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_4033076
_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         'C13 H14 N2 O4'
_chemical_formula_sum            'C13 H14 N2 O4'
_chemical_formula_weight         262.26
_chemical_name_systematic
'(E)-Ethyl 3-(4,6-dimethyl-3-oxoisoxazolo[3,4-b]pyridin-1(3H)-yl)acrylate'
_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
_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                69.107(11)
_cell_angle_beta                 76.089(10)
_cell_angle_gamma                74.028(11)
_cell_formula_units_Z            2
_cell_length_a                   6.7758(8)
_cell_length_b                   9.5853(11)
_cell_length_c                   11.3689(13)
_cell_measurement_reflns_used    3649
_cell_measurement_temperature    294
_cell_measurement_theta_max      25.1860
_cell_measurement_theta_min      3.3480
_cell_volume                     654.83(14)
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -54.00  46.00   1.00   17.50    --   15.67 -77.00 -60.00  100
  2  \w    -25.00  58.00   1.00   17.50    --   15.67 -99.00  60.00   83
  3  \w     -6.00  84.00   1.00   17.50    --   15.67  57.00 -90.00   90
  4  \w    -87.00  13.00   1.00   17.50    --  -16.84 -77.00-180.00  100
  5  \w    -37.00  52.00   1.00   17.50    --  -16.84  57.00 120.00   89
  6  \w    -37.00  52.00   1.00   17.50    --  -16.84  57.00-150.00   89
  7  \w    -86.00   5.00   1.00   17.50    --  -16.84 -57.00  60.00   91
  8  \w    -86.00   5.00   1.00   17.50    --  -16.84 -57.00 -30.00   91
  9  \w    -77.00   0.00   1.00   17.50    --  -16.84 129.00 140.84   77
 10  \w    -57.00  89.00   1.00   17.50    --   15.67   0.00-150.00  146
 11  \w    -57.00  89.00   1.00   17.50    --   15.67   0.00-180.00  146
 12  \w    -25.00  58.00   1.00   17.50    --   15.67 -99.00   0.00   83
 13  \w    -25.00  58.00   1.00   17.50    --   15.67 -99.00 -30.00   83
 14  \w    -93.00 -92.00   1.00   17.50    --  -16.84 179.00 -90.00    1
;
_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      0.0088676000
_diffrn_orient_matrix_UB_12      0.0762901000
_diffrn_orient_matrix_UB_13      -0.0354441000
_diffrn_orient_matrix_UB_21      -0.0583811000
_diffrn_orient_matrix_UB_22      0.0001592000
_diffrn_orient_matrix_UB_23      -0.0441567000
_diffrn_orient_matrix_UB_31      -0.0931349000
_diffrn_orient_matrix_UB_32      0.0271971000
_diffrn_orient_matrix_UB_33      0.0369902000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0385
_diffrn_reflns_av_unetI/netI     0.0272
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            15047
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         3.167
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.100
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.98971
_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    1.330
_exptl_crystal_description       needle
_exptl_crystal_F_000             276
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.127
_refine_diff_density_min         -0.198
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     177
_refine_ls_number_reflns         2315
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0763
_refine_ls_R_factor_gt           0.0496
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1449
_refine_ls_wR_factor_ref         0.1678
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1538
_reflns_number_total             2315
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01851_si_002.cif
_cod_data_source_block           2a
_cod_original_cell_volume        654.84(15)
_cod_database_code               4033076
_shelx_shelxl_version_number     2016/6
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.30
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(H11D)=Sof(H11E)=Sof(H11F)=1-FVAR(1)
 Sof(H11A)=Sof(H11B)=Sof(H11C)=FVAR(1)
 Sof(H12D)=Sof(H12E)=Sof(H12F)=1-FVAR(2)
 Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(2)
3.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B)
3.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C13(H13), C14(H14)
3.c Disordered Me refined as rotating group:
 C11(H11A,H11B,H11C,H11D,H11E,H11F), C12(H12A,H12B,H12C,H12D,H12E,H12F)
3.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
;
_olex2_date_sample_data_collection 2016-04-11
_olex2_submission_original_sample_id jf042
_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 1.056
_oxdiff_exptl_absorpt_empirical_full_min 0.933