Reduction of 2,2,2-trichloro-1-arylethanones by RMgX: mechanistic investigation and the synthesis of substituted alpha,alpha-dichloroketones
Ali H. Essa; Reinner I. Lerrick; Floriana Tuna; Ross W. Harrington; William Clegg; Michael J. Hall; Chem.Commun. 49 (2013) 2756–; doi:10.1039/c3cc39147g

data_7109026
_publ_section_title
;
 Reduction of 2,2,2-trichloro-1-arylethanones by RMgX: mechanistic
 investigation and the synthesis of substituted
 alpha,alpha-dichloroketones
;
_journal_name_full               Chem.Commun.
_journal_page_first              2756
_journal_paper_doi               10.1039/c3cc39147g
_journal_volume                  49
_journal_year                    2013
_chemical_formula_moiety         'C15 H15 Cl2 N O3'
_chemical_formula_sum            'C15 H15 Cl2 N O3'
_chemical_formula_weight         328.18
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 106.344(8)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   8.9648(6)
_cell_length_b                   12.0920(7)
_cell_length_c                   14.0270(11)
_cell_measurement_reflns_used    3062
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      28.37
_cell_measurement_theta_min      2.90
_cell_volume                     1459.11(18)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET)
(compiled Jan 20 2011,15:58:25)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET)
(compiled Jan 20 2011,15:58:25)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET)
(compiled Jan 20 2011,15:58:25)
;
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL and local programs'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_structure_solution    'Bruker SHELXTL'
_diffrn_ambient_temperature      150(2)
_diffrn_detector_area_resol_mean 10.3968
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.858
_diffrn_measurement_device_type
'Oxford Diffraction Gemini A Ultra diffractometer'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  none
_diffrn_radiation_source         'sealed tube with Enhance optics'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0284
_diffrn_reflns_av_sigmaI/netI    0.0348
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            9278
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         28.43
_diffrn_reflns_theta_min         2.91
_exptl_absorpt_coefficient_mu    0.454
_exptl_absorpt_correction_T_max  0.876
_exptl_absorpt_correction_T_min  0.839
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET)
(compiled Jan 20 2011,15:58:25)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.494
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             680
_exptl_crystal_size_max          0.40
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.30
_refine_diff_density_max         0.318
_refine_diff_density_min         -0.208
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     196
_refine_ls_number_reflns         3145
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0509
_refine_ls_R_factor_gt           0.0369
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0342P)^2^+0.6168P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0784
_refine_ls_wR_factor_ref         0.0868
_reflns_number_gt                2539
_reflns_number_total             3145
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            c3cc39147g.txt
_cod_data_source_block           mjh76_3b
_cod_original_cell_volume        1459.11(17)
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               7109026
_computing_special_details
;
TITL mjh76 in P2(1)/n
CELL 0.71073 8.9648 12.0920 14.0270 90.000 106.344 90.000
ZERR 4.00 0.0006 0.0007 0.0011 0.000 0.008 0.000
LATT 1
SYMM 0.5-X, 0.5+Y, 0.5-Z
SFAC C H N O CL
UNIT 60 60 4 12 8
TEMP -123
L.S. 8
BOND $H
CONF
FMAP 2
PLAN 5
ACTA 50
REM colourless block
SIZE 0.40 0.30 0.30
HTAB O2 O1
HTAB O2 O4_$1
EQIV $1 x-1, y, z
REM EXTI 0.000000
WGHT 0.034200 0.616800
FVAR 0.57892
CL2 5 0.043584 0.170386 0.091792 11.00000 0.02707 0.02969 =
0.03375 -0.00089 0.01462 -0.00252
O4 4 0.684497 0.048045 0.402942 11.00000 0.01937 0.02649 =
0.04127 0.00199 0.00809 0.00235
CL1 5 -0.050520 -0.041150 0.155331 11.00000 0.02913 0.01808 =
0.05278 -0.00189 0.00447 0.00063
C7 1 -0.051360 0.105044 0.172907 11.00000 0.02319 0.01650 =
0.03541 0.00190 0.01312 -0.00077
O1 4 -0.261572 0.195566 0.211799 11.00000 0.02781 0.04010 =
0.03550 -0.00011 0.01216 0.00902
O2 4 -0.029428 0.080079 0.347671 11.00000 0.02312 0.05068 =
0.03872 0.01319 0.01393 0.00521
C11 1 0.419880 -0.021644 0.368889 11.00000 0.02530 0.02057 =
0.03271 0.00477 0.00914 0.00263
AFIX 43
H11A 2 0.454379 -0.094867 0.387540 11.00000 -1.20000
AFIX 0
N 3 -0.473727 0.171475 0.017328 11.00000 0.02077 0.03487 =
0.03731 0.01085 0.00839 -0.00196
C14 1 0.317545 0.191229 0.315094 11.00000 0.02607 0.01920 =
0.03207 -0.00034 0.01002 0.00202
AFIX 43
H14A 2 0.283199 0.264650 0.297203 11.00000 -1.20000
AFIX 0
C12 1 0.526817 0.062142 0.372175 11.00000 0.02003 0.02594 =
0.02422 -0.00094 0.00800 0.00079
C6 1 -0.222724 0.147960 0.145490 11.00000 0.02266 0.02211 =
0.03319 0.00482 0.01075 -0.00031
C9 1 0.208643 0.107868 0.310240 11.00000 0.02105 0.02608 =
0.02517 -0.00034 0.00942 0.00126
C10 1 0.262468 0.002131 0.338240 11.00000 0.02397 0.02440 =
0.03580 0.00433 0.01026 -0.00207
AFIX 43
H10A 2 0.189698 -0.055508 0.336391 11.00000 -1.20000
AFIX 0
C15 1 0.740523 -0.062368 0.424445 11.00000 0.02641 0.03064 =
0.04283 0.00349 0.00799 0.00844
AFIX 137
H15A 2 0.854138 -0.061391 0.449919 11.00000 -1.50000
H15B 2 0.709721 -0.106876 0.363659 11.00000 -1.50000
H15C 2 0.696148 -0.094584 0.474509 11.00000 -1.50000
AFIX 0
C8 1 0.037564 0.135126 0.281049 11.00000 0.02168 0.02536 =
0.03101 0.00216 0.01081 0.00160
AFIX 13
H8A 2 0.026595 0.216533 0.289678 11.00000 -1.20000
AFIX 0
C13 1 0.474891 0.168666 0.345572 11.00000 0.02378 0.02189 =
0.03528 -0.00124 0.00961 -0.00382
AFIX 43
H13A 2 0.547772 0.226449 0.348295 11.00000 -1.20000
AFIX 0
C4 1 -0.298112 0.074948 -0.033601 11.00000 0.03344 0.02729 =
0.03757 0.00156 0.01114 -0.00416
AFIX 43
H4A 2 -0.204711 0.039141 -0.035589 11.00000 -1.20000
AFIX 0
C3 1 -0.434536 0.079627 -0.110775 11.00000 0.04399 0.03754 =
0.03327 0.00287 0.00698 -0.01241
AFIX 43
H3A 2 -0.452152 0.047385 -0.174751 11.00000 -1.20000
AFIX 0
C5 1 -0.321745 0.131785 0.047243 11.00000 0.02208 0.02314 =
0.03596 0.00533 0.00999 -0.00210
C1 1 -0.556335 0.234366 0.075295 11.00000 0.02054 0.05199 =
0.04917 0.01042 0.01239 0.00683
AFIX 137
H1A 2 -0.656231 0.259614 0.031753 11.00000 -1.50000
H1B 2 -0.493782 0.298503 0.105319 11.00000 -1.50000
H1C 2 -0.574505 0.187242 0.127765 11.00000 -1.50000
AFIX 0
C2 1 -0.538883 0.139625 -0.077029 11.00000 0.02723 0.04470 =
0.03871 0.01370 0.00197 -0.00955
AFIX 43
H2A 2 -0.642177 0.156294 -0.114773 11.00000 -1.20000
AFIX 0
H2 2 -0.121763 0.103024 0.338064 11.00000 0.05620
HKLF 4
REM mjh76 in P2(1)/n
REM R1 = 0.0369 for 2539 Fo > 4sig(Fo) and 0.0509 for all 3145 data
REM 196 parameters refined using 0 restraints
END
;