CN104355955B - Method for synthetizing carbamate - Google Patents
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- CN104355955B CN104355955B CN201410558058.8A CN201410558058A CN104355955B CN 104355955 B CN104355955 B CN 104355955B CN 201410558058 A CN201410558058 A CN 201410558058A CN 104355955 B CN104355955 B CN 104355955B
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- ZUSNRCQLPSZULU-UHFFFAOYSA-N CC(c1c(cccc2)c2ccc1)OC(N1CCCC1)=O Chemical compound CC(c1c(cccc2)c2ccc1)OC(N1CCCC1)=O ZUSNRCQLPSZULU-UHFFFAOYSA-N 0.000 description 1
- VACKECGGJDCBMH-UHFFFAOYSA-N CCN(CC)C(OC(C)c(cc1)ccc1Br)=O Chemical compound CCN(CC)C(OC(C)c(cc1)ccc1Br)=O VACKECGGJDCBMH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a method for synthetizing carbamate. The method comprises the following steps: adding sulfonyl hydrazones, amine and solvents in a high-pressure kettle, adding alkali as an accelerant, introducing carbon dioxide, performing a stirring reaction for 6-72 hours at the temperature of 40-150 DEG C, cooling the high-pressure kettle to the room temperature after the reaction is completed, slowly releasing carbon dioxide which is not reacted to constant pressure, filtering a reaction liquid, decompressing and stewing the solvents to obtain crude products, and obtaining a series of carbamate chemical compounds through refining in a column chromatography. The method for synthetizing carbamate is safe and simple to operate, the prices of raw materials are low, the raw materials are easy to obtain, the adaptability for functional groups is high, the adaptability for substrates is wide, the method is environmental-friendly, industrial production is facilitated, and the method is widely applied to the synthesis of agricultural chemicals, medicines and natural products.
Description
Technical field
The present invention relates to medication chemistry synthesis technical field is and in particular to arrive a kind of method of synthesis of carbamates.
Background technology
Carbamate compound matter is the nitrogen-containing compound that a class has biological and pharmacoligical activities, is widely used as pesticide
As Insecticides (tech) ＆ Herbicides (tech) etc..Carbamate is also to build natural product and the important framing structure of medicine, such as prezista,
The brand medicine of the market sales such as lunesta, the xeloda and vesicare just fragment containing carbamate.Additionally, ammonia
Carbamate class compound is also the important raw material of a class, intermediate, has important purposes in organic synthesiss.Therefore, ammonia
The synthesis of carbamate is widely paid close attention to always.
Traditionally carbamate is with phosgene or isocyanates material as Material synthesis, due to phosgene or different
Cyanate material high poison is explosive, the environmental pollution easily causing during use, the safety seriously threatening people, so in industry
It is extremely limited (s.ozaki, chem.rev.1972,72,457-496 in application；r.a.batey,
v.santhakumar,c.y.ishii,s.d.taylor,tetrahedron lett.1998,39,6267-6270).
In recent years, some replaced with other raw materials high poison phosgene, isocyanates synthesis of carbamates method also successively
Be reported, mainly have (1) compound through catalytic reduction of nitro carbonylation (a.m.tafesh, j.weiguny,
chem.rev.1996,96,2035-2052)；(2) amine oxidation carbonylation (f.shi, y.deng,
chem.commun.2001,443-444)；(3) Huffman and curtius' rearrangement (a.yoshimura, m.w.luedtke,
v.v.zhdankin,j.org.chem.2012,77,2087-2091；h.lebel,o.leogane,org.lett.2005,7,
4107-4110；h.lebel,o.leogane,org.lett.2006,8,5717-5720)；(4) Methanamide and 'beta '-ketoester or 2-
Carbonyl replace phenol oxidative coupling reaction (g.s.kumar, c.u.maheswari, r.a.kumar, m.l.kantam,
k.r.reddy,angew.chem.int.ed.2011,50,11748-11751；n.t.s.phan,t.t.nguyen,
p.h.l.vu,chemcatchem 2013,5,3068-3077)；(5) with carbon dioxide as raw material.Carbon dioxide is because it is on ground
Rich content on ball, low price, nontoxic, reproducible the features such as, replace phosgene with it as synthesis of carbamates
Raw material cause everybody great interest (s.l.peterson, s.m.stucka, c.j.dinsmore, org.lett.2010,
12,1340-1343；y.takeda,s.okumura,s.tone,i.sasaki,s.minakata,org.lett.2012,14,
4874-4877；w.mcghee,d.riley,k.christ,y.pan,b.parnas,j.org.chem.1995,60,2820-
2830；d.chaturvedi,tetrahedron2012,68,15-45；m.abla,j.-c.choi,t.sakakura,
chem.commun.2001,2238-2239；j.m.hooker,a.t.reibel,s.m.hill,m.j.schueller,
j.s.fowler,angew.chem.int.ed.2009,48,3482-3485).
Content of the invention
The invention provides a kind of method of synthesis of carbamates, the method raw material is easy to get, cheap, safe operation
Simply, and with carbon dioxide as raw material it is not necessary to transition-metal catalyst, environmental friendliness.
The principle of the present invention is with carbon dioxide, amine and sulphonyl hydrazone as raw material, under the promotion of alkali, three component reaction occurs
One-step synthesis carbamate.Due to being raw material using carbon dioxide, reduce the harm to environment, and all raw materials are inexpensively easy
, method is simple, safe operation, thus has potential practical value.
The purpose of the present invention is achieved through the following technical solutions:
A kind of synthetic method of carbamate: in autoclave, add sulphonyl hydrazone, amine and solvent, addition alkali is
Accelerator, is passed through carbon dioxide, stirring reaction 6～72 hours at 50～150 DEG C, and reaction is cooled to room temperature after terminating, release
Haunt reaction carbon dioxide to normal pressure, reacting liquid filtering, remove solvent under reduced pressure and obtain crude product, through column chromatography purification obtain amino
Formic acid esters；
Above-mentioned reaction is shown below:
Wherein, r1Including phenyl, xenyl, p-bromophenyl, rubigan, to iodophenyl, p-methylphenyl, to cyano group benzene
Base, p-trifluoromethyl phenyl, p-nitrophenyl, o-bromophenyl, a bromophenyl, 3,4- Dichlorobenzene base, 1- naphthyl, 2- benzofuran
Base, 2- thienyl or 4- pyridine radicals；
r2Including hydrogen, methyl, cyclopropyl or phenyl；
r3And r4Including hydrogen, methyl, ethyl, propyl group, normal-butyl or benzyl；OrFor nafoxidine, hexahydropyridine
Or morpholine；
r5Including p-methylphenyl, phenyl, p-methoxyphenyl, 2- naphthyl, p- nitrobenzophenone, p-bromophenyl, benzyl, first
Base or normal-butyl.
In said method, autoclave adopts gap type high-pressure reactor or continuous high pressure reactor.
In said method, described sulphonyl hydrazone is 1:(1～20 with the mol ratio of amine).
In said method, the pressure of carbon dioxide is 0.5～10mpa.
In said method, solvent is acetonitrile, oxolane, n, in n- dimethylformamide, dimethyl sulfoxide, methanol or water
More than one.
In said method, described alkali is sodium carbonate, potassium carbonate, cesium carbonate, Feldalat NM, potassium tert-butoxide, sodium tert-butoxide, tertiary fourth
Lithium alkoxide, 1,4- diazabicylo [2.2.2] octane or 1,8- diazabicylo [5.4.0] 11 carbon -7- alkene.
In said method, the amount of alkali is added to be (1～5) with the mol ratio of sulphonyl hydrazone: 1.
In said method, reaction temperature is 50～150 DEG C.
In said method, the response time is 6～72 hours.
In said method, product is isolated and purified after terminating by reaction using column chromatography；Described column chromatography eluent is oil
Ether and the mixed solvent of ethyl acetate, the volume ratio between petroleum ether and ethyl acetate is 5～50:1.
The present invention, with respect to existing technology, has advantages below and an effect:
The synthetic method safe operation of carbamate of the present invention is simple, advantages of nontoxic raw materials, cheap, be readily obtained, right
Functional group adaptability is good, to substrate wide adaptability, environmental friendliness, has good prospects for commercial application.
Brief description
Fig. 1 is the hydrogen spectrogram of embodiment 1-8 products obtained therefrom；
Fig. 2 is the carbon spectrogram of embodiment 1-8 products obtained therefrom；
Fig. 3 be embodiment 9 product hydrogen spectrogram；
Fig. 4 be embodiment 9 product carbon spectrogram；
Fig. 5 be embodiment 10 product hydrogen spectrogram；
Fig. 6 be embodiment 10 product carbon spectrogram；
Fig. 7 be embodiment 11 product hydrogen spectrogram；
Fig. 8 be embodiment 11 product carbon spectrogram；
Fig. 9 be embodiment 12 product hydrogen spectrogram；
Figure 10 be embodiment 12 product carbon spectrogram；
Figure 11 be embodiment 13 product hydrogen spectrogram；
Figure 12 be embodiment 13 product carbon spectrogram；
Figure 13 be embodiment 14 product hydrogen spectrogram；
Figure 14 be embodiment 14 product carbon spectrogram.
Specific embodiment
With reference to specific embodiments and the drawings, the present invention is described in further detail, but the embodiment party of the present invention
Formula and the substrate not limited to this adapting to.
Embodiment 1
Autoclave adds 0.5 mM of parabromoacetophenone Tosylhydrazone, 0.5 mM of nafoxidine,
0.5 mM of potassium carbonate, 3 milliliters of acetonitriles, it is filled with the co of 0.5mpa2, after 50 DEG C of stirring reactions 6 hours, stop heating and stir
Mix, be cooled to room temperature, be slowly vented unreacted co2.Reacting liquid filtering, filtrate decompression revolving removes solvent, then passes through post layer
Analysis isolates and purifies, and obtains target product, and column chromatography eluent used is the petroleum ether of 30:1 for volume ratio: ethyl acetate mixing
Solvent, yield 8%.
Embodiment 2
Autoclave adds 0.5 mM of parabromoacetophenone Tosylhydrazone, 10 mMs of nafoxidines,
2.5 mMs of potassium carbonate, 6 milliliters of acetonitriles, it is filled with the co of 10mpa2, after 150 DEG C of stirring reactions 72 hours, stop heating and stir
Mix, be cooled to room temperature, be slowly vented unreacted co2.Reacting liquid filtering, filtrate decompression revolving removes solvent, then passes through post layer
Analysis isolates and purifies, and obtains target product, and column chromatography eluent used is the petroleum ether of 30:1 for volume ratio: ethyl acetate mixing
Solvent, yield 58%.
Embodiment 3
0.5 mM of parabromoacetophenone Tosylhydrazone, 5 mMs of nafoxidines, 1 millis are added in autoclave
Mole of potassium carbonate, 3 milliliters of acetonitriles, it is filled with the co of 6mpa2, after 120 DEG C of stirring reactions 24 hours, stop heating and stir, cold
But to room temperature, slowly it is vented unreacted co2.Reacting liquid filtering, filtrate decompression revolving removes solvent, then passes through column chromatography for separation
Purification, obtains target product, and column chromatography eluent used is the petroleum ether of 30:1: ethyl acetate mixed solvent for volume ratio,
Yield 49%.
Embodiment 4
Autoclave adds 0.5 mM of parabromoacetophenone Tosylhydrazone, 5 mMs of nafoxidines, 1.5
MM tert-butyl alcohol lithium, 3 milliliters of acetonitriles, it is filled with the co of 4mpa2, after 90 DEG C of stirring reactions 24 hours, stop heating and stir,
It is cooled to room temperature, be slowly vented unreacted co2.Reacting liquid filtering, filtrate decompression revolving removes solvent, then is divided by column chromatography
From purification, obtain target product, column chromatography eluent used is the petroleum ether of 30:1 for volume ratio: ethyl acetate mixing is molten
Agent, yield 45%.
Embodiment 5
Autoclave adds 0.5 mM of parabromoacetophenone Tosylhydrazone, 2 mMs of nafoxidines, 1.5
MM Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane, 2 milliliters of n, n- dimethylformamide, it is filled with the co of 2mpa2, stir at 100 DEG C
After mixing reaction 48 hours, stop heating and stir, be cooled to room temperature, be slowly vented unreacted co2.Reacting liquid filtering, filtrate
Vacuum rotary steam removes solvent, then passes through column chromatographic isolation and purification, obtains target product, and column chromatography eluent used is volume ratio
Petroleum ether for 30:1: ethyl acetate mixed solvent, yield 28%.
Embodiment 6
Autoclave adds 0.5 mM of parabromoacetophenone Tosylhydrazone, 5 mMs of nafoxidines, 1.5
MM potassium carbonate, the mixed solvent (volume ratio: oxolane: water=15:1) of 3 milliliters of oxolane/water, it is filled with 6mpa's
co2, after 120 DEG C of stirring reactions 48 hours, stop heating and stir, be cooled to room temperature, be slowly vented unreacted co2.Reaction
Liquid filters, and filtrate decompression revolving removes solvent, then passes through column chromatographic isolation and purification, obtains target product, column chromatography used is washed
De- liquid is the petroleum ether of 30:1: ethyl acetate mixed solvent, yield 71% for volume ratio.
Embodiment 7
0.5 mM of parabromoacetophenone benzene sulfonyl hydrazone, 5 mMs of nafoxidines, 1.5 mmoles are added in autoclave
That potassium carbonate, the mixed solvent (volume ratio: oxolane: water=15:1) of 3 milliliters of oxolane/water, it is filled with the co of 6mpa2,
After 120 DEG C of stirring reactions 48 hours, stop heating and stir, be cooled to room temperature, be slowly vented unreacted co2.Reactant liquor
Filter, filtrate decompression revolving removes solvent, then pass through column chromatographic isolation and purification, obtain target product, column chromatography eluting used
Liquid is the petroleum ether of 30:1: ethyl acetate mixed solvent, yield 63% for volume ratio.
Embodiment 8
Autoclave adds 0.5 mM of parabromoacetophenone brosyl hydrazone, 5 mMs of nafoxidines, 1.5
MM potassium carbonate, 3 milliliters of acetonitriles, it is filled with the co of 4mpa2, after 120 DEG C of stirring reactions 48 hours, stop heating and stir,
It is cooled to room temperature, be slowly vented unreacted co2.Reacting liquid filtering, filtrate decompression revolving removes solvent, then is divided by column chromatography
From purification, obtain target product, column chromatography eluent used is the petroleum ether of 30:1 for volume ratio: ethyl acetate mixing is molten
Agent, yield 43%.
The structural characterization data of embodiment 1-8 products therefrom is as follows:
1h nmr(400mhz,cdcl3): δ=7.45 (d, j=8.4,2h), 7.23 (d, j=8.4,2h), 5.77 (q, j=
6.8,1h), 3.37 (br, 4h), 1.85 (br, 4h), 1.51 (d, j=6.8,3h).
13c nmr(100mhz,cdcl3): δ=154.2,141.8,131.5,127.7,121.3,71.8,45.9,45.9,
25.6,25.0,22.8.
ir(kbr):2978,2874,1710,1695,1594,1490,1419,1346,1327,1178,1127,1098,
1069,1008,967,890,866,822,766,716,538cm-1.
Ms (ei): m/z (%)=297 [m+],238,183,104(100),70.
hrms esi(m/z):calcd for c13h16brno2na(m+na)+:320.0257,found:320.0260.
Infer that according to data above the structure of products therefrom is as follows:
Embodiment 9
Autoclave adds 0.5 mM of parachloroacetophenone Tosylhydrazone, 5 mMs of nafoxidines, 1.5
MM potassium carbonate, the mixed solvent (volume ratio: oxolane: water=15:1) of 3 milliliters of oxolane/water, it is filled with 6mpa's
co2, after 120 DEG C of stirring reactions 48 hours, stop heating and stir, be cooled to room temperature, be slowly vented unreacted co2.Reaction
Liquid filters, and filtrate decompression revolving removes solvent, then passes through column chromatographic isolation and purification, obtains target product, column chromatography used is washed
De- liquid is the petroleum ether of 30:1: ethyl acetate mixed solvent, yield 62% for volume ratio.
The structural characterization data of products therefrom is as follows:
1h nmr(400mhz,cdcl3): δ=7.29 (br, 4h), 5.78 (q, j=6.4,1h), 3.38 (br, 4h), 1.85
(br, 4h), 1.51 (d, j=6.4,3h).
13c nmr(100mhz,cdcl3): δ=154.3,141.3,133.2,128.5,127.3,71.8,45.9,25.3,
25.3,22.8.
ir(kbr):2976,2877,1704,1492,1411,1337,1179,1096,1012,827,767cm-1.
Ms (ei): m/z (%)=253 [m+],194,139(100),103,70.
hrms esi(m/z):calcd for c13h16clno2na(m+na)+:276.0762,found:276.0761.
Infer that products therefrom obtains structure according to data above as follows:
Embodiment 10
Add 0.5 mM to trifluoromethyl acetophenone Tosylhydrazone, 5 mMs of tetrahydrochysene pyrroles in autoclave
Cough up, 1.5 mMs of potassium carbonate, the mixed solvent (volume ratio: oxolane: water=15:1) of 3 milliliters of oxolane/water, be filled with
The co of 6mpa2, after 120 DEG C of stirring reactions 48 hours, stop heating and stir, be cooled to room temperature, slow emptying is unreacted
co2.Reacting liquid filtering, filtrate decompression revolving removes solvent, then passes through column chromatographic isolation and purification, obtains target product, used
Column chromatography eluent is the petroleum ether of 30:1: ethyl acetate mixed solvent, yield 68% for volume ratio.
The structural characterization data of products therefrom is as follows:
1h nmr(400mhz,cdcl3): δ=7.58 (d, j=8.0,2h), 7.46 (d, j=7.6,2h), 5.85 (q, j=
6.8,1h), 3.38 (br, 4h), 1.86 (br, 4h), 1.53 (d, j=6.8,3h).
13c nmr(100mhz,cdcl3): δ=154.1,146.8,129.6 (j=32.2), 126.1,125.4 (j=
3.7),122.7,71.8,46.1,45.8,25.6,24.9,22.8.ir(kbr):2978,2880,1706,1413,1326,
1168,1124,1072,1016,842,766cm-1.
Ms (ei): m/z (%)=287 [m+],228,173(100),153,133,114,98,70.
hrms esi(m/z):calcd for c14h16f3no2na(m+na)+:310.1025,found:310.1031.
Infer that products therefrom obtains structure according to data above as follows:
Embodiment 11
0.5 mM of 1- acetonaphthone Tosylhydrazone, 5 mMs of nafoxidines, 1.5 millis are added in autoclave
Mole of potassium carbonate, the mixed solvent (volume ratio: oxolane: water=15:1) of 3 milliliters of oxolane/water, it is filled with 6mpa's
co2, after 120 DEG C of stirring reactions 48 hours, stop heating and stir, be cooled to room temperature, be slowly vented unreacted co2.Reaction
Liquid filters, and filtrate decompression revolving removes solvent, then passes through column chromatographic isolation and purification, obtains target product, column chromatography used is washed
De- liquid is the petroleum ether of 30:1: ethyl acetate mixed solvent, yield 57% for volume ratio.
The structural characterization data of products therefrom is as follows:
1h nmr(400mhz,cdcl3): δ=8.19 (d, j=8.4,1h), 7.86 (d, j=8.0,1h), 7.79 (d, j=
8.0,1h), 7.60 (d, j=7.2,1h), 7.55 7.43 (m, 3h), 6.59 (q, j=6.8,1h), 3.55 3.34 (m, 4h),
1.86 (br, 4h), 1.72 (d, j=6.8,3h).
13c nmr(100mhz,cdcl3): δ=154.4,138.4,133.8,130.2,128.7,128.0,126.0,
125.5,125.3,123.5,123.1,70.1,46.1,45.8,25.6,25.9,22.5.
ir(kbr):2975,2876,1701,1597,1512,1414,1176,1098,869,774cm-1.
Ms (ei): m/z (%)=269 [m+],210,155(100),127,98,70.
hrms esi(m/z):calcd for c17h19no2na(m+na)+:292.1308,found:292.1310.
Infer that products therefrom obtains structure according to data above as follows:
Embodiment 12
0.5 mM of parabromoacetophenone Tosylhydrazone, 5 mMs of diethylamine, 1.5 millis are added in autoclave
Mole of potassium carbonate, 3 milliliters of acetonitriles, it is filled with the co of 6mpa2, after 120 DEG C of stirring reactions 48 hours, stop heating and stir, cold
But to room temperature, slowly it is vented unreacted co2.Reacting liquid filtering, filtrate decompression revolving removes solvent, then passes through column chromatography for separation
Purification, obtains target product, and column chromatography eluent used is the petroleum ether of 30:1: ethyl acetate mixed solvent for volume ratio,
Yield 41%.
The structural characterization data of products therefrom is as follows:
1h nmr(400mhz,cdcl3): δ=7.46 (d, j=8.0,2h), 7.22 (d, j=8.0,2h), 5.76 (q, j=
6.4,1h), 3.29 (q, j=6.8,4h), 1.51 (d, j=6.8,3h), 1.12 (t, j=6.8,6h).
13c nmr(100mhz,cdcl3): δ=155.1,141.8,131.5,127.6,121.3,72.0,41.8,41.2,
22.6,14.1,13.5.ir(kbr):2978,2932,2874,1701,1478,1424,1377,1272,1170,1071,
1009,972,821,788,534cm-1.
Ms (ei): m/z (%)=299 [m+],242,183,104(100),100,72.
hrms esi(m/z):calcd for c13h19brno2(m+h)+:300.0594,found:300.0593.
Infer that products therefrom obtains structure according to data above as follows:
Embodiment 13
Autoclave adds 0.5 mM to methyl naphthaldehyde Tosylhydrazone, 5 mMs of nafoxidines,
1.5 mMs of potassium carbonate, 3 milliliters of acetonitriles, it is filled with the co of 6mpa2, after 120 DEG C of stirring reactions 48 hours, stop heating and stir
Mix, be cooled to room temperature, be slowly vented unreacted co2.Reacting liquid filtering, filtrate decompression revolving removes solvent, then passes through post layer
Analysis isolates and purifies, and obtains target product, and column chromatography eluent used is the petroleum ether of 20:1 for volume ratio: ethyl acetate mixing
Solvent, yield 39%.
The structural characterization data of products therefrom is as follows:
1h nmr(400mhz,cdcl3): δ=7.27 (d, j=7.6,2h), 7.15 (d, j=7.2,2h), 5.09 (s,
2h),3.38(br,4h),2.34(s,3h),1.84(br,4h).
13c nmr(100mhz,cdcl3): δ=155.0,137.6,134.1,129.1,128.0,66.5,46.0,25.3,
21.1.ir(kbr):2959,2877,1702,1419,1351,1263,1178,1097,805,761cm-1.
Ms (ei): m/z (%)=219 [m+],174,114,105(100),70.
hrms esi(m/z):calcd for c13h17no2na(m+na)+:242.1151,found:242.1149.
Infer that products therefrom obtains structure according to data above as follows:
Embodiment 14
Add 0.5 mM to bromonaphthalene ethyl ketone Tosylhydrazone, 5 mMs of n-butylamines, 1.5 millis in autoclave
Mole of potassium carbonate, the mixed solvent (volume ratio: oxolane: water=15:1) of 3 milliliters of oxolane/water, it is filled with 6mpa's
co2, after 120 DEG C of stirring reactions 48 hours, stop heating and stir, be cooled to room temperature, be slowly vented unreacted co2.Reaction
Liquid filters, and filtrate decompression revolving removes solvent, then passes through column chromatographic isolation and purification, obtains target product, column chromatography used is washed
De- liquid is the petroleum ether of 20:1: ethyl acetate mixed solvent, yield 42% for volume ratio.
The structural characterization data of products therefrom is as follows:
1h nmr(400mhz,cdcl3): δ=7.45, (d, j=8.0,2h), 7.21 (d, j=8.4,2h), 5.73 (q, j
=5.6,1h), 4.90 4.44 (m, 1h), 3.23 3.09 (m, 2h), 1.54 1.42 (m, 5h), 1.35 1.28 (m, 2h),
0.91 (t, j=7.2,3h).
13c nmr(100mhz,cdcl3): δ=155.7,141.4,131.5,127.7,121.5,71.8,40.7,32.0,
22.3,19.8,13.7.
ir(kbr):3335,2983,2959,2871,1692,1595,1539,1462,1404,1376,1247,1139,
1072,1011,930,824,778,533cm-1.
Ms (ei): m/z (%)=299 [m+],199,183,121,104(100).
hrms esi(m/z):calcd for c13h18brno2na(m+na)+:322.0413,found:322.0411.
Infer that products therefrom obtains structure according to data above as follows:
Claims (6)
1. a kind of synthetic method of carbamate it is characterised in that in autoclave, adds sulphonyl hydrazone, amine and solvent,
Addition alkali is accelerator, is passed through carbon dioxide, stirring reaction 6～72 hours at 50～150 DEG C, and reaction is cooled to room after terminating
Temperature, the carbon dioxide discharging reaction of haunting, to normal pressure, reacting liquid filtering, removes solvent under reduced pressure and obtains crude product, through column chromatography purification
Obtain carbamate；Described alkali is sodium carbonate, potassium carbonate, cesium carbonate, Feldalat NM, potassium tert-butoxide, sodium tert-butoxide, the tert-butyl alcohol
Lithium, 1,4- diazabicylo [2.2.2] octane or 1,8- diazabicylo [5.4.0] 11 carbon -7- alkene；
Above-mentioned reaction is shown below:
Wherein, r1Selected from phenyl, xenyl, p-bromophenyl, rubigan, to iodophenyl, p-methylphenyl, to cyano-phenyl, to three
Trifluoromethylphenyl, p-nitrophenyl, o-bromophenyl, a bromophenyl, 3,4- Dichlorobenzene base, 1- naphthyl, 2- benzofuranyl, 2- thiophene
Fen base or 4- pyridine radicals；
r2Including hydrogen, methyl, cyclopropyl or phenyl；
r3And r4Selected from hydrogen, methyl, ethyl, propyl group, normal-butyl or benzyl；OrFor nafoxidine, hexahydropyridine or
Quinoline；
r5Selected from p-methylphenyl, phenyl, p-methoxyphenyl, 2- naphthyl, p- nitrobenzophenone, p-bromophenyl, benzyl, methyl or just
Butyl.
2. a kind of carbamate according to claim 1 synthetic method it is characterised in that: described sulphonyl hydrazone and amine
Mol ratio is 1:(1～20).
3. a kind of carbamate according to claim 1 synthetic method it is characterised in that: the pressure of carbon dioxide is
0.5～10mpa.
4. a kind of carbamate according to claim 1 synthetic method it is characterised in that: solvent be acetonitrile, tetrahydrochysene
Furan, n, one or more of n- dimethylformamide, dimethyl sulfoxide, methanol or water.
5. a kind of carbamate according to claim 4 synthetic method it is characterised in that: add the amount of alkali and sulphonyl
The mol ratio of hydrazone is (1～5): 1.
6. a kind of carbamate according to claim 1 synthetic method it is characterised in that: reaction terminate after adopt post
Product is isolated and purified by chromatography；Described column chromatography eluent is mixed solvent, petroleum ether and the acetic acid of petroleum ether and ethyl acetate
Volume ratio between ethyl ester is 5～50:1.
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