고 에너지 작용기를 함유한 옥세탄 단량체의 합성법 개발

Abstract

고 에너지 옥세탄의 상용화를 위하여 실험 방법의 개선과 촉매에 따른 수율변화를 실험하였다. 이번 실험은 3-hydroxymethyl-3-methyloxetane(HMMO), 3-Methyl-3-(toluene-sulfonyloxymethyl)oxetane(TMMO), 3-azidomethyl-3-methyl-oxetane(AMMO), 3,3-bis(hydroxylmethyl)oxetane(BHMO), 3,3-bis(toluenesulfonyloxymethyl)oxetane(BTMO), 3,3-bis(azido-methyl)oxetane(BAMO)를 합성하였다. HMMO의 합성 출발물질로는 1,1,1-tris(hydroxymethyl)ethane과 diethyl carbonate 를, TMMO의 경우 HMMO와 p-toluenesulfonyl chloride를, BHMO합성에는 출발물질로 pentaerythritol과 diethyl carbonate를, BTMO의 경우 BHMO와 p-toluenesulfonyl chloride를 사용하여 합성하였다. 3-Methyl-3-nitratomethyloxetane(NMMO)을 합성하기 위하여 HMMO에 acetic acid anhydride와 anhydrous nitric acid의 혼합물을 적가하였다. TMMO와 BTMO를 NaN₃(sodium azide)로 반응시켜 각각 3-azidomethyl-3-methyloxetane(AMMO)와 3,3-bis(azidomethyl)oxetane(BAMO)을 합성하였다. 제조공정을 줄이기 위해 TMMO와 BTMO의 crude product를 NaN₃로 각각 반응시켜 순수한 AMMO와 BAMO를 얻었다. AMMO는 66%, BAMO는 70%로써 정제한 TMMO와 BTMO로 합성하였을 경우보다 각각 16%와 18%가 감소되었지만 BHMO로부터 최종 수율을 비교해 보면 차이가 별로 없으며 오히려 정제단계공정을 줄임으로써 pure product를 얻기까지의 공정 시간 감소와 용매사용을 줄일 수 있었다. BHMO의 경우 Na와 NaH를 촉매로 사용하였을 때 각각 47%와 60%였던 수율이 t-sodium butoxide를 촉매로 사용함 으로써 화재위험도 줄고 수율도 3~16%정도 증가하였다.; This study effectively improved synthetic process and yield of an energetic oxetane. In this experiment, 3-hydroxymethyl-3-methyloxetane(HMMO), 3-methyl-3-(tol-uenesulfonyloxymethyl)oxetane(TMMO), 3-azidomethyl-3-methyloxetane(AMMO), 3,3-bis(hydroxylmethyl)oxetane(BH-MO), 3,3-bis(toluenesulfonyloxymethyl)oxetane(BTMO), 3,3-bis(azidomethyl)oxetane(BAMO) were synthesized. 1,1,1-Tris(hydroxymethyl)ethane and pentaerythritol and diethyl carbonate were used as starting reagents for synthesis of HMMO and BHMO, respectively. TMMO and BTMO were prepared from reacting HMMO and BHMO with p-toluenesulfonyl chloride, respectively. AMMO and BAMO were respectively synthesized by substitution reaction of tosyl groups of TMMO and BTMO with azide. A mixture of acetic acid anhydride and anhydrous nitric acid was added into HMMO solution to obtain 3-methyl-3-nitratomethyl-oxetane (NMMO). In order to simplify the procedure by removing recystalization, AMMO and BAMO were prepared by respectively reacting the crude TMMO and crude BTMO with NaN3. Although the obtained yields of AMMO and BAMO decreased by 16% and 18% comparing to the previous synthetic method which used pure TMMO and BTMO, this procedure drastically reduces the process time and does not require the recrystallization steps. Therefore, the entire efficiency of the synthesizing process is much better than that of the previous synthesizing method. In addition, the fire hazard, which existed in the previous synthetic method, was completely eliminated because sodium t-butoxide was used as catalyst instead of sodium metal or NaH for synthesizing BHMO.