US3853944A - Substituted nitroalkyl nitrate and peroxynitrate - Google Patents
Substituted nitroalkyl nitrate and peroxynitrate Download PDFInfo
- Publication number
- US3853944A US3853944A US00311993A US31199372A US3853944A US 3853944 A US3853944 A US 3853944A US 00311993 A US00311993 A US 00311993A US 31199372 A US31199372 A US 31199372A US 3853944 A US3853944 A US 3853944A
- Authority
- US
- United States
- Prior art keywords
- solution
- oxygen
- mole
- nitrate
- nitroalkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 nitroalkyl nitrate Chemical class 0.000 title claims abstract description 21
- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 229910004679 ONO2 Inorganic materials 0.000 claims abstract 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 abstract description 72
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 47
- 229910052760 oxygen Inorganic materials 0.000 abstract description 47
- 239000001301 oxygen Substances 0.000 abstract description 47
- 239000007788 liquid Substances 0.000 abstract description 20
- 150000001336 alkenes Chemical class 0.000 abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 9
- 125000000217 alkyl group Chemical group 0.000 abstract description 8
- 239000000543 intermediate Substances 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- 125000004971 nitroalkyl group Chemical group 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002431 hydrogen Chemical group 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 239000000417 fungicide Substances 0.000 abstract description 2
- 239000003502 gasoline Substances 0.000 abstract description 2
- 239000002917 insecticide Substances 0.000 abstract description 2
- 239000003350 kerosene Substances 0.000 abstract description 2
- 239000003879 lubricant additive Substances 0.000 abstract description 2
- 239000003209 petroleum derivative Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000002816 fuel additive Substances 0.000 abstract 2
- 244000046052 Phaseolus vulgaris Species 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 66
- 238000006243 chemical reaction Methods 0.000 description 33
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 32
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 30
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 20
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000000746 allylic group Chemical group 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SJWKGDGUQTWDRV-UHFFFAOYSA-N 2-Propenyl heptanoate Chemical compound CCCCCCC(=O)OCC=C SJWKGDGUQTWDRV-UHFFFAOYSA-N 0.000 description 1
- IVKYUXHYUAMPMT-UHFFFAOYSA-N 2-methylprop-2-enyl acetate Chemical compound CC(=C)COC(C)=O IVKYUXHYUAMPMT-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JSDZSLGMRRSAHD-UHFFFAOYSA-N 3-methylbutan-2-ylcyclopropane Chemical compound CC(C)C(C)C1CC1 JSDZSLGMRRSAHD-UHFFFAOYSA-N 0.000 description 1
- LYJHVEDILOKZCG-UHFFFAOYSA-N Allyl benzoate Chemical compound C=CCOC(=O)C1=CC=CC=C1 LYJHVEDILOKZCG-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical class O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- SCUZIHSJSPFAIB-UHFFFAOYSA-L dipotassium;dioxido(sulfanylidene)-$l^{4}-sulfane Chemical class [K+].[K+].[O-]S([S-])=O SCUZIHSJSPFAIB-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JFZUABNDWZQLIJ-UHFFFAOYSA-N methyl 2-[(2-chloroacetyl)amino]benzoate Chemical compound COC(=O)C1=CC=CC=C1NC(=O)CCl JFZUABNDWZQLIJ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical class [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 1
- XIVPVSIDXBTZLM-UHFFFAOYSA-N prop-2-enyl 2,2,2-trifluoroacetate Chemical compound FC(F)(F)C(=O)OCC=C XIVPVSIDXBTZLM-UHFFFAOYSA-N 0.000 description 1
- OTRMXXQNSIVZNR-UHFFFAOYSA-N prop-2-enyl nitrate Chemical compound [O-][N+](=O)OCC=C OTRMXXQNSIVZNR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- LDTLADDKFLAYJA-UHFFFAOYSA-L sodium metabisulphite Chemical class [Na+].[Na+].[O-]S(=O)OS([O-])=O LDTLADDKFLAYJA-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
- C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/39—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups
- C07C205/40—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups and esterified hydroxy groups bound to acyclic carbon atoms of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/40—Peroxy compounds containing nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/16—Nitriles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/20—Containing nitrogen-to-oxygen bonds
- C10M2215/202—Containing nitrogen-to-oxygen bonds containing nitro groups
Definitions
- ABSTRACT Nitroalkyl nitrate and peroxynitrates characterized by the formula:
- R and R are hydrogen or alkyl of from 1 to 10 carbons, where X is R O,CN, Cl, phenyl, ONO
- R is alkyl of from 1 to 10 carbons of phenyl and R is hydrogen, phenyl or alkyl of from I to 10 carbons, and where Y is OONO or ONO said nitroalkyl nitrates being prepared by first contacting a substituted alkene of the formula:
- R, R and X are as heretofore defined with a mixture of dinitrogen tetroxide and oxygen to form substituted nitroalkyl peroxynitrate of the formula:
- nitrate and peroxynitrate compounds containing multiple substituents on a hydrocarbon backbone, the substituent combination in the nitrate subclass being found useful to 'enhance pour output of petroleum distillates such as gasoline and kerosene.
- said nitrate subclass is useful in the preparation of surfactants, lubricant additives, insecticides, fungicides, pharmaceuticals and polymers, e.g., their conversion via reduction to amine followed by reaction with ethylene oxide to form surfactants.
- acetoxynitro alcohols prepared by hydrogenating acetoxy nitro nitrates are useful as intermediates in the formation of aminodiols which would have use as monomers for dispersant type additives, as substances for gas scrubbers and as solvents for extraction processes.
- the functional group in the allylic position could stabilize any incipient radical being formed at said position.
- the radical would have been formed by attack at this position by nitrogen dioxide or oxygen.
- Functional groups such as Cl, and --OR are known to stabilize radicals. If allylic nitroxidation had occurred, a complex mixture would have formed rather than the subject products.
- Nitrogen dioxide does coordinate with compounds containing hetero-atoms. It was through that this cooxidation might affect the path of the reaction by tying up the nitrogen dioxide causing the nitroalkyl peroxy radical to decompose to nitroalkyl ketones and alcohols rather than forming the compounds.
- R and R are hydrogen or alkyl of from 1 to 10 carbons and X is selected from the group consisting of W0, 0
- R-CH-C CH I I 2 x R1 where R, R and X are as heretofore defined, is contacted simultaneously with dinitrogen tetroxide and oxygen in a mole ratio substituted alkene to dinitrogen tetroxide to oxygen of between about l:O.5:l and 111.5230 at a temperature between about -40 and 20C. to form a substituted nitroalkyl peroxynitrate characterized by the formula:
- R, R and X are as heretofore defined.
- oxygen and dinitrogen tetroxide are respectively introduced into the reaction system at a rate of between about 0.5 and 1.8 liters/- minute/kilogram substituted olefins and between about 2 and 20 grams/minute/kilogram substituted alkene.
- oxygen and dinitrogen tetroxide are respectively introduced into the reaction system at a rate of between about 0.5 and 1.8 liters/- minute/kilogram substituted olefins and between about 2 and 20 grams/minute/kilogram substituted alkene.
- the formed substituted nitroalkyl peroxynitrate intermediates are normally purified by stripping off of volatiles under reduced pressure or, if of a high enough molecular weight, isolated as insoluble material, e.g., via filtration.
- the first stage reaction is also advantageously conducted in the presence of an inert liquid diluent in order to facilitate contact between the substituted alkene, tetroxide and oxygen reactants.
- the inert liquid diluent desirably constitutes between about 75 and 90 wt. of the reaction mixture.
- suitable inert diluents contemplated herein are those inert liquid diluents having a boiling point between about 30 and 100C. such as n-hexane, heptane, diethylether and carbon tetrachloride, the latter being most preferred.
- the reaction time of the first stage is normally the time it takes to pass the desired dinitrogen tetroxide into the substituted alkene containing solution.
- the dinitrogen tetroxide employed is actually an equilibrium mixture of dinitrogen tetroxide and nitrogen dioxide with the equilibrium being given to essentially 100% dinitrogen tetroxide at C, and essentially 100% nitrogen dioxide at 140C. at 1 atmosphere pressure. Therefore, hereinbefore and hereinafter the terms dinitrogen tetroxide and nitrogen dioxide refer to the equilibrium mixture of N 0,, and No present at the particular temperature described.
- the oxygen employed may be in the form of pure oxygen or a mixture, e.g., air or in admixture with inert gas such as nitrogen.
- R-CH-C-CH NO where R, R and Xare as heretofore defined.
- the reaction is normally conducted for the length of time required to add the reducing agent. When the reaction is conducted below room temperature, the final reaction mixture is allowed to warm to room temperature before workup.
- the resultant substituted nitroalkyl nitrate can be recovered by standard means such as via fractional distillation under reduced pressure, chromatography and selective removal of impurities by solid absorbents. Generally, fraactional distillation is not employed with separation of low molecular weight products due to their heat and shock sensitivity.
- inert liquids diluent is advantageously employed in an amount of between about 80 and 90 wt. based on the reaction mixture to facilitate contact of the reducing agent with the peroxynitrate and normally is the very same inert, liquid employed in the first stage.
- this inert diluent are those inert liquid diluents recited as suitable in the first stage.
- reducing agents contemplated herein are nitric oxide, trialkylphosphite of 3 to 6 carbons such as trimethylphosphite, triethylphosphite, sulfur dioxides, alkali metal sulfite, bisulfites and thiosulfites such as sodium sulfites, potassium sulfites, sodium disulfites, potassium thiosulfites, aqueous solutions of ferrous salts such as aqueous solutions of ferric chloride and ferrous sulfate.
- nitric oxide such as trimethylphosphite, triethylphosphite, sulfur dioxides, alkali metal sulfite, bisulfites and thiosulfites such as sodium sulfites, potassium sulfites, sodium disulfites, potassium thiosulfites, aqueous solutions of ferrous salts such as aqueous solutions of ferric chloride and ferrous sulfate.
- R-cH-c CH N 0 0 0 0 ON 9N2 r 2 I 1 X RE X R1 where R and R and X are as heretofore defined.
- nitroalkyl peroxynitrate intermediate and nitroalkyl nitrate product contemplated herein are as follows:
- EXAMPLE I This example illustrates the preparation of 1-nitro-3- acetoxy-Z-propyl peroxynitrate and l-nitro-3-acetoxy- 2-propyl nitrate.
- the solution prepared in Stage I was cooled to 1 0C. There was added 0.055 mole of nitric oxide by passing the nitric oxide through a solution at a flow rate of 60.8 mi. per minute. After this addition, the solution was kept at C. for 30 minutes and then allowed to warm to room temperature. The solvent is removed in vacuum to give 21 grams (90% yield) of l-nitro-3- acetoxy-Z-propyl nitrate.
- EXAMPLE 11 This example illustrates the preparation, yield and analysis of a series of specific substituted nitroalkyl nitrate products encompassed by the invention.
- the addition was carried out by allowing a stream of oxygen to pass over the liquid nitrogen tetroxide and thence (20:1 oxygen/nitrogen dioxide mole ratio) into the reaction vessel. After the addition, the system was swept with oxygen for 30 minutes and the resultant solution was determined to contain 1-nitro-3-benzoyloxy-3- propyl peroxy nitrate.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
WHERE R, R1 and X are as heretofore defined and second contacting said peroxynitrate with a reducing agent to form said substituted nitroalkyl nitrate, the first and second contacting being conducted in the presence of inert liquid. The nitroalkyl final products of the invention are useful as fuel additives to increase power output of petroleum distillates such as gasoline and kerosene. Further, they are useful as intermediates in the preparation of surfactants, fuel and lubricant additives, insecticides, fungicides (e.g. controlling early blight in bean plants), pharmaceuticals and polymers.
WHERE R, R1 and X are as heretofore defined with a mixture of dinitrogen tetroxide and oxygen to form substituted nitroalkyl peroxynitrate of the formula:
where R2 is alkyl of from 1 to 10 carbons of phenyl and R3 is hydrogen, phenyl or alkyl of from 1 to 10 carbons, and where Y is -OONO2 or -ONO2, said nitroalkyl nitrates being prepared by first contacting a substituted alkene of the formula:
WHERE R and R1 are hydrogen or alkyl of from 1 to 10 carbons, where X is R2O-,-CN, Cl, phenyl, -ONO2,
Nitroalkyl nitrate and peroxynitrates characterized by the formula:
WHERE R, R1 and X are as heretofore defined with a mixture of dinitrogen tetroxide and oxygen to form substituted nitroalkyl peroxynitrate of the formula:
where R2 is alkyl of from 1 to 10 carbons of phenyl and R3 is hydrogen, phenyl or alkyl of from 1 to 10 carbons, and where Y is -OONO2 or -ONO2, said nitroalkyl nitrates being prepared by first contacting a substituted alkene of the formula:
WHERE R and R1 are hydrogen or alkyl of from 1 to 10 carbons, where X is R2O-,-CN, Cl, phenyl, -ONO2,
Nitroalkyl nitrate and peroxynitrates characterized by the formula:
Description
Elite States Cummings atet [191 1*Dec. 10, 1974 SUBSTITUTED NITROALKYL NITRATE AND PEROXYNITRATE [75] Inventor: William M. Cummings, Fishkill,
[73] Assignee: Texaco Inc., New York, NY.
[ Notice: The portion of the term of this patent subsequent to May 8, 1990,
has been disclaimed.
22 Filed: Dec. 4, 1972 211 Appl. No.: 311,993
Related US. Application Data [62] Division of Ser. No. 144,212, May l7, l97l, Pat. No.
[52] US. Cl 260/465.1, 44/72, 260/453 R, 260/466, 260/467, 260/476 R, 260/478, 260/487, 260/488 R, 260/488 R, 424/304, 424/298 [51] Int. Cl. C07c 121/16 [58] Field of Search 260/465.1
[56] References Cited UNITED STATES PATENTS 3,732,283 5/l973 Cummings 260/465.l XR
Primary ExaminerJoseph P. Brust Attorney, Agent, or Firm-T. H. Whaley; C. G. Ries [57] ABSTRACT Nitroalkyl nitrate and peroxynitrates characterized by the formula:
-NO RC'IHCIJCH 2 where R and R are hydrogen or alkyl of from 1 to 10 carbons, where X is R O,CN, Cl, phenyl, ONO
where R is alkyl of from 1 to 10 carbons of phenyl and R is hydrogen, phenyl or alkyl of from I to 10 carbons, and where Y is OONO or ONO said nitroalkyl nitrates being prepared by first contacting a substituted alkene of the formula:
where R, R and X are as heretofore defined with a mixture of dinitrogen tetroxide and oxygen to form substituted nitroalkyl peroxynitrate of the formula:
(lJONO 3 Claims, No Drawings SUBSTITUTED NITROALKYL NITRATE AND PEROXYNITRATE This is a division of application Ser. No. 144,212, filed May 17, 1971. now US. Pat. No. 3,732,283 issued May 8, 1973.
BACKGROUND OF INVENTION In the area of petroleum additives there is continual demand for single additives to perform multiple functions. These multipurpose additives are often the result of the sum of the functions of the substituent groups, each substituent contributing to one or more functions. Further, compounds of multisubstituents are also in demand as building block intermediates in specialty product manufacture. Often the formation of such multisubstituents is difficult to accomplish since the adding of one substituent to a hydrocarbon backbone often results in the undesired prevention, modification or removal of one or more of the other desired substituents thereon or to be placed thereon.
DESCRIPTION OF THE INVENTION I have discovered and this constitutes my invention a new group of nitrate and peroxynitrate compounds containing multiple substituents on a hydrocarbon backbone, the substituent combination in the nitrate subclass being found useful to 'enhance pour output of petroleum distillates such as gasoline and kerosene. In addition, said nitrate subclass is useful in the preparation of surfactants, lubricant additives, insecticides, fungicides, pharmaceuticals and polymers, e.g., their conversion via reduction to amine followed by reaction with ethylene oxide to form surfactants. In respect to further uses, acetoxynitro alcohols prepared by hydrogenating acetoxy nitro nitrates are useful as intermediates in the formation of aminodiols which would have use as monomers for dispersant type additives, as substances for gas scrubbers and as solvents for extraction processes.
I have unexpectedly discovered that the procedure as generally outlined in U.S. Pat. No. 3,282,983 is suitable to prepare the multisubstituted products of the invention. One reason for this unexpectedness prior to the invention was it was not known what the effect of allylic substitution would do to the nitroxidation sequence. Some of the alternative chemical pathways which said procedure could have taken but did not are as follows:
1. The functional group in the allylic position could stabilize any incipient radical being formed at said position. The radical would have been formed by attack at this position by nitrogen dioxide or oxygen. Functional groups such as Cl, and --OR are known to stabilize radicals. If allylic nitroxidation had occurred, a complex mixture would have formed rather than the subject products.
2. If the free radical resulting from the addition of nitrogen dioxide to the double bond was stabilized a possibility could exist that the addition of oxygen might become reversible and more dinitro compound would form. Substituents such as II II might have been able to stabilize the free radical via a cyclic intermediate.
3. Nitrogen dioxide does coordinate with compounds containing hetero-atoms. It was through that this cooxidation might affect the path of the reaction by tying up the nitrogen dioxide causing the nitroalkyl peroxy radical to decompose to nitroalkyl ketones and alcohols rather than forming the compounds.
Specifically, I have discovered a new class of compounds characterized by the formula:
where R and R are hydrogen or alkyl of from 1 to 10 carbons and X is selected from the group consisting of W0, 0
Cl, phenyl 01 ONO where R is alkyl of from 1 to 10 carbons or phenyl and R is hydrogen alkyl of from 1 to 10 carbons or phenyl and where Y is ONO 0r 'OONO2- The products of the invention are prepared in a twostage process as follows:
STAGE I In the first stage a substituted alkene of the formula:
R-CH-C=CH I I 2 x R1 where R, R and X are as heretofore defined, is contacted simultaneously with dinitrogen tetroxide and oxygen in a mole ratio substituted alkene to dinitrogen tetroxide to oxygen of between about l:O.5:l and 111.5230 at a temperature between about -40 and 20C. to form a substituted nitroalkyl peroxynitrate characterized by the formula:
where R, R and X are as heretofore defined.
Under preferred conditions, oxygen and dinitrogen tetroxide are respectively introduced into the reaction system at a rate of between about 0.5 and 1.8 liters/- minute/kilogram substituted olefins and between about 2 and 20 grams/minute/kilogram substituted alkene. For optimum results it is desirable to adjust conditions of the first stage within the described condition framework so that the reaction mixture remains essentially colorless.
If desired, the formed substituted nitroalkyl peroxynitrate intermediates are normally purified by stripping off of volatiles under reduced pressure or, if of a high enough molecular weight, isolated as insoluble material, e.g., via filtration.
The first stage reaction is also advantageously conducted in the presence of an inert liquid diluent in order to facilitate contact between the substituted alkene, tetroxide and oxygen reactants. The inert liquid diluent desirably constitutes between about 75 and 90 wt. of the reaction mixture. Examples of suitable inert diluents contemplated herein are those inert liquid diluents having a boiling point between about 30 and 100C. such as n-hexane, heptane, diethylether and carbon tetrachloride, the latter being most preferred.
The reaction time of the first stage is normally the time it takes to pass the desired dinitrogen tetroxide into the substituted alkene containing solution.
lt is to be noted the dinitrogen tetroxide employed is actually an equilibrium mixture of dinitrogen tetroxide and nitrogen dioxide with the equilibrium being given to essentially 100% dinitrogen tetroxide at C, and essentially 100% nitrogen dioxide at 140C. at 1 atmosphere pressure. Therefore, hereinbefore and hereinafter the terms dinitrogen tetroxide and nitrogen dioxide refer to the equilibrium mixture of N 0,, and No present at the particular temperature described.
The oxygen employed may be in the form of pure oxygen or a mixture, e.g., air or in admixture with inert gas such as nitrogen.
R-CH-C-CH NO where R, R and Xare as heretofore defined. The reaction is normally conducted for the length of time required to add the reducing agent. When the reaction is conducted below room temperature, the final reaction mixture is allowed to warm to room temperature before workup.
The resultant substituted nitroalkyl nitrate can be recovered by standard means such as via fractional distillation under reduced pressure, chromatography and selective removal of impurities by solid absorbents. Generally, fraactional distillation is not employed with separation of low molecular weight products due to their heat and shock sensitivity.
As in the first stage, inert liquids diluent is advantageously employed in an amount of between about 80 and 90 wt. based on the reaction mixture to facilitate contact of the reducing agent with the peroxynitrate and normally is the very same inert, liquid employed in the first stage. Examples of this inert diluent are those inert liquid diluents recited as suitable in the first stage.
Specific examples of the reducing agents contemplated herein are nitric oxide, trialkylphosphite of 3 to 6 carbons such as trimethylphosphite, triethylphosphite, sulfur dioxides, alkali metal sulfite, bisulfites and thiosulfites such as sodium sulfites, potassium sulfites, sodium disulfites, potassium thiosulfites, aqueous solutions of ferrous salts such as aqueous solutions of ferric chloride and ferrous sulfate.
The procedure can be further described by the following equations utilizing nitric oxide as the reducing agent:
a) R-cH-c=CH N 0 0 0 0 ON 9N2 r 2 I 1 X RE X R1 where R and R and X are as heretofore defined.
Specific examples of the substituted alkene reactant,
nitroalkyl peroxynitrate intermediate and nitroalkyl nitrate product contemplated herein are as follows:
a) R-CH-C=CH 1 l 2 x R ooNo 'lb) R-cH-c-ca -No oNo c) R('1H(?-CH NO x. R where R and R are hydrogen, methyl, pentyl and/or decyl and X is The following operating examples further illustrate the invention but are not to be construed as limitations thereof.
EXAMPLE I This example illustrates the preparation of 1-nitro-3- acetoxy-Z-propyl peroxynitrate and l-nitro-3-acetoxy- 2-propyl nitrate.
To a 0.13 mole carbon tetrachloride solution of allyl acetate (13 grams in mls. carbon tetrachloride) maintained at 0C. there was added 8 mls. (0.13 mole) of nitrogen tetroxixe over a period of 6 hours. The addition is carried out by allowing a stream of oxygen to pass over the liquid nitrogen tetroxide and thence into the reaction vessel. The mole ratio of nitrogen dioxide to oxygen remained at about 1:20 during the reaction. After the nitrogen tetroxide has been added, the oxygen is allowed to flow through the reaction mixture until the solution becomes colorless. Infrared analysis (0.1 mm NaCl cell) of the solution showed that the l-nitro-3-acetoxy-2-propyl peroxynitrate was present therein (bands at 5.8, 6.4, 7.3 mu). The solvent can be removed therefrom under reduced pressure (about l-2 mm Hg) to give neat peroxynitrate.
The solution prepared in Stage I was cooled to 1 0C. There was added 0.055 mole of nitric oxide by passing the nitric oxide through a solution at a flow rate of 60.8 mi. per minute. After this addition, the solution was kept at C. for 30 minutes and then allowed to warm to room temperature. The solvent is removed in vacuum to give 21 grams (90% yield) of l-nitro-3- acetoxy-Z-propyl nitrate.
EXAMPLE 11 This example illustrates the preparation, yield and analysis of a series of specific substituted nitroalkyl nitrate products encompassed by the invention.
1Nitro-3-formyloxy-2-propyl Nitrate To a 0.13 mole (1 1.2 grams) carbon tetrachloride solution of allyl forrnate there was slowly added 8 mls. (0.13 mole) of nitrogen tetroxide at about 05C. always maintaining the reaction solution colorless. The addition was carried out by allowing a stream of oxygen to pass over the liquid nitrogen tetroxide and thence (:1 oxygen/nitrogen dioxide mole ratio) into the reaction vessel. After the addition, the system was swept with oxygen for minutes and the resultant solution was determined to contain 1-nitro-3-formyloxy-2- propyl peroxynitrate.
This solution was then cooled to 10C. and 0.13 mole of nitric oxide was added at a flow rate of 60.8 ml./min. After this, the solution was kept at 10C. for 30 minutes and then allowed to warm to room temperature. The solvent was removed in vacuum to give 17.5 grams (70% yield) of l-nitro-3formyloxy-2-propyl nitrate.
lNitro-3trifluoroacetoyloxy-2-propyl Nitrate To a 0.13 mole (20 grams) carbon tetrachloride solution of allyl trifluoroacetate there was slowly added 80 mls. (0.13 mole) ,of nitrogen tetroxide at about O-5C. always maintaining the solution reaction colorless. The addition was carried out by allowing a stream of oxygen to pass over the liquid nitrogen tetroxide and thence (20:1 oxygen/nitrogen dioxide mole ratio) into the reaction vessel. After the addition, the system was swept with oxygen for 30 minutes and the resultant solution was determined to contain 1nitro-3-trifluoroacetoxyloxy-2-propyl peroxynitrate.
This solution was then cooled to 10C. and 0.13 mole of nitric oxide was added at a flow rate of 60.8 ml./min. After this, the solution was kept at lOC. for 30 minutes and then allowed to warm to room temperature. The solvent was removed in vacuum to give 21.8 grams (65% yield) of 1nitro-3trifluoroacetoyloxy-2- propyl nitrate.
1Nitro-Z-methyl-3acetoyloxy-Z-propyl Nitrate To a 0.13 mole (14.6 grams) carbon tetrachloride solution of methallyl acetate there was slowly added 8.0 mls. (0.13 mole) of nitrogen tetroxide at about 05C. always maintaining the reaction solution colorless. The addition was carried out by allowing a stream of oxygen to pass over the liquid nitrogen tetroxide and thence (20:1 oxyogen/nitrogen dioxide mole ratio) into the reaction vessel. After the addition, the system was swept with oxygen for 30 minutes and the resultant solution was determined to contain 1nitro-2methyl-3-acetoyl- 2-propy1 peroxynitrate.
This solution was then cooled to lOC. and 0.13 mole of nitric oxide was added at a flow rate of 60.8 mls./minute. After this, the solution was kept at 10C. for 30 minutes and then allowed to warm to room temperature. The solvent was removed in vacuum to give 25.0 grams yield) of l-nitro-2-methyl-3- acetoyloxy-Z-propyl nitrate.
1Nitro-3propionoyloxy-Z-propyl Nitrate To a 0.13 mole (15.2 grams) carbon tetrachloride solution of allyl propionate there was slowly added 8.0 mils. (0.13 mole) of nitrogen tetroxide at about 05C. always maintaining the reaction solution colorless. The addition was carried out by allowing a stream of oxygen to pass over the liquid nitrogen tetroxide and thence (20:1 oxygen/nitrogen dioxide mole ratio) into the reaction vessel. After the addition, the system was swept with oxygen for 30 minutes and the resultant solution was determined to contain 1nitro-3propionoyloxy-2- propyl peroxynitrate.
This solution was then cooled to 10C. and 0.13 mole of nitric oxide was added at a flow rate of 60.8 mils./min., After this, the solution was kept at lOC. for 30 minutes and then allowed to warm to room temperature. The solvent was removed in vacuum to give 25.5 grams yield) of lnitro-3-propionoyloxy-2- propyl nitrate.
1 Nitro-3heptanoyloxy-2-propyl-Nitrate To a 0.13 mole (22.0 grams) carbon tetrachloride solution of allyl heptanoate there was slowly added 8.0 m/s. (0.13 mole) of nitrogen tetroxide at about 05C. always maintaining the reaction solution colorless. The addition was carried out by allowing a stream of oxygen to pass over the liquid nitrogen tetroxide and thence (20:1 oxygen/nitrogen dioxide mole ratio) into the reaction vessel. After the addition, the system was swept with oxygen for 30 minutes and the resultant solution was determined to contain 1nitro-3-heptanoyloxy-2- propyl peroxynitrate.
This solution was then carried to 10C. and 0.13 mole of nitric oxide was added at a flow rate of 60.8 ml. min. After this, the solution was kept at -l0C. for 30 minutes and then allowed to warm to room temperature. The solvent was removed in vacuum to give 35 grams (97% yield) of 1nitro-3heptanoyloxy-2-propyl nitrate. lNitro-3-benzoyloxy-2-propyl Nitrate To a 0.13 mole (21.0 grams) carbon tetrachloride solution of allyl benzoate there was slowly added 8.0 mls. (0.13 mole) of nitrogen tetroxide at about 05C. always maintaining the reaction solution colorless. The addition was carried out by allowing a stream of oxygen to pass over the liquid nitrogen tetroxide and thence (20:1 oxygen/nitrogen dioxide mole ratio) into the reaction vessel. After the addition, the system was swept with oxygen for 30 minutes and the resultant solution was determined to contain 1-nitro-3-benzoyloxy-3- propyl peroxy nitrate.
This solution was then cooled to lOC. and 0.13 mole of nitric oxide was added at a flow rate of 60.8 ml./min. After this, the solution was kept at lOC. for 30 minutes and then allowed to warm to room temperature. The solvent was removed in vacuum to give 31.4 grams (91% yield) of 1nitro-3benzoyloxy-2-propyl nitrate.
1Nitro-3nitrato-3-propyl Nitrate To a 0.13 mole (13.5 grams) carbon tetrachloride solution of allyl nitrate there was slowly added 8.0 mls. (0.13 mole) of nitrogen tetroxide at about -5C. always maintaining the reaction solution colorless. The addition was carried out by allowing a stream of oxygen to pass over the liquid nitrogen tetroxide and thence (20:1 oxygen/nitrogen dioxide mole ratio) into the reaction vesseL'After the addition, the system was swept with oxygen for 30 minutes and the resultant solution was determined to contain 1nitro-3nitrato-2-propyl peroxynitrate.
This solution was then cooled to C. and 0.13 mole of nitric oxide was added at a flow rate of 60.8 ml./min. After this, the solution was kept at l0C. for 30 minutes and then allowed to warm to room temperature. The solvent was removed in vacuum to give 2.7 grams, (10% yield) of l-nitro-3-nitrato-2-propyl nitrate.
l-Nitro-3-chloro-2-propyl Nitrate To a 0.13 mole (10 grams) carbon tetrachloride solution of allyl chloride there was slowly added 8.0 mls. (0.13 mole) of nitrogen tetroxide at about 05C. always maintaining the reaction solution colorless. The addition was carried out by allowing a stream of oxygen to pass over the liquid nitrogen tetroxide and then (:1 oxygen/nitrogen dioxide mole ratio) into the reaction vessel. After the addition, the system was swept with oxygen for 30 minutes and the resultant solution was determined to contain 1nitro-3-chloro-2-propyl peroxynitrate.
This solution was then cooled to l0C. and 0.13 mole of nitric oxide was added at a flow rate of 60.8 ml./min. After this, the solution was kept at l0C. for 30 minutes and then allowed to warm to room temperature. The solvent was removed in vacuum to give 17.7 grams (80% yield) of 1nitro-3-chloro-2-propyl nitrate.
(2-Nitrato-3-nitropropyl) ethyl Ether To a 0.13 mole l 1.1 grams) carbon tetrachloride solution of allyl ethyl ether there was slowly added 8.0 mls. (0.13 mole) of nitrogen tetroxide at about 0C. always maintaining the reaction solution colorless. The addition was carried out by allowinga stream of oxygen to pass over the liquid nitrogen tetroxide and thence 20:1 oxygen/nitrogen dioxide mole ratio) into the reaction vessel. After the addition, the system was swept with oxygen for 30 minutes and the resultant solution was determined to contain (2-peroxynitrato-3- nitropropyl) ethyl ether.
This solution was then cooled to 10C. and 0.13 mole of nitric oxide was added at a flow rate of 60.8 ml./min. After this, the solution was kept at l0C. for 30 minutes and then allowed to warm to room temperature. The solvent was removed in vacuum to give 19.8 grams (80% yield) of (2-nitrato-3-nitropropyl) ethyl ether.
(2-Nitrato-3-nitropropyl) phenyl Ether To a 0.13 mole (17.8 grams) carbon tetrachloride solution of allyl phenyl ether there was slowly added 8.0 mls. (0.13 mole) of nitrogen tetroxide at about 0C. always maintaining the reaction solution colorless. The addition was carried out by allowing a stream of oxygen to pass over the liquid nitrogen tetroxide and thence (20:1 oxygen/nitrogen dioxide mole ratio) into the reaction vessel. After the addition, the system was swept with oxygen for 30 minutes and the resultant solution was determined to contain (2-peroxynitrato-3- nitropropyl) phenyl ether.
This solution was then cooled to 10C. and 0.13 mole of nitric oxide was added at a flow rate of 60.8 ml./min. After this, the solution was kept at -10C. for 30 minutes and then allowed to warm up to room temperature. The solvent was removed in vacuum to give 24.8 grams (82% yield) of (2-nitrato-3-nitropropyl) phenyl ether.
lNitro-3-phenyl-2-propyl Nitrate To a 0.13 mole (15.4 grams) carbon tetrachloride so lution of allyl benzene there was slowly added 8.0 mls.(0.13 mole) of nitrogen tetroxide at about 0C. always maintaining the reaction solution colorless. The addition was carried out by allowing a stream of oxygen to pass over the liquid nitrogen tetroxide and thence (20:1 oxygen/nitrogen dioxide mole ratio) into the reaction vessel. After the addition, the system was swept with oxygen for 30 minutes and the resultant solution was detemrined to contain 1nitro-3-phenyl-2-propyl peroxynitrate.
This solution was then cooled to -l0C. and 0.13 mole of nitric oxide was added at a flow rate of 60.8 mls./minute. After this, the solution was kept at l0C. for 30 minutes and then allowed to warm to room tem perature. The solvent was removed in vacuum to give 26.0 grams (90% yield) of 1nitro-3-phenyl-2-propyl nitrate.
1-Nitro-3-cyano-2-propyl Nitrate To a 0.13 mole (8.7 grams) carbon tetrachloride solution of allyl cyanide there was slowly added 8.0 mls. (0.13 mole) of nitrogen tetroxide at about 0C. always maintaining the reaction solution colorless. The addition was carried out by allowing a stream of oxygen to pass over the liquid nitrogen tetroxide and thence (20:1 oxygen/nitrogen dioxide mole ratio) into the reaction vessel. After the addition, the system was swept with oxygen for 30 minutes and the resultant solution was determined to contain l-nitro-3-cyano-2-propyl peroxynitrate.
This solution was then cooled to l0C. and 0.13 mole of nitric oxide was added at a flow rate of 60.8 mls./min. After this, the solution was kept at l0C. for
30 minutes and then allowed to warm to room tempera ture. The solvent was removed in vacuum to give 15.6 grams yield) of l-nitro-3-cyano-2-propyl nitrate.
I claim:
1. A nitroalkyl nitrate characterized by the formula:
I R-CH-C-CH NQ ll xR
Claims (3)
1. A NITROALKYL NITRATE CHARACTERIZED BY THE FORMULA:
2. A nitroalkyl nitrate in accordance with claim 1 where R and R1 are hydrogen, X is -CN and Y is -OONO2.
3. A nitroalkyl nitrate in accordance with claim 1 where R and R1 are hydrogen, X is -CN and Y is -ONO2.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00311993A US3853944A (en) | 1971-05-17 | 1972-12-04 | Substituted nitroalkyl nitrate and peroxynitrate |
US430305A US3910987A (en) | 1972-12-04 | 1974-01-02 | Substituted nitroalkyl peroxynitrate |
US430306A US3910981A (en) | 1972-12-04 | 1974-01-02 | Nitroalkyl nitrates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14421271A | 1971-05-17 | 1971-05-17 | |
US00311993A US3853944A (en) | 1971-05-17 | 1972-12-04 | Substituted nitroalkyl nitrate and peroxynitrate |
Publications (1)
Publication Number | Publication Date |
---|---|
US3853944A true US3853944A (en) | 1974-12-10 |
Family
ID=26841776
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00311993A Expired - Lifetime US3853944A (en) | 1971-05-17 | 1972-12-04 | Substituted nitroalkyl nitrate and peroxynitrate |
Country Status (1)
Country | Link |
---|---|
US (1) | US3853944A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4417903A (en) * | 1982-10-15 | 1983-11-29 | Ethyl Corporation | Diesel fuel composition |
US4561862A (en) * | 1985-04-08 | 1985-12-31 | Olin Corporation | Use of selected beta-nitroalkenes as cetane number boosters for diesel fuel |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3732283A (en) * | 1971-05-17 | 1973-05-08 | Texaco Inc | Substituted nitroalkyl nitrate and peroxynitrate |
-
1972
- 1972-12-04 US US00311993A patent/US3853944A/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3732283A (en) * | 1971-05-17 | 1973-05-08 | Texaco Inc | Substituted nitroalkyl nitrate and peroxynitrate |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4417903A (en) * | 1982-10-15 | 1983-11-29 | Ethyl Corporation | Diesel fuel composition |
US4561862A (en) * | 1985-04-08 | 1985-12-31 | Olin Corporation | Use of selected beta-nitroalkenes as cetane number boosters for diesel fuel |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2278965A (en) | Metal derivatives of amino methylene aldehydes | |
CA1068297A (en) | Process for preparing oxalic acid and esters of same | |
US5136101A (en) | Process for the preparation of ketones | |
CA1061804A (en) | Process for the selective hydrogenation in gaseous phase of polyunsaturated compounds | |
US3732283A (en) | Substituted nitroalkyl nitrate and peroxynitrate | |
US3853944A (en) | Substituted nitroalkyl nitrate and peroxynitrate | |
US3282983A (en) | Preparation of nitroalkyl nitrates | |
US3235601A (en) | Process for the production of civetone and homologues | |
US3910981A (en) | Nitroalkyl nitrates | |
US3910987A (en) | Substituted nitroalkyl peroxynitrate | |
US3719701A (en) | Process for the preparation of unsaturated nitriles | |
US2837578A (en) | Chloro-nitro compounds and their preparation | |
US2916506A (en) | Manufacture of cyclopentadienylmanganese compounds | |
US3470219A (en) | Transaddition reaction between an olefin and a saturated aliphatic monocarboxylic acid | |
US4080180A (en) | Methyl 1,1,3,3-tetramethylbutyl ether and admixture thereof with diisobutylene | |
US3833625A (en) | Process for the selective oxidation of ketones | |
US3423463A (en) | Method for the preparation of difluoroamino compounds | |
US3022357A (en) | Purification of fluorocarbons | |
Goaller et al. | Polyethylene Oxides as Organic Reactions Activators II. 1 An Easy Generation of Dihalocarbenes | |
US3068304A (en) | Separation of acetylenic impurities using a cuprous and cupric chloride solution | |
US3007790A (en) | Production of halogenated compounds | |
US2299223A (en) | Process for the catalytic production of olefin-sulphur dioxide compounds of high molecular weight | |
US3801666A (en) | Concentrated cuprous nitrate/propionitrile solutions as complexing agents for olefin separations | |
US2973372A (en) | Dihydropyran ozonides and the method of making the same | |
US2299222A (en) | Process for the catalytic production of olefin-sulphur dioxide compounds of high molecular weight |