DE1919103A1 - 1,2,3-substituted 4,4,5,5-tetra-alkyl-delta'-dehydro- and imidazolidines - Google Patents

Description

Synvar Associates, 3221 Porter Drive, Palo Alto, California

(V.St.A.)

1,2,3-substituted 4,4,5,5-tetraalkyl-Δ'-dehydro- and

-imidazolidine

The invention "relates to Δ'-dehydro- and -imidazolidines, as they are stated in the patent application P 1815788.5 "be en, wherein the carbon atom in position 2 is linked to an oxygen or halogen atom. In addition, everyone is Ring nitrogen is oxidized to the hydroxide or oxide state.

The "preferred embodiment of the invention relates to a large one new class of compounds with the general formula:

wherein the substituents have the following meanings ι

9Q9846 / 1197

-z-

R ₁ , Rp, R, and R. are alkyl groups, alkenyl groups, alkynyl groups or aryl groups each having about 1 "to 12 carbon atoms or" form part of an alkylene or alkenylene group

group R ₁ Rp or R-. R., these alkylene and alkeny

len groups each contain about 3 "to 10 carbon atoms»

each of the atom pairs N ₁ A, IiL Cp and C p Y is through one

Single or double bond linked, with the proviso that,

if the atomic pair N ₁ Cp linked by a single bond

is, O p Y is linked by a double bond and if

the atom pair N ₁ --- C _{0 is} connected by a double bond,

both atom pairs C _n Y and N., A with a single weave

are connected"

A and B denote hydroxyl groups and oxygen atoms, while Y denotes iodine, chlorine and bromine (in this case denoted by X); an oxygen atom (in this case denoted by 0) and a substituted oxygen atom (in this case _{denoted by -OR 1} -). If the atom pair C ^ Y is connected by a double bond, then Y is an oxygen atom (a carbonyl oxygen). R ₁ - is an organic group, as described below and, by definition, corresponds to the Rein group of patent application P 1815788.5

The definition given above includes the following types of compounds in which R ₁ , R ₉ , R have the meanings given above;

Around

the

(D

R.

909846/1197

'4 ^! 4th

OH

OH

Γ Ι ·

"1

N- 0-

O-

Γ I

Γ I

ο-

Γ ι

R.

^R 4

f3 909846/1197

The compounds according to the formulas I, II, III, IV and V are suitable .sich as antioxidants. In general, the free radical structures of the compounds with the formulas I, IV and V are suitable for the measurement of weak magnetic fields by known methods. Furthermore, as a result of their ice-free radical structure, the compounds corresponding to the formulas I, IV and V show an electron spin resonance (ESR), which is why they can be used as "spin labeling substances ¹¹ for attachment to biologically active molecules. If they are used for this purpose, so · it is usually desirable to choose a suitable functional group as part of R .., R ₂ , Rj or R. which will act as "hooks" to connect or attach the free radical molecule to the biologically active molecule of formula III in combination with strong acids as oxidizing agents.

All compounds within the scope of the present invention have the imidazole ring basic structure with the required tertiary carbon atoms in ring positions 4 and 5. Furthermore, both ring nitrogen atoms in all compounds are in the oxidized state, ie in the form of an oxide or a hydroxide. All compounds can be referred to as hydroimidazoles, since at least one of the imidazole ring double bonds that normally occur is saturated. On the other hand, those compounds which contain a double bond in the ring can be referred to as dehydroimidazolidines, while those compounds which have no double bond in the ring can be referred to as imidazolidines. If one considers the formulas I to V, it can be seen that the compounds of the formulas I, IV and V as 1,2,3-substituted-4,4,5,5-tetraalkyl Δ '-dehydroimidazolidine may be referred to as the compounds with the formulas II and III can be designated as 1,2,3-substituted 4,4,5,5-tetraalkylimidazolidines. With the presence of the hydroimidazole ring structure, of tertiary C, - \ and tertiary CV carbon atoms in the ring and the two .ring - nitrogen atoms, which are oxidized to the oxide or hydroxide state, the greatest possible scope of protection for nature

9098 4 67-1197 BADORlGiWAL

of the substituents R- to R ^ in the formulas "claimed. Details this point of view will be discussed below in context with the numerous manufacturing processes for the "compounds discussed? more detailed explanations can be found in patent application P 1815788.5

For the sake of simplicity, however, reference is often only made to the simplest structure which gives the required tertiary character of the C 1 and C 4 ring carbon atoms. For this purpose, the symbol I ^ T ^ T is used ^to ^ n the structure

⁰¹ H.

CH-.

used.

In a process for making all connections with the Formulas II to V are based on the compounds of formula I. the end. Furthermore, the compounds with the formulas II to IV can be made from all other compounds, respectively correspond to the other compounds of the corresponding formulas II to IV, this compound being essentially is subjected to an oxidation reaction or reduction reaction. Most of the compounds according to the invention can be used as Intermediate products for the manufacture of the other compounds to be considered in the context of "the invention;" . . - .- ... .

In addition, the compounds with the formulas II to IV can be derived directly from μ icinaleno-iamino-carbon compounds, ie from diamines, in which the hydroxyla-amino groups on similar tertiary carbon atoms ---- s% ekeii _r .Mi4-eiiiem. further Heaktion-steilaehmer mt-dervSt-riüijktur / i -... ■ - - .. ·· ■. , _Λ .,. . . -. .,.,.

bad original

where the free valences of C_ are linked to one or more atoms or groups, which can be eliminated together with a proton from each of the hydroxylamino-nitrogen atoms. Relationships to, create *., The one. Binding of C _? on the two hydroxylamino nitrogen atoms. Furthermore, the compounds of the formula I can be prepared by halogenating the compounds according to patent application P 1815788.5, in which Rt is hydrogen. A typical process for carrying out this type of reaction is given in patent application P 1815788.5 and is carried out as follows: A solution of the bis-hydroxylamine (1 equivalent) in tetrahydrofuran or benzene is ^{treated with at least 1 equivalent of HCXX 1} X ", whereupon more than 1 equivalent an acid such as fH-COOH or benzenesulphous acid is added. After heating on a steam bath for a period of 1 minute to 10 hours, the acid is extracted with sodium carbonate. The resulting solution changes its color as a result of oxidation in air Free radicals can be isolated by evaporation and chromatography or crystallization.

A specific example _f in which this operation is applied is as follows!

- '■ - - ■ I.

In addition to the "above were in the patent application '

special ^;

Reaction pathways for the preparation of the compounds "in which a Hydrogen atom is connected to the Cp carbon atom, indicated. In the first method, a corresponding ester is used decarboxylated (the ester can first be selected according to one of the general Process for the preparation of the substituted imidazoles accordingly of the earlier patent application, an organic radical being bonded to Cp instead of hydrogen.). The ester is used appropriately to produce the desired compound treated according to the reaction scheme given below:

COOCH.

H " ¹

-COO-

0-

a.

b.

c.

2 ml of a solution of the ester & ± (about 2 mg) was shaken with aqueous sodium carbonate. A red color appeared in the aqueous layer, which was identified as belonging to the compound ΐκ by ESR spectroscopy. When this solution was acidified, the ESR spectrum of the compound c_ »appeared. This compound can be isolated by evaporating the aqueous solution in vacuo and extracting the residue with benzene. The benzene solution of the radical c_j_ obtained can be evaporated to obtain it.

Another special reaction concerns the oxidation of one Tetrahydroimidazole, which can conveniently be prepared from a bis-hydroxylamine and Hy-ir oxy acetaldehyde. The production the desired compound, in which a_Wasseratoffatom, with C_ connected ;, runs as follows:, -, o /.- T - · ν .-> -.-;

909846/1197 ;:

OH
I. / ^H PbO ^ - C.
j PbO ₉ - 0 ·
J CH ₂ OH ^ -CH ₂ OH 4 I. OH 0- 0-

a.

Id.

3 mg 1, ß-

hydroimidazole (& /) were suspended in 1 ml of benzene. Then 100 mg of lead dioxide was added and the mixture was shaken periodically. The benzene solution was examined every 15 minutes by thin layer chromatography (silica gel / ethyl acetate). At the beginning there was only one radical which was identical to that obtained by the oxidation of 1, B-dihydroxy ^ -hydroxymethyl - ^^ i ^ -tetramethyltetrahydroimidazole (a ^) with manganese dioxide. However, a second radical began to form from the first radical and this conversion was complete in three hours. It could be shown that this radical was 1,3-dioxy-4,4,5,5-tetramethyl-4,5-dihydroimidazole (b_j_), which according to thin-layer chromatography and electron spin resonance with the 1,3- Dihydroxy-4,4,5 »5-tetramethyl-tetrahydroimidazole (c ^) produced radical was identical.

OH

• N

OH

(c)

In the reactions given above, only the simplest one was used bis-hydroxylamine structure used, which has the required

9 09 8 /, 6/1 197

The tertiary structure of the C. and C.sub.c carbon atoms is provided by four methyl groups / The reaction given for illustration also provides a cyclization when R ₁ , R ", R- and R. other-alkyl, alkenyl, alkynyl or Represent aryl groups (these terms are always intended to include substituents of the hydrocarbon type or of the non-hydrocarbon type, if desired), including those cases in which R ₁ -Rp and R ^ -R / cyclic groups with the Form carbon atoms Cp- "or C." In the "preferred embodiment, R ^, Rp, R ^ and R are each alkyl, alkenyl, alkyl, aryl, or aryl-substituted alkyl groups each having from about 1" to 12 carbon atoms; R ₁ -Rp and / or R -.- R can also be alkylene or alkenylene groups each having about 3 "to 10 carbon atoms, it being possible for the alkylene or alkenylene groups to also contain further alkyl or aryl substituents.

To be an intermediate for the "compounds according to the invention, which contains the atomic arrangement desired in each case, one only needs to select the corresponding bis-hydroxylamine and perform any of the reactions noted above to form the hydroimidazole ring. The bis-hydroxylamine is obtained by reducing a corresponding dinitro compound. The Dinitro Compounds and the Processes for Their Manufacture are known per se.

The general reaction scheme is given below and involves the reaction of the salt of a secondary nitro compound and a halonitro compound having the halogen atom and the nitrogen group on the same carbon atom: ■

909846/1197

R,

R.

CHNO,

C ~ -N0,

R-

R.

!, Br
h ^m 2

CHNO,

NO,

C-NO,

C-NHOH

R ₃ C NHOH

a.

b.

General reaction procedures

In the preparation of the compounds according to the invention under Use of 1,3-dioxy-4,4-, 5,5-tetralakyltetrahydroimidesols the starting materials are the reqktionssohema given below generally applicable:

909846/1197

Halogenating agents

O-

(D

OH

(II) OH

(IV)

ο-Ι.

-ii

• Ν

I ο.

-0-

Ii

(in)

For the Faehir. It is strangely understandable that all of the above given reactions in any suitable solvent can be made. Furthermore, all customary oxidizing and reducing agents can be used to obtain the specified

BATH ORIGINAL

9098 46/1197

Products are used. Suitable oxidizing agents are, for example, PbO ₂ , I ₂ , Br ₂ , Cl ₂ , di-tert.-butylnitroxide, ON (SO ₃ O ₂ MnOp, O _? And the like. Suitable reducing agents are, for example, H ₂ + catalyst!, · H ₅ O ₂ , NaOH, Na · NH, and the like. Suitable acidic or basic catalysts include all strong acids such as sulfuric acid, hydrochloric acid, phosphoric acid, trifluoroacetic acid and the like, "or all OH-containing bases such as sodium hydroxide and the like. As in more detail below is explained, the compounds with the formula V are most easily obtained by reacting an alcohol having the desired R ^ - grouping with 2-haloimidazoles according to the formula I.

To further illustrate the invention are the following Examples given. However, the details of the examples are intended are not to be regarded as limitations on the invention, since, as any person skilled in the art is aware, modifications can be made.

Preparation of the compounds with the formula I.

The following shows the preparation of typical compounds with the formula I:

1,3-Dioxy-2-iodo-4- ■ ·, 4,5,5-tetramethyl-4,5-dihydroimidazoi

^J 2

NaHCO.

A. Ad 1, B-Dihydroxy ^^^^ - tetramethyltetrahydroimidazole (1.0 g, 0.00625 mol) in water (4OO ml) becomes lead dioxide (10 g) given, and the mixture is stirred for half an hour, and then filtered through "CeIite". The filtrate that the

9 0 9 8 46/1197 =

contains red 1,3-DiOXy ^, 4,5,5-tetramethyl-4,5-dihydroimidazole, add sodium bicarbonate (1.0 g), potassium iodide (5.0 g) and iodine (1.8 g, 0.007 mol). The mixture is heated gently 'Stirred, and the course of the reaction is monitored by thin layer chromatography tracked. Is the 1,3 ~ dioxy-4,4,5,5-tetramethyl-4,5-dihydroimidazole radical can no longer be detected, the solution is extracted with the same volume Chloroform. The chloroform solution is mixed with a small amount of sodium thiosulphate solution and then twice with water washed-. The solution is dried over sodium sulfate, filtered and the chloroform is removed in vacuo, the above mentioned compound (0.9 g, 51 #) is obtained. F. (from Ben- '"" -. zol / petroleum ether) 145 - 146 °.

Analysis; Calculated for

_? N _? 0 y

C 29.68; H 4.27; N 9.90; J 44.8O

• Found: C, 29.86; H 4.23; N 9.74; J 44.84.

Molecular weight (mass spectrometry) 283,

311, 322, 528 m / L ( £ 17,700, 22,600, 1,200).

B. Using JCN instead of iodine and potassium iodide the above compound was obtained using the same procedure.

1,3-Dioxy-2-bromo-4,4,5,5-tetramethyl-4,5-dihydroimidazole

BrCN

NaHCO.

ο-Ι.

■ Ν

-Br

09846/1197

A. 1,3-Dioxy-4,4,5,5-tetramethyl-4,5-dihydroimidazole radical (2OO mg, 1.27 x 10 -3 mol) and sodium bicarbonate (2OO mg) were dissolved in water (80 ml) . Then, cyanogen bromide was (320 mg, 3 x 10 "- * mol) was added undc.das mixture was stirred for one hour at 30 ⁰ C. The progress of the reaction was followed by Dünnschihtchromatographie, and after the complete disappearance of the starting radical the solution washed with. The chloroform extract was washed twice with a little water, dried over sodium sulfate, filtered and the chloroform was removed in vacuo without excessive heating to give the bromine compound (243 mg, 81 io) which varied between 90 and 100 ° decomposed and melted between 140 and 150 °.

Analysis ; Calculated for C ₇ H ₁₂ NpO ₂

C 35.60; H 5.135 N 11.86; Br 33.84. Found: C, 35.78; H 5.22; N-11.92; Br 33.78.

Molecular weight (mass spectrometry) 236 Ti ^ x ^an01 320, 540, 565 m / t (£ 15,600, 1 240, 1 158).

B. Using the same procedure with, however when bromine was used instead of cyanogen bromide, the same product was obtained in somewhat lower yield.

1,3-Dioxy-2-chloro-4,4,5 »5-tetramethyl-4,5-dihydroimidazole

NaOCl

909846/1197

1, 3-dihydroxy-4.4-5.5-tetramethylimidazole (100 mg, 6.25 x 1O ~ ⁴ mol) "was added to a 1.25 $ solution of sodium hypochlorite (200 ml), the solution stirred vigorously for 5 minutes The solution was then extracted with an equal volume of chloroform and dried over sodium sulfate. After filtering off, the chloroform was gently evaporated under reduced pressure. When only a small amount of chloroform was left, about ether was added and the resulting solution was added Chromatographed on silica gel (length of column; 45 cm, diameter: 3 cm) using ether as an eluent, the fraction containing the purple radical was collected and the solvent was carefully removed to give the above-identified compound was (15 mg, 12.5 #) which was very unstable at room temperature.

315, 536, 562 W / L ( £ 19,300, 1 350, 1 340)

The ESR spectrum gave a typical curve with 5 lines (a · ^ - 7.25 G in benzene).

The person skilled in the art will recognize that various halogenating agents can be used in the preparation of the compounds of the formula I from 1,3-dioxy-4,4,5,5-tetraalkyl-4,5-dihydroimidazoles. For example, chlorinating agents such as NaOCl, CH-.CONHCl, tC-HgOCl and Cl ₅ ; Brominating agents such as NaOBr, Brρ, N-bromosuceinimide, pyridinium perbromide and BrCN; and iodizing agents such as NaOI, Jp, NaI-v and JCN can be used.

Preparation of the compounds with the formula II

The preparation of a typical compound with the formula II proceeds as follows:

1,3-dihydroxy ~ 2-oxo-4,4,5,5-tetramethyltetrahydroimidazole

909846/1197

1979103

NHOH NHOH

= 0

An excess of ethyl chloroformate was added to NN ¹ -dihydroxy-2,3-diamino-2,3-dimethyl'b-utane (250 rag) which was suspended in benzene (50 ml), whereupon the solution was boiled for 5 minutes was heated. The solution was then extracted with aqueous sodium bicarbonate (50 ml). The above-mentioned compound was obtained by neutralizing and evaporating the aqueous
Solution isolated with subsequent extraction of the residue.

Preparation of the compounds with the formula III

Typical compounds according to formula III can be prepared as follows:

1,3-Dioxy-2-oxo-4,4,5,5-tetramethyltetrahydroimidazole

A. Starting from 1,3-dioxy-2-iodo-4,4,5,5-tetramethyltetrahydroimidazole:

A mixture of 100 mg of 1,3-dioxy-2-iodo-4,4,5,5-tetramethyltetrahydroimidazole and 100 ml of 4-N sulfuric acid was 15 minutes heated on a steam bath. The solution was then extracted with an equal volume of chloroform. The chloroform extract

909846/1197

:. c · ■ -

was washed with a little water, dried over sodium sulfate, filtered off, and the solvent was removed to give the above-mentioned compound (28 mg, yield 46 %); P. (from ethyl acetate) 190 ° (dec.); F . (from a suspension in petroleum ether) 198-200 ° (decomp.).

Analysis; Calculated for C ^ H ₁ NpO- .:

C 48.83 / 0; H 7.03 f °; N 16.27 f °. Found: C 48.76 f ° ', H 6.86 <fc, N 16.411 °.

Moletailargewicht (mass spectrometry) '172. λ _ma ^ ^AN01 -310, 424 m _A (£ 3580, 7750)

^{(n 77} ° ^Cm " ¹

B. Starting from ethyl chloroformate and NN'-dihydroxy-2,3-diamino-2,3-aimethy! Butane:

NHOH NHOH

ClCOOC ₂ H ₅

An excess of ethyl chloroformate was added to NN-i-dihydroxy-2,3-diamino-2,3-dimethylbutane (250 mg) suspended in benzene (50 ml) and the solution was heated to boiling for 5 minutes. The solution was then extracted with aqueous sodium bicarbonate (50 ml). Bromine was then added dropwise to this solution until it turned intense yellow. The solution was then extracted with chloroform (50 ml) and the extract was washed with water and dried over sodium sulfate. Filtration and evaporation gave an orange colored residue which was chromatographed on silica gel using ether as the eluent. The yellow band was collected and evaporation of the fractions gave 1,3-dipxy-2-pXQ-4,4 _r 5,5-tetramethyl-tetrahydroimidazole (3 mg),

9098A6 / 1197

the one with the one from 1 .-, 3-dioxy ~ 2-iodo-4,4,5r5-tetrameth; yl-4f5? -dihydroimidazole received was identical. .....-.-

In the formation of 1 ^ -Dioxy - ^ - oxo - ^^. F 5,5-tetraalkyl .-- 4, -5rdihydroimidazoles directly from vicinal NjN'-dihydroxyaminoalkanes there are numerous reagents with the general formula u

wherein R ¹ and R "represent interchangeable groups such as halogens, -O-alkyl groups, -O-aryl groups, S-alkyl groups, and the like, useful. Specific examples of suitable substances for R ¹ and R "are for example Br, J, Gl, OCH ,, OC ₂ H ₅ , OC ₃ H ₇ ZO- /, SCH ,, SC ₂ H ₅ and SC ₃ H ₇ .

C. Starting from 1,3- ^ ioxy-2- «iodo-4,4,5,5-tetramethyltetrahydroimidazole tmd a base: \

1,3-Dioxy-2-iodo-4,4,5,5-tetramethyl-4,5-dihydroimidazole (10 mg) was added to a 2N sodium hydroxide solution (30 ml) and the mixture was heated and stirred for one hour. The aqueous mixture was extracted with chloroform until no more dye went into the chloroform. Then 4N sulfuric acid was added dropwise and the solution was periodically extracted with chloroform. At the point of neutralization, the aqueous solution turned orange. Then was excess acid added _? and the solution was extracted with chloroform (2 × 30 ml). The latter extract was dried (sodium sulfate), filtered / and the chloroform was removed to give the aforementioned compound (5 mg, $ 20). QQ 9.8 4 6 / T1 -9 ^

Preparation of compounds having the formula IV

3-Dioxy-2-hydroxy-4,4,5,5-tetramethyl-4,5-dihydroimidazole anion

OH'

1,3-Dioxy-2-oxo-4,4,5,5-tetramethyl-2,3,4,5-tetrahydroimidazole (3 mg) was dissolved in water (2 ml). Then a few drops of 2N sodium hydroxide solution and then 2 drops of 30% Hydrogen peroxide added. A dark blue formed Solution, and the blue color could not be extracted into organic solvents. The ESR spectrum indicated education of the above-mentioned compound (a ™ = 8.75 G in water). The solid, dark blue color was obtained on evaporation of the water Salt mixed with sodium hydroxide.

Starting from the 2-halogen compounds of formula I one can. attach different substituents in place of the halogen. In particular, numerous alcohols can be used to replace the halogen radical (-X) with an alkoxy group (-0R ^), wherein R, - can be any alkyl or aryl group with or without substituents. The terms "alkyl" or "aryl" as used herein are intended to encompass simple alkyl and iryl groups, but also those with various substituents, including those substituents that fall into the other category. The term "alkyl ¹¹ ;" is also intended to include aryl groups and substituted aryl groups. In all cases, R, -, regardless of whether it is an alkyl or xryl group, can contain functional hydrocarbon or non-hydrocarbon substituents and can be saturated or aliphatic

909846 £ ΐ197

be unsaturated. Typical non-hydrocarbon substituents ■ include halogen, hydroxyl, alkoxyl, aryloxy, amino, alkyl ■ udder Arylamino, mercapto, alkyl or aryl mercapto, trialkylsilyl, Perfluoroalkyl-, nitro-, carboxyl- * hydroxylamino-, Nitrile and other substituents.

Typical alcohols for the reaction with the halogen radical to produce a compound with the formula V are, for example
those given below. In any case, the end product contains an R ^ group which corresponds to one of the following symbols minus the hydrogen atoms on the hydroxyl group:

CH-.OH

C ₂ H ₅ OH

^ OC M , CHJ3H
i ο 4 2

HOOCCH ₂ OH

CTJ ΓΊΙ rttl Πΐΐ Γ · ΤΙΓΊΤ ΠΤΊ AlT

CH ₃ CH ₂ CHCH ₂ C = CH
OH

003846/1137

CH ₂ OH

CH ₃ O

CH 0

CHCH ₂ OH

OH

OH -CHC,

Manufacture of connections with Formula V

1,3-dioxy-2-ethoxy-4? 4,5,5-tetramethyl-4,5-dihydroimidazole

0-

• IT

-Br

846/1197

-N-

I ^% 0.

To 1,3-dioxy-2- "bromo-4,4,5,5-tetraHi & $ liyl-4,5-dihydroimidazole (100 mg) in 20 ml of ethanol were §0 mg of sodium ethoxide in 1.1 ml Ethanol was added dropwise. The solution was about 20 minutes "at room temperature ditched. After evaporating the solvent and chromatographing the residue on silica gel the deep red colored radical was isolated. It had a characteristic ESR spectrum with five lines.

1,3-Dioxy-2-benzyloxy-4,4,5f5-tetramethyl-4,5-dihydroimidazole

ΟΙ

Br

C ^ -H ₁ -CH ₀ O Na ¹

A.

_{1,3-dioxy-2-'brom-4,4,5,5-tetramethyl-f} 4,5-dihydroimidazole (100 mg) in 20 ml of dry dimethoxyethane containing 500 mg Natriumbenzyloxyd, was approximately 20 minutes "at Räumtemperatur The solvent was then removed and the product isolated as in the previous example, and the resulting red radical was identified by its ESR spectrum.

The invention has been described above in a few details for illustration purposes only; certain changes and modifications can be made within the scope of the invention, which is limited only by the scope of protection of the claims. " ■ · ■ '■

- patent claims -

9 09 8liHiaf

Claims (1)

Claim a patent ϊ where the substituents have the following meanings: The groups R ₁ , R ", R, and R * are alkyl groups, alkenyl groups, alkynyl groups, aryl groups each having about 1 to 12 carbon atoms" or form part of an alkylene or alkenylene group R ₁ —-R «or R, R.- each with about 3 to 10 carbon atoms; each of the atomic pairs N1 A «■ K ₁ --C ^, and C ^ - ^ Y is through a single or double bond, with the proviso that when the atomic pair R « « -! - ^ is connected by a single bond, C p Y OUi ¹ GfLein ^ double bond is connected and if the atomic pair H ^ ■ C ^ is connected by a double bond, then both pairs G "- ~ -Y and N ^ - *" A are connected by a single bond? A and B denote hydroxyl groups and oxygen atoms, while Y denotes iodine, chlorine or bromine (denoted by X in this Pall), oxygen (denoted by O) or ORt, where Rr denotes an organic radical, with the proviso that when the atom pair C ^ ₁ -Y is linked by a double bond, Y is an oxygen atom. 909846/1197 2. imidazoles according to claim 1, characterized by the formula: R. "R. O- Γ I 1 0. C ₂ - τ 3. imidazoles according to claim 1, characterized by the formula: OH R, 3 OH 4. imidazoles according to claim 1, characterized by the formula: O- 909846/1197 5. imidazoles according to claim 1, characterized by the formula! R. 0- - O- 6. imidazoles according to claim 1, characterized by the formula: R. 7 · imidazoles according to claim 1, characterized in that R.J, Rp, R and R. represent lower alkyl groups. 8. imidazoles according to claim 7, characterized in that R., Rp, R ^ and R, represent methyl groups. 9. imidazoles according to claim 2, characterized in that X represents chlorine, 10. imidazoles according to claim 2, characterized in that X represents bromine. 11. imidazoles according to claim 2, characterized in that X represents iodine. 909846/1197 12. imidazoles according to claim 6, characterized in that Rp. Represents a methyl group. 13 · imidazoles according to claim 6, characterized in that Rc represents an ethyl group. Η. Imidazoles according to Claim 6, characterized in that Rr represents a phenyl group. 15 · imidazoles according to claim 6, characterized in that R _{5 represents} a benzyl group. . 16. imidazoles according to claim 6, characterized in that Rr represents a carboxymethyl group. 17. imidazoles according to claim 6, characterized in that Rp- represents a 2,2-dimethoxyethyl group. 18. imidazoles according to claim 6, characterized in that Rp- represents a 3-cholesteryl group. 19. Process for the preparation of the imidazoles according to claim
1 - 18, characterized in that there are connections
with the formula R ₁ O R ₄ 0. 909846/1197 in the r .., r _? , R-. and R. have the meaning given above, halogenated to compounds of the formula (I), the halogen atom optionally by, an oxygen atom or a substituted oxygen atom OR _n . (in which R ₁ - has the meaning given above) and the compounds of the formulas (II), (III), (IV) and (V) obtained thereby are optionally converted into one another. 20. Process for the preparation of the imidazoles according to claim 1,
3-8 and 12-18, in which Y is an oxygen atom or a substituted oxygen atom ORc- (in which Rr- has the meaning given above), characterized in that vicinal diamino-carbon compounds having the structure R. 1 ι 5 I.
ΓΙ I. 4th ^. I. 4th NHOH
NHOH in which R ₁ , Rp, R-, and R. have the meanings given above, with a further reactant having the structure wherein the free valences of 0 _Λ with one or more
Groups are linked together with a proton of
each of the hydroxylamino nitrogen atoms under formation
a bond between C "and the two hydroxylamino nitrogen atoms can be eliminated, and
the compounds obtained with the formula (II), if appropriate, into the compounds with the formulas (III), (IV)
or (V) transferred. 909846/1197 2 * 1. Use of the compounds with the formulas (I), (II), (III), (IV) and (V) as antioxidants. 22. Use of the compounds with the formulas (I), (IV) and (V) , as spin labeling substances. 23, Use of the compounds of formula (III) as oxidizing agents in combination with strong acids. COPY 909846/1197