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_7158120
_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         'C9 H9 F3 N2 O2'
_chemical_formula_sum            'C9 H9 F3 N2 O2'
_chemical_formula_weight         234.18
_chemical_melting_point          459
_chemical_name_systematic
'2,2,2--Trifluoroethyl (4--methylpyridin--2--yl)carbamate'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -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                114.870(4)
_cell_angle_beta                 94.157(4)
_cell_angle_gamma                90.003(3)
_cell_formula_units_Z            2
_cell_length_a                   4.8119(2)
_cell_length_b                   10.5336(4)
_cell_length_c                   10.7314(4)
_cell_measurement_reflns_used    4497
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      77.0780
_cell_measurement_theta_min      4.5430
_cell_volume                     491.92(4)
_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                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.974
_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    -22.00   4.00   0.50    0.06    --   47.20 -57.00  30.00   52
  2  \w      8.00  62.00   0.50    0.06    --   47.20 -57.00  30.00  108
  3  \w     32.00  72.00   0.50    0.06    --   47.20-108.00 -65.00   80
  4  \w     75.00 104.00   0.50    0.30    --  107.75-108.00 -65.00   58
  5  \w     60.00 104.00   0.50    0.30    --  107.75 -77.00   0.00   88
  6  \w     83.00 112.00   0.50    0.30    --  107.75-125.00   0.00   58
  7  \w     58.00 106.00   0.50    0.30    --  107.75 -77.00 -60.00   96
  8  \w     58.00 109.00   0.50    0.30    --  107.75-125.00-120.00  102
  9  \w     39.00  65.00   0.50    0.30    --  107.75-108.00 -65.00   52
 10  \w     36.00  80.00   0.50    0.30    --  107.75-125.00 -60.00   88
 11  \w     43.00  78.00   0.50    0.30    --  107.75 -94.00 -60.00   70
 12  \w     42.00  99.00   0.50    0.30    --  107.75 -94.00-120.00  114
 13  \w     45.00  71.00   0.50    0.30    --  107.75 -61.00-180.00   52
 14  \w      1.00  27.00   0.50    0.06    --   47.20-108.00 -65.00   52
 15  \w    -26.00  42.00   0.50    0.06    --   47.20 -37.00 -60.00  136
 16  \w    -10.00  15.00   0.50    0.06    --   47.20 -19.00-120.00   50
 17  \w     95.00 175.00   0.50    0.30    --  107.75  15.00 -30.00  160
 18  \w    108.00 133.00   0.50    0.30    --  107.75 108.00  31.00   50
 19  \w     98.00 149.00   0.50    0.30    --  107.75  45.00  60.00  102
 20  \w    102.00 178.00   0.50    0.30    --  107.75  15.00  30.00  152
 21  \w     74.00 108.00   0.50    0.06    --   47.20 125.00   0.00   68
 22  \w     35.00  71.00   0.50    0.30    --  107.75 -61.00 150.00   72
 23  \w     38.00  64.00   0.50    0.30    --  107.75 -94.00 120.00   52
 24  \w     73.00 112.00   0.50    0.30    --  107.75-125.00 150.00   78
 25  \w     36.00  62.00   0.50    0.30    --  107.75-125.00 150.00   52
 26  \w     36.00  87.00   0.50    0.30    --  107.75 -77.00 120.00  102
 27  \w    -41.00 -15.00   0.50    0.06    --  -47.20 108.00  31.00   52
 28  \w    -81.00 -55.00   0.50    0.06    --  -47.20 108.00  31.00   52
 29  \w   -115.00 -86.00   0.50    0.06    --  -47.20-125.00 -30.00   58
 30  \w   -120.00 -95.00   0.50    0.06    --  -47.20-125.00   0.00   50
 31  \w   -116.00 -77.00   0.50    0.06    --  -47.20-125.00  30.00   78
 32  \w   -149.00-110.00   0.50    0.30    -- -106.00-108.00 -65.00   78
 33  \w   -158.00-111.00   0.50    0.30    -- -106.00 -61.00 -30.00   94
 34  \w   -175.00 -95.00   0.50    0.30    -- -106.00 -15.00 120.00  160
 35  \w    -70.00 -36.00   0.50    0.30    -- -106.00  61.00 120.00   68
 36  \w    -70.00 -33.00   0.50    0.30    -- -106.00  61.00  90.00   74
 37  \w    -61.00 -35.00   0.50    0.30    -- -106.00  61.00  30.00   52
 38  \w    -62.00 -37.00   0.50    0.30    -- -106.00  61.00   0.00   50
 39  \w    -90.00 -64.00   0.50    0.30    -- -106.00 108.00  31.00   52
 40  \w    -91.00 -66.00   0.50    0.30    -- -106.00 139.00 -35.49   50
 41  \w   -122.00 -97.00   0.50    0.30    -- -106.00 139.00 -35.49   50
 42  \w   -127.00 -68.00   0.50    0.30    -- -106.00 146.00  69.05  118
 43  \w   -112.00 -57.00   0.50    0.30    -- -106.00 125.00-180.00  110
 44  \w   -159.00-100.00   0.50    0.30    -- -106.00 -15.00-180.00  118
 45  \w     74.00  99.00   0.50    0.06    --   47.20 125.00 -30.00   50
 46  \w      2.00  28.00   0.50    0.06    --   22.00  73.00  48.50   52
 47  \w     -6.00  20.00   0.50    0.06    --   26.00  96.00-161.96   52
 48  \w     17.00  42.00   0.50    0.06    --   46.00  90.00 107.69   50
 49  \w     26.00  52.00   0.50    0.06    --   47.20  77.00 -90.00   52
 50  \w     28.00  54.00   0.50    0.06    --   47.20  77.00  60.00   52
 51  \w     36.00  62.00   0.50    0.06    --   47.20  57.00   0.00   52
 52  \w     35.00  68.00   0.50    0.06    --   47.20  37.00 -30.00   66
 53  \w     41.00  68.00   0.50    0.06    --   47.20  37.00-180.00   54
 54  \w     57.00  84.00   0.50    0.06    --   47.20  19.00   0.00   54
 55  \w     29.00  60.00   0.50    0.06    --   50.00  80.00 143.22   62
 56  \w     27.00  52.00   0.50    0.06    --   50.00  77.00  37.26   50
 57  \w     33.00  59.00   0.50    0.06    --   54.00  73.00-130.58   52
 58  \w     36.00  62.00   0.50    0.06    --   58.00  76.00 162.06   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1339909000
_diffrn_orient_matrix_UB_12      -0.0824192000
_diffrn_orient_matrix_UB_13      -0.1475916000
_diffrn_orient_matrix_UB_21      -0.1346196000
_diffrn_orient_matrix_UB_22      -0.1050472000
_diffrn_orient_matrix_UB_23      0.0450653000
_diffrn_orient_matrix_UB_31      -0.2590045000
_diffrn_orient_matrix_UB_32      0.0904854000
_diffrn_orient_matrix_UB_33      0.0371960000
_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  0.0372
_diffrn_reflns_av_unetI/netI     0.0310
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            6782
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.323
_diffrn_reflns_theta_min         4.556
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.327
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82280
_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 light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.581
_exptl_crystal_description       prism
_exptl_crystal_F_000             240
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Chloroform'
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.252
_refine_diff_density_min         -0.285
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     146
_refine_ls_number_reflns         2033
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.093
_refine_ls_R_factor_all          0.0385
_refine_ls_R_factor_gt           0.0366
_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^)+(0.0591P)^2^+0.1184P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1019
_refine_ls_wR_factor_ref         0.1039
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1872
_reflns_number_total             2033
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob00783a2.cif
_cod_data_source_block           15941_bsc-297
_cod_depositor_comments
'Adding full bibliography for 7158119--7158123.cif.'
_cod_database_code               7158120
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C9 H9 F3 N2 O2'
_shelx_estimated_absorpt_t_max   0.868
_shelx_estimated_absorpt_t_min   0.806
_reflns_odcompleteness_completeness 99.55
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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:
 C8(H8A,H8B)
2.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C3(H3), C5(H5), C6(H6)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_shelx_res_checksum              11214
_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 1.414
_oxdiff_exptl_absorpt_empirical_full_min 0.710