -30.00   88
  3  \w    -25.00  22.00   1.00   19.54    --  -17.40 -99.00   0.00   47
  4  \w    -25.00  22.00   1.00   19.54    --  -17.40 -99.00 -90.00   47
  5  \w    -44.00  50.00   1.00   19.54    --  -17.40  77.00-120.00   94
  6  \w    -85.00   9.00   1.00   19.54    --  -17.40 -77.00 120.00   94
  7  \w     -1.00  77.00   1.00   19.54    --   15.84  57.00  30.00   78
  8  \w    -34.00  50.00   1.00   19.54    --  -17.40  57.00 120.00   84
;
_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      -0.0785149000
_diffrn_orient_matrix_UB_12      -0.0291856000
_diffrn_orient_matrix_UB_13      0.0055797000
_diffrn_orient_matrix_UB_21      0.0111579000
_diffrn_orient_matrix_UB_22      0.0191022000
_diffrn_orient_matrix_UB_23      0.0270376000
_diffrn_orient_matrix_UB_31      -0.0563837000
_diffrn_orient_matrix_UB_32      0.0444078000
_diffrn_orient_matrix_UB_33      -0.0079585000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0402
_diffrn_reflns_av_unetI/netI     0.0431
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            26666
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.214
_diffrn_reflns_theta_max         26.343
_diffrn_reflns_theta_min         2.957
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.163
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.24800
_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    1.240
_exptl_crystal_description       block
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.495
_refine_diff_density_min         -0.300
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     297
_refine_ls_number_reflns         4642
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0851
_refine_ls_R_factor_gt           0.0527
_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^)+(0.0515P)^2^+0.4560P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1182
_refine_ls_wR_factor_ref         0.1361
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3038
_reflns_number_total             4642
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02029_si_002.cif
_cod_data_source_block           20181226-s
_cod_database_code               4033967
_shelxl_version_number           2014-1
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.976
_reflns_odcompleteness_completeness 99.82
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 S1, C20
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B)
3.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C5(H5), C27(H27), C12(H12), C15(H15), C1(H1), C4(H4), C23(H23),
 C25(H25), C3(H3), C13(H13), C24(H24), C14(H14), C26(H26), C2(H2)
3.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
;
_shelx_res_checksum              324
_shelx_hkl_checksum              66040
_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 3.358
_oxdiff_exptl_absorpt_empirical_full_min 0.675