US2941005A

US2941005A - 1, 2-diamino-1-alkene compounds

Info

Publication number: US2941005A
Application number: US525347A
Authority: US
Inventors: John E Mahan
Original assignee: Phillips Petroleum Co
Current assignee: Phillips Petroleum Co
Priority date: 1955-07-29
Filing date: 1955-07-29
Publication date: 1960-06-14
Anticipated expiration: 1977-06-14

Description

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2,941,005 1,2-DIAM1NO-1-ALKENE COD/[POUNDS John E. Mahan, Bartlesville, kla., assignor to Phillips Petroleum Company, a corporation of Delaware Filed July 29, 1955, Ser. No. 525,347

4 Claims. (Cl. 260-583) No Drawing.

other aspect this invention relates to a method for propelling rockets. In another aspect this invention relates to 1,2-diamino-l-alkenes as new compounds. In still another aspect this invention relates to new fuel compositions comprising a liquid hydrocarbon and at least one of said 1,2-diaminol-alkenes.

This application is a continuation-in-part of my c0- pending application Serial No. 366,381, filed July 6, 1953 which in turn is a continuation-in-part of my copending application Serial No. 257,973, filed November 23, 1951, now abandoned.

- My invention is concerned with new and novel rocket propellants and their utilization. A rocket or jet pro pulsion device, such as is discussed herein is defined as a rigid container for matter and energy, so arranged that a portion of the matter can absorb the energy in kinetic, form and subsequently eject it in a specified direction. Thetype rocket to which my'invention is particularly applied is that type rocket propulsion device designated as a pure rocket, i.e., a thrust producer which does not make use of its surrounding atmosphere. A rocket of the type with which my invention is concerned is propelled in response to the steps of introducing a propellant mais thus necessary that the combustion chamber, although being strong enough to stand high pressure and tempera-. ture, need be only large enough toinsure combustion. The flow of liquid propellants into the combustion chamber can be regulated at will so that the thrust resulting from continuous or intermittent bursts of power can be sustained. Intermittent burning of the fuel contributes to a longer life of the combustion chamber and of the thrust nozzle.

-Various methods and liquid combinations'have been found to be useful as rocket propellants. 'Some propellants consist of a single material, and are termed monoprop'ellan Those propellants involving two materials are termed bipropellants and normally consist of an 2,941,05 Patented June 14, 1960- with aniline or furfural alcohol as the hypergolic fuel component.

When employing 90-100 percent nitric acid, i.e., white fuming nitric acid as theoxidizer in a rocket bipropellant fuel, it is often necessary, dependent upon the specific fuel component, to obtain more effective ignition than would normally be obtained, by dissolving from 6 to 23 percent by weight of nitrogen dioxide in white fuming nitric acid, thereby forming"red fuming nitric acid. A fuel component of the bipropellant type described herein is spontaneously ignited upon contacting the oxidizer. For this reason such a bipropellant material is referred to herein as being hypergolic. A ratio of oxidizer to hypergolic fuel, based upon stoichiometric amounts, can be utilized within the limits of 0.5 :l to 1.5:1 if desired. The efliciency of combustion is less at a ratio below 1:1 and the use of the oxidizer is less economical at ratios above 121. However, practical consideration may neces: sitate the use of higher ratios, 'even as high as 6:1.

Each of the following objects of the invention will be obtained by the various aspects of this invention.

I thrust to a rocket-type device. Another object is to provide as new compounds the 1,2-diamino-l-alkenes characterized by the structural, formula given and defined below. Another object is to provide an improved fastburning fuel. Other and further objects will be apparent to those skilled in the art upon study of the accompanying disclosure.

In accordance with the broad aspects of this invention, I have found that organic polyamines, either in the presence or absence of normally liquid hydrocarbons form a fuel component which is highly"hypergolic and suitable for use in the propulsion of rockets, guided missiles, and the like, in conjunction with an oxidizer. I have further found that these organic polyamines together with selected mercaptans, both more fullyset forth hereinbelow, either in the presence or absence of normally liquid hydrocarbons, form a fuel component which is also highly hypergolic and suitable for the uses set forth above. The fuels of the present invention are composed of (1) at least one organic polyamine or mixture thereof, or (2) at least one organic polyamine or mixture thereof with at least one selected mercaptan, either of the latter components being suitable in a major. or minor amount. When a selected mercaptan is used as one of .the fuel constituents, it is preferred that the mixtures contain at least 10 percent of the organic poly-.-

plication Serial No. 257,973, filed November 23, 51,

there are disclosed and now being claimed those organic polyamines selected from the group consisting of 1,3 butanediarnine, 1,2-propanediamine, triethylenetetramine, and tetraethylenepentamine.

In accordance with the invention in my copending application Serial No. 366,381, filed July 6, 1953 there are disclosed and now being claimed. those organic polyamlnes which contain at least two groups attached to one or more carbon atoms, wherein Ris selected from the group consisting, of a hydrogen at'o'rii' and hydrocarbon radicals selected from the group consistin'g of alli yl, a'lken'yl, cycloalkyl, cycloalkenyl, aryl, alk'aryl', and a'ralkyl radicals and the hydrocarbon of said polyainine is selected from the same group, the total number of'c'arb'o'n atoms in said polyamine being not greater than 30 and at least one R of at least two groups-being a hydrocarbon radical.

In both of the said cope'n'ding applications the carbon atom to' which the substituent group is attached may be a cyclic (.carbocyclic) carbon atom, a carbon atom of a side chain group attached to a yclic- (car'bocyclic) carbon atom or'a carbon atom of an acyclic molecule.

The following organic polyarnines are useful in the practice of theinvention of my copending application Serial 'No; 366,381: the aliphatic polyamines which include the various alkane polyamines such as N,N'-diethy1-l,4 hexanediamine; N,N,N,N'-tetraallylmethylenediamine; N,N,N',N' -tetramethylmethylenediamine; N,N,N',N-tetramethylethane-1,2-diarnine; N,N,N',N-tetramethylbutane-1,4-diamine; V N,N,N',N'-tetrarnethy1propane-1,3-diamine; and N,N,N',N-tetramethylpropane-1,Z-diamine.

Various alkenylene polyamines are also very efficient hypergolic materials and include V N,N,N',N' tetramethylpropene 1,3-diamine; N,N, N',N'atetraallylpropene-1,3-diarnine; N, N,N,N'-tetraethylpropene-1,3-diamine; N,N,N,NT :tetrn Z-methylallyl) prop ene- 1 ,3 -dia.mine; N,N ,N',N'-tetracrotylpropene-1,3-diamine; N,N-diallyl-N',N'-di(3-bu1tenyl)propene-1,3-diamine; N,N,N',N'-tetraallyl-Zmethylpropene-1,3-diamine; N,N'-diallyl -N,N-dimethylprop erie-l ,3 -di amine; N,N'-dicrotyl-N,N'-dipropylpropene-1 ,3 -diamine; E,N,N,N'-tetramethyl-2-methylpropene-l,3-diamine; and

e like.v

In addition to the above recited specific compounds, the total reaction mixture or fractions thereof from the preparation of N,N,N',N tetraallyl-, tetramethylallyl-, or tetracrotylpropene-l,3-diamine, is useful as constituent of hypergolic fuel compositions according to the said- Serial No. 366,381. These compounds are kno-wnin the art and can be prepared by the manner described in US. Patent 2,565,529 by C. W. Smith, wherein a suitable alpha, beta -unsaturated aldehyde is reacted with one or more'secondary monoamines having attached to the nitro gen atom at least one alkenyl group with an olefinic b ondinthe 2,3-position relative to the hydrogen atom or by other similar methods. I

As indicated hereinbefore, and in accordance with my .4- groups containing only carbon, hydrogen and nitrogen atoms.

Further according to the invention there are now provided as new compounds the 1,2-diamino-l-alkenes characterized by the structural formula R I R \N-C=CN/ R/ 7 IR) '\R wherein: R is a member selected from the group consisting of a hydrogen atom, alkyl, cycloalkyl, alkenyl, and

cycloalkenyl hydrocarbon radicals; each R is a memher selected from the group consisting of alkyl, cycloalkyl, alkenyl and cycloalkenyl hydrocarbon radicals, and the .Rs can be alike and unlike; the total number of carbon atoms in the molecule does not exceed 24; and the total number of carbon atoms? in Ry. does not exceed 8., It is to be understood that herein and in the claims the above named hydrocarbon radicals includes the various combinations of said radicals suclr as alkylcycloalkyl, cyclo= .alkenylalkyl, cycloalkylalkenyl, alkylcycloalkenyl, alkenyl- N,N,N',N'-tetramethyl-1,2-diarnino8,7-dimethyl-1,7-octadiene, N',N,N',-N tetrabutyl' 2 ethylcyclohexyl-l,Z-diarninoethylene, and

N,N- dimethyl N,N-"-did-hexyll-cyclopentenyl-1,2-diamino-l-butene, N,N-' dimethyl N,N'-di(Z-butenyl)-5-cyclopentyl-l',2'diw aminol,4-pentadiene, N,N' dimethyl N,N'-di(2-cyclopentylethyl) -l,2-diamino- 4-methyL1-pentene, I N,N' diethyl. N,N'-di(3 ethyl 2-cyclopentenyl)1,2-di

aminefl-propene,

- N,N' di'm'ethyl N-N' -di(5-allyl-2-cycloheireny1) 1,231-

. 'ary' amine as disclosed and claimed in the copending.

aminoethylene.v V I have further found that the new compounds of my invention are especially useful as hypergolic fuels. Indeed, s'aid newcornp'ounds are superior to any previously known hypergols shown bythe data 'given below in Example XIV and Table II. Examples I to XII, given below, areincluded' for comparison purposes to show the superiority of my new compounds as hypergolic fuels 7 vas compared with other organic polyar'nin'es.

' The new compounds of my invention can be prepared 7 by reacting under suitable conditions, an alpha-halo-alde hyd'e, having at l'e'astone hydrogen atom attached to the carbon atom alphat'o the aldehyde group, with a secondapplication of R. C; Doss and H. W. Best, Serial No.

525,346, filed rui za, 1955, now Patent No. 2,881,217, issued April 7, 19591 Said method oflpr'epafrin'g my new compounds is illustrated below? in Example XIII and 7 Table I invention, the'amin'o groups of the above=desoribed poly Representative ha'lo-aldehydewhich can be used in preparing my new compounds include, among'othei's, the following: chloroacetaldehyde, 2-brom0-p1'0pionaldehyde,

eit'maeimaea ae d Representative secondary amineswhich caii be used in preparaing my new compounds include, among others, the following: dimethylamine, diethylamine, methylethylamine, dibutylamine, dipropylamine, diisopropylamine, dial-lylamine, and N-methylcyclohexylamine.

The fuel constituents of the-present invention are hypergolic in an undiluted state and are alsohypergolic when admixed with non-hypergolic materials, particularly hy drocarbons, in a state of dilution as 'highas 70 percent by Suitable non-hypergolic materials which golic fuels in addition to white or red fuming nitric acid and can be used in the bipropellant fuel compositions of our invention. Suitable oxidants include materials such as hydrogen peroxide, ozone, nitrogen tetroxide, liquid oxygen and mixed acids, especially anhydrous mixtures of-nitric and sulfuric acids such as 80 to 90 percent by volume of white or red fuming nitric acid and to percent by volume anhydrous or fuming sulfuric acid. It is within the scope of this invention to employ, preferably dissolved in the oxidizer, ignition catalysts or oxidation catalysts. These oxidation catalysts include certain metal salts, such as the chlorides and naphthenates of iron, zinc, cobalt and similar heavy materials.

As an added feature of this invention my new compounds are also useful for providing fast burning fuels for use in rocket engines and the like wherein a hypergolic' fuel is not necessarily required. For example, the fuel components of this invention are dispersed in a hydrocarbon, such as the hydrocarbon diluents described above. Even if the resulting solution is not hypergolic with an oxidant such as fuming nitric acid, it can be used together with an oxidant and a suitable igniter as a rocket propellant. These fast burning fuels are particularly useful if, for various reasons, a hypergolic fuel is not desired or required. The organic polyamines of this invention may be added to a hydrocarbon fuel in a minor amount, usual- .1y from 1 to 20 percent by volume of the total mixture to produce fast-burning fuels which are non-hypergolic. Suitable fast-burning fuels comprise from 1 to 20 percent by volume of an organic polyamine described above with 90 to 99 percent by volume of a petroleum fraction gasoline boiling range. Specifically, such a fuel can comprise between 1 and 20 percent by volume of a 1,2-diamino-l- 'alkene and 80 to 99 percent by volume normal heptane.

As pointed out above, selected mercaptans can be used to form a portion of the hypergolic fuel constituents of this invention in admixture with the above described organic polyamines. Likewise selected mercaptans can be used with my new 1,2-diamino-l-alkenes. The mercaptans which are suitable for use as such a hypergolic fuel constituent include compounds of the general formula RSH, wherein K is-selected from the group consisting of alkyl and alkenyl groups containing from 3 to 10 carbon atoms. Illustrative of the mercaptans used in this invention are tert-butyl mercaptan, isopropyl mercaptan, allyl mercaptan, n-butyl mercaptan, n-hexyl mercaptan, terthexyl mercaptan, tert-octyl mercaptan, nonyl mercaptan, tert-decyl mercaptan, 2-butene l-thiol, 3-butene-l-thiol, isobutyl mercaptan, and the like.

A fuel of the present invention, i.e., mixtures consisting of, at least one 1,2-diam ino-l-alkene and at least one mercaptan are hypergolic in an undiluted state and are amines 5 also hypergolic when admixed with non-hypergolic ma: terials, particularly those normally liquid hydrocarbons set forth above, when using such hydrocarbons in amounts as high as 50 percent by volume of hydrocarbon when white fuming nitric acid is used as the oxidant. v The invention is further illustrated in the following ex amples. The reactants and their proportions and the specific ingredients-are presented as being typical and not to be construed as unduly limiting the invention.

' EXAMPLE I p Maximum Dilution, Percent volume n-heptane or benzene Polyamine Oxldant rab imnednmma.

o 4. triethylenetetramlne tetraethylenepentamine...

-' 1 n-Heptane diluent. i Benzene diluent.

EXAMPLE II A reaction flask fitted with thermometer, dropping funnel, reflux condenser and stirring unit was charged with a mixture of 50 grams of finely powdered anhydrous potassium carbonate, grams of diethyl ether and 194 grams of diallylamine. As the mixture was stirred vigorously, 56 grams of acrolein were slowly added with cooling to maintain the reaction mixture between 10 and 15 C. (50 to 59 F.). After all the acrolein had been added, the reaction mixture was kept at 5 to 10 C. (41 to 50 F.) and stirred for 17 hours. The contents of the reactor were then filtered to remove the solid desiccant; a dark-red filtrate was recovered. The ether and low boiling components, including unreacted acrolein and diallylamine, were removed by fractional distillation. The higher boiling material was then transferred to a vacuum distillation apparatus and distilled under reduced pressure. A summary of the distillation results is presented in the following table: a I a N,N,N',N-tetraallylpropene-1,3-diamine and the other materials recovered from the fractionation of Example I were tested for spontaneous ignition employing fuming nitric acid as the oxidant. The temperature of the fuel and oxidant was maintained at room temperature (21 C.). In each test 0.13 ml. of the fuel or a diluted solution thereof was dropped into a 1" x 8" test tube con pro edure otExamplelv. Results.aresetgforthbelowz ('n-heptane) was employed to determine the amount of V axln l m e dilution which each fuel would tolerate and retain its hy- 7 Fuel oxidant I g g; 722E116; pergolic properties. The resultsrare set forth in. the foll. V Retgggfin t Iowmg I T Hypergohclty" p d ffifiii atgo li Plastic resi ue.

- fifif Fuel l ii gng ggrlastlclresldue dlssolvedinn-heptane.---. i: 28;

ofHyper-'1 J. I

golicity l 7 Fraction No-1 .Q 4-,. E I Z3 -Ajrlml for the preparation-of N,NgN,N' -tetra llylpm- Fraction No. 2 (N,N,N,Netetraallylpro- 3g pene 1.,3.-diamine was conducted 1n the manner described f m R I: 7 in Examplel except that the reaction mixture. was stlrred Fmmn i {WFNAmfor 16. hours. After filtering off thepotassium carbonate, a Y the reaction mixture was stripped of ether. Then half of In addition to the room temperature tests previously the de-etheri-fied. materiabwas refraction ated to remove rib ,N',N',- r allyl-1,3-diaminopropene and everything up to diallylamineunder reduced pressure other materials recovered from the fractionationproce- (h d temperature 35 ,C., corn); The. remaining half dure of Example I were also tested for spontaneous igniofthis materialv was refractionated to'remo ve everything tion at 40 C. Prior to testing, the temperature of the up to and including diallylamine under reduced pressure fuel and oxidant was lowered to 4() C. Testswere con- (head temperature, 117 C., corn). These two materials Y ducted employing 0.13 ml. of fuel or a diluted solution were tested for self-ignition properties at 21 C. and at thereof and 0.3 ml. of fuming nitric'acid. Results are 25 -4.0 C. in the manner set forth in previous examples. recorded below. Results are recorded below:- r r Maximum Per- Maximum Dtcent Dilution 7 Test lution with I Q withn-heptane Fuel 'Ternpeb Oxldant n-heptane Fuel Oxidant with "ature, wlthRetenv Retention of C. tlon of V Hypergolicity Hypergoliclty at 40 C. V k

. I RFNA 70 Grude roduct (ether removed)- 21 V Fraction No. 2 (N,N,N,N-tetraallylpr0- $fi"-- p A pene-lfidiamine). RFNA"" 40 Do 10 Fraction No. 3 10 70 f Crude product (ether and 60 r diaglylamine removed). V 40 'In addition to the above tests, the crude reaction mix- 0 N ture obtained from the, procedure of Example I was also 7 V tested for self-ignition properties. Prior to testing, ether & .EXAMPLE VI 7 fi p f mammals were f??? by geatmg A drop test apparatus comprising an injection nozzle f E mix i Warm i 61 u inserted to within 1 of. the bottom of a 1"): 8" test uce 'f g g e a Wa er asplra esu S tube was employed to determine the ignition delay in are 6 5 milliseconds r N,N,N,N'-tetraallylpropeneeI,3-diamine.

I A small quantity of fuel (0.2 ml.) was placed in the botl tom of the test tube and 0.3 ml. of'whit'e fuming nitric cent Dllutiorr, Fuel Oxidant with n-lleptane acld was in ected mm the fuel. A constant pressure nitrog gfi gen surge chamber provided a source of approximately Hypergolicity 40 p.s.i.g; pressure to inject the oxidizer into the fuel. vA solenoid coil actuated the injector to provide an accurately Crude Reaction Mixture from the Run FNA Not diluted metered/amount of oxidant. The ignition delay interval a fig f' (that and low WFNAI, Do. was determined as the time between contact of the oxigznaterals removed). V D0 RFNA... 60. dlzerw th the fuel and the presence of flame as sensed 'by a photocell. 7

r V N, N ,N",N'-tetraallylpropene-1,3-diarnine was tested em- EXAMPLE V ploying' the apparatus described and was found to have A, run; for the preparation of N',N,N',N'-tetraallylproan 1 lgmtlondelayof 6-3jm11hsewndS- pene-1,3-dia-mine was conducted in-the manner described I extremely short delay compared to k inExarnplel except that the reaction mixture was stirred" lhypergollc fuels, for x P ffurfuryl alcohol, a 19 9* for 12.5 hours. The reaction mixture was very dark rhypergohc fuel; had an lgmtlon delay of 2731111155? in color and viscous. This material was. distilled to re- Fi as deltermmed. the m apparatus and test P move unreacted diallylamine and other volatile materials cedureleaving a black, plastic residue in'thekettle. This material 7 EXAMPLE VII fi f9? silmliallwus lgmtlon emP1Qy1ngf uming N,MN,N'-Tetramethylpropene-1,3-diarnine was premmc afld ll Willie. conducted W111i the pared from dimethylarnine and acrolein by substantially fuel and Q ldant maintained at room. temperature (21 the, same procedure. as previously employed. for C.). In the first test, a small particle of the solid, plastic N,N,N,N'-tetraallylpropene-l,3 -cliamine; The crude ma.- residue was dropped into 0.3 ml. of. fuming nitric acid'in terial,. in, 73.8 percentv yield, was distilled in an 18inch a 1" x 8" test tube. in addition thisresiduewas dissolved column. A 30. percent: theoretical yield of distilled in ptane and the maximumdilution that the material product was obtained, along with 22 percent solid'kettle would tolerateand. maintain its self-ignition properties residue. A was. determined. 0.13, mlrof fuel solution, was employed These materials wereexamined for dilution data'and with. 0.3. ml. of fuming nitric acid as describedinthetest 1T ignition delay- 'withfithe drop tester usingstandard tecl'vv niqu'est Toluene Dilution B.P., Ignition Delay,

Material 0. a Room temp. 40 0. milliseconds RFNA WFNA RFNA WFNA N,1N3,N,N-Tetramethylpropene- 1 48 1. 4589 70 7O 10 15.5 24 C.

Crude N ,N ,N,N'-Tetramethyl- 1. 4668 70 70 20 10.5 24 C.

propene-1,3-diamine. Plastic kettle product Hypergolic 1 At 103 mm. Hg.

EXAMPLE VIII manner described hereinbefore. Tests were conducted Each of the fuel mixtures described hereinbelow was 15 with fuel and oxidant at room temperature (21 C.)

tested for spontaneous ignition employing fuming nitric Results are recorded below.

Maximum Percent Dilution Fuel Composition Oxldant with n- Heptane with Retention of Hypergolicity Red Fuming Nitric Acid No ignition. f jfi i z T x {White Fuming Nitric Acid Do.

9 6 Red Filming Nitric Acid described above dissolved in tertbutyl mercaptan. }White Fuming Nitric Acid 50.

acid as the oxidant. -The temperature of the fuel and 30 EXAMPLE X oxidant was maintained at 21 C. In each test, 0.13 ml. i of the fuel or a diluted solution thereof was dropped into A run for the preparation of N,N,N,N' tetraallyl a 1 inch by 8 inch test tube containing 0.3 ml. of fuming propene-1,3-diamine was conducted in the manner def nitric acid. The inert diluent was employed to determine scribed in Example III except that the reaction mixture the amount of dilution which each fuel would tolerate wasstirred for 16 hours. After filtering oif the potassium and retain its hypergolic properties. The results are set carbonate the reaction mixture was stripped of ether. A forth below. portion of this material was 'refractionated to remove Maximum Per-' cent Dilution Fuel Composition Oxidant with n- Heptane with Retention of Hypergolicity Red Fuming Nitric Acid No ignition. gert'butyl 'ifg White Filming Nitric Acid Do. 7 v Ween i i e Red Fumin Nitric Acid 20 a1ly1propene-13-diamine in tertb Y butyl memapfim White Fuming Nitric Acid- 10. v

1 Prepared by the run described in Example III.

EXAMPLE IX everything up to and including diallylamine under reduced pressure (head temperature 117 C., corr.). This material was admixed with tert-butyl mercaptan in varying proportions and the fuel compositions so formed were tested for self-ignition properties by the process described in previous examples. Results are set forth below. I v

A run for the preparation of N,N,N,N-tetraallylpropene-1,3-diamine was conducted in the manner described in Example III except that the reaction mixture was stirred for 12.5 hours. The reaction mixture was Maximum Percent Dilution Fuel Composition Oxidant with'n- Heptane with Retention of Hypergolicity 100 percent tert-butyl mercaptan g g% fi gg 2g No gg 10 percent crude N,N,N',N'-tetraal.lyldF m Nit A 20 1,3-diaminopropene(etheranddialiyl m 3 01 amine removed). White Fummg Nitric Acid 20.

very dark in color and viscous. This material was dis- EXAMPLE XI .stilled to remove unreacted diallylammeand pther volatile Sever-a1 of the alkane polyamines and alkenylene poly: .materials. leaving a black, plastic residue in the kettle. iamines were tested f ignition delays 'a p tester .A small amount of this residue was dissolved in fertinjecting while fuming nitric acid into a small quantitj 'of butyl mercaptan (readily soluble) and the composition fuel and determining the ignition delay interval between so formed was tested for self-ignition properties in the the contact of the acid and'fuel and the presence of flame -11 as sensed by a photocell. The materials and ignition delays are set forth below.

Material Fuming Nitric Acid, Milliseconds N,N,N;N-tetramethylmethylenediamine- N ,N ,N,N -Tetramethylpropanc-1,3-diamine- N,N,N,N-Tetramethylpropane-1,2-diamine EXAMPLE Xll intervalbetween the contact of the acid' and fuel and the presence of flame, as sensed by a photocell. The materials and ignition delays are set forth below.

Ignition Delay with White sewn.

- N i- H enema-momma 12 VT able [Pressuremm. mercury.]

Overhead Distillate Distillate, Refrac- Out No Temp Collected, tive Index 7 0. gms.

9. 1 l. 4643 9. 8 1. 4655 g. 1. 4658 Product 413 11 4648 Mainly methylcyclopentanecollected in a trap maintained in a Dry Ice-acetone bath to prevent vapors from entering vacuum pump.

milliseconds V ylene and N,N,N',N-tetramethy1-1,2-propanediamine.

Ignition Delay, Milliseeonds, at 75 F.

Material Red White Fumlng Fuming Nitric Nitric Acid Acid N,N,N,N-tetramethylethane-1,Z-dialnine 9. 3 N,N,N,N-Tctramethylbutane-1,2-diamine.- I 14 N,N,NQNGTetramethyl-Lbutene-3;4-diamine. -4. 1. N,N,N,N-2-Pentamethylpropane-l,B-diamine 22 N=,N,N ,N -Tetrarneth3dbutane-l,4-(1iamine. 7. 4 7 N,N,Nf,N-Tetramethyl-2-butenc-1,4-diamine. 4.3 4 'N,N,N,N-Tetramethy1hexane-l,G-diamine 8. 8 5

EXAMPLE XIII 7 To a one liter glass reaction vessel there was added 200 milliliters of methylcyclopentane and 220 milliliters of dimethylamine. The reaction vessel was placed in an acetone-Dry Ice bath and, after cooling to' 8 C., 186 grams of a percent aqueous solution of chloroacetaldehyde was added dropwise with stirring. The temperature of the reaction mixture was maintained between 10 and 0 C. for the approximately 30 minutes required to add the chloroacetaldehyde. The temperature of the black colored mixture was permitted to rise to room tem-- I perature (about 25 C.) and stirred 2 hours at this tem-' perature;

The aqueous layer of the reaction mixture was sepa- A sodium fusion was made on Cut Number 5 and a qualitative test for halogen indicated none was present. Solutions of potassium permanganate and bromine were absorbed by the product, indicating the presence of a double bond. A titration of a portion of the product,

made with hydrochloric acid, caused decomposition yielding the free amine. v 7 g V Cuts 4 and 7 were hydrogenated in the presence of nickel in a Parr hydrogenation bomb at 40 p.s.i-g. and room temperature. The refractive index of the hydrogenated sample was 1.4180 at 25 C. as compared with 1.4170 at 25 C'. for a sample of N,N,N',N'-tetramethyl'ethanediamine. These testsserved to characterize the product as N,N,N',N'-tetramethyl-1,2 diaminoethylene.

The product yield was 38 percent of theoretical based on the chloroacetaldehyde charged.

EXAMPLE XIV A drop test apparatus comprising an injection nozzle inserted to within. 1" of the bottom of a l" x 8" test tube was employed to determine the ignition delay in of N,N,N',N'-tetramethyl-1,2-diaminoeth- A small quantity of fuel (0.2 ml.) was placed in. the bottom of the test tube and 0.3 :ml. of white fuming nitric acid was injected into the fuel. A constant pressure nitrogen surge chamber. provided a source of approximately 40 p.s.i.g. pressure to inject the oxidizer into the fuel. A solenoid coil actuated the injector to provide an accurately metered amount of oxidant. The ignition delay interval was determined as the time between contact of the oxidizer with the fuel and the presence of flame as sensed by a" photocell. Table II' gives the data obtained on the ignition delays obtained by this method.

This value was obtained using a different acid and at a dificrent time from the value given in Example XI. V

As can be seen from the data given in the above Table II, the compound N,N,N',N-tetramethyl-1,2-diaminoethylene, which is representative of the new compounds of my invention, exhibits an ignition delay which is superior to that of N,N,N,N'-tetramethyl-1,2 propanediamine, or any of the other. hypergols tested in the other examples. These data show that my new hypergols are superior to any other hypergols previous- 7 1y known prior to my invention.

The superiority of my new compounds is further shown by a comparison with ethylene diamine, a known hypergolic fuel. Ethylene diamine has an ignition delay of 929 milliseconds at 75 F. as determined by the same apparatus and test procedure employed in Example 7 XIV.

As will be evident to those skilled in the art, various modifications, substitutions and changes may be made or followed in the light of theforegoing disclosure without departing from the spirit or scope of this invention;

I claim:

-1. A 1,2-diamino-1-a1kene selected from the group consisting of N,N,NN-tetramethy1 1,2 diaminoethylene; N,N,N',N tetIaethy1-1,2-diaminoethylene; and N,N'- dimethy1-N,N'-diethy1-1,2-diamiuoethy1ene.

2. N,N,N',N'-tetramethy1-1,2-diaminoethylene.

3. N,N,N,N'-tetraethy1-LZ-diaminoethylene.

4. N,N' dimethyl N,N' diethy1 1,2 diaminoethylene.

References Cited in the file of this patent UNITED STATES PATENTS Carmody July 10, 1956

Claims

1. A 1,2-DIAMINO-1-ALKENE SELECTED FROM THE GROUP CONSISTING OF N,N,N''N''-TETRAMETHYL - 1,2 - DIAMINOETHYLENE, N,N,N'',N''-TETRAETHYL-1,2-DIAMINOETHYLENE, AND N,N''DIMETHYL-N,N''-DIETHYL-1,2-DIAMINOETHYLENE.