化学性质
呋喃酚纯品为无色液体。沸点(78℃/40.0Pa)和(92℃/267Pa),相对密度1.101(20℃),黏度为170.12×10⁻³Pa·s,比热容为1.40J/(g·℃),汽化热为108.7J/g,燃烧热为5164.6kJ/mol。它能溶于二氯甲烷、甲苯、醇和醚等有机溶剂,但不溶于水。
用途
2,3-二氢-2,2-二甲基-7-羟基苯并呋喃(简称7-羟基呋喃酚或呋喃酚)是合成克百威(呋喃丹)的重要中间体。它是生产农药克百威的主要中间体之一。
生产方法
在国外,除了美国FMC公司外,挪威鲍利葛公司和日本三菱公司也有生产克百威的中间体呋喃酚。匈牙利有少量生产,但质量不佳。文献报道了多种合成路线,包括邻硝基酚法、愈创木酚法、邻氯苯酚法、羟基苯乙酮法、邻异丙基酚法、环己酮法、苯并呋喃法和邻苯二酚法等。其中,邻苯二酚法的反应步骤最少,收率可达64%,原料邻苯二酚价格低廉且易得,因此该方法是较为理想的选择。
以邻苯二酚为原料合成呋喃酚的方法有三种,其中最适宜的是与甲基烯丙基氯(MAC)反应的方法。此过程总收率为64%以上,并已被美国FMC公司成功应用于工业生产装置。
2-甲基烯丙基氯(MAC)的合成
异丁烯和液氯分别计量并汽化后,按一定配比通入反应器内,反应强烈放热。需严格控制反应接触时间并在瞬间混合均匀进行反应。反应后的物料进入反应蒸发器移除反应热,再通过吸收冷凝器将氯化氢吸收成盐酸。随后经过冷却和油酸分离步骤,盐酸可作为副产品出售;有机层经分馏得到MAC产品,含量可达95%~98%。
邻(2-甲基烯丙氧基)苯酚(简称单醚)的合成
将邻苯二酚、无水碳酸钠和溶剂按合理比例加入反应釜中,并在搅拌下滴加2-甲基烯丙基氯。控制反应温度,分出生成的水分后冷却并过滤除去盐渣,再减压脱溶得到产品单醚。
2,3-二氢-2,2-二甲基-7-羟基苯并呋喃(简称呋喃酚)的合成
将单醚、催化剂和二甲苯按一定比例加入闭环釜中,在搅拌加热至反应温度后进行闭环反应。随后减压脱溶蒸出二甲苯循环套用,脱溶后的物料进行减压精馏,所得产物呋喃酚含量≥95%,精馏残渣送三废处理。
中文名称 | 英文名称 | CAS号 | 化学式 | 分子量 |
---|---|---|---|---|
克百威 | 2,3-dihydro-2,2-dimethyl-7-benzofuranol methylcarbamate | 1563-66-2 | C12H15NO3 | 221.256 |
苯并呋喃,7-氯-2,3-二氢-2,2-二甲基- | 7-chloro-2,3-dihydro-2,2-dimethylbenzofuran | 10178-55-9 | C10H11ClO | 182.65 |
7-溴-2,2-二甲基-2,3-二氢-1-苯并呋喃 | 7-bromo-2,3-dihydro-2,2-dimethylbenzofuran | 10178-57-1 | C10H11BrO | 227.101 |
丁硫克百威 | carbosulfan | 55285-14-8 | C20H32N2O3S | 380.552 |
中文名称 | 英文名称 | CAS号 | 化学式 | 分子量 |
---|---|---|---|---|
—— | 7-methoxy-2,2-dimethyl-2,3-dihydrobenzofuran | —— | C11H14O2 | 178.231 |
—— | 7-isopropoxy-2,2-dimethyl-2,3-dihydrobenzofuran | 1346169-07-0 | C13H18O2 | 206.285 |
—— | 2-(2,2-dimethyl-2,3-dihydrobenzofuran-7-oxy)ethanol | —— | C12H16O3 | 208.257 |
—— | 2,2-dimethyl-7-(prop-2-enyloxy)-2,3-dihydrobenzofuran | 87386-25-2 | C13H16O2 | 204.269 |
7-(2-氯-乙氧基)-2,2-二甲基-2,3-二氢-苯并呋喃 | 7-(2-chloro-ethoxy)-2,2-dimethyl-2,3-dihydro-benzofuran | 104392-19-0 | C12H15ClO2 | 226.703 |
—— | 7-(2-bromoethoxy)-2,2-dimethyl-2,3-dihydrobenzofuran | 150375-54-5 | C12H15BrO2 | 271.154 |
—— | 3-(2,2-dimethyl-2,3-dihydrobenzofuran-7-oxy)propanol | —— | C13H18O3 | 222.284 |
2-(2,2-二甲基-2,3-二氢苯并呋喃-7-基氧基)乙胺 | 2-(2,2-dimethyl-2,3-dihydro-benzofuran-7-yloxy)-ethylamine | 680203-71-8 | C12H17NO2 | 207.272 |
—— | 7-(3-bromopropoxy)-2,3-dihydro-2,2-dimethylbenzofuran | 250289-95-3 | C13H17BrO2 | 285.181 |
—— | 3-((2,2-dimethyl-2,3-dihydrobenzofuran-7-yl)oxy)propanenitrile | —— | C13H15NO2 | 217.268 |
—— | 4-(2,2-dimethyl-2,3-dihydrobenzofuran-7-oxy)butanol | 884604-54-0 | C14H20O3 | 236.311 |
—— | 1-(2,2-dimethyl[2,3]dihydrobenzofuran-7-yloxy)-4-bromobutane | 1094709-97-3 | C14H19BrO2 | 299.208 |
—— | 2,2-dimethyl-6-(prop-2-enyl)-2,3-dihydrobenzofuran-7-ol | 87386-26-3 | C13H16O2 | 204.269 |
(2,2-二甲基-2,3-二氢-苯并呋喃-7-基氧基)-乙酸 | 2-((2,2-dimethyl-2,3-dihydrobenzofuran-7-yl)oxy)acetic acid | 265119-94-6 | C12H14O4 | 222.241 |
—— | 4-((2,2-dimethyl-2,3-dihydrobenzofuran-7-yl)oxy)butanoic acid | —— | C14H18O4 | 250.295 |
7-乙酰氧基-2,3-二氢-2,2-二甲基-苯并呋喃 | 2,2-dimethyl-2,3-dihydrobenzofuran-7-yl acetate | 21620-95-1 | C12H14O3 | 206.241 |
—— | 5-chloro-2,2-dimethyl-2,3-dihydrobenzofuran-7-ol | 4790-91-4 | C10H11ClO2 | 198.649 |
—— | methyl 2-((2,2-dimethyl-2,3-dihydrobenzofuran-7-yl)oxy)acetate | —— | C13H16O4 | 236.268 |
—— | ethyl 2-((2,2-dimethyl-2,3-2,3-dihydrobenzofuran-7-yl)oxy)acetate | —— | C14H18O4 | 250.295 |
—— | 2-((2,2-dimethyl-2,3-dihydrobenzofuran-7-yl)oxy)acetohydrazide | —— | C12H16N2O3 | 236.271 |
—— | 2,3-dihydro-2,2-dimethyl-7-benzofuranyl chloroformate | 4790-86-7 | C11H11ClO3 | 226.66 |
—— | 7-(3-isopropylamino-2-hydroxypropoxy)-2,3-dihydro-2,2-dimethylbenzofuran | —— | C16H25NO3 | 279.379 |
2,3-二氢-2,2-二甲基苯并呋喃 | 2,2-dimethyl-2,3-dihydro-1-benzofuran | 6337-33-3 | C10H12O | 148.205 |
—— | 7-(3-t-butylamino-2-hydroxypropoxy)-2,3-dihydro-2,2-dimethylbenzofuran | —— | C17H27NO3 | 293.406 |
—— | 7-[3-(1-methyl)propylamino-2-hydroxypropoxy]-2,3-dihydro-2,2-dimethylbenzofuran | —— | C17H27NO3 | 293.406 |
克百威 | 2,3-dihydro-2,2-dimethyl-7-benzofuranol methylcarbamate | 1563-66-2 | C12H15NO3 | 221.256 |
—— | 2,3-dihydro-2,2-dimethyl-5-methylthio-7-benzofuranol | —— | C11H14O2S | 210.297 |
—— | 7-(3-diisopropylamino-2-hydroxypropoxy)-2,3-dihydro-2,2-dimethylbenzofuran | —— | C19H31NO3 | 321.46 |
—— | hydroxymethylcarbamic acid 2,2-dimethyl-2,3-dihydrobenzofuran-7-yl ester | 18999-70-7 | C12H15NO4 | 237.255 |
—— | 3-(4-(((2,2-dimethyl-2,3-dihydrobenzofuran-7-yl)oxy)methyl)bicyclo[2.2.2]octan-1-yl)propanoic acid | —— | C22H30O4 | 358.478 |
—— | (±)-2-[(2,2-dimethyl-2,3-dihydro-1-benzofuran-7-yl)oxy]-3-phenylpropanoic acid | —— | C19H20O4 | 312.365 |
7-羟基-2,2-二甲基-3(2H)-苯并呋喃酮 | 2,3-dihydro-2,2-dimethyl-3-oxobenzofuran-7-ol | 17781-16-7 | C10H10O3 | 178.188 |
—— | 2,2-Dimethyl-2,3-dihydro-1-benzofuran-7-yl 1-chloroethyl carbonate | 101506-44-9 | C13H15ClO4 | 270.713 |
—— | 7-[3-(4-benzyl-1-piperazinyl)propoxy]-2,3-dihydro-2,2-dimethylbenzofuran | —— | C24H32N2O2 | 380.53 |
4-溴-7-甲氧基-2,2-二甲基-2,3-二氢-1-苯并呋喃 | 4-Bromo-7-methoxy-2,2-dimethyl-2,3-dihydro-benzofuran | 185406-76-2 | C11H13BrO2 | 257.127 |
4-[[(2,3-二氢-2,2-二甲基-7-苯并呋喃氧基)羰基]氨基]丁酸 | 4-[[(2,3-dihydro-2,2-dimethyl-7-benzofuranyloxy)carbonyl]amino]butanoic acid | 223922-62-1 | C15H19NO5 | 293.32 |
—— | 7-[3-(4-phenyl-1-piperazinyl)propoxy]-2,3-dihydro-2,2-dimethylbenzofuran | —— | C23H30N2O2 | 366.503 |
—— | 2,2-dimethyl-2,3-dihydrobenzofuran-7-yl 4-fluorophenethylcarbamate | —— | C19H20FNO3 | 329.371 |
—— | 2,2-dimethyl-2,3-dihydrobenzofuran-7-yl cyclohexylcarbamate | —— | C17H23NO3 | 289.375 |
—— | 4,6-dibromo-2,2-dimethyl-2,3-dihydro-1-benzofuran-7-ol | 478010-80-9 | C10H10Br2O2 | 321.996 |
—— | 5-(((2,2-dimethyl-2,3-dihydrobenzofuran-7-yl)oxy)methyl)-1,3,4-thiadiazol-2-amine | —— | C13H15N3O2S | 277.347 |
—— | 2,3-dihydro-2,2-dimethyl-5-nitro-7-benzofuranol | 113194-07-3 | C10H11NO4 | 209.202 |
—— | 2,2-dimethyl-2,3-dihydrobenzofuran-7-yl trifluoromethanesulfonate | 308110-31-8 | C11H11F3O4S | 296.267 |
—— | 7-[3-[4-(2-pyrimidinyl)-1-piperazinyl]propoxy]-2,3-dihydro-2,2-dimethylbenzofuran | —— | C21H28N4O2 | 368.479 |
—— | 2,3-dihydro-2,2-dimethyl-6-nitro-7-benzofuranol | 832713-81-2 | C10H11NO4 | 209.202 |
—— | 2,3-dihydro-2,2-dimethyl-7-benzofuranyl N-chloroacetyl-N-methylcarbamate | 32515-39-2 | C14H16ClNO4 | 297.738 |
—— | 7-[3-[4-(4-fluorophenyl)-1-piperazinyl]propoxy]-2,3-dihydro-2,2-dimethylbenzofuran | —— | C23H29FN2O2 | 384.494 |
—— | 2,2-dimethyl-7,8-dihydro-2H-furo[3,2-h]chromen-6(3H)-one | —— | C13H14O3 | 218.252 |
—— | 2-[4-(2,2-dimethyl(2,3-dihydrobenzo[2,3-b]furan-7-yloxy))butoxy]-1,3-dichloro-5-(phenylmethoxy)benzene | 791063-98-4 | C27H28Cl2O4 | 487.423 |
(2,2-二甲基-2,3-二氢-1-苯并呋喃-7-基)甲醇 | 2,3-dihydro-2,2-dimethylbenzofuran-7-ylmethanol | 38002-89-0 | C11H14O2 | 178.231 |
—— | 7-[3-(4-phenyl-1-piperazinyl)-2-hydroxypropoxy]-2,3-dihydro-2,2-dimethylbenzofuran | —— | C23H30N2O3 | 382.503 |
2,2-二甲基-2,3-二羟基-1-苯并呋喃-7-甲醛 | 2,2-dimethyl-2,3-dihydrobenzofuran-7-carbaldehyde | 38002-88-9 | C11H12O2 | 176.215 |
—— | 3-(4-(((5-chloro-2,2-dimethyl-2,3-dihydrobenzofuran-7-yl)oxy)methyl)bicyclo[2.2.2]octan-1-yl)propanoic acid | —— | C22H29ClO4 | 392.923 |
—— | 2,2-Dimethyl-2,3-dihydro-7-[N-methyl-N-(N'-methyl-N'-fluorocarbonyl-aminosulfenyl)-carbamoyloxy]benzofuran | —— | C14H17FN2O4S | 328.364 |
—— | 7-[N-methyl-N-(N'-methyl-N'-fluorocarbonylaminothiosulfenyl)carbamoyloxy]-2,3-dihydro-2,2-dimethylbenzofuran | —— | C14H17FN2O4S2 | 360.43 |
—— | N-(2-isobutyronitrilesulfenyl)-(2,3-dihydro-2,2-dimethyl-7-benzofuranyl)-N-methyl carbamate | 78744-19-1 | C16H20N2O3S | 320.412 |
—— | 3-(2,2-dimethyl-2,3-dihydrobenzofuran-7-yl)propanoic acid | —— | C13H16O3 | 220.268 |
—— | F15063 | 680203-70-7 | C24H29NO2 | 363.5 |
2,2-二甲基-2,3-二氢-1-呋喃-7-胺 | 2,3-dihydro-2,2-dimethylbenzofuran-7-amine | 68298-46-4 | C10H13NO | 163.219 |
—— | 7-[3-[4-(4-fluorophenyl)-1-piperazinyl]-2-hydroxypropoxy]-2,3-dihydro-2,2-dimethylbenzofuran | —— | C23H29FN2O3 | 400.493 |
—— | 7-[3-[4-(2-methoxyphenyl)-1-piperazinyl]propoxy]-2,3-dihydro-2,2-dimethylbenzofuran | —— | C24H32N2O3 | 396.53 |
—— | 7-[3-[4-(2-pyridyl)-1-piperazinyl]propoxy]-2,3-dihydro-2,2-dimethylbenzofuran | —— | C22H29N3O2 | 367.491 |
—— | 3-chloro-4-(2,3-dihydro-2,2-dimethyl-7-benzofuranyloxy)-1-nitrobenzene | 83054-76-6 | C16H14ClNO4 | 319.744 |
—— | (E)-3-(4-(((5-chloro-2,2-dimethyl-2,3-dihydrobenzofuran-7-yl)oxy)methyl)bicyclo[2.2.2]octan-1-yl)acrylic acid | —— | C22H27ClO4 | 390.907 |
—— | 4,5,6-tribromo-2,2-dimethyl-2,3-dihydrobenzofuran-7-ol | —— | C10H9Br3O2 | 400.892 |
—— | 2,2-Dimethyl-2,3-dihydro-7-[N-methyl-N-(4-tert-butylphenylthiosulfenyl)carbamoyloxy] benzofuran | —— | C22H27NO3S2 | 417.593 |
—— | 3,5-dichloro-4-(2,3-dihydro-2,2-dimethyl-7-benzofuranyloxy)-1-nitrobenzene | 83054-15-3 | C16H13Cl2NO4 | 354.19 |
—— | O-Ethyl-O-(2,3-dihydro-2,2-dimethyl-7-benzofuranyl)ethylthionophosphonate | 96408-50-3 | C14H21O3PS | 300.359 |
—— | 2,3-dihydro-2,2-dimethyl-4-nitro-7-benzofuranol | —— | C10H11NO4 | 209.202 |
—— | 7-[3-[4-(2-methoxyphenyl)-1-piperazinyl]-2-hydroxypropoxy]-2,3-dihydro-2,2-dimethylbenzofuran | —— | C24H32N2O4 | 412.529 |
—— | 7-[3-[4-(2-pyridyl)-1-piperazinyl]-2-hydroxypropoxy]-2,3-dihydro-2,2-dimethylbenzofuran | —— | C22H29N3O3 | 383.491 |
—— | 4-Benzoyl-7-methoxy-2,2-dimethyl-2,3-dihydrobenzofuran | —— | C18H18O3 | 282.339 |
—— | 2-(2-(2,2-dimethyl-2,3-dihydrobenzofuran-7-oxy)ethyl)isoindoline-1,3-dione | 928403-39-8 | C20H19NO4 | 337.375 |
—— | O-Ethyl-S-n-propyl-O-(2,3-dihydro-2,2-dimethyl-7-benzofuranyl)thiophosphate | 96408-29-6 | C15H23O4PS | 330.385 |
—— | 5-chloro-2,2-dimethyl-2,3-dihydro-1-benzofuran-7-amine | 1189580-19-5 | C10H12ClNO | 197.664 |
—— | 2-(((2,2-dimethyl-2,3-dihydrobenzofuran-7-yl)oxy)methyl)-5-(4-methoxyphenyl)-1,3,4-oxadiazole | —— | C20H20N2O4 | 352.39 |
—— | [2-(2,2-dimethyl-2,3-dihydrobenzofuran-7-yl-oxy)ethyl]-(5-cyclopenten-1-ylpyridin-3-ylmethyl)amine | —— | C23H28N2O2 | 364.488 |
—— | 2,2,5,7-tetramethyl-2,3,7,8-tetrahydro-5H-furo<2,3-g>benzopyran-9-ol | —— | C15H20O3 | 248.322 |
—— | methyl 2,2-dimethyl-2,3-dihydro-1-benzofuran-7-carboxylate | 99517-60-9 | C12H14O3 | 206.241 |
—— | 2-(2,2-dimethyl-2,3-dihydrobenzofuran-7-yloxy)-3-nitropyridine | 790249-60-4 | C15H14N2O4 | 286.287 |
—— | N-(benzo[d]thiazol-2-yl)-2-((2,2-dimethyl-2,3-dihydrobenzofuran-7-yl)oxy)acetamide | —— | C19H18N2O3S | 354.43 |