Catalyst-free synthesis of substituted pyridin-2-yl, quinolin-2-yl, and isoquinolin-1-yl carbamates from the corresponding hetaryl ureas and alcohols.
Kasatkina, Svetlana O.; Geyl, Kirill K.; Baykov, Sergey V.; Boyarskaya, Irina A.; Boyarskiy, Vadim P.; Organic & biomolecular chemistry 19 (2021) 6059–6065; doi:10.1039/d1ob00783a

data_7158122
_publ_section_title
;
 Catalyst-free synthesis of substituted pyridin-2-yl, quinolin-2-yl, and
 isoquinolin-1-yl carbamates from the corresponding hetaryl ureas and
 alcohols.
;
_journal_issue                   27
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              6059
_journal_page_last               6065
_journal_paper_doi               10.1039/d1ob00783a
_journal_volume                  19
_journal_year                    2021
_chemical_formula_moiety         'C13 H18 N2 O2'
_chemical_formula_sum            'C13 H18 N2 O2'
_chemical_formula_weight         234.29
_chemical_melting_point          444
_chemical_name_systematic
'Cyclohexyl (4--methylpyridin--2--yl)carbamate'
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-12-08
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2020-12-16 deposited with the CCDC.	2021-06-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.429(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.3092(2)
_cell_length_b                   12.0788(4)
_cell_length_c                   11.8379(3)
_cell_measurement_reflns_used    3524
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.0200
_cell_measurement_theta_min      5.2220
_cell_volume                     1187.05(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3829
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_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    -65.00  33.00   1.00    9.63    --  -41.44  38.00 150.00   98
  2  \w      3.00  29.00   1.00    9.63    --  -41.44  77.00-150.00   26
  3  \w    -73.00 -11.00   1.00    9.63    --  -41.44  77.00-150.00   62
  4  \w    -93.00 -40.00   1.00    9.63    --  -41.44 178.00-180.00   53
  5  \w    104.00 175.00   1.00   38.52    --  112.00  77.00-150.00   71
  6  \w     42.00  89.00   1.00   38.52    --  112.00 -77.00-120.00   47
  7  \w     46.00 103.00   1.00   38.52    --  112.00-126.00   0.00   57
  8  \w     42.00  96.00   1.00   38.52    --  112.00-126.00 150.00   54
  9  \w     85.00 178.00   1.00   38.52    --  112.00  30.00 -60.00   93
 10  \w     41.00 107.00   1.00   38.52    --  112.00 -61.00 150.00   66
 11  \w     63.00  88.00   1.00   38.52    --  112.00 -61.00  30.00   25
 12  \w    106.00 136.00   1.00   38.52    --  112.00 -61.00  30.00   30
 13  \w     88.00 113.00   1.00   38.52    --  112.00-126.00-180.00   25
 14  \w    120.00 145.00   1.00   38.52    --  112.00 -77.00-120.00   25
 15  \w     46.00  72.00   1.00   38.52    --  112.00-126.00-180.00   26
 16  \w    -90.00 -63.00   1.00    9.63    --  -41.44 -38.00   0.00   27
 17  \w    -51.00 -23.00   1.00    9.63    --  -41.44 -38.00   0.00   28
 18  \w   -115.00 -39.00   1.00    9.63    --  -41.44 -38.00  90.00   76
 19  \w     83.00 130.00   1.00    9.63    --   41.44 178.00  90.00   47
 20  \w     79.00 105.00   1.00    9.63    --   41.44 178.00-180.00   26
 21  \w     61.00  87.00   1.00    9.63    --   41.44 178.00 -30.00   26
 22  \w     88.00 114.00   1.00   38.52    --  112.00  61.00-120.00   26
 23  \w    104.00 130.00   1.00   38.52    --  112.00  77.00 -60.00   26
 24  \w    139.00 173.00   1.00   38.52    --  112.00  77.00 -30.00   34
 25  \w    126.00 174.00   1.00   38.52    --  112.00  77.00   0.00   48
 26  \w    144.00 177.00   1.00   38.52    --  112.00  77.00  60.00   33
 27  \w    141.00 174.00   1.00   38.52    --  112.00  77.00 -60.00   33
 28  \w     61.00 100.00   1.00   38.52    --  112.00 -95.00-180.00   39
 29  \w    130.00 157.00   1.00   38.52    --  112.00 126.00  30.00   27
 30  \w    137.00 175.00   1.00   38.52    --  112.00  61.00  30.00   38
 31  \w     88.00 132.00   1.00   38.52    --  112.00  61.00  30.00   44
 32  \w     86.00 169.00   1.00   38.52    --  112.00  30.00  90.00   83
 33  \w     80.00 113.00   1.00   38.52    --  112.00-126.00 -30.00   33
 34  \w     60.00 104.00   1.00   38.52    --  112.00  15.00  60.00   44
 35  \w     88.00 113.00   1.00   38.52    --  112.00-126.00 -60.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1429448000
_diffrn_orient_matrix_UB_12      -0.0662596000
_diffrn_orient_matrix_UB_13      0.0437761000
_diffrn_orient_matrix_UB_21      0.0211199000
_diffrn_orient_matrix_UB_22      -0.0869691000
_diffrn_orient_matrix_UB_23      -0.0934461000
_diffrn_orient_matrix_UB_31      0.1163797000
_diffrn_orient_matrix_UB_32      -0.0656992000
_diffrn_orient_matrix_UB_33      0.0795051000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0425
_diffrn_reflns_av_unetI/netI     0.0317
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            10645
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.149
_diffrn_reflns_theta_min         5.234
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.719
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64480
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.71a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear whiteish white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.311
_exptl_crystal_description       prism
_exptl_crystal_F_000             504
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Chloroform'
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.350
_refine_diff_density_min         -0.200
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     155
_refine_ls_number_reflns         2462
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0465
_refine_ls_R_factor_gt           0.0382
_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^)+(0.0544P)^2^+0.2470P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0975
_refine_ls_wR_factor_ref         0.1032
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2093
_reflns_number_total             2462
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob00783a2.cif
_cod_data_source_block           bsc-296
_cod_depositor_comments
'Adding full bibliography for 7158119--7158123.cif.'
_cod_database_code               7158122
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C9 H9 F3 N2 O2 '
_shelx_estimated_absorpt_t_max   0.919
_shelx_estimated_absorpt_t_min   0.887
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     73.59
_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 Ternary CH refined with riding coordinates:
 C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C10(H10A,H10B)
2.c Aromatic/amide H refined with riding coordinates:
 N2(H2), C3(H3), C5(H5), C6(H6)
2.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_shelx_res_checksum              11116
_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 2.070
_oxdiff_exptl_absorpt_empirical_full_min 0.510