雙吡啶硫酮的合成改進

以2-巰基吡啶-N-氧化物為原料,30%過氧化氫-尿素加合物為氧化劑合成了雙吡啶硫酮,最佳反應條件是:n(原料):n(氧化劑)=1:1.25,反應溫度45℃,反應時間1.75 h。粗產物用乙醇重結晶,純度為99.6%,收率為91.6%。并用元素分析、紅外光譜和氫核磁共振譜對產物的結構進行了表征。 At the molar ratio of 1:1.25 and the reaction temperature of 45°C, Dipyrithion was obtained through reacting 2-pyridinethiol-N-oxide with 30% hydrogen peroxide-urea adduct for 1.75 h. The yield and purity were 91.6% and 99.6% respectively. The structures were characterized by elementary analysis, IR and 1H NMR

2,2’-(3-硝基-4-氯苯基)次甲基雙(3-羥基-5,5-二甲基-2-環己烯-1-酮)合成與晶體結構

以3-硝基-4-氯苯甲醛和5,5-二甲基-1,3-環己二酮為原料,二甲基甲酰胺為溶劑,不需催化劑合成一種新的氧雜蒽二酮開環衍生物2,2’-(3-硝基-4-氯苯基)次甲基雙(3-羥基-5,5-二甲基-2-環己烯-1-酮)晶體,確定最佳反應條件是:芳醛和脂肪環酮的摩爾投料比為1∶2,反應溫度為80℃,反應時間為1 h;并對其進行熔點、元素分析、紅外光譜、氫核磁共振及X-射線單晶衍射測定。該晶體為單斜晶系,空間群=P21/n,a=1.95777 (13) nm,b=1.22720 (9) nm,c=1.99687 (14) nm,β=107.719 (2) °,V=4.5700 (6) nm3,Z=8,dC=1.302 g/m3,μ=0.205 mm-1,F (000) =1888。 At the molar ratio of 1:1.2 and 80°C, a novel crystal 2, 2'-(3-nitro-4-chlorobenzyl) methylene bis(3-hydroxy-5, 5-dimethyl-2-cyclohexene-1-one), was synthesized through reacting 3-nitro-4-chlorobenzaldehyde with 5, 5-Dimethyl-1, 3-cyclohexanedione using DMF as the solvent for 1 h in the absence of any catalyst. The structure was characterized by melting points, elemental analysis, IR, 1H NMR and X-ray single crystal diffractometer. The result shows the crystal in monoclinic crystal system and P21/n space group. Crystallographic date: a=1.95777(13) nm, b=1.22720(9) nm, c=1.99687(14) nm, β=107.719(2)°, V=4.5700(6) nm3, Z=8, dC=1.302 g/m3, μ=0.205 mm-1, F(000)=1888

FeCl3/ZnCl2加壓催化酰化制備4-氯二苯甲酮工業化技術

研究了在加壓和FeCl3/ZnCl2催化下,4-氯苯甲酰氯和苯發生Friedel-Crafts反應制備4-氯二苯甲酮的工藝。157.6 g苯、88.2 g 4-氯苯甲酰氯和1.3 g FeCl3/ZnCl2混合于1 L的高壓釜中,在壓力為(0.85～1.1)×106Pa、溫度為175～185℃的條件下反應8 h,經純化處理得到4-氯二甲苯酮93.1 g,摩爾收率為86.2%,w(4-氯二苯甲酮)=99.8%(HPLC)。探討了壓力、催化劑和投料比等對收率的影響。經過一次性投料4-氯苯甲酰氯175 kg的生產型中試驗證,4-氯二苯甲酮摩爾收率為82.7%。 The preparation of 4-chlorobenzophenone by acylation of benzene with 4-chlorobenzoyl chloride in the presence of FeCl3/ZnCl2 catalyst under pressure was studied.157.6 g benzene was mixed with 88.2 g 4-chlorobenzoyl chloride and 1.3 g FeCl3/ZnCl2 in a 1 L autoclave.The mixture reacted for 8 h under(0.85-1.1)×106 Pa and at 175-185 ℃ to give 93.1 g 4-chlorobenzophenone with a yield of 86.2% and a purity of 99.8%(by HPLC).The effects of pressure,catalyst and ratio of raw materials on the yield were also investigated.The experimental results were proved by a productive scale-up test,in which 175 kg 4-chlorobenzoyl chloride was used as raw material to afford 4-chlorobenzophenone in a molar yield of 82.7%

合成2-(三溴甲磺酰基)吡啶的工藝改進

聚乙二醇-400催化2-氯吡啶(1)與甲硫醇鈉反應合成了2-甲硫基吡啶(2);2與次溴酸鈉經氧化和溴化反應合成了2-三溴甲磺酰吡啶(3),其結構經1H NMR,IR和元素分析確證。合成2的最佳反應條件為:1 100mmol,甲硫醇鈉0.12 mol,聚乙二醇-400(1.2 mL)為催化劑,于80℃反應4 h,收率98%。合成3的最佳反應條件為:2 95 mmol,n(2)∶n(溴素)=1.00∶6.58,于8℃反應5 h,收率95.1%,純度99.6%。 2-Methylthiopyridine( 2) was obtained by reaction of 2-chloropyridine and sodium methylmercaptide using polyethylene glycol 400 as the phase transfer catalyst． 2-Pyridyl tribromomethyl sulfone( 3) was synthesized by oxdation and bromination reaction of 2． The structures were confirmed by 1 H NMＲ，IＲ and elemental analysis． The optimum reaction conditions at 80 ℃ for 4 h of synthesizing 2 were as followes: 1 was 100 mmol，sodium methylmercaptide was 0． 12 mol，and PEG-400( 1． 2mL) was the catalyst，the yield was 98% ． The optimum reaction conditions at 8 ℃ for 5 h of synthesizing 3 were as followes: 2 was 95 mmol，n( 2) ∶ n( bromine) = 1． 00 ∶ 6． 58，the yield was 99． 6% and the purity was 95． 1%

一种平喘药中间体1,1-环丙烷二甲醇的制备

以季戊四醇與氫溴酸為原料、硫酸二乙酯-醋酸為催化劑,回流10h合成二溴新戊二醇,收率為91.7%;以二溴新戊二醇與鋅粉為原料、乙醇-水為溶劑合成1.1-環丙烷二甲醇,最佳條件是:n(二溴新戊二醇)∶n(鋅粉)=1∶1.05,反應溫度80℃(微回流),反應時間7h,收率為87.3%,純度為98.7%,并用元素分析、IR和1 H NMR對1.1-環丙烷二甲醇結構進行了表征。Refluxing for 10 h, 2, 2-bis (bromomethyl)-l, 3-propanediol was synthesised at yield of 91.7% from pentaerythritol and bromohydric acid with diethylsulfate and acetic acid as catalysts. Then at the molar ratio of 1 : 1. 05 and 80 °C, 1, 1-bis (hydroxymethyl) cyclopropane was obtained through reacting 2, 2-bis (bromomethyl)-1, 3-propanediol with zinc powder in ethanol-water medium for 7 h. The yield and purity were 87. 3% and 98. 7% respectively. The structures were characterized by elementary analysis, IR and 1H NMR