SE519778C2 - Methods of preparing nitroform - Google Patents

Methods of preparing nitroform

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Publication number
SE519778C2
SE519778C2 SE0102908A SE0102908A SE519778C2 SE 519778 C2 SE519778 C2 SE 519778C2 SE 0102908 A SE0102908 A SE 0102908A SE 0102908 A SE0102908 A SE 0102908A SE 519778 C2 SE519778 C2 SE 519778C2
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SE
Sweden
Prior art keywords
nitroform
gem
nitration
process according
group
Prior art date
Application number
SE0102908A
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Swedish (sv)
Other versions
SE0102908D0 (en
SE0102908L (en
Inventor
Abraham Langlet
Nikolai Latypov
Ulf Wellmar
Original Assignee
Totalfoersvarets Forskningsins
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Application filed by Totalfoersvarets Forskningsins filed Critical Totalfoersvarets Forskningsins
Priority to SE0102908A priority Critical patent/SE519778C2/en
Publication of SE0102908D0 publication Critical patent/SE0102908D0/en
Priority to PCT/SE2002/001551 priority patent/WO2003018514A1/en
Publication of SE0102908L publication Critical patent/SE0102908L/en
Publication of SE519778C2 publication Critical patent/SE519778C2/en

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06Preparation of nitro compounds
    • C07C201/08Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06Preparation of nitro compounds
    • C07C201/12Preparation of nitro compounds by reactions not involving the formation of nitro groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A method of preparing nitroform (trinitromethane) by nitrating a starting material which is dissolved or suspended in sulphuric acid. A nitrating agent consisting of nitric acid, nitrate salts or nitrogen pentoxide is added to the sulphuric acid solution/suspension at a temperature from -10 DEG C to +80 DEG C. The starting material is selected from a group consisting of a) a gem-dinitroacetyl urea with the general formula wherein Y is H or a group, wherein Y is an alkoxy or amino group, and salts thereof; b) gem-dinitroacetyl guanidine, and c) 4,6-hydroxypyrimidine. In nitration, a gem-trinitro compound is formed which in hydrolysis splits off nitroform.

Description

25 30 35 519 778 3) 4,6-hydroxypyrimidin. 5 30 35 519 778 3) 4,6-hydroxypyrimidine.

Vid nitreringen sätts ett nitrermedel bestående av salpetersyra, nitratsalter eller kvävepentoxid till svavelsyralösningen/suspensionen. Nitreringen blir på detta sätt lätt att styra. Startmaterialet tillförs vid nitreringen ytterligare nitrogrupper och bildar en gem-trinitroförening, som genom hydrolys avspjälkar nitrofonn. Nitreringen genomförs vid en temperatur av från -10°C till +80°C, företrädesvis från +10°C till +60°C. Svavelsyran kan ha en koncentration av 70-100 %, företrädesvis ca 95% Salpetersyran, som är det föredragna nitrermedlet, tillsätts som koncentrerad syra, särskilt med en koncentration av 85-100%. Det molära förhållandet mellan nitrer- medel och substrat kan vara 2,0-6,0:1, och är företrädesvis 3,0-4,0:1. Goda utbyten har erhållits med ett så lågt molärl förhållande som 3,0:1, vilket i kombination med en återanvändning av svavelsyran, som nämns nedan, gör metoden ekonomiskt attraktiv. Nitreringen kan utföras i en vanlig rostfri reaktor utan speciella arrange- mang.During the nitration, a nitrating agent consisting of nitric acid, nitrate salts or nitric oxide is added to the sulfuric acid solution / suspension. In this way, the nitriding becomes easy to control. During the nitration, additional nitro groups are added to the nitration and form a gemin trinitro compound, which cleaves nitrophone by hydrolysis. The nitration is carried out at a temperature of from -10 ° C to + 80 ° C, preferably from + 10 ° C to + 60 ° C. The sulfuric acid may have a concentration of 70-100%, preferably about 95% The nitric acid, which is the preferred nitrating agent, is added as concentrated acid, especially with a concentration of 85-100%. The molar ratio of nitrating agent to substrate may be 2.0-6.0: 1, and is preferably 3.0-4.0: 1. Good yields have been obtained with a molar ratio as low as 3.0: 1, which in combination with a reuse of the sulfuric acid, mentioned below, makes the method economically attractive. The nitriding can be carried out in an ordinary stainless steel reactor without special arrangements.

Efter slutförd nitrering hydrolyseras produkten (gem-trinitroföreningen) för avspjäl- kande av nitroform genom att reaktionsblandningen blandas med ett vattenhaltigt medium, t.ex. slås på krossad is, späds med vatten eller dyl. Bildad nitroform kan extraheras från reaktionsblandningen med ett polärt extraktionsmedel som är stabilt i den aktuella miljön, t.ex. metylenklorid eller dietyleter. Ett neutraliseringsmedel kan därefter tillsättas för att fälla ut motsvarande salt av nitroform. Det är även möjligt att direkt från nitreringsblandningen extrahera den primärt bildade gem-trinitroföre- ningen och därefter hydrolysera denna för avspjälkande av nitroform, t.ex. genom tillsats av en bas. Svavelsyran kan då användas flera gånger Startmaterialet enligt a) ovan kan framställas genom nitrering av barbitursyra till gem-5,5-dinitrobarbitursyra, som därefter hydrolyseras med vatten för att ge gem- dinitroacetylurea eller behandlas med en ringöppnande nukleofil, t.ex. ammoniak, metanol, etanol, isopropanol eller en amin, för att ge substituerad gem-dinitro- acetylurea. Detta beskrivs i Langlet et al.: Synthesis and reactions of 5,5-dinitro- barbituric acid, Conference Proceedings, XlX:th European Colloquium on Hetero- cyclic Chemistry, Aveiro Portugal, July 19-22, 2000, p. A-70. Startmaterialet enligt b) ovan kan på motsvarande sätt framställas genom nitrering av 2-amino-4,6-di- hydroxypyrimidin följt av hydrolys med vatten, såsom beskrivs i Latypov et al.: A new convenient route to gem-dinitroalifatic compounds, Conference Proceedings, 10 15 20 25 30 519 778 3 31st International Conference of ICT: 2000. Startmaterialet enligt c) är en kommersiellt tillgänglig produkt.After completion of nitration, the product (gem-trinitro compound) is hydrolyzed to decompose nitroform by mixing the reaction mixture with an aqueous medium, e.g. beaten on crushed ice, diluted with water or the like. The nitroform formed can be extracted from the reaction mixture with a polar extractant which is stable in the actual environment, e.g. methylene chloride or diethyl ether. A neutralizing agent may then be added to precipitate the corresponding nitroform salt. It is also possible to extract directly from the nitration mixture the primarily formed gemtrinitro compound and then hydrolyze it to cleave nitroform, e.g. by adding a base. The sulfuric acid can then be used fl times The starting material according to a) above can be prepared by nitration of barbituric acid to gem-5,5-dinitrobarbituric acid, which is then hydrolyzed with water to give gem-dinitroacetylurea or treated with a ring-opening nucleophile, e.g. ammonia, methanol, ethanol, isopropanol or an amine, to give substituted gem-dinitroacetylurea. This is described in Langlet et al .: Synthesis and reactions of 5,5-dinitro-barbituric acid, Conference Proceedings, XlX: th European Colloquium on Heterocyclic Chemistry, Aveiro Portugal, July 19-22, 2000, p. A-70 . The starting material according to b) above can be similarly prepared by nitration of 2-amino-4,6-dihydroxypyrimidine followed by hydrolysis with water, as described in Latypov et al .: A new convenient route to gem-dinitroaliphatic compounds, Conference Proceedings , 10 15 20 25 30 519 778 3 31st International Conference of ICT: 2000. The starting material according to c) is a commercially available product.

Uppfinningen skall i det följande belysas med exempel.The invention will be illustrated by examples below.

Exempel 1 Kaliumdinitroacetylurea (6,8 g) löstes i svavelsyra (20 ml, 95% koncentration). Kon- centrerad salpetersyra (1,4 ml) tillsattes droppvis. Temperaturen höjdes till ca. 40°C under en timme. Reaktionsblandningen hälldes på 60g krossad is och extraherades därefter med 2x50 ml dietyleter. Eterfasen torkades med natriumsulfat. Kaliumhyd- roxid löst i etanol tillsattes. En gul fällning av kaliumnitroform (4,6 g; 68% utbyte) erhölls.Example 1 Potassium dinitroacetylurea (6.8 g) was dissolved in sulfuric acid (20 ml, 95% concentration). Concentrated nitric acid (1.4 ml) was added dropwise. The temperature was raised to approx. 40 ° C for one hour. The reaction mixture was poured onto 60g of crushed ice and then extracted with 2x50 ml of diethyl ether. The ether phase was dried over sodium sulfate. Potassium hydroxide dissolved in ethanol was added. A yellow precipitate of potassium nitroform (4.6 g; 68% yield) was obtained.

Exempel 2. 4,6-dihydroxypyrimidin (4g) löstes i svavelsyra (20ml, 95% konc.). Rykande salpetersyra tillsattes (6ml) under kylning med is och hölls därefter vid rumstempe- ratur under 12 timmar. Reaktionsblandningen hälldes på krossad is och extrahera- des med metylenklorid. Utbyte av nítroform 60%, mätt med UV-spektroskopi i metylenklorid.Example 2. 4,6-Dihydroxypyrimidine (4g) was dissolved in sulfuric acid (20ml, 95% conc.). Fuming nitric acid was added (6ml) while cooling with ice and then kept at room temperature for 12 hours. The reaction mixture was poured onto crushed ice and extracted with methylene chloride. Yield of nitroform 60%, measured by UV spectroscopy in methylene chloride.

Exempel 3.Example 3.

Dinitroacetylurea (Bg) löstes i svavelsyra (20ml, 95% konc.). Koncentrerad salpeter- syra (0,57ml) tillsattes. Reaktionsblandningen stod under omröming i en timme vid 20°C. Därefter hälldes den på 74 g krossad is, värmdes till 50°C i 10 minuter och extraherades med 2x125 ml metylenklorid. Utbyte av nítroform 62%.Dinitroacetylurea (Bg) was dissolved in sulfuric acid (20ml, 95% conc.). Concentrated nitric acid (0.57 ml) was added. The reaction mixture was stirred for one hour at 20 ° C. It was then poured onto 74 g of crushed ice, heated to 50 ° C for 10 minutes and extracted with 2x125 ml of methylene chloride. Yield of nitroform 62%.

Exempel 4.Example 4.

Dinitroacetylurea (3 g) löstes i svavelsyra (20ml, 95% konc.). Koncentrerad salpe- tersyra (0,57 ml) tillsattes. Reaktionsblandningen stod under omrörning i en timme vid 20°C med ett lock (täckande skikt) bestående av 30 ml metylenklorid. Metylen- kloriden avskiljdes från reaktionsblandningen och blandades med 30 ml n-heptan.Dinitroacetylurea (3 g) was dissolved in sulfuric acid (20ml, 95% conc.). Concentrated nitric acid (0.57 ml) was added. The reaction mixture was stirred for one hour at 20 ° C with a lid (covering layer) consisting of 30 ml of methylene chloride. The methylene chloride was separated from the reaction mixture and mixed with 30 ml of n-heptane.

Blandningen indunstades till 20 ml då trinitroacetylurea föll ut. Trinitroacetylurean kunde nu lätt 'nydroiyseras med kaiiumhydroxid för avspjäikande av kaliumnitroform.The mixture was evaporated to 20 ml when trinitroacetylurea precipitated. The trinitroacetylurea could now be easily redoxylated with potassium hydroxide to remove potassium nitroform.

Claims (6)

10 15 20 25 30 35 519 778 4 Patentkrav:10 15 20 25 30 35 519 778 4 Patent claims: 1. Sätt att framställa nitroform, kännetecknat av att ett startmaterial valt ur en grupp bestående av a) en gem-dinitroacetylurea med den allmänna formeln OzNj/:NOZ O NH O lïlH X där X är H eller en grupp *KY , där Y är en alkoxy- eller amino-grupp, O och salter därav; b) gem-dinitroacetylguanidin, och c) 4,6-hydroxypyrimidin, löses eller suspenderas i svavelsyra; att startmaterialet nitreras i nämnda svavelsyralösning/suspension genom tillsats av ett nitrermedel valt från gruppen salpetersyra, nitratsalter och kvävepentoxid, för bildande av en gem-trinitroförening, och att gem-trinitroföreningen hydrolyseras för avspjälkande av nitroform.Process for the preparation of nitroform, characterized in that a starting material selected from a group consisting of a) a gem-dinitroacetylurea of the general formula O 2 N 2 /: NO 2 O NH 0 11 H an alkoxy or amino group, O and salts thereof; b) gem-dinitroacetylguanidine, and c) 4,6-hydroxypyrimidine, dissolved or suspended in sulfuric acid; that the starting material is nitrated in said sulfuric acid solution / suspension by adding a nitrating agent selected from the group of nitric acid, nitrate salts and nitrogen pentoxide, to form a gem trinitro compound, and that the gem trinitro compound is hydrolyzed to cleave nitroform. 2. Sätt enligt krav 1, kännetecknat av att Y är NH2, metoxy, etoxy eller isopropoxy.Process according to Claim 1, characterized in that Y is NH 2, methoxy, ethoxy or isopropoxy. 3. Sätt enligt krav 1, kännetecknat av att nítrerlngen genomförs vid en temperatur av från -10°C till +80°C.Process according to Claim 1, characterized in that the nitration is carried out at a temperature of from -10 ° C to + 80 ° C. 4. Sätt enligt krav 1, kännetecknat av att nítrerlngen genomförs vid en temperatur av från +10°C till +60°CProcess according to Claim 1, characterized in that the nitration is carried out at a temperature of from + 10 ° C to + 60 ° C. 5. Sätt enligt krav 1, kännetecknat av att gem-trinitroföreningen hydrolyseras genom att den vid nitreringen erhållna reaktionsblandriingen blandas med ett vattenhaltigt medium och att avspjälkad nitroform extraheras från den så uppkomna bland- ningen. 519 778 55. A process according to claim 1, characterized in that the gemin trinitro compound is hydrolyzed by mixing the reaction mixture obtained during the nitration with an aqueous medium and extracting the cleaved nitroform from the mixture thus obtained. 519 778 5 6. Sätt enligt krav 1, kännetecknat av att gem-trinitroföreningen extraheras från den vid nitreringen erhålina reaktionsblandningen och därefter hydrolyseras för avspjäl- kande av nítroform.Process according to Claim 1, characterized in that the gem-trinitro compound is extracted from the reaction mixture obtained during the nitration and then hydrolysed to decompose nitroform.
SE0102908A 2001-08-31 2001-08-31 Methods of preparing nitroform SE519778C2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
SE0102908A SE519778C2 (en) 2001-08-31 2001-08-31 Methods of preparing nitroform
PCT/SE2002/001551 WO2003018514A1 (en) 2001-08-31 2002-08-30 Method of preparing nitroform

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
SE0102908A SE519778C2 (en) 2001-08-31 2001-08-31 Methods of preparing nitroform

Publications (3)

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SE0102908D0 SE0102908D0 (en) 2001-08-31
SE0102908L SE0102908L (en) 2003-03-01
SE519778C2 true SE519778C2 (en) 2003-04-08

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CN105111087B (en) * 2015-08-19 2017-05-17 南京理工大学 Trinitroethanol preparation method with improved process safety

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3125606A (en) * 1964-03-17 Process for the manufacture of
US3007960A (en) * 1958-11-10 1961-11-07 Purdue Research Foundation N-trinitroalkyl-n-nitroaminoalkyl acids and derivatives thereof
US3491160A (en) * 1968-02-05 1970-01-20 Escambia Chem Corp Process for producing nitroform
US4122124A (en) * 1977-12-05 1978-10-24 Rockwell International Corporation Production of trinitromethane
AU2724197A (en) * 1996-04-16 1997-11-07 Arco Chemical Technology L.P. Reducing tetranitromethane in compositions containing nitroaromatic compounds

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WO2003018514A9 (en) 2004-04-22
SE0102908D0 (en) 2001-08-31
SE0102908L (en) 2003-03-01
WO2003018514A1 (en) 2003-03-06

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