Water → HCID 86584460、化合物

HRID 397253

反応式

HRID 397253 の反応式
[CH2:1]([OH:8])[C:2]#[C:3][C:4]#[C:5][CH2:6][OH:7].[C:9]1([CH3:21])[CH:14]=[CH:13][C:12]([S:15]([N:18]=[C:19]=[O:20])(=[O:17])=[O:16])=[CH:11][CH:10]=1.O>CS(C)=O>[C:9]1([CH3:21])[CH:10]=[CH:11][C:12]([S:15]([NH:18][C:19]([O:7][CH2:6][CH3:5])=[O:20])(=[O:16])=[O:17])=[CH:13][CH:14]=1.[CH2:1]([OH:8])[C:2]#[C:3][C:4]#[C:5][CH2:6][OH:7]

参加物

5

反応物 3

HCID 962WaterHCID 77703p-Toluenesulfonyl isocyanateHCID 94973Diacetylene glycol

生成物 1

HCID 86584460HCID 86584460、化合物収率 255.8%

試薬・触媒・溶媒 1

HCID 679Dimethyl Sulfoxide溶媒2 回

実験手順

A 500-ml tree-neck flask equipped with a stirrer, a dropping funnel and an inlet for feeding argon was charged with anhydrous (additionally dried over 4A molecular sieves) dimethylsulfoxide (DMSO) (200 ml) and 11.0 g (0.1 mol) of 2,4-hexadiyn-1,6-diol. To the vigorously stirred mixture, a solution of p-toluenesulfonyl isocyanate (Aldrich) (40 ml, 0.22 mol) in 50 ml of dry DMSO was added drop-wise for 0.5 h. After stirring for additional 2 hrs at room temperature, the mixture was discharged into 1000 ml of chilled water. The water layer was decanted off the yellow heavy oil, and the oil was triturated with diethyl ether, giving a cake of fine crystals which rapidly attained blue color under effect of UV light. Recrystallization from hot ethanol/ethyl acetate 2:1 mixture gave 45.2 g (yield 90%) of 2,4-hexadiyn-1,6-diol p-toluenesulfonyl urethane as fine white crystals with m.p. 128-130° C. The crystals were readily polymerizable under effect of both UV-irradiation and temperature. Analysis: I.R. (KBr pellet, cm−1: 3080 (Ar—H stretching), 2980+2920 (CH stretching), 1596 (phenyl C═C stretching), 1368 (S—O), 1184 (S—O), 742 (Ar—H). NIR-FT Raman: 2270 cm−1 (diacetylenic monomer —C═C— stretch), 2105 cm−1 (polymer backbone —C≡C— stretch), 1540 cm−1 (polymer backbone —C═C— stretch). Having been held in an oven at 85° C. for 2 hrs and then analyzed as described in Example 1, the compound gave an intense NIR Raman spectrum identical to that shown in FIG. 1(J, top). The simultaneous presence of the two Raman bands in 2300-1900 cm−1 spectral region, one (weak) belonging to ν(—C≡C—) vibrations of the monomer and the other (strong) belonging to ν(—C≡C—) vibrations of corresponding polymer, evidenced for partial polymerization of the compound.

後処理

  1. customA 500-ml tree-neck flask equipped with a stirrer, a dropping funnel and an inlet
  2. additionwas charged with anhydrous (
  3. customThe water layer was decanted off the yellow heavy oil
  4. customthe oil was triturated with diethyl ether
  5. customgiving a cake of fine crystals which rapidly attained blue color under effect of UV light
  6. customRecrystallization from hot ethanol/ethyl acetate 2:1 mixture

出典と根拠

ORDレコード
ord-56a552e7f78f4b81a39ee11508b22230
出典データセット
uspto-grants-2003_08
特許番号
US06610351B2

関連ノート

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