The Synthesis Of1-methyl-2-nitro-3-((Tetrahydrofuran-2-yl) Methyl) Guanidine

Dinotefuran pesticides, which has the high insecticidal activity, low toxicity and lasting effect, being safe to crop, mammals, birds, fish and environment, is a new type, efficient and environmentally friendly pesticides. This paper,taking furfural as raw materials, synthesised the target product l-methyl-2-nitro-3-((tetrahydrofuran-2-yl)methyl)guanidine by two methods, the intermediate compounds and the target product were characterized by MS. Conclusions are as follows:1.(tetrahydrofuran-2-yl)methyl methanesulfonate was synthesized by the following methods. Furfural reacted under the catalysis of25%sodium hydroxide solution, at the temperature of5～10℃for0.5～1h, and obtained furan-2-ylmethanol, the yield was75.0%; Then furfuryl alcohol hydrogenated under the catalysis of Rany Ni, at the temperature of80℃for4h, the pressure was7.0MPa. The yield of (tetrahydrofuran-2-yl)-methanol was95.4%; Then (tetrahydrofuran-2-yl)methanol reacted with methyl sulfochloridate in the absence of water under oxygen-free conditions, at room temperature for3h, with the molar ratio (methyl sulfochloridate to (tetrahydrofuran-2-yl)methanol)1.3, the yield of (tetrahydrofuran-2-yl)methylmethanesulfonate was87.0%;2. The synthesis methods of N-(1,5-dimethyl-1,3,5-triazinan-2-ylidene)-nitramide was as follows:Thiourea and dimethyl sulfate reacted at the temperature of110-120℃for4h, with the molar ratio (dimethyl sulfate to thiourea)0.67:1, the yield of methyl carbamimidothioate sulfate was92.0%; methyl carbamimidothioate sulfate reacted with the mixture of sulfuric acid and nitric acid at the temperature of-5℃for1h,the yield of methyl nitrocarbamimidothioate was89.7%; Methylamine reacted with methyl nitrocarbamimidothioate at the temperature of70～80℃for3h, with the molar ratio (methylamine to methyl nitrocarbamimidothioate)1.5, the yield of l-methyl-3-nitroguanidine was87.0%;1-methyl-3-nitroguanidine reacted with methylamine and formaldehyde at the temperature of60℃for3h, with the molar ratio (methylamine to1-methyl-3-nitroguanidine)1.7, and the molar ratio (formaldehyde to1-methyl-3-nitroguanidine)3.3,the yield of N-(1,5-dimethyl-1,3,5-triazinan-2-ylidene)nitramide was56.0%.3.The target product1-methyl-2-nitro-3-((tetrahydrofuran-2-y1)methyl) guanidine was synthesized by the two following methods:(Tetrahydrofuran-2-y1)methylmethanesulfonate and N-(1,5-dimethyl-1,3,5-triazinan-2-ylidene) nitramide reacted at the temperature of50℃for3h under the catalysis of NaH, and with the molar ratio ((tetrahydrofuran-2-y1)methy-1methanesul-fonate to N-(1,5-dimethyl-1,3,5-triazinan-2-ylidene)nitramide)1.2, then beening hydrolyzed by hydrochloric acid for3h,then abtained the target product,the yield was53.5％and the total yield was13.4％.The research shows that the every step synthsis yield of1-methyl-2-nitro-3-((tetrahydrofuran-2-y1)methyl)guanidine by2-THF amine and O-methyl-N’-methyl-N-nitrocarbamimidate was high.So it’s possible to achieve industrial production, and the synthetic route has greater market competitiveness.