Synthesis of 4-Acylpyrazoles from Saturated Ketones and Hydrazones Featured with Multiple C(sp(3))-H Bond Functionalization and C-C Bond Cleavage and Reorganization.
Tian, Miaomiao; Shi, Xiaonan; Zhang, Xinying; Fan, Xuesen; The Journal of organic chemistry 82 (2017) 7363–7372; doi:10.1021/acs.joc.7b01013

data_4032680
_publ_section_title
;
 Synthesis of 4-Acylpyrazoles from Saturated Ketones and Hydrazones
 Featured with Multiple C(sp(3))-H Bond Functionalization and C-C Bond
 Cleavage and Reorganization.
;
_journal_issue                   14
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              7363
_journal_page_last               7372
_journal_paper_doi               10.1021/acs.joc.7b01013
_journal_volume                  82
_journal_year                    2017
_chemical_formula_moiety         'C22 H15 Cl N2 O'
_chemical_formula_sum            'C22 H15 Cl N2 O'
_chemical_formula_weight         358.81
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-04-24
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.510(8)
_cell_angle_gamma                90
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_cell_length_a                   9.1818(9)
_cell_length_b                   11.7411(12)
_cell_length_c                   16.5296(14)
_cell_measurement_reflns_used    2649
_cell_measurement_temperature    290.38(10)
_cell_measurement_theta_max      27.7110
_cell_measurement_theta_min      4.2620
_cell_volume                     1781.3(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      290.38(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0528
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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     16.00  71.00   1.00    8.27    --   15.98  77.00-120.00   55
  2  \w     -1.00  83.00   1.00    8.27    --   15.98  57.00-180.00   84
  3  \w     36.00  63.00   1.00    8.27    --   15.98 178.00  30.00   27
  4  \w    -77.00 -36.00   1.00    8.27    --  -16.99 -38.00 150.00   41
  5  \w     57.00  87.00   1.00    8.27    --   15.98-178.00-180.00   30
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0764353000
_diffrn_orient_matrix_UB_12      0.0049700000
_diffrn_orient_matrix_UB_13      -0.0067596000
_diffrn_orient_matrix_UB_21      0.0081463000
_diffrn_orient_matrix_UB_22      -0.0158635000
_diffrn_orient_matrix_UB_23      -0.0408795000
_diffrn_orient_matrix_UB_31      -0.0086928000
_diffrn_orient_matrix_UB_32      -0.0582073000
_diffrn_orient_matrix_UB_33      0.0107062000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0238
_diffrn_reflns_av_unetI/netI     0.0320
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            7409
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.100
_diffrn_reflns_theta_max         25.100
_diffrn_reflns_theta_min         3.274
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.227
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55552
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.338
_exptl_crystal_description       block
_exptl_crystal_F_000             744
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.488
_refine_diff_density_min         -0.623
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     235
_refine_ls_number_reflns         3155
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0690
_refine_ls_R_factor_gt           0.0515
_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^)+(0.0516P)^2^+0.8288P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1179
_refine_ls_wR_factor_ref         0.1262
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2442
_reflns_number_total             3155
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01013_si_002.cif
_cod_data_source_block           3g
_cod_depositor_comments          'Adding full bibliography for 4032680.cif.'
_cod_database_code               4032680
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C1 H1 N1 '
_reflns_odcompleteness_completeness 99.56
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C12(H12), C14(H14), C15(H15),
 C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22)
;
_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 1.845
_oxdiff_exptl_absorpt_empirical_full_min 0.450