Hydrochloric Acid → 4-ethynylbenzoyl Chloride

HRID 1285230

反応式

HRID 1285230 の反応式
C(O[C:4](=[O:11])[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)#C.Br[C:13]1[CH:21]=[CH:20][C:16]([C:17]([OH:19])=[O:18])=[CH:15][CH:14]=1.[CH3:22][Si:23]([C:26]#[CH:27])([CH3:25])[CH3:24].[Br-].C([NH+](CC)CC)C.[ClH:36]>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C(N(CC)CC)C.N1C=CC=CC=1>[C:21]([C:8]1[CH:7]=[CH:6][C:5]([C:4]([Cl:36])=[O:11])=[CH:10][CH:9]=1)#[CH:13].[CH3:22][Si:23]([C:26]#[C:27][C:13]1[CH:21]=[CH:20][C:16]([C:17]([OH:19])=[O:18])=[CH:15][CH:14]=1)([CH3:25])[CH3:24]

参加物

10

反応物 5

HCID 313Hydrochloric AcidHCID 114644-Bromobenzoic acidHCID 12493Triethylamine hydrobromideHCID 66111TrimethylsilylacetyleneHCID 15632868Ethynyl benzoate

生成物 2

HCID 109317874-ethynylbenzoyl ChlorideHCID 136281904-[(Trimethylsilyl)ethynyl]benzoic acid

試薬・触媒・溶媒 3

HCID 178418476HCID 178418476、化合物触媒HCID 1049Pyridine溶媒HCID 8471Triethylamine溶媒

実験手順

An alternate and more direct approach to the preparation of the ethynylbenzoate-terminated PS involved the reaction of the hydroxy-terminated PS with 4-ethynylbenzoyl chloride as in Eq. 2. The 4-ethynylbenzoyl chloride was prepared as follows: 4-Bromobenzoic acid (11.0 g, 0.055 mole; source, Aldrich Chemical Company), dichlorobis(triphenylphosphine)palladium (0.3 g; source, Strem Chemical, Inc.), pyridine (60 ml), triethylamine (40 ml), and trimethylsilylacetylene (8.3 g, 0.085 mole; source, Silar Laboratories Inc.) were stirred under nitrogen at 70°-74° C. for six hours. The yellow solution turned brown and a precipitate appeared (presumably triethylammonium bromide). The reaction mixture was poured into cold dilute aqueous hydrochloric acid (10° C.-20° C.) to yield 4-trimethylsilylethynylbenzoic acid as a crude tan solid (11.0 g), m.p. 175°-185° C. decomp. [lit. m.p. 181°-182.5° C.)]. The tan solid was dissolved in dilute aqueous sodium hydroxide solution, filtered, and the filtrate acidified to yield a light tan solid (9.6 g). Recrystallization twice from toluene provided 4-ethynylbenzoic acid as golden needles (4.3 g), m.p. 222°-223° C. decomp. (Sample introduced in a preheated melting point apparatus at 220° C.)[lit m.p. 218° C. decomp.] [IR, strong sharp absorption at 3300 cm-1 characteristic of H--C≡C stretch. Mass spectroscopy (MS), molecular ion (M+) at 146 [4-ethynylbenzoic acid (mol. wt. 146)], major fragments m/e 129 (HC≡C--C6H4 -CO+) and 101 (HC≡C--C6H4 +)]. 4-Ethynylbenzoic acid (4.2 g) was stirred in thionyl chloride (30 ml) containing a few drops of N,N-dimethylformamide at ambient temperature overnight (8-20 hours). The light orange solution was concentrated to dryness at temperature <40° C. in vacuo to yield an orange crystalline solid which was thoroughly washed with cold n-hexane (5° C.-10° C.). The resultant yellow crystalline solid (3.1 g) was dissolved in warm n-hexane (30 ml) and the solution cooled to 5° C. to 10° C. Since no solid appeared, the solution was partially concentrated to yield 4-ethynylbenzoyl chloride as crude yellow needles (3.0 g), m.p. 32°-34° C., (IR, H--C≡C at 3300 cm-1, C=O doublet at 1800 and 1770 cm-1). Sublimination in nitrogen atmosphere under vacuum provided white crystalline needles, m.p. 69°-70° C.

後処理

  1. customterminated PS
  2. customthe reaction of the hydroxy-
  3. customterminated PS with 4-ethynylbenzoyl chloride as in Eq. 2

出典と根拠

ORDレコード
ord-028a701f37164df3b17ecc61d81c45e2
出典データセット
uspto-grants-1986_01
特許番号
US04565886

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