以甲基苯基硫醚为原料,经付克酰基化、胺取代两步反应制得2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮(光引发剂MMMP),中间体、产物结构经1 H NMR,MS表征。重点考察了催化剂用量、温度、时间对付克酰基化反应收率的影响,以及原料配比、催...以甲基苯基硫醚为原料,经付克酰基化、胺取代两步反应制得2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮(光引发剂MMMP),中间体、产物结构经1 H NMR,MS表征。重点考察了催化剂用量、温度、时间对付克酰基化反应收率的影响,以及原料配比、催化剂用量、溶剂种类对胺取代反应收率的影响,两步反应总收率达到85.0%。新工艺操作简单,反应条件温和,成本低,原料利用率高,适合工业化生产。展开更多
A series of experiments were conducted in a self-made smog chamber at （300 ＋ 1） K and 1.01 × 10^5 Pa to simulate the photochemical reaction of ethyl methyl sulfide （EMS） and NOx. The results showed that the ...A series of experiments were conducted in a self-made smog chamber at （300 ＋ 1） K and 1.01 × 10^5 Pa to simulate the photochemical reaction of ethyl methyl sulfide （EMS） and NOx. The results showed that the higher the initial concentration of EMS, the more ozone was generated in the simulative reactions. It was found that the light intensity plays a very important role in the evaluation of ozone formation potential for EMS. The parameters of d（Oa-NO） and IR （incremental reactivity） were used to quantify the potential of EMS on ozone formation. The obtained maximum IR values in this article for the five simulative reactions were 1.55 × 10^-2, 0.99 × 10^-2, 1.36 × 10^-2, 2.47 × 10^-2, and 1.65 × 10^-2, respectively. A comparison between the results we obtained here and the results we obtained previously for di-tert-butyl peroxide and acetylene showed that the potential reactivity of EMS on ozone formation was at a relatively low level.展开更多
The rate constants for the ozone reactions with n-butyl methyl sulfide (n-BMS, CH3CH2CH2CH2SCH3), sec-butyl methyl sulfide (s-BMS, CH3CH2(CH3)CHSCH3) and tert-butyl methyl sulfide (t-BMS, (CH3)3CSCH3) were measured us...The rate constants for the ozone reactions with n-butyl methyl sulfide (n-BMS, CH3CH2CH2CH2SCH3), sec-butyl methyl sulfide (s-BMS, CH3CH2(CH3)CHSCH3) and tert-butyl methyl sulfide (t-BMS, (CH3)3CSCH3) were measured using our smog chamber under supposedly pseudo-first-order conditions at 300±2 K and 760 Torr. The experimental determined rate constants for n-butyl, s-butyl and t-butyl methyl sulfide are (1.23 ± 0.06)×10-19, (5.08 ± 0.19)×10?20 and (2.26 ± 0.14)×10?20 cm3·molecule-1·s-1, respectively. The reactivity-structure relationship of the reactions was discussed and used to illustrate the mechanism of the ozone reaction with thioethers. The results enrich the kinetics data of atmospheric chemistry.展开更多
文摘以甲基苯基硫醚为原料,经付克酰基化、胺取代两步反应制得2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮(光引发剂MMMP),中间体、产物结构经1 H NMR,MS表征。重点考察了催化剂用量、温度、时间对付克酰基化反应收率的影响,以及原料配比、催化剂用量、溶剂种类对胺取代反应收率的影响,两步反应总收率达到85.0%。新工艺操作简单,反应条件温和,成本低,原料利用率高,适合工业化生产。
基金supported by the Knowledge Innovation Program of the Chinese Academy of Sciences(No. KZCX2-YW-205)the National Natural Sci-ence Foundation of China (No. 20577052, 20673123,20503035).
文摘A series of experiments were conducted in a self-made smog chamber at （300 ＋ 1） K and 1.01 × 10^5 Pa to simulate the photochemical reaction of ethyl methyl sulfide （EMS） and NOx. The results showed that the higher the initial concentration of EMS, the more ozone was generated in the simulative reactions. It was found that the light intensity plays a very important role in the evaluation of ozone formation potential for EMS. The parameters of d（Oa-NO） and IR （incremental reactivity） were used to quantify the potential of EMS on ozone formation. The obtained maximum IR values in this article for the five simulative reactions were 1.55 × 10^-2, 0.99 × 10^-2, 1.36 × 10^-2, 2.47 × 10^-2, and 1.65 × 10^-2, respectively. A comparison between the results we obtained here and the results we obtained previously for di-tert-butyl peroxide and acetylene showed that the potential reactivity of EMS on ozone formation was at a relatively low level.
基金Knowledge Innovation Program of the Chinese Academy of Sciences (Grant No. KZCX2-YW-205)National Basic Research Program of China (973 Program) (Grant No. 2006CB403701)National Natural Science Foundation of China (Grant Nos. 20577052 and 20673123)
文摘The rate constants for the ozone reactions with n-butyl methyl sulfide (n-BMS, CH3CH2CH2CH2SCH3), sec-butyl methyl sulfide (s-BMS, CH3CH2(CH3)CHSCH3) and tert-butyl methyl sulfide (t-BMS, (CH3)3CSCH3) were measured using our smog chamber under supposedly pseudo-first-order conditions at 300±2 K and 760 Torr. The experimental determined rate constants for n-butyl, s-butyl and t-butyl methyl sulfide are (1.23 ± 0.06)×10-19, (5.08 ± 0.19)×10?20 and (2.26 ± 0.14)×10?20 cm3·molecule-1·s-1, respectively. The reactivity-structure relationship of the reactions was discussed and used to illustrate the mechanism of the ozone reaction with thioethers. The results enrich the kinetics data of atmospheric chemistry.
