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_4033082
_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         'C27 H30 N2 O9'
_chemical_formula_sum            'C27 H30 N2 O9'
_chemical_formula_weight         526.53
_chemical_name_systematic
'(2E,3E)-Diethyl 2-(((E)-3-ethoxy-3-oxoprop-1-enyloxy)methylene)-3-((3-(ethoxycarbonyl)quinolin-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
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                100.611(5)
_cell_angle_beta                 95.091(5)
_cell_angle_gamma                112.613(6)
_cell_formula_units_Z            2
_cell_length_a                   8.8727(6)
_cell_length_b                   11.1374(7)
_cell_length_c                   15.4529(9)
_cell_measurement_reflns_used    5268
_cell_measurement_temperature    294.74(10)
_cell_measurement_theta_max      28.08
_cell_measurement_theta_min      3.3690
_cell_volume                     1363.95(17)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 
;
_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      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  -54.00   35.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       15.6289  -37.0000    0.0000 89

  2 omega  -25.00   22.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.6446  -99.0000   30.0000 47

  3 omega  -25.00   22.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.6446  -99.0000  -60.0000 47

  4 omega  -43.00   51.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.6446   77.0000  -90.0000 94

  5 omega  -33.00   51.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.6446   57.0000   90.0000 84

  6 omega  -84.00   10.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.6446  -77.0000  150.0000 94

  7 omega  -25.00   55.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       15.6289  -99.0000   30.0000 80

  8 omega  -20.00   58.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       15.6289 -105.0000 -178.0000 78

  9 omega  -84.00   -9.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.6446  -57.0000    0.0000 75
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0120779000
_diffrn_orient_matrix_UB_12      -0.0453235000
_diffrn_orient_matrix_UB_13      0.0281526000
_diffrn_orient_matrix_UB_21      0.0531482000
_diffrn_orient_matrix_UB_22      0.0533558000
_diffrn_orient_matrix_UB_23      0.0361545000
_diffrn_orient_matrix_UB_31      -0.0690520000
_diffrn_orient_matrix_UB_32      0.0119492000
_diffrn_orient_matrix_UB_33      0.0122760000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0204
_diffrn_reflns_av_unetI/netI     0.0224
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            18187
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.024
_diffrn_reflns_theta_max         25.024
_diffrn_reflns_theta_min         2.991
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.097
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.987
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 ing spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.282
_exptl_crystal_description       block
_exptl_crystal_F_000             556
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.5
_refine_diff_density_max         0.254
_refine_diff_density_min         -0.194
_refine_diff_density_rms         0.032
_refine_ls_extinction_coef       0.0072(15)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     368
_refine_ls_number_reflns         4810
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0659
_refine_ls_R_factor_gt           0.0453
_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^)+(0.0559P)^2^+0.3482P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1138
_refine_ls_wR_factor_ref         0.1280
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3495
_reflns_number_total             4810
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01851_si_002.cif
_cod_data_source_block           5b
_cod_original_cell_volume        1363.95(16)
_cod_database_code               4033082
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C14 H12 N4 O2 I2'
_shelx_estimated_absorpt_t_max   0.953
_shelx_estimated_absorpt_t_min   0.944
_reflns_odcompleteness_completeness 99.82
_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. Restrained distances
 O31-C32A
 1.45 with sigma of 0.005
 O31-C32
 1.45 with sigma of 0.005
 C33-C32A
 1.5 with sigma of 0.005
 C33A-C32
 1.5 with sigma of 0.005
3. Others
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C32)=Sof(H32C)=Sof(H32D)=1-FVAR(1)
 Sof(C32A)=Sof(H32A)=Sof(H32B)=Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C27(H27A,H27B), C32A(H32A,H32B), C37(H37A,H37B), C32(H32C,H32D)
4.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), N11(H11), C12(H12), C15(H15),
 C17(H17), C18(H18)
4.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C28(H28A,H28B,H28C), C33(H33A,H33B,H33C), C38(H38A,H38B,
 H38C), C33A(H33D,H33E,H33F)
;
_olex2_submission_special_instructions 'No special instructions were received'