DE1670356A1 - Process for the preparation of nitroazolines - Google Patents

Description

Commercial Solvents Corporation, Terre Haute, Indiana, USA

Process for the production of Ni troazolinen

Priority: 488 776 dated September 20, 1965 in TJSA

The invention relates to new Nitroazolinverbindun- and MtroimidaPiolinverVinlungen and methods for de-J ¹ Bn animal husbandry. Specifically, it relates to the production of 2- (TTi.fcroalkyl) -2-a? .Olines including aryl-, alkyluri'i-alkenyl-substituted nitroalkylazolines. The invention is even more particularly concerned with a method for producing the following nitroazoline compounds:

2- (3-nitro-3-alkyl) -2-oxazolines, 2- (1-A.lkyl -?! - nitroalkyl) -2-oxazolines, 2- (i-arylalkyl-3-nitroalkyl) -2-oxazolines , 2- (1-alkenyl-3-nitroalkyl) -2-oxazolines, 2- (1-aryl-3-nitroalkyl) -2-oxazolines, 2- (3-nitro-3-alkyl) -2-imidazolines, 2- (1-alkyl-3-nitroalkyl) -2-imidazolines, 2- (1-arylalkyl-3-nitroalkyl) -2-imidazolines, 2- (1-alkenyl-3-nitroalkyl) -2-imidazolines, 2- (1-aryl-3-nitroalkyl) -2-imidazolines,

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_BATH

2-Oxazoline and 2-Imidazonline have the following general formula:

-C σι t

wherein 1 is either the oxygen of the oxazoline ring or the Is imide nitrogen of the imidasoline ring. It corresponds to the usual nomenclature, X to designate with the position 1 and the remaining ring atoms in the numerical sequence in the direction name that gives nitrogen the lowest number, i.e. counterclockwise in the above formula. Therefore the carbon atom between I and II gets the position 2, the nitrogen the position 3 etc. A carbon atom that bonded to the carbon atom in the 2-position is here referred to as the α-carbon atom.

There are many references in the literature to the preparation of substituted oxazolines and imidazolines, and Compounds which are substituted in any position on the ring are known. Different methods of manufacture of oxazolines and imidazolines are known, but the most common method is that of an organic monocarboxylic acid to implement with a 1,2-alkanolamine and then through Dehydration to gain an oxazoline or to react the organic acid with a 1,2-diamine and then the Obtain imidazoline by dehydration. The Carboneäurereet forms the substituent in the 2-position, and others Substituents, if any, are obtained through the structures the respective alkanolamines and diamines.

There is no publication in the oxazoline or imidazoline art about a method of introducing one Nitroalkyl group on the a-carbon atom after the formation of the Ring. There is also no description of a nitroaliphatic Remainder on the α-carbon atom in the 2-position.

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BATH ORIGINAL

One aim of the invention is to obtain new nitroazolines and a process for their production «A second and further objects of the invention are to provide 2- (3-nitro-3-alkyl) -2-oxazolines, 2- (i-alkyl-3-nitroalkyl) -2-oxazolines, 2- (1-Arylalky1-3-nitroalkyl) -2-oxazoline, 2- (1-Alkeny1-3-nitroalkyl) -2-oxazoline, 2- (i-Aryl-3-nitroalkyl) -2-oxazolines, 2- (3-nitro-3-alkyl) -2-imidazolines, 2- (1-alkyl-3-nitroalkyl) -2-iraidazolines, 2- (i-Arylalkyl-3-nitroalkyl) -2-imidazolines, 2- (i-Alkenyl-3-nitroalkyl) -2-imidazolines and 2- (i-Aryl-3-nitroalkyl) -2-imidazolines to win. Other objects of the invention will be readily apparent to those skilled in the art.

The following azoline compounds are made from this Invention captured.

2- (3-nitro-3-alkyl) -2-oxazolines, 2- (1-alkyl-3-nitroalkyl) -2-oxazolines, 2- (1-arylalkyl-3-nitroalkyl) -2-oxazolines, 2- (1-alkenyl-3-nitroalkyl) -2-oxazoline, 2- (1-Aryl-3-nitroalkyl) ~ 2-oxazoline, 2- (3-NitΓθ-3-alkyl) -2-imidazoline, 2- (i-alkyl-3-nitroalkyl) -2-imidazolines, 2- (i-Arylalkyl-3-nitroalkyl) -2-imidazolines, 2- (1-alkenyl-3-nitroalkyl) -2-imidazolines, 2- (i-Aryl-3-nitroalkyl) -2-imidazolines.

These oxazolines and imidazolines can be described by the following general structural formula:

H ₀ C CR ₀

«= · Ι t * - X N

f t 3

HC-CH ₀ -C-CH,

R ₁ BOp

wherein X is 0 or NY, where Y is hydrogen, an alkyl radical, aryl radical. Is arylalkyl radical or hydroxyalkyl radical, R _{1 is} a water, alkyl, alkenyl, aryl or arylalkyl radical with

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1 to about 20 carbon atoms, R ₂ and R hydrogen atoms, alkyl radicals with 1 to 3 carbon atoms, the hydroxymethyl group or the acyloxymethyl group, where R 1 and R can be only hydrogen atoms or alkyl groups with 1 to 3 carbon atoms when X is NT. R ₂ and R can be the same or different.

If X means O, the following oxazoline is obtained:

H ₉ C "■" CR ₉ <= - 1 ι <= ■ ON

* HC-CH ₉ -C-CH,

ι * ι -> R ₁ NO ₂

When R _{1 is} hydrogen, the following oxazoline is obtained:

H ₉ CCR ₉

^ I 1 ^

0 _v NV OH,

II ■>

Hfl ι \\ Λ _ Γ * / "* ΤΓ _ v ^ —un ₉ —ν — un—

NO ₂

If X means NY, you get the following imidazoline:

H ₂ C - CR ₂ YN N

C ^ CH ₅

HC-CH ₂ -C-CH-

R ₁ NO «

and when R _{1 is} a hydrogen atom the following imidazoline is obtained:

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2 CH
t 3 2 H ₉ C CR
* = ■ dd -C-CH
» Y-N N NO V H ₂ C-CH ₂

The new compounds according to the invention can be obtained by reacting one mole of a secondary nitroalkane in the presence of a condensation catalyst with about 1 mol of a 2-Kthenylazollns of the general formula

HC CR ₉

X _v N

R ₁ -C = CH ₂

are obtained, wherein X, R ₁ , R ₂ and R _{T have} the above meaning. If X is 0 and R _{1 is} a hydrogen atom, the compound obtained is a 2- (3-nitro-3-alkyl) -2-oxazo-III. If X is 0 and R _{1 is} an alkyl group, a 2- (i-alkyl-3-nitroalkyl) -2-oxazoline is obtained. When X is 0 and R _{1 is} an arylalkyl group, the compound obtained is a 2- (i-arylalkyl-3-nitroalkyl) -2-oxazoline. If * X 0 and R _{1 are} an alkenyl group, a 2- (1-alkenyl-3-nitroalkyl) -2-oxazoline is obtained. When X is 0 and R ₁ is an aryl group, one gains a 2- (i-aryl-3-nitroalkyl) -2-oxazoline when X _e NY and R ₁ represents a hydrogen atom, the obtained compound is a 2- (3-nitro -3-alkyl) -2-imidazoline. If X is NY and R _{1 is} an alkyl radical, a 2- (1-alkyl-3-nitroalkyl) -2-imidazoline is obtained. If X is NY and R _{1 is} an arylalkyl radical, a 2- (i-arylalkyl-3-nitroalkyl) -2-imidazoline is obtained. If X WI and R _{1 is} an alkenyl group, Bo is the one obtained *. Compound a 2- (1-alkenyl-3-nitroalkyl) -2-imidazoline. When X is NY and R _{1 is} an aryl group, the compound obtained is a 2- (i-aryl-3-nitroalkyl) -2-imidazoline.

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In general, the reaction is carried out in such a way that the reaction participants and the catalyst in a suitable reaction vessel that is equipped with a Is equipped with a reflux condenser and a stirrer. If wanted, a solvent can be used and, in general, a solvent is preferred. The amount of catalyst used is preferably about 0.5 to about 5 weight s-ji based on the weight of the azoline, i.e. the weight of the Oxazolines or imidazolines. Heat is supplied from a heat source and the mixture is reacted at reflux temperature, until the ITitroalkane is used up. If no Uitro ^ alkane more condensed at the top of the reflux condenser

and the pot temperature has risen to at least 150 ° C, the reaction is essentially complete. The entire reaction product can, if desired, be used as such, however, it is usually preferred to clean it. Any known purification method, such as extraction or distillation, can be used be used.

Distillation is a preferred method for compounds with sufficient thermal stability. To obtain a distilled crude product, the reaction product is distilled under reduced pressure of about 10 to about 15 mm, and the top fractions and the last fractions are discarded. If yet a further refining forthcoming Trains t r, the distilled crude product is fractionated mm at a pressure of about 1 to. 5 The temperature at which these distillations take place is usually below 200.degree. C. and varies according to the ethenylazoline used and according to the pressure prevailing during the distillation. In general, the temperature is higher when R _{1 is} a long chain group than when R _{1 is} a short chain group.

Di · making a connection through this implementation let in Example 3 described.

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In another embodiment of the invention, the ithenyl isoline is prepared in situ and is then reacted with the nitroalkane to form the nitro derivative. One method is to mix about 1 mole of a 2-substituted azoline, such as a 2-alkylazoline, a 2-alkenylazoline, or a 2-arylalkylazoline, with about 1 mole of an i-hydroxy-c-alkyl - ^ - nitroalkane, such as To implement 2-nitro-2-methyl-1-propanol, preferably in the presence of a fondensation catalyst. This reaction is fttwa 1 mole of water free _f which are removed from the reaction mixtures must, before the reaction is completed. The reaction is advantageously carried out in the presence of a water-removing solvent at reflux temperatures and at normal pressure. Heating is continued until no more water of reaction is released, which can be determined by using a water separator at the top of the reflux condenser. The water-removing solvent, such as hexane, octane, benzene, toluene, xylene, 2-nitropropane, etc., reduces the viscosity of the reaction mixture and removes the reaction water azeotropically. After removal of the water and dehydrating solvent by distillation, the entire product of the reaction can be used if desired, but it is usually preferred to purify it.

It is known that hydroxynitroalkanes decompose to nitroalkane and aldehyde under alkaline conditions. In this embodiment it is possible for the hydroxynitroalkane to form under the reaction conditions decomposed by formaldehyde and ITitroalkane. The formaldehyde then reacts with the 2-substituted azoline to form Ethenylazoline, which in turn reacts as described above with the Titroalkanrest, which arose from the Hydroxynitroalkan is. The preparation of a compound of the invention according to this embodiment is in Example 1 described.

BATH 209818/1156 ^B

η -

i-.ub.titW.rt .., «11.

In

"In,. K .. (In-

n der _β 1 · 1β) <»η

In -U,

the Azolin Lopndet is.

^after -

ung of formaldehyde with

^Elnr ' ^{elhel + Pn of} making the

η is called T ^ ™ '"**" example n. From now

on they are _e .1iitro " _e oll". referred to as TUtrooxasoline and Nitroimldasoline.

The ITltrooxazoUne and Nitpeimidaaolln · of the invention can all plasticizers for mtrcrtluln «and alo« like product, for the division of tolhooxa.olln.n and AmJnoi.id azolines are used. will.

.The Nitrooxazoline and Nitroimidar.on the Τ.τηηάην ^ are all plasticizers in Nitror.ellulose lacquer in the GUlnhn. ■ Weiae USER as let known to those skilled ff _lr other plasticizers. I _n general, this N1 trcoxanoHne and Nitroimidasoline in herkemmUchen.Lacken in "" INEP Men.e of e.wa 75 Ms approximately 125 weight * used de "NitrozeUuloneeewichtes.

Aminooxaaolines and Anilnoilnieas "lJn" can _9V * d _Pn N-itrooxaeollnen and Witroinddaaolinen according to the invention by hydrogenation in the presence of a hydrogenation catalyst such as Raney nickel, at about 68 atU (1G00 psig) up to about 30 ° C well known in the art Methods will be established.

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COPY
BATH ORIGINAL

However, if R ₁ , R ₂ or R 1 contain unsaturated bonds, these are likely to be hydrogenated in the presence of Raney-lUckel.

Ar.olines which can be used for the preparation of nitrooxazolines and nitroimidazolines by the process of the invention are commercially available or ketones. The commercially available 2-substituted oxazolines and 2-substituted imidazolines with an alkyl, arylalkyl or alkenyl group in the 2-poeition are satisfactory to the process according to the invention. Various methods for the preparation of 2-substituted oxazolines and 2-Substituted midazolines are known in the art, and any ancestor which yields an alkyl, alkenyl, or arylalkyl group in the 2-position leads to oxazolines and imidazolines, which are satisfactory for the process of the invention. Oxazolines, which are described in of the 4- and 5-Poaition, and imidazolines which are substituted in the 1-, 4- and 5-ΓΌβ "ΙΚ.Ιοη" are also to be used, preceded by an alkyl, alkenyl or aryl alkyl group in the 2-Ponltion boHitzen.A process which gives more satisfactory results for the production of compounds is described by HL Wehrraeiol.or in J.Org.Chera. 26, 3921 (19Ci).

Those used in your method according to the invention Kthenyla'iol Ine can easily atm 2-Alkyloxazolinen, 2-Arylalkyloxar. 2-AlkenyloxazoTinen, 2-Alkylimidazolinen, P-Arylalkyllidazolinen and 2-Alkenyliraidazolinen by treatment learn the same with a source of formaldehyde, such as formaldehyde or paraformaldehyde, can be obtained as would be known to those skilled in the art is known and is described in Beißpiel 14. Also lot by H.T .. Wehrraeioter in J.Org.Chpin. 27, 4418 (1962) a zuerledetiiitellenrtea Procedure here '/. U beBOhrleben.

The general ketonic 2-substituent oxazolines leloht lurfth implementation of an allphatlechen or aromatic Monooarboxylic acid with 2 or more carbon atoms with one Alkunolamin dor general formula

j 209818/1156

k copy

BATH ORIGINAL

wherein R ₂ and H-alkyl radicals rait. 1 to 3 carbon atoms or hydroxymothyl group are obtained. R ₂ R, know the same or different soin. Dienes alkanolamines are, for example oweIne 2-amino-2-mGthyl-1-propanol _t 2-amino-3-methyl-1,3-propend lol, 2-amino-2-hydroxyraethyl-1,3-propanediol and 2-Amlno- 2-ethyl-1,3-propiindiol. If either R ₂ or R- or both hydroxyalkyl groups are bovine, the resulting hydroxyoxazole can be phatiucher in with e? .1. or aromatic monocarboxylic acids can be esterified by methods known in the art, and these oxazoline esters are also useful in the process of this invention. When the carboxylic acid is saturated, Int. R _{1 is} an alkyl group, if the carboxylic acid, on the other hand, is unsaturated, int R- is an alkenyl group, and if the carbonic acid is a member of the phenylaliphatic group, R _{1 is} an arylalkyl or aryl group. If, for example, the mono carbonic acid is phenyl acetate, R _{1 means} . Aryl.

If the alkanolamine is a triol, R ₂ and R 1 are hydroxyraethyl groups, provided 1 mole of a monocarboxylic acid is used to form the oxaeoln. These hydroxymethyl groups can then be esterified with the aid of an aliphatic, an aromatic or an arylalkyl monocarbon acid to form acyloxymethyl groups. Either the same or a different acid can be used to form the oxazoline. If it is preferred that the hydroxymethyl group be esterified with the same acid that is used to form the oxazoline, the alkanolamine is conveniently reacted with 3 moles of the acid to form the diester oxazoline in a single step.

If in similar catfish the alkanolamine is a oil If 1 and 1 mole of Acure is used, either R «or R- is a hydroxymethyl group and the other group is an alkyl res L

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COPY BATH

with 1 to 3 carbon atoms. Di «? Hydroxymethyl group can in a similar way either on the same side as the oxazole in-Mldung under the use of ? Mol3Hure or in a separate Stage to be esterified »

2-Alky3- or 2-Alkenyliraidazolines know similarly easily mis of a honocarbonic acid with 2 or more carbon atoms can be obtained by serving with a diamine the general formula

Y-NH-CHo-C-R.

• .ini <5e ^f .zt, in which R ₂ and R, a hydrogen atom or alkyl radicals with 1 "am J carbon atoms ■ -slnd4 · R« and R, can be preceded by four. Y means ..% in hydrogen, a low molecular weight At.kylgrup.pe, aryl group, arylalkyl group uppe odor Hydroxyalkylgi * These diamines are for example 1, 2-ÄUiylendinmin, 1,2-Proi.ylendiamin, K. IiTop'ropyl-2-methyl-1, S- propanediamine, N-phenyl-P-methyl-ijS-propanediamine, N - (? - Hy'lrpxyMthyl ') - 2-methyl-1, i-prOpanediamine, N - (? - AiDinoi8obut.yl) -1iut.ylamine and N - (2-Aminoisobutyl) -ben.ftylftraln.

The MonooarbonoMurpn, which can be used to form the Oxar.oline, Ttiidttxolino and their udders, have the formula R ₁ CIUOOOH, where R _{1 is} a water atom, an alkyl, aryl-alkyl, alkenyl or aryl group with 1 to about 20 Kohlstorr: \ tomßn no can. These SHurs are the saturated or unsaturated acids from the PettsHur series, including phpnyl-substituted Petthurs, starting with Eseigs Jin ro. An upper limit on the length of the carbon chain, if any, is not known, but it is practical to use acids with 22 carbon atoms or less, since these are relatively cheap acetic acid, propionic acid, phenylprnpionic acid, caproic acid, coconut juice fat whores, TaIg-HlfottnMiiren, oleic acid, RtoarlnsMure, PischHlsHuren uow.

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COPY BAD ORIGINAL

The nitroalkanes used in the process of the invention are secondary nitroalkanes having 3 to 6 carbon atoms in the molecule including, for example, 2-nitropropane, 2-nitrobutane, nitrocyclohexane and preferably 2-nitropropane. The monohydroxynitroalkanes obtained after the process of the invention are those having 4 to 6 carbon atoms in the molecule and having the ITitro group as well an alkyl group in the 2-position, such as preferably 2-nitro-2-methyl-1-propanol. Commercial grade materials are fully satisfactory for the process of the invention.

Fe acid catalysts suitable for the process of the invention

analyzers are inorganic mineral acids such as sulfuric acid, Hydrochloric and phosphoric acids, organic Carboxylic acids and sulfonic acids, such as formic acid, benzenesulfonic acid, p-lylenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acids, inorganic and organic salts such as sodium bisulfate, Monoammonium chloride, calcium chloride, zinc chloride, aluminum chloride, ammonium chloride, ammonium bromide, hydroxylammonium chloride, Boron trifluoride, boron trifluoride ether complex, and halogen such as iodine. Iodine, p-xylene sulfonic acid, zinc chloride and Sodium bisulfate has been found to be particularly advantageous catalysts.

The present invention is further illustrated by the following examples:

example 1

The preparation of 2- (3-Mtro-1,3-dirnethylbutyl) -4,4-dimethyl-2-oxazoline was carried out as follows:

60 g (0.5 mol) of 2-nitro-2-methyl-1-propanol, 74.0 g (0.58 mol) of 2-ethyl-4,4-dimethyl-2-oxazoline were placed in a 500 ml round bottom flask and 1 g of iodine as a catalyst. The TTitromethylpropanol readily dissolved in the oxazoline under V, ^r ärmeaufnahmp. 100 ml of toluene to setste to support nswasser Eeaktio-order the removal of. The flask was with a

209818/1156 bad original

~ 13 -

-1B "Yigreux column connected to a water separator and a reflux condenser. Sufficient heat was also added to initiate reflux. That Heating to reflux conditions was continued for about 17 hours during which time the temperature gradually increased rose to about 164 ° 0.

The remainder was distilled in a short path distillation. One fraction was found with a boiling point of 39 156 ° 0 at 20 mm and a second fraction with a boiling range from 88 to 172 ° C at 1 mm. The rest was discarded, the two fractions were combined and again distilled in an 18 "-Vigreux column The product was mainly 2- (3-nitro-1,3-dimethylbutyl) -4,4-dimethyl-2-oxazoline and had the following characteristics «

Molecular weight (calculated) 228.3

Neutralization equivalent 230.6 Purity. £ 99.0

Nitrogen (theoretical $ 12.3) $ 11.8

Infrared spectrum: In accordance

with the structure

Boiling range at 1 mm 87 to 93 ° C

The nitrooxazoline obtained in the above implementation is used as a plasticizer in a nitrocellulose lacquer the same amount as the nitrocellulose weight incorporated. When the lacquer is applied to a surface of an object and dried, it forms a permanent, flexible one Movie.

Example 2

2- (3-Nitro-1,3-dimethylbutyl) -4,4-diiBethyl-2-oxazoline was prepared with 2-nitropropane and paraforraaldehyde instead of 2-nitro-2-raethyl-1-propanol, which was used in Example 1 In a 500 ml flask were placed 33 g paraformaldehyde, 131.5 g 2-ethyl-4,4-dimethyl-2-oxazoline, 153 _t 5 g 2-nitropropane nM 4 g iodine as a catalyst. The one for this example

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BATH ORIGINAL

The amount of catalyst chosen was greater than that in Example 1 in order to reduce the reaction time. The 2-nitropropane acted as a dehydrating agent until it was essentially consumed by the reaction. The flask was equipped with a sealed stirrer and a thermometer, and a Vigreux column, 18 ⁿ connected, which was provided with a water separator and a reflux condenser. The mixture was heated to reflux for about 9 hours, during which time the temperature rose to about 152 ° C.

The pot residue was in a short path distillation distilled, and a fraction with a boiling range of 106 to 125 ° C at 1.5 to 2.5 mm was passed through an 18 "-Vigreux column fractionated. A relatively pure fraction with a boiling range from 90 to was removed as the main product 100 ° σ at 1.5 mm.

Example 3

Example 2 was repeated with the exception that 2-isopropenyl-4i4-dimethyl-2-oxazoline was used instead of 2-ethyl-4i4-diroethyl-2-oxazoline and the paraformaldehyde was omitted. The expected product, 2 <- (3-ffitro-1,3-dimethylbutyl) -4 | 4-'dimethyl-2-oxazoline _J was obtained

Examples 4 to 21

Following the procedure of Example 2, compounds were made obtained according to the general formula with the substituents listed in Table I in R.J-, Rg- and R-Formation, when the starting oxazolines are selected from those listed in Table X. Acids and alkanolamines had been obtained.

BAD ORiGINAL 209818/1156

Table I.

1: 1 example
No. Starting oxazole xr i, gained from hydr oxyme thy1 -aminomethane 2-amino-1-butanol ^R l Substituents CH R ₃ CH ^! . ι · r '\ i'i 1 tu j, ■ · -. 4th hydroxymethyl -aminomethane Tris (hydroxymethyl) aminomethane H CH ^ CH ^ OH ■ ί μ 11 ^.: .u / lly droxy] - 5 acid hydr oxyme thy1 -aminomethane H ^R 2 CH ³ OH CH ₂ OH 1: 1 6th Vinegar- Alkanolamine Tris (hydroxymethyl) aminomethane H CHpOOCCH CHpOOCCH ti 2 7th It 2-Amino-2-meoyl-1-propanol H CHpOOCCH ;:
CHpOOCCH ;; 1- 3 8th It 2-amino-2-methyl-1,3-propanediol H CH ^ OH ^J ° 2 5
CH ^ 1: 1 9 Il Tris-f (hydroxymethyl) aminomethane H CpH- CHpOH 1: 1 10 It Tris (hydroxymethyl) aminoraethane H CHpOOCC H ₁₁ 1: 1 11 ti 2-amino-2-methyl-1,3-propanediol CH " o ^H a
2 5
rvtt J
GH » CH ₂ OH ° ^X 1: 2 12th It 2-amino-2-ethyl-1,3-propanediol ^C 4 a CKOOCC H Urine Uxi XJL <£ _? 1: 2 13th Propionic 2-amino-2-ethyl-1,3-propanediol 1 O? 1 CHpOH ^{X / J} - CHjOOCC ₁₇ H ₃₅ ^ 14th Capron 2-amino-2-ethyl-l>, 3-propanediol η ^ w ■ * · ch | oooo ₁₇ h _3: CHpOOCC H es 1: 2 15th Lauric Tris (hydroxymethyl) aminomethane C- / -H _qq cS ₂ cocch / to lsi 16 dd 2-amino-2-methyl-1,3-propanediol C ¹⁶ H ³³ 00 1: 2 17th Stearin- 2-Araino-2-ethyl-1,3-propanediol C ¹⁶ S ^31
C 6 ^H "5 CH ₀ OOC (CH ₀ ).
b ^{2 2} V-> - * 1: 1 18th Stearin- 2-amino-2-methyl-1,3-propanediol CH ₂ OOC (OH ₂ ) (^ OD 1: 3 19th Beehive Tris 6 5 * ^ * 1: 1 20th 6 i- Tris ^ 1: 1 Linolenic Tris 21 »Enyl- cr> vinegar- Phenyl -
propionic

Example 22

2- (3-nitro-3-methylbutyl) -4,4-bis (benzoxyraethyl) -2-oxazoline was prepared by following the procedure of Example 2 with the exception that instead of 2-ethyl-4,4-dimethyl-2-oxazoline 360 g of 2-methyl-4,4-bis (benzoxymethyl) -2-oxazoline was used,

Example 23

The preparation of 2- (3 ~ ITitro-3-niethyl) -4,4-dimethyl-2-oxazoline was carried out as follows:

To a 500 ml flask was placed 33 g of paraformaldehyde and 115 g of 2,4,4-trimethyl-2-oxazoline, this mixture was heated with stirring to 80 to 84 ° 0 for 2 hours, then continued 150 g of 2-Eitr © propane and 5 g of Katriurabisulfät su. This The mixture was then heated to reflux temperature for 4 hours, during which time the temperature rose to 137.degree.

The remainder in the reaction vessel was distilled in a short path distillation through an 18 ^w Vigreux column, and a fraction with a boiling range from 93 to 113 ° C. at 0.8 mm was removed. This fraction was fractionated through an 18 "Vigreux column, and a fraction was taken at 90 to 94 ° C. at 0.3 mm and contained 54 g of the product. The analytical values confirmed the expected structure,

Example 24

The preparation of 2- (3-nitro-1,3-dimethylbutyl) -1-isopropyl-4,4-dimethyl-2-imidazoline was carried out as follows:

A 500 ml flask was charged with 85 g of 1-isopropyl-2-ethyl-4,4-dimethyl-2-imidazoline, 16.5 g paraformaldehyde, 45 g 2-nitropropane, 50 ml benzene and 2 g zinc chloride as Catalyst. The mixture was stirred and refluxed for about 5 hours. The mixture was then distilled in a short path distillation. the

209818/1156 bad or _1S1N al

Top fraction and the last fractions were discarded, the rest was ^{fractionated through an 18 M} Vigreux column. A relatively pure fraction was obtained at 90 to 95 ° 0 at 0.3 mm.

The nitroimidasoline produced according to this process is in a HitrozelüiiDselack as a softener in about the same amount as the weight of the nitrocellulose incorporated, when this varnish is applied to the surface of an object and drying it, a permanent flexible film was obtained.

Example 25

The procedure of Example 24 was repeated except that paraformaldehyde and 2-nitropropane were used instead 2-nitro-2-methyl-1-propanol was used. 2- (3-tfitro-1,3-dimethylbutyl) -1-isopropyl-4f4-dimethyl-2-imidazoline was obtained.

Example 26

The process according to Example 24 was repeated with the exception that all starting aazoline was used instead of 1-isopropyl-2-ethyl-4,4-dimethyl-2-imidazoline i-Isopropyl-2-isopropenyl-4,4-dimethyl-2-imidazoline and because paraformaldehyde was omitted. This gave 2- (3-nitro-1,3-dimethylhutyl) -1-isopropyl-4,4-dilnethyl-2-inιidazoline.

Examples 27 to 36

Following the procedure of Example 24, compounds of the general formula with the following substituents in the R ₁ - * Eo ~ ^and R · »- and Y-poeitions were obtained.

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Table II JLusgangs imidazoline, obtained from Substituents

] Example
No. acid Diamine ^R l H ^R 2 H ■ J j ^R 3 H j CH Y H , - 27 JBssig- 1,2-ethylenedlamine C_ / rH "_ H CH CH ₃ H H 27a oil- 1,2-ethyl * ndiaa ± n CBL ■ * CHo CH H CH ₃ H 2 · PropiOB » l _f 2-propylenediamine
ir ^ -Xaopropyl-2-methyl-1,2- C ₄ H ₀ CH ₃ * CH CH ^ CH 29 Caproa- propanediamine
N -Paenyl-2-m tfcyl-1,2- ^C 10 ^H 21 j
CH CH ₃ CH ₃ 30th Lauric . propanediamine
V- (hydroxyethyl) -2-methyl ^C l6 ^H 33 j
CH C ₂ H ₄ OH 31 St ear ia- 1,2-propanediamine H N- ( 2-jioinoiaobutyl ) butylamine c ¹⁶ ? ³³
16 31 CH ₃ CH C ₄ H ₉ 32 Stearin- H _T (2-Aminoia obuty1) benzylamine CH ^ CH ₃ C ₆ H ^ CH ₂ 33 Beehive M- (2-HydroxyätAyl) -2.jaatb.yl- c_ ^ H ₉₀ CH ₃ CH C ₂ H ₄ OH ₂ 34 oil- 1,2-propanediamine C ₆ H ₅ 1.2-vÄ.thylenediamine
H ¹ -FaAnyl-2-methyl-1,2- VJ J
H H CH H 4t 35 Linolenic . propanediamine
ir-Phanyl-2-methyl-1,2- H CH j
CH C ₆ H 4 ^ 36 Phanyl . propanediamine
H ^ -Benayl-2-raethyl-1,2- ^C 6 ^H 5 37 • aaig-
Äeaig- ₁ propanediamine
N -Xthyl-2-methyl-1,2- H CH C ₆ H CH 38 H ' . propanediamine
N ^ -hydroxyethyl-2-metb.yl-l, Z- H ₁ propanediamine ^C 2 ^H 5 39 N N -isopropyl-2-methyl-1,2- C ₆ H ₅ CH ₂ C ₂ H ₄ OH 40 M. propanediamine ^C 3 ^H 7 41 Phenyl propionic

Claims (7)

Claims 1. Process for the preparation of nitroazolines, characterized in that a mixture of a secondary Nitroalkanes with an ethenylazoline of the general formula H «C 'C — Β.« X ΪΓ O = CH ₉ ι ^{c R} 1 wherein X is 0 or NY, where Y is hydrogen, alkyl, aryl, arylalkyl or hydroxyalkyl, R. is hydrogen, alkyl, arylalkyl, alkenyl or aryl having 1 to about 20 carbon atoms, R ₂ and R are hydrogen, alkyl having 1 to 3 carbon atoms , Hydroxymethyl or acyloxymethyl, where Rg and R-hydrogen or alkyl radicals with 1 to 3 carbon atoms, when X is NY, in a molar ratio of 1: 1 in the presence of about 0.5 to 5 weight-jS based on the weight of the Ethenylazoline, a condensation catalyst, is heated at reflux temperature until the temperature has risen to about 150 C and then the nitroazoline compound formed wins. 2. The method according to claim 1, characterized in that the ethenyl azoline is 2-Ä * thenyl-2-oxasoline or 2-ethenyl-2-imidafcolin used. 3. Process for the preparation of nitroazolines according to claim 1, characterized in that a Gemisclmttgeines 1-hydroxy-2-alkyl-2-nitroalkanes and one 2-substituted 2-azoline in a molar ratio of about 1: 1 in the presence of an inert solvent and about 0.5 to about 5 weight percent based on the weight of the 2-substituted one 2-azoline of a condensation catalyst heated to a temperature of about 100 to 200 ° 0, at the same time that 209818/1156 water formed during the reaction is removed until TTmsot-zung is essentially complete, and then the nitroazoline wins from the reaction mixture. 4. The method according to Ans |> ruch 3, characterized in that that as a 2-substituted 2-azoline is a 2-substituted 2-oxazoline or 2-imidazole is used in. 5. Process for the division of uritroazolines, characterized in that by converting an A?, olins the general formula HO CE ₀ t t ^ X IT CH ₉ ι ^c in which R _{1 is} hydrogen, alkyl, arylalkyl, -alkenyl or aryl having 1 to about 20 carbon atoms, R _? and R ^ is hydrogen, alkyl with 1 to 3 carbon atoms, hydroxymethyl or acyloxymethyl, where R ₀ and R ~ are hydrogen or alkyl radicals with 1 to 3 carbon atoms, if I is NY, with formaldehyde from a formaldehyde source in a molar ratio of about 1: 1 and with heating until water of reaction has been given off in a ratio of about 1 TToI per mole of azoline, a 2-ethenyl ~ 2 ~ az; olin produces, a secondary nitroalkane in a ratio of about 1 mole per mole of asoline and about 0.5 to 5% by weight of a condensation catalyst, based on the weight of the 2-kthenylazoline, is added, then heated and the nitroazoline is recovered. 6. The method according to claim 5, characterized in that a correspondingly substituted oxasoline or imidazoline is used as the 2-ithenyl-2-a2oline. 209818/1156 ^BAD ° ^RIGINAI 7. Procedure for the division of KitroazolLuen according to claims 5 and 6, characterized in that one the mixture to a temperature of about 100 "to 200 ° G heated and at the same time that formed during the reaction Removed water, TdIs the reaction essentially "ended is. 2 0 9 8 18/1156 ^ ORIGINAL