SU424363A3 - METHOD OF OBTAINING NITROGEN - Google Patents

Description

The present invention relates to the method of obtaining the azo dyes of 6-oxyyry D011-2-OVOGO with a group of substituents in positions 3, 4. P1 is known about the method of producing azo-dyes of 6-oxyiridone-2-nd series by combining an aromatic diazo compound with 6-oxyphenoiYoMYOXYMOXYOYM. 3, 4, and not having a substitute in position 5. However, in the lime method of obtaining the quality of the target product is low, which can be explained by poor quality and low persistence during storage of the original products. To obtain a high-quality product, a method of obtaining azo dyes is proposed by combining aryl diazoni with a 6-hydroxypyridone-2 substituted in the 3 and 4 positions, in position 5 of which a bromine or carbamide dihydrogen atom is present. According to the proposed preposition, the pyridoiam of the indicated tin should be given, the alkyl-i.t. aryl-radical is substituted in io 4, and the alkyl, aryl, amino, acnlamino or amiocarbonyl group in iozhenozheno 3 or which are washed by a hydrocarbon chain which attachments in position x 3 and 4 and form a five-, shcheti- or semichleiyoe ring. These pyridopes correspond to the formula ./. C de Z - a hydrogen atom or a substituent; X is a hydrogen atom or —OH; RI is an alkyl or arnyl radical, and Ro is an alkyl, aryl, a.m. n, acylamino or aminocarbonyl group, or R, and R2 together form a chain of three to five atoms. Z - substituents can be alkyl groups, advantageously with 1-4 carbon atoms, which can also be substituted by an amino group; ari. formulations, for example, phenyl, which can be replaced by methyl, chloro chlorine or chlorine; aralkyl, nairnmer beynl, or cycloalkenes, such as cyclohexyl. As an example of the radicals R, you can specify the alklnye groups with the carbon number 1-4 and the arpyl radicals of the benzene series, nairnmer ethyl, butyl, phenyl, tolyl and chlorophenyl. As RI, it is preferable to metnl. Ro can be an alkalp or uri isis group, apalogue 1 of R |, and the upp, proppopil, beisoyl, / r-toluenesulfo: kilamo-1n and NTbCO group. CROs, R and R can form a chain of 3, 4 or 5 atolls of carbon - pasjj; e; i; iyio, as for example trimetlply, tetrametraplet I peptaggetplep, plp peeter, pappier, coyur closes in position 3, 4 in the base ring. From what Zametetel R. ;, you mete n way to get 11; 5-6ipOM- p 5-aiMinioKa: p6onncibniiix compound formula of formula. If R2 is an alkpl, arpl, alcplep ILTH azplampiogruppa, 5-bro: lseded nnp are prepared bromoprovenpsm corresponding to the compound formula, where X is a hydrogen atom; 5-bromsoedpneni in kotory.h R2 - ampiorpyiiiia, gpdrolpzom obtained 5-bromo-W-ADC /: ah; 11nosoedp enpy and b-bromo-W-amipokarbon lpye eoedinepp (prepared in sickle bromprovamiem kpslote Nez ge1tseinyh in polozheppp 5 3 acyl compounds B-AmpococarbOyls Compound, in which Rs Alppeans, aryl, Aeras, and Aisplap, get Gpdrolpzom 3,5-dpiinainoBbix Conn 11, Sedan. amppocarbony; s nosdpipppy with nosleduyp. Restappered nitrosogroup. 3-appdami; 105 amppocarbonplipy So you can get a payload; I eat a 3-ampposedpee. The optimal conditions for the process are that the suspension is prepared; n, preferably, the solution of pridondone in the medium and the dopazoppie ss-eipipeine are added. 14, in the presence of pyridine, urea, pdlochp or salts of weak acid methl / a p of weak acid, panrimer of coal, slurry, patr plp calp, acidic or primary acidic phosphoric acid or calc. | Get n: 1 products. Can be used for painting. raznap111kh: 1 tarpalov, moreover, the choice of one or another is determined by the chemical structure of the diazo-yellow compound. Naphmer When gsnazuppapp,; azoic compound containing psigo ;; iu p. these sandgly sulfo groups li, perhaps, as a result, a water soluble cracker is obtained. The latter can be used for printing, printing and crafting various materials;}, PG, eg silk, wool, high impregnated samples, noligdroxyl materials of EodokistpG; structures, nanrpmer reperipropyl iiculose, such as viscose and prichlorocellulose, and -; -.,; cf. hlonka or ly :. Many dyes for okrapl ;; ; -pu nitrogen-containing materials, n particles of wool from acid baths. In this connection, mention may be made, for example, of diazotizing aniline-melt pastilplimpo-ml ;: e;: ul (rocklops of industrial stage, nn b), using the first connection, with a single n; 1 and ns: cocoleum; A cellulose-reactive group can prepare a dye, yyyy for coloring and printing pulp. 1Yu: 1iami; 1ypom Iioret ivykh textile .mat. :: rpalah. with the opposes, in the presence of the log n, if necessary, under the conditions of tteogrev. To this name, iiepayio, is the turn of the diazotically horned species of: ioconde nscia arol; aticheoky sulfroic broodenydiagia, for example.; / - and / r-flepple :: diamip mono- or dis-shape; :: cone;: nep mp, panrimer tri- and tetrachloropyri: -; :: dpps or chloropropane cyapuric acid, mycoprotein with methyl; eppt, ammonia pl or shchtfProviiyy myoampa.lp beizo; 1nogo il11 pafgaltalovogo rada. Dyes of similar conditions can be obtained in the following way; c:; achala, ka1, this is described in section a), sy1; azo-1 is generated, then it is led ;, the role: for the purpose of turning XenXr-i-pynnbi into. and codepsiating with the instructions of the polygrouping. mp connection lp. c) The use of a diazenic aromatic amine, which does not contain vodorT yur yp {nh groups, can be prepared insoluble in water) aspta., HpiMe ne. mbifi in the form of a disn (rsiogo k | for example, pulsed p.cellulose, or CiHiTet lychek and surface-active agents, or ;; ko:; b ;; on; iyel el1achpuyu; n; 1X n disp) g fuygts; 1X: -: ounoi; e ;; com. For this H; el11, a cruel is being prepared; it contains the disierge number of people; ;: K) as nii: compotept in yuiko; zmmelchen. The manufacture of such a ;; ac: t :: Pioneer with a pesvest1; by methods ;;, ;;: the crust is crushed into ave ;; suts7 ;; perg; 1yr to m pope n ta. Pol) chg1 ;; nc s |; tel isol1 za for the garlic stone pulp ;;. ; i polyethylene terephthalate. salg propez kra no ;; and stapdart ;;; / i. the measures are painted by the priest or in the eyes; 1and the leader. nanpn: .iepca / ;; 1cyl acid, phenol, opyl p-ox ;; d ;; feiplp, l; 1b are those, rmof ;; keatspo.nn; i process, in which weaving; i iio;: oSch | 1 d; e; hersp ;; the crapetel is then exposed; heat treatment; 1D: pr ;: 80--210CH 1: l; temperature, possibly, more than JP ;; ptDyD: r 3 as pr; year; x for this pt ;; ar omecheeky p ;.; ip are used, for example, an1:; m:; ь ;, they are up to and including 3; 3;; places ;; those, 1i, and irimer N0, C1, Br. CH3, CH3, CN; i alkoxycapbonplnl; 1 alknosulfo; 1ilgrupp, prp; with h indications; Secondary spruces are present in the l; molecule in the o-p / g-yolozhde PPPo; goy; 1 gel-; o lmppo; runia, or are used am ;;; s. hetero ring; 111e heterocyclic; 7 member1; second ring with 2 or 3 heteroatoms m., preferably one is a nitrogen atom and the other or two others are sulfur or hydrogen atoms in the nucleus, tianpHiMcp amncotiazoles, 1 dazo: Y, triazoles, beistiazoles and diadiazoles . d) When using a doped aromatic ammonia compound containing hydroxy. carboxylic acid and carboxylic acid in the org position relative to amino acid, a dye is obtained, which can be converted into chromic or cobalt complexes by conventional metallization. The latter, in the absence of sulfonic acids of B1. X groups and groups of carboxylic acids, are dispersed in water and a weakly acidic bath and used to crush and seal pas animal fibers, for example silk, leather and especially wool, and some synthetic materials, narnl. High polyamides, high polyurethane n polypropylene. These dyes can be added to slightly acidic, neutral, or slightly alkaline VA (H1Y, preferably acetic acid baths. In addition, chromic, cobalt, or copper complexes containing sulfonic acid groups, and nolnnye similarly, can It is used as a colorant dye, in accordance with section a), or hydrolyzed — it is converted into a dye that interacts with cellulose, as described in section b). Examples of suitable aromatic alpuvs for this purpose include o-amipophenols, o-aminonaphols and nitranyl acid and their derivatives containing 50h, P1, CI and / or N02 as substituents. d) When using a diazonium compound and an aromatic amino acid containing a quaternary ammonium group, a dye is obtained which is suitable for splicing and printing many synthetic fibers, for example polyvini.chloride fibers, polyamides, polyurethanes, polyethylene terephthalates, and especially polyacrylonitrile and poly1EPylidene “Ida. POLYACRYLONITRIUM OO) Eternal fibers are polymers that contain more than 80%, for example, 80-95% acrylonitrile, and the remaining 5-20% can be, for example, vinyl acetate, vinylpyridine, vinyl chloride, 1,1-dichloroethylene, acrylic acid, acrylic esters, methacrylic acid or methacrylic acid. Specified dye; - usually weak electrolytes and acTJi4HO are undoubtedly a good solution of solvent or polarized solvents. Slipping edges can be introduced into water, neutral or weak, in a weak medium, preferably in boiling temperature and atmospheric pressure, or at higher temperatures. Among the names of mynames for danrgh, AMnn targets include, for example, amipoacetophenes or propiofenont, in which the methyl or ethylene group contains a quaternary ammonium group. Dyes, having .che soo; These properties can be given by, for example, 3 of those that Kazan 1 1 in c), and the introduction of an effective ammonium group after setting: first, a dye is synthesized that contains a halogen-saturated alknl. On the other hand, the reaction with amyom is carried out, and, at first, the beauty of the gel is stabilized, which is possessed by am.schogrune, and then the reaction with the alkylating agent is performed by HiecT. the purpose of obtaining a quaternary am.monnevone group of the method. they are well known to specialists in this field. PRI m. M 1. 1.38 weight. part / montroaniline is dissolved in warm sweet water (25 weight parts) of concentrated hydrochloric acid {36 1 pad., 10 weight. h.). The solution is cooled and down to 20 wt. h. ice To the resulting /...;ssse add 5 wt. h. 2 n. The solution of sodium nitride and the mixture is stirred for 1 hour at a temperature of about -5 ° C, and then, in excess of the nitrogenous acid, is removed by adding a complete solution of sulfamic acid. 2.75 wt.% is dissolved in slightly alkaline water (alkalized with sodium hydroxide solution). including 5-bromo-3-aminocarbonyl-1-ethyl-6-hydroxy-4-methyl-neridone-2 and 10 wt. including sodium acetate; To the resulting solution is added the solution described above. The mixture is stirred for 30 minutes at 0-5 ° C, then the yellow precipitate is filtered off, which is 3-aminocarbonylH-1-ethyl-6-hydroxy-4-methyl-5- (4-ntrophenylazo) -niridone-2. Recrystallized 1 from ice acetic acid to obtain a product, the crystals of which nourish the needle form and pl. 264 ° C. Found, C 51.9; H 4.8; N C.sH.sOsNs. Calculated C, 52.2; H 4.4; N 20.3. This product provides the substance obtained by combining m of diazotized l-nitroaniline with 3-a. Aminocarbonyl-1-methyl-6-hydroxy-4-methyl pyridone-2. 5-Bromo-3-aminocarbon l-α-ethyl-6-hydroxy-4-methylniridone-2 is prepared as follows. In 100 weight. including 96% sulfuric acid dissolve 9 weight. Part 3-niai-1-ethyl-6-hydroxy-4-methlbn-ridon-2 (a) lipH continuous change and temperature 30-40 0. Then, within 1 hour, add from 4 wt. hours of bromine, l solution is stirred for Hi hour at those: inureture 50-55 ° C, and then it is poured into a mixture of 400 weight. h. ice with water. C. the mixture is stirred for 3 hours, after which the precipitate is filtered off. The latter are washed with cold water and existed at a temperature of 40 ° C. A solid product with mp. 1-18-152 ° C. Ethnic acid alcohol was isolated from the mixture in the form of small needle-like crystals. T. pl. 166 ° C. Found,%: C 39.5; H 4.0; N 9.9; Br 28.4. Senpksz.

Bi i4iK ieiio,; i ,: With Bg29,1.

The same product can be obtained if instead of 8 weight. including Orom, take 6.6 wt. h.

Para. Cm 2. If B: i.e., toe popolusmago in npiiMcpe 1 5-brol1-3-amipocarboiyl-1-et 1L-6-ox 1-4-, methyllilyrylon-2, take 2.24 wt. h. 5-a: .1; w10carbon11l - 1,3-dethyl-6-ox1Ci-4-methylpyr11Doiaa-2, then a yellow precipitate of 1,3-diethyl-6h) xi-4-.stil-5- (4 -itro (Le11-alazo) -11irdo11a-2. When recrystallized from ice, acetic acid produced mines with mp 188-190 ° C.

Indeideo,%: C 57.9; II 5.4; By 17.4.

C, BM ,, 0., 1.,.

Calculated,%: C 58.2; S 5.5; K 17.0.

In terms of its properties, the product is identical to the substances), half of the combination.dnasotropic / migrailium with 1.3% of β-methyl-b-oxy-4-dget1 day 1rndon-2.

5-amnocarboyl 11l-1,3-diethyl - () - oxCl-4-methylnir; .1Don-2 can be reported in a way.

C. mixture and (from 10 parts by weight of 74 parts of ethnl-a-ethyl acetoacetate; n 5 (;, 5 parts by weight of ethyl acetate, are mixed thoroughly at 5–40 ° C and then added to parts by weight of 70% ethylamine water. The solution is stirred at 50 hours npiH 50-55 ° C for rcHeniie

evaporated to dryness in a vacuum. The residue is dissolved in 600 wt. including water n extracted twice 50 wt. including sulfuric zfpr. The aqueous fraction is treated with actinic acid carbonate, Phil TpyjOT II acidified with hydrochloric acid (36 Twadel) in Congo red. C. the mixture is stirred for 1 hour, the noc / ie of which separates the precipitate of 5 - cyano-1,3-diethyl-6-ox-4-methylglyrpond-2, which is extracted from water and produces small prnzm . T. pl. product 157 ° C.

Found,%: C 63.6; P 6.7; 13.6.

ScN.OrK.

Calculated,%; C, 64.0; H 6.8; N 13.6.

(), 83 weight. including this product is added to 36 weight. h. 96% of the sickle kn.tot, and the solution is mixed with a mixture of 50–55 ° C in a flow of 16 hours, and then poured onto 200 weights. h. use water with. Sediment 5-a; ai} 1ocarboppl-1, 3-dpethyl-6-oxp 4-.1ethnlp) Ridona-2 was prepared, washed three times with 50 see. including cold water, cyniaT in vacuum at 40 ° C. Poduchippa solid product n. t. and, 123-125 ° C.

Peidsno,%; C 56.3; P 6.7; X 133

C ,, H, BO .. X ..

Calculated,%; C 56.8; P 7.3; N 13.1.

All subsequent tests are listed in Table 1. 1. Decree 1N Diazocomopent diazotizers and is combined with Pi Idon.

Ai; an example

. Chloride / 3- (4-am1 po4snplsulfo11ila.) -Ethylpprplipip

Chlorine hydrate {). , 1Gamiofe 11Ltr11: .Atila: .pu11P

О-Л:,: 1111Ооо: 1зо, 1су.П1фо purposeto

2-a; n1 0-4-bs11: yuilami11obozolgu.11 (| yk 1slota 2 - ;;.,: 1111011; | ft., 5-pp and 10% 1: oa:, obn.chol-4- su, whose (1) is about 11 SLOT 2La1Ai-4CH11 Troa1P1lp11

2-LOR-4-1; | 1troa NILIN

Chlorides, | ZDZ-chloro-4-am11Iopheylsulfonyllamino).

Chloride /)-( 2,5-l. 11 chlor-4am: 1fsp; Ls l .; foiyl, pi10) etp.myrridinip

Lii.-ii1-2,5 -.-: ps -lfoxslot

Combined co.

5-am 1iocarboiyi.1-6-hydroxy -), 3-tr11.stilpyrido :: - 2

3-aminocarbonyl-1,3-di-11. propnl-4-mst1: .1-6 - oxyirido11-2

3-amiociohioii.- | -5-o) O.: -, 4-d; 1.megil-6 - oxgly) doi-2

D) -am: -1ioca1 bo11I.1-3-11. and t; l-1-ethyl-b-scs - 4 -.; etil 1111 rido11-2

5-ami11ocarbo1: silt - 3.4 - trimstyle ;; - til-O-oxnirpond-2

5-am1P {okarbop1M-3,4-tetra ethyl 11-1 -met ;;. 1 - hydroxy: || 1 to; 1-3

5-amiococoo; il-3, -1-tit: 1a,: st11leyi-1st. - 6-ОКС11 рИ .О11-2

3 - ansT1: lam11 1 - 5-amiocarbopl-ET1.: - 6-ok; I-4-MOT1 LP1 | rIDOP-2

.5-ami; okarbopi. - 6 (-ii: iOi; .ia:.: Iino -, 4-dimCTI.1-o- () xi11Iri.Y11-2

1 - / V a p; tyl-5-am11iocarbo11i.1-3,4-d :: mst; p-6-oxy-11ridon-2

5-a: 1P Ioka: yonil-3,4-peita. stylep-ethyl-b - oxy1 |; rIDON-2

Isaiace) and -1.3 - ;; oi: they - 4 -: et;:. 1-6-oks;: 11I | 1 1DO 1-2

5-bilyu.-3.4-di.1ethyl-2,6-d 101; c 111; rido.; - 2

o-amine) carbo1P1l-1-eti.1-6-hydroxy-3-3; et; 1-4 - f:; l l 11ir11 doi-2

3-al Iiokarboi11l-5-i |) OM-6-oK: 11 - 4-ms-tyl-1-fsly.1Ir1 D011-2

3-am111; okarbonyl-o-orom-0-o; -; c11 - 4-.stil-1 ;;;;; 1 tro (11011 and 1) 1iridoi-2

3-a, .I1I) carbo11il-5-br ().: - 1- (2-x.10rfo; 111l) -b-hydroxy-p-MiT11.)) 1DOI-2

Zd3-amypobs11 :-) 11.0-5-amyiokario11i.1-1,4-di. Mgt ;; l - () - oksip11r; | DON-2

No

Dpazokomiopept example

5-1Itroai1 li11-3-sul (foxlot

4- / 3-sulfatoethylsulfonyl || Il and

I5-b-eulfatoethylsulfo-1P1l-2-amyioig | phthal; 1 - 1

Isulphonic acid

I2-al 1sho-6-11Itrophenol-4-sulfonic acid

i2-a 1 iofiol-4,6-disulfonic acid

j

1-m1I1o-2-hydrox11naphthal11sulfonic acids

I2-ami110-6-x lor phenol-4-sulfonic acid

1-amio-2-oxy. 6-11 trp1 1 naphtally-4-sulfonic acid

I3 -, / 3-sulfatoethylsulfonyl and 11L I1

Example 30. 2,68 weight. including 1,3-fe111dia., 6-disulfonic acids dissolved in 100 wt. including water and add 2ii. sodium carbonate solution to pH 4-5. The solution is cooled down to 0-5.degree. C. p is added to the pen: -; eshivaeluy suspension of cyanuric chloride (1.95 parts by weight) in a mixture (parts by weight) acetone: water: ice: disulfator - 10:40, 40: 1, respectively. The resulting mixture is not stirred at-5 ° C for 1.5 hours, the pH being maintained at 4-b, for which 2N is added from time to time. sodium carbonate solution. Then add 5 wt. including hydrochloric acid (35 ° Twadel) and in a small excess solution of sodium nitrite. Excess nitrous acid is removed by adding 10% aqueous sulfamic acid.

2.1 weight. h. 5 am; 1-carbonyl-3,4-dimethyl-1-ethyl-6-oxngone-2-1 is dissolved in 50 wt. h. Baud and add 2n. sodium carbonate solution to pH 8-9. The resulting solution is cooled to 0-5 ° C and then the paFiee prepared solution is added to it (see para. 1). The RP was slowly adjusted to 6-7 by the addition of sodium carbonate solution, and the mixture was seasoned at-5 ° C for 1 hour. Then g is added 2.5 wt. including 2-aminonaphtali-5-sulfonic acids and the resulting mixture peremetnnyvat at 30-40 ° C, pH 6-7 for

Continued.

Matching to; po11eit

5-a.1И10carbonyl-1-cyclohe1 with 1l-3-ethyl-4-etyliphenyl-2

5-a, mi || okarboii.-1-1,3, 4-three methi l-6-o1; s and; iridoi-2

5-a.m11iocarboi11L-1-ethyl-6-ox11-3,4-dimet; 1lpir11doi-2

5-a.minocarbo: 111l-1- / 3-am1i1oethyl-6-oxy-DI and T1 LP1 | p11DO1 | -2

5-am1I1Okarioiil-1- / 3-s || Oet11L-6-oxy-dpmetiliridon-2

5-a: lliokabboi l-l, 3-dpetlll-6-oksi-4- .tetilyr 1DON-2

1: ac. The resulting mass is heated to 50-60 ° C, 20-weight is introduced into it. % solution of psvarsnnoy salt, cooled to 10 ° C. The resulting product is filtered off, washed with 50 weight. including 30% saline solution n suN1at in vacuum at 40 ° C. The product contains .05 moles of reactive chlorine per azo group; in the presence of an acid bonding agent, the cellulose fiber is stained with a bright greenish yellow color. Painted resistant to handling ;; chlorine.

This 5-aminocarbonyl-3.4-dimeth, h-1-ethnl-b-oxypyridone-2 required for this test can be obtained in a manner similar to 5-amn jucarbonl-1, 3-d11 ethnyl-6-oxn-4 - methnnridone-2, the synthesis of which is described in example 2. To do this, instead of 74 wt. including ethyl ester of α-ethyl acetoacetic acid rowing to take 67 weight. including ethyl ether to-mytilanetoacetic H; acid. Product p.meot t. Pl. i5:) - 152С.

C 56.9; H 6.4; N 13.8.

Paylo,%

CioHnN.Oa. about: C 57.1; P 6.7; X 3.3.

Deducted

All subsequent prnmery summarized in the table below. 2

In tab. 2 double lumen lacunctures of the active component are combined with a matching component.