Ethanethiol → HCID 135869713, compound

HRID 2263695Notes

Reaction equation

HRID 2263695 reaction equation
[Cl:1][C:2]1[CH:29]=[CH:28][C:5]2[NH:6][C:7](=[O:27])[CH:8]([CH2:19][C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=3[CH3:26])[N:9]=[C:10]([C:11]3[CH:16]=[CH:15][C:14]([O:17]C)=[CH:13][CH:12]=3)[C:4]=2[CH:3]=1.CCS.[Al](Br)(Br)Br>C(Br)Br>[Cl:1][C:2]1[CH:29]=[CH:28][C:5]2[NH:6][C:7](=[O:27])[CH:8]([CH2:19][C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=3[CH3:26])[N:9]=[C:10]([C:11]3[CH:16]=[CH:15][C:14]([OH:17])=[CH:13][CH:12]=3)[C:4]=2[CH:3]=1

Participants

5

Reactant 3

HCID 6343EthanethiolHCID 24409Aluminum bromideHCID 59594405HCID 59594405, compound

Product 1

HCID 135869713HCID 135869713, compoundYield 80%

Reagents, catalysts & solvents 1

HCID 3024DibromomethaneSolvent

Procedure

To a solution of (Z)-7-chloro-5-(4-methoxyphenyl)-3-(2-methylbenzyl)-1H-benzo[e][1,4]diazepin-2(3H)-one precursor (0.6 g, 1.4 mmol) in CH2Br2 (20 mL) was added EtSH (7 mL) and then AlBr3 (1.7 g, 6.3 mmol, 4.5 eq). The resulting mixture was stirred overnight and then treated with ice (20 g) and after one hour filtered. The resulting solid was triturated with 50% DCM/heptane and then vacuum dried to give 445 mg (yield of 80%) of (Z)-7-chloro-5-(4-hydroxyphenyl)-3-(2-methylbenzyl)-1H-benzo[e][1,4]diazepin-2(3H)-one as a light yellow solid. 1H NMR (300 MHz, DMSO-d6) δ 2.31 (s, 3H), 3.25-3.45 (m, 2H), 3.73 (dd, 1H), 6.80 (d, 2H), 7.02-7.18 (m, 3H), 7.2-7.3 (m, 5H), 7.64 (dd, 1H), 10.0 (br s, 1H), 10.7 (br s, 1H). MS, m/z 391.7 [M+1] The following compounds were prepared based on the above procedure: (Z)-7-Chloro-5-(4-hydroxyphenyl)-3-(2-methylbenzyl)-1-methyl-1H-benzo[e][1,4]diazepin-2(3H)-one. 1H NMR (300 MHz, DMSO-d6) δ 2.32 (s, 3H), 3.3-3.5 (m, 5H; contains singlet for NMe at 3.36), 3.90 (t, 1H), 6.87 (d, 2H), 7.05-7.15 (m, 3H), 7.20 (m, 1H), 7.29 (fine d, 1H), 7.35 (d, 2H), 7.65 (d, 1H), 7.78 (dd, 1H), 9-11 (br s, 1H). MS, m/z 405.3 [M+1]. (Z)-7-Chloro-5-(4-hydroxyphenyl)-3-(3-methylbenzyl)-1H-benzo[e][1,4]diazepin-2(3H)-one. 1H NMR (300 MHz, DMSO-d6) δ 2.28 (s, 3H), 3.2-3.4 (m, 2H; contains water signal), 3.63 (t, 1H), 6.79 (d, 2H), 7.00 (d, 1H), 7.05-7.15 (m, 3H), 7.20 (m, 1H), 7.29 (fine d, 1H), 7.31 (d, 2H), 7.62 (dd, 1H), 9.95 (s, 1H), 10.61 (s, 1H). MS, m/z 391.7 [M+1]. (Z)-7-Chloro-5-(4-hydroxyphenyl)-3-(3-methylbenzyl)-1-methyl-1H-benzo[e][1,4]diazepin-2(3H)-one. 1H NMR (300 MHz, DMSO-d6) δ 2.25 (s, 3H), 3.25-3.45 (m, 5H; contains singlet for NMe at 3.35), 3.83 (t, 1H), 6.87 (d, 2H), 6.99 (d, 1H), 7.05-7.2 (m, 3H), 7.28 (fine d, 1H), 7.38 (d, 2H), 7.63 (d, 1H), 7.77 (dd, 1H), 10.2 (br s, 1H). MS, m/z 405.3 [M+1]. (Z)-7-Chloro-5-(4-hydroxyphenyl)-3-(4-methylbenzyl)-1H-benzo[e][1,4]diazepin-2(3H)-one. 1H NMR (300 MHz, DMSO-d6) δ 2.23 (s, 3H), 3.2-3.4 (m, 3H), 3.80 (m, 1H), 6.86 (d, 2H), 7.09 (d, 2H), 7.23 (d, 2H), 7.25-7.35 (m, 4H), 7.71 (dd, 1H), 10.3 (br s, 1H), 10.9 (br s, 1H). MS, m/z 391.8 [M+1]. (Z)-7-Chloro-5-(4-hydroxyphenyl)-3-(4-methylbenzyl)-1-methyl-1H-benzo[e][1,4]diazepin-2(3H)-one. 1H NMR (300 MHz, DMSO-d6) δ 2.24 (s, 3H), 3.25-3.4 (m, 5H; contains singlet for NMe at 3.34), 3.82 (t, 1H), 6.87 (d, 2H), 7.07 (d, 2H), 7.19 (d, 2H), 7.28 (fine d, 1H), 7.37 (d, 2H), 7.63 (d, 1H), 7.76 (dd, 1H), 9.5-11 (br s, 1H). MS, m/z 405.3 [M+1]. (Z)-7-Chloro-3-(2-ethylbenzyl)-5-(4-hydroxyphenyl)-1H-benzo[e][1,4]diazepin-2(3H)-one.

Workup

  1. filtrationfiltered
  2. customThe resulting solid was triturated with 50% DCM/heptane
  3. customvacuum dried

Sources & evidence

ORD record
ord-ef55fde92bae443a907a7dc3dee4ccbf
Source dataset
uspto-grants-2010_12
Patent number
US07851465B2

Reaction notes

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