PL103621B1 - THE METHOD OF MAKING THE ALPHA-DOUBLE TROUBLES - Google Patents
THE METHOD OF MAKING THE ALPHA-DOUBLE TROUBLES Download PDFInfo
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- PL103621B1 PL103621B1 PL19204376A PL19204376A PL103621B1 PL 103621 B1 PL103621 B1 PL 103621B1 PL 19204376 A PL19204376 A PL 19204376A PL 19204376 A PL19204376 A PL 19204376A PL 103621 B1 PL103621 B1 PL 103621B1
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- Prior art keywords
- aqueous solution
- nitro compound
- salt
- benzene
- general formula
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title 1
- 239000007864 aqueous solution Substances 0.000 claims description 9
- -1 alkali metal nitrite Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 150000002828 nitro derivatives Chemical class 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 150000002730 mercury Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OWJVEZJJRYZWNI-UHFFFAOYSA-N 1,1-dinitrocyclohexane Chemical compound [O-][N+](=O)C1([N+]([O-])=O)CCCCC1 OWJVEZJJRYZWNI-UHFFFAOYSA-N 0.000 description 1
- FGLBSLMDCBOPQK-UHFFFAOYSA-N 2-nitropropane Chemical compound CC(C)[N+]([O-])=O FGLBSLMDCBOPQK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- NJNQUTDUIPVROZ-UHFFFAOYSA-N nitrocyclohexane Chemical compound [O-][N+](=O)C1CCCCC1 NJNQUTDUIPVROZ-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Przedmiotem wynalazku jest sposób wytwarzania a-dwunitrozwiazków o wzorze 1, w którym R1 i R2 kaz¬ de oddzielnie oznaczaja grupy alkilowe o 1—6 atomach wegla takie same lub rózne lub R1 i R2 razem z atomem wegla, do którego sa przylaczone tworza piecio- lub szescioczlonowy pierscien alicykliczny lub heterocykliczny zawierajacy jeden lub dwa heteroatomy takie jak tlen lub azot. Zwiazki te znajduja zastosowanie w syntezie orga¬ nicznej.The present invention relates to a process for the preparation of α-dinitro compounds of formula I, wherein R 1 and R 2 are each de separately represent alkyl groups with 1 to 6 carbon atoms, the same or different, or R1 and R2 together with the carbon to which they are attached forms a five- or six-membered alicyclic or heterocyclic ring containing one or two heteroatoms such as oxygen or nitrogen. These compounds find use in the synthesis of organisms unlike.
Dotychczas a-dwunitrozwiazki tego typu otrzymywano przez dzialanie wodnym roztworem azotanu srebra lub rteci na wodny roztwór nitrozwiazku i azotynu metalu alkalicznego lub przez dzialanie roztworem azotanu srebra lub rteci na wodny roztwór soli nitrozwiazku i azotynu metalu alkalicznego. W obu przypadkach do mie¬ szaniny reakcyjnej dodawano rozpuszczalnik organiczny, zwykle eter etylowy. Niezaleznie od charakteru konco¬ wego produktu z mieszaniny poreakcyjnej oddzielano przez saczenie lub wirowanie drobna zawiesine metalicz¬ nego srebra lub soli rteci jednowartosciowej i po przemyciu osadu rozpuszczalnikiem organicznym ekstrahowano produkt z wodnego przesaczu. Koniecznosc oddzielenia drobnokrystalicznego osadu stanowi duze utrudnienie, technologiczne.Until now, α-dinitro compounds of this type have been obtained by treatment with an aqueous solution of silver nitrate or mercury into an aqueous solution of an alkali metal nitro compound and nitrite or by treatment with a nitrate solution of silver or mercury to an aqueous solution of an alkali metal nitro compound and nitrite salt. In both cases, to the city An organic solvent, usually diethyl ether, was added to the reaction mixture. Regardless of the nature of the end After the reaction mixture was filtered or centrifuged, a fine metallic suspension was separated of silver or monovalent mercury salt, and after washing the precipitate with an organic solvent, it was extracted water glue product. The necessity to separate the fine-crystalline sediment is a great difficulty, technological.
Stosowanie soli rteciowych poza ich wysoka toksycznoscia, powoduje znaczny spadek wydajnosci procesu.The use of mercury salts, apart from their high toxicity, causes a significant decrease in the efficiency of the process.
Mechanizm dzialania azotanu srebra lub rteci nie jest w pelni wyjasniony i przyjmuje sie, ze w stanie przejscio¬ wym jeden lub dwa atomy srebra lub rteci wchodza w sklad kompleksu zawierajacego anion nitrozwiazku i anion azotynowy.The mechanism of action of silver nitrate or mercury is not fully explained and it is assumed that in a transient state one or two silver or mercury atoms are part of a complex containing a nitro compound anion and an anion nitrite.
Okazalo sie, ze sposób wedlug wynalazku pozwala wyeliminowac powyzsze wady i niedogodnosci znanych sposobów.It has turned out that the method according to the invention overcomes the above known drawbacks and drawbacks ways.
Sposób wedlug wynalazku polega na dzialaniu wodnym roztworem zelazicyjanku potasu na wodny roz¬ twór soli drugorzedowego nitrozwiazku o wzorze ogólnym 2, w którym R1 i R2 maja wyzej podane znaczenie2 103 621 i azotynu sodowego, w temperaturze 0—30 C. Wodny roztwór zelazicyjanku potasu wkrapla sie dowodnego roz¬ tworu soli nitrozwiazku i azotynu sodowego w temperaturze 0—30°C, utrzymujac mieszanine reakcyjna w tym zakresie temperatur przez 2—30 minut i ekstrahuje produkt koncowy rozpuszczalnikiem organicznym, zwykle benzenem. Produkt krystaliczny odsacza sie bezposrednio z mieszaniny poreakcyjnej. Reakcja z zelazicyjankiem potasu przebiega wylacznie z drugorzedowymi nitrozwiazkami pozwalajac uzyskac zadane dwunitrozwiazki w prosty sposób z wysoka wydajnoscia.The method according to the invention consists in treating the aqueous solution with an aqueous solution of potassium ferrocyanide Salt formation of a secondary nitro compound of general formula (II) in which R1 and R2 have the meaning given above2 103 621 and sodium nitrite at a temperature of 0-30 C. An aqueous solution of potassium ferricyanide is added dropwise to an aqueous solution the formation of the salt of the nitro compound and sodium nitrite at a temperature of 0-30 ° C, maintaining the reaction mixture at this temperature range for 2 to 30 minutes, and the final product is extracted with an organic solvent, usually with benzene. The crystalline product is directly filtered off from the reaction mixture. Reaction with ferriticide potassium runs only with secondary nitro compounds, allowing to obtain the desired two-liter compounds the simple way with high efficiency.
Przedmiot wynalazku jest blizej wyjasniony w przykladach wykonania.The subject of the invention is explained in more detail in the working examples.
Przyklad I. W roztworze 3 g NaOH (0,075 mola) w 30 ml wody rozpuszcza sie 4,45 g 2-nitropropanu (0,05 mola), dodaje sie 6,9 g NaN02 (0,1 mola) i 50 ml benzenu. Nastepnie w temperaturze 30°C wkrapla sie roztwór 33 g zelazicyjnku potasu (0,1 mola) w 100 ml wody, miesza w ciagu 25 minut, warstwe benzenowa oddziela sie, a warstwe wodna ekstrahuje dwukrotnie 25 ml benzenu. Polaczone roztwory benzenowe przemywa sie 25 ml wody i suszy siarczanem magnezu. Po oddestylowaniu benzenu pod zmniejszonym cisnieniem produkt równiez destyluje sie pod zmniejszonym cisnieniem. Otrzymuje sie 2,7 g 2,2-dwunitropropanu, co stanowi 40% wydajnosci teoretycznej.Example I. In a solution of 3 g NaOH (0.075 mol) in 30 ml of water, 4.45 g of 2-nitropropane are dissolved (0.05 mol), 6.9 g of NaNO 2 (0.1 mol) and 50 ml of benzene are added. Then it is added dropwise at 30 ° C solution of 33 g of potassium ironicide (0.1 mole) in 100 ml of water, stirred for 25 minutes, benzene layer is separated and the aqueous layer is extracted twice with 25 ml of benzene. The combined benzene solutions were washed take 25 ml of water and dry with magnesium sulfate. After distilling the benzene under reduced pressure, the product also distilled under reduced pressure. 2.7 g of 2,2-dinitropane are obtained, which is 40% theoretical capacity.
T f z y k l a d II. /Postepuje sie analogicznie jak w przykladzie I, lecz roztwór zelazicyjanku potasu wkrapla sie w temperaturze 3°C i miesza w ciagu 0,5 godziny. Wydajnosc 2,2-dwunitropropanu wzrasta do 60%.T f z y k l a d II. / The procedure is analogous to that in example I, but the potassium ferrocyanide solution is added dropwise at 3 ° C and stirred for 0.5 hours. The yield of 2,2-dinitropane increases to 60%.
Przyklad Iii. 4,0 g 2-metylo-5-nitrodioksanu-l,3 (0,026 mola) rozpuszcza sie w roztworze 2 g NaOH (0,5 mola) w 30 ml wody, dodaje 6,0 g NaOH2 i 50 ml benzenu. Do mieszaniny tej w temperaturze 5°C wkrapla sie roztwór 16,6 g zelazicyjanku potasu (0,05 mola) w 70 ml wody i miesza w ciagu 0,5 godziny. Warstwe orga¬ niczna oddziela sie, a warstwe wodna ekstrahuje 30 ml benzenu. Polaczone roztwory benzenowe przemywa sie ml wody i suszy siarczanem magnezu. Po oddestylowaniu pod zmniejszonym cisnieniem benzenu produkt równiez oddestylowuje sie pod zmniejszonym cisnieniem. Otrzymuje sie 4,0 g 2-metylo-5,5-dwunitrodioksanu, co stanowi 80% wydajnosci teoretycznej.Example III. 4.0 g of 2-methyl-5-nitrodioxane-1,3 (0.026 mol) are dissolved in a solution of 2 g of NaOH (0.5 mol) in 30 ml of water, added 6.0 g of NaOH2 and 50 ml of benzene. He drops it into this mixture at 5 ° C a solution of 16.6 g of potassium ferrocyanide (0.05 mol) in 70 ml of water is mixed and stirred for 0.5 hours. Organic layer The fraction was separated and the aqueous layer was extracted with 30 ml of benzene. The combined benzene solutions are washed ml of water and dried with magnesium sulfate. After benzene was distilled off under reduced pressure, the product also distilled under reduced pressure. 4.0 g of 2-methyl-5,5-dinitrodioxane are obtained, which is 80% of the theoretical amount.
Przyklad IV. Postepujac analogicznie jak w przykladzie II z 6,55 g (0,05 mola) nitrocykloheksanu i takich samych ilosci pozostalych substratów otrzymuje sie 5,3 g 1,1-dwunitrocykloheksanu, co stanowi 60% wydajnosci teoretycznej.Example IV. Proceeding analogously to example II with 6.55 g (0.05 mol) of nitrocyclohexane and the same amounts of the remaining substrates, 5.3 g of 1,1-dinitrocyclohexane are obtained, which is 60% theoretical capacity.
Przyklad V. Postepujac analogicznie jak w przykladzie III z 4,7 g (0,025 mola) N-butylo-4-nitropi- perydyny i takich samych ilosci pozostalych substratów otrzymuje sie 3,6 gN-butylo-4,4-dwunitropiperydyny, co stanowi 62% wydajnosci teoretycznej.Example 5 Following the same procedure as in Example III with 4.7 g (0.025 mol) of N-butyl-4-nitropi peridine and the same amounts of other substrates, 3.6 g of N-butyl-4,4-dinitropiperidine are obtained, which is 62% of the theoretical amount.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL19204376A PL103621B1 (en) | 1976-08-27 | 1976-08-27 | THE METHOD OF MAKING THE ALPHA-DOUBLE TROUBLES |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL19204376A PL103621B1 (en) | 1976-08-27 | 1976-08-27 | THE METHOD OF MAKING THE ALPHA-DOUBLE TROUBLES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL192043A1 PL192043A1 (en) | 1978-03-13 |
| PL103621B1 true PL103621B1 (en) | 1979-06-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL19204376A PL103621B1 (en) | 1976-08-27 | 1976-08-27 | THE METHOD OF MAKING THE ALPHA-DOUBLE TROUBLES |
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7713401B2 (en) * | 2007-08-08 | 2010-05-11 | Battelle Energy Alliance, Llc | Methods for performing electrochemical nitration reactions |
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1976
- 1976-08-27 PL PL19204376A patent/PL103621B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7713401B2 (en) * | 2007-08-08 | 2010-05-11 | Battelle Energy Alliance, Llc | Methods for performing electrochemical nitration reactions |
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| Publication number | Publication date |
|---|---|
| PL192043A1 (en) | 1978-03-13 |
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| LAPS | Decisions on the lapse of the protection rights |
Effective date: 20071015 |