Himic anhydride

Off-white to tan solid

A method for preparing high-purity cis-5-norbornene-exo-2, 3-dicarboxylic acid anhydride by microwave reaction is disclosed. The method comprises the following steps: using cis-5-norbornene-endo-2, 3-dicarboxylic anhydride as raw material, Specific steps are as follows:(1) In a 1 L reaction flask, 200 g of cis-5-norbornene-endo-2, 3-dicarboxylic anhydride and 600 mL of toluene were stirred and placed in a microwave autoclave. The temperature was raised to 200 ° C, 100-200GHz microwave for 8 minutes;(2) The reaction was completed, the reactor of step (1) was cooled to 110 ° C, stirred in an oil bath for 30 minutes to crystallize, cooled to room temperature, filtered and dried to give the product cis-5-norbornene- Dicarboxylic anhydride 160.2 g; Yield: 80.1percent; Purity: 98.2percent; Oxide impurity content: 0.06percent.Nadic anhydride (ACROS, 225 g, 1.4 mol, pure endo isomer) was put into the 500 ml 2-neck round bottom flask, and refluxed while the temperature was increased to 180° C. Next, while it was agitated at 300 rpm, it was reacted for 6 hours, the reactants were cooled and recrystallized with benzene. The product that was rearranged by 80percent exo isomers were obtained by carrying out the recrystallization twice (yield: 40percent). [0082] The NMR analysis results of the pure endo isomer compound are described below. [0083] The synthetic procedure is a modification of the previously published method [16]. cis-5-norbornene-endo-2, 3-dicarboxylic anhydride (250 g, 1.52 mol) was heated to 185 °C for 4-5 h. After cooling to room temperature, the endo/exo mixture was further purified by recrystallization in ethyl acetate four times to obtain pure cis-5-norbornene exo-2, 3-dicarboxylic anhydride. Yield: 82 g (32.8percent), purity: >98percent exo isomer, mp: 141-143 °C, lit. 143 °C[16] . Synthesis of Monomer 2: (1) Conversion of the endo to the exo isomer was adapted from previous literature procedures. (Canonne, et al., J Org Chem 1982, 47, 3953) 100 g (0.60 mol) of 5-Norbornene-2, 3-dicarboxylic anhydride (endo) was placed in a 250 mL round bottom flask and heated at 210° C. under nitrogen for 2 hours. The flask was cooled to 120° C. after which toluene (100 mL) was added. This solution was allowed to cool to room temperature. The resulting mixture was filtered and the residue was recrystallized 4 times from toluene to give white crystals of 5-norbornene-2, 3-dicarboxylic anhydride (exo), (14 g, 0.14 mol, 14percent yield, mp=143° C.). In a 1 L flask, 260 g (2.65 mol) of maleic anhydride and 500 mL of ethyl acetate were stirred, and then 200 mL of hexane was added to dissolve it completely. The flask was charged with 175 g (2.65 mol) of the cyclopentadiene prepared in the above (1) in a state of lowering the temperature with an ice bath. After the whole amount was added, the ice bath was removed, and the reaction was conducted at 60 ° C for 1 hour. After completion of the reaction, the reaction product was allowed to stand at -20 for 8 hours to effect recrystallization. The obtained solid was filtered and dried to obtain 360 g of a white compound represented by the formula (3) (yield: 82.7percent). The obtained compounds were identified by NMR (1H and 13C) (JEOL, JNM-LA400) and IR (AVATAR, 360 FT-IR), and the results are shown in FIGS. 2 and 3, respectively.In a 1 L flask, 260 g (2.65 mol) of maleic anhydride and 500 mL of ethyl acetate were stirred, and then 200 mL of hexane was added to dissolve it completely.The flask was charged with 175 g (2.65 mol) of the cyclopentadiene prepared in the above (1) in a state of lowering the temperature with an ice bath.After the whole amount was added, the ice bath was removed, and the reaction was conducted at 60 ° C for 1 hour.After completion of the reaction, the reaction product was allowed to stand at -20 for 8 hours to effect recrystallization.The obtained solid was filtered and dried to obtain 360 g of a white compound represented by the formula (3) (yield: 82.7percent).EXAMPLE 1This example illustrates the performance of a Diels-Alder cyclo-addition reaction in a surfactant reaction medium of the invention.In a centrifuge tube immersed in a water bath at 55°C, 0.2 grams of maleic anhydride were dissolved in 1.6 mL of a surfactant medium comprising a poly (ethylene oxide) alcohol having the formula CTo 5.0 g of stereoisomerized methyl-5-norbornene-2, 3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48percent) and 5.0 g of 5-norbornene-2, 3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48percent) were added 18.5 g of water and 16.5 g of a 30 wtpercent aqueous solution of sodium hydroxide (1.1 equivalents relative to 5-norbornene-2, 3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 7.4 g (exo stereoisomeric ratio for the general formula (1) type = 87percent).(Example 1) To 10.0 g of 5-norbornene-2, 3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 26percent) were added 33.6 g of water and 16.3 g of a 30 wtpercent aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2, 3-dicarboxylic anhydride mixture, 1.4 equivalents relative to 5-norbornene-endo-2, 3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 1.17 g (exo stereoisomeric ratio for the general formula (1) type = 88percent).; (Example 2) To 10.0 g of 5-norbornene-2, 3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 75percent) were added 11.1 g of water and 16.3 g of a 30 wtpercent aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2, 3-dicarboxylic anhydride mixture, 4.0 equivalents relative to 5-norbornene-endo-2, 3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 10.33 g (exo stereoisomeric ratio for the general formula (1) type = 84percent).; (Example 3) With the exception of using 33.7 g of water, preparation was conducted in the same manner as the The obtained solid was 7.21 g (exo stereoisomeric ratio for the general formula (1) type = 92percent).; (Example 4) To 10.0 g of 5-norbornene-2, 3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48percent) were added 33.6 g of water and 16.3 g of a 30 wtpercent aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2, 3-dicarboxylic anhydride mixture, 1.9 equivalents relative to 5-norbornene-endo-2, 3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 4.48 g (exo stereoisomeric ratio for the general formula (1) type = 88percent).; (Example 5) To 10.0 g of 5-norbornene-2, 3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 75percent) were added 39.3 g of water and 8.2 g of a 30 wtpercent aqueous solution of sodium hydroxide (0.5 equivalents relative to the 5-norbornene-2, 3-dicarboxylic anhydride mixture, 2.0 equivalents relative to 5-norbornene-endo-2, 3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 6.62 g (exo stereoisomeric ratio for the general formula (1) type = 86percent).; (Example 6) To 10.0 g of 5-norbornene-2, 3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 75percent) were added 27.9 g of water and 24.5 g of a 30 wtpercent aqueous solution of sodium hydroxide (1.5 equivalents relative to the 5-norbornene-2, 3-dicarboxylic anhydride mixture, 6.0 equivalents relative to 5-norbornene-endo-2, 3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 9.90 g (exo stereoisomeric ratio for the general formula (1) type = 91percent).; (Example 7) To 10.0 g of 5-norbornene-2, 3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 75percent) were added 16.8 g of water and 8.2 g of a 30 wtpercent aqueous solution of sodium hydroxide (0.5 equivalents relative to the 5-norbornene-2, 3-dicarboxylic anhydride mixture, 2.0 equivalents relative to 5-norbornene-endo-2, 3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 9.42 g (exo stereoisomeric ratio for the general formula (1) type = 79percent).; (Example 8) To 10.0 g of 5-norbornene-2, 3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48percent) were added 42.4 g of water and 4.1 g of a 30 wtpercent aqueous solution of sodium hydroxide (0.25 equivalents relative to the 5-norbornene-2, 3-dicarboxylic anhydride mixture, 0.5 equivalents relative to 5-norbornene-endo-2, 3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 2.81 g (exo stereoisomeric ratio for the general formula (1) type = 89percent).; (Example 9) To 10.0 g of 5-norbornene-2, 3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 75percent) were added 21.0 g of water and 2.1 g of a 30 wtpercent aqueous solution of sodium hydroxide (0.13 equivalents relative to the 5-norbornene-2, 3-dicarboxylic anhydride mixture, 0.5 equivalents relative to 5-norbornene-endo-2, 3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 5.82 g (exo stereoisomeric ratio for the general formula (1) type = 96percent).; (Example 10) To 10.0 g of 5-norbornene-2, 3-dicarboxylic anhydride (endo stereoisomeric ratio for the general formula (1) type = 78percent) were added 13.6 g of water and 16.4 g of a 30 wtpercent aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2, 3-dicarboxylic anhydride mixture, 1.3 equivalents relative to 5-norbornene-endo-2, 3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration. The endo stereoisomeric ratio for the 5-norbornene-2, 3-dicarboxylic acid contained within the resulting filtrate was 95percent. Furthermore, the filtration residue was 4.21 g (exo stereoisomeric ratio for the general formula (1) type = 46percent).; (Example 11) To 10.0 g of 5-norbornene-2, 3-dicarboxylic anhydride (endo stereoisomeric ratio for the general formula (1) type = 25percent) were added 13.6 g of water and 16.3 g of a 30 wtpercent aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2, 3-dicarboxylic anhydride mixture, 4.0 equivalents relative to 5-norbornene-endo-2, 3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration. The endo stereoisomeric ratio for the 5-norbornene-2, 3-dicarboxylic acid contained within the resulting filtrate was 87percent. Furthermore, the filtration residue was 11.15 g (exo stereoisomeric ratio for the general formula (1) type = 89percent).; (Example 12) To 10.0 g of 5-norbornene-2, 3-dicarboxylic anhydride (endo stereoisomeric ratio for the general formula (1) type = 78percent) were added 1.1 g of water and 16.3 g of a 30 wtpercent aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2, 3-dicarboxylic anhydride mixture, 1.3 equivalents relative to 5-norbornene-endo-2, 3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration. The endo stereoisomeric ratio for the 5-norbornene-2, 3-dicarboxylic acid contained within the resulting filtrate was 96percent. Furthermore, the filtration residue was 12.11 g (exo stereoisomeric ratio for the general formula (1) type = 26percent).(Example 26) To 10.0 g of 5-norbornene-2, 3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48percent) were added 48.9 g of water and 1.6 g of a 30 wtpercent aqueous solution of sodium hydroxide (0.1 equivalents relative to the 5-norbornene-2, 3-dicarboxylic anhydride, 0.19 equivalents relative to 5-norbornene-endo-2, 3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 4.47 g (exo stereoisomeric ratio for the general formula (1) type = 50percent).; (Example 27) To 10.0 g of 5-norbornene-2, 3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48percent) were added 3.3 g of water and 87 g of a 45 wtpercent aqueous solution of sodium hydroxide (8.1 equivalents relative to the 5-norbornene-2, 3-dicarboxylic anhydride, 15.6 equivalents relative to 5-norbornene-endo-2, 3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 15.0 g (exo stereoisomeric ratio for the general formula (1) type = 51 percent).; (Example 28) To 10.0 g of 5-norbornene-2, 3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48percent) was added 8.6 g of a 30 wtpercent aqueous solution of sodium hydroxide (0.5 equivalents relative to the 5-norbornene-2, 3-dicarboxylic anhydride, 1.0 equivalents relative to 5-norbornene-endo-2, 3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 11.8 g (exo stereoisomeric ratio for the general formula (1) type = 52percent).; (Example 29) To 10.0 g of 5-norbornene-2, 3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48percent) were added 3.8 g of water and 66 g of a 30 wtpercent aqueous solution of sodium hydroxide (4.1 equivalents relative to the 5-norbornene-2, 3-dicarboxylic anhydride, 7.9 equivalents relative to 5-norbornene-endo-2, 3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 14.8 g (exo stereoisomeric ratio for the general formula (1) type = 55percent).Example 1Synthesis of monomers Exo-norbornene dicarboxylic anhydride (1)acetona />;[ /- f*

Molecular Weight:164.16
XLogP3:0.7
Hydrogen Bond Acceptor Count:3
Exact Mass:164.047344113
Monoisotopic Mass:164.047344113
Topological Polar Surface Area:43.4
Heavy Atom Count:12
Complexity:277
Defined Atom Stereocenter Count:4
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes