Effects of an Electron-Withdrawing Group on Thermal Decomposition of 4-Alkylidene-1-pyrazolines: A Novel Stereoselective Formation of Alkylidenecyclopropane Due to Participation of π-Electrons on the Methylene Carbon in Decomposition
Masashi Hamaguchi; Masahiro Nakaishi; Toshikazu Nagai; Hatsue Tamura; Journal of Organic Chemistry 68 (2003) 9711–9722; doi:10.1021/jo035321i

data_4022579
_publ_section_title
;
 Effects of an Electron-Withdrawing Group on Thermal Decomposition
 of 4-Alkylidene-1-pyrazolines: A Novel Stereoselective
 Formation of Alkylidenecyclopropane Due to Participation of
 \p-Electrons on the Methylene Carbon in Decomposition
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              9711
_journal_page_last               9722
_journal_paper_doi               10.1021/jo035321i
_journal_volume                  68
_journal_year                    2003
_chemical_formula_moiety         'C13 H13 O4 N3'
_chemical_formula_sum            'C13 H13 N3 O4'
_chemical_formula_weight         275.26
_chemical_name_systematic
;
 3-Methoxycarbonyl-4-methylene-3-p-nitrobenzylpyrazoline-1
;
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90
_cell_angle_beta                 94.722(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.3658(5)
_cell_length_b                   13.203(1)
_cell_length_c                   13.713(2)
_cell_measurement_reflns_used    8632
_cell_measurement_temperature    200
_cell_measurement_theta_max      29.9
_cell_measurement_theta_min      2.8
_cell_volume                     1329.0(2)
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      200
_diffrn_detector_area_resol_mean 10.00
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device_type  'Rigaku RAXIS-RAPID Imaging Plate'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71069
_diffrn_reflns_av_R_equivalents  0.052
_diffrn_reflns_av_sigmaI/netI    0.044
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            14033
_diffrn_reflns_theta_full        29.97
_diffrn_reflns_theta_max         29.97
_diffrn_reflns_theta_min         3.04
_exptl_absorpt_coefficient_mu    0.104
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.376
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             576
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.236
_refine_diff_density_min         -0.267
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     182
_refine_ls_number_reflns         3819
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0940
_refine_ls_R_factor_gt           0.0556
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0766P)^2^+0.0465P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1417
_refine_ls_wR_factor_ref         0.1549
_reflns_number_gt                2417
_reflns_number_total             3819
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo035321isi20030908_050733.cif
_cod_data_source_block           14a
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_original_formula_sum        'C13 H13 O4 N3'
_cod_database_code               4022579