Guanidine → N-diaminomethylene-2-methyl-4-(1-cyclopenten-3-yl)-5-methylsulfonylbenzamide

HRID 2892

反応式

HRID 2892 の反応式
[NH2:1][C:2]([NH2:4])=[NH:3].[Cl-].NC(N)=[NH2+].[Na].[CH3:11][C:12]1[CH:20]=[C:19]([CH:21]2[CH2:25][CH2:24][CH:23]=[CH:22]2)[C:18]([S:26]([CH3:29])(=[O:28])=[O:27])=[CH:17][C:13]=1[C:14](Cl)=[O:15].CC1C(=S(=O)=O)C(Br)=C(C)C=C1C(OC)=O.C1CCCC=1>COCCOC>[NH2:3][C:2]([NH2:4])=[N:1][C:14](=[O:15])[C:13]1[CH:17]=[C:18]([S:26]([CH3:29])(=[O:28])=[O:27])[C:19]([CH:21]2[CH2:25][CH2:24][CH:23]=[CH:22]2)=[CH:20][C:12]=1[CH3:11]

参加物

8

反応物 6

HCID 3520GuanidineHCID 8882CyclopenteneHCID 5360545SodiumHCID 5460839Carbamimidoylazanium ChlorideHCID 153387682-Methyl-4-(1-cyclopentene-3-yl)-5-methylsulfonylbenzoyl chlorideHCID 86752332Methyl 2-methyl-4-bromo-5-methyl-sulfonyl-benzoate

生成物 1

HCID 9818569N-diaminomethylene-2-methyl-4-(1-cyclopenten-3-yl)-5-methylsulfonylbenzamide

試薬・触媒・溶媒 1

HCID 80711,2-Dimethoxyethane溶媒

実験手順

A fresh guanidine solution prepared from 5.6 g of guanidinium chloride and 1.6 g of sodium in 40 ml of ethylene glycol dimethyl ether is added to a solution of 1.2 g of 2-methyl-4-(1-cyclopentene-3-yl)-5-methylsulfonylbenzoyl chloride [obtainable by reaction of methyl 2-methyl-4-bromo-5-methyl-sulfonyl-benzoate with cyclopentene in the presence of Pd(II)acetate and tri-o-tolylphosphine, separation of the two isomers by means of a Prebar® stainless steel cartridge 250-50, filled with LiChroprep RP-18; eluent 0.1 m NaH2PO4 buffer/acetonitrile 9:1 with an increasing gradient to 1:1, and subsequent hydrolysis and conversion into the acid chloride with SOCl2 ], in 20 ml of ethylene glycol dimethyl ether with ice-cooling and the mixture is stirred at room temperature for 2 hours. The reaction mixture is then poured onto ice-water, acidified and washed with ethyl acetate and the pH of the solution is adjusted to 10. Customary working-up gives N-diaminomethylene-2-methyl-4-(1-cyclopentene-3-yl)-5-methylsulfonylbenzamide, which can be recrystallized from acetonitrile/diethyl ether, melting point 212°-214°.

後処理

  1. customin the presence of Pd(II)acetate and tri-o-tolylphosphine, separation of the two isomers by means of a Prebar® stainless steel cartridge 250-50
  2. additionfilled with LiChroprep RP-18
  3. customeluent 0.1 m NaH2PO4 buffer/acetonitrile 9:1 with an increasing gradient to 1:1, and subsequent hydrolysis and conversion into the acid chloride with SOCl2 ], in 20 ml of ethylene glycol dimethyl ether with ice-
  4. temperaturecooling
  5. additionThe reaction mixture is then poured onto ice-water
  6. washwashed with ethyl acetate

出典と根拠

ORDレコード
ord-f0a8b290beed4251bf550b18be2b89c0
出典データセット
uspto-grants-1998_03
特許番号
US05731351

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