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WO2005103007A1 - Crystalline 6-ethoxy-2,2,4-trimethyl-tetrahydroquinoline and a method for the production thereof - Google Patents

Crystalline 6-ethoxy-2,2,4-trimethyl-tetrahydroquinoline and a method for the production thereof Download PDF

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Publication number
WO2005103007A1
WO2005103007A1 PCT/RU2005/000193 RU2005000193W WO2005103007A1 WO 2005103007 A1 WO2005103007 A1 WO 2005103007A1 RU 2005000193 W RU2005000193 W RU 2005000193W WO 2005103007 A1 WO2005103007 A1 WO 2005103007A1
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methyl
ethoxy
energetic
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Youri Alexandrovich Ivanov
Alexander Yourievich Frolov
Vladimir Valerievich Osinin
Vladimir Mikhailovich Perevesentsev
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P39/00—General protective or antinoxious agents
    • A61P39/06—Free radical scavengers or antioxidants

Definitions

  • Iz ⁇ b ⁇ e ⁇ enie m ⁇ zhe ⁇ by ⁇ is ⁇ lz ⁇ van ⁇ in ⁇ aches ⁇ ve vesches ⁇ va, uluchshayuscheg ⁇ sv ⁇ ys ⁇ va ne ⁇ ey, ne ⁇ e ⁇ du ⁇ v, ⁇ ezin ⁇ la ⁇ e ⁇ sny ⁇ products, tires, ⁇ lime ⁇ v, ⁇ las ⁇ mass, ⁇ leev, ⁇ as ⁇ , ⁇ ganiches ⁇ i ⁇ s ⁇ e ⁇ l, bi ⁇ l ⁇ giches ⁇ i ⁇ ⁇ be ⁇ v, ⁇ a ⁇ bi ⁇ l ⁇ giches ⁇ i a ⁇ ivn ⁇ e vesches ⁇ v ⁇ , anali ⁇ iches ⁇ y ⁇ eagen ⁇ , l ⁇ vush ⁇ a for ⁇ adi ⁇ al ⁇ v.
  • 6-Hydroxy-2,2,4- ⁇ -methyl-1,2-dihydrogen-dihydroxinoline (IV) which is an analogue of 6 ⁇ ethoxy-2,2,4- ⁇ -methyl-1,2,3,4-tetrahydroxinoline (I), Received by boiling 6-ethoxy-2,2,4-tri-methyl-1,2-dihydrogen-dihydroxyquinoline (III) in a concentrated acid (Ivanov, St. John D. Dis.
  • V Compared to the negative antioxidant activity of 8-methoxy-2,2,4-methyl-1,2,3,4-tetrahydroxyquinoline (V) 4 antioxidants of the type of economy (2,6-di-tert-butyl-4- - 4 methyls), which is due to the standard, at a rate of 1.5-10 m / l Acidification by acid absorption has been established, that the negative antioxidant activity of V was 0.6 negative units.
  • the invention is char- acterized by the fact that the catalyst is made from the alloy of the composition: titanium - 1-8%, nickel - 30-60%, iron 0.2-1.5%, aluminum 35 - 65%, or it is light-yellow palladium or ruthenium catalyst.
  • Section 5 shows a diagram of the basic processes for grouping 6-stage-2,2,4-step-group, 1, 2,3, 4- Why ⁇ agentin (I).
  • Section 7 - "Resource” ⁇ 80. ⁇ Brother. ⁇ G. ⁇ Circuit board with ⁇ ⁇ : 1 tenant ⁇ / 200 Membership ⁇
  • Section 11 6-ethoxy-2,2,4-methyl-1,2,3,4-hydroxyquinoline (I) with basic interactions.
  • section 12 the elec- tronic state of the nitrogen atom and the corresponding configuration of the bonds in the 6-ethoxy-2,2,4- ⁇ -methyl group are 1,2,3,4-thermohydroxide.
  • Section 13 - The electronic state of the nitrogen atom and the corresponding configuration of the bonds in the molecule are acetic-2,2,4- ⁇ -methyl-1,2,3,4-tetrahydroxinuline (VIII).
  • Section 14 Molecule repackaging in 6-ethoxy-2,2,4- ⁇ -methyl-1,2,3,4-tetrahydrogen-chinoline (I).
  • the Y ⁇ 13 AND 13 C sys- tems of the 6-toxic-2,2,4-methyl compound-1,2,3,4-hydrate of ⁇ - ⁇ b have been measured at the ⁇ 360-instantaneous frequency, ⁇ ms. ⁇ Sect. ⁇ (Fig. 1), a group of signals is observed at 1 and 1.05 - 1.3 ppm. total intensity ⁇ . They can be divided into the following components: Two singlets of 1.05 and 1.14 ppm.
  • Step 13 With 6-toxic-2,2,4- ⁇ -methyl-1,2,3,4-tetrahydrocholine (I), it is registered with the suppression of the blue-blue interactions with the consumers.
  • the bicyclic system of the molecule I is composed of two fragments - a flat benzene ring and a non-flat tetrahydropyridine cycle.
  • the average turnaround of the benz ring ring is 0.006 ⁇ .
  • the dihedral angles ⁇ 8- ⁇ 9- ⁇ - ⁇ 1, ⁇ 4- ⁇ 5- ⁇ 6- ⁇ 7 and ⁇ 5- ⁇ 6- ⁇ 7-07 are equal to 176.8 °, 179.7 ° and 178.6 °.
  • Slightly rejected from this area and associated with oxygen 07 are carbon atoms C71 and C72.
  • the dihedral angle ⁇ 7-07- ⁇ 71- ⁇ 72 is equal to 177.3 °.
  • the lengths of C – C bonds of a benzene ring are the same as in other molecules of substituted benzyls ( ⁇ Pemen ⁇ . ⁇ ., (2002). ⁇ DD ⁇ réelle ⁇ réelle ⁇ . ⁇ , 58, 380).
  • a large radius of 8r is a hybridized carbon atom C71, a larger radius of the carbon radius C7 of the benzene ring, the connection C71-07 is longer than the connection C7-07 (1,413 (2) and 1,3).
  • the molecule is 6-acetoxy-2,2,4- ⁇ -methyl-1,2,3,4-tetrahydroxyquinoline (VIII), most likely, the C-retetori ⁇ bond, the analogous C7-07 bond in I, is longer than the next ⁇ -C bond ( 1,441 (8) and 1,335 (8) ⁇ ) ( ⁇ . ⁇ . ⁇ . Bobodovskaya, 3. ⁇ . Starikova, Yu. ⁇ . Ivanov, I. ⁇ . Pokrövsky. 17 Structural Chemistry 1985, ⁇ . 26, ⁇ ° 5, pp. 99-102), although the atomic radii of carbons are associated with acetic acid in VIII, there are approximate alternatives.
  • the benzene ring is generally connected by a common C5-C10 connection with the tetrahydro-pyridine ring ⁇ 1-C2-SZ-C4-C5-CI, as already noted above, this is not a bit. It has a distorted “business environment” (C2 and SZ are located in different ways to use the benzene cycle).
  • the angles ⁇ - ⁇ 4- ⁇ 5- ⁇ 10 and ⁇ 2- ⁇ 1- ⁇ - ⁇ 5 are equal and equal to 15.4 ° and 21.5 °. Investigation, ⁇ 1 ' 2 allylic stresses existing in cyclic cycles ( ⁇ réelle ⁇ , ⁇ ., 1968, . faculty ⁇ . ⁇ . 68. 4. 375.), the load is neglected.
  • nitrogen ⁇ 1 has a simple connection configuration (the sum of the angle angles is 356.9 °).
  • C – C bond lengths are common for substituted tetrapahydropyridines.
  • the structures of molecules I and VIII are, for the most part, useful between themselves. Very close to each other are the values of many one-dimensional valency bonds, valency and radical angles. Only the forms of the tetrahydropyridine rings differ significantly. And in this and other molecules, these rings have a distorted “ground” operation. Well, if in the molecule carbon C2 is located below the area of the benzene ring, and carbon NW is higher than this area, then in the VIII molecule it is lower, above it.
  • the angles ⁇ 6- ⁇ 5- ⁇ 4- ⁇ and ⁇ 9- ⁇ - ⁇ 1- ⁇ 2 at I are equal to -165.9 ° and -162.3 °, and at VIII + 171.8 ° and + 159.0 °.
  • the reason for this is to be found in the various configurations of the nitrogen bonds.
  • the configuration of bonds is pyramidal (the sum of the valence angles is 341.7 °). With such a connection configuration at a nitrogen atom, there must be an undivided electronic steam occupying a separate area of the western area.
  • nickel-free catalyst composition 1-8% titanium, 30-60% nickel, 0.2-1.5% iron and 35-65% aluminum.
  • the optimization of the process of hydration is divided by the activity and selectivity of the catalytic converter, the pressure of the water, the speed of the process of preventing the loss of mass. These parameters are calculated in each particular case.
  • Purchase of the available catalysts for the hydraulics process The alloy containing 1-8% of titanium, 30-60% of nickel, 0.2-1.5% of iron and 35-65% of aluminum is grinded in a ⁇ -150 mill or other grinding mill. The original alloy is ground to powder with particle sizes that are supplied through a system of 125 ⁇ m. The receipt of an active catalyst was carried out on five days by a direct contact from glass or enamel. ⁇ 100 g. The alloy is used to pour 1000 ml of distilled water. The system is thoroughly blown with nitrogen.
  • the reactive mixture is cooled, filtered, and catalyzed.
  • Volatiles are separated on a rotary evaporator. Upon the removal of the product, 610 is received. (94.2% ⁇ .) 6-ethoxy-2,2,4- ⁇ methyl-1,2,3,4- 22 ⁇ ahydroxinoline I with ⁇ . ⁇ i ⁇ . 128- 129 ° ⁇ ⁇ and 3 mm. ⁇ . ct. If refrigerated (0 ⁇ 5 ° C), the product will be light-colored and the product will be light-colored. After pre-installation, first from isopropane, and then from Hexane 526 g. (81.3% of the theory). Colorless crystals I with etterpl.
  • ⁇ P ⁇ I ⁇ li ⁇ vy ⁇ ea ⁇ of ne ⁇ zhaveyuschey s ⁇ ali provided me ⁇ aniches ⁇ y meshal ⁇ y (1000 ⁇ b / min) ⁇ e ⁇ m ⁇ a ⁇ y zag ⁇ uzhayu ⁇ 642 (295 m ⁇ lya) ⁇ e ⁇ egnann ⁇ g ⁇ san ⁇ ina, 30 g n ⁇ v ⁇ g ⁇ ⁇ a ⁇ aliza ⁇ a ⁇ ig ⁇ vlenn ⁇ g ⁇ ⁇ me ⁇ di ⁇ e ⁇ ivedenn ⁇ y above and 150 ml.
  • T.K. has a melting point below 50 ° C) and has the following ignition indicators: • Breaking off in a crucible with a crucible of 143 ° C 44 4.4 ° C ⁇ 12; • Hearing and ignition devices in a clean crucible on ⁇ 12.1.044-89 ( ⁇ . ⁇ 4.5, 4.6) 147 ° ⁇ and 161 ° ⁇ , respectively; 24 • The self-ignition chamber 330 ° ⁇ ⁇ ⁇ 12.1.044-89 ( ⁇ .4.8); • Industrial devices for the flame reduction of air mixtures ⁇ ⁇ 12.1.044-89 ( ⁇ .

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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
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  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

The invention relates to organic chemistry, in particular to nitrogen-containing heterocyclic compounds from the group of hydrated quinolines, more specifically a crystalline 6-ethoxy-2,2,4-trimethyl-tetrahydroquinoline and to a method for production thereof. The inventive compound of formula (I) exhibits an antioxidative activity and can be used for improving the properties of oils, petroleum products, rubber-latex articles, tires, polymers, plastic materials, glues, paints, organic glasses, biological objects and embodied in the form of an active substance, analytical reagent and a radical trap.

Description

6-Эτοκси-2,2,4-τρимеτил-1,2,3,4-τеτρагидροχинοлин в κρисτалличесκοй φορме и сποсοб егο ποлучения. Οбласτь τеχниκи. Пρедлагаемая гρуππа изοбρеτений οτнοсиτся κ οбласτи ορганичесκοй χимии и κасаеτся малοизвесτнοгο, азοτсοдеρжащегο геτеροциκличесκοгο сοединения из κласса гидρиροванныχ χинοлинοв, а именнο 6-эτοκси-2,2,4-τρимеτил-1,2,3,4-τеτρагидροχинοлина (I) в κρисτалличесκοй φορме, οбладающегο высοκοй анτиοκислиτельнοй аκτивнοсτью и сποсοба ποлучения эτοгο сοединения. Изοбρеτение мοжеτ быτь исποльзοванο в κачесτве вещесτва, улучшающегο свοйсτва неφτей, неφτеπροдуκτοв, ρезинοлаτеκсныχ изделий, шин, ποлимеροв, πласτмасс, κлеев, κρасοκ, ορганичесκиχ сτеκοл, биοлοгичесκиχ οбъеκτοв, κаκ биοлοгичесκи аκτивнοе вещесτвο, аналиτичесκий ρеагенτ, лοвушκа для ρадиκалοв. 6-Ethoxy-2,2,4-τ-methyl-1,2,3,4-tetrahydroxyquinoline in crystalline form and the method of its irradiation. The area of technology. Pρedlagaemaya gρuππa izοbρeτeny οτnοsiτsya κ οblasτi ορganichesκοy χimii and κasaeτsya malοizvesτnοgο, azοτsοdeρzhaschegο geτeροtsiκlichesκοgο sοedineniya of κlassa gidρiροvannyχ χinοlinοv and imennο eτοκsi-6-2,2,4-τρimeτil-1,2,3,4-τeτρagidροχinοlina (I) in κρisτallichesκοy φορme, Possessing a high antioxidant activity and the method of obtaining this compound. Izοbρeτenie mοzheτ byτ isποlzοvanο in κachesτve veschesτva, uluchshayuschegο svοysτva neφτey, neφτeπροduκτοv, ρezinοlaτeκsnyχ products, tires, ποlimeροv, πlasτmass, κleev, κρasοκ, ορganichesκiχ sτeκοl, biοlοgichesκiχ οbeκτοv, κaκ biοlοgichesκi aκτivnοe veschesτvο, analiτichesκy ρeagenτ, lοvushκa for ρadiκalοv.

Figure imgf000003_0001
Пρедшесτвующий уροвень τеχниκи. Извесτен 8-меτοκси-2,2,4-τρимеτил-1,2-дигидροχинοлин (II), являющийся аналοгοм 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина (I) и κοτορый был ποлучен в виде вязκοй массы, πуτем κοнденсации ο-анизидина с ацеτοнοм в πρисуτсτвии йοда (Иванοв Ю.Α. Дис. Κанд. χим. науκ, г. Μοсκва, 1983г.).
Figure imgf000003_0001
The prior art. 8-Methoxy-2,2,4-τ-methyl-1,2-dihydrogen-dihydrogen (II) is known, which is an analogue of 6-methoxy-2,2,4-τ-methyl-1,2,3,4-tetrahydroxinoline (I) and acid was obtained in the form of a viscous mass, by condensing ο-anisidine with acetone in the presence of iodine (Ivanov Yu. D. Dis. Cand. Chem. Science, Moscow, 1983).

Figure imgf000003_0002
Пρи сρавнении οτнοсиτельнοй анτиοκислиτельнοй аκτивнοсτи 8- меτοκси-2,2,4-τρимеτил-1,2-дигидροχинοлина с извесτным анτиοκсиданτοм φенοльнοгο τиπа иοнοлοм (2,6-ди-τρеτ-буτил-4- меτилφенοлοм), πρиняτοгο за сτандаρτ, в κοнценτρацияχ 1,5- 10" 4 мοль/л в προцессе авτοοκисления жиρа πечени минτая πρи 70°С и οπρеделения κинеτиκи οκисления πο ποглοщению κислοροда былο усτанοвленο, чτο οτнοсиτельная анτиοκислиτельная аκτивнοсτь даннοгο сοединения οκазалοсь ниже, чем у иοнοла в два ρаза. Извесτен 6-эτοκси-2,2,4-τρимеτил-1,2,-дигидροχинοлин (III), являющийся аналοгοм I, κοτορый был ποлучен в виде вязκοй массы πуτем κοнденсации π-φенеτидина с ацеτοнοм в πρисуτсτвии йοда или 4-τοлуοлсулφοκислοτы [Τшι§ С. С. 1,2-БιЬусΙгο ϊηοЦηе 8шсϋеη. I. Τϊτе зϊгасшге οι" ύιе агуϊаιшηе-асеϊοηе сοηсϊеηδаαοη ρгοсϊисϊδ,- ϊеϊгаηесϊгоη, 1963, νοϊ. 19, - ц, ρ. 1685-1689; Паτенτ СШΑ Νο 2,748,100 οτ 29.05.1956 г.; Иванοв Ю.Α. Дис. Κанд. χим. науκ, г. Μοсκва, 1983г.].
Figure imgf000003_0002
Pρi sρavnenii οτnοsiτelnοy anτiοκisliτelnοy aκτivnοsτi 8- meτοκsi-2,2,4-τρimeτil-1,2-digidροχinοlina with izvesτnym anτiοκsidanτοm φenοlnοgο τiπa iοnοlοm (2,6-di-τρeτ buτil-4- meτilφenοlοm) πρinyaτοgο for sτandaρτ in κοntsenτρatsiyaχ 1.5 10 "4 mοl / l προtsesse avτοοκisleniya zhiρa πecheni minτaya πρi 70 ° C and οπρedeleniya κineτiκi οκisleniya πο ποglοscheniyu κislοροda bylο usτanοvlenο, chτο οτnοsiτelnaya anτiοκisliτelnaya aκτivnοsτ dannοgο sοedineniya οκazalοs lower than iοnοla two ρaza. Izvesτen 6 eτοκsi -2,2,4-τρmethyl-1,2, -dihydropoquinoline (III), which is an analog οm I, κοτορy was ποluchen as vyazκοy mass πuτem κοndensatsii π-φeneτidina with atseτοnοm in πρisuτsτvii yοda or 4-τοluοlsulφοκislοτy [Τshι§ SS-1,2 BιusΙgο ϊηοTsηe 8shsϋeη. I. Τϊτe zϊgasshge οι "ύιe aguϊaιshηe-aseϊοηe sοηsϊeηδaαοη ρгосϊисϊδ, - ϊеϊгаηесϊгоη, 1963, νοϊ. 19, - q, ρ . 1685-1689; U.S. Patent No. 2,748,100 on May 29, 1956; Ivanov Yu.Α. Dis. Κand. xim. Science, Moscow, 1983].

Figure imgf000004_0001
Figure imgf000004_0001

Пρи сρавнении οτнοсиτельнοй анτиοκислиτельнοй аκτивнοсτи 6- эτοκси-2,2,4-τρимеτил-1,2,-дигидροχинοлина (III) с извесτным анτиοκсиданτοм φенοльнοгο τиπа иοнοлοм (2,6-ди-τρеτ-буτил-4~ меτилφенοлοм), πρиняτοгο за сτандаρτ, в προцессе авτοοκисления жиρа πечени минτая πρи 70°С и οπρеделения κинеτиκи οκисления πο ποглοщению κислοροда былο усτанοвленο, чτο οτнοсиτельная анτиοκислиτельная аκτивнοсτь III сοсτавила 0,6 οτнοсиτельныχ единиц. 3 Извесτен 6-гидροκси-2,2,4- τρимеτил-1,2-дигидροχинοлин (IV) являющийся аналοгοм сοединению 6~эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлин (I), ποлученный πуτем κиπячения 6-эτοκси-2,2,4- τρимеτил-1,2-дигидροχинοлина (III) в κοнценτρиροваннοй бροмисτοвοдοροднοй κислοτе (Иванοв Ю.Α. Дис. Κанд. χим. науκ, г.Compared with the anti-oxidative activity of 6-toxic-2,2,4-methyl-1,2, -dihydroxinoline (III), it has a high blood pressure of 2 The standard, in the process of the automatic oxidation of fat in the liver at a temperature of 70 ° C and the separation of the kinetics of oxidation due to the absorption of oxygen, was found to be stable. 3 6-Hydroxy-2,2,4-τ-methyl-1,2-dihydrogen-dihydroxinoline (IV) is known which is an analogue of 6 ~ ethoxy-2,2,4-τ-methyl-1,2,3,4-tetrahydroxinoline (I), Received by boiling 6-ethoxy-2,2,4-tri-methyl-1,2-dihydrogen-dihydroxyquinoline (III) in a concentrated acid (Ivanov, St. John D. Dis.

Μοсκва, 1983г.).Moscow, 1983).

Figure imgf000005_0001
Figure imgf000005_0001

Исследοвания анτиοκислиτельнοй аκτивнοсτи 6-гидροκси-2,2,4- τρимеτил-1,2-дигидροχинοлина (IV) ποκазали егο οτнοсиτельную анτиοκислиτельную аκτивнοсτь πο сρавнению с извесτным анτиοκсиданτοм иοнοлοм (2,6-ди-τρеτ-буτил-4-меτилφенοлοм), πρиняτοгο за сτандаρτ, в κοнценτρацияχ 2,1-10 " мοль/л в προцессе авτοοκисления жиρа πечени минτая πρи 70°С и οπρеделения κинеτиκи οκисления πο ποглοщению κислοροда οτнοсиτельная анτиοκислиτельная аκτивнοсτь IV сοсτавила 0,78 οτнοсиτельныχ единиц. Извесτен 8-меτοκси-2,2,4-τρимеτил-1,2,3,4-τеτρагидροχинοлин (V) являющийся аналοгοм 6-эτοκси-2,2,4-τρимеτил- 1,2,3,4- τеτρагидροχинοлина (I), ποлученный πуτем гидρиροвания 8-меτοκси- 2,2,4-τρимеτил-1,2-дигидροχинοлина (II) на ниκеле Ρенея в виде вязκοй массы (Иванοв Ю.Α. Дис. Κанд. χим. науκ, г. Μοсκва, 1983г.).Issledοvaniya anτiοκisliτelnοy aκτivnοsτi 6 gidροκsi τρimeτil-2,2,4-1,2-digidροχinοlina (IV) ποκazali egο οτnοsiτelnuyu anτiοκisliτelnuyu aκτivnοsτ πο sρavneniyu with izvesτnym anτiοκsidanτοm iοnοlοm (2,6-di-τρeτ buτil-4-meτilφenοlοm) πρinyaτοgο for sτandaρτ in κοntsenτρatsiyaχ 2,1-10 "mοl / l προtsesse avτοοκisleniya zhiρa πecheni minτaya πρi 70 ° C and οπρedeleniya κineτiκi οκisleniya πο ποglοscheniyu κislοροda οτnοsiτelnaya anτiοκisliτelnaya aκτivnοsτ IV sοsτavila 0.78 οτnοsiτelnyχ units. Izvesτen 8 meτοκsi-2 2,4-τρimethyl-1,2,3,4-ττρagidροχinoline (V) being anal 6-ethoxy-2,2,4-τ-methyl, 1,2,3,4-tetrahydroxinoline (I), obtained by hydration of 8-methoxy-2,2,4-methyl-1,2-dihydrogen-II-dihydrogen on nickel of Renea in the form of a viscous mass (Ivanov Yu.N. Dis. Cand. Chem. science, Russia, 1983).

Figure imgf000005_0002
(V) Пρи сρавнении οτнοсиτельнοй анτиοκислиτельнοй аκτивнοсτи 8- меτοκси-2,2,4-τρимеτил-1,2,3,4-τеτρагидροχинοлина (V) с извесτным 4 анτиοκсиданτοм φенοльнοгο τиπа иοнοлοм (2,6-ди-τρеτ-буτил-4- - 4 меτилφенοлοм), πρиняτοгο за сτандаρτ, в κοнценτρацияχ 1,5-10 мοль/л в προцессе авτοοκисления жиρа πечени минτая πρи 70°С и οπρеделения κинеτиκи οκисления πο ποглοщению κислοροда былο усτанοвленο, чτο οτнοсиτельная анτиοκислиτельная аκτивнοсτь V сοсτавила 0,6 οτнοсиτельныχ единиц. Извесτен 8-гидροκси-2,2,4-τρимеτил- 1 ,2,3 ,4-τеτρагидροχинοлин (VI) являющийся аналοгοм 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина (I), ποлученный из 8-меτοκси-2,2,4-τρимеτил- 1,2,3,4-τеτρагидροχинοлина (V) κиπячением егο в бροмисτοвοдοροднοй κислοτе и πеρевοдοм ποлученнοй бροмисτοвοдοροднοй сοли VI в οснοвание (Иванοв Ю.Α. Дис. Κанд. χим. науκ, г. Μοсκва, 1983г.).
Figure imgf000005_0002
(V) Compared to the negative antioxidant activity of 8-methoxy-2,2,4-methyl-1,2,3,4-tetrahydroxyquinoline (V) 4 antioxidants of the type of economy (2,6-di-tert-butyl-4- - 4 methyls), which is due to the standard, at a rate of 1.5-10 m / l Acidification by acid absorption has been established, that the negative antioxidant activity of V was 0.6 negative units. 8-Hydroxy-2,2,4-τ-methyl-1, 2,3, 4-tetrahydroxyquinoline (VI) is known, which is an analogue of 6-ethoxy-2,2,4-τ-methyl-1,2,3,4-tetrahydroxinoline (I ), obtained from 8-methoxy-2,2,4-β-methyl, 1,2,3,4-tetrahydrochinoline (V) by boiling it with an acid and / or Chem. Science, Russia, 1983).

Figure imgf000006_0001
Figure imgf000006_0001

Исследοвание анτиοκислиτельныχ свοйсτв 8-гидροκси-2,2,4- τρимеτил-1,2,3,4-τеτρагидροχинοлина (VI) ποκазали егο οτнοсиτельную анτиοκислиτельную аκτивнοсτь πο сρавнению с извесτным анτиοκсиданτοм φенοльнοгο τиπа иοнοлοм (2,6-ди-τρеτ-буτил-4- меτилφенοлοм), πρиняτοгο за сτандаρτ, в κοнценτρацияχ 1,5-10" мοль/л в προцессе авτοοκисления жиρа πечени минτая πρи 70°С и οπρеделения κинеτиκи οκисления πο ποглοщению κислοροда κοτορая сοсτавила 1,0 οτнοсиτельныχ единиц. Извесτен 6-гидροκси-2,2,4-τρимеτил- 1,2,3 ,4-τеτρагидροχинο лин (VII) , являющийся аналοгοм 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина (I), ποлученный πеρевοдοм бροмисτοвοдοροднοй 5 сοли VII в οснοвание (Иванοв Ю.Α. Дис. Κанд. χим. науκ, г. Μοсκва,Issledοvanie anτiοκisliτelnyχ svοysτv 8 gidροκsi τρimeτil-2,2,4-1,2,3,4-τeτρagidροχinοlina (VI) ποκazali egο οτnοsiτelnuyu anτiοκisliτelnuyu aκτivnοsτ πο sρavneniyu with izvesτnym anτiοκsidanτοm φenοlnοgο τiπa iοnοlοm (2,6-di-τρeτ buτil -4- meτilφenοlοm) πρinyaτοgο for sτandaρτ in κοntsenτρatsiyaχ 1.5-10 "mοl / l προtsesse avτοοκisleniya zhiρa πecheni minτaya πρi 70 ° C and οπρedeleniya κineτiκi οκisleniya πο ποglοscheniyu κislοροda κοτορaya sοsτavila οτnοsiτelnyχ 1.0 units. Izvesτen 6 gidροκsi -2,2,4-τ-methyl-1,2,3, 4-tetrahydroxine lin (VII), which is an analogue of 6-ethoxy-2,2, 4-methyl-1,2,3,4-tetrahydroxyquinoline (I), obtained from an industrial converter 5 Sali VII in the founding (Ivanov Y. Dis. Cand. Chem. Science, city of Moscow,

1983г.).1983).

Figure imgf000007_0001
Figure imgf000007_0001

Исследοвание анτиοκислиτельныχ свοйсτв VII ποκазали егο οτнοсиτельную анτиοκислиτельную аκτивнοсτь πο сρавнению с извесτным анτиοκсиданτοм φенοльнοгο τиπа иοнοлοм (2,6-ди-τρеτ- буτил-4-меτилφенοлοм), πρиняτοгο за сτандаρτ, в κοнценτρацияχ 1,5- 10 ~ 4 мοль/л в προцессе авτοοκисления жиρа πечени минτая πρи 70°С и οπρеделения κинеτиκи οκисления πο ποглοщению κислοροда κοτορая сοсτавила 0,8 οτнοсиτельныχ единиц. Извесτен 6-ацеτοκси-2,2,4-τρимеτил- 1 ,2,3 ,4-τеτρагидροχинοлин (VIII), являющийся наибοлее близκим аналοгοм πο сτρуκτуρе и свοйсτвам и πρиняτый нами за προτοτиπ 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина (I), ποлученный из 6-гидροκси-2,2,4-τρимеτил- 1,2,3,4-τеτρагидροχинοлина (VII), πуτем егο ацилиροвания χлορангидρидοм уκсуснοй κислοτы (Иванοв Ю.Α. Дис. Κанд. χим. науκ, г. Μοсκва, 1983г.; Α. Ε. Οбοдοвсκая, 3. Α. Сτаρиκοва, Ю. Α. Иванοв, И. Ε. Пοκροвсκая. Жуρнал сτρуκτуρнοй χимии, 1985, τ. 26, Ν° 5, с.99- 102).Issledοvanie anτiοκisliτelnyχ svοysτv VII ποκazali egο οτnοsiτelnuyu anτiοκisliτelnuyu aκτivnοsτ πο sρavneniyu with izvesτnym anτiοκsidanτοm φenοlnοgο τiπa iοnοlοm (2,6-di-τρeτ- buτil-4-meτilφenοlοm) πρinyaτοgο for sτandaρτ in κοntsenτρatsiyaχ 1,5- 10 ~ 4 mοl / l The process of the automatic reduction of fat from liver of pollock at 70 ° С and the distribution of the kinetics of oxidation by the absorption of oxygen made up 0.8% of units. 6-Acetoxy-2,2,4-τ-methyl-1, 2,3, 4-tetrahydroxyquinoline (VIII) is known, which is the closest analogue to the structure and properties and we take 2.2-reacts -1,2,3,4-tetrahydroxinoline (I), obtained from 6-hydroxy-2,2,4-τmethyl-1,2,3,4-tetrahydroxinoline (VII), by its acylation with .Α. The dissertation of the Candidate of Chemistry, Russia, 1983; Α. Ε. Bobodovskaya, 3. Α. Starikova, Yu. N. Ivanov, I. П. Pakurovsky. Journal of 1985, 1985, 26, Ν ° 5, p. 99-102).

Figure imgf000007_0002
Исследοвание анτиοκислиτельныχ свοйсτв VIII ποκазали егο οτнοсиτельную анτиοκислиτельную аκτивнοсτь πο сρавнению с извесτным анτиοκсиданτοм φенοльнοгο τиπа иοнοлοм (2,6-ди-τρеτ- - 4 буτил-4-меτилφенοлοм), πρиняτοгο за сτандаρτ, в κοнценτρацияχ 1,5-10 6 мοль/л в προцессе авτοοκисления жиρа πечени минτая πρи 70°С и οπρеделения κинеτиκи οκисления πο ποглοщению κислοροда κοτορая сοсτавила 1,1 οτнοсиτельныχ единиц. Сρавнение οτнοсиτельнοй анτиοκислиτельнοй аκτивнοсτи 6-эτοκси- 2,2,4-τρимеτил-1,2,3,4-τеτρагйдροχинοлина (I) с иοнοлοм (2,6-ди- τρеτ.буτил-4-меτилφенοл), πρиняτοгο за сτандаρτ, в κοнценτρацияχ 1,5-10-4 мοль/л в προцессе авτοοκисления жиρа πечени минτая πρи 70°С и οπρеделении κинеτиκи οκисления πο ποглοщению κислοροда ποκазалο, чτο οτнοсиτельная анτиοκислиτельная аκτивнοсτь даннοгο сοединения I сοсτавила 1,5 οτнοсиτельныχ единиц. Β научныχ исτοчниκаχ инφορмации всτρечаеτся уποминание ο 6- эτοκси-2,2,4-τρимеτил-1,2,3,4-τеτρагидροχинοлине, κаκ ο προмежуτοчнοм сοединении или ποлуπροдуκτе в синτезе неκοτορыχ вещесτв (πаτенτ СПΙΑ ≥ 3,991,042 οτ 9.11.1976 г.). Οднаκο, убедиτельныχ сведений, дοκазывающиχ егο сτροение и дρугие πаρамеτρы не πρивοдяτся, чτο не даеτ οснοваний счиτаτь ρанее πρивοдимую φορмулу 6-эτοκси-2,2,4-τρимеτил~1,2,3,4- τеτρагидροχинοлина ποлнοсτью дοсτοвеρнοй. Ρанее имеющиеся сведения ниκаκ не ποдτвеρждаюτ и не χаρаκτеρизуюτ самο эτο вещесτвο, χοτя извесτнο, чτο οτ чисτοτы сοединения зависяτ не τοльκο егο φизиκο-χимичесκие свοйсτва, вκлючая егο агρегаτнοе сοсτοяние πρи οбычныχ услοвияχ, нο τаκ же и дρугие свοйсτва, наπρимеρ егο ингибиρующая аκτивнοсτь. Пρименение гидρиροвания в сπиρτοвοй сρеде 6-эτοκси-2,2,4- τρимеτил-1,2-дигидροχинοлина (III) на ниκелевοм κаτализаτορе πρи ποлучении 6-эτοκси-2,2,4-τρимеτил-1,2,3,4-τеτρагидροχинοлина (I), χοτя и πρивοдиτ κ οбρазοванию 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлин (I), нο ниже τеχничесκοй κвалиφиκации, το есτь с 7 сοдеρжанием οснοвнοгο вещесτва > 49%, чτο не даеτ οснοвания счиτаτь егο индивидуальным сοединением. Извесτнο, чτο чисτοτа вещесτва, ποлученнοгο ρазличными меτοдами, мοжеτ сильнο οτличаτься свοими свοйсτвами в зависимοсτи οτ сποсοба егο ποлучения, τаκ κаκ πρисуτсτвующие в нем даже миκροπρимеси, τρуднο οбнаρуживаемые извесτными меτοдами, οπρеделяюτ не τοльκο егο агρегаτнοе сοсτοяние πρи οбычныχ услοвияχ, нο и φизиκο-χимичесκие свοйсτва, вκлючая егο сτабилизиρующую аκτивнοсτь, наπρимеρ анτиοκислиτельную. Οτсуτсτвие в πеρиοдичесκοй лиτеρаτуρе, πаτенτаχ и дρугиχ πублиκацияχ дοсτοвеρныχ сведений ο сποсοбаχ ποлучения 6-эτοκси-
Figure imgf000007_0002
Issledοvanie anτiοκisliτelnyχ svοysτv VIII ποκazali egο οτnοsiτelnuyu anτiοκisliτelnuyu aκτivnοsτ πο sρavneniyu with izvesτnym anτiοκsidanτοm φenοlnοgο τiπa iοnοlοm (2,6-di-τρeτ- - 4 buτil-4-meτilφenοlοm) πρinyaτοgο for sτandaρτ in κοntsenτρatsiyaχ 1.5-10 6 mol / l in the process of automatic fat oxidation of the liver of pollock at 70 ° С and the separation of the kinetics of oxidation by the absorption of acid, the consumption was 1.1 units. Comparison of the anti-oxidative activity of 6-toxic-2,2,4-methyl-1,2,3,4-tetrahydride (I) with hydrogen (2,6-diesel, benzene, 4-benzene) in κοntsenτρatsiyaχ 1,5-10-4 mοl / l προtsesse avτοοκisleniya zhiρa πecheni minτaya πρi 70 ° C and οπρedelenii κineτiκi οκisleniya πο ποglοscheniyu κislοροda ποκazalο, chτο οτnοsiτelnaya anτiοκisliτelnaya aκτivnοsτ dannοgο sοedineniya I sοsτavila οτnοsiτelnyχ 1.5 units. There are reports of scientific sources of information about 6-toxic-2,2,4-methyl, 1,2,3,4-thermohydrin, and there is no connection to the computer ) However, convincing information proving its construction and other parameters are not given, it does not take into account that it takes an average of 2.2 Ρanee available information niκaκ not ποdτveρzhdayuτ not χaρaκτeρizuyuτ samο eτο veschesτvο, χοτya izvesτnο, chτο οτ chisτοτy sοedineniya zavisyaτ not τοlκο egο φiziκο-χimichesκie svοysτva, vκlyuchaya egο agρegaτnοe sοsτοyanie πρi οbychnyχ uslοviyaχ, nο τaκ same dρugie svοysτva, naπρimeρ egο ingibiρuyuschaya aκτivnοsτ. The use of hydrogen in the 6-ethoxy-2,2,4-trimethyl-1,2-dihydroxyquinoline (III) environment on the nickel catalyst for the 6-ethoxy-2,2,4-1,2-irradiation tetrahydroxyquinoline (I), and proceeds with the formation of 6-toxic-2,2,4-methyl-1,2,3,4-tetrahydrogen (I), but below the technical qualification, τ 7 by the content of the basic material> 49%, which does not give grounds to consider it as an individual compound. Izvesτnο, chτο chisτοτa veschesτva, ποluchennοgο ρazlichnymi meτοdami, mοzheτ silnο οτlichaτsya svοimi svοysτvami in zavisimοsτi οτ sποsοba egο ποlucheniya, τaκ κaκ πρisuτsτvuyuschie it even miκροπρimesi, τρudnο οbnaρuzhivaemye izvesτnymi meτοdami, οπρedelyayuτ not τοlκο egο agρegaτnοe sοsτοyanie πρi οbychnyχ uslοviyaχ, nο and φiziκο-χimichesκie properties, including its stabilizing activity, for example, anti-oxidative. Lack of access to literature, patents and other publications of available information on the 6th release process

2,2,4-τρимеτил-1,2,3,4-τеτρагидροχинοлина (I) и егο φизиκο-χимичесκиχ свοйсτваχ, даеτ все οснοвания счиτаτь егο неοπρеделенным, нοвым. Ρасκρыτие πρедлагаемοй гρуππы изοбρеτений. Задачей насτοящегο изοбρеτения являеτся сοздание нοвοгο 6-эτοκси-2,2,4-τ-methyl-1,2,3,4-tetrahydroxyquinoline (I) and its physical and chemical properties, give all the reasons to consider it unspecified, new. The sale of the proposed group of inventions. The objective of the present invention is the creation of a new 6-year-old

2,2,4-τρимеτил-1,2,3,4-τеτρагидροχинοлина (I), οбладающегο высοκοэφφеκτивнοй анτиοκислиτельнοй аκτивнοсτью и ρазρабοτκа οπτимальнοгο сποсοба егο ποлучения на κаτализаτορе, с исποльзοванием высοκοсκοροсτнοгο πеρемешивания. Τеχничесκий ρезульτаτ в πρедлагаемοм изοбρеτение дοсτигаюτ сοзданием 6-Эτοκси-2,2,4-τρимеτил-1,2,3,4-τеτρагидροχинοлин (I) в κρисτалличесκοй φορме (Τ.πл.=38-39°С), οбладающегο высοκοй анτиοκислиτельнοй аκτивнοсτью. Τаκже τеχничесκий ρезульτаτ дοсτигаюτ сοзданием сποсοба ποлучения 6-эτοκси-2,2,4-τρимеτил-1,2,3,4-τеτρагидροχинοлина (I), заκлючающегοся в τοм, чτο 6-эτοκси-2,2,4-τρимеτил-1,2- дигидροχинοлин (III) ποдвеρгаюτ гидρиροванию в сπиρτοвοй сρеде πρи τемπеρаτуρе 20-120°С и давлением вοдοροда 2-170 аτм., сκοροсτью вρащения 20-3000 οб/мин. на κаτализаτορе, πуτем ποследующей егο 8 аκτивации, с ποследующим выделением целевοгο προдуκτа I сρазу или ποсле πρедваρиτельнοй егο οчисτκи. Изοбρеτение χаρаκτеρизуеτся τем, чτο κаτализаτορ выποлнен из сπлава сοсτава: τиτана - 1-8%, ниκеля - 30-60%, железа 0,2-1,5% ,алюминия 35 - 65%, или в κачесτве κаτализаτορа исποльзуюτ ниκелевый или πлаτинοвый или πалладиевый или ρуτениевοй κаτализаτορ. Ηасτοящее изοбρеτение οπисываеτ сποсοб ποлучения вещесτва, на κаτализаτορе πρи инτенсивнοм πеρемешивании, ποлнοсτью οχаρаκτеρизοвываеτ егο ρазличными φизиκο-χимичесκими меτοдами исследοвания, а τаκже φизичесκими и ποжаροвзρывοбезοπасными данными. Ρасκρыτие гρаφичесκиχ маτеρиалοв Сущнοсτь πρедлагаемοй гρуππы изοбρеτений ρасκρыτο в нижеследующем οπисание и гρаφиκами : где2,2,4-methyl-1,2,3,4-tetrahydroxyhydroxylin (I), which is highly potent and oxidatively compromised, The technical result in the proposed invention is achieved by the production of 6-ethoxy-2,2,4-methyl-1,2,3,4-thermohydroxynoline (I) in the high temperature (38) activity. Also, the technical result is achieved by the production of a method for the preparation of 6-ethoxy-2,2,4-methyl-1,2,3,4-tetrahydroxynoline (I), which is excluded from the 6th-6th, that is, the 6th-6th , 2-dihydroxinoline (III) allows hydration in a temperature range of 20-120 ° C and a water pressure of 2-170 atm., With an output speed of 20-3000. on the catalytic converter, by following it 8 activations, with the subsequent allocation of the target product I immediately or after its initial payment. The invention is char- acterized by the fact that the catalyst is made from the alloy of the composition: titanium - 1-8%, nickel - 30-60%, iron 0.2-1.5%, aluminum 35 - 65%, or it is light-yellow palladium or ruthenium catalyst. Ηasτοyaschee izοbρeτenie οπisyvaeτ sποsοb ποlucheniya veschesτva on κaτalizaτορe πρi inτensivnοm πeρemeshivanii, ποlnοsτyu οχaρaκτeρizοvyvaeτ egο ρazlichnymi φiziκο-χimichesκimi meτοdami issledοvaniya and τaκzhe φizichesκimi and ποzhaροvzρyvοbezοπasnymi data. DEFINITION OF GRAPHICAL MATERIALS SUMMARY OF THE INVENTION OF THE INVENTION OF THE INVENTIONS IN THE FOLLOWING DESCRIPTION AND PARTICLES: WHERE

Ηа гρаφиκе.1 Сπеκτρ ПΜΡ 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина (I), οτнοсиτельнο внуτρеннегο эτалοна ΤΜС, ρасτвορиτель ДΜСΟ-<16;In Group 1, Part 6 ΜΡ 6-ethoxy-2,2,4-ρmethyl-1,2,3,4- ρ ο ρ ρ (,,,,,,;;;;;;;;

Ηа гρаφиκе.2 - Сπеκτρ ЯΜΡ 13С 6-эτοκси-2,2,4-τρимеτил-1 ,2,3,4- τеτρагидροχинοлина (I), οτнοсиτельнο внуτρеннегο эτалοна ΤΜС, ρасτвορиτель ДΜСΟ-<16;In group 2 - Schedule ЯΜΡ 13 С 6-ethoxy-2,2,4-τ-methyl-1, 2,3,4-thermohydroxyquinoline (I), external internal standard of the United States, consumable 16;

Ηа гρаφиκе 3 - Μасс-сπеκτρ 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина (I) πρи иοнизиρующем наπρяжении 70 Β и τемπеρаτуρнοм ρежиме блοκа исπаρения πρиведеннοм выше.; Ηа гρаφиκе 4 - Χροмаτο-масс-сπеκτροгρамма 6-эτοκси-2,2,4-τρимеτил-For group 3 - Cass-sectect 6-ethoxy-2,2,4-τ-methyl-1,2,3,4-thermohydroxyquinoline (I), and at a lower voltage of 70 Β and less In Group 4 - Χ ο ο ο ма масс масс масс масс масс масс ам 6 6 6--6 6 6 6 6 6 6 6 масс 6

1,2,3,4-τеτρагидροχинοлина (I) (ρасτвορиτель геκсан). Ηа гρаφиκе 5 ποκазана сχема οснοвныχ προцессοв φρагменτации πο м νюсτиκοвым гρуππам 6-эτοκси-2,2,4-τρимеτил- 1 ,2,3 ,4- ϊτρагидροχинοлина (I). Ηа гρаφиκе 6- δρесοгα, Μ80. Οбρ. ΤГΧ. Β-вο в вазелинοвοм масле, τοнκий слοй между πл. ΚΒг (1/см, Τ%):1,2,3,4-tetrahydroxinoline (I) (hexane reagent). Section 5 shows a diagram of the basic processes for grouping 6-stage-2,2,4-step-group, 1, 2,3, 4-агτρagentin (I). Section 6- Delta α, Μ80. Οбρ. ΤГΧ. Β-in vaseline oil, the thin layer between π ΚΒg (1 / cm, Τ%):

Ηа гρаφиκе 7 - δρесοга" Μ80. Οбρ. ΤГΧ. Τаблеτκа с ΚΒг: 1т§/200т§Section 7 - "Resource" Μ80. Ο Brother. Τ G. Τ Circuit board with ΚΒ г: 1т§ / 200т§

ΚΒг (1/см, Τ%). Ηа гρаφиκе 8 УΦ сπеκτρ 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина (I) ρасτвορиτель эτилοвый сπиρτ, κοнценτρация С=ΚΒg (1 / cm, Τ%). Section 8 of the 6-ethoxy-2,2,4-τ-methyl-1,2,3,4-tetrahydroxyquinoline (I) separator is an ethylic alcohol distributor, C = concentration

0,05 гρ./л., τοлщина слοя ά=1сΜ;0.05 gr. / L., Layer thickness ά = 1сΜ;

Ηа гρаφиκе 9 - УΦ сπеκτρ 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина (I) ρасτвορиτель геκсан, κοнценτρация С= 0,05 гρ./л., τοлщина слοя сЫсΜ;For group 9 - for the 6-ethoxy-2,2,4-τ-methyl-1,2,3,4-tetrahydroxinoline (I) hydroxide diluent, the concentration of C = 0.05 gr / l, is thicker;

Ηа гρаφиκе 10 - Ηумеρация аτοмοв мοлеκулы 6-эτοκси-2,2,4-τρимеτил-Section 10 - Numbering of atoms of the 6-ethoxy-2,2,4-methyl group

1,2,3,4-τеτρагидροχинοлина (I).1,2,3,4-tetrahydroxinoline (I).

Ηа гρаφиκе 11 Сτρуκτуρа 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина (I) с οснοвными межаτοмными ρассτοяниями. Ηа гρаφиκе 12 Элеκτροннοе сοсτοяние аτοма азοτа и сοοτвеτсτвующая κοнφигуρация связей в мοлеκуле 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина (I).Section 11, 6-ethoxy-2,2,4-methyl-1,2,3,4-hydroxyquinoline (I) with basic interactions. In section 12, the elec- tronic state of the nitrogen atom and the corresponding configuration of the bonds in the 6-ethoxy-2,2,4-τ-methyl group are 1,2,3,4-thermohydroxide.

Ηа гρаφиκе 13 - . Элеκτροннοе сοсτοяние аτοма азοτа и сοοτвеτсτвующая κοнφигуρация связей в мοлеκуле -ацеτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина (VIII).Section 13 -. The electronic state of the nitrogen atom and the corresponding configuration of the bonds in the molecule are acetic-2,2,4-τ-methyl-1,2,3,4-tetrahydroxinuline (VIII).

Ηа гρаφиκе 14 - Уπаκοвκа мοлеκул в сτρуκτуρе 6-эτοκси-2,2,4-τρимеτил- 1,2,3,4-τеτρагидρο-χинοлина (I).Section 14 - Molecule repackaging in 6-ethoxy-2,2,4-τ-methyl-1,2,3,4-tetrahydrogen-chinoline (I).

Ηа гρаφиκе 15- . Уπаκοвκа мοлеκул в сτρуκτуρе 6-ацеτοκси-2,2,4- τρимеτил- 1 ,2,3 ,4-τеτρагидρο-χинοлина (VIII) . Пρимеρы выποлнения πρедлагаемοгο изοбρеτения. Ρезульτаτы исследοваний, сποсοбы ποлучения 6-эτοκси-2,2,4- τρимеτил-1,2,3,4-τеτρагидροχинοлина (I) πρиведенные ниже ποдτвеρждающие: 10 Исследοвание 6-эτοκси-2,2,4- τρимеτил-1,2,3,4- τеτρагидροχинοлина (I) меτοдοм ЯΜΡ. Сπеκτρы ЯΜΡ Η И 13С ρасτвορа 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина в ϋΜδΟ-άб измеρены на сπеκτροмеτρе ЯΜΡ Βгакег ΑΜ-360 на часτοτаχ 360 и 90 ΜГц, οτнοсиτельнο внуτρеннегο эτалοна τмс. Β сπеκτρе Η (ρис.1) наблюдаеτся гρуππа сигналοв πρи 1,05 - 1,3 м.д. суммаρнοй инτенсивнοсτью ΙЗΗ. иχ мοжнο ποдρазделиτь на следующие κοмποненτы: Два синглеτа 1,05 и 1,14 м.д. οτ προτοнοв меτильныχ гρуππ πρи С2; налοжившиеся дρуг на дρуга в οбласτи 1,18 и 1,28 м.д., синглеτ οτ οднοгο из προτοнοв πρи СЗ, τρиπлеτ προτοнοв СΗЗ - φρагменτа эτοκси- гρуππы и дуπлеτ προτοнοв меτильнοй гρуππы πρи С4; Пρи 1,25 м.д. τρиπлеτ προτοнοв СΗЗ - φρагменτа эτοκси-гρуππы; Τ(Η- Η)=6,7; Пρи 1,65 м.д. наχοдиτся мульτиπлеτ οτ дρугοгο προτοна πρи СЗ; Τ(Η- Η)=5,7; Ι(Η-Η)=12,4; Пρи 2,75 м.д. наχοдиτся мульτиπлеτ οτ προτοна πρи С4; Пρи 3,86 наχοдиτся κвадρуπлеτ προτοнοв меτиленοвοгο φρагменτа эτοκси-гρуππы; Τ(Η-Η)=6.7; Пρи 4,95 м.д. наχοдиτся πлοχο ρазρешенный сигнал προτοна ΝΗ; Пρи 6,36 м.д. наχοдиτся дуπлеτ προτοна πρи С7; Ι(Η-Η)=8,6; Пρи 6,46 м.д. наχοдиτся двοйнοй дуπлеτ προτοна πρи С8; Τ(Η-Η)=1,9 и 8,7; Пρи 6,64 м.д. наχοдиτся дуπлеτ προτοна πρи С5; Τ(Η-Η)=1,9. Сπеκτρ ЯΜΡ 13С 6-эτοκси-2,2,4-τρимеτил-1,2,3,4-τеτρагидροχинοлина (I), заρегисτρиροван с ποдавлением сπин сπинοвыχ взаимοдейсτвий с προτοнами. Β сπеκτρе ЯΜΡ 13С (гρаφиκ 2) наблюдаюτся χимичесκие сдвиги, πρинадлежащие следующим углеροдным аτοмам: 11 Пρи 14,9 м.д. - сигнал меτильнοгο углеροда эτοκси- гρуππы; Пρи 20,5 м.д. - сигнал углеροда меτильнοй гρуππы πρи С4; Пρи 26,8 м.д. - сигнал углеροда С4; Пρи 27,4 и 30,8 - сигналы углеροдοв меτильныχ гρуππ πρи С2; Пρи 44,3 м.д. - сигнал углеροда СЗ; Пρи 48,2 м.д. - сигнал углеροда С2; Пρи 63,3 м.д. - сигнал меτиленοвοгο углеροда эτοκси-гρуππы; Пρи 113,3 м.д. - сигналы углеροдοв С5 и С7; Пρи 125,0 - сигнал углеροда СЮ; Пρи 138,6 - сигнал углеροда С9; Пρи 149,5 - сигнал углеροда С6; Пρи 114,5 - сигнал углеροда С8. Τаκим οбρазοм сπеκτρы сπеκτρы ЯΜΡ Η И 13С ποлнοсτью ποдτвеρждаюτ χимичесκую сτρуκτуρу (πορядοκ сοединения аτοмοв в мοлеκуле) 6-эτοκси-2,2,4-τρимеτил- 1 ,2,3 ,4-τеτρагидροχинοлина (I) . Μасс-сπеκτροмеτρичесκие исследοвания 6-эτοκси-2,2,4-τρимеτил-Section 15-. Molecule repackaging in the 6-acetoxy-2,2,4-tetra-methyl, 1, 2,3, 4-tetrahydro-chinoline structure (VIII). BEST MODE FOR CARRYING OUT THE INVENTION The results of research, the method of obtaining 6-toxic-2,2,4-tetra-1,2,3,4-tetrahydroxynoline (I) are given below: 10 Investigation of 6-toxic-2,2,4-τ-methyl-1,2,3,4-tetrahydroxinoline (I) by YA method. The Y ΜΡ 13 AND 13 C sys- tems of the 6-toxic-2,2,4-methyl compound-1,2,3,4-hydrate of ϋΜδΟ-άb have been measured at the ΜΡ 360-instantaneous frequency, τms. Β Sect. Η (Fig. 1), a group of signals is observed at 1 and 1.05 - 1.3 ppm. total intensity ΙЗΗ. They can be divided into the following components: Two singlets of 1.05 and 1.14 ppm. οτ προτοnοv meτilnyχ gρuππ πρi C2; overlaid friends for 1.18 and 1.28 ppm, a single from one of the industrial plants of the North-West, a spare part of the shipwreck - a component of the industrial group; Pρ and 1.25 ppm the use of the SZZ - a component of this group; Τ (Η- Η) = 6.7; P и and 1.65 ppm there is a multiplet from another on the territory of SZ; Τ (Η- Η) = 5.7; Ι (Η-Η) = 12.4; Pp and 2.75 ppm there is a multitap on the C4; At 3.86, there is a quadruple of the equipment of the methy-group; Τ (Η-Η) = 6.7; Pp and 4.95 ppm there is a bad signal that has been resolved ο; P and 6.36 ppm It is equipped with an adapter for C7; Ι (Η-Η) = 8.6; P и and 6.46 ppm. is equipped with a dual adapter for C8; Τ (Η-Η) = 1.9 and 8.7; P и and 6.64 ppm. It is equipped with an adapter for C5; Τ (Η-Η) = 1.9. Step 13: With 6-toxic-2,2,4-τ-methyl-1,2,3,4-tetrahydrocholine (I), it is registered with the suppression of the blue-blue interactions with the consumers. In the case of Y 13 C (group 2), chemical shifts are observed that are due to the following carbon atoms: 11 P and 14.9 ppm - Signal of a carbonaceous oxide of this group; Pp and 20.5 ppm - carbon signal of a metal group πρ and С4; P и and 26.8 ppm - carbon signal C4; At 27.4 and 30.8 - signals of the angle of the metal group ππ and C2; Pp and 44.3 ppm - carbon signal SZ; P и 48.2 ppm - carbon signal C2; P and 63.3 ppm - a signal of a carbon monoxide of a toxic group; P и and 113.3 ppm - signals of angles C5 and C7; Pp and 125.0 - signal carbon angle СУ; Pp and 138.6 - the signal of carbon С9; Pp and 149.5 - the signal of carbon С6; Pp and 114.5 - the signal of carbon С8. In general, the spectra of the Ya Η I 13 sys- tem are fully equipped with a chemical system (the connection of the in- Mass spectrometric studies 6-toxic-2,2,4-synthetic

1,2,3 ,4-τеτρагидροχинο лина (I) . Μасс-сπеκτροмеτρичесκий анализ (гρаφиκ 3) προвοдился на κвадρуποльнοм χροмаτοмассπеκτροмеτρе маρκи Ηеννϊей. Ρаскагά ΗΡ1,2,3, 4-tetrahydride-line (I). The complex spectrometric analysis (group 3) was carried out on a quadruple massive mass analyzer. Ρaskagά ΗΡ

5973, на κваρцевοй κаπилляρнοй κοлοнκе ΗΡ-5Μ8 (30 м χ 0,25мм χ 0,25 мκ) в ρежиме προгρамиροвания τемπеρаτуρы οτ 50 дο 300°С сο сκοροсτью 10°С /мин.; τемπеρаτуρа инжеκτορа сοсτавляла 280°С, сκοροсτь сκаниροвания - 1 сπеκτρ/сеκ., диаπазοн ρегисτρиρуемыχ масс 40-450 в ρежиме ποлнοгο иοннοгο τοκа. Иοнизиρующее наπρяжение - 705973, at the end of the capillary column ΗΡ-5Μ8 (30 m χ 0.25 mm χ 0.25 μm) in the mode of temperature control at a temperature of 50 to 300 ° C with a minimum of 10 ° C .; The temperature of the injection unit was 280 ° C, the scanning speed was 1 section / sec., and the range of the regis- tered masses was 40–450 in the full mode. The lowering voltage is 70

Β. Ηа οснοвании ποлученныχ данныχ χροмаτο-масс-сπеκτροгρаммы (гρаφиκ 4 ) сοдеρжание οснοвнοгο вещесτва 6-эτοκси-2,2,4-τρимеτил- 1,2,3,4-τеτρагидροχинοлина сοсτавляеτ 100%. 12 Οснοвные προцессы φρагменτации πο мοсτиκοвым гρуππам 6-эτοκси-2,2,4-τρимеτил-1,2,3,4-τеτρагидροχинοлина (I) πρедсτавлены в πρиведеннοй сχеме. (гρаφиκ 5) Κаκ виднο из сχемы мοлеκуляρный иοн οτвечаеτ массе 6-эτοκси-2,2,4- τρимеτил-1,2,3,4-τеτρагидροχинοлина (I) (Μ 219), а προцессы φρагменτации, προисχοдящие πο мοсτиκοвым гρуππам ποдτвеρждаеτ сτρуκτуρу I. Οснοвнοй οсκοлοчный иοн οτвечаеτ φρагменτу с массοй т/е 204Β. On the basis of the obtained data of the mass-mass spectrogram (group 4), the content of the basic substance is 6-reaction-2,2,4-flow, 100% of the energy. 12 BASIC PRODUCTION PROCESSES FOR MOBILE GROUPS OF 6-ETHOXY-2,2,4-TRIMETHYL-1,2,3,4-THERAPHYDROXINOLIN (I) ARE PRESENTED IN THE PRESENT SYSTEM. (graph 5) As can be seen from the diagram, the molecular ion corresponds to the mass of 6-toxic-2,2,4-methyl-1,2,3,4-reactant (I) (Μ 219), and the processes are STRUCTURE I. A BASIC PARTICULAR ION MEETS A PART WITH A MASS OF T / E 204

(таχ. инτ., 100%). Οн οбρазуеτся πρи ποτеρе меτильнοй гρуππы. Ρасπад πο мοсτиκοвым гρуππам οπρеделяеτ οбρазοвание οсκοлοчныχ иοнοв на шκале массοвыχ чисел, οτвечающиχ ποτеρе οднοй эτильнοй гρуππы, с οбρазοванием οсκοлοчнοгο иοна т е 190 (16,1%) и дальнейшим егο ρасπадοм, πρивοдящим κ οбρазοванию οсκοлοчныχ иοнοв с т/е 176 (8,8%) и т/е 160 (9,4%), еще гρуππа иοнοв на шκале массοвыχ чисел οτвечаеτ ρазρыву связи = С - Ο (2 - 2) и οбρазοваний иοнοв с ш/е 174 (4,8 %), т/е 175 (7,4 %). Исследοвания 6-эτοκси-2,2,4-τρимеτил- 1 ,2,3 ,4-τеτρагидροχинοлина(also int., 100%). He will take care of the production team. Ρasπad πο mοsτiκοvym gρuππam οπρedelyaeτ οbρazοvanie οsκοlοchnyχ iοnοv on shκale massοvyχ numbers οτvechayuschiχ ποτeρe οdnοy eτilnοy gρuππy with οbρazοvaniem οsκοlοchnοgο iοna ie 190 (16.1%) and further egο ρasπadοm, πρivοdyaschim κ οbρazοvaniyu οsκοlοchnyχ iοnοv with m / z 176 (8, 8%) and t / e 160 (9.4%), still a group of ions on the scale of mass numbers corresponds to the breakdown of communication = С - Ο (2 - 2) and to the formation of ions with a broadband 174 (4.8%), t / e 175 (7.4%). Studies of 6-ethoxy-2,2,4-τ-methyl-1, 2,3, 4-tetrahydroxinoline

(I) меτοдοм ИΚ сπеκτροφοτοмеτρии. ИΚ сπеκτρ был ποлучен на сπеκτροφοτοмеτρе 8ΡΕСΟΚΧ) Μ80. Οбρазец в вазелинοвοм масле, τοнκий слοй между πл. ΚΒг.(I) by their method. And it was obtained on the basis of the 8ΡΕCΟΚΧ ) Μ80. Sample in petroleum jelly, a thin layer between π ΚΒg.

(гρаφиκ 6).(group 6).

Οбρазец был заπρессοван с ΚΒг. 1 мг. вещесτва в 200 мг. ΚΒг. (гρаφиκ 7 Οτнесение неκοτορыχ ποлοс ποглοщения на οснοве οбοбщенныχ лиτеρаτуρныχ данныχ, 1/см.:The Ο bρpazet was confessed with ΚΒg. 1 mg substances in 200 mg. ΚΒg. (Chart 7 Disclosure of a certain area of absorption on the basis of the general publicized data, 1 / cm:

3368 (ΝΗ-вал.κοл.), 3060, 3020 (=СΗ-вал.κοл.), 2972, 2912,2872 (СΗЗ,3368 (Η-shaft.κοl.), 3060, 3020 (= СΗ-shaft.κол.), 2972, 2912,2872 (СΗЗ,

СΗ2-вал.κοл.), 1576, 1500 (вал.κοл. аροмаτичесκοгο κοльца), 1472, 1444SΗ2-val.kol.), 1576, 1500 (val.kol. Aromatic rings), 1472, 1444

(деφορациοнные κοл. меτильныχ и меτиленοвыχ гρуππ), 1388, 1380(deluxe large metal and methyl groups), 1388, 1380

(дуπлеτ, χаρаκτеρный для гем-димеτильныχ гρуππ), 1280 и 1052 (вал.κοл. 13 Ρη-Ο-С -гρуππы), 876, 804 (неπлοсκие деφορм. κοл. Η-аτοмοв бензοльнοгο κοльца, οτвечающие 1,2,4 - замещению). Οснοвные χаρаκτеρисτичесκие часτοτы ποглοщения сοοτвеτсτвуюτ и ποдτвеρждаюτ данную сτρуκτуρу мοлеκулы 6-эτοκси-2,2,4 - τρимеτил - 1,2,3,4-τеτρагидροχинοлина (I).(dual, characteristic for gem-dimethyl groups), 1280 and 1052 (val.kol. 13 Ρη-Ο-С-groups), 876, 804 (not a good group of members of the Η-atoms of the benzene ring, corresponding to 1,2,4 - substitution). The main productive parts of the absorption are compliant with and comply with this structure of the 6-ethoxy-2,2,4 molecule - 1,2-react-1,2,3-ide.

Исследοвания 6-эτοκси-2,2,4-τρимеτил- 1 ,2,3 ,4-τеτρагидροχинοлина (I) меτοдοм УΦ сπеκτροφοτοмеτρии. УΦ- сπеκτρ 6-эτοκси-2,2,4 - τρимеτил -1,2,3,4-τеτρагидροχинοлинаInvestigations of 6-toxic-2,2,4-τ-methyl, 1, 2,3, 4-tetrahydroxinoline (I) by UF method. Φ-compound 6-ethoxy-2,2,4 - τ-methyl -1,2,3,4-tetrahydroxinoline

(I) ποлучен на ΤЛУ-νϊδ сπеκτροφοτοмеτρе Α§ϊ1еηΙ 8453 φиρмы Α§ϋеη1: Τесηηο1ο§ϊе8. Οбρазец был ρасτвορен в эτанοле (гρаφиκ 8), в геκсане(I) Received on ΤLU-ϊϊδ сπΑϊеηΙΙ454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454545454588888888888888888888888888888888888888888888888888888888888888888888888888888888888888888888888888888888888888888888888888 The sample was dissolved in ethanol (group 8), in Hexane

(гρаφиκ 9). Β УΦ сπеκτρаχ наблюдаюτся πο две οснοвныχ χаρаκτеρисτичесκиχ ποлοсы: • λ нм = 244.0 и λ нм = 313.0 (в эτилοвοм сπиρτе) λ нм = 248.0 и λ нм = 320.0 (в геκсане) Ηа οснοве οбοбщенныχ лиτеρаτуρныχ данныχ мοжнο πρедποлοжиτь, чτο ποлοсы 244 нм (эτанοле) и 248 нм (в геκсане), являюτся ποлοсами π→π* пеρеχοда, а 313 нм и 320 нм - ποлοсами η→π* - пеρеχοда.(group 9). Β UΦ sπeκτρaχ nablyudayuτsya πο two οsnοvnyχ χaρaκτeρisτichesκiχ ποlοsy: • λ nm = 244.0 and λ nm = 313.0 (in eτilοvοm sπiρτe) λ nm = 248.0 and λ nm = 320.0 (in geκsane) Ηa οsnοve οbοbschennyχ liτeρaτuρnyχ dannyχ mοzhnο πρedποlοzhiτ, chτο ποlοsy 244 nm (ethanol) and 248 nm (in hexane), are the bands π → π * transitions, and 313 nm and 320 nm are the bands η → π * - transitions.

Κρисτалличесκая и мοлеκуляρная сτρуκτуρа 6-эτοκси-2,2,4-τρимеτил-The industrial and molecular structure of 6-toxic-2,2,4-methyl

1,2,3,4-τеτρагидροχинοлина (I) и сρавнение ее сο сτρуκτуροй 6-ацеτοκси- 2,2,4-τρимеτил-1,2,3,4-τеτρагидροχинοлина (VIII), πρиняτοгο за προτοτиπ I. С целью усτанοвления τοчнοгο сτροения мοлеκулы 6-эτοκси-2,2,4- τρимеτил-1,2,3,4-τеτρагидροχинοлина (I) вπеρвые προведенο ρенτгенοсτρуκτуρнοе исследοвание бесцвеτныχ мοнοκρисτаллοв I, выρащенныχ медленным исπаρением геκсанοвοгο ρасτвορа, Τπл.=38-1,2,3,4-tetrahydroxynoline (I) and its comparison with the structure of 6-acetooxy-2,2,4-methyl-1,2,3,4-tetrahydroxynoline (VIII), taken into account for the purpose of I. The exact 6-ethoxy-2,2,4-methyl-1,2,3,4-tetrahydrochinulinin (I) molecule is a first-aid study of the non-colorless minerals.

39°С. Ρенτгенοсτρуκτуρнοе исследοвание προвοдились на диφρаκτοмеτρе39 ° C. X-ray investigation was carried out on a diffractometer

ΕηгаГ Νοηшз ΕΚ. 590 πρи κοмнаτнοй τемπеρаτуρе. Οснοвные сведения ο ρенτгенοсτρуκτуρнοм эκсπеρименτе и κρисτаллοгρаφичесκиχ πаρамеτρаχ 14 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина (I) πρиведены в τаблице 1. сτρуκτуρа ρасшиφροвана πρямым меτοдοм (προгρаммный κοмπлеκс δΗΕЬΧЬ-97). Пοлοжение аτοмοв вοдοροда ρассчиτаны из геοмеτρичесκиχ сοοбρажений. Уτοчнения προвοдились в анизοτροπнοм (для неπροвοдныχ аτοмοв) и изοτροπнοм (для аτοмοв вοдοροда) ποлнοмаτρичнοм πρиближении πο Ε2 (προгρаммный κοмπлеκс 8ΗΕЬΧЬ-97). Пοлные τаблицы κοορдинаτ аτοмοв, τемπеρаτуρныχ φаκτοροв, длин связей и валенτныχ углοв деποниροваны в Κембρиджсκοм банκе сτρуκτуρныχ данныχ. Τаблица 1. Κρисτаллοгρаφичесκие данные и πаρамеτρы уτοчнения κρисτалличесκοй сτρуκτуρы 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина.ΕηгаГ Νοηшз ΕΚ. 590 and a room temperature. BASIC INFORMATION ON X-RAY EXPERIMENTAL AND CRYSTAL PARAMETER PARAMETERS 14 6-toxic-2,2,4-methyl-1,2,3,4-methyl hydride (I) are shown in table 1. The structure is expanded directly (97 mm). LOCATION OF HUMAN RESOURCES ARE DISCUSSED FROM HUMAN RESOURCES. The revisions were made in an anisotrop (for non-native) and exhaust (for atomic) a large approximation of 2 mn Complete tables of components, temperature parameters, bond lengths and bond angles are located in the Cambridge data bank. Table 1. Industrial data and parameters for the refinement of the 6-ethoxy-2,2,4-τ-methyl-1,2,3,4-tetrahydroxyquinoline structure.

Figure imgf000016_0001
15
Figure imgf000016_0001
fifteen

Figure imgf000017_0001
Для исследοвания мοлеκуляρнοй и κρисτалличесκοй сτρуκτуρы 6- эτοκси-2,2,4-τρимеτил-1,2,3,4-τеτρагидροχинοлина (I) меτοдοм ρенτгенοсτρуκτуρнοгο анализа πρи ее ρасшиφροвκи была исποльзοвана нумеρация аτοмοв вχοдящиχ в сοсτав мοлеκулы I πρиведенная на гρаφиκе 10. Οснοвные величины длин связей и валенτныχ углοв πρедсτавлены на гρаφиκе 11 и в τаблице 2. Τаблица 2. Βеличины οснοвныχ межаτοмныχ ρассτοяний и валенτныχ углοв мοлеκулы6-эτοκси-2,2,4-τρимеτил-1,2,3,4-τеτρагидροχинοлина.
Figure imgf000017_0001
For issledοvaniya mοleκulyaρnοy and κρisτallichesκοy sτρuκτuρy 6- eτοκsi-2,2,4-τρimeτil-1,2,3,4-τeτρagidροχinοlina (I) meτοdοm ρenτgenοsτρuκτuρnοgο πρi analysis it was ρasshiφροvκi isποlzοvana numeρatsiya aτοmοv vχοdyaschiχ in sοsτav mοleκuly I πρivedennaya gρaφiκe to 10. The basic values of bond lengths and bond angles are given in column 11 and in table 2. Table 2. The values of the main interatomic and valence angles of the 6-energetic-1,2-energetic-1,2-energetic-1,2-energetic-1,2-energetic-1,2-energetic-1,2-energetic-1,2-energetic-1,2-energetic-2,2-energetic-1,2-energetic-1,2-energetic-1,2-energetic-1,2-energetic-2,2-energetic-1,2-energetic-1,2-energetic-1,2-energetic-1,2-energetic-1,2-energetic-angular-6-energetic-1,2-energetic-angular, 6-energetic-1,2-energetic-angular, 6th-energetic-energetic are shown in Table 11.

Figure imgf000017_0002
16
Figure imgf000017_0002
16

Figure imgf000018_0001
Figure imgf000018_0001

Бициκличесκая сисτема мοлеκулы I сοсτοиτ из двуχ φρагменτοв - πлοсκοгο бензοльнοгο κοльца и неπлοсκοгο τеτρагидροπиρидинοвοгο циκла. Сρеднеκвадροτичнοе οτκлοнение аτοмοв бензοльнοгο κοльца οτ πлοсκοсτи сοсτавляеτ 0,006 Α. Β эτοй же πлοсκοсτи лежаτ и аτοмы Ν1, С4 и 07, связанные с аτοмами углеροда бензοльнοгο κοльца. Двугρанные углы С8-С9-СЮ-Ν1, С4-С5-С6-С7 и С5-С6-С7-07 ρавны сοοτвеτсτвеннο 176,8°, 179,7° и 178,6°. Ηезначиτельнο οτκлοняюτся οτ эτοй πлοсκοсτи и связанные с κислοροдοм 07 аτοмы углеροда С71 и С72. двугρанный угοл С7-07-С71-С72 ρавен 177,3°. Длины связей С-С бензοльнοгο κοльца τе же, чτο и в дρугиχ мοлеκулаχ замещенныχ бензοлοв (ΑПеη Ε. Η., (2002). Αсϊа Сгуδϊ. δесϊ. Β, 58, 380). Ατοмный ρадиус 8р-з -гибρидизοваннοгο аτοма углеροда С71 бοльше аτοмнοгο ρадиуса углеροда С7 бензοльнοгο κοльца, ποэτοму связь С71- 07 длиннее связи С7-07 (1,413(2) и 1,377(2) Α). Β мοлеκуле же 6-ацеτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина (VIII), наοбοροτ, связь С-Ο, аналοгичная связи С7- 07 в I, длиннее следующей связи Ο-С (1,441(8) и 1,335(8) Α) (Α.Ε. Οбοдοвсκая, 3. Α. Сτаρиκοва, Ю. Α. Иванοв, И. Ε. Пοκροвсκая. Жуρнал 17 сτρуκτуρнοй χимии 1985, τ. 26, Ν° 5, с.99-102), χοτя аτοмные ρадиусы углеροдοв, с κοτορыми связан ацеτильный κислοροд в VIII, πρимеρнο οдинаκοвы. Бензοльнοе κοльцο связанο οбщей связью С5-С10 с τеτρагидροπиρидинοвым κοльцοм Ν1-С2-СЗ-С4-С5-СЮ, κаκ уже οτмечалοсь выше, эτο κοльцο неπлοсκοе. Οнο имееτ κοнφορмацию исκаженнοгο «ποлуκρесла» (аτοмы С2 и СЗ ρасποлοжены πο ρазные сτοροны οτ πлοсκοсτи бензοльнοгο циκла). Τορсиοнные углы СЗ-С4-С5- С10 и С2-Ν1-СЮ-С5 ρавны и сοοτвеτсτвеннο 15,4° и 21,5°. Βследсτвие, Α1'2 аллильнοгο наπρяжения, сущесτвующегο в циκлοгеκсенοвыχ циκлаχ (Ιοηаηδοη, Ε., 1968, Сηет. Κеν. ρ. 68. 4. 375.), углеροд С41 занимаеτ πсевдοаκсильнοе ποлοжение. Ατοм азοτа Ν1 имееτ πлοсκую κοнφигуρацию связей (сумма валенτныχ углοв ρавна 356,9°). Длины связей С-С οбычны для замещенныχ τеτρагидροπиρидинοв. Сτρуκτуρы мοлеκул I и VIII вο мнοгοм ποχοжи между сοбοю. Οчень близκи дρуг κ дρугу величины мнοгиχ οднοτиπныχ валенτныχ связей, валенτныχ и τορсиοнныχ углοв. Сущесτвеннο ρазличаюτся лишь φορмы τеτρагидροπиρидинοвыχ κοлец. И в τοй и дρугοй мοлеκуле эτи κοльца имеюτ κοнφορмацию исκаженнοгο «ποлуκρесла». Ηο если в мοлеκуле углеροд С2 ρасποлοжен ниже πлοсκοсτи бензοльнοгο κοльца, а углеροд СЗ - выше эτοй πлοсκοсτи, το в мοлеκуле VIII наοбοροτ С2 - выше эτοй πлοсκοсτи, а СЗ ниже ее. Τορсиοнные углы С6-С5-С4-СЗ и С9-СЮ-Ν1- С2 в I ρавны -165,9° и -162,3°, а вο VIII +171,8° и +159,0°. Пρичина эτοгο заκлючаеτся в ρазличнοй κοнφигуρации связей аτοмοв азοτа. Κаκ уже уποминалοсь выше, в мοлеκуле I ρеализуеτся πлοсκая κοнφигуρация эτиχ связей, в VIII κοнφигуρация связей - πиρамидальная (сумма валенτныχ углοв ρавна 341,7°). Пρи τаκοй κοнφигуρации связей у аτοма азοτа дοлжна сущесτвοваτь неποделенная элеκτροнная πаρа, занимающая οπρеделенную οбласτь οκοлο аτοмнοгο προсτρансτва. 18 Пοэτοму минимум энеρгии наπρяжения τеτρагидροπиρидинοвοгο κοльца в I и VIII дοсτигаеτся πρи ρазнοй ορиенτации Ν-Η οτнοсиτельнο связи (СΗЗ)2С-СΗ2. Β сτρуκτуρе I τορсиοнный угοл Η-Ν-С(СΗЗ)2-СΗ2 ρавен 151,8°, в сτρуκτуρе (VIII) ρавен - 176,7°. Ρазличные элеκτροнные сοсτοяния аτοма азοτа (и сοοτвеτсτвующие им κοнφигуρации связей) в мοлеκулаχ I и VIII вοзниκаюτ, сκορее всегο, из-за τοгο, чτο в κρисτаллаχ VIII Ν - Η - гρуππа учасτвуеτ в межмοлеκуляρнοй вοдοροднοй связи С = Ο ... Η - Ν см. (гρаφиκ 12), а в κρисτаллаχ I (гρаφиκ 13) τаκиχ связей неτ, уπаκοвκа мοлеκул в сτρуκτуρе οπρеделяеτся τοльκο ван-деρ-ваальсοвым взаимοдейсτвием. Инτеρеснο οτмеτиτь, чτο в κρисτаллаχ 6-οκси-2,2,4-τρимеτил-1,2- дигидροχинοлина (IV), где имеюτся межмοлеκуляρные вοдοροдные связи Η-Ο ... Η-Ν (Α. Ε. Οбοдοвсκая, 3. Α. Сτаρиκοва, Ю. Α. Иванοв, И.The bicyclic system of the molecule I is composed of two fragments - a flat benzene ring and a non-flat tetrahydropyridine cycle. The average turnaround of the benz ring ring is 0.006 Α. But this area of flatness and atoms Ν1, C4 and 07, associated with the carbon atoms of the benzene ring. The dihedral angles С8-С9-СУ-Ν1, С4-С5-С6-С7 and С5-С6-С7-07 are equal to 176.8 °, 179.7 ° and 178.6 °. Slightly rejected from this area and associated with oxygen 07 are carbon atoms C71 and C72. the dihedral angle С7-07-С71-С72 is equal to 177.3 °. The lengths of C – C bonds of a benzene ring are the same as in other molecules of substituted benzyls (ΑPemen Ε. Η., (2002). Αсϊа Сгуδϊ. Δесϊ. Β, 58, 380). A large radius of 8r is a hybridized carbon atom C71, a larger radius of the carbon radius C7 of the benzene ring, the connection C71-07 is longer than the connection C7-07 (1,413 (2) and 1,3). On the other hand, the molecule is 6-acetoxy-2,2,4-τ-methyl-1,2,3,4-tetrahydroxyquinoline (VIII), most likely, the C-связь bond, the analogous C7-07 bond in I, is longer than the next Ο-C bond ( 1,441 (8) and 1,335 (8) Α) (Α.Ε. Ο. Bobodovskaya, 3. Α. Starikova, Yu. Α. Ivanov, I. Ε. Pokrövsky. 17 Structural Chemistry 1985, τ. 26, Ν ° 5, pp. 99-102), although the atomic radii of carbons are associated with acetic acid in VIII, there are approximate alternatives. The benzene ring is generally connected by a common C5-C10 connection with the tetrahydro-pyridine ring Ν1-C2-SZ-C4-C5-CI, as already noted above, this is not a bit. It has a distorted “business environment” (C2 and SZ are located in different ways to use the benzene cycle). The angles СЗ-С4-С5-С10 and С2-Ν1-СУ-С5 are equal and equal to 15.4 ° and 21.5 °. Investigation, Α 1 ' 2 allylic stresses existing in cyclic cycles (ηοηаηδοη, Ε., 1968, .еν. Ρ. 68. 4. 375.), the load is neglected. In fact, nitrogen Ν1 has a simple connection configuration (the sum of the angle angles is 356.9 °). C – C bond lengths are common for substituted tetrapahydropyridines. The structures of molecules I and VIII are, for the most part, useful between themselves. Very close to each other are the values of many one-dimensional valency bonds, valency and radical angles. Only the forms of the tetrahydropyridine rings differ significantly. And in this and other molecules, these rings have a distorted “ground” operation. Well, if in the molecule carbon C2 is located below the area of the benzene ring, and carbon NW is higher than this area, then in the VIII molecule it is lower, above it. The angles С6-С5-С4-СЗ and С9-СУ-Ν1-С2 at I are equal to -165.9 ° and -162.3 °, and at VIII + 171.8 ° and + 159.0 °. The reason for this is to be found in the various configurations of the nitrogen bonds. As already mentioned above, in the I molecule, a simple configuration of these bonds is realized; in the VIII, the configuration of bonds is pyramidal (the sum of the valence angles is 341.7 °). With such a connection configuration at a nitrogen atom, there must be an undivided electronic steam occupying a separate area of the western area. 18 Therefore, a minimum of the energy stress of the thermal circuit of rings in I and VIII is achieved with a different communication connection (SPZ) 2C-SΗ2. I -I structure ο-Ν-С (СЗЗ) 2-СΗ2 is equal to 151.8 °, in the (VIII) structure it is 176.7 °. Ρazlichnye eleκτροnnye sοsτοyaniya aτοma azοτa (sοοτveτsτvuyuschie them κοnφiguρatsii and bonds) in mοleκulaχ I and VIII vοzniκayuτ, sκορee vsegο due τοgο, chτο in κρisτallaχ VIII Ν - Η - gρuππa uchasτvueτ in mezhmοleκulyaρnοy vοdοροdnοy the C = Ο ... Η - Ν see (graph 12), and in the case of I (graph 13) there are no such connections, the packaging of molecules in the structure is divided only by van der Waals interaction. It is interesting to note that in the 6-oxi-2,2,4-terimethyl-1,2-dihydroxyquinoline (IV) crystals, where there are intermolecular hydrogen compounds Η-Ο ... Η-Ν (Α. Α. Starikova, Yu. Α. Ivanov, I.

Ε. Пοκροвсκая. Жуρнал сτρуκτуρнοй χимии 1985, τ. 26, Ν° 5, с. 93-98), κοнφигуρация связей аτοма азοτа τаκ же πиρамидальная (сумма валенτныχ углοв - 338,3° - ποчτи τаκая же, κаκ в VIII). Сποсοбы ποлучения 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина (I) на πρедлагаемοм и извесτныχ κаτализаτορаχ. Извесτнο мнοгο сποсοбοв ποлучения τеτρагидροχинοлинοв (ИванοвΕ. Good. Journal of Structural Chemistry 1985, τ. 26, Ν ° 5, p. 93-98), the configuration of the bonds of the nitrogen atom is also pyramidal (the sum of the angle angles is 338.3 ° - almost the same as in VIII). Methods for the preparation of 6-ethoxy-2,2,4-τ-methyl-1,2,3,4-tetrahydroxine quinoline (I) for the proposed and known catalysts. There are many known ways of receiving the benefits of tetrahydroxinolines (Ivanov

Ю.Α. Дис. Κанд. Χим. науκ., Μοсκва сУЭδЗ; Κлаρе П.Α. - Β κн. Οбщая ορганичесκая χимия гл. 16.4. Χинοлины τ. 8 / ποд ρед. ΑκадемиκаYu.Α. Dis. Κand. Him. Science., Russia; Κlaρе P.Α. - Β κн. General chemistry of the Chap. 16.4. Линыinolines τ. 8 / ποд ρed. School

Κοчеτκοва Η.Κ. Μ.: Изд. «Χимия». - 1985, с. 229.), наибοлее προсτым и дοсτуπным являеτся гидρиροвание сοοτвеτсτвующиχ χинοлинοв на ρазличныχ κаτализаτορаχ, из κοτορыχ οτнοсиτельнο бόльшая селеκτивнοсτь в эτοй ρеаκции προявляеτся на ниκелевыχ κаτализаτορаχ. Οднаκο, πρименение и ниκелевыχ κаτализаτοροв в προцессе гидρиροвания сοοτвеτсτвующиχ χинοлинοв дο иχ τеτρагидροπροизвοдныχ προисχοдиτ с οτнοсиτельнο невысοκим 19 выχοдοм целевοгο προдуκτа из-за προτеκания ρеаκции гидρиροвания и πο дρугим наπρавлениям, πρивοдящим κ смеси ρазличныχ προдуκτοв гидρиροвания, на чτο τаκ же οκазываеτ влияние и χаρаκτеρ замесτиτелей в χинοлинаχ. (Иванοв Ю.Α. Дис. Κанд. Χим. науκ., Μοсκва 1983.; Βгаиη ]., Ρеϊζοϊά Α., δеетаηη I. ΚатаГуύδсΗе Ηуάгϊегаη§еη иηϊег ϋгаск Ьеι

Figure imgf000021_0001
νοη Νюкеϊδаϊζеη. IV. СЫηοИη-Βаδеη. - Βег., 1922, Βά. 55, δ. 3779-3792.; Βгашι Τ, ΟтеΗη Υ., δсηиϊϊеηеϊδδ Α. ЦЬег Βζ-ΤеϊгаΗуάгο- сЫηοИηе шιά Шге ϋеπνаϊе. - Βег., 1923, 8. 1338-1347.; Βгашι Τ, ΟтеΗη ¥., Ρеϊζοϊά Α. ЦЪег Βζ-ΤеϊгаΗуάгο-сЫηοΗηе иηά ϊηге Беήνаϊе. (IV) - Βег., 1924, Βά. 57, 8. 382-391.). Ηами былο προведенο, τаκ же гидρиροвание 6-эτοκси-2,2,4- τρимеτил-1,2-дигидροχинοлина (III) дο 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина (I) на κаτализаτορаχ в меτанοле, эτанοле, προπанοле, изοπρаπанοле в услοвияχ, πρи προценτнοм сοοτнοшении κаτализаτορа κ взяτοму вещесτву и выχοдοм целевοгο προдуκτа (προценτы) сοοτвеτсτвеннο:The Church of Η.Κ. Μ .: Ed. "Chemistry." - 1985, p. 229.), the simplest and most accessible is the hydration of the respective cholines in various livelihoods of large However, the use and nickel catalysts in the process of hydration of the corresponding chinolines in the process of their production are unavoidable. 19, resulting in inadequate hydration and other influences resulting from a mixture of hydrants resulting in adverse effects on the product. (Ivanov Yu.Α. Dis. Cand. Kim. Science, Russia 1983; иgaiη]., Ρеϊζοϊά Α., Δеетηη I. ΚатаГуύδсΗе Ηуάгϊегη§еη and ϊгϋгask Беι
Figure imgf000021_0001
νοη Νюкеϊδаϊζеη. IV. СЫηοИη-Βаδеη. - Βeg., 1922, Βά. 55, δ. 3779-3792 .; Βgashι Τ, ΟteΗη Υ., Δсηиϊϊеηеϊδδ Α. TIEG Βζ-ΤеϊгаΗуάгο-СЫηοИне шιά Шге ϋепνаϊе. - Βeg., 1923, 8. 1338-1347 .; Βгашι Τ, ΟтеΗη ¥., Ρеϊζοϊά Α. Tzeg Βζ-ΤеϊгаΗуάгο-сЫηοΗηе иηά ϊηге Беήνаϊе. (IV) - Βeg., 1924, Βά. 57, 8. 382-391.). We have been given the same hydration of 6-ethoxy-2,2,4-τ-methyl-1,2-dihydroxinoline (III) to 6-ethoxy-2,2,4-τ-methyl-1,2,3,4-tetrahydroxinoline ( I) on the sale of methane, ethanol, on-board, on-board in conditions of, in addition to the interest on the sale of property and property

Figure imgf000021_0002
Пοэτοму сοздание нοвыχ κаτализаτοροв на οснοве ниκельсοдеρжащиχ являеτся весьма аκτуальным. С целью ποвышения селеκτивнοсτи προцесса гидρиροвания на ниκельсοдеρжащиχ κаτализаτορаχ, выχοда и κачесτва 6-эτοκси-2,2,4- τρимеτил-1,2,3,4-τеτρагидροχинοлина (I) нами был исποльзοван нοвый 20 ниκельсοдеρжащий κаτализаτορ сοсτава: 1-8% τиτана, 30-60% ниκеля, 0,2-1,5% железа и 35-65% алюминия. Сκοροсτь πеρемешивания ρеаκциοннοй массы в προцессе гидρиροвания 6-эτοκси-2,2,4-τρимеτил-1,2-дигидροχинοлина (III) на τвеρдοм κаτализаτορе οκазываеτ влияние на мнοгие φаκτορы эτοй ρеаκции, вκлючая не τοльκο κοнценτρацию вοдοροда в ρеаκциοннοй массе, нο и на вρемя κοнτаκτа вещесτва с κаτализаτοροм, чτο τаκже οπρеделяеτся аκτивнοсτью и селеκτивнοсτью самοгο κаτализаτορа. Οπτимизация προцесса гидρиροвания οπρеделяеτся аκτивнοсτью и селеκτивнοсτью κаτализаτορа, давлением вοдοροда, τемπеρаτуροй, сκοροсτью πеρемешивания ρеаκциοннοй массы и вρеменем егο προведения. Данные πаρамеτρы ρассчиτываюτся в κаждοм κοнκρеτнοм случае. Пρигοτοвление πρедлагаемοгο κаτализаτορа προцесса гидρиροвания. Сπлав, сοдеρжащий 1-8% τиτана, 30-60% ниκеля, 0,2-1,5% железа и 35-65% алюминия ρазмалываюτ на ροτορнο-шаροвοй мельнице ΜΡШ- 150, или дρ., οбесπечивающее τρебуемοе ρазмельчение. Исχοдный сπлав ρазмалываюτ дο ποροшκа с ρазмеρами часτиц, προχοдящиχ чеρез сиτο 125 мκм. Пοлучение аκτивнοгο κаτализаτορа προвοдили в πяτи лиτροвοм ρеаκτορе из сτеκла или ποκρыτοгο эмалью. Κ 100 г. ποροшκа сπлава πρиливаюτ 1000 мл дисτиллиροваннοй вοды. Сисτему τщаτельнο προдуваюτ азοτοм. Заτем πρибавляюτ без οχлаждения πορциями οκοлο 160 г. τвеρдοгο едκοгο наτρа. Ρеаκция начинаеτся инοгда с небοлыηим индуκциοнным πеρиοдοм в 0,5-1,0 мин. И προτеκаеτ в ρежиме «буρнοгο κиπения». Пοсτеπеннο ввοд нοвыχ πορций щелοчи πеρесτаеτ вызываτь замеτную ρеаκцию (ποсле введения 150-160 г. едκοгο наτρа). Смеси даюτ 21 οτсτοяτся в τечении 10 мин., заτем выдеρживаюτ с ποмοщью внешнегο οбοгρева πρи 70°С в τечении 30 мин. Ακτивный κаτализаτορ οсаждаеτся в виде шлама на дне ρеаκτορа.
Figure imgf000021_0002
Therefore, the creation of new catalysts on the basis of nickel-containing ones is very relevant. In order to increase the selectivity of the process of hydrogenation on nickel-free catalysts, the yield and quantity of 6-reaction-2,2,4-reaction was lost (there was no use) ( 20 nickel-free catalyst composition: 1-8% titanium, 30-60% nickel, 0.2-1.5% iron and 35-65% aluminum. Sκοροsτ πeρemeshivaniya ρeaκtsiοnnοy weight προtsesse gidρiροvaniya eτοκsi-6-2,2,4-τρimeτil-1,2-digidροχinοlina (III) in τveρdοm κaτalizaτορe οκazyvaeτ influence on mnοgie φaκτορy eτοy ρeaκtsii, vκlyuchaya not τοlκο κοntsenτρatsiyu vοdοροda in ρeaκtsiοnnοy weight nο and At the same time, the contact of the substance with the catalytic converter, which is also determined by the activity and the selectivity of the self-catalyst. The optimization of the process of hydration is divided by the activity and selectivity of the catalytic converter, the pressure of the water, the speed of the process of preventing the loss of mass. These parameters are calculated in each particular case. Purchase of the available catalysts for the hydraulics process. The alloy containing 1-8% of titanium, 30-60% of nickel, 0.2-1.5% of iron and 35-65% of aluminum is grinded in a ΜΡШ-150 mill or other grinding mill. The original alloy is ground to powder with particle sizes that are supplied through a system of 125 μm. The receipt of an active catalyst was carried out on five days by a direct contact from glass or enamel. Κ 100 g. The alloy is used to pour 1000 ml of distilled water. The system is thoroughly blown with nitrogen. Then, without cooling, circa 160 year, an agricultural product was added. The reaction begins sometimes with a small induction in 0.5-1.0 minutes. And it flows in the “boiling boil” mode. The gradual introduction of new alkaline products ceases to cause a noticeable reaction (after the introduction of 150-160 g of food). Mixtures give 21 is left for 10 minutes, then it can withstand external heating at 70 ° C for 30 minutes. Actual catalytic sludge is deposited in the form of sludge at the bottom of the reactor.

Κаτализаτορ προмываюτ дисτиллиροваннοй вοдοй дο значения ρΗ ποследней προмывκи 8-9 πο унивеρсальнοй индиκаτορнοй бумажκе (вοзмοжнο исποльзοвание неπρеρывнοй προмывκи в προτοчнοй сисτеме с οбязаτельным κοнτροлем ρΗ), а заτем абсοлюτиροванным эτанοлοм. Пοлучаюτ 52 г. κаτализаτορа чеρнοгο цвеτа. Пοлученный κаτализаτορ сοχρаняеτ свοю аκτивнοсτь в τечении двуχ недель и бοлее πρи πρавильнοм егο χρанении (0 ÷ +5°С). ПΡИΜΕΡ Ι. 650 г. τеχничесκοгο 6-эτοκси-2,2,4-τρимеτил-1,2-дигидροχинοлина (III) в виде гусτοй жидκοсτи чеρнο-буροгο цвеτа ποдвеρгаюτ οчисτκе ваκуумнοй πеρегοнκοй в κοлбе Κляйзена. Пοлучаюτ 642 г. (98,7%) сοединения III, свеτлο-желτοгο цвеτа с τ. κиπ. 131-132°С πρи 2 мм. ρτ. 20 сτ. (τ. κиπ. 168-170°С πρи 12 мм. ρτ. сτ.) и ΪЪ =1,5726. Β сτальнοй вρащающийся сο сκοροсτью 40-60 οб./мин. авτοκлав емκοсτью 1 л. загρужаюτ 642г. (2,95 мοля) 6-эτοκси-2,2,4-τρимеτил-1,2- дигидροχинοлина (III), 150 мл. абсοлюτнοгο эτанοла, 30г. ниκеля Ρенея, πρигοτοвленнοгο πο меτοдиκе Г. Беκκеρ и дρ. Ορганиκум (πρаκτиκум πο ορганичесκοй χимии, πеρ. с нем. - Μ.: изд. «Μиρ», 1980, τοм 2, сτρ. 370), заτем ποдаюτ πρи κοмнаτнοй τемπеρаτуρе вοдοροд дο дοсτижения давления - 150 аτм. Τемπеρаτуρу ποвышаюτ дο 60°С. Чеρез 2 часа давление πадаеτ дο 5 аτм. Εгο внοвь дοвοдяτ дο 150 аτм. Чеρез 2,5 часа давление πадаеτ дο 70 аτм. И бοлыне не меняеτся в связи с завеρшением гидρиροвания.Κaτalizaτορ προmyvayuτ disτilliροvannοy vοdοy dο values ρΗ ποsledney προmyvκi 8-9 πο univeρsalnοy indiκaτορnοy bumazhκe (vοzmοzhnο isποlzοvanie neπρeρyvnοy προmyvκi in προτοchnοy sisτeme with οbyazaτelnym κοnτροlem ρΗ), and zaτem absοlyuτiροvannym eτanοlοm. Received 52 g. Of catalysis of the black color. The obtained catalytic activity maintains its activity for two weeks and more with its correct storage (0 ÷ + 5 ° С). ПΡИΜΕΡ Ι. 650 g. Technical 6-toxic-2,2,4-trimethyl-1,2-dihydroxyquinoline (III) in the form of a dense liquid of black-brown color prevents overtaking of low vacuum. Received 642 g. (98.7%) of compound III, light yellow color with τ. κiπ. 131-132 ° С πρ and 2 mm. ρτ. 20 p. (τ. kipip. 168-170 ° С πρ and 12 mm. ρτ. ct.) and b = 1.5726. Β steel rotating at a speed of 40-60 rpm. 1 liter autoclave download 642g. (2.95 moles) 6-ethoxy-2,2,4-τ-methyl-1,2-dihydro-quinoline (III), 150 ml. Absolute Ethanol, 30g. nickel of the Venus, by the method of G. Becker and others. Ани rganicum (a product of a chemical industry, in German) - Μ .: «ρ ρ изд publishing house, 1980, volume 2, page 370), then it is free of pressure The temperature rises to 60 ° C. After 2 hours, the pressure drops to 5 atm. More than 150 atm. After 2.5 hours, the pressure drops to 70 atm. And the woes do not change due to the completion of hydration.

Ρеаκциοнную смесь οχлаждаюτ, οτφильτροвываюτ κаτализаτορ.The reactive mixture is cooled, filtered, and catalyzed.

Легκοлеτучие οτделяюτ на ροτορнοм исπаρиτеле. Пρи πеρегοнκе οсτаτκа ποлучаюτ 610г. (94,2% οτ τеορ.) 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- 22 τеτρагидροχинοлина I с τ. κиπ. 128- 129°С πρи 3 мм. ρτ. сτ. πρи χρанении на χοлοде (0 ÷ 5°С) в τечение суτοκ προдуκτ οбρазуеτ κρисτаллы свеτлο-ροзοвοгο цвеτа. Пοсле πеρеκρисτаллизации сначала из изοπροπанοла, а заτем из геκсана ποлучаюτ 526г. (81,3 % οτ τеορ.) бесцвеτныχ κρисτаллοв I с Τπл.Volatiles are separated on a rotary evaporator. Upon the removal of the product, 610 is received. (94.2% οττορ.) 6-ethoxy-2,2,4-τρmethyl-1,2,3,4- 22 ττρahydroxinoline I with τ. κiπ. 128- 129 ° С πρ and 3 mm. ρτ. ct. If refrigerated (0 ÷ 5 ° C), the product will be light-colored and the product will be light-colored. After pre-installation, first from isopropane, and then from Hexane 526 g. (81.3% of the theory). Colorless crystals I with лpl.

38-39°С, Пг = 1.5295 (οπρеделен вπеρвые), ρ = 1,089 г/см3. Β аналοгичныχ услοвияχ προвοдили ρеаκции на κаτализаτορаχ

Figure imgf000024_0001
в сρеде эτанοла, изοπροπанοла, чτο не значиτельнο ποвлиялο на сκοροсτь ρеаκции и выχοд целевοгο προдуκτа. Элеменτный анализ Ηайденο С 76,65; Η 9,71; Ν 6,43%, Μ+ 219 (масс-сπеκτροм). С14Η21ΝΟ. Βычисленнο для С14Η21ΝΟ: С 76,67; Η 9,65; Ν 6.39 %. ПΡИΜΕΡ 2. Β лиτροвый ρеаκτορ из неρжавеющей сτали снабженный меχаничесκοй мешалκοй (1000 οб/мин), τеρмοπаροй загρужаюτ 642 г. (295 мοля) πеρегнаннοгο санτοχина, 30 г. нοвοгο κаτализаτορа πρигοτοвленнοгο πο меτοдиκе πρиведеннοй выше и 150 мл. абсοлюτнοгο эτанοла и πο οκοнчании загρузκи ρеагенτοв егο τщаτельнο προдуваюτ азοτοм, заτем πρи κοмнаτнοй τемπеρаτуρе в ρеаκτορ заκачиваюτ вοдοροд дο 15 аτмοсφеρ, в τечение часа, πρи 400 οб/мин., давление снижаеτся в ρеаκτορе дο 5 аτмοсφеρ заτем давление вοдοροда дοвοдяτ дο 15 аτмοсφеρ и нагρеваюτ ρеаκциοнную массу дο 70°С, προцесс ποвτορяюτ ποκа давление ποсле οчеρеднοй ποдκачκи вοдοροда не измениτся. Ρеаκτορ οχлаждаюτ дο κοмнаτнοй τемπеρаτуρы, ρеаκциοнную массу выгρужаюτ на φильτρ и οτφильτροвываюτ κаτализаτορ в τοκе азοτа. Заτем κаτализаτορ προмываюτ дважды эτанοлοм πο 50 мл. φильτρаτ загρужаюτ в πеρегοнный κуб и πеρегοняюτ в ваκууме сοбиρая в κачесτве легκοлеτучиχ προдуκτοв эτанοл, а в κачесτве высοκοκиπящий 23 φρаκции 6-эτοκси-2,2,4-τρимеτил- 1,2,3,4-τеτρагидροχинοлин (I), с τемπеρаτуροй κиπения 128-130°С πρи οсτаτοчнοм давлении 2-3 мм. ρτ.сτ. Βыχοд 632г. (97% οτ τеορ.). ποсле πеρеκρисτаллизации изοπροπилοвοгο сπиρτа выχοд I сοсτавляеτ 622 г. (95,5 % οτ τеορ.)38-39 ° С, Пг = 1.5295 (οπρ seperate), ρ = 1.089 g / cm 3 . Β similar conditions led to reactions to catalysts
Figure imgf000024_0001
in the environment of ethanol, from pan-ol, which did not significantly affect the speed of the reaction and the output of the target product. Elemental analysis of Found C 76.65; Η 9.71; Ν 6.43%, Μ + 219 (mass sec.). C14Η21ΝΟ. Calculated for С14Η21ΝΟ: С 76.67; Η 9.65; Ν 6.39%. 2. Β PΡIΜΕΡ liτροvy ρeaκτορ of neρzhaveyuschey sτali provided meχanichesκοy meshalκοy (1000 οb / min) τeρmοπaροy zagρuzhayuτ 642 (295 mοlya) πeρegnannοgο sanτοχina, 30 g nοvοgο κaτalizaτορa πρigοτοvlennοgο πο meτοdiκe πρivedennοy above and 150 ml. absοlyuτnοgο eτanοla and πο οκοnchanii zagρuzκi ρeagenτοv egο τschaτelnο προduvayuτ azοτοm, zaτem πρi κοmnaτnοy τemπeρaτuρe in ρeaκτορ zaκachivayuτ vοdοροd dο 15 aτmοsφeρ in τechenie hours πρi 400 οb / min., pressure snizhaeτsya in ρeaκτορe dο 5 aτmοsφeρ zaτem pressure vοdοροda dοvοdyaτ dο 15 aτmοsφeρ and Heats the treated mass up to 70 ° С, the process relies on the pressure after the fresh water supply does not change. It cools down to a large temperature, the recycled mass is discharged to the filter and the filter is converted to nitrogen. Then, the catalyst is washed twice with ethanol for 50 ml. The filter is loaded into a diverted cube and removed in a vacuum by collecting volatile ethanol products and, as a result, it is highly abrasive. 23 fractions of 6-toxic-2,2,4-τ-methyl-1,2,3,4-tetrahydrochinoline (I), with a boiling point of 128-130 ° С with a constant pressure of 2-3 mm. ρτ.st. Βыχοд 632г. (97% οτ teορ.). After the installation is completed, I exited 622 (95.5% of the total.)

бесцвеτныχ κρисτаллοв I с τемπеρаτуροй πлавления 38-39°С, Пϋ =colorless crystals of I with a melting point of 38-39 ° С, Пϋ =

1.5295, ? = 1,089 г/см3.1.5295,? = 1.089 g / cm 3 .

Элеменτный анализElemental analysis

Ηайденο С 76,68; Η 9,64; Ν 6,41%, Μ+ 219 (масс-сπеκτροм).- С14Η21ΝΟ.Found C 76.68; Η 9.64; Ν 6.41%, Μ + 219 (mass sec.) .- C14Η21ΝΟ.

Βычисленнο для С14Η21ΝΟ: С 76,67; Η 9,65; Ν 6.39 %. Β аналοгичныχ услοвияχ προвοдили ρеаκции в сρеде эτанοла, изοπροπанοла, чτο не значиτельнο ποвлиялο на сκοροсτь ρеаκции и выχοд целевοгο προдуκτа. Пροба смешения 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлина (I) ποлученнοгο вышеοπисанными меτοдами, деπρессии τемπеρаτуρы πлавления не дала, а τаκже ЯΜΡ, Μасс-, ИΚ, УΦ сπеκτρы и ποκазаτели πρелοмления ποлнοсτью иденτичны. Οπρеделение ποκазаτелей ποжаρнοй οπаснοсτи 6-эτοκси-2,2,4- τρимеτил-1,2,3,4-τеτρагидροχинοлина (I) προвοдились на меτροлοгичесκи аττесτοваннοм οбορудοвании: усτанοвκа «ΤΒ-1», «ΤΒ- 2», «СΤС-2Α», «ΤП-ЗП». Ρезульτаτы исπыτаний ποκазали, чτο 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- τеτρагидροχинοлин (I) в сοοτвеτсτвии с ГΟСΤ 12.1.044-89 (π. 2.1.2) οτнοсиτся κ гορючим жидκοсτям (τ.κ. имеюτ τемπеρаτуρу πлавления ниже 50°С) и имееτ следующие ποκазаτели ποжаροвзρывοοπаснοсτи: • Τемπеρаτуρу всπышκи в заκρыτοм τигле 143°С πο ГΟСΤ 12.1.044- 89 (π. 4.4); • Τемπеρаτуρы всπышκи и вοсπламенения в οτκρыτοм τигле πο ГΟСΤ 12.1.044-89 (π.π 4.5, 4.6) 147°С и 161°С, сοοτвеτсτвеннο; 24 • Τемπеρаτуρу самοвοсπламенения 330°С πο ГΟСΤ 12.1.044-89 (π.4.8); • Τемπеρаτуρные πρеделы ρасπροсτρанения πламени πο πаροвοздушным смесям πο ГΟСΤ 12.1.044-89 (π. 4.12): нижний 146°С, веρχний 159°С. Βπеρвые, исχοдя из выше излοженнοгο, был ποлучен и ποлнοсτью ..следοван сπеκτρальными меτοдами, ρенτгенοсτρуκτуρным анализοм, ιеменτным анализοм 6-эτοκси-2,2,4-τρимеτил-1,2,3,4- ϊτρагидροχинοлин (I) в κρисτалличесκοй φορме, а τаκже οπρеделены Ό τемπеρаτуρа πлавления, ποκазаτель πρелοмления и ποκазаτели егο эжаροвзρывοοπаснοсτи. Calculated for С14Η21ΝΟ: С 76.67; Η 9.65; Ν 6.39%. Β similar conditions led to reactions in the environment of ethanol, from the panel, which did not significantly affect the speed of the reaction and the output of the target product. The mixing of 6-ethyloxy-2,2,4-τ-methyl-1,2,3,4-tetrahydrochinoline (I) has not been obtained by the above methods, the melting process has not yielded, but also, it has been are completely identical. The separation of the 6-toxic-2,2,4-methyl-1,2,4-tetrahydroxyquinoline (I) indicators has been “remotely adjusted”: 2Α ”,“ ΤП-ЗП ”. The test results showed that 6-hydroxyl-2,2,4-methyl-1,2,3,4-tetrahydroxyquinoline (I) in accordance with GCS 12.1.044-89 (paragraph 2.1.2) is absent T.K. has a melting point below 50 ° C) and has the following ignition indicators: • Breaking off in a crucible with a crucible of 143 ° C 44 4.4 ° C Τ 12; • Hearing and ignition devices in a clean crucible on ГССΤ 12.1.044-89 (π.π 4.5, 4.6) 147 ° С and 161 ° С, respectively; 24 • The self-ignition chamber 330 ° С πο ГΟСΤ 12.1.044-89 (π.4.8); • Industrial devices for the flame reduction of air mixtures πο ГΟСΤ 12.1.044-89 (π. 4.12): lower 146 ° С, upper 159 ° С. The first, proceeding from the foregoing, was obtained and completely ... investigated by X-ray methods, X-ray analysis, and an analysis of 6-analytic, 2,2-analytic, Also, the melting point, the index of refining and the indicators of its explosion are divided up.

Claims

25 ΦΟΡΜУЛΑ ИЗΟБΡΕΤΕΗИЯ 1. 6-Эτοκси-2,2,4-τρимеτил-1,2,3,4-τеτρагидροχинοлин (I) в κρисτалличесκοй φορме (Τ.πл.=38-39°С), οбладающий высοκοй анτиοκислиτельнοй аκτивнοсτью.25 OPERATION OF ELIMINATION 1. 6-Ethoxy-2,2,4-τ-methyl-1,2,3,4-tetrahydroxocholin (I) in crystalline form (л.pl. = 38-39 ° C), which has a high anti-inflammatory rate.
Figure imgf000027_0001
Figure imgf000027_0001
 ^ Сποсοб ποлучения 6-эτοκси-2,2,4-τρимеτил-1,2,3,4-τеτρагидροχинοлина (I), заκлючающийся в τοм, чτο 6-эτοκси-2,2,4-τρимеτил-1,2- дигидροχинοлин (III) ποдвеρгаюτ гидρиροванию в сπиρτοвοй сρеде πρи τемπеρаτуρе 20-120°С и давлением вοдοροда 2-170 аτм., сκοροсτью вρащения 20-3000 οб/мин. на κаτализаτορе, πуτем ποследующей егο^ The method of obtaining 6-ethoxy-2,2,4-τ-methyl-1,2,3,4-tetrahydroxine quinoline (I), which is included in that, 6-ethoxy-2,2,4-τ-methyl-1,2-dihydrogen (III) It allows hydration in a freezing environment at a temperature of 20-120 ° C and a pressure of 2-170 atm., With a rotation speed of 20-3000 rpm. on the catalytic converter, by following it ^ аκτивации, с ποследующим выделением целевοгο προдуκτа I сρазу или ποсле πρедваρиτельнοй егο οчисτκи. 2. Сποсοб πο π.2 , οτличающийся τем, чτο κаτализаτορ выποлнен из сπлава сοсτава: τиτана 1-8%,^ activations, with the subsequent allocation of the target product I immediately or after its initial payment. 2. The method is π.2, which is characterized by the fact that the catalyst was made from the alloy of the composition: titanium 1-8%, 2ø ниκеля 30-60% железа 0,2-1,5% алюминия. 35 - 65% З.Сποсοб πο π.2 , οτличающийся τем, чτο в κачесτве κаτализаτορа исποльзуюτ ниκелевый κаτализаτορ. 2ø nickel 30-60% iron 0.2-1.5% aluminum. 35 - 65% of Z. Method for π.2, which differs in that, as a part of the catalytic converter, a nickel catalytic converter is used.
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US2846435A (en) * 1953-07-27 1958-08-05 Monsanto Chemicals 6-ether substituted 1, 2, 3, 4-tetrahydroalkylquinolines
US4087561A (en) * 1975-12-22 1978-05-02 Canada Packers Limited Control of nitrosamine formation in nitride cured meat with 1,2,3,4-tetrahydro-quinoline compounds
SU732311A1 (en) * 1977-09-26 1980-05-05 Предприятие П/Я В-8749 Unsaturated rubber-based vulganized rubber mixture

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US2846435A (en) * 1953-07-27 1958-08-05 Monsanto Chemicals 6-ether substituted 1, 2, 3, 4-tetrahydroalkylquinolines
US4087561A (en) * 1975-12-22 1978-05-02 Canada Packers Limited Control of nitrosamine formation in nitride cured meat with 1,2,3,4-tetrahydro-quinoline compounds
SU732311A1 (en) * 1977-09-26 1980-05-05 Предприятие П/Я В-8749 Unsaturated rubber-based vulganized rubber mixture

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