The Elusive Paal-Knorr Intermediates in the Trofimov Synthesis of Pyrroles: Experimental and Theoretical Studies.
Sączewski, Jarosław; Fedorowicz, Joanna; Gdaniec, Maria; Wiśniewska, Paulina; Sieniawska, Emilia; Drażba, Zuzanna; Rzewnicka, Justyna; Balewski, Łukasz; The Journal of organic chemistry 82 (2017) 9737–9743; doi:10.1021/acs.joc.7b01851

data_4033078
_publ_section_title
;
 The Elusive Paal-Knorr Intermediates in the Trofimov Synthesis of
 Pyrroles: Experimental and Theoretical Studies.
;
_journal_issue                   18
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              9737
_journal_page_last               9743
_journal_paper_doi               10.1021/acs.joc.7b01851
_journal_volume                  82
_journal_year                    2017
_chemical_formula_moiety         'C12 H12 N2 O3'
_chemical_formula_sum            'C12 H12 N2 O3'
_chemical_formula_weight         232.24
_chemical_name_systematic
(E)-4,6-Dimethyl-1-(3-oxobut-1-enyl)isoxazolo[3,4-b]pyridin-3(1H)-one
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_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
_audit_creation_date             2017-07-21
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.361(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   4.98625(15)
_cell_length_b                   15.4076(5)
_cell_length_c                   14.7032(5)
_cell_measurement_reflns_used    4028
_cell_measurement_temperature    130.15
_cell_measurement_theta_max      74.8809
_cell_measurement_theta_min      2.8656
_cell_volume                     1120.28(6)
_computing_cell_refinement
'CrysAlisPro, Agilent Technologies, Version 1.171.36.21t'
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21t (release 14-08-2012 CrysAlis171 .NET)
(compiled Aug 14 2012,18:12:40)
;
_computing_data_reduction
'CrysAlisPro, Agilent Technologies, Version 1.171.36.21t'
_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_temperature      130.15
_diffrn_detector_area_resol_mean 10.5357
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
  1 omega   62.00  112.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.7129   37.0000 -120.0000 50

  2 omega   18.00   56.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.7129   37.0000 -120.0000 38

  3 omega  -26.00   63.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.7129  -37.0000   60.0000 89

  4 omega  -61.00  -13.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000   30.0000   30.0000 48

  5 omega   33.00   58.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0526  -30.0000   90.0000 25

  6 omega   33.00   66.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0526  -30.0000 -150.0000 33

  7 omega   38.00   68.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0526  -30.0000  -90.0000 30

  8 omega   37.00   73.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0526  -45.0000    0.0000 36

  9 omega  123.00  158.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0526   45.0000  -90.0000 35

 10 omega   42.00   95.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0526  -94.0000  120.0000 53

 11 omega   40.00   66.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0526  -30.0000   60.0000 26

 12 omega   33.00   66.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0526  -30.0000 -180.0000 33

 13 omega   82.00  118.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0526   30.0000  -30.0000 36

 14 omega  133.00  158.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0526   30.0000  -30.0000 25

 15 omega   33.00   68.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0526  -30.0000   30.0000 35

 16 omega   35.00   67.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0526  -30.0000    0.0000 32

 17 omega   86.00  153.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0526   45.0000 -180.0000 67

 18 omega -117.00   -8.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.7129  -72.0000   48.0000 109

 19 omega -119.00   -7.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.7129  -77.0000 -180.0000 112

 20 omega    2.00   98.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       40.7129 -125.0000  -60.0000 96

 21 omega   27.00   56.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0526  -94.0000  -60.0000 29

 22 omega   81.00  156.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0526   61.0000    0.0000 75
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0883984000
_diffrn_orient_matrix_UB_12      -0.0315624000
_diffrn_orient_matrix_UB_13      -0.0910319000
_diffrn_orient_matrix_UB_21      0.2074189000
_diffrn_orient_matrix_UB_22      0.0744837000
_diffrn_orient_matrix_UB_23      0.0037121000
_diffrn_orient_matrix_UB_31      0.2149487000
_diffrn_orient_matrix_UB_32      -0.0587664000
_diffrn_orient_matrix_UB_33      0.0535032000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0222
_diffrn_reflns_av_unetI/netI     0.0207
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            6226
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.247
_diffrn_reflns_theta_min         6.070
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.837
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69619
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro, Agilent Technologies, Version 1.171.36.21t Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.377
_exptl_crystal_description       block
_exptl_crystal_F_000             488
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.198
_refine_diff_density_min         -0.189
_refine_diff_density_rms         0.038
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     155
_refine_ls_number_reflns         2031
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0416
_refine_ls_R_factor_gt           0.0372
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0537P)^2^+0.3387P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1005
_refine_ls_wR_factor_ref         0.1042
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1812
_reflns_number_total             2031
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01851_si_002.cif
_cod_data_source_block           2c
_cod_database_code               4033078
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C12 H12 N2 O3'
_shelx_estimated_absorpt_t_max   0.850
_shelx_estimated_absorpt_t_min   0.731
_reflns_odcompleteness_completeness 99.58
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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 C(H,H,H,H,H,H) groups
2. Others
 Fixed Sof: H11A(0.5) H11B(0.5) H11C(0.5) H11D(0.5) H11E(0.5) H11F(0.5)
 H17A(0.5) H17B(0.5) H17C(0.5) H17D(0.5) H17E(0.5) H17F(0.5)
3.a Aromatic/amide H refined with riding coordinates:
 C5(H5), C13(H13), C14(H14)
3.b Disordered Me refined with riding coordinates:
 C11(H11A,H11B,H11C,H11D,H11E,H11F), C17(H17A,H17B,H17C,H17D,H17E,H17F)
3.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
;
_olex2_submission_special_instructions 'No special instructions were received'