A base-promoted cascade reaction of α,β-unsaturated N-tosylhydrazones with o-hydroxybenzyl alcohols: highly regioselective synthesis of N-sec-alkylpyrazoles.
Chen, Lian-Mei; Zhao, Juan; Xia, An-Jie; Guo, Xiao-Qiang; Gan, Ya; Zhou, Chuang; Yang, Zai-Jun; Yang, Jun; Kang, Tai-Ran; Organic & biomolecular chemistry 17 (2019) 8561–8570; doi:10.1039/c9ob01780a

data_7157062
_publ_section_title
;
 A base-promoted cascade reaction of \a,\b-unsaturated N-tosylhydrazones
 with o-hydroxybenzyl alcohols: highly regioselective synthesis of
 N-sec-alkylpyrazoles.
;
_journal_issue                   37
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              8561
_journal_page_last               8570
_journal_paper_doi               10.1039/c9ob01780a
_journal_volume                  17
_journal_year                    2019
_chemical_formula_moiety         'C23 H20 N2 O2'
_chemical_formula_sum            'C23 H20 N2 O2'
_chemical_formula_weight         356.41
_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             2019-09-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-09-03 deposited with the CCDC.    2019-09-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.8985(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.34970(18)
_cell_length_b                   9.15478(16)
_cell_length_c                   21.8715(4)
_cell_measurement_reflns_used    4033
_cell_measurement_temperature    293.1(3)
_cell_measurement_theta_max      72.2180
_cell_measurement_theta_min      4.7490
_cell_volume                     1869.68(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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      293.1(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_details
;
  1 omega  -31.00   53.00   1.0000    1.4000
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -57.0000   60.0000 84

  2 omega   20.00  104.00   1.0000    1.4000
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000 -180.0000 84

  3 omega   23.00   90.00   1.0000    1.4000
omega____ theta____ kappa____ phi______ frames
    -       36.2921 -125.0000   90.0000 67

  4 omega  -31.00   63.00   1.0000    1.4000
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -77.0000 -120.0000 94

  5 omega   10.00  104.00   1.0000    1.4000
omega____ theta____ kappa____ phi______ frames
    -       36.2921   77.0000    0.0000 94

  6 omega    1.00   75.00   1.0000    1.4000
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -99.0000 -180.0000 74

  7 omega    1.00   75.00   1.0000    1.4000
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -99.0000  150.0000 74

  8 omega   38.00   91.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000    0.0000 53

  9 omega   40.00   98.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -90.0000 58

 10 omega   38.00   91.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -30.0000 53

 11 omega   38.00   91.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -120.0000 53

 12 omega   38.00  116.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000   30.0000 78

 13 omega   40.00   98.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   60.0000 58

 14 omega  100.00  178.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000 -180.0000 78

 15 omega   87.00  178.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000 -180.0000 91

 16 omega   38.00   91.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -90.0000 53

 17 omega   41.00  126.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000    0.0000 85

 18 omega   20.00   96.00   1.0000    1.4000
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000  -90.0000 76
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0639273000
_diffrn_orient_matrix_UB_12      0.0455771000
_diffrn_orient_matrix_UB_13      0.0607095000
_diffrn_orient_matrix_UB_21      0.1445429000
_diffrn_orient_matrix_UB_22      -0.0317527000
_diffrn_orient_matrix_UB_23      0.0343325000
_diffrn_orient_matrix_UB_31      0.0472058000
_diffrn_orient_matrix_UB_32      0.1588637000
_diffrn_orient_matrix_UB_33      -0.0105234000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0325
_diffrn_reflns_av_unetI/netI     0.0244
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            10657
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.528
_diffrn_reflns_theta_min         4.736
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.649
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69091
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.266
_exptl_crystal_description       needle
_exptl_crystal_F_000             752
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.221
_refine_diff_density_min         -0.242
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     246
_refine_ls_number_reflns         3641
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0574
_refine_ls_R_factor_gt           0.0505
_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^)+(0.0940P)^2^+0.2219P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1393
_refine_ls_wR_factor_ref         0.1510
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3115
_reflns_number_total             3641
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob01780a2.cif
_cod_data_source_block           ktr-002
_cod_depositor_comments          'Adding full bibliography for 7157062.cif.'
_cod_database_code               7157062
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C008(H008)
2.b Aromatic/amide H refined with riding coordinates:
 C00C(H00C), C00D(H00D), C00E(H00E), C00F(H00F), C00G(H00G), C00H(H00H),
 C00I(H00I), C00J(H00J), C00K(H00K), C00L(H00L), C00M(H00M), C00N(H00N),
 C00O(H00O), C00Q(H00Q), C00R(H00R)
2.c Idealised Me refined as rotating group:
 C00P(H00A,H00B,H00P)
2.d Idealised tetrahedral OH refined as rotating group:
 O001(H001)
;
_shelx_res_checksum              25907
_olex2_submission_special_instructions 'No special instructions were received'