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_4033083
_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         'C15 H20 N2 O5'
_chemical_formula_sum            'C15 H20 N2 O5'
_chemical_formula_weight         308.33
_chemical_name_systematic
'Ethyl 2-(3-ethoxy-3-oxopropanamido)-4,6-dimethylnicotinate'
_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             2017-07-24
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 112.155(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.9426(6)
_cell_length_b                   17.6300(11)
_cell_length_c                   8.9922(5)
_cell_measurement_reflns_used    3249
_cell_measurement_temperature    294
_cell_measurement_theta_max      24.2590
_cell_measurement_theta_min      3.0520
_cell_volume                     1606.68(17)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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      294
_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
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -14.00  86.00   1.00   10.00    --   15.67  77.00 -60.00  100
  2  \w     34.00  92.00   1.00   10.00    --   15.67 179.00-180.00   58
  3  \w     -6.00  84.00   1.00   10.00    --   15.67  57.00  60.00   90
  4  \w     34.00  92.00   1.00   10.00    --   15.67 179.00 150.00   58
  5  \w    -57.00  41.00   1.00   10.00    --   15.67 -37.00 -90.00   98
  6  \w    -25.00  25.00   1.00   10.00    --  -16.84 -99.00-180.00   50
  7  \w    -37.00  52.00   1.00   10.00    --  -16.84  57.00-180.00   89
  8  \w    -86.00 -79.00   1.00   10.00    --  -16.84 -57.00 150.00    7
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0626411000
_diffrn_orient_matrix_UB_12      -0.0178257000
_diffrn_orient_matrix_UB_13      0.0328378000
_diffrn_orient_matrix_UB_21      -0.0303354000
_diffrn_orient_matrix_UB_22      -0.0336590000
_diffrn_orient_matrix_UB_23      0.0125252000
_diffrn_orient_matrix_UB_31      -0.0073579000
_diffrn_orient_matrix_UB_32      -0.0129608000
_diffrn_orient_matrix_UB_33      -0.0775782000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0378
_diffrn_reflns_av_unetI/netI     0.0347
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            15582
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.022
_diffrn_reflns_theta_min         3.063
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.096
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97724
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015) 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    1.275
_exptl_crystal_description       plate
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.252
_refine_diff_density_min         -0.227
_refine_diff_density_rms         0.038
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         2828
_refine_ls_number_restraints     67
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0787
_refine_ls_R_factor_gt           0.0500
_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^)+(0.0668P)^2^+0.3872P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1230
_refine_ls_wR_factor_ref         0.1396
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1976
_reflns_number_total             2828
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01851_si_002.cif
_cod_data_source_block           6
_cod_original_cell_volume        1606.67(17)
_cod_database_code               4033083
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C13 H20 N2 O5'
_reflns_odcompleteness_completeness 97.02
_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 C(H,H,H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C18-O19
 1.2 with sigma of 0.005
 O20-C21
 1.45 with sigma of 0.005
 C12-C13 = C21-C22A
 1.5 with sigma of 0.005
 C18-O19A
 1.2 with sigma of 0.005
 O20-C21A
 1.45 with sigma of 0.005
 C21A-C22A
 1.5 with sigma of 0.005
 C22A-C21A
 1.5 with sigma of 0.005
 C21-C22
 1.5 with sigma of 0.005
 O20-C22A
 2.44 with sigma of 0.021
 O20-C22
 2.44 with sigma of 0.021
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(O19A) \\sim Ueq, : with sigma of 0.01 and sigma for terminal atoms of 0.2
: with sigma of 0.0001 and sigma for terminal atoms of 0.05
5. Others
 Sof(H8A)=Sof(H8C)=Sof(H8D)=1-FVAR(1)
 Sof(H8B)=Sof(H8E)=Sof(H8F)=FVAR(1)
 Sof(O19A)=Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(C22A)=Sof(H22A)=Sof(H22B)=
 Sof(H22C)=1-FVAR(2)
 Sof(O19)=Sof(C21)=Sof(H21C)=Sof(H21D)=Sof(C22)=Sof(H22D)=Sof(H22E)=Sof(H22F)=
 FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C17(H17A,H17B), C21A(H21A,H21B), C21(H21C,H21D)
6.b Aromatic/amide H refined with riding coordinates:
 C5(H5), N14(H14)
6.c Disordered Me refined as rotating group:
 C8(H8A,H8B,H8C,H8D,H8E,H8F)
6.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C13(H13A,H13B,H13C), C22A(H22A,H22B,H22C), C22(H22D,H22E,H22F)
;
_olex2_submission_original_sample_id JF055
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.049
_oxdiff_exptl_absorpt_empirical_full_min 0.953