1,2-Dibromopropane → 5,6-Dihydro-6-methyl-3-(2-thienyl)-1,4,2-oxadiazine

HRID 841853ノート

反応式

HRID 841853 の反応式
CS[C:3]([C:5]1[S:6][CH:7]=[CH:8][CH:9]=1)=S.Cl.[NH2:11][OH:12].C([N:15]([CH2:18][CH3:19])CC)C.Br[CH2:21]C(Br)C>CO.O>[CH3:21][CH:19]1[O:12][NH:11][C:3]([C:5]2[S:6][CH:7]=[CH:8][CH:9]=2)=[N:15][CH2:18]1

参加物

7

反応物 4

HCID 65531,2-DibromopropaneHCID 8471Triethylamine3 回HCID 443297Hydroxyamine hydrochloride2 回HCID 12473607Methyl thiophene-2-carbodithioate

生成物 1

HCID 226173535,6-Dihydro-6-methyl-3-(2-thienyl)-1,4,2-oxadiazine

試薬・触媒・溶媒 2

HCID 887Methanol溶媒2 回HCID 962Water溶媒

実験手順

Methyl-2-thiophenecarbodithioate (47 g, 0.27 mol) in methanol (250 ml) at 0-5° C., was stirred and treated with powdered hydroxylamine hydrochloride (20 g) and followed by dropwise addition of triethylamine (50 ml) in methanol (50 ml) over 2 hours, to prepare a reaction mixture. Additional hydroxylamine hydrochloride (5 g) and triethylamine (10 ml) was added consecutively to the reaction mixture and after 45 minutes, the reaction mixture turned yellow (from red). 1,2-Dibromopropane (26 ml) was then added to the yellow reaction mixture, followed by addition of triethylamine (75 ml). The resultant new reaction mixture was refluxed for 4 hours and then left overnight at ambient temperature. The methanol was removed from the reaction mixture to leave a residue. Water was added to the residue which was then extracted into ethyl acetate, washed with dilute hydrochloric acid (2N, 100 ml), water, and dried (MgSO4). The ethyl acetate was then removed to leave a brown oil which was crystallized with cyclohexane to produce two crops of 5,6-dihydro-6-methyl-3-(2-thienyl)-1,4,2-oxadiazine (11.7 g and 3.7 g, mp 70-72° C.) Found: C 48.90, H 4.66, N 7.17, C8H9NOS2 requires C 48.24, H 4.52, N 7.07

後処理

  1. customto prepare a reaction mixture
  2. temperatureThe resultant new reaction mixture was refluxed for 4 hours
  3. customThe methanol was removed from the reaction mixture
  4. customto leave a residue
  5. extractionwas then extracted into ethyl acetate
  6. washwashed with dilute hydrochloric acid (2N, 100 ml), water
  7. dry with materialdried (MgSO4)
  8. customThe ethyl acetate was then removed
  9. customto leave a brown oil which
  10. customwas crystallized with cyclohexane

出典と根拠

ORDレコード
ord-5b23202e3a894e7ebcfed37ba407ebb6
出典データセット
uspto-grants-2002_04
特許番号
US06372297B1

反応ノート

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