CN110683975B - Synthesis method of dialkyl amino alkyl dithioformate - Google Patents

Synthesis method of dialkyl amino alkyl dithioformate Download PDF

Info

Publication number
CN110683975B
CN110683975B CN201911015040.2A CN201911015040A CN110683975B CN 110683975 B CN110683975 B CN 110683975B CN 201911015040 A CN201911015040 A CN 201911015040A CN 110683975 B CN110683975 B CN 110683975B
Authority
CN
China
Prior art keywords
ammonium
trimethyl
sodium
alkyl
nmr
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911015040.2A
Other languages
Chinese (zh)
Other versions
CN110683975A (en
Inventor
曾庆乐
陈虹艺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chengdu Univeristy of Technology
Original Assignee
Chengdu Univeristy of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chengdu Univeristy of Technology filed Critical Chengdu Univeristy of Technology
Priority to CN201911015040.2A priority Critical patent/CN110683975B/en
Publication of CN110683975A publication Critical patent/CN110683975A/en
Application granted granted Critical
Publication of CN110683975B publication Critical patent/CN110683975B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/14—Dithiocarbamic acids; Derivatives thereof
    • C07C333/18—Esters of dithiocarbamic acids
    • C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

Abstract

Among organic sulfur compounds, alkyl dialkylaminodithiocarbamates play a very important role. Studies have shown that alkyl dialkylaminodithiocarboxylates and derivatives thereof have a wide range of biological properties and pharmacological activity. For example, numerous studies have shown that alkyl dialkylaminodithiocarboxylates have a variety of activities, including antiproliferative, antiglaucoma, antibacterial, antifungal, breast cancer treatment and cholinesterase inhibition, and are useful as myocardial imaging agents. They are known to be HIV-1 NCp7 inhibitors, antiviral agents, and non-flavonoid TRPV1 antagonists. Alkyl dialkylaminodithiocarbamates are produced in large quantities worldwide due to their wide range of uses. The present application provides a method for efficiently synthesizing alkyl dialkylamido dithioformates. Under the catalysis of CuI, chiral quaternary ammonium salt and dialkyl amino dithioformate are firstly utilized to carry out C-S cross coupling to prepare dialkyl amino dithioformate. The target product is further converted and coupled with aryl bromide to obtain chiral thioether with high purity enantiomer. The synthesis process has the advantages of mild reaction conditions, wide universality, no toxicity or danger, generally high yield, wide substrate range and the like.

Description

Synthesis method of dialkyl amino alkyl dithioformate
Technical Field
The patent relates to the research field of organic synthesis, drug synthesis and organic chemical industry, and specifically relates to a method for synthesizing dialkyl amino dithio formate compounds in one step by carrying out C-S cross coupling on alkyl quaternary ammonium salt and dialkyl amino dithio formate.
Background
Dialkylaminodithiocarbamates and derivatives thereof have a wide range of biological properties and pharmacological activity. Benzyldithiocarbamates (e.g., 4-methoxybenzyl-N, N-diethyldithiocarbamates) which exhibit excellent herbicidal activity against gramineous and broadleaf plants belong to the class of alkyl dialkylaminodithioates (s.wakamori, y.yoshida, y.ishi, agric.biol.chem.1969,33, 1367. kazaa 1376.) furthermore, many studies have shown that dialkyldithiocarbamates also exhibit various activities in biomedicine, including anti-proliferation (s.l.cao, y.han, c.z.yuan, y.wang, z.xahou, j.liao, r.t.gao, b.b.mao, b.l.zhao, z.f.li, x.xmdu, eur.j.chem.2013, 64,401.) anti-glaucoma (f.carcarota, m.agrawa, a.r.f.84. tsuzaa, m.c.t.c.t.franca, m.t.c.t.t.t.t.2012).
Figure BDA0002244012030000011
K.G raven, arch, pharm, chem, life sci, 2005, 96.), spermicide (n.lal, s.jangircir, v.bala, d.mandalapu, a.sarswat, l.kumar, a.jain, l.kumar, b.kushwaha, a.k, Pandey, s.krishna, t.rawat, p.k.shukla, j.p.maikhuri, m.i.siddiqi, g.gupta, v.l. Sharma, eur.j.chem.2016, 115,275.), treatment of breast cancer (g.brahemi, f.r.kona, a.fia, d.buukac, j.soukova, a.bunkove, a.fina, a.2010, branalj.35j, choline esterase, g.g.wu.
Figure BDA0002244012030000012
Z.A.
Figure BDA0002244012030000013
Arch, pharm, chem, life sci.2013,346, 571; S.Levent, U.S. Cevik, B.N.Saglik, Y.Ozkay, O.D.Can, U.D.Ozkay, U.Ucucu, phosphorous Sulfur Silicon Relat.Elem.2017,192, 469; yuan, z.shang, x.qiang, z.tan, y.deng, res.chem.intermed.2014,40,787.), and as myocardial imaging agents (c.bolzati, m.cavazza-Ceccato, s.agostini, f.refloco, y.yamamichi, s.tokunaga, d.carta, n.savarese, d.bernardin, g.bandoli, Bioconjugate chem.2010,21,928.). Furthermore, they showed in vitro antitumor activity against human myeloid leukemia K562 cells (s.l.cao, y.p.feng, y.y.jiang, s.y.liu, g.y.ding, r.t.li, bioorg.med.chem.lett.2005,15,1915). They are also known to be HIV-1 NCp7 inhibitors, antiviral agents (a. goel, s.j.majur, r.j.fattah, t.l. Hartman, j.a.turpin, m.huang, w.g.rice, e.applla, j.k.inman, bioorg.med.chem.lett.2002, 12,767.), and non-flavonoid TRPV1 antagonists (h.sudhani, s.k.t.basha, s.muni, c.reddy, b.sreear, s.adam, c.n.raju, res.chem.inter.2016, 42,7471., y.g.suh, y.s.lee, k.h.min, o.h.park, j.k.k.parm, seh.parm, seh.parg.seh, seh.j.j.h, sej.j.h.j.j.h.h, sej.h.j.h.h.h.h, sej.j.h.j.h.h.h.h.h, sej.j.j.h.h.j, sej.j.h.h.h.h.h.h.h.h.h.h.h.35, sej.h.h.h.h.h.h.
In addition, benzyldithiocarbamates are used as surface initiators for the synthesis of flame retardants (i.kaur, s.k. Verma, surf.coat.technol.2)010,205,2082-2090.). They may also be used as compositions comprising11A radiolabelling reagent for the C isotope (p.w.miller, d.binder, chem.eur.j.2012,18,433-436.). (1) the major reports on benzyldithiocarbamates are (1) the preparation by one-pot reaction of benzyl halides, amines and carbon disulfide (Azizi, N.; Aryanasab, F.; Saidi, M.R. org. Lett. 2006,8, 5275-. (2) Obtained by reaction of benzyl halide and tetramethylthiuram disulfide (Wu, Z.; Lai, M.; Zhang, S.; Zhong, X.; Song, H.; ZHao, M.Eur.J.org.chem.2018, 7033-. (3) The reaction of amines with expensive and toxic reagents such as thiophosgene or isothiocyanates is used (Tilles, H.J.Am.chem.Soc.1959,81, 714-. However, these methods require the use of halogenated compounds and the reaction is often accompanied by toxic and unpleasant odors. The use of thiophosgene and the preparation of isothiocyanates are also dangerous and are accompanied by the formation of many by-products. Secondly, there are serious disadvantages to the synthesis of some valuable chiral alkyl aminodithioates.
Therefore, to remedy these deficiencies, we have developed a method for efficiently synthesizing dialkyl amino dithiocarbamates, and by this method chiral alkyl amino dithiocarbamates can be efficiently synthesized and converted into chiral thioethers.
To the best of our knowledge, no literature reports are found which are the same as the present application.
Disclosure of Invention
The invention provides a method for synthesizing dialkyl amino alkyl dithioformate.
The synthesis method of dialkyl amino alkyl dithioformate disclosed by the invention is completed in one step, namely under the catalysis of CuI with a catalytic amount, alkyl quaternary ammonium salt and various types of dialkyl amino sodium dithioformate are synthesized into the dialkyl amino alkyl dithioformate in acetonitrile at the temperature of 80 ℃. The dialkyl amino dithio formate is lithium salt, sodium salt and potassium salt, the sodium salt with the best reaction universality is the sodium salt, and the dialkyl amino dithio formate is specifically divided into aryl amino sodium dithio formate and alkyl amino sodium dithio formate.
Figure DEST_PATH_IMAGE001
The present invention is illustrated in more detail by the following examples, which are not to be construed as limiting the scope of the invention.
Detailed Description
Example one
To a dry ground tube with a magnetic stirrer were added benzyltrimethyl-trifluoromethanesulfonate (1.0 mmol), sodium N, N-diethylaminodithioformate (2.0 mmol), CuI (5 mol% relative to benzyltrimethyl-trifluoromethanesulfonate), and acetonitrile (3 ml), and finally the ground tube was sealed with a rubber stopper. The tube was placed in an 80 ℃ oil bath and stirred for 18 hours. The reaction mixture was then cooled to room temperature, quenched with 15mL of saturated NaCl solution and extracted with ethyl acetate (3X 20 mL). And the combined organic layers were dried over anhydrous magnesium sulfate and then adsorbed on some silica gel under reduced pressure on a rotary evaporator. The silica gel on which the sample was adsorbed was transferred to a silica gel column. After purification by silica gel column chromatography (petroleum ether: ethyl acetate 20: 1 as eluent), the yield of benzyl N, N-diethylaminodithiocarbamate was 95% as a yellow oily liquid. The reaction equation is shown below.
Figure BDA0002244012030000032
The structural characterization data for the product benzyl N, N-diethylaminodithiocarbamate is as follows:
1H NMR(400MHz,CDCl3)δ7.40–7.35(m,2H),7.32–7.23(m,3H),4.53(s, 2H),4.03(q,J＝7.1Hz,2H),3.71(q,J＝7.2Hz,2H),1.26(d,J＝7.5Hz,6H).
13C NMR(101MHz,CDCl3)δ195.29,136.06,129.36,128.53,127.41,49.44, 46.70,42.20,12.46,11.58.
MS(EI):m/z(％)＝239(55)[M]+,207(10),148(100),116(35),91(65).
example two
(o-methylbenzyl) trimethyltrifluoromethanesulfonic acid ammonium salt was substituted for benzyltrimethyltrifluoromethanesulfonic acid ammonium salt in example one, and the yield of N, N-diethylaminodithiocarbamic acid (2-methylbenzyl) ester as a yellow oily liquid was 95%.
1H NMR(400MHz,CDCl3)δ7.28(dd,J＝7.2,1.6Hz,1H),7.16–7.03(m,3H), 4.41(s,2H),3.97(q,J＝7.1Hz,2H),3.63(q,J＝7.1Hz,2H),2.32(s,3H),1.19(dd, J＝12.9,5.8Hz,6H).
13C NMR(101MHz,CDCl3)δ195.42,137.44,133.34,130.48,130.45,127.90, 126.19,49.26,46.69,40.83,19.34,12.43,11.60.
MS(EI):m/z(％)＝253(50)[M]+,220(5),148(100),105(90),88(40).
EXAMPLE III
(m-methylbenzyl) trimethyltrifluoromethanesulfonic acid ammonium salt was substituted for benzyltrimethyltrifluoromethanesulfonic acid ammonium salt in example one, and the yield of N, N-diethylaminodithiocarbamic acid (3-methylbenzyl) ester was 92% as a yellow oily liquid.
1H NMR(400MHz,CDCl3)δ7.24–7.06(m,3H),7.05–6.90(m,1H),4.42(s, 2H),3.97(q,J＝7.0Hz,2H),3.65(q,J＝7.2Hz,2H),2.26(s,3H),1.20(q,J＝5.9, 5.2Hz,6H).
13C NMR(101MHz,CDCl3)δ195.39,138.29,135.76,130.15,128.52,128.30, 126.48,49.43,46.74,42.33,21.38,12.51,11.63.
MS(EI):m/z(％)＝253(60)[M]+,207(10),148(100),105(70),88(55).
Example four
(p-methylbenzyl) trimethyltrifluoromethanesulfonic acid ammonium salt was substituted for benzyltrimethyltrifluoromethanesulfonic acid ammonium salt in example one, and the yield of N, N-diethylaminodithiocarbamic acid (4-methylbenzyl) ester as a yellow oily liquid was 97%.
1H NMR(400MHz,CDCl3)δ7.34–7.27(m,2H),7.15(d,J＝7.8Hz,2H),4.52 (s,2H),4.07(q,J＝7.1Hz,2H),3.74(q,J＝7.1Hz,2H),2.35(s,3H),1.30(q,J＝6.9 Hz,6H).
13C NMR(101MHz,CDCl3)δ195.40,137.20,132.74,129.30,129.27,49.35, 46.68,42.04,21.13,12.45,11.59.
MS(EI):m/z(％)＝253(45)[M]+,207(5),148(60),105(100),88(30).
EXAMPLE five
Trimethyl (o-fluorobenzyl) ammonium trifluoromethanesulfonate was substituted for benzyltrimethyl ammonium trifluoromethanesulfonate in example one to give 2-fluorobenzyl N, N-diethylaminodithioformate as a yellow oily liquid in a yield of 84%.
1H NMR(400MHz,CDCl3)δ7.42(td,J＝7.6,1.9Hz,1H),7.24–7.12(m,1H), 7.06–6.92(m,2H),4.53(d,J＝1.2Hz,2H),3.97(q,J＝7.1Hz,2H),3.65(q,J＝7.2 Hz,2H),1.20(td,J＝7.2,2.8Hz,6H).
13C NMR(101MHz,CDCl3)δ194.92,161.10(d,J＝247.6Hz),131.52(d,J＝ 3.8Hz),129.26(d,J＝8.0Hz),124.13(d,J＝3.8Hz),123.52(d,J＝15.0Hz),115.36 (d,J＝21.4Hz),49.56,46.72,35.02(d,J＝2.4Hz),12.46,11.57.
MS(EI):m/z(％)＝257(45)[M]+,148(100),109(50),88(45).
EXAMPLE six
Trimethyl (m-fluorobenzyl) ammonium trifluoromethanesulfonate was substituted for benzyltrimethyl ammonium trifluoromethanesulfonate in example one to give 3-fluorobenzyl N, N-diethylaminodithioformate as a yellow oily liquid in 83% yield.
1H NMR(400MHz,CDCl3)δ7.19(td,J＝8.0,5.9Hz,1H),7.09(dt,J＝7.7,1.3 Hz,1H),7.03(dt,J＝9.8,2.1Hz,1H),6.87(tdd,J＝8.4,2.6,1.0Hz,1H),4.48(s,2H), 3.97(q,J＝7.1Hz,2H),3.66(q,J＝7.2Hz,2H),1.21(t,J＝7.1Hz,6H).
13C NMR(101MHz,CDCl3)δ194.72,162.77(d,J＝246.0Hz),138.98(d,J＝ 7.6Hz),129.97(d,J＝8.2Hz),124.99(d,J＝2.8Hz),116.21(d,J＝21.7Hz),114.36 (d,J＝21.2Hz),49.69,46.79,41.41(d,J＝1.9Hz),12.53,11.59.
MS(EI):m/z(％)＝257(45)[M]+,207(5),148(100),109(45),88(45).
EXAMPLE seven
(p-fluorobenzyl) trimethyltrifluoromethanesulfonic acid ammonium salt was substituted for benzyltrimethyltrifluoromethanesulfonic acid ammonium salt in example one to give N, N-diethylaminodithiocarbamic acid (4-fluorobenzyl) ester as a yellow oily liquid in a yield of 85%.
1H NMR(400MHz,CDCl3)δ7.33–7.24(m,2H),6.97–6.87(m,2H),4.45(s, 2H),3.97(q,J＝7.1Hz,2H),3.65(q,J＝7.1Hz,2H),1.21(td,J＝7.2,2.8Hz,6H).
13C NMR(101MHz,CDCl3)δ194.90,162.10(d,J＝246.1Hz),131.98(d,J＝ 3.4Hz),130.94(d,J＝8.1Hz),115.39(d,J＝21.7Hz),49.51,46.72,41.22,12.46, 11.56.
MS(EI):m/z(％)＝257(45)[M]+,148(100),109(65),88(45).
Example eight
(m-methoxybenzyl) trimethyltrifluoromethanesulfonic acid ammonium salt was substituted for benzyltrimethyltrifluoromethanesulfonic acid ammonium salt in example one, and the yield of N, N-diethylaminodithiocarbamic acid (3-methoxybenzyl) ester as a yellow oily liquid was 94%.
1H NMR(400MHz,CDCl3)δ7.19–7.12(m,1H),6.92–6.85(m,2H),6.73(ddd, J＝8.3,2.6,1.0Hz,1H),4.44(s,2H),3.97(q,J＝7.1Hz,2H),3.72(s,3H),3.65(q,J ＝7.1Hz,2H),1.21(td,J＝7.3,3.1Hz,6H).
13C NMR(101MHz,CDCl3)δ195.25,159.69,137.56,129.58,121.72,114.87, 113.13,55.23,49.49,46.75,42.25,12.51,11.62.
MS(EI):m/z(％)＝269(55)[M]+,236(5),206(5),148(100),116(50),88(50).
Example nine
(p-methoxybenzyl) trimethyltrifluoromethanesulfonic acid ammonium salt was substituted for benzyltrimethyltrifluoromethanesulfonic acid ammonium salt in example one, and N, N-diethylaminodithiocarbamic acid (4-methoxybenzyl) ester was obtained as a yellow oily liquid in a yield of 98%.
1H NMR(400MHz,CDCl3)δ7.26–7.21(m,2H),6.79–6.74(m,2H),4.41(s, 2H),3.96(q,J＝7.1Hz,2H),3.71(s,3H),3.64(q,J＝7.1Hz,2H),1.22–1.16(m, 6H).
13C NMR(101MHz,CDCl3)δ195.44,159.01,130.58,127.76,114.03,55.29, 49.34,46.72,41.84,12.49,11.63.
MS(EI):m/z(％)＝269(50)[M]+,236(5),206(5),148(100),116(45),88(50).
Example ten
(m-chlorobenzyl) trimethyltrifluoromethanesulfonic acid ammonium salt was substituted for benzyltrimethyltrifluoromethanesulfonic acid ammonium salt in example one, and the yield of N, N-diethylaminodithiocarbamic acid (2-chlorobenzyl) ester as a yellow oily liquid was 89%.
1H NMR(400MHz,CDCl3)δ7.49(dd,J＝5.8,3.6Hz,1H),7.29(dd,J＝5.8,3.5 Hz,1H),7.16–7.11(m,2H),4.62(s,2H),3.97(q,J＝7.1Hz,2H),3.65(q,J＝7.2Hz, 2H),1.20(t,J＝7.2Hz,6H).
13C NMR(101MHz,CDCl3)δ194.98,134.57,134.44,131.59,129.55,128.93, 126.95,49.67,46.79,39.65,12.52,11.62.
MS(EI):m/z(％)＝273(50)[M]+,207(5),148(100),116(25),88(35).
EXAMPLE eleven
(p-trifluoromethylbenzyl) trimethyltrifluoromethanesulfonic acid ammonium salt was substituted for benzyltrimethyltrifluoromethanesulfonic acid ammonium salt in example one, and N, N-diethylaminodithiocarbamic acid (4-trifluoromethylbenzyl) ester was obtained in a yield of 78% as a yellow oily liquid.
1H NMR(400MHz,CDCl3)δ7.48(d,J＝8.3Hz,2H),7.43(d,J＝8.2Hz,2H), 4.54(s,2H),3.97(q,J＝7.1Hz,2H),3.66(q,J＝7.1Hz,2H),1.21(t,J＝7.1Hz,6H).
13C NMR(101MHz,CDCl3)δ194.41,140.94,129.63,129.38,125.44(d,J＝3.7 Hz),122.78,49.82,46.82,41.13,12.54,11.57.
MS(EI):m/z(％)＝307(25)[M]+,207(5),159(20),148(100),116(25),88(35).
Example twelve
(p-cyanomethylbenzyl) trimethyltrifluoromethanesulfonic acid ammonium salt was substituted for benzyltrimethyltrifluoromethanesulfonic acid ammonium salt in example one to obtain N, N-diethylaminodithiocarbamic acid (4-cyanobenzyl) ester as a yellow oily liquid in a yield of 81%.
1H NMR(400MHz,CDCl3)δ7.56–7.48(m,2H),7.43(d,J＝8.3Hz,2H),4.56 (s,2H),3.96(q,J＝7.1Hz,2H),3.67(q,J＝7.2Hz,2H),1.22(t,J＝7.1Hz,6H).
13C NMR(101MHz,CDCl3)δ193.95,142.74,132.20,129.96,118.77,111.01, 49.95,46.84,40.94,12.53,11.52.
MS(EI):m/z(％)＝264(25)[M]+,148(100),116(40),88(35).
EXAMPLE thirteen
Sodium N, N-Dimethylaminodithioformate in example one was replaced with sodium N, N-diethylaminodithioformate, and the yield of benzyl N, N-dimethylaminodithioate obtained as a yellow oily liquid was 77%.
1H NMR(400MHz,CDCl3)δ7.45–7.38(m,2H),7.42–7.24(m,3H),4.58(s, 2H),3.59(s,3H),3.37(s,3H).
13C NMR(101MHz,CDCl3)δ196.86,136.12,129.35,128.61,127.52,45.38, 42.64,41.44.
MS(EI):m/z(％)＝211(60)[M]+,178(30),146(10),120(40),88(100).
Example fourteen
Sodium N, N-di-tert-butylaminodithioformate was substituted for sodium N, N-diethylaminodithioformate in example one to obtain benzyl N, N-di-tert-butylaminodithioformate as a yellow oily liquid in a yield of 97%.
1H NMR(400MHz,CDCl3)δ7.35–7.15(m,5H),4.46(s,2H),3.80(d,J＝7.5 Hz,2H),3.49(d,J＝7.6Hz,2H),2.42(dt,J＝13.8,7.0Hz,1H),2.22(dt,J＝13.9,7.0 Hz,1H),0.86(d,J＝6.7Hz,12H).
13C NMR(101MHz,CDCl3)δ197.04,135.98,129.45,128.57,127.46,62.99, 60.89,42.57,27.54,26.29,20.27.
MS(EI):m/z(％)＝295(30)[M]+,204(100),172(10),116(20),91(90).
Example fifteen
Sodium pyrrolidine dithiocarbamate was substituted for sodium N, N-diethylaminodithiocarbamate in example one, giving a yield of 97% of benzyl pyrrolidine dithiocarbamate as a yellow oil.
1H NMR(400MHz,CDCl3)δ7.43–7.35(m,2H),7.35–7.21(m,3H),4.58(s, 2H),3.95(tt,J＝6.9,1.0Hz,2H),3.63(tt,J＝6.8,1.0Hz,2H),2.06(pd,J＝6.7,1.2 Hz,2H),1.97(pd,J＝6.7,1.3Hz,2H).
13C NMR(101MHz,CDCl3)δ192.43,136.51,129.29,128.59,127.43,55.06, 50.56,41.30,26.11,24.31.
MS(EI):m/z(％)＝237(75)[M]+,207(50),146(100),114(80),91(80).
Example sixteen
Sodium piperidinedithiocarbamate instead of sodium N, N-diethylaminodithiocarbamate in example one, a yield of 95% of benzyl piperidinedithiocarbamate was obtained as a yellow oily liquid.
1H NMR(400MHz,CDCl3)δ7.42–7.35(m,2H),7.31(ddt,J＝7.9,6.3,1.1Hz, 2H),7.30–7.21(m,1H),4.56(s,2H),4.30(s,2H),3.86(s,2H),1.75–1.62(m,6H).
13C NMR(101MHz,CDCl3)δ195.27,136.08,129.41,128.59,127.48,52.90, 51.33,42.27,25.76(d,J＝48.0Hz),24.31.
MS(EI):m/z(％)＝251(40)[M]+,207(35),191(5),160(80),128(30),121(5), 84(100).
Example seventeen
Sodium N, N-dibenzylaminodithioformate was substituted for sodium N, N-diethylaminodithioformate in example one to obtain benzyl N, N-dibenzylaminodithioformate in a yield of 95% as a white solid.
1H NMR(400MHz,CDCl3)δ7.37–7.29(m,2H),7.24(ddt,J＝20.5,8.6,6.8 Hz,11H),7.12(d,J＝7.3Hz,2H),5.26(s,2H),4.82(s,2H),4.56(s,2H).
13C NMR(101MHz,CDCl3)δ199.32,135.65(d,J＝12.8Hz),134.60,129.47, 128.89(d,J＝11.6Hz),128.64,127.96,127.62,127.21,56.12,54.02,43.12.
HRMS(ESI)m/z[M+H]+Calcd for C22H21NS2 363.1115,found 364.1179.
EXAMPLE eighteen
Sodium 1- (1-naphthyl) ethylcarbamodithioate instead of sodium N, N-diethylcarbamodithioate in example one, a yield of benzyl 1- (1-naphthyl) ethylcarbamodithioate was 77% as a yellow oily liquid.
1H NMR(400MHz,CDCl3)δ8.03(d,J＝8.2Hz,1H),7.92–7.76(m,2H),7.60 –7.41(m,4H),7.36–7.16(m,5H),7.16–6.94(m,1H),6.49(p,J＝6.9Hz,1H),4.56 –4.39(m,2H),1.76(d,J＝6.8Hz,3H).
13C NMR(101MHz,CDCl3)δ196.01,136.53,136.37,133.93,131.34,128.99, 128.84,128.64,127.54,126.99,126.11,125.18,123.39,123.09,122.37,52.22,39.98, 18.79.
HRMS(ESI)m/z[M+H]+Calcd for C20H19NS2 337.0959,found 338.1026.
Example nineteen
Sodium 1-phenethylaminodithioformate instead of sodium N, N-diethylaminodithioformate in example one gave a yield of benzyl 1-phenethylaminodithioformate as a yellow oily liquid of 77%.
1H NMR(400MHz,CDCl3)δ7.27(dd,J＝7.8,6.6Hz,4H),7.23(d,J＝4.9Hz, 2H),7.24–7.13(m,4H),7.07–6.95(m,1H),5.70(p,J＝7.1Hz,1H),4.51–4.33(m, 2H),1.54–1.48(m,3H).
13C NMR(101MHz,CDCl3)δ196.35,141.39,136.44,129.09,128.85,128.71, 127.85,127.59,126.49,55.98,40.01,20.68.
HRMS(ESI)m/z[M+H]+Calcd for C16H17NS2 287.0802,found 288.0873.
Example twenty
Trimethyl (m-methoxybenzyl) ammonium trifluoromethanesulfonate was substituted for benzyltrimethyl ammonium trifluoromethanesulfonate in example one, and sodium pyrrolidine dithiocarbamate was substituted for sodium N, N-diethylaminodithiocarbamate in example one, giving a yield of 3-methoxybenzyl pyrrolidine dithiocarbamate as a yellow oily liquid of 93%.
1H NMR(400MHz,CDCl3)δ7.26–7.18(m,1H),7.01–6.93(m,2H),6.80(ddd, J＝8.3,2.6,1.1Hz,1H),4.56(s,2H),3.95(tt,J＝6.9,1.0Hz,2H),3.79(s,3H),3.67 –3.59(m,2H),2.12–1.92(m,4H).
13C NMR(101MHz,CDCl3)δ192.38,159.69,138.01,129.58,121.60,114.76, 113.08,55.24,55.07,50.56,41.30,26.11,24.31.
MS(EI):m/z(％)＝267(85)[M]+,234(25),207(10),146(90),114(100),91(30).
Example twenty one
Trimethyl (m-methoxybenzyl) ammonium trifluoromethanesulfonate was substituted for benzyltrimethyl ammonium trifluoromethanesulfonate in example one, and sodium piperidinodithioate was substituted for sodium N, N-diethylaminodithiocarbamate in example one, to give a yellow oily liquid piperidine dithiocarboxylic acid (3-methoxybenzyl) ester in a yield of 93%.
1H NMR(400MHz,CDCl3)δ7.22(t,J＝7.8Hz,1H),7.00–6.92(m,2H),6.80 (ddd,J＝8.3,2.6,1.0Hz,1H),4.54(s,2H),4.30(s,2H),3.86(s,2H),3.79(s,3H), 1.79–1.65(m,6H).
13C NMR(101MHz,CDCl3)δ195.22,159.70,137.58,129.58,121.72,114.84, 113.16,55.24,52.92,51.34,42.28,25.54,24.30.
MS(EI):m/z(％)＝281(50)[M]+,248(10),207(10),160(90),120(35),84(100).
Example twenty two
Trimethyl (p-methylbenzyl) ammonium trifluoromethanesulfonate was substituted for benzyltrimethyl ammonium trifluoromethanesulfonate in example one, and sodium pyrrolidine dithiocarbamate was substituted for sodium N, N-diethylaminodithiocarbamate in example one, to give a yellow oily liquid pyrrolidine dithiocarbamate (4-methylbenzyl) ester in a yield of 96%.
1H NMR(400MHz,CDCl3)δ7.31–7.24(m,2H),7.15–7.08(m,2H),4.54(s, 2H),3.94(td,J＝6.9,1.1Hz,2H),3.66–3.57(m,2H),2.32(s,3H),2.05(pd,J＝6.6, 1.2Hz,2H),1.97(pd,J＝6.7,1.3Hz,2H).
13C NMR(101MHz,CDCl3)δ192.57,137.17,133.28,129.30,129.20,54.98, 50.53,41.12,26.10,24.31,21.16.
MS(EI):m/z(％)＝251(60)[M]+,218(15),146(50),105(100),120(35),91(10).
Example twenty three
Trimethyl (p-methylbenzyl) ammonium trifluoromethanesulfonate was substituted for benzyltrimethyl ammonium trifluoromethanesulfonate in example one, and sodium piperidinodithioate was substituted for sodium N, N-diethylaminodithioate in example one, to give 4-methylbenzyl piperidinodithioate as a yellow oily liquid in a yield of 93%.
1H NMR(400MHz,CDCl3)δ7.30–7.24(m,2H),7.11(d,J＝7.9Hz,2H),4.52 (s,2H),4.29(s,2H),3.85(s,2H),2.32(s,3H),1.72–1.64(m,6H).
13C NMR(101MHz,CDCl3)δ195.41,137.23,132.83,129.32,129.31,52.78, 51.30,42.10,25.74(d,J＝43.8Hz),24.31,21.17.
MS(EI):m/z(％)＝265(50)[M]+,232(10),160(75),128(35),105(100),84(85).
Example twenty-four
Trimethyl (o-methylbenzyl) ammonium trifluoromethanesulfonate was substituted for benzyltrimethyl ammonium trifluoromethanesulfonate in example one, and sodium piperidinodithioate was substituted for sodium N, N-diethylaminodithioate in example one, to give 2-methylbenzyl piperidinodithioate as a yellow oily liquid in a yield of 91%.
1H NMR(400MHz,CDCl3)δ7.35(dt,J＝7.0,1.2Hz,1H),7.23–7.10(m,3H), 4.51(s,2H),4.30(s,2H),3.84(s,2H),2.39(s,3H),1.69(q,J＝10.5,8.4Hz,6H).13C NMR(101MHz,CDCl3)δ195.45,137.45,133.41,130.49,127.94,126.23,52.66, 51.32,40.89,25.76(d,J＝43.3Hz),24.31,19.37.
MS(EI):m/z(％)＝265(50)[M]+,232(10),160(95),128(35),105(75),84(100).
Example twenty-five
Trimethyl (o-methylbenzyl) ammonium trifluoromethanesulfonate was substituted for benzyltrimethyl ammonium trifluoromethanesulfonate in example one, and sodium pyrrolidine dithiocarbamate was substituted for sodium N, N-diethylaminodithiocarbamate in example one, to give pyrrolidine dithiocarbamate (2-methylbenzyl) ester as a yellow oily liquid in a yield of 90%.
1H NMR(400MHz,CDCl3)δ7.37(dd,J＝6.9,1.5Hz,1H),7.23–7.10(m,3H), 4.54(s,2H),3.99–3.91(m,2H),3.61(tt,J＝6.8,1.0Hz,2H),2.39(s,3H),2.11– 1.91(m,4H).
13C NMR(101MHz,CDCl3)δ192.58,137.31,133.71,130.47,130.38,127.89, 126.23,54.90,50.53,39.96,26.11,24.32,19.40.
MS(EI):m/z(％)＝251(50)[M]+,218(25),146(70),105(100),91(5).
Example twenty-six
Trimethyl (1-phenylethyl) ammonium trifluoromethanesulfonate was substituted for benzyltrimethyl ammonium trifluoromethanesulfonate in example one to give N, N-diethylaminodithiocarbamic acid (1-phenylethyl) ester as a yellow oily liquid in a yield of 85%.
1H NMR(400MHz,CDCl3)δ7.39–7.30(m,2H),7.29–7.11(m,3H),5.20(q, J＝7.0Hz,1H),3.94(q,J＝7.1Hz,2H),3.62(q,J＝7.2Hz,2H),1.71(d,J＝7.1Hz, 3H),1.18(dt,J＝9.7,7.0Hz,6H).
13C NMR(101MHz,CDCl3)δ194.68,142.28,128.52,127.91,127.35,50.85, 49.29,46.66,22.13,12.53,11.66.
MS(EI):m/z(％)＝253(20)[M]+,207(10),149(40),105(100),88(20).
Example twenty-seven
Trimethyl (1-phenethyl) ammonium trifluoromethanesulfonate was substituted for benzyltrimethyl ammonium trifluoromethanesulfonate in example one, and sodium pyrrolidine dithiocarbamate was substituted for sodium N, N-diethylaminodithiocarbamate in example one, to give a yellow oily liquid pyrrolidine dithiocarbamate (1-phenethyl) ester in 84% yield.
1H NMR(400MHz,CDCl3)δ7.42(ddd,J＝8.1,1.4,0.7Hz,2H),7.31(ddd,J＝ 7.5,6.7,1.2Hz,2H),7.28–7.18(m,1H),5.30(q,J＝7.1Hz,1H),3.98–3.83(m,2H), 3.65–3.48(m,2H),2.09–1.84(m,4H),1.77(dd,J＝7.1,0.7Hz,3H).
13C NMR(101MHz,CDCl3)δ191.81,142.26,128.51,127.76,127.33,54.81, 50.51,50.05,26.01,24.21,22.10.
MS(EI):m/z(％)＝251(20)[M]+,207(25),191(5),147(40),105(100),91(15).
Example twenty-eight
Trimethyl (1-phenylethyl) ammonium trifluoromethanesulfonate was substituted for benzyltrimethyl ammonium trifluoromethanesulfonate in example one, and sodium piperidinodithioate was substituted for sodium N, N-diethylaminodithiocarbamate in example one, to give a yellow oily liquid piperidine dithiocarboxylic acid (1-phenylethyl) ester in a yield of 86%.
1H NMR(400MHz,CDCl3)δ7.45–7.38(m,2H),7.38–7.27(m,2H),7.27– 7.19(m,1H),5.27(q,J＝7.1Hz,1H),4.26(s,2H),3.82(s,2H),1.77(d,J＝7.0Hz, 3H),1.64(d,J＝17.8Hz,6H).
13C NMR(101MHz,CDCl3)δ194.59,142.19,128.49,127.86,127.35,52.62, 50.89,29.69,25.70(d,J＝51.6Hz),24.29,22.12.
MS(EI):m/z(％)＝265(10)[M]+,207(100),191(10),161(10),128(20),104
(90),84(55).
Example twenty-nine
Trimethyl (1- (1-naphthyl) ethyl) ammonium trifluoromethanesulfonate was substituted for benzyltrimethyl ammonium trifluoromethanesulfonate in example one to give 1- (1-naphthyl) ethyl) N, N-diethylaminodithioformate as a yellow oily liquid in a yield of 86%.
1H NMR(400MHz,CDCl3)δ8.24–8.17(m,1H),7.88–7.80(m,1H),7.78(d, J＝8.2Hz,1H),7.65–7.38(m,4H),6.01(q,J＝6.8Hz,1H),4.05(ddq,J＝27.3,13.7, 6.9Hz,2H),3.64(dp,J＝18.3,7.3Hz,2H),1.94(d,J＝6.9Hz,3H),1.29(d,J＝7.1 Hz,3H),1.17(t,J＝7.1Hz,3H).
13C NMR(101MHz,CDCl3)δ194.89,136.92,133.88,131.07,128.73,128.34, 126.50,125.86,125.12,124.98,124.03,49.36,46.86,46.56,21.29,12.47,11.69.
HRMS(ESI)m/z[M+H]+Calcd for C17H21NS2 303.1115,found 304.1177.
Example thirty
Trimethyl (1- (1- (1,2,3, 4-tetrahydronaphthyl)) ethyl) ammonium trifluoromethanesulfonate was substituted for benzyltrimethyl ammonium trifluoromethanesulfonate in example one to give N, N-diethylaminodithiocarboxylic acid (1- (1- (1,2,3, 4-tetrahydronaphthyl))) ester as a yellow oily liquid in a yield of 82%.
1H NMR(400MHz,CDCl3)δ7.44–7.36(m,1H),7.19–7.08(m,2H),7.11– 7.04(m,1H),5.49(t,J＝4.2Hz,1H),4.06(q,J＝7.1Hz,2H),3.81–3.61(m,J＝7.2 Hz,2H),2.79(dddd,J＝22.8,16.7,11.1,5.3Hz,2H),2.39–2.28(m,1H),2.16(dddd, J＝14.1,11.5,4.7,3.1Hz,1H),2.08–1.90(m,1H),1.94–1.82(m,1H),1.32–1.20 (m,6H).
13C NMR(101MHz,CDCl3)δ195.27,138.30,134.78,130.89,129.15,127.16, 125.97,51.01,49.38,46.72,30.04,29.24,19.89,12.53,11.71.
MS(EI):m/z(％)＝279(35)[M]+,207(15),149(65),131(100),104(80),91(20).
Example thirty one
Trimethyl (3-phenyl-N-propyl) ammonium trifluoromethanesulfonate was substituted for benzyltrimethyl ammonium trifluoromethanesulfonate in example one to give N, N-diethylaminodithiocarboxylic acid (3-phenyl-N-propyl) ester as a yellow oily liquid in a yield of 73%.
1H NMR(400MHz,CDCl3)δ7.28–7.10(m,5H),3.97(q,J＝7.1Hz,2H),3.66 (q,J＝7.2Hz,2H),3.50–3.42(m,2H),2.98–2.89(m,2H),1.20(t,J＝7.1Hz,6H).
13C NMR(101MHz,CDCl3)δ195.40,140.32,128.69,128.43,126.37,49.39, 46.66,38.08,35.22,12.44,11.62.
MS(EI):m/z(％)＝253(15)[M]+,207(5),149(65),116(100),88(30).
Example thirty-two
To a dry ground tube with a magnetic stirrer was added benzyl bromide (1.0 mmol), (R) -1-phenylethyl dithiocarbamate (1.5 mmol), potassium hydroxide (3.0 mmol), and water (1.0 ml), and finally the ground tube was sealed with a rubber stopper and charged with argon. The tube was placed in a 50 ℃ oil bath and stirred for 24 hours. The reaction mixture was then cooled to room temperature, quenched with 15mL of saturated NaCl solution and extracted with ethyl acetate (3X 20 mL). And the combined organic layers were dried over anhydrous magnesium sulfate and then adsorbed on some silica gel under reduced pressure on a rotary evaporator. The silica gel on which the sample was adsorbed was transferred to a silica gel column. After purification by silica gel column chromatography (petroleum ether eluent), the (R) -benzyl (1-phenylethyl) sulfide was obtained in 81% yield as a colorless oily liquid, and the ee value: 96 percent. The reaction equation is shown below.
Figure BDA0002244012030000151
The structural characterization data for the product (R) -benzyl (1-phenylethyl) sulfide is as follows:
1H NMR(400MHz,Chloroform-d)δ7.37–7.17(m,10H),3.80(q,J＝7.0Hz, 1H),3.61–3.38(m,2H),1.52(d,J＝7.1Hz,3H).
13C NMR(101MHz,CDCl3)δ143.84,138.47,128.92,128.53,128.43,127.49, 127.11,126.87,43.58,35.75,22.59.
MS(EI):m/z(％)＝228(15)[M]+,105(100),91(10).
example thirty-three
P-bromobenzene was substituted for benzyl bromide in example thirty-two to give (R) - (1-phenylethyl) (p-tolyl) sulfide as a colorless oily liquid in 88% yield and ee value: 95 percent.
Example thirty-four
P-bromobenzene instead of benzyl bromide in example thirty-two, (S) -diethylaminodithiocarboxylic acid (1-phenylethyl) ester instead of (R) -diethylaminodithiocarboxylic acid (1-phenylethyl) ester in example thirty-two gave colorless oily liquid (S) - (1-phenylethyl) (p-tolyl) sulfide in a yield of 82%, ee value: 96 percent.
1H NMR(400MHz,CDCl3)δ7.31–7.22(m,4H),7.25–7.14(m,3H),7.06– 6.99(m,2H),4.26(q,J＝7.0Hz,1H),2.29(s,3H),1.60(d,J＝7.0Hz,3H).
13C NMR(101MHz,CDCl3)δ143.38,137.39,133.23,131.29,129.48,128.36, 127.32,127.07,48.40,22.20,21.13.
MS(EI):m/z(％)＝228(10)[M]+,124(30),105(100),91(10).
Example thirty-five
O-bromobenzene instead of benzyl bromide in example thirty-two, (S) -diethylaminodithiocarboxylic acid (1-phenylethyl) ester instead of (R) -diethylaminodithiocarboxylic acid (1-phenylethyl) ester in example thirty-two gave colorless oily liquid (S) - (1-phenylethyl) (o-tolyl) sulfide in a yield of 82%, ee value: 97 percent.
Example thirty-six
O-bromobenzene was substituted for benzyl bromide in example thirty-two to give (R) - (1-phenylethyl) (p-tolyl) sulfide as a colorless oily liquid in 79% yield, ee value: 96 percent.
1H NMR(400MHz,CDCl3)δ7.32–7.23(m,4H),7.28–7.19(m,1H),7.23– 7.13(m,1H),7.17–7.05(m,2H),7.10–7.01(m,1H),4.29(q,J＝7.0Hz,1H),2.32 (s,3H),1.64(d,J＝7.0Hz,3H).
13C NMR(101MHz,CDCl3)δ143.27,140.02,134.51,132.71,130.15,128.41, 127.21,127.14,127.12,126.20,47.33,22.26,20.67.
MS(EI):m/z(％)＝228(10)[M]+,124(10),105(100),91(5).
Example thirty-seven
(R) -1- (1- (1,2,3, 4-tetrahydronaphthyl))) ester instead of (R) -1-phenethyl-dithiocarbamate in example thirty-two, gave (R) -benzyl (1- (1- (1,2,3, 4-tetrahydronaphthyl))) sulfide as a colorless oily liquid in a yield of 92%, ee value: 96 percent.
Example thirty-eight
The yield of (S) -benzyl (1- (1- (1,2,3, 4-tetrahydronaphthyl))) sulfide, which was a colorless oily liquid, was 88% instead of (S) -diethylaminodithiocarboxylic acid (1-phenethyl) ester in example thirty-two, and the ee value was: 98 percent.
1H NMR(400MHz,CDCl3)δ7.35–7.20(m,4H),7.16(ddt,J＝8.1,6.6,2.6Hz, 2H),7.07–6.92(m,3H),3.90(t,J＝4.4Hz,1H),3.77–3.61(m,2H),2.74(dt,J＝ 16.8,5.1Hz,1H),2.64(ddd,J＝16.5,9.9,5.8Hz,1H),2.17–1.85(m,3H),1.69 (ddddd,J＝13.1,8.7,5.6,3.0,0.9Hz,1H).
13C NMR(101MHz,CDCl3)δ138.55,137.53,136.34,130.33,129.15,128.96, 128.53,126.96,126.74,125.66,43.23,36.19,29.12,28.82,19.11.
MS(EI):m/z(％)＝254(5)[M]+,131(100),115(10),91(25).

Claims (4)

1. A method for synthesizing dialkyl amino alkyl dithioformate is characterized in that: under the catalysis of CuI with catalyst amount, alkyl quaternary ammonium salt and dialkyl dithiocarbamate are subjected to C-S cross coupling in acetonitrile at 80 ℃ to synthesize dialkyl amino dithiocarbamate, and the reaction equation is shown as follows
Figure FDA0002910733930000011
Wherein n is 0 or 2, Z is CH3,CH2Or H, NuE is the sodium salt of a dialkyldithiocarbamate, the quaternary alkyl ammonium salt being ammonium N, N, N-trimethyl (phenyl) methyltrifluoromethane sulfonate, ammonium N, N, N-trimethyl (o-tolyl) methyltrifluoromethane sulfonate, ammonium N, N, N-trimethyl (m-tolyl) methyltrifluoromethane sulfonate, ammonium N, N, N-trimethyl (p-tolyl) methyltrifluoromethane sulfonate, ammonium N, N, N-trimethyl (o-fluorophenyl) methyltrifluoromethane sulfonate, ammonium N, N, N-trimethyl (m-fluorophenyl) methyltrifluoromethane sulfonate, ammonium N, N, N-trimethyl (o-chlorophenyl) methyltrifluoromethane sulfonate, ammonium N, N, N-trimethyl (m-methoxyphenyl) methyltrifluoromethane sulfonate, ammonium N, N, N-trimethyl (p-methoxyphenyl) methyltrifluoromethane sulfonate, (4-cyanophenyl) -ammonium N, N, N-trimethylmethylammonium trifluoromethanesulfonate, ammonium N, N, N-trimethyl (4-trifluoromethylphenyl) methyltrifluoromethane sulfonate, (R) -ammonium N, N, N-trimethyl-1-phenethyltrifluoromethanesulfonate, (S) -ammonium N, N, N-trimethyl-1-phenethyltrifluoromethanesulfonate, (R) -ammonium N, N, N-trimethyl-1- (1-naphthyl) ethyltrifluoromethanesulfonate, (S) -ammonium N, N, N-trimethyl-1- (1-naphthyl) ethyltrifluoromethanesulfonate, ammonium N, N-trimethyl-1- (1-naphthyl) ethyltrifluoromethanesulfonate, (S) -ammonium N, N-trimethyl-1- (1- (1,2,3, 4-tetrahydronaphthyl)) ethyltrifluoromethanesulfonate, (R) -ammonium N, N-trimethyl-1- (1- (1,2,3, 4-tetrahydronaphthyl)) ethyltrifluoromethanesulfonate, ammonium N, N-trimethyl-3-phenyl-N-propyltrifluoromethanesulfonate.
2. The method for synthesizing an alkyl dialkyldithiocarbamate according to claim 1, wherein the sodium salt of dialkyldithiocarbamate is sodium N, N-diethyldithiocarbamate, sodium N, N-dimethyldithiocarbamate, sodium N, N-di-t-butyldithiocarbamate, sodium pyrrolidinodithioate, sodium piperidinodithioate, sodium N, N-dibenzylaminodithiocarbamate, (S) -1- (1-naphthyl) sodium ethyldithiocarbamate, (R) -1- (1-naphthyl) sodium ethyldithiocarbamate, sodium 1- (1-naphthyl) sodium ethyldithiocarbamate, (S) -1-sodium phenylethyldithiocarbamate, (R) -1-sodium phenylethylaminodithiocarbamate, sodium 1-phenethylaminodithiocarbamate.
3. The method for synthesizing an alkyl dialkylaminodithiocarbamate according to claim 1, wherein the amount of the catalyst is 5 mol% of the molar amount of the CuI.
4. A process for the synthesis of an alkyl dialkyl dithiocarbamate as claimed in claim 1, wherein the chiral configuration of the alkyl dialkyl dithiocarbamate product is determined by the starting materials, the chirality of the dialkyl dithiocarbamate remains in the original configuration in the product, and the chiral quaternary ammonium salt is completely inverted in the product, i.e. the quaternary ammonium salt in the R configuration gives the product a configuration of S, and vice versa.
CN201911015040.2A 2019-10-23 2019-10-23 Synthesis method of dialkyl amino alkyl dithioformate Active CN110683975B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911015040.2A CN110683975B (en) 2019-10-23 2019-10-23 Synthesis method of dialkyl amino alkyl dithioformate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911015040.2A CN110683975B (en) 2019-10-23 2019-10-23 Synthesis method of dialkyl amino alkyl dithioformate

Publications (2)

Publication Number Publication Date
CN110683975A CN110683975A (en) 2020-01-14
CN110683975B true CN110683975B (en) 2021-04-09

Family

ID=69113971

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911015040.2A Active CN110683975B (en) 2019-10-23 2019-10-23 Synthesis method of dialkyl amino alkyl dithioformate

Country Status (1)

Country Link
CN (1) CN110683975B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112028802B (en) * 2020-06-22 2023-04-07 浙江农林大学暨阳学院 Method for preparing N, N-dimethyl phenyl dithioacetate compound by grinding method
CN112321469B (en) * 2020-11-04 2022-07-12 成都理工大学 Synthetic method of dibenzyl sulfide
CN113264861B (en) * 2021-06-02 2022-08-26 河南农业大学 Preparation method of alkyl dithiocarbamate
CO2022007001A1 (en) 2022-05-25 2022-06-21 Univ Santiago De Cali Metal-coordinated aromatic amine derivatives as bactericidal materials and their production process

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1727332A (en) * 2004-07-27 2006-02-01 北京大学 Compound in category of aryl methylamino dithio formic ether, preparation method and application
CN101759654A (en) * 2010-01-20 2010-06-30 首都师范大学 4-quinazolinone-6-methylamino dithiocarbamate as well as medical composition and application thereof
CN101823990A (en) * 2010-04-23 2010-09-08 中国科学院新疆理化技术研究所 Amino-acid ester dithiocarbamic acid ester compound as well as preparation method and application thereof
CN102066450A (en) * 2008-06-30 2011-05-18 三井化学株式会社 Polymerizable composition for polythiourethane optical material, polythiourethane optical material obtained from same polymerizable composition, and polymerization catalyst for polythiourethane optical material
CN102234271A (en) * 2010-04-21 2011-11-09 北京大学 Aryl (alkyl) amino dithio formate compounds, and preparation method and application thereof
CN104817490A (en) * 2015-05-13 2015-08-05 北京大学 Novel aminodithioformate compounds, and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1727332A (en) * 2004-07-27 2006-02-01 北京大学 Compound in category of aryl methylamino dithio formic ether, preparation method and application
CN102066450A (en) * 2008-06-30 2011-05-18 三井化学株式会社 Polymerizable composition for polythiourethane optical material, polythiourethane optical material obtained from same polymerizable composition, and polymerization catalyst for polythiourethane optical material
CN101759654A (en) * 2010-01-20 2010-06-30 首都师范大学 4-quinazolinone-6-methylamino dithiocarbamate as well as medical composition and application thereof
CN102234271A (en) * 2010-04-21 2011-11-09 北京大学 Aryl (alkyl) amino dithio formate compounds, and preparation method and application thereof
CN101823990A (en) * 2010-04-23 2010-09-08 中国科学院新疆理化技术研究所 Amino-acid ester dithiocarbamic acid ester compound as well as preparation method and application thereof
CN104817490A (en) * 2015-05-13 2015-08-05 北京大学 Novel aminodithioformate compounds, and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Acetyl chloride--3,5-di(tert-butyl)-4-hydroxy-N,N-dimethylbenzylamine salt in the benzylation of organic and inorganic sulfur-containing compounds;D. B. Gorbunov等;《Russian Chemical Bulletin》;19940131;第43卷(第1期);P93-97 *

Also Published As

Publication number Publication date
CN110683975A (en) 2020-01-14

Similar Documents

Publication Publication Date Title
CN110683975B (en) Synthesis method of dialkyl amino alkyl dithioformate
US10087202B2 (en) Chiral aziridine phosphoramidate compounds
UA79157C2 (en) Method for the synthesis of thiophenecarboxylic acid esters and the use thereof
Eggerding et al. Synthesis of the monothiosquarate and 1, 2-dithiosquarate ions and their derivatives
CN110218229B (en) Beta-mercapto azaphospho heterocyclic derivative and preparation method thereof
US9771364B2 (en) Process for preparation of (2S,5R)-6-sulphooxy-7-oxo-2-[((3R)-piperidine-3-carbonyl)-hydrazinocarbonyl]-1,6-diaza-bicyclo[3.2.1] octane
KR20220158761A (en) Preparation of cyclosporine derivatives
EP2178847A2 (en) Process for preparing pyrimidine derivatives
WO2015130660A1 (en) Synthesis of racemic amphetamine derivatives by cuprate addition reaction with aziridine phosphoramidate compounds
FI80700B (en) FOERFARANDE FOER FRAMSTAELLNING AV TERAPEUTISKT ANVAENDBARA MITOMYCINANALOGER.
JPH02306947A (en) Preparation of chiral bata-amino acid
CN112608262B (en) Oxalic acid diselenide ester compound and synthesis method and application thereof
US9321794B2 (en) Synthesis of racemic amphetamine derivatives by cuprate addition reaction with aziridine phosphoramidate compounds
Khabibullina et al. Synthesis of N-Substituted Thiazacycloalkanes by Cyclothiomethylation of Primary Aliphatic Amines and Amino Derivatives of Maleopimaric Acid
JPH0641463B2 (en) Method for producing thiotetronic acid
Berredjem et al. Simple and efficient synthesis of new chiral N, N′‐sulfonyl bis‐oxazolidin‐2‐ones
FI83085C (en) Process for the preparation of therapeutically useful pyridazo / 1,2-a // 1,2 / diazepine derivatives
KR100897610B1 (en) Process for the preparation of n-phosphorylamidine using cu catalyst
CN110573521B (en) Process for preparing 4' -thionucleosides and intermediates in the process
Bourry et al. Studies on pyrrolidinones: Some attempts to improve the anticancer properties of methyl n‐(3, 4, 4′, 5‐tetramethoxybenzhydryl) pyroglutamate (HEI 81)
CN107629052B (en) A kind of pyrrolo- [3,4b] quinoline -9- aminated compounds and its preparation method and application
CN106256818B (en) A kind of indone with trifluoromethylthio and its derivative and preparation method thereof
JP2017533184A (en) Complex and preparation method thereof
Wojaczyńska et al. Chiral pyrrolidine thioethers and 2-azanorbornane derivatives bearing additional nitrogen functions. Enantiopure ligands for palladium-catalyzed Tsuji-Trost reaction.
US20030060637A1 (en) Cyclic aniline sulfide and process for preparing the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant