تفاعل #11034

ord-b9f824f0c5e2416cb52f40f910d00786

معادلة التفاعل

O=S(=O)(O)Cl
chlorosulfonic acid
O=S(=O)(O)O
sulfuric acid
O=C(O)/C=C/C(=O)O.O=C(O)/C=C\C(=O)O
fumaric acid maleic acid
COC(=O)/C=C(\Oc1ccccc1[N+](=O)[O-])C(=O)OC
dimethyl 2-(2-nitrophenoxy)fumarate
COC(=O)/C=C(/Oc1ccccc1[N+](=O)[O-])C(=O)OC
dimethyl 2-(2-nitrophenoxy)maleate
COC(=O)c1cc(=O)c2cccc([N+](=O)[O-])c2o1
8-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran
المردود 88.0%

ظروف التفاعل

درجة الحرارة
60°CELSIUS
الظروف التفصيلية
See reaction.notes.procedure_details.

المعالجة

  1. 1
    أخرىA reaction container equipped with a stirrer, a cooling tube
  2. 2
    workup.ADDITIONwas added dropwise at an inner temperature of 60° C. over 6 hours
  3. 3
    workup.ADDITIONAfter completion of addition
  4. 4
    درجة الحرارةthe inner temperature was raised to 95° C.
  5. 5
    أخرىto obtain a reaction solution

الإجراء التجريبي

A reaction container equipped with a stirrer, a cooling tube and a thermometer was charged with 50.2 parts by weight of chlorosulfonic acid. Thereto, 25.1 parts by weight of 98% sulfuric acid was added dropwise over 1 hour and the mixture was then warmed to 60° C. Thereto, 25.6 parts by weight of a mixture (content: 89.6% by weight, fumaric acid/maleic acid ratio=54/46) containing dimethyl 2-(2-nitrophenoxy)fumarate and dimethyl 2-(2-nitrophenoxy)maleate was added dropwise at an inner temperature of 60° C. over 6 hours. After completion of addition, the inner temperature was raised to 95° C. and the mixture was stirred and kept at the same temperature for 4 hours to obtain a reaction solution containing 8-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran (reaction yield: 88%). The reaction solution was poured gradually into 113 parts by weight of water at 85° C. or below. The mixture was kept at an inner temperature of 85° C. for 6 hours and then cooled gradually to an inner temperature of 25° C. Precipitated crystals were filtered and dried to obtain 16.7 parts by weight of a crystalline mixture of 8-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran and 8-nitro-2-carboxy-4-oxo-4H-1-benzopyran (the content of 8-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran: 3.8% by weight; the content of 8-nitro-2-carboxy-4-oxo-4H-1-benzopyran: 96.0% by weight). The yield of 8-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran was 5.3% and the yield of 8-nitro-2-carboxy-4-oxo-4H-1-benzopyran was 81.5%.

المصدر

DOI: 10.6084/m9.figshare.5104873.v1براءة الاختراع: US07094914B2uspto-grants-2006_08