CN102746185B - Preparation process of aromatic nitrile compound - Google Patents
Preparation process of aromatic nitrile compound Download PDFInfo
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- CN102746185B CN102746185B CN201210238672.7A CN201210238672A CN102746185B CN 102746185 B CN102746185 B CN 102746185B CN 201210238672 A CN201210238672 A CN 201210238672A CN 102746185 B CN102746185 B CN 102746185B
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- -1 aromatic nitrile compound Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims abstract description 9
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 5
- 238000005194 fractionation Methods 0.000 claims abstract description 5
- 238000011084 recovery Methods 0.000 claims abstract description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 9
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 8
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 8
- 150000001499 aryl bromides Chemical class 0.000 claims description 7
- 235000007715 potassium iodide Nutrition 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical group CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- 229960004839 potassium iodide Drugs 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000003120 aryl bromide group Chemical group 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 8
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 6
- 230000006837 decompression Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 abstract 1
- 239000000276 potassium ferrocyanide Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000012847 fine chemical Substances 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 4
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- NWPNXBQSRGKSJB-UHFFFAOYSA-N 2-methylbenzonitrile Chemical compound CC1=CC=CC=C1C#N NWPNXBQSRGKSJB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 2
- 238000006206 glycosylation reaction Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WSEQXVZVJXJVFP-HXUWFJFHSA-N (R)-citalopram Chemical compound C1([C@@]2(C3=CC=C(C=C3CO2)C#N)CCCN(C)C)=CC=C(F)C=C1 WSEQXVZVJXJVFP-HXUWFJFHSA-N 0.000 description 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 1
- XEEGWTLAFIZLSF-UHFFFAOYSA-N 1-oxo-3h-2-benzofuran-5-carbonitrile Chemical compound N#CC1=CC=C2C(=O)OCC2=C1 XEEGWTLAFIZLSF-UHFFFAOYSA-N 0.000 description 1
- QVTPWONEVZJCCS-UHFFFAOYSA-N 2-formylbenzonitrile Chemical compound O=CC1=CC=CC=C1C#N QVTPWONEVZJCCS-UHFFFAOYSA-N 0.000 description 1
- WLPATYNQCGVFFH-UHFFFAOYSA-N 2-phenylbenzonitrile Chemical group N#CC1=CC=CC=C1C1=CC=CC=C1 WLPATYNQCGVFFH-UHFFFAOYSA-N 0.000 description 1
- RPTUSVTUFVMDQK-UHFFFAOYSA-N Hidralazin Chemical class C1=CC=C2C(NN)=NN=CC2=C1 RPTUSVTUFVMDQK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000935 antidepressant agent Substances 0.000 description 1
- 239000002220 antihypertensive agent Substances 0.000 description 1
- 229940127088 antihypertensive drug Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229960001653 citalopram Drugs 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 230000033772 system development Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation process of an aromatic nitrile compound. According to the preparation process, alkylbenzene is used as a reaction solvent, copper iodide, potassium iodide and N, N'- dimethyl ethylenediamine are used as a combined catalyst, bromo-aromatic hydrocarbon reacts with potassium ferrocyanide in nitrogen at 120-170 DEG C for 24-60 hours to obtain a mixture, and then the mixture is cooled to room temperature to be filtered. After the solvent is recovered, a filtrate is processed through decompression fractionation or recrystallized to obtain the corresponding aromatic nitrile compound. An obtained product has the advantage of high yield and purity. Compared with the existing synthetic method, the preparation process has the advantages of mild reaction condition, short reaction process, utilization of cheap nontoxic cyano chemical reagent, simplicity in feeding and post treatment, easiness in recovery of the catalyst, and easiness in realization of industrial production.
Description
Technical field
The present invention relates to the preparation method of organic synthesis intermediate, relate in particular to a kind of preparation technology of aromatic nitriles compound.
Background technology
Aromatic nitriles is important fine-chemical intermediate, and both hydrolyzable was prepared acid and also can be reduced into amine, was widely used in medicine, agricultural chemicals, dyestuff, additives for plastics and Fine Organic Chemical product preparation field; Important fragrant nitrile fine-chemical intermediate has antidepressant drug citalopram key intermediate 5-Cyano-phthalide, antihypertensive drug key intermediate sartanbiphenyl, hydralazine class pharmaceutical intermediate o-cyanobenzaldehyde, liquid crystal material 4 '-alkyl-4-cyanobiphenyl etc.
At present, aromatic nitriles mainly contains three kinds of operational paths in producing both at home and abroad: (1) null method; (2) oxidation proceses of ammonia; (3) method of substitution.Null method is to be eliminated reaction and obtain aromatic nitriles through dehydration again through amination by aromatic carboxylic acid or aldehyde under catalyzer condition; have simple to operate, yield is high, abundant raw material can prepare the features such as aliphatic nitrile compound; shortcoming is that the cost of corresponding aromatic carboxylic acid or aldehyde is higher; therefore this method is generally only suitable for preparation [the Synth Commun of scientific experiment chamber; 1989 (1), 189; EP790234,1997; US 5618965,1997; Mol Online, 1998,12 (3), 94].Second method oxidation proceses of ammonia is the main method that heavy industrialization is prepared fragrant nitrile, and this method is under catalyzer condition, to make methyl aromatic substance react with ammonia and oxygen.Oxidation proceses of ammonia used catalyst mostly is V, Ti, and cr, B, the various oxide compounds such as Mo or several oxide compound are pressed mixture [Chim.Ind., 1988,70 (4), 58 of different ratios composition; DE254111,1988; Chim. Ind. 74 (30,183; EP525367,1993].This production method feature is that alkylaromatic hydrocarbon raw material sources are wide, comparatively favourable for the relatively simple fragrant carbonitrile derivatives of scale operation structure, and shortcoming is that reaction preference is slightly poor, severe reaction conditions, and also aroamtic hydrocarbon raw material must have methyl in corresponding position; And in existing part fine-chemical intermediate aromatic nitriles, their precursor methyl aromatic derivatives does not have industrial goods can be for maybe preparing, contrary they precursor halogenated aryl hydrocarbon and the assorted aromatic hydrocarbons of halo from industrial in a large number can be for maybe prepare cheapness, thereby process cyanogen glycosylation reaction to prepare fragrant nitrile be another feasible approach in industrial production.The third method method of substitution is that halogenated aryl hydrocarbon and cyano group reagent carry out substitution reaction and obtains fragrant nitrile and assorted aromatic nitriles.Tradition cyano group reagent has sodium cyanide (NaCN), potassium cyanide (KCN), TMSCN, Zn (CN)
2, CuCN, (CH
3)
2c (OH) CN.Wherein NaCN and KCN severe toxicity; Zn (CN)
2large with CuCN toxicity, and because need stoichiometry to use, can cause serious heavy metal contamination; The easy moisture absorption of TMSCN, processes inconvenience, with (CH
3)
2c (OH) CN equally all can emit hypertoxic prussic acid gas in reaction process, causes severe environmental pollution [Tetrahedron, 1984,40 (9), 1433; J. Org. Chem., 1979,44 (24), 4443; JACS, 2003,125 (100,2890, Org. lett. 2004,6 (170,2837].
One of main research strategy that green organic chemistry new technology is carried out is to use green reagent and adopt low pollution, highly selective, efficient catalyzer.Start with from green organic synthesis technology, the cyanogen glycosylation reaction of selecting important halogenated aryl hydrocarbon is research object, evade poisonous reagents such as using potassium cyanide, sodium cyanide and cuprous cyanide, take the green reagent yellow prussiate of potash of low toxicity cheap and easy to get (even can as foodstuff additive) as cyano group reagent, research adopts low pollution, highly selective, efficient cheap metal catalyzer and ligand system, and the synthetic common technology of green of system development fine-chemical intermediate aromatic nitriles has important realistic meaning.
Summary of the invention
The object of this invention is to provide a kind of preparation technology of aromatic nitriles compound.
The preparation technology of aromatic nitriles compound of the present invention, take alkylbenzene as reaction solvent, with cuprous iodide, potassiumiodide and N, N '-dimethyl-ethylenediamine is combination catalyst, aryl bromide and yellow prussiate of potash react 24-60 hour at 120-170 ℃ under nitrogen protection, cool to room temperature subsequently, filtration, carries out vacuum fractionation after filtrate recovery solvent or recrystallization obtains corresponding aromatic nitriles compound; The molar equivalent ratio of said aryl bromide and yellow prussiate of potash is 1:0.15～0.3, the consumption of cuprous iodide is 1%～20% molar equivalent of aryl bromide, the consumption of potassiumiodide is 1～2 molar equivalent of cuprous iodide, N, 0.8～1.2 molar equivalent that the consumption of N '-dimethyl-ethylenediamine is aryl bromide;
Reaction formula is:
R in formula
1, R
2=hydrogen, trifluoromethyl, fluorine, nitro, amino, aldehyde radical, C
1～C
4alkyl or C
1～C
4the aryl of cyclohexyl, aryl or replacement of-oxyl, cyclohexyl or replacement, the substituting group on the substituting group on the aryl of described replacement and the cyclohexyl of replacement is trifluoromethyl, fluorine, C
1～C
4alkyl or C
1～C
4-oxyl, R
1and R
2can be identical or different.
Described reaction solvent alkylbenzene is sym-trimethylbenzene, ethylbenzene or dimethylbenzene.
The present invention, compared with existing synthetic method, has the following advantages:
1) reaction conditions gentleness;
2) reaction process flow process is short;
3) use cheap nontoxic cyano group reagent;
4) feed intake and aftertreatment all very simple, be easy to reclaim catalyzer, be easy to realize industrialized production.
Embodiment
Following examples will contribute to understand the present invention, but be not limited to content of the present invention:
Embodiment 1
In 100 liters of reactors, under nitrogen protection, add successively 30 liters of dimethylbenzene, 30 moles to methyl bromobenzene, 6 moles of yellow prussiate of potash, 0.573 kilogram (3 moles, 0.1 equivalent) cuprous iodide, (6 moles of 1 kilogram of potassiumiodides, 0.2 equivalent), 2.64 kilogram N, (30 moles of N '-dimethyl-ethylenediamines, 1.0 equivalents), under nitrogen protection 145 ℃ of stirring reactions 50 hours, finish reaction, cool to room temperature, suction filtration reclaims inorganic salt, filtrate decompression reclaims solvent xylene, residue carries out fractionation can reclaim N, N '-dimethyl-ethylenediamine, and obtain methyl benzonitrile, productive rate 91%, white solid, mp 25-26 ° C,
1h NMR (CDCl3): 2.42 (s, 3H), 7.27 (d,
j=8.0 Hz, 2H), 7.54 (d,
j=8.2 Hz, 2H),
13c NMR (CDCl3): 21.8,109.3,119.1,129.8,132.0,143.6, IR (KBr): (CN) 2226 cm
-1, EI-MS
m/z: 117 (M+, 100).
Embodiment 2
In 100 liters of reactors, under nitrogen protection, add successively 50 liters of dimethylbenzene, 30 moles to bromo biphenyl, 5.5 moles of yellow prussiate of potash, 0.573 kilogram (3 moles, 0.1 equivalent) cuprous iodide, (6 moles of 1 kilogram of potassiumiodides, 0.2 equivalent), 2.64 kilogram N, (30 moles of N '-dimethyl-ethylenediamines, 1.0 equivalents), under nitrogen protection 150 ℃ of stirring reactions 48 hours, finish reaction, cool to room temperature, suction filtration reclaims inorganic salt, filtrate decompression reclaims solvent xylene and N, N '-dimethyl-ethylenediamine, residue carries out ethyl alcohol recrystallization acquisition to cyanobiphenyl, productive rate 71%, white solid, mp 81-82 ° C,
1h NMR (CDCl3): 7.39-7.53 (m, 3H), 7.56-7.62 (m, 2H), 7.66-7.75 (m, 4H),
13c NMR (CDCl3): 110.8,118.9,127.2. 127.7,128.6,129.1,132.6,139.1,145.6, IR (KBr): (CN) 2225 cm-1, EI-MS
m/z: 179 (M
+, 100).
Embodiment 3
In 100 liters of reactors, under nitrogen protection, add successively 40 liters of sym-trimethylbenzene, 30 moles of bromo-4 '-ethyl biphenyls of 4-, 6 moles of yellow prussiate of potash, 2.5 moles of cuprous iodides, 5 moles of potassiumiodides, 24 moles of N, N '-dimethyl-ethylenediamine, under nitrogen protection 165 ℃ of stirring reactions 48 hours, finish reaction, cool to room temperature, suction filtration reclaims inorganic salt, filtrate decompression reclaims solvent sym-trimethylbenzene and N, N '-dimethyl-ethylenediamine, residue carries out high-vacuum fractionation and obtains liquid crystal intermediates 4-cyano group-4 '-ethyl biphenyl, productive rate 85%, mp73～74 ℃, 22 ℃ of clearing points,
1h NMR (400 MHz CDCl
3): 1. 28 (m, 3 H ,-CH3), 2. 74 (m, 2H ,-CH2-), 7.36～7. 85 (m, 8H ,-Ar-) ppm.
Claims (1)
1. the preparation technology of an aromatic nitriles compound, it is characterized in that it is take alkylbenzene as reaction solvent, with cuprous iodide, potassiumiodide and N, N '-dimethyl-ethylenediamine is combination catalyst, aryl bromide and yellow prussiate of potash react 24-60 hour at 120-170 ℃ under nitrogen protection, cool to room temperature subsequently, filtration, carries out vacuum fractionation after filtrate recovery solvent or recrystallization obtains corresponding aromatic nitriles compound; The molar equivalent ratio of said aryl bromide and yellow prussiate of potash is 1:0.15～0.3, the consumption of cuprous iodide is 1%～20% molar equivalent of aryl bromide, the consumption of potassiumiodide is 1～2 molar equivalent of cuprous iodide, N, 0.8～1.2 molar equivalent that the consumption of N '-dimethyl-ethylenediamine is aryl bromide; Reaction solvent alkylbenzene is sym-trimethylbenzene, ethylbenzene or dimethylbenzene;
Reaction formula is:
R in formula
1, R
2=hydrogen, trifluoromethyl, fluorine, C
1～C
4alkyl or C
1～C
4the aryl of-oxyl, aryl or replacement, the substituting group on the aryl of described replacement is C
1～C
4alkyl or C
1～C
4-oxyl, R
1and R
2can be identical or different.
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| CN104829491B (en) * | 2015-04-20 | 2017-04-19 | 华南理工大学 | Method for synthesizing aromaticnitrile |
| CN106083654B (en) * | 2016-06-08 | 2018-11-16 | 上海博栋化学科技有限公司 | A kind of synthetic method of biphenyl nitrile compound |
| CN106676573B (en) * | 2017-01-16 | 2018-11-09 | 浙江工业大学 | A method of synthesizing aromatic nitriles by raw material electrochemical catalysis of alcohol |
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Non-Patent Citations (4)
| Title |
|---|
| A State-of-the-Art Cyanation of Aryl Bromides: A Novel and Versatile Copper Catalyst System Inspired by Nature;Thomas Schareina, et al.;《Chemistry-A European Journal》;20070507;第13卷;第6251页表2 Entry 3 * |
| An environmentally benign procedure for the Cu-catalyzed cyanation of aryl bromides;Thomas Schareina, et al.;《Tetrahedron Letters》;20051231;第46卷;第2586页左栏第1段至第2588页右栏倒数第1段 * |
| Thomas Schareina, et al..A State-of-the-Art Cyanation of Aryl Bromides: A Novel and Versatile Copper Catalyst System Inspired by Nature.《Chemistry-A European Journal》.2007,第13卷第6251页表2 Entry 3. |
| Thomas Schareina, et al..An environmentally benign procedure for the Cu-catalyzed cyanation of aryl bromides.《Tetrahedron Letters》.2005,第46卷第2586页左栏第1段至第2588页右栏倒数第1段. |
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| CN102746185A (en) | 2012-10-24 |
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