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_4033081
_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         'C25 H32 N2 O9'
_chemical_formula_sum            'C25 H32 N2 O9'
_chemical_formula_weight         504.52
_chemical_name_systematic
'(2E,3E)-Diethyl 2-(((E)-3-ethoxy-3-oxoprop-1-enyloxy)methylene)-3-((3-(ethoxycarbonyl)-4,6-dimethylpyridin-2-ylamino)methylene)succinate'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-07-21
_audit_creation_method
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Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                79.378(4)
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_cell_angle_gamma                76.203(4)
_cell_formula_units_Z            2
_cell_length_a                   8.2258(4)
_cell_length_b                   11.9963(6)
_cell_length_c                   14.8642(8)
_cell_measurement_reflns_used    6693
_cell_measurement_temperature    294.74(10)
_cell_measurement_theta_max      24.3190
_cell_measurement_theta_min      3.4130
_cell_volume                     1377.45(13)
_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
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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)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      294.74(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1544
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega   -1.00   83.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       15.3164   57.0000  120.0000 84

  2 omega  -52.00   32.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       15.3164  -57.0000 -150.0000 84

  3 omega  -52.00   32.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       15.3164  -57.0000 -120.0000 84

  4 omega   -4.00   85.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       15.3164   37.0000   30.0000 89

  5 omega  -25.00   23.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.3321  -99.0000  120.0000 48

  6 omega  -25.00   23.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.3321  -99.0000    0.0000 48

  7 omega  -89.00  -34.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.3321 -179.0000   60.0000 55

  8 omega   -1.00   83.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       15.3164   57.0000 -150.0000 84

  9 omega  -52.00   32.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       15.3164  -57.0000  -30.0000 84

 10 omega  -25.00   54.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       15.3164  -99.0000   90.0000 79

 11 omega   -3.00   69.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       15.3164 -125.0000 -115.0000 72

 12 omega  -87.00   13.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.3321  -19.0000 -180.0000 100

 13 omega  -89.00  -32.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.3321  179.0000  -90.0000 57

 14 omega  -25.00   54.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       15.3164  -99.0000  -60.0000 79

 15 omega  -25.00   54.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       15.3164  -99.0000  120.0000 79

 16 omega  -25.00   54.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       15.3164  -99.0000  -30.0000 79

 17 omega   -1.00   83.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       15.3164   57.0000  -60.0000 84

 18 omega  -70.00    3.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.3321  125.0000  -37.0000 73

 19 omega  -25.00   23.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.3321  -99.0000 -120.0000 48

 20 omega  -25.00   31.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       15.3164  -99.0000  150.0000 56

 21 omega   34.00   88.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       15.3164  179.0000   90.0000 54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0677450000
_diffrn_orient_matrix_UB_12      -0.0467011000
_diffrn_orient_matrix_UB_13      0.0101288000
_diffrn_orient_matrix_UB_21      0.0281011000
_diffrn_orient_matrix_UB_22      -0.0029864000
_diffrn_orient_matrix_UB_23      -0.0482357000
_diffrn_orient_matrix_UB_31      0.0525889000
_diffrn_orient_matrix_UB_32      0.0398918000
_diffrn_orient_matrix_UB_33      -0.0024286000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0390
_diffrn_reflns_av_unetI/netI     0.0248
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            41403
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.025
_diffrn_reflns_theta_max         25.025
_diffrn_reflns_theta_min         3.122
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.093
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.99325
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.216
_exptl_crystal_description       plate
_exptl_crystal_F_000             536
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.316
_refine_diff_density_min         -0.213
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     327
_refine_ls_number_reflns         4864
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0973
_refine_ls_R_factor_gt           0.0641
_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^)+(0.0773P)^2^+0.5719P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1604
_refine_ls_wR_factor_ref         0.1825
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3249
_reflns_number_total             4864
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01851_si_002.cif
_cod_data_source_block           5a
_cod_database_code               4033081
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C25 H32 N2 O9 '
_chemical_oxdiff_usercomment     'slupki, bezbawne'
_shelx_estimated_absorpt_t_max   0.986
_shelx_estimated_absorpt_t_min   0.946
_reflns_odcompleteness_completeness 99.84
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C23(H23A,H23B), C28(H28A,H28B), C33(H33A,H33B)
2.b Me refined with riding coordinates:
 C19(H19A,H19B,H19C), C24(H24A,H24B,H24C), C29(H29A,H29B,H29C), C34(H34A,H34B,
 H34C)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), N7(H7), C8(H8), C11(H11), C13(H13), C14(H14)
2.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C)
;
_olex2_submission_special_instructions 'No special instructions were received'