CN112920089B - 一种光催化合成取代脲类化合物的方法 - Google Patents
一种光催化合成取代脲类化合物的方法 Download PDFInfo
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- CN112920089B CN112920089B CN202110137787.6A CN202110137787A CN112920089B CN 112920089 B CN112920089 B CN 112920089B CN 202110137787 A CN202110137787 A CN 202110137787A CN 112920089 B CN112920089 B CN 112920089B
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- substituted urea
- catalyst
- urea
- solvent
- reaction
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000004202 carbamide Substances 0.000 title claims abstract description 23
- -1 urea compound Chemical class 0.000 title claims abstract description 21
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 6
- 150000003672 ureas Chemical class 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000005286 illumination Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052724 xenon Inorganic materials 0.000 claims description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 4
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 9
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000010189 synthetic method Methods 0.000 abstract description 3
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 231100000086 high toxicity Toxicity 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 14
- 238000001819 mass spectrum Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- KATOLVAXCGIBLO-UHFFFAOYSA-N 1,3-dibenzylurea Chemical compound C=1C=CC=CC=1CNC(=O)NCC1=CC=CC=C1 KATOLVAXCGIBLO-UHFFFAOYSA-N 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 7
- 239000012265 solid product Substances 0.000 description 7
- KBUJZXRBTOBXKN-UHFFFAOYSA-N 1,3-bis(furan-2-ylmethyl)urea Chemical compound C=1C=COC=1CNC(=O)NCC1=CC=CO1 KBUJZXRBTOBXKN-UHFFFAOYSA-N 0.000 description 6
- OAXACVUBJMHKTD-UHFFFAOYSA-N 1,3-dinaphthalen-1-ylurea Chemical compound C1=CC=C2C(NC(NC=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 OAXACVUBJMHKTD-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- NLCAUVFHXKUYMZ-UHFFFAOYSA-N 1,3-dioctylurea Chemical compound CCCCCCCCNC(=O)NCCCCCCCC NLCAUVFHXKUYMZ-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- AQSQFWLMFCKKMG-UHFFFAOYSA-N 1,3-dibutylurea Chemical compound CCCCNC(=O)NCCCC AQSQFWLMFCKKMG-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
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- KVGMATYUUPJFQL-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++] KVGMATYUUPJFQL-UHFFFAOYSA-N 0.000 description 2
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- UTFRXHNWUFPRPQ-UHFFFAOYSA-N 2,3-dichloro-1-methyl-4-propan-2-ylbenzene;ruthenium(2+) Chemical class [Ru+2].CC(C)C1=CC=C(C)C(Cl)=C1Cl UTFRXHNWUFPRPQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及有机合成技术领域，具体涉及一种光催化合成取代脲类化合物的方法。所述方法具体包括：将四卤甲烷与溶剂混合后，先后加入胺类化合物、催化剂，在含氧氛围和光照条件下搅拌反应后经分离纯化获得取代脲类化合物；本发明的合成方法的原料来源广泛，反应后产的副产物为卤素单质，附加值高，一方面避免了采用毒性大的光气、三光气等为原料，另一方面避免产生大量的废弃物，且催化剂可循环使用，减少了制备过程对环境的影响，提高了反应的原子利用率。
Description
技术领域
本发明涉及有机合成技术领域，具体涉及一种光催化合成取代脲类化合物的方法。
背景技术
取代脲是一类重要的精细化学品，广泛应用于工业、农业、制药等行业。在取代脲的结构单元中含有不同取代的肽键，因而其具有优良的生物活性，在医药和生物领域具有举足轻重的地位。取代脲不仅在除草、植物生长调节、杀虫、以及杀菌、抗植物病毒等方面具有重要的用途，也可用于药物和染料的制备，取代脲还可作为石油、烃类燃料以及聚合物的添加剂，如缓蚀剂、抗氧剂、抗沉淀剂等。
取代脲化合物的合成方法主要有：光气法、三光气法、氯甲酸乙酯法、叠氮化合物法、一氧化碳羰基化法、N-取代三氯乙酰苯胺法、N-丁间酮酰苯胺法、硝基胺甲酰化法等。工业上合成取代脲的传统方法是采用光气或基于光气的异氰酸酯法，通过异氰酸酯与胺的加成得到取代脲。光气法虽然比较实用，光气的制备也较容易，价格低廉，但光气有剧毒，对人和环境的危害都较大。叠氮化合物本身容易***，操作过程控制难度大、危险性高，而且反应过程中均需要合成异氰酸酯，然而异氰酸酯容易与反应体系中水、醇等含有活泼氢的化合物发生副反应，并且其毒性较大又不易运输和保存。一氧化碳羰基化法需用硒以及钌、锗、钯等贵金属和它们的化合物作催化剂，反应一般需要较高的温度和压力下进行，成本较高。专利CN104557618A公开了以尿素、苄醇为原料，在过渡金属催化剂铱络合物、碱和叔戊醇作用下，在微波反应器中100-130℃反应数小时得到N,N’-二烷基脲。专利CN201710413634.3公开了一种在溶剂聚乙二醇或聚乙二醇的水溶液中，在碱、碘化物和氧化剂的作用下，加入钯催化剂，催化伯胺与一氧化碳的直接交叉偶联反应制备不对称二取代脲类化合物。专利CN201811512934.8公开了以N-烃酰氧基酰胺为原料，以二氯(对甲基异丙苯)钌(II)二聚体配合物为催化剂，在醋酸银的存在下，反应制得N,N’-二取代脲类化合物。专利CN201510734338.4公开了以超顺磁纳米颗粒负载的离子液体为催化剂，芳香胺与碳酸二甲酯、碳酸二乙酯缩合反应8～14小时，得到相应的N,N′-二取代脲衍生物。随着人们环保意识的不断增强，因此，仍需进一步开发反应路线简单、高效、低成本、环境友好的取代脲化合物的合成方法。
发明内容
针对现有技术存在的上述技术问题问题，本发明以有机胺类化合物和四卤甲烷为原料在催化剂和光照条件下，直接反应制备获得取代脲类化合物，原料来源广泛，反应时间短，操作简便，后处理过程简单，产品收率高。
本发明提供了一种光催化合成取代脲类化合物的方法，所述方法具体包括：
将四卤甲烷与溶剂混合后，先后加入如式I～III的胺类化合物、催化剂，在含氧氛围和光照条件下搅拌反应后经分离纯化获得如式IV～VI结构的取代脲类化合物；
其中，
所述R1为C2～C20烷基、C3～C20环烷基、C3～C20烯烃基、C3～C20炔烃基、C3～C20杂环基、C5～C12杂芳基或C6～C20芳香基；
所述R2、R3为H、C1～C20烷基、C3～C20环烷基、C3～C20烯烃基、C3～C20炔烃基或C6～C20芳香基；
所述烷基、环烷基可以进一步被卤素、羟基、烷氧基单取代或相同或不同的多取代。
进一步的，所述溶剂为：甲苯、苯、正己烷、三氟甲苯、二氯甲烷、二氯乙烷、环己烷、甲醇、乙醇、***、异丙醇、丁醇、四氢呋喃、乙腈、二氧六环、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、三氯甲烷、四氯甲烷中的任意一种或几种。
进一步的，所述催化剂为四氧化三锰、二氧化钛、氧化锌、氧化锡、二氧化锆、四氧化三铁、四氧化三钴、硫化镉、二氧化锰中的一种或几种。
进一步的，所述反应在碱存在或不存在的条件下进行；所述碱为碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、碳酸铯、氢氧化钠、氢氧化钾、碳酸钡、碳酸钙、氢氧化锂、氢氧化钡、三乙胺、叔丁基醇钠、乙醇钠、甲醇钠中的一种或几种。。
进一步的，所述四卤甲烷与有机胺类化合物的摩尔比为1:1.8-4.0。
进一步的，所述光照条件具体为：
采用发光二极管、氙灯、汞灯、金卤灯中的一种或一种以上为光发生装置进行光照。
进一步的，所述搅拌反应的时间为8-12h。
进一步的，所述分离纯化具体包括：
将所述搅拌反应后的产物静置分层或过滤取滤液层，将所述滤液层脱除溶剂获得取代脲类化合物。
本发明的上述方案有如下的有益效果：
1)本发明以有机胺和四卤甲烷为原料，并以金属氧化物为催化剂催化制备获得，上述原料来源广泛，反应后产生的副产物为卤素单质，附加值高，一方面避免了采用毒性大的光气、三光气等为原料，另一方面避免产生大量的废弃物，且催化剂可循环使用，减少了制备过程对环境的影响，提高了反应的原子利用率。
2)本发明的反应条件为含氧氛围即为空气条件，并在常温常压下进行，采用光照条件替代传统的加热以及高压条件，反应条件温和，生产安全性高，且降低了反应成本。
3)本发明所述的取代脲的合成方法具有很好的底物适用性，而且工艺条件温和，绿色环保，工艺简单，操作方法简单易行，有利于推广应用。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例提供的1,3-二萘基脲的红外光谱图；
图2为本发明实施例提供的1,3-二正丁基脲的红外光谱图；
图3为本发明实施例提供的1,3-二糠基脲的红外光谱图；
图4为本发明实施例提供的1,3-二苄基脲的质谱图；
图5为本发明实施例提供的1,3-二萘基脲的质谱图；
图6为本发明实施例提供的1,3-二糠基脲的质谱图；
图7为本发明实施例提供的1,3-二正辛基脲的质谱图；
图8为本发明实施例提供的1,3-二邻甲苯基脲的质谱图。
具体实施方式
为使本发明要解决的技术问题、技术方案和优点更加清楚，下面将结合附图及具体实施例进行详细描述，但本发明的保护范围并不限于以下具体实施例。
除非另有定义，下文中所使用的所有专业术语与本领域技术人员通常理解含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的，并不是旨在限制本发明的保护范围。
除非另有特别说明，本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。
在本发明实施例中，以式I与四卤甲烷为例，在光照和催化剂的作用下发生如式(1)的反应。其中四卤甲烷在光照条件下形成碳自由基和卤自由基，碳自由基与富电子的氧气作用，再与胺类反应形成脲类化合物，卤自由基两两结合形成卤素单质。
以下以具体的实施例进行进一步说明。
实施例1
将34.62份四溴化碳(含量为97％)加入装有100.00份三氟甲苯的反应器中，加入21.76份苄胺(含量为98.5％)，再加入0.31份四氧化三锰(99.5％)和32.37份碳酸铯(含量为99.9％)，在Led灯为光源照射下，搅拌反应12小时后，静置分层，上层为黄色透明液体，下层为红黑色油状的溴单质，将上层溶液蒸馏回收甲苯溶剂，得到浅灰色的1,3-二苄基脲固体产品。
实施例2
将34.80份四溴化碳(含量为97.0％)加入装有100.00份三氟甲苯的反应器中，加入28.50份1-萘胺(含量为99.0％)，再加入0.31份四氧化三锰(99.5％)和10.76份碳酸钠(含量为99.8％)，在Led灯为光源照射下，搅拌反应10小时后，静置分层，上层为黄色透明液体，下层为红黑色油状的溴单质，将上层溶液蒸馏回收三氟甲苯溶剂，得到灰黑色的1,3-二萘基脲固体产品。
实施例3
将34.48份四溴化碳(含量为97.0％)加入装有85.00份甲苯的反应器中，加入14.78份正丁胺(含量为99.0％)，再加入0.31份四氧化三锰(99.5％)和10.88份碳酸钠(含量为99.8％)，在氙灯为光源照射下，搅拌反应10小时后，静置分层，上层为浅黄色透明液体，下层为红黑色油状的溴单质，将上层溶液蒸馏回收甲苯溶剂，得到黄棕色的1,3-二正丁基脲固体产品。
实施例4
将34.52份四溴化碳(含量为97.0％)加入装有85.00份甲苯的反应器中，加入26.11份正辛胺(含量为99.0％)，再加入0.30份四氧化三锰(99.5％)和10.83份碳酸钠(含量为99.8％)，在氙灯为光源照射下，搅拌反应10小时后，蒸馏回收甲苯溶剂，得到焦黄色的1,3-二正辛基脲固体产品。
实施例5
将15.54份四氯化碳(含量为99.0％)加入装有85.00份三氟甲苯的反应器中，加入19.62份糠胺(含量为99.0％)，再加入0.29份二氧化钛(99％)和32.08份碳酸铯(含量为99.9％)，在氙灯为光源照射下，搅拌反应10小时后，收集反应过程生成的氯气，将得到的油状溶液蒸馏回收三氟甲苯溶剂，得到深棕色的1,3-二糠基脲液体产品。
实施例6
将34.70份四溴化碳(含量为99.5％)加入装有80.00份甲苯的反应器中，加入21.87份邻甲基苯胺(含量为98％)，再加入0.50份二氧化锰(98％)和10.64份碳酸钠(含量为99.8％)，在Led灯为光源照射下，搅拌反应12小时后，静置分层，上层为黄色透明液体，下层为红黑色油状的溴单质，将上层溶液蒸馏回收甲苯溶剂，得到紫色的1,3-二邻甲氧基苯基脲固体产品。
实施例7
将34.60份四溴化碳(含量为97.0％)加入装有85.00份甲苯的反应器中，加入48.78份二异辛胺(含量为99.0％)，再加入0.30份四氧化三锰(99.5％)和10.76份碳酸钠(含量为99.5％)，在氙灯为光源照射下，搅拌反应10小时后，静置分层，上层为黄色透明液体，下层为红黑色油状的溴单质，将上层溶液蒸馏回收甲苯溶剂，得到棕色的1,1,3,3-四异辛基脲固体产品。
实施例8
将33.50份四溴化碳(含量为99.0％)加入装有80.00份正己烷的反应器中，加入18.72份苯胺(含量为99.5％)，再加入0.30份二氧化钛(99.0％)和11.50份碳酸钠(含量为99.5％)，在氙灯为光源照射下，搅拌反应10小时后，静置分层，上层为浅黄色透明液体，下层为红黑色油状的溴单质，将上层溶液蒸馏回收甲苯溶剂，得到棕色的1,3-二苯基脲固体产品。
将获得的取代脲类化合物产品称重，并根据原料的加入量计算其理论产量，计算收率，其中实施例1-8制备取代脲类化合物的收率分别为90％、91％、88％、86％、91％、90％、87％和88％。
结构表征
将获得的取代脲类化合物分离提纯后，并采用质谱、红外光谱多种表征方式进行结构表征，以下以实施例1-6获得的取代脲类化合物的表征结果为例。
实施例1获得的1,3-二苄基脲的质谱如图4所示，谱图中质荷比为241.1335的峰是[M+H]离子峰，1,3-二苄基脲的理论[M+H]的MS为241.1335。
实施例2获得的1,3-二萘基脲的红外光谱如图1所示，其主要特征峰有(cm-1)：3367.59归属N-H伸缩振动，1623.77归属C＝O伸缩振动，1576.74归属N-H变形振动峰，1513.85归属C＝C伸缩振动，768.98归属C-H面内变形振动峰。1,3-二萘基脲质谱如图5所示，谱图中质荷比为311.1177的峰是[M-H]离子峰，1,3-二萘基脲的理论[M-H]的MS为311.1190；
实施例3获得的1,3-二正丁基脲的红外光谱如图2所示，其主要特征峰有(cm-1)：3324.20归属N-H伸缩振动峰，2962.13、2871.29归属-CH3的伸缩振动峰，2933.68归属-CH2的伸缩振动峰，1634.38归属C＝O伸缩振动，1563.99归属N-H变形振动峰，1323.41归属N-C-N伸缩振动峰。
实施例4获得的1,3-二正辛基脲的质谱如图7所示，谱图中质荷比为363.2005的峰是[M+Br-]离子峰，1,3-二正辛基脲的理论[M+Br-]的MS为：363.2016。
实施例5获得的1,3-二糠基脲的红外光谱如图3所示，其主要特征峰有(cm-1)：3395.55归属N-H伸缩振动峰，1637.75归属C＝O伸缩振动，1561.09归属N-H变形振动峰，1401.99归属C＝C环伸缩振动峰，1347.99归属N-C-N伸缩振动峰。1,3-二糠基脲的质谱如图6所示，谱图中质荷比为221.0927的峰是[M+H]离子峰，1,3-二糠基脲的理论[M+H]的MS为221.0921。
实施例6获得的1,3-二邻甲氧基苯基脲的质谱如图8所示，谱图中质荷比为273.1232的峰是[M+Br-]离子峰，1,3-二邻甲氧基苯基脲的理论[M+H]的MS为273.1234。
以上所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明所述原理的前提下，还可以作出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (5)
1.一种光催化合成取代脲类化合物的方法，其特征在于，所述方法具体包括：
将四卤甲烷与溶剂混合后，先后加入如式I～III的胺类化合物、催化剂，在含氧氛围和光照条件下搅拌反应后经分离纯化获得如式IV～VI结构的取代脲类化合物；所述光照条件具体为：
采用发光二极管、氙灯、金卤灯中的一种或一种以上为光发生装置进行光照；所述催化剂为四氧化三锰、二氧化钛、二氧化锰中的一种或几种；
其中，
所述R1为C2～C20烷基；
所述R2、R3为H；
所述烷基可以进一步被卤素、羟基单取代或相同或不同的多取代；
所述反应在碱存在的条件下进行；所述碱为碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、碳酸铯、氢氧化钠、氢氧化钾中的一种或几种。
2.根据权利要求1所述的光催化合成取代脲类化合物的方法，其特征在于，所述溶剂为：甲苯、苯、正己烷、三氟甲苯、二氯甲烷、二氯乙烷、环己烷、甲醇、乙醇、***、异丙醇、丁醇、四氢呋喃、乙腈、二氧六环、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、三氯甲烷、四氯甲烷中的任意一种或几种。
3.根据权利要求1所述的光催化合成取代脲类化合物的方法，其特征在于，所述四卤甲烷与有机胺类化合物的摩尔比为1:1.8-4.0。
4.根据权利要求1所述的光催化合成取代脲类化合物的方法，其特征在于，所述搅拌反应的时间为8-12h。
5.根据权利要求1所述的光催化合成取代脲类化合物的方法，其特征在于，所述分离纯化具体包括：
将所述搅拌反应后的产物静置分层或过滤取滤液层，将所述滤液层脱除溶剂获得取代脲类化合物。
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