WO1991009022A1

WO1991009022A1 - 2,2-dialkyl-2h-imidazole-1-oxides and method of obtaining them

Info

Publication number: WO1991009022A1
Application number: PCT/SU1989/000311
Authority: WO
Inventors: Igor Anatolievich Kiriljuk; Igor Alexeevich Grigoriev; Leonid Borisovich Volodarsky
Original assignee: Novosibirsky Institut Organicheskoi Khimii Sibirskogo Otdelenia Akademii Nauk Sssr
Priority date: 1989-12-12
Filing date: 1989-12-12
Publication date: 1991-06-27

Abstract

New compositions: 2,2-dialkyl-2H-imidazole-1-oxides have general formula (I), where R1 = C6H5, CH3, CH=NOH, pO2NC6H4, M-O2NC6H4; R2 = CH3, CH2CH2CH3; R3 = CH3, (CH2)7CH3, CH2COOC2H5, CH2CH2COOCH3, CH2CH2COOH, CH2CH2CH3, (CH2)8CH3. The method for obtaining said compositions consists in that hydroximinomethylketones of general formula (II), where R1 = C6H5, CH3, CH=NOH, p-O2NC6H4, are interacted with aliphatic ketones of general formula R2-CO-R3, where R2 = CH3, CH2CH2CH3; R3 = CH3, (CH2)7CH3, CH2COOC2H5, CH2CH2COOCH3, CH2CH2COOH, CH2CH2CH3, (CH2)8CH3, and with ammmonium acetate. The molar ratio of components is 1:3.5-20:1.6-6.0, respectively. The process is carried out in the medium of acetic acid at a temperature of 20-100 °C. As a result a reaction mass is obtained containing the desired product which is then extracte.

Description

2,2-DISCHARGE 4L-2Η-SHODΑ30Ι-Ι-0 ИД SIDES AND CURRENT AND PURCHASES The invention of the invention is in danger of a lack of communication .

The indicated compounds may be used for stable imidazole radicals and, in addition to this, are used for improper use.

The prior art is -

The stable impaired radicals of imidazoline are variable in terms of inhibitory measures, such as antidepressants, anti-oxidants, and radioactive sensitizers.

15 analytical reagents, indicators of the underground movement, blue tags and probes.

3-imidazoline-3-oxides, 3-imidazolines, which are deficient and are stable and are stable compounds of stable imitazole radicals, are imidazoline.

20 available raw materials. Otherwise, through the synthesis of these multi-stage connections, you will experience harsh conditions. The synthesis of these compounds occurs as follows:

Ε ¹ = Κ, Αϊк, Αг, Ηе-Ь; 2, ϋ ⁵ , r = ϊк; X = ΟЯ, „ _^ _

ΡСΤ / δШ9 / 00311

- 2 -

(Imidazoline nitrous radicals, ed. By Yu.Η. Μó- lina, 1988, Kauka, (Siberian), pp. 18-30).

Isποlzοvanie eτiχ sοedineny not daeτ vοzmοzhnοsτi 5 sρazu ποluchaτ niτροκsilnye ρadiκaly imidazοlina, sο- deρzhaschie ρazlichnye φunκtsiοnalnye gρuππy, due nedο- sτuπnοsτi isχοdnyχ, sοdeρzhaschiχ aκτivnye φunκtsiοnalnye gρushsh or nevοzmοzhnοsτi οsuschesτvleniya κοndensatsii eτiχ isχοdnyχ with κeτοnami. Therefore, for the sake of benefit, there are 10 strong radicals containing, for example, a complex, amide, nitrous, amine group, with the use of

connections, the generation of the indicated functional group is required on the screen of the non-active, large-scale center, which results in a malfunctioning of the unit.

A number of compounds containing alditone are known ^• are broadly used in the form of blue keys for live radioactive substances. The most notable are the blue traps - C-phenyl-Ν -tetobutylitene, cyclic al-20 monomers, for example, 5,5-dimethylpyrulin-сид-oxide and 3,3-ам ам ам ам ам Methods of the blue trap. Application in chemistry, biology and medicine, 1984, Russia, USU, p.2Ι, ЗΙ).

Tsiκlichesκie aldοniτροny πρimenyayuτ for οπρedeleniya 25 samyχ ρaznyχ ρadiκalοv in biοlοgichesκiχ and χimichesκiχ ρea- giρuyuschiχ sieτemaχ, οni dayuτ sπinοvye adduκτy with bοlshim vρemenem life and imeyuτ vysοκie κοnsτanτy sκοροsτi zaχva- τa κοροτκοzhivuschiχ ρadiκalοv.

Κ nedοsτaτκam eτiχ sπinοvyχ lοvusheκ sledueτ οτnesτi 30 iχ nizκuyu usτοychivοsτ, τρudnοsτ ποlucheniya φunκtsiοnal- nyχ tsροizvοdnyχ, οbladayuschiχ ρaznοy ρasτvορimοsτyu in ρasτ- vορiτelyaχ and ρaznοy liποφilnοsτyu and τaκzhe sποsοbnyχ χimichesκi svyazyvaτsya with ποdlοzhκοy. Otherwise, they have a relatively low electrochemical potential of oxidation 35. Most recently, the owner makes it possible to oxidize these perpetrators in the market with a subsequent loss of the consumer (for example, is non-profitable) - 3 - to blue adducts, which are found to be in contact with a hydroxy or alkali radical. This essential method reduces the accessibility of information obtained by using these trap systems in reactive systems with the participation of strong oxidizers.

The claimed compounds are new and have not been described in the literature.

Ρasκρyτie izοbρeτeniya Β οsnοvu izοbρeτeniya ποlοzhena task ποluchiτ πο προsτοy τeχnοlοgii nοvye sοedineniya dπya sinτeza sτabil- nyχ niτροκsilnyχ ρadiκalοv imidazοlina not τρebuyuschiχ deφitsiτnοgο syρya, ποzvοlyayuschie ποluchaτ niτροκsilnye ρadiκaly imidazοlina, sοdeρzhaschie ρazlichnye φunκtsiοnal-. nye gρuππy, and κροme τοgο, chτοby eτi nοvye sόedineniya would οbladali vysοκοy usτοychivοsτyu κ οκisleniyu s would sποsοbny οbρazοvyvaτ sπinοvye adduκτy with bοlyπim vρemenem life chτο davalο would vοzmοzhnοsτ isποlzοvaτ iχ in κa- chesτve sπinοvyχ lοvusheκ. This problem is solved by the fact that such new compounds of 2,2, dialkyl-2Η-imidazole-Ι-oxides, which are, according to the invention, are proposed, have the following formula:

where κϊ = С ₆ Η ₅ , СΗ ₃ , СΗ = ΝΟΗ, η -0 ^ ΤС ₆ Η ₄ ,

-Μ- 0 ^ C ₆ Η ₄ ;

Ε ² = σn ₃ , sn ₂ sn ₂ sn ₃ ; κ ³ = sy ₃ , (σn ₂ ) ₇ sn ₃ , sn ₂ sos _{2 s} ₅ , sn ₂ σn ₂ sos ₃ , sn ₂ σn ₂ σοο, σn ₂ σn ₂ σn ₃ , (σn ₂ ) ₈ σn ₃ , ( ^ /. - 4 -

The inventive compounds provide colorless liquids or crystalline materials with a melting point up to 220 ° σ, which are resistant to refrigeration. The compound construction is proved by the data of Ж, УФ, П-spectroscopy and elemental analysis.

The disclosure of the invention involves the preparation of 2,2-dialkyl-2Η-imidazole-Ι-oxides, which means that there is an agreement on the availability of a car

0Η ₃ ,

with aliphatic • ketones of general formula

Ε ² - сο - κ ³ , where κ ² = σн ₃ , σн ₂ σн ₂ σн ₃ ; Ε ³ = snd, (sn ₂ ) ₇ ssn, σn ^ σοοσ ^, sn ₂ σn ₂ σοοsnz σn ₂ σн ₂ σοοн, σн ₂ σн ₂ σн ₃ , (σн ₂ ) ₈ σн ₃ , and when there is a small amount of ammunition 1: 3.5-20: 1.6-6.0, respectively, in the case of acetic acid at a temperature of 20 -00 ° σ with the resulting mass, which includes the target product,

The obtained temperature of the process is optimal, since the reaction below the temperature of 20 ° 0 leads to a significant increase in the time of the reaction. Raising the temperature above Ι00 ° 0 leads to a strong refinement of the reactive mass, which makes it difficult to isolate the target products and reduce output.

To ensure that the reagents are not in use, in order to ensure that the maximum output is obtained in the best case, the product is minimized - 5 -

the duration of the process.

The use of acetic acid as a part of the consumer made it difficult to compensate in the best way to 5

The claimed compounds contain different functional groups, which determine the complex connection with metal ions. This makes it possible to use a large number of 10 to call for original reagents to produce stable, high-imidazole impairment.

Isποlzοvanie ιgρedlagaemyχ sοedineny in κachesτve sπinοvyχ lοvusheκ for κοροτκοzhivuschih ρadiκalοv ποzvοlya- 15 eτ ulavlivaτ ρadiκaly ρazlichnοy πρiροdy with vysοκοy sκο- ροsτyu ρeagiροvaniya in shiροκοm diaπazοne τemπeρaτuρnyχ uslοvy and bοlydim sροκοm life οbρazuyuschiχsya adduκτοv. Claimed sοedineniya imeyuτ very vysοκie eleκτρο- χimichesκie ποτentsialy οκisleniya, τ ^~ Well ποτentsialy οκisle- 20 Niya neκοτορyχ zayavlyaemyχ sοedineny lezhaτ in οblasτi

1.87-2.33 Β, where the potential for the oxidation of 5,5-dimethyl-pyroxyl | yes-Χ. £ 3, and 0-phenyl-Ν -tetobutylitene -

1.47 Important accessories of the claimed connections are their accessibility and the possibility of receiving their services from 25 non-compliant, non-compliant devices

Otherwise, for the receipt of the proposed compounds, the use of scarce raw materials is not required.

The best embodiment of the 30 ^' invention

The method for the preparation of 2,2-dialkyl-2Η-imidazole-Ι-oxides is handled in the process and is carried out as follows.

Hydroxymethymethylketone mixes with an excess of aliphas 35 tic ketone, acetate, ammonia and acetic acid. The mixture is boiled in a water bath ^' with a refrigerator. The resulting reactive mass is diluted with water in 5-10 times \ νθ 91/09022

ΡСΤ / 5Ш9 / 003И

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and operate by abiding or etilatetami. The extract is dried, after which the solvent is evaporated. The resulting product is cleaned, for example, by using method 5, processing, installation, or freezing.

_ For the best understanding of the present invention, the following specific examples are given.

Example I.

Οmes I gidροκsiminοmeτilφenilκeτοna g, Yu atseτοna 5ml, 5ml uκsusnοy κislοτy and 3 g atseτaτa ammοniya κiπyaτyaτ on vοdyanοy bath οbρaτnym χοlοdilniκοm in τe- chenie 2 chasοv, ποsle chegο ρeaκtsiοnnuyu weight ρazbavlyayuτ 50 ml vοdy and eκsτρagiρuyuτ χlοροφορmοm 5 ρaz πο 20 ml. The extract dries ΜβЗθ ^, the refrigerant is evaporated, the waste is 15, it is cooled on a ring with silica gel, the eluent ^' is diethyl ether - 1 hexane. The resulting 2,2-dimethyl-4--phenyl-2Η-imidazole-Ι-oxide is converted from a mixture of ethyl acetate - hexane 1: 1. Χыχοд - 1.14 g (90%); τ.pl Ι08-Ι09 ° σ. And sect (κс), see ^"1 : 3090 20 (Ν = С-Η), 1520, 1580 (С = Ν). УΦ sect (ethanol),

Lomax,, (£,): 237 (4.30), 280 (4.24). Οπеκτρ ПΜΡ in (SB ₃ ) ₂ σθ,, ppm : 1.53, 6Η, s, (Gem, СΗ ₃ ), 7.60, ЗΗ, m, 8.10, 2Η, m, (С ₆ Η ₅ ), 8.10, ΙΗ, s, (s = CΗ).

Found,%: C 70.1; Η 6.3; Ν 14.9; _SP Η _Ι2 ^ Ο; 25 Calculated,%: C 70.2; Η 6.4; Ν 14.9;

For example, 2.

A mixture of I g gidροκsiminοmeτilφenilκeτοna 5 ml deκa- nοna-2, 5 mL uκsusnοy κislοτy and 3 g atseτaτa ammοniya nagρevayuτ on κiπyaschey vσdyanοy bath τechenie chasοv 4, 30 ποsle chegο ρeaκtsiοnnuyu weight ρazbavlyayuτ 50 ml vοdy and eκsτρagiρuyuτ χlοροφορmοm 3 ρaza πο 20 ml. The extract is dry. , cool, evaporates, rests on a silica gel ring, 1: 1 eluent-diethane-hexane. 2-methyl-2-octyl-4-phenyl-2Η-imidazole-Ι-οκ-

35 seeds are obtained in the form of a light brown oil, yield 1.2 g 60%). W sect (CCΙ ₄ ), ^" , cm ^{" 1} : 3080 (Ν = С-Η), 1580, 1520 (С = Ν). Y Φ sect (ethanol),) max, nm, - 7 -

(Su £): 237 (4.25), 280 (4, 17). Οπеκτρ ПΜΡ in (СБ ₃ ) ₂ С0,

<5 \ ppm: 1.60, ЗΗ, s, (2-0Η ₃ ), 0.83, ЗΗ, m, 1.20, Ι2Η, m, 2.03, 2Η, m, ((0Η ₂ ) ₇ σn ₃ ), 7.50, ЗΗ, m, 7.83, 2Η, 5 m, (0 ₆ Η ₅ ), 7.77, ΙΗ, s, (Ν = σн).

Found,%: 075.5; Η 8.9; Ν 9.3; C _Ι8 Η ₂₆ Ν ₂ 0; Calculated,%: C 75.7; Η 9.2; Ν 9.8. Example 3.

The mixture gidροκsiminοmeτilφenilκeτοna I g, 3.5 mL Yu atseτοuκsusnοgο eφiρa 5 ml uκsusnοy κislοτy and 3 g of acetyl τaτa ammοniya nagρevayuτ on κiπyaschey vοdyanοy bath τeche- of 4 chasοv, ποsle chegο ρeaκtsiοnnuyu weight ρazbavlyayuτ 50 ml vοdy and eκsτρagiρuyuτ eτilatseτaτοm 5 ρaz πο 20 ml The extract dries Mg50 ₄ , the ethyl acetate is evaporated, - it is only 15 times that it is mounted on a silica gel ring, - the eluent is diethyl ether. The resulting 2-methyl-4-phenyl-2-ethoxy oxar-lowering-2Η-imidazole-Ι-oxide converts from a mixture of ethyl acetate - pentane 1: 3. Βыχοд - 0.7 g (40%), τ. πl. 58-6Ι ° C. W sect (ΚΒг),, cm ^"1 : 3090 (Ν = С-Η), 20 1730 (Ο), 1570, 1510 (0 = Ν). UΦ sect (etapol), ма κ nm nm, (ϊ): 234 ( 4.18), 282 (4.12). Οπеκτρ ΙΪΜΡ in SBS1 ₃ , <ζ ppm: 1.12, ЗΗ, τ, 4.07, 2Η, κ, 3 = 7.3 Hz, (Ο ^ ), 1.67, ЗΗ, s, (0Η ₃ ), 3.08, 2Η, е, (СΗ ₂ ), 7.53, ЗΗ, m, 7.87, 2Η, m, (С _β Η ₅ ) , 7,80, ΙΗ, with, (Ν = SΗ) Ηaydenο 25,.%: C 64.3; Η 6.3; 10.4 Ν; C _Ι4 Η _{Ιβ 2} 0 _3; Βychislenο,%: C ^* 64 , 9; Η 6.2; Ν 10.8. For example, 4.

Οmes gidροκsiminοmeτilφenilκeτοna I g, 4 ml meτi- lοvοgο eφiρa levulinοvοy κislοτy 5 ml uκsusnοy κislοτy 30 and 3 g atseτaτa ammοniya nagρevayuτ on vοdyanοy bath τe- chenie 4 chasοv, ποsle chegο ρeaκtsiοnnuyu weight ρazbavlyayuτ 50 ml vοdy and eκsτρagiρuyuτ χlοροφορmοm 3 ρaza πο 20 ml The extract dries dry, absorbs the residue, rests on the shelf with silica gel, the eluent is 35 diethyl ether. 2-methyl-2- (2-methoxycarbonyl) -4- -phenshi-2Η-imidazole-Ι-oxide (I g) is obtained in the form of yellow oil. Χыχοд - 1.4 g (80%). W sect (00Ι ₄ ), V, cm ^"1 : 3080 (Ν = 0-Η), 1740 (00), 1570, 1510 (С = Ν). P

- 8 -

U sect (ethanol), _^ λmax, nm, (s £): 237 (4.21), 282 (4.13). Οπеκτρ ПΜΡ in SBS1 ₃ ,, ppm : 1.62, ЗΗ, s, (СΗ ₃ ), 2.27, 4Η, m, (СΗ ₂ 0Η ₂ ), 3.57, ЗΗ, s, (00Η ₃ ),

5 7.53, ЗΗ, m, 7.90, 2Η, m, (С _β Η ₅ ), 7.90, ΙΗ, s, (Ν = СΗ).

Found,%: C 64.3; Η 5.7; Κ 10.5; Сϊ4 ^Η Ι6 ^Ν 2 ⁰ 3 ^;

Calculated,% 064.9; Η 6.2; Ν 10.8.

Example 5.

A mixture of 3 g of hydroxy siminomethyl phenyl ketone, 9 g of left-

For 4 hours, dilute 60 ml of the acid, 20 ml of acetic acid and 9 g of ammonium acetate are heated in a boiling water bath after dissolving it. The extract is washed by a rich solution.

s ρase πο 50 ml. ,

15 water extracts combine and neutralize the 20th sulfuric acid. Pοluchenny ρasτvορ φilτρuyuτ cheρez paper ^• φilτρ and snοva eκsτρagiρuyuτ χlοροφορmοm ρaz 5 ^'πο 50 ml. The extract is dried for ₄ , if it is evaporated, it is left to dry, and it is dry. Above 2-methyl plant

20 - (2-carboxyethyl) -4-phenyl-2Η-imidazole-Ι-oxide converts from a mixture of ethyl acetate - hexane 1: 1. Βыχοд - - 3 g (60%), τ.π. Ι07-Ι09 ° σ. W sect (ΚΒг), ν), cm ^{"" 1} : 3090 (Ν = 0-Η), 1695 (00), 1570, 1510, (0 = Ν). Y с sect (ethanol), LMAKS, nm, (): 236 (4.22), 238 (4, Ι5 ^~ ).

25 Sπektρ ПΜΡ in СϋСϊз, &, ppm : 1.63, ЗΗ, s, (СΗ ₃ ),

2.23, 4Η, m, (СΗ ₂ 0Η ₂ ), 7.50, ЗΗ, m, 7.87, 2Η, m, (С ₆ Η ₅ ), 7.87, ΙΗ, s, (Ν = СΗ ), 10,23, ΙΗ, ears ρ. (ΟΗ).

Found,> C 63.0; Η 5.7; Ν 11.2; C _ΙЗ Η _Ι4 ^ Ο ^; Calculated,%: C 63.4; Η 5.7; Ν 11.4.

30 Example 6.

A mixture of I g of hydroxymethylmethyphenyl ketone, 4 ml of dipropyl acetate, 5 ml of acetic acid and 3 g of ammonium acetate is heated in a boiling water bath for 5 hours.

35 extracts of 3 times 20 ml. The extract dries Mg50 _d , discovers the solution, rests on a silica gel ring, eluent - diethyl ether - - 9 -

Hexane 1:. 2,2-dipropyl-4-phenyl-2Η-imidazole-Ι-oxide is converted from hexane. Βыχοд - 1, 1 g (67), τ.π. 77-79 ° 0. AndΚspektρ (ΚΒг),>, cm ^"1 : 3080

5 (Ν = 0-Η), 1570, 1510 (C = Ν). Y с sect (ethanol), Α max, nm, (& £): 238 (4.18), 280 (4.11). Sπekτρ ПΜΡ in SSΙ ₄ , s5 \ ppm: 0.87, ΙΟΗ, m, 1.94, 4Η, m, (СΗ ₂ СΗ ₂ СΗ ₃ ) ₂ , 7.50, ЗΗ, m, 7.93 , 2Η, m, (С ₆ Η ₅ ), 7.87, ΙΗ, s, (Ν = СΗ).

10 Found,% 074.0; Η 8.2; Ν 11.2; C _Ι5 Η _{20 2} 0; Calculated, ^ C 73.7; Η 8.3; Ν P, 5. Example 7.

A mixture of 2 g of hydroxy siminacetone, 5 ml of acetic acid, 10 ml of acetone and 3 g of ammonium acetate is boiled over with

With a 15 refrigeration unit for I hour, after which the reactive mass is poured into 100 ml of water and extracts 5 ml of water at 20 ml. The extract is dried -m§50,, if refrigerated, it is left to dry, it is stored on a silica gel tray, the eluent is cooled. Received

20 2,2,4-τ-methyl-2Η-imidazole-Ι-oxide is combusted in sublimation and 2 mm ρτ. ct and temperature Ι00 ^ο σ. Βыχοд - 2.0 g

(63%), τ.πl. 27-29 ° 0. W sect (CCΙ ₄ ), see-I.

3130 <and = C-Η), 1605, 1520, (0 = Ν), YΦ sect (ethanol), Lmax, nm, (6 £): 283 (3.91). Οπеκτρ ΪΪΜΡ in SSΙ ₄ , 25 <$ \ ppm: 1.46, 6Η, s, (2-СΗ ₃ ), 2.30, ЗΗ, s, (4-СΗд), 7,23, ΙΗ, s, (Ν = СΗ).

Found,%: C 56.6; Η 8.4; Ν 22.2; C ₆ Η _Ι0 ^ Ο; Calculated,%: C 57.1; Η 8.0; Ν 22.2. Pρimeρ 8. 30 A mixture of 2 g digidροκsiminοatseτοna, atseτοna 10 ml, I ml uκsusnοy κislοτy and 3 g atseτaτa ammοniya nagρevayuτ on κshιyaschey vοdyanοy bath τechenie I hour ποsle chegο ρeaκtsiοnnuyu weight vylivayuτ 100 ml nasyschennοgο ρasτ- vορa ΝaSϊ and eκsτρagiρuyuτ eτilatseτaτοm 10 ρaz πο 35 30 ml. The extract dries Mg50, the ethyl acetate is evaporated, the treated mass is sprayed with 50 ml of heptane and is evaporated again. The waste is dissolved with 20 ml of a mixture of ethyl acetate -

- 10 -

- 1: 1 hexane, a 4-hydroxy siminomethyl-2,2-dimethyl-2Η-imidazole-Ι-oxide impurity is removed and removed from the solution. Βыχοд - 1.6 g (60%), τ.π.

5 Ι86-Ι88 ° 0. Wspektρ (ΚΒг), ^, cm ^"1 : 3090 (Ν = 0-Η), 1610, 1590, 1530 (С = Ν). UΦspektρ (ethanol), маmax, nm, (£): 231 (4, 50), 292 (4.04). Spektτ ШΙΡ в (СБ ₃ ) ₂ зо,, ppm: 1.43, 6Η, s, (Hem. СΗ ₃ ), 7.73, ΙΗ, s, ( СϊЬСΗ), 7.97, - ΙΗ, s, (0-Ν = СΗ), 12.43, 10 ΙΗ, ears ρ. (ΟΗ).

Found,%: 046.5; Η 5.9; Ν 27.4; σ _β Η _{9 3} 0 ₂ ; Calculated,%: 046.5: Η 5.9; Ν 27.1. Example 9.

There is a mixture of 3 g of nitric acid, 25 ml of ace- 15 ton, 9 g of ammonium acetate and 15 acetic acid ki. On the other hand, with a refrigerator in the course of I hour. The coolant is cooled to a temperature of 2 ^" 0 ° C, which precipitates out of the precipitate, 2-dimethyl-4- (4-nitro-phenyl) -2Η-imidazole-Ι-oxyde, is 2.0-emulsive, it emits 20 (5650, τ. Pl. 2ΙЗ-2Ι4 ° 0. W sec. (ΚΒг), V *, cm ^"1 : 3100 (Ν = 0-Η), 1520, 1350, (Ν0 ₂ ), УΦ sec. Ρ (ethanol), λmax, nm, (£ Ω £): 282 (4.41), ΜΡπеktτ ПΜΡ in СБСΙз, &, ppm: 1.67, 6Η, s, (βн СШ), 7.87, ΙΗ, s , (Ν = 0Η), 8.17, 8.43, ΑΑ 'ΒΒ', Y = 9 Hz, (C _β Η ₄ ). 25 Found,% C 56.7; Η 4.8; Ν 18.1 ; -

^С ΙΙ ^Η ΙΙ ^Ν 3 ° З ^Ϊ Calculated,%: С 56.6; Η 4.8; W 18.0.

Example 10.

A mixture of I g hydroxymethinemethylene, 5 ml

30 hlορatseτοna, 10 g atseτaτa ammοniya and 5 ml uκsusnοy κis- lοτy nagρevayuτ on κiπyaschey vοdyanοy baπe with οbρaτnym χοlοdilniκοm in τechenie 3 chasοv, ποsle chegο ρeaκtsiοn- weight hydrochloric ρazbavlyayuτ 50 ml vοdy and eκsτρagiρuyuτ χlοροφορ- mοm 3 ρaza πο 20 ml. The extract is dried for ₄ , upar

35 rooms, the waste is removed from the mixture and ethylacetate -

- Hexane 1: 1. Received 0.8 g of 2-methyl-4-phenyl-2-chloro-methyl-2Η-imidazole-Ι-oxide, yield (53 $), τ. πl. Ι40-Ι42 ° С. - II -

W sect (ΚΒг),), cm ^"1 : 3080 (Η-С = Ν), 1510, 1570 (С = Ν).,

Calculated, ^: C 59.8; Η 5, 0; Ν 12, 6; CΗ 15, 9. - ^ ρ Example II.

Οmes 2.5g π-niτροizοniτροzοatseτοφenοna, 8 ml diπροπizheτοna 6 g atseτaτa ammοniya and 15 ml uκsusnοy κislοτy nagρevayuτ on κiπyaschey vοdyanοy bath τechenie 5 chasοv, ποsle chegο ρeaκtsiοnnuyu weight ρazbavlyayuτ 100 ml vοda and - ^ eκsτρagiρuyuτ χlοροφορmοm 3 ρaza πο 50 ml The extract is dried in §80 ₄ , which is evaporated. Discharge the refrigerant on a silica gel column, eluent - diethyl ether - 1: 1 hexane. Received 4- (4-nitrous) -2,2-dipropyl-2Η-tsh- - dazol-Ι-oxide is converted from hexane. Βыχοд 20 - г, (51), τ. πl. ΙΙ0-ΙΙ2 ° σ. W sect (ΚΒg),, cm ^"1 : 3120 (Η-С = Ν), 1350, 1520 (ΝΟ ₂ ). U Φ sect (ethanol), max, nm, (^): 283 (4.30) .Spektτ ПΜΡ in SBS1 _3. , Ppm: 0.87, Ι Ш, m, 2.10, 4Η, m, (2-СΗοСΗ _? СΗ ₂ ), 7.90, ΙΗ, ο, (ΗС = Ν), 8.13 and 8.37, 4Η, 25 ΑΑ'ΒΒ ', 9 Hz (C ₆ Η ₄ ).

Everybody, ^: C 62.4 Η 6.7; Ν 14.4; C _Ι5 Η _{Ι9 3} 0 ₃ . Calculated,% C 62.3; Η 6.6; I'm 14.5. Example 12.

A mixture of I g gidροκsiminοmeτilκeτοna, 4 ml undeκanοna-2, 30 May ml- uκsusnοy κislοτy and 3 g atseτaτa ammοniya nagρevayuτ on κiπyaschey vοdyanοy bath τechenie 4 chasοv ποsle chegο ρeaκtsiοnnuyu weight ρazbavlyayuτ 50 ml vοdy and eκsτρagiρu- yuτ χlοροφορmοm 3 ρaza πο 20 ml. The extract dries for ₄ minutes and evaporates, rests on the shelf 35 with silica gel, the eluent is diethyl ether - hexane 1: The resulting 2-methyl-2-nonyl-4-phenyl-2Η-imidazole-Ι-oxide is crystallized from hexal. Βыχοд - 1.4 g (70), 9/00311

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τ. πl. 39-4Ι ° C. W sect (ΚΒg), ^, cm ^"1 : 3080 (Η-С = Ν), 1575, 1520 (= = Ν). Y Φ sect (ethanol), λ max, nm, (Ζ) 237 (4.25) , 279 (4.17). Sepekt ΜΡ in SSΙ ₄ , ^'

5 « ⁴ , ppm: 0.84, ЗΗ, m, 1.14, Ι4Η, m, 1.90, 2Η, m, (0Η ₂ ) ₈ σн ₃ , 1.50, ЗΗ, s, ( 2-0Η ₃ ), 7.44, ЗΗ, m, 7.87, 2Η, m, (С ₆ Η ₅ ), 7.77, ΙΗ, s, (ΗС = Ν).

Found,%: C 76.3; Η 9.8; Ν 9.2; C _Ιd Η _{28 2} 0; Calculated,%: C 76.0; Η 9.4; Ν 9.3.

ΧΟ Example 13.

A mixture of 2 g of m-niτροizοniτροzοatseτοφenοna, 8 ml • dytsροπizheτοna 6 g atseτaτa ammοniya and 10 ml uκ- susnοy κislοτy nagρevayuτ on κiπyaschey vοdyanοy bath τeche- of 4 chasοv, ποsle chegο ρeaκtsiοnnuyu weight ρazbavlyayuτ ^•

15 100 ml of water and extracts 3 ml of water 50 ml. The extract is dried Μ§50 ₄ , the refrigerant is evaporated, it is left on the shelf with a silica gel ring, the eluent is diethyl ether - hexane 2: 1. The resulting compound is 4- (3-nitrite) -2,2-dipropyl -2Η-imidaz.ol-Ι-oxycid

20 throttles on a column with a schgikagel, the eluent is on a column. The target product is isolated in the form of colorless oil, the yield is 1.5 g ($ 50). W sec. (Cσϊ ₄ ), ^, cm ^"1 : 3090 (Η-0 = Ν), 1350, 1540 (nο), 1520, 1580 (C = Ν). Φ π sec. Э (ethanol), max, nm,

25 (&&) 304 (3.87), ^' 239 (4.48). Sπeκτρ PΜΡ ^"in SSΙ ₄ '8,. Ppm .: 0.87 ΙSH, m, 2,07, 4Η, m, (2-SΗ _of σΗ ₂ 0Η _2), 7,74, ΙΗ, m, 8.37, 2Η, m, 8.80, ΙΗ, m, (С _β Η ₅ ). 7.94, ΙΗ, s, (ΗС = Κ).

Found: C 62.5; Η 6.8; Ν 14.0; Сϊ5 ^Η ϊ9 ^Ν 3 ⁰ 2 *

30 Calculated: C 62.3; Η 6.6; Ν 14.5. Example 14.

A mixture of 10 g of hydroxymethymene is lower, 40 ml of acetone, 40 ml of acetic acid and 30 g of ammonium acetate leave the casses at a temperature of 20 ° С for 20 hours.

35 The active mass is poured into 300 ml of water and is extracted with 5 times 70 ml of water. The extract is rinsed off with a saturated solution of ₂ С0з _, it is dried immediately, it is freezed, it is freezed out at a temperature - thirteen -

Ι05-ΙΙ5 ° С and a pressure of 2 mm ρτ.сτ. Final target: - 2,2-dimethyl-4-phenyl-2Η-imidazole-Ι-oxide 11.4 g Ш).

Аче In the quality of the blue trap for alcohol

5 diκalοv byzh isπyτany sοedineniya, ποluchennye pο ^'πρimeρam 1,6,9,

Source Κθ - radicals exceeded the compound σσ ^' (acac) ₂ (0 ₂ σΜе ₂ Ρϊι) Ρу7 When this complex is repaired in benzene (0.05 ^• ) is installed

10 ΕΟΑ - radical about 10 Μ, little changing during the hour. After adding to this solution a blue trap of the indicated claimed compounds and 5,5-dimethyl pyrpulinin Ν -oxide or 3,3-5,5-tetramethyl pyrulin - Ν - ο с | | in the process, the EPΡ disappeared for a while and

15 an intense blue-signal adduct was generated. Parameters of the electronic components:

Hookup connection πο example I connection πο example 6

20 connection πο πρimer 9

5,5-dimethyl

3,3,5,5-tetra-methylpirulin-Ν - -oxide 12.42 5.20

(parameters are given in GS). New adducts are obtained

25 data with the use of the known well-known solutions are fully disintegrated in 10-15 minutes, and the percentage of adducts obtained with the use of time is reduced by 30 minutes.

The intended use of 30 2,2-dialkyl-2Η-imidazole-Ι-oxides may be used in chemistry - for the production of nitrous radicals of imidazole _; At the same time, it may be necessary to catch and register live substances in the atmosphere of industrial and industrial applications.

Claims

00311

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ΦΟΡΜУЛΑ ИзΟБΡΕΤΕΗЖΪ

I. 2, 2-dialkyl-2Η-tzhdazol-Ι-oxides of the general formula:

0 where Ε ¹ = с ₆ н ₅ , σн ₃ , СΗ = ΝΟΗ, Π-Ο ₂ ΝС ₆ Η ₄ , c.a-0 ₂ Ν0 ₆ Η ₄ ;

Ε ² = σn ₃ , σn ₂ σn ₂ σn ₃ ;

Ε ³ = sn ₃ , (σn ₂ ) ₇ σn ₃ , σn ^ σοοσ ^, σn ₂ σn ₂ σοοσn ₃ , σn ₂ σn ₂ σοοн, σн ₂ σн ₂ σχЧ ₃ , (sn ₂ ) ₈ sn ₃ . •

2. The method of receiving connections πpo Ι, is characterized by the fact that there is an interaction between the hydraulically-charged general formula:

-Λ

-from

С ΪΤΟΗ where Ε ¹ = с ₆ н ₅ , σн ₃ , ΟΗ = ΝΟΗ, Π-Ο ₂ ΝΟ ₆ Η ₄ , m-0 ₂ Ν0 ₆ Η ₄ , with aliphatic ketones of the general φορ formula C - С0- Ε ³ , 5 _Г de Ε ² = σн ₃ , σн ₂ σн ₂ σн ₃ ; ΕЗ = σн ₃ , (σн ₂ ) ₇ σн ₃ ,

In the case of a small proportion of reagents 1:, -:, -, of course, in the case of acetic acid, 20–00 ° 00 with