CN100457721C - Process for preparing 2,4-difluorocyanobenzene - Google Patents
Process for preparing 2,4-difluorocyanobenzene Download PDFInfo
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- CN100457721C CN100457721C CNB2006101548451A CN200610154845A CN100457721C CN 100457721 C CN100457721 C CN 100457721C CN B2006101548451 A CNB2006101548451 A CN B2006101548451A CN 200610154845 A CN200610154845 A CN 200610154845A CN 100457721 C CN100457721 C CN 100457721C
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- CN
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- Prior art keywords
- formonitrile hcn
- alkaline
- molar equivalent
- production technique
- difluoro bromobenzene
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- LJFDXXUKKMEQKE-UHFFFAOYSA-N 2,4-difluorobenzonitrile Chemical compound FC1=CC=C(C#N)C(F)=C1 LJFDXXUKKMEQKE-UHFFFAOYSA-N 0.000 title description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 21
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 17
- NCXNVJKVXAJWTE-UHFFFAOYSA-N C#N.FC1=CC=CC(=C1)F Chemical compound C#N.FC1=CC=CC(=C1)F NCXNVJKVXAJWTE-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 230000006837 decompression Effects 0.000 claims description 8
- 238000005194 fractionation Methods 0.000 claims description 8
- MGHBDQZXPCTTIH-UHFFFAOYSA-N 1-bromo-2,4-difluorobenzene Chemical compound FC1=CC=C(Br)C(F)=C1 MGHBDQZXPCTTIH-UHFFFAOYSA-N 0.000 claims description 7
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 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 description 5
- 239000002253 acid Substances 0.000 claims description 4
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000015320 potassium carbonate Nutrition 0.000 claims description 4
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical group [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims description 4
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 6
- 231100000614 poison Toxicity 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000002574 poison Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 3
- UEMGWPRHOOEKTA-UHFFFAOYSA-N 1,3-difluorobenzene Chemical compound FC1=CC=CC(F)=C1 UEMGWPRHOOEKTA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GRUHREVRSOOQJG-UHFFFAOYSA-N 2,4-dichlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C(Cl)=C1 GRUHREVRSOOQJG-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a manufacturing method of 2, 4-difluocyanobenzene, which comprises the following steps: adopting N, N-dimethylacetamide as reacting solvent and 0.1-5% palladium complex as catalyst; making 0.5-2% alkaline metal carbonate as alkaline; reacting 2, 4-difluobromobenzene and ferrocyanide with molar rate at 1: 0.15-0.3 to react under 100-150 Deg C for 1-6h; filtering; decompressing the filtrate; fractioning to obtain the product. The invention shortens reacting flow path, which is simple to feed and dispose without poison in the whole course.
Description
Technical field
The present invention relates to the medicine intermediate preparation method, relate in particular to a kind of production technique of 2,4 difluorobenzene formonitrile HCN.
Background technology
The 2,4 difluorobenzene nitrile can be used for the synthetic of medicine, agricultural chemicals and fluoropolymer.Strong with its synthetic agricultural chemicals selectivity, usage quantity is few, to human low toxicity, low residue is the very wide environment friendly agricultural of a kind of development prospect.Therefore how efficiently Synthetic 2, the 4-difluorobenzonilyile receives people's huge concern.Synthetic more existing bibliographical informations of 2,4 difluorobenzene nitrile are that raw material is fluoridized Synthetic 2 such as document JP 60-72850, CN85100467 with the 2,4 dichloro benzene nitrile, the 4-difluorobenzonilyile:
Document JP 1990-113037 with a pentanoic be raw material through diazotization, introduce the cyano group Synthetic 2, the 4-difluorobenzonilyile:
Document DE 2239799,1974 with the m-difluorobenzene be raw material through methylation reaction, ammonia oxidation Synthetic 2, the 4--difluorobenzonilyile:
Above-mentioned these synthesis technique Preparation of Catalyst complexity, reaction process is long cycle time, the condition harshness, or have many experimentations to relate to variety of problems such as poisonous reagent, high-temperature and high-pressure conditions, low-yield, aftertreatment complexity.Thereby under the condition of safety gentleness, the synthesis technique that solves the 2,4 difluorobenzene nitrile efficiently is very important and urgent.
Summary of the invention
The production technique that the purpose of this invention is to provide a kind of 2,4 difluorobenzene formonitrile HCN.
It is to be reaction solvent with the N,N-dimethylacetamide, is catalyzer with the palladium complex; make alkali with alkaline carbonate, 2,4-difluoro bromobenzene and alkaline ferro prussiate reacted 1～6 hour at 100～150 ℃ under nitrogen protection; subsequent filtration, the filtrate decompression fractionation obtains the 2,4 difluorobenzene formonitrile HCN.2, the molar equivalent ratio of 4-difluoro bromobenzene and alkaline ferro prussiate is 1: 0.15～0.3; The consumption of palladium catalyst title complex is 2,0.1～5% molar equivalent of 4-difluoro bromobenzene; The alkaline carbonate consumption is 2,0.5～2 molar equivalent of 4-difluoro bromobenzene.Reaction formula is:
Described palladium catalyst title complex is palladium or two (dibenzalacetone acid) palladium; The alkaline ferro prussiate is yellow prussiate of soda or yellow prussiate of potash; Alkaline carbonate is yellow soda ash or salt of wormwood.Reaction times is preferably 1～5 hour.Temperature of reaction is preferably 100～140 ℃.2, the molar equivalent ratio of 4-difluoro bromobenzene and alkaline ferro prussiate is preferably 1: 0.15～and 0.3; The consumption of palladium catalyst title complex is preferably 2,0.1～5% molar equivalent of 4-difluoro bromobenzene; The consumption of alkaline carbonate is preferably 2,1～2 molar equivalent of 4-difluoro bromobenzene.
The present invention compares with existing synthetic method, has the following advantages:
1) reaction conditions safety gentleness, the productive rate height;
2) reaction process is short;
3) use cheap, nontoxic alkaline ferro prussiate to make cyanating reagent;
4) feed intake and aftertreatment all very simple, pollute for a short time, be easy to realize industrialized production.
Specific implementation method
The molecular formula of 2,4 difluorobenzene formonitrile HCN is:
The concrete reactions steps of the production technique of 2,4 difluorobenzene formonitrile HCN is as follows:
With the N,N-dimethylacetamide is reaction solvent, is catalyzer with the palladium complex; make alkali with alkaline carbonate, 2,4-difluoro bromobenzene and alkaline ferro prussiate reacted 1～6 hour at 100～150 ℃ under nitrogen protection; subsequent filtration, the filtrate decompression fractionation obtains the 2,4 difluorobenzene formonitrile HCN.Wherein 2, the molar equivalent ratio of 4-difluoro bromobenzene and alkaline ferro prussiate is 1: 0.15-0.3; The consumption of palladium catalyst title complex is 2,0.1～5% molar equivalent of 4-difluoro bromobenzene; The alkaline carbonate consumption is 2,0.5～2 molar equivalent of 4-difluoro bromobenzene.The recommendation response time is 1～5 hour; The recommendation response temperature is 100～140 ℃; Recommend 2, the molar equivalent ratio of 4-difluoro bromobenzene and alkaline ferro prussiate is 1: 0.15～0.3; Recommending the consumption of palladium catalyst title complex is 2,0.1～5% molar equivalent of 4-difluoro bromobenzene; Recommending the consumption of alkaline carbonate is 2,1～2 molar equivalent of 4-difluoro bromobenzene.
Following examples will help to understand the present invention, but be not limited to content of the present invention:
Embodiment 1
In 1000 milliliters of three-necked bottles; add 500 milliliters of N,N-dimethylacetamide solvents under the nitrogen protection successively, 57.6 gram (300 mmoles) 2; the 4-difluoro bromobenzene; 25 gram (60 mmoles, 0.2 equivalent) three hydration yellow prussiate of potash, 680 milligrams of (3 mmoles; 0.3mol%) palladium catalyzer; 35 gram yellow soda ash (330 mmoles, 1.1 equivalents), under nitrogen protection 100 ℃ of stirring reactions 2 hours; finish reaction; subsequent filtration, filtrate decompression fractionation obtain white crystal 2,4 difluorobenzene formonitrile HCN; productive rate 85%; purity 98%, boiling point 84-86 ℃ (2666.4Pa), 47～49 ℃ of fusing points.
Embodiment 2
In 1000 milliliters of three-necked bottles; add 500 milliliters of N under the nitrogen protection successively; the N-dimethylacetamide solvent, 57.6 gram (300 mmoles) 2,4-difluoro bromobenzene; 28 gram (66 mmoles; 0.3 three hydration yellow prussiate of potash equivalent), 340 milligrams of (1.5 mmoles, 0.5mol%) palladium catalyzer; 31.8 gram yellow soda ash (300 mmoles; 1.0 equivalent), under nitrogen protection,, finish reaction 120 ℃ of stirring reactions 3 hours; subsequent filtration; the filtrate decompression fractionation obtains white crystal 2,4 difluorobenzene first formonitrile HCN, productive rate 90%; purity 99%, 48～49 ℃ of fusing points.
Embodiment 3
In 1000 milliliters of three-necked bottles; add 500 milliliters of N under the nitrogen protection successively; the N-dimethylacetamide solvent; 57.6 gram (300 mmole) 2,4-difluoro bromobenzene, 27 gram (66 mmoles; 0.22 three hydration yellow prussiate of soda equivalent); 15 mmoles (5mol%) two (dibenzalacetone acid) palladium catalyst, 31.8 gram yellow soda ash (300 mmoles, 1.0 equivalents); under nitrogen protection 120 ℃ of stirring reactions 1 hour; finish reaction, subsequent filtration, the filtrate decompression fractionation obtains white crystal 2; 4-two fluorobenzene first formonitrile HCNs; productive rate 87%, purity 98%, 47～49 ℃ of fusing points.
Embodiment 4
In 1000 milliliters of three-necked bottles; add 500 milliliters of N under the nitrogen protection successively; the N-dimethylacetamide solvent; 57.6 gram (300 mmole) 2,4-difluoro bromobenzene, 20 gram (45 mmoles; 0.15 three hydration yellow prussiate of potash equivalent); 0.3 mmole (0.1mol%) two (dibenzalacetone acid) palladium catalyst, 33 gram salt of wormwood (300 mmoles, 1.0 equivalents); under nitrogen protection 140 ℃ of stirring reactions 5 hours; finish reaction, subsequent filtration, the filtrate decompression fractionation obtains white crystal 2; the 4-difluorobenzonitrile; productive rate 70%, purity 97%, 46～48 ℃ of fusing points.
Embodiment 5
In 1000 milliliters of three-necked bottles; add 500 milliliters of N under the nitrogen protection successively; the N-dimethylacetamide solvent, 57.6 gram (300 mmoles) 2,4-difluoro bromobenzene; 27 gram (66 mmoles; 0.25 three hydration yellow prussiate of soda equivalent), 270 milligrams of (1.2 mmoles, 0.4mol%) palladium catalyzer; 66 gram salt of wormwood (600 mmoles; 2.0 equivalent), under nitrogen protection,, finish reaction 150 ℃ of stirring reactions 6 hours; subsequent filtration; the filtrate decompression fractionation obtains white crystal 2,4 difluorobenzene formonitrile HCN, productive rate 80%; purity 99%, 47～49 ℃ of fusing points.
Claims (7)
1. one kind 2, the production technique of 4-difluorobenzonitrile, it is characterized in that it is is reaction solvent with the N,N-dimethylacetamide, is catalyzer with the palladium complex, make alkali with alkaline carbonate, 2,4-difluoro bromobenzene and alkaline ferro prussiate reacted subsequent filtration 1～6 hour at 100～150 ℃ under nitrogen protection, the filtrate decompression fractionation obtains the 2,4 difluorobenzene formonitrile HCN; 2, the molar equivalent ratio of 4-difluoro bromobenzene and alkaline ferro prussiate is 1: 0.15～0.3; The consumption of palladium catalyst title complex is 2, and 0.1～5% molar equivalent of 4-difluoro bromobenzene, alkaline carbonate consumption are 2,0.5～2 molar equivalent of 4-difluoro bromobenzene.
2. the production technique of a kind of 2,4 difluorobenzene formonitrile HCN according to claim 1 is characterized in that described palladium catalyst title complex is palladium or two (dibenzalacetone acid) palladium.
3. the production technique of a kind of 2,4 difluorobenzene formonitrile HCN according to claim 1 is characterized in that described alkaline ferro prussiate is yellow prussiate of soda or yellow prussiate of potash.
4. the production technique of a kind of 2,4 difluorobenzene formonitrile HCN according to claim 1 is characterized in that described alkaline carbonate is yellow soda ash or salt of wormwood.
5. the production technique of a kind of 2,4 difluorobenzene formonitrile HCN according to claim 1 is characterized in that the described reaction times is 1～5 hour.
6. the production technique of a kind of 2,4 difluorobenzene formonitrile HCN according to claim 1 is characterized in that described temperature of reaction is 100～140 ℃.
7. the production technique of a kind of 2,4 difluorobenzene formonitrile HCN according to claim 1 is characterized in that describedly 2, and the molar equivalent ratio of 4-difluoro bromobenzene and alkaline ferro prussiate is 1: 0.15～0.3; The consumption of palladium catalyst title complex is 2,0.1～5% molar equivalent of 4-difluoro bromobenzene; The consumption of alkaline carbonate is 2,1～2 molar equivalent of 4-difluoro bromobenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101548451A CN100457721C (en) | 2006-11-27 | 2006-11-27 | Process for preparing 2,4-difluorocyanobenzene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101548451A CN100457721C (en) | 2006-11-27 | 2006-11-27 | Process for preparing 2,4-difluorocyanobenzene |
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| Publication Number | Publication Date |
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| CN1962622A CN1962622A (en) | 2007-05-16 |
| CN100457721C true CN100457721C (en) | 2009-02-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102452957A (en) * | 2010-10-29 | 2012-05-16 | 海洋王照明科技股份有限公司 | Synthesis method of 2,6-difluorobenzonitrile |
| CN110396059A (en) * | 2019-08-01 | 2019-11-01 | 苏州汉德创宏生化科技有限公司 | A kind of synthetic method of 5- cyanoindole |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100467A (en) * | 1985-04-01 | 1986-07-16 | 中国科学院上海有机化学研究所 | The preparation method of fluoro benzonitrile |
| DE10323574A1 (en) * | 2003-05-26 | 2004-12-30 | Degussa Ag | (Hetero)aromatic nitrile production, for use e.g. as agrochemical or pharmaceutical intermediate, from corresponding chloride or bromide and hydrocyanic acid in presence of palladium complex catalyst |
-
2006
- 2006-11-27 CN CNB2006101548451A patent/CN100457721C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100467A (en) * | 1985-04-01 | 1986-07-16 | 中国科学院上海有机化学研究所 | The preparation method of fluoro benzonitrile |
| DE10323574A1 (en) * | 2003-05-26 | 2004-12-30 | Degussa Ag | (Hetero)aromatic nitrile production, for use e.g. as agrochemical or pharmaceutical intermediate, from corresponding chloride or bromide and hydrocyanic acid in presence of palladium complex catalyst |
Non-Patent Citations (4)
| Title |
|---|
| Improving palladium-catalyzed cyanation ofarylhallides:development of a state-of-the-art methodologyusingpotassium hexacyanoferrate(II) as cyanating agent. Thomas Schareina et al.Journal of Organometallic Chemistry,Vol.689 . 2004 |
| Improving palladium-catalyzed cyanation ofarylhallides:development of a state-of-the-art methodologyusingpotassium hexacyanoferrate(II) as cyanating agent. Thomas Schareina et al.Journal of Organometallic Chemistry,Vol.689 . 2004 * |
| Potassium hexacyanoferrate(II)－a new cyanating agent forthe palladium-catalyzed cyanation of aryl halides. Thomas Schareina et al.Chem.Commun.. 2004 |
| Potassium hexacyanoferrate(II)－a new cyanating agent forthe palladium-catalyzed cyanation of aryl halides. Thomas Schareina et al.Chem.Commun.. 2004 * |
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