Abstract
A practical four-step synthesis of pymetrozine is reported, starting from a green chemical dimethyl carbonate and using the key intermediate methyl (E)-1-(2-oxopropyl)-2-(pyridin-3-ylmethylene)hydrazine-1-carboxylate. The main advantages of the route include inexpensive starting materials, environmental friendliness, short synthetic route, easy-to-use synthetic method and acceptable overall yield. A scale-up experiment was carried out to provide pymetrozine with 99.84% purity in 53.2% total yield.
Keywords
References
1.
Kristtinsson H.
, and
Switzerland B.
, U.S. Patent: 4 931 439, issued 5 June 1990.
2.
He M.H.
,
Luo W.C.
, and
Mu L.Y.
, World Pesticides , 2002 , 24 , 46 .
3.
Liu Y.H.
, and
Mei L.K.
, Sichuan Chem. Ind. , 2000 , 3 , 51 .
4.
Muller K.H.
,
König K.
, and
Heitkämper P.
, U.S. Patent: 4 952 701, issued 28 August 1990.
5.
Butterworth J.H.
, and
Morgan E.D.
, Chem. Commun. , 1968 , 23 .
6.
Garcia E.S.
,
de Azanbuja P.
,
Forster H.
, and
Rembold H.
, J. Biosci. , 1984 , 39C , 1155 .
7.
Wang S.D.
,
Zeng W.P.
,
Duan X.S.
,
Qin Y.J.
, and
Mao C.H.
, Agrochem. Res. Appl. , 2007 , 11 , 23 .
8.
Gao C.J.
, Xiandai Nongyao , 2012 , 11 , 16 .
9.
Tao Y.C.
, and
Yang Y.L.
, CN Patent: 102558152A, issued 11 July 2012.
10.
Wang B.Z.
,
Ke S.Y.
,
Kishore B.
,
Xu X.Y.
,
Zou Z.Y.
, and
Li Z.
, Synth. Commun. , 2012 , 42 , 2327 .
11.
Ji Y.X.
,
Jiang Y.T.
,
Yao X.Y.
,
Wang J.S.
,
Long X.G.
,
Zheng C.
, and
Xie J.
. CN Patent: 103724327A, issued 16 April 2014.
12.
Applegate J.M.
,
Diehr H.J.
,
Jelich K.
, and
Lantzsch R.
, U.S. Patent: 5 756 752A, issued 26 May 1998.
13.
Zhang B.Y.
,
Duan X.S.
, and
Feng C.
, CN Patent: 101012206A, issued 8 August 2007.
14.
Yan X.
,
Zhou S.
,
Wang Y.
,
Ge Z.
,
Cheng T.
, and
Li R.
, Tetrahedron , 2012 , 68 , 7978 .
15.
Ouyang J.F.
,
Huang C.G.
,
Chen Q.L.
,
Zhang H.
,
Sun J.L.
, and
Lei X.F.
, CN Patent: 104803936A, issued 29 July 2015.
16.
Zhang J.P.
,
Li X.Y.
,
Dong Y.W.
,
Qin Y.G.
,
Li X.L.
,
Song B.A.
, and
Yang X.L.
, Chin. Chem. Lett. , 2017 , 28 , 1238 .
17.
Wagner B.
,
Hiller W.
,
Ohno H.
, and
Krause N.
, Org. Biomol. Chem. , 2016 , 14 , 1579 .
18.
Li G.X.
, Jingxi Huagong , 2002 , 19 , 336 .
19.
Li Z.
, and
Yang J.Y.
, Xibei Shifan Daxue Xuebao, Ziran Kexueban , 2005 , 41 , 45 .
20.
Yin X.
,
Wu J.T.
,
Jin X.
,
Xu C.X.
,
He P.
,
Li T.
,
Wang K.
,
Qin J.
, and
Zhang J.G.
, RSC Adv. , 2015 , 5 , 60005 .
21.
Yeole A.
,
Vaidya S.
, and
Bagal M.
, Heterocycl. Lett. , 2017 , 7 , 863 .
22.
Fei N.
,
Sauter B.
, and
Gillingham D.
, Chem. Commun. , 2016 , 52 , 7501 .
23.
van Dijken D.J.
,
Kovaříček P.
,
Ihrig S.P.
,
Hecht S.
, J. Am. Chem. Soc. , 2015 , 137 , 14982 .
24.
Armesto D.
,
Gallego M.G.
,
Horspool W.M.
, and
Ramos A.
, Tetrahedron Lett. , 1988 , 29 , 3581 .
25.
Sumakanth M.
,
Malla R.V.
,
Krishnan V.S.H.
, and
Sastry B.S.
, J. Pharm. Res. , 2007 , 6 , 166 .
26.
Tang H.T.
,
Zhou Y.B.
,
Zhu Y.
,
Sun H.C.
,
Lin M.
, and
Zhan Z.P.
, Chem. Asian J. , 2014 , 9 , 1278 .
27.
Chung H.A.
,
Kang Y.J.
,
Kweon D.H.
,
Lee W.S.
, and
Yoon Y.J.
, J. Heterocycl. Chem. , 2000 , 37 , 1443 .
28.
Forest M.C.
,
Lahouratate P.
,
Martin M.
,
Nadler G.
,
Quiniou M.J.
, and
Zimmermann R.G.
, J. Med. Chem. , 1992 , 35 , 163 .
29.
Zhang J.P.
,
Li X.Y.
,
Dong Y.W.
,
Qin Y.G.
,
Li X.L.
,
Song B.A.
, and
Yang X.L.
, Chin. Chem. Lett. , 2017 , 6 , 1238 .