Reactions of 3,3,3-Trihalogeno-1-nitropropenes with Arenes in the Superacid CF<sub>3</sub>SO<sub>3</sub>H: Synthesis of ( Z)-3,3,3-Trihalogeno-1,2-diarylpropan-1-one Oximes and Study on the Reaction Mechanism.
Golushko, Andrei A.; Sandzhieva, Maria A.; Ivanov, Alexander Yu; Boyarskaya, Irina A.; Khoroshilova, Olesya V.; Barkov, Alexey Yu; Vasilyev, Aleksander V.; The Journal of organic chemistry 83 (2018) 10142–10157; doi:10.1021/acs.joc.8b01406

data_4035035
_publ_section_title
;
 Reactions of 3,3,3-Trihalogeno-1-nitropropenes with Arenes in the
 Superacid CF<sub>3</sub>SO<sub>3</sub>H: Synthesis of (
 Z)-3,3,3-Trihalogeno-1,2-diarylpropan-1-one Oximes and Study on the
 Reaction Mechanism.
;
_journal_issue                   17
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10142
_journal_page_last               10157
_journal_paper_doi               10.1021/acs.joc.8b01406
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C15 H10 F5 N O'
_chemical_formula_sum            'C15 H10 F5 N O'
_chemical_formula_weight         315.24
_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
_audit_creation_date             2017-12-20
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 115.110(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.4462(2)
_cell_length_b                   13.3919(2)
_cell_length_c                   10.8689(2)
_cell_measurement_reflns_used    21579
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.8710
_cell_measurement_theta_min      3.2600
_cell_volume                     1376.80(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_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      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_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    -92.00 -58.00   0.50    1.00    --  -41.49-159.00-130.00   68
  2  \w    -46.00 -21.00   0.50    1.00    --  -41.49 159.00 -97.00   50
  3  \w    -93.00 -64.00   0.50    1.00    --  -41.49 159.00 -97.00   58
  4  \w    -70.00 -43.00   0.50    1.00    --  -41.49 118.00 109.00   54
  5  \w     54.00 103.00   0.50    1.00    --   41.49 159.00 -97.00   98
  6  \w     73.00  98.00   0.50    1.00    --   41.49-159.00-130.00   50
  7  \w     78.00 127.00   0.50    2.00    --  101.00 118.00 109.00   98
  8  \w     75.00 109.00   0.50    2.00    --  101.00 159.00 -97.00   68
  9  \w     64.00  89.00   0.50    2.00    --  101.00-159.00-130.00   50
 10  \w     61.00 107.00   0.50    2.00    --  101.00-118.00  23.00   92
 11  \w    -18.00   9.00   0.50    1.00    --  -41.49  65.00  90.00   54
 12  \w    -51.00 -22.00   0.50    1.00    --  -41.49  65.00  90.00   58
 13  \w   -107.00 -34.00   0.50    1.00    --  -41.49 -32.00  60.00  146
 14  \w    -97.00 -24.00   0.50    1.00    --  -41.49 138.00-120.00  146
 15  \w    -14.00  22.00   0.50    1.00    --  -41.49  54.00 -60.00   72
 16  \w    -65.00  12.00   0.50    1.00    --  -41.49  11.00 -90.00  154
 17  \w    -48.00 -22.00   0.50    1.00    --  -41.49  54.00 -60.00   52
 18  \w     44.00  97.00   0.50    1.00    --   41.49  32.00 -30.00  106
 19  \w     42.00  67.00   0.50    1.00    --   41.49  32.00-150.00   50
 20  \w     13.00  38.00   0.50    1.00    --   41.49-118.00  23.00   50
 21  \w     38.00 114.00   0.50    2.00    --  101.00 -42.00   0.00  152
 22  \w    113.00 157.00   0.50    2.00    --  101.00  33.00 -30.00   88
 23  \w     39.00 117.00   0.50    2.00    --  101.00-116.00  53.54  156
 24  \w     47.00  73.00   0.50    2.00    --  101.00 -87.00   0.00   52
 25  \w     82.00 157.00   0.50    2.00    --  101.00 111.00  90.00  150
 26  \w     36.00 128.00   0.50    2.00    --  101.00 -87.00-180.00  184
 27  \w    124.00 157.00   0.50    2.00    --  101.00  33.00-120.00   66
 28  \w     80.00 105.00   0.50    2.00    --  101.00  77.00 -30.00   50
 29  \w     59.00 118.00   0.50    2.00    --  101.00 -68.00  60.00  118
 30  \w     93.00 121.00   0.50    2.00    --  101.00  33.00-120.00   56
 31  \w    117.00 142.00   0.50    2.00    --  101.00  77.00 -30.00   50
 32  \w    107.00 151.00   0.50    2.00    --  101.00  42.00  30.00   88
 33  \w     47.00 113.00   0.50    2.00    --  101.00 -42.00-180.00  132
 34  \w     49.00 116.00   0.50    2.00    --  101.00 -93.00  60.00  134
 35  \w     89.00 115.00   0.50    2.00    --  101.00-133.00   0.00   52
 36  \w     93.00 141.00   0.50    2.00    --  101.00  33.00 -60.00   96
 37  \w     44.00  73.00   0.50    2.00    --  101.00 -42.00 150.00   58
 38  \w    120.00 146.00   0.50    2.00    --  101.00 118.00 109.00   52
 39  \w    -22.00   4.00   0.50    1.00    --  -41.49  43.00 150.00   52
 40  \w    -37.00  21.00   0.50    1.00    --  -41.49  43.00  90.00  116
 41  \w     34.00  99.00   0.50    1.00    --   41.49  65.00-120.00  130
 42  \w     34.00  59.00   0.50    1.00    --   41.49 -54.00 150.00   50
 43  \w    121.00 147.00   0.50    2.00    --  101.00  68.00  30.00   52
 44  \w     81.00 143.00   0.50    2.00    --  101.00  93.00 150.00  124
 45  \w     86.00 157.00   0.50    2.00    --  101.00  59.00  90.00  142
 46  \w     55.00  81.00   0.50    2.00    --  101.00 -77.00-150.00   52
 47  \w     81.00 111.00   0.50    2.00    --  101.00  68.00  30.00   60
 48  \w     97.00 125.00   0.50    2.00    --  101.00 -77.00-150.00   56
 49  \w     46.00  74.00   0.50    2.00    --  101.00 -68.00   0.00   56
 50  \w     86.00 112.00   0.50    2.00    --  101.00  68.00-150.00   52
 51  \w    122.00 157.00   0.50    2.00    --  101.00  68.00-150.00   70
 52  \w     87.00 112.00   0.50    2.00    --  101.00  59.00  60.00   50
 53  \w     40.00  66.00   0.50    2.00    --  101.00 -77.00 120.00   52
 54  \w     75.00 106.00   0.50    2.00    --  101.00-133.00-120.00   62
 55  \w    131.00 157.00   0.50    2.00    --  101.00  59.00  60.00   52
 56  \w     95.00 121.00   0.50    2.00    --  101.00 -77.00 120.00   52
 57  \w     65.00  91.00   0.50    2.00    --  101.00-111.00   0.00   52
 58  \w     41.00  67.00   0.50    2.00    --  101.00-133.00-120.00   52
 59  \w     96.00 122.00   0.50    2.00    --  101.00  17.00  60.00   52
 60  \w    132.00 157.00   0.50    2.00    --  101.00  17.00  60.00   50
 61  \w     39.00  65.00   0.50    2.00    --  101.00   0.00   0.00   52
 62  \w     88.00 132.00   0.50    2.00    --  101.00   0.00   0.00   88
 63  \w     83.00 118.00   0.50    2.00    --  101.00-133.00-150.00   70
 64  \w     36.00  94.00   0.50    2.00    --  101.00 -25.00  30.00  116
 65  \w     90.00 115.00   0.50    2.00    --  101.00-111.00-120.00   50
 66  \w     84.00 124.00   0.50    2.00    --  101.00 -77.00 -30.00   80
 67  \w     93.00 121.00   0.50    2.00    --  101.00-133.00  30.00   56
 68  \w     90.00 116.00   0.50    2.00    --  101.00 -77.00-180.00   52
 69  \w     47.00 110.00   0.50    2.00    --  101.00 -25.00 -60.00  126
 70  \w     54.00  80.00   0.50    2.00    --  101.00 159.00 -97.00   52
 71  \w    -26.00   0.00   0.50    1.00    --  -41.49  54.00 -90.00   52
 72  \w    -56.00 -30.00   0.50    1.00    --  -41.49  54.00 -90.00   52
 73  \w     39.00  77.00   0.50    1.00    --   41.49  32.00  30.00   76
 74  \w     63.00 105.00   0.50    2.00    --  101.00 -50.00  90.00   84
 75  \w    102.00 129.00   0.50    2.00    --  101.00  33.00 -90.00   54
 76  \w     79.00 105.00   0.50    2.00    --  101.00  77.00   0.00   52
 77  \w     38.00  64.00   0.50    2.00    --  101.00 -33.00  30.00   52
 78  \w    132.00 157.00   0.50    2.00    --  101.00  77.00   0.00   50
 79  \w     74.00 100.00   0.50    2.00    --  101.00 -25.00-150.00   52
 80  \w     85.00 118.00   0.50    2.00    --  101.00  77.00 120.00   66
 81  \w     61.00 113.00   0.50    2.00    --  101.00 -59.00-180.00  104
 82  \w     85.00 111.00   0.50    2.00    --  101.00 -50.00-150.00   52
 83  \w     93.00 119.00   0.50    2.00    --  101.00 -87.00  90.00   52
 84  \w    110.00 136.00   0.50    2.00    --  101.00  25.00-150.00   52
 85  \w     16.00  42.00   0.50    1.00    --   41.49  77.00 150.00   52
 86  \w    -34.00  -9.00   0.50    1.00    --   16.00 128.00  29.74   50
 87  \w    -28.00  -3.00   0.50    1.00    --   16.00 119.00-168.23   50
 88  \w    -12.00  13.00   0.50    1.00    --   24.00 105.00  67.57   50
 89  \w     -3.00  22.00   0.50    1.00    --   28.00  95.00-167.23   50
 90  \w     -3.00  22.00   0.50    1.00    --   28.00  96.00 -64.94   50
 91  \w      4.00  29.00   0.50    1.00    --   32.00  88.00 -90.94   50
 92  \w      9.00  34.00   0.50    1.00    --   36.00  85.00   2.92   50
 93  \w      9.00  34.00   0.50    1.00    --   36.00  85.00 169.87   50
 94  \w      9.00  34.00   0.50    1.00    --   36.00  84.00  56.23   50
 95  \w     10.00  35.00   0.50    1.00    --   36.00  83.00 105.32   50
 96  \w      9.00  34.00   0.50    1.00    --   36.00  85.00 137.14   50
 97  \w     15.00  40.00   0.50    1.00    --   40.00  81.00 -24.85   50
 98  \w     16.00  41.00   0.50    1.00    --   41.49  78.00 -17.80   50
 99  \w     19.00  44.00   0.50    1.00    --   44.00  80.00 -54.26   50
100  \w     19.00  44.00   0.50    1.00    --   44.00  79.00-133.85   50
101  \w     19.00  44.00   0.50    1.00    --   44.00  81.00-124.85   50
102  \w     19.00  44.00   0.50    1.00    --   44.00  81.00-156.16   50
103  \w     19.00  44.00   0.50    1.00    --   44.00  79.00-163.00   50
104  \w     19.00  44.00   0.50    1.00    --   44.00  81.00 -78.38   50
105  \w     23.00  49.00   0.50    1.00    --   48.00  76.00  65.49   52
106  \w     30.00  56.00   0.50    1.00    --   52.00  75.00 138.08   52
107  \w     81.00 107.00   0.50    1.00    --   52.00  76.00 104.56   52
108  \w     27.00  52.00   0.50    1.00    --   52.00  76.00 104.56   50
109  \w     27.00  52.00   0.50    1.00    --   52.00  76.00  13.76   50
110  \w     31.00  57.00   0.50    1.00    --   56.00  77.00 -51.23   52
111  \w     40.00  83.00   0.50    1.00    --   56.00  68.00  51.31   86
112  \w     35.00  72.00   0.50    1.00    --   56.00  70.00-137.05   74
113  \w     84.00 110.00   0.50    1.00    --   56.00  70.00-137.05   52
114  \w     36.00  62.00   0.50    1.00    --   60.00  77.00-126.17   52
115  \w     37.00  62.00   0.50    1.00    --   60.00  74.00  76.26   50
116  \w     41.00  67.00   0.50    1.00    --   64.00  72.00-178.98   52
117  \w     46.00  84.00   0.50    1.00    --   68.00  70.00  21.64   76
118  \w     47.00  78.00   0.50    1.00    --   68.00  67.00 -24.35   62
119  \w     46.00  71.00   0.50    1.00    --   68.00  70.00-116.73   50
120  \w     43.00  69.00   0.50    1.00    --   68.00  76.00 150.52   52
121  \w     47.00  83.00   0.50    2.00    --   72.00  77.00-100.11   72
122  \w     53.00  79.00   0.50    2.00    --   72.00  64.00  94.51   52
123  \w     47.00  76.00   0.50    2.00    --   72.00  77.00 -65.13   58
124  \w     52.00  78.00   0.50    2.00    --   76.00  75.00  53.77   52
125  \w     55.00  93.00   0.50    2.00    --   76.00  72.00 128.90   76
126  \w     96.00 122.00   0.50    2.00    --   76.00  75.00  53.77   52
127  \w     52.00  81.00   0.50    2.00    --   76.00  75.00  99.85   58
128  \w     63.00 115.00   0.50    2.00    --   80.00  65.00-174.44  104
129  \w     62.00  88.00   0.50    2.00    --   84.00  77.00 148.46   52
130  \w     70.00 117.00   0.50    2.00    --   88.00  59.00-110.17   94
131  \w     76.00 107.00   0.50    2.00    --  101.00  77.00 -60.00   62
132  \w     76.00 108.00   0.50    2.00    --  101.00  77.00-120.00   64
133  \w     90.00 145.00   0.50    2.00    --  101.00 133.00 120.00  110
134  \w    123.00 149.00   0.50    2.00    --  101.00  42.00 -90.00   52
135  \w     88.00 115.00   0.50    2.00    --  101.00  42.00 -90.00   54
136  \w     77.00 111.00   0.50    2.00    --  101.00  77.00-150.00   68
137  \w     76.00 102.00   0.50    2.00    --  101.00  77.00 150.00   52
138  \w     80.00 106.00   0.50    2.00    --  101.00 -25.00 150.00   52
139  \w    132.00 157.00   0.50    2.00    --  101.00  68.00 -30.00   50
140  \w     45.00  74.00   0.50    2.00    --  101.00 -25.00 150.00   58
141  \w     80.00 105.00   0.50    2.00    --  101.00  68.00 -30.00   50
142  \w    122.00 148.00   0.50    2.00    --  101.00  77.00  30.00   52
143  \w     84.00 156.00   0.50    2.00    --  101.00  59.00   0.00  144
144  \w     81.00 116.00   0.50    2.00    --  101.00  77.00  30.00   70
145  \w    121.00 147.00   0.50    2.00    --  101.00  77.00-180.00   52
146  \w     77.00 110.00   0.50    2.00    --  101.00  77.00-180.00   66
147  \w     84.00 120.00   0.50    2.00    --  101.00  59.00  60.00   72
148  \w    117.00 143.00   0.50    2.00    --  101.00  77.00 120.00   52
149  \w     76.00 101.00   0.50    2.00    --  101.00  77.00 120.00   50
150  \w     76.00 102.00   0.50    2.00    --  101.00  77.00 -90.00   52
151  \w    122.00 156.00   0.50    2.00    --  101.00  68.00  60.00   68
152  \w     80.00 105.00   0.50    2.00    --  101.00  68.00  60.00   50
153  \w     43.00  91.00   0.50    2.00    --  101.00 -33.00  90.00   96
154  \w     80.00 105.00   0.50    2.00    --  101.00  68.00-150.00   50
155  \w     76.00 115.00   0.50    2.00    --  101.00  77.00 -77.50   78
156  \w    132.00 157.00   0.50    2.00    --  101.00  75.00  68.11   50
157  \w     77.00 118.00   0.50    2.00    --  101.00  75.00  68.11   82
158  \w     81.00 128.00   0.50    2.00    --  101.00  68.00 150.00   94
159  \w     81.00 107.00   0.50    2.00    --  101.00  68.00   0.00   52
160  \w     76.00 110.00   0.50    2.00    --  101.00  77.00  90.00   68
161  \w     93.00 119.00   0.50    2.00    --  101.00  33.00 150.00   52
162  \w     84.00 110.00   0.50    2.00    --  101.00  59.00 -30.00   52
163  \w     80.00 112.00   0.50    2.00    --  101.00  68.00-180.00   64
164  \w    121.00 147.00   0.50    2.00    --  101.00  77.00-120.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1017824000
_diffrn_orient_matrix_UB_12      0.0469435000
_diffrn_orient_matrix_UB_13      -0.0528105000
_diffrn_orient_matrix_UB_21      -0.0273274000
_diffrn_orient_matrix_UB_22      0.1038675000
_diffrn_orient_matrix_UB_23      0.0449375000
_diffrn_orient_matrix_UB_31      0.1242077000
_diffrn_orient_matrix_UB_32      -0.0156698000
_diffrn_orient_matrix_UB_33      0.1403012000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0226
_diffrn_reflns_av_unetI/netI     0.0072
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            29668
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.238
_diffrn_reflns_theta_min         4.921
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.256
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80617
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.35a (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.521
_exptl_crystal_description       prism
_exptl_crystal_F_000             640
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.420
_refine_diff_density_min         -0.262
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         2714
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0392
_refine_ls_R_factor_gt           0.0389
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0543P)^2^+0.7038P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1069
_refine_ls_wR_factor_ref         0.1071
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2669
_reflns_number_total             2714
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01406_si_005.cif
_cod_data_source_block           7072-8245_rqo113
_cod_database_code               4035035
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C60 H48 F16 N8 O4 '
_shelx_estimated_absorpt_t_max   0.787
_shelx_estimated_absorpt_t_min   0.787
_reflns_odcompleteness_completeness 99.34
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2. Others
 Sof(H4)=Sof(F1)=1-FVAR(1)
 Sof(F15)=Sof(H2)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C8(H8)
3.b Aromatic/amide H refined with riding coordinates:
 C22(H22), C18(H18), C21(H21), C2(H2), C19(H19), C3(H3), C4(H4), C6(H6), C5(H5)
3.c Idealised tetrahedral OH refined as rotating group:
 O14(H14)
;
_shelx_res_checksum              43244
_shelx_hkl_checksum              54376
_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 5.364
_oxdiff_exptl_absorpt_empirical_full_min 0.728