CN111018759A - Method for preparing organic cyanide - Google Patents
Method for preparing organic cyanide Download PDFInfo
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- CN111018759A CN111018759A CN201911410894.0A CN201911410894A CN111018759A CN 111018759 A CN111018759 A CN 111018759A CN 201911410894 A CN201911410894 A CN 201911410894A CN 111018759 A CN111018759 A CN 111018759A
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- cyanide
- thiocyanate
- organic
- organosulfur
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- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 17
- -1 cyanide compound Chemical class 0.000 claims abstract description 18
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims abstract description 16
- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 9
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 4
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 2
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 2
- 125000000172 C5-C10 aryl group Chemical group 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N (2-methylphenyl)methanol Chemical compound CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 2
- TXIRPFGRGWWMSB-UHFFFAOYSA-N (2-methylphenyl)methyl thiocyanate Chemical compound CC1=CC=CC=C1CSC#N TXIRPFGRGWWMSB-UHFFFAOYSA-N 0.000 description 2
- PZXHWNKSYWWTLT-UHFFFAOYSA-N (3-chlorophenyl)methyl thiocyanate Chemical compound ClC1=CC=CC(CSC#N)=C1 PZXHWNKSYWWTLT-UHFFFAOYSA-N 0.000 description 2
- CBHLTVQLRVHABK-UHFFFAOYSA-N (3-nitrophenyl)methyl thiocyanate Chemical compound [O-][N+](=O)C1=CC=CC(CSC#N)=C1 CBHLTVQLRVHABK-UHFFFAOYSA-N 0.000 description 2
- BITPFECHCVOXNN-UHFFFAOYSA-N (4-bromophenyl)methyl thiocyanate Chemical compound BrC1=CC=C(CSC#N)C=C1 BITPFECHCVOXNN-UHFFFAOYSA-N 0.000 description 2
- NUMYTLIHYKESKM-UHFFFAOYSA-N (4-nitrophenyl)methyl thiocyanate Chemical compound [O-][N+](=O)C1=CC=C(CSC#N)C=C1 NUMYTLIHYKESKM-UHFFFAOYSA-N 0.000 description 2
- 239000005935 Sulfuryl fluoride Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229940116357 potassium thiocyanate Drugs 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZSRDNPVYGSFUMD-UHFFFAOYSA-N (3-chlorophenyl)methanol Chemical compound OCC1=CC=CC(Cl)=C1 ZSRDNPVYGSFUMD-UHFFFAOYSA-N 0.000 description 1
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 1
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 description 1
- CWNPOQFCIIFQDM-UHFFFAOYSA-N 3-nitrobenzyl alcohol Chemical compound OCC1=CC=CC([N+]([O-])=O)=C1 CWNPOQFCIIFQDM-UHFFFAOYSA-N 0.000 description 1
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- VEDDBHYQWFOITD-UHFFFAOYSA-N para-bromobenzyl alcohol Chemical compound OCC1=CC=C(Br)C=C1 VEDDBHYQWFOITD-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/02—Thiocyanates
- C07C331/04—Thiocyanates having sulfur atoms of thiocyanate groups bound to acyclic carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing an organosulfur cyanide compound comprising: mixing benzyl alcohol compound (I), thiocyanate, alkaline substance and organic solvent in SO2F2Reacting for 3-6 h at 25-50 ℃ in the atmosphere, and then carrying out post-treatment on the reaction liquid to obtain organic cyanide (II); the invention uses cheap, easily obtained and environment-friendly SO2F2The organic cyanide is used as an accelerant to efficiently promote alcohol and thiocyanate to prepare the organic cyanide, so that the step of introducing halogen into a preset position of a molecular structure in advance in the traditional production process is reduced, the applicability of the substrate is wide, the corresponding organic cyanide can be obtained with a good yield, the operation process is simple, and the organic cyanide is suitable for large-scale preparation;
Description
Technical Field
The present invention relates to the utilization of sulfuryl fluoride (SO)2F2) The new method for preparing the organic cyanide by efficiently promoting the reaction of alcohol and thiocyanate as an accelerant.
Background
Organic thiocyanide, especially alkyl thiocyanide, has special physical properties and chemical stability, so that it can be extensively used in medicine, dye and natural product. One of the most commonly used methods for preparing alkyl thiocyanide compounds is the nucleophilic substitution reaction of thiocyanate and alkyl halide or pseudohalide. Bijan Mombeni Goodajdar et al reported benzyl halides and ammonium thiocyanate in Mn-DIL-MnCl4-H2Method for preparing organic thiocyanide by reaction in O system [ applied organic chemical chem.2019,33, e4647]. However, in the production process, halogen is often required to be introduced into a predetermined position of a molecular structure in advance, and the halogen atom is replaced by thiocyanate ions, so that from the viewpoint of the reaction process, the experimental steps are complicated, and the step economy and atom economy of the reaction are poor.
In recent years, direct functionalization of thiols and benzyl alcohol compounds has become an attractive strategy for preparing alkyl thiocyanides. Cheng et al reported a copper catalyzed method for the synthesis of thiocyanide from disulfide and Azobisisobutyronitrile (AIBN) [ chem. Asgharzadeh et al reported a process for the preparation of thiocyanide by the reaction of an alcohol and ammonium thiocyanate with the aid of chlorodiphenylphosphine [ Phosphorus, sulfurr, and Silicon 2014,189,796 ]. However, the above methods have some disadvantages such as the need for transition metal and initiator, low yield, environmental unfriendliness of the system, and inconvenience for large-scale application.
Sulfuryl fluoride (SO)2F2) Is a cheap and easily available reagent, and is widely used for preparing various compounds due to the unique chemical property. Qin et al report the use of SO under mild conditions for the first time2F2And potassium carbonate, a process for the preparation of acetylenic compounds by direct dehydration/dehydrogenation of alcohols. The method uses cheap and easily-obtained reagents, solvents and inorganic bases, and does not need transition metals [ J.Am.chem.Soc.2018,140,17666]. Ding et al reported the use of SO2F2And triethylamine facilitate the rapid conversion of an aldehyde or aldoxime to the corresponding nitrile [ Synlett 2019,30,1484.]。
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides aA clean, environment-friendly and economic novel method for synthesizing organic cyanide. The invention relates to the use of inexpensive, readily available, environmentally friendly SO2F2As an accelerator, to promote the synthesis of organosulfur cyanide from alcohol and thiocyanate.
The technical scheme of the invention is as follows:
a process for preparing an organosulfur cyanide compound comprising:
mixing benzyl alcohol compound (I), thiocyanate, alkaline substance and organic solvent in SO2F2Reacting for 3-6 h at 25-50 ℃ in an atmosphere (normal pressure), and then carrying out post-treatment on the reaction liquid to obtain organic cyanide (II);
the mass ratio of the benzyl alcohol compound (I), the thiocyanate and the alkaline substance is 1: 1: 2-5;
the thiocyanate is: NH (NH)4SCN (ammonium thiocyanate), NaSCN (sodium thiocyanate) or KSCN (potassium thiocyanate);
the alkaline substance is: DBU (1, 8-diazabicycloundec-7-ene), Et3N (triethylamine), DMAP (4-N, N-dimethylaminopyridine), Na2CO3(sodium carbonate), Cs2CO3(cesium carbonate) or CH3ONa (sodium methoxide);
the organic solvent is selected from ethyl acetate, dichloromethane, tetrahydrofuran, toluene or methanol, and the volume usage of the organic solvent is 2-5 mL/mmol based on the substance of the benzyl alcohol compound (I);
the post-treatment method of the reaction liquid comprises the following steps: after the reaction is finished, adding water into the reaction liquid for dilution, extracting with ethyl acetate, combining organic phases, washing with saturated saline solution, drying with anhydrous sodium sulfate, performing suction filtration, concentrating and drying the filtrate to obtain organic cyanide (II);
in formula (I) or (II):
R1hydrogen, C1-C3 alkyl, C1-C3 alkoxy, nitro, halogen or C5-C10 aryl, preferably for example: hydrogen and methylA group selected from methoxy, nitro, chloro, bromo or phenyl.
The invention has the following beneficial effects:
1. using cheap, easily available and environment-friendly SO2F2As an accelerant, the method can efficiently promote alcohol and thiocyanate to prepare the organic cyanide, and reduces the step of introducing halogen at the preset position of the molecular structure in the traditional production process.
2. The substrate has wide applicability, and the corresponding organic cyanide can be obtained with better yield.
3. The operation process is simple and is suitable for large-scale preparation.
Detailed Description
The invention is further described below by means of specific examples, without restricting its scope to these.
Example 1: preparation of 4-bromobenzylthiocyanide
In a 500ml single-neck flask, 26.18g (140mmol) of 4-bromobenzyl alcohol (formula I, R ═ 4-Br), 13.61g (140mmol) of potassium thiocyanate, 280ml of dichloromethane, 28.00g (2.0eq.288mmol) of cesium carbonate in this order were placed2F2Stirring for 6 hours at 30 ℃ in the atmosphere, after the reaction is finished, adding water into the reaction liquid for dilution, extracting with ethyl acetate, combining organic phases, washing with saturated saline solution, drying with anhydrous sodium sulfate, filtering, concentrating and drying the filtrate to obtain 28.59g of 4-bromobenzyl thiocyanide with the yield of 90%.
Hydrogen nuclear magnetic resonance spectroscopy (500MHz, CDCl)3)(δ,ppm):7.52–7.48(m,2H),7.25–7.20(m,2H),4.07(s,2H)。
Example 2: preparation of 4-nitrobenzyl thiocyanide
In a 500ml single-neck flask, 4-nitrobenzyl alcohol (formula I, R) is added in turn＝4-NO2)22.97g (150mmol), 12.16g (150mmol) of sodium thiocyanate, 300ml of methanol, 24.31g (3.0eq.450mmol) of sodium methoxide in SO2F2Stirring for 4 hours at 40 ℃ in the atmosphere, after the reaction is finished, adding water into the reaction liquid for dilution, extracting with ethyl acetate, combining organic phases, washing with saturated saline solution, drying with anhydrous sodium sulfate, filtering, concentrating and drying the filtrate to obtain 26.77g of 4-nitrobenzyl thiocyanate with the yield of 92%.
NMR spectrum (500MHz, Chloroform-d) (delta, ppm): 8.27(d, J ═ 8.7Hz,2H),7.57(d, J ═ 8.7Hz,2H),4.21(s, 2H).
Example 3: preparation of 3-nitrobenzyl thiocyanide
To a 1000ml single neck flask at room temperature was added 3-nitrobenzyl alcohol (formula I, R ═ 3-NO) in sequence2)30.62g (200mmol), 15.22g (200mmol) ammonium thiocyanate, 400ml tetrahydrofuran, 84.72g (4.0eq.800mmol) sodium carbonate in SO2F2Stirring for 5h in the atmosphere, after the reaction is finished, adding water into the reaction liquid for dilution, extracting with ethyl acetate, combining organic phases, washing with saturated saline solution, drying with anhydrous sodium sulfate, filtering, concentrating and drying the filtrate to obtain 36.09g of 3-nitrobenzyl thiocyanate with the yield of 93 percent.
Hydrogen nuclear magnetic resonance spectrum (500MHz, Chloroform-d) (delta, ppm): 8.30-8.19 (m,2H),7.75(d, J ═ 7.7Hz,1H),7.62(t, J ═ 7.9Hz,1H),4.25(s, 2H).
Example 4: preparation of 2-methylbenzylthiocyanide
In a 1000ml single neck flask, 2-methylbenzyl alcohol (formula I, R ═ 2-CH) was added in sequence3)24.43g (200mmol), 15.22g (200mmol) ammonium thiocyanate, 400ml toluene, 100.00g (5.0eq.943mmol) sodium carbonate in SO2F2Stirring for 2h at 50 ℃ in the atmosphere, after the reaction is finished,the reaction solution was diluted with water, extracted with ethyl acetate, the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated and dried to obtain 28.40g of 2-methylbenzylthiocyanide in a yield of 87%.
NMR spectrum (500MHz, Chloroform-d) (delta, ppm) 7.43-7.04 (m,4H),4.18(s,2H),2.39(s, 3H).
Example 5: preparation of 3-chlorobenzyl thiocyanide
17.11g (120mmol) of 3-chlorobenzyl alcohol (formula I, R3-Cl), 9.13g (120mmol) of ammonium thiocyanate, 240ml of ethyl acetate, 50.88g (4.0eq.480mmol) of sodium carbonate in sequence in a 500ml single-neck flask at room temperature were added2F2Stirring for 5h in the atmosphere, after the reaction is finished, adding water into the reaction solution for dilution, extracting with ethyl acetate, combining organic phases, washing with saturated saline solution, drying with anhydrous sodium sulfate, filtering, concentrating and drying the filtrate to obtain 15.19g of 3-chlorobenzyl thiocyanide with the yield of 83%.
NMR spectrum (500MHz, Chloroform-d) (delta, ppm): 7.37-7.31 (m,3H),7.25(dt, J ═ 6.3,1.8Hz,1H),4.09(s, 2H).
Claims (4)
1. A process for preparing an organosulfur cyanide compound, comprising:
mixing benzyl alcohol compound (I), thiocyanate, alkaline substance and organic solvent in SO2F2Reacting for 3-6 h at 25-50 ℃ in the atmosphere, and then carrying out post-treatment on the reaction liquid to obtain organic cyanide (II);
the mass ratio of the benzyl alcohol compound (I), the thiocyanate and the alkaline substance is 1: 1: 2-5;
the thiocyanate is: NH (NH)4SCN, NaSCN or KSCN;
the alkaline substance is: DBU, Et3N、DMAP、Na2CO3、Cs2CO3Or CH3ONa；
In formula (I) or (II):
R1hydrogen, C1-C3 alkyl, C1-C3 alkoxy, nitro, halogen or C5-C10 aryl.
2. The method for preparing organosulfur cyanide according to claim 1, wherein the organic solvent is selected from the group consisting of ethyl acetate, dichloromethane, tetrahydrofuran, toluene and methanol.
3. The method for preparing organosulfur cyanide according to claim 1, wherein the volume of the organic solvent is 2 to 5mL/mmol based on the amount of the benzyl alcohol compound (I).
4. The method for producing an organosulfur cyanide compound according to claim 1, wherein the reaction solution is post-treated by: after the reaction is finished, adding water into the reaction liquid for dilution, extracting by using ethyl acetate, combining organic phases, washing by using saturated saline solution, drying by using anhydrous sodium sulfate, filtering, concentrating the filtrate and drying to obtain the organic cyanide (II).
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04297451A (en) * | 1991-03-26 | 1992-10-21 | Sankyo Kagaku Kk | Production of isothiocyanic acid ester |
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2019
- 2019-12-31 CN CN201911410894.0A patent/CN111018759B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04297451A (en) * | 1991-03-26 | 1992-10-21 | Sankyo Kagaku Kk | Production of isothiocyanic acid ester |
Non-Patent Citations (4)
| Title |
|---|
| GUOFU ZHANG ET AL.: "Sulfuryl Fluoride Promoted Thiocyanation of Alcohols: A Practical Method for Preparing Thiocyanates", 《SYN LETT》 * |
| JOHN M. MOTTO ET AL.: "Synthetic scope, computational chemistry and mechanism of a base induced 5-endo cyclization of benzyl alkynyl sulfides", 《TETRAHEDRON》 * |
| WAN-YIN FANG ET AL.: "Cascade Process for Direct Transformation of Aldehydes (RCHO) to Nitriles (RCN) Using Inorganic Reagents NH2OH/Na2CO3/SO2F2 in DMSO", 《J.ORG.CHEM》 * |
| Y.TAMURA ET AL: "THIOCYANATION AND CYANATION USING A NEW COMBINED REAGENT OF TRIPHENYLPHOSPHINE AND THIOCYANOGEN", 《TETRAHEDRON LETTERS》 * |
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