SU645567A3 - Method of obtaining 3,5-disubstituted pyrazols - Google Patents

Description

adol-equivalents of hydrazine, -forming-DI-disubstituted PI; rasol1IN formula

IV

lde Y, Y, Z, and .Z have the specified values, dehydrogenate in the presence of a catalyst selected from the group consisting of 1p.1 palladium on coal, platinum on coal, or shrededly VOCs1H (Ovlenii chromite, and OMs are heated to boiling temperature. Process: catalytic dehydrogenation is carried out substantially. In the presence of an inert gas selected from the group consisting of nitrogen, aipiroH, hedium or carbon dioxide.

The process of interaction (moderation of a compound of formula II with the connection of formula III. Of a horizon in an aqueous solution of the threshed. Aa | KO: GO n-a-ra or edzhoi al al-tredy from 20 to 30 ° C.

in the examples, parts and percentages are given to nio-weights, and the results of the analyzes are given in 1 percent, ah.

Example 1. .Preparation 3, | 5-diphenyl / ir. Azol.

In accordance with the corresponding reactor, the reactor is charged 31.85. Weight. including acetophanyuva, 28,13 iBec. h., bnzaldehyde and II57,58 weight. including methanol, after which 1.0.61 wt. h. 50% aqueous hydrofluoride H1AtIrI at a temperature of 20 ° C ° C. Reacp; oo; n; Noe mixture is not strained for 4 hours, i.ri 20–30 ° C. After some time, the resulting juice is partially acidic ( pH 5-7) as a result of the addition of 36% hydrochloric acid. The reaction mixture is cooled to a temperature of from -5 to 0 ° C. Nitrogen is introduced into the system and 20.86 wt. Is added at a maximum temporal temperature of 35 ° C. h. peed, times, I1ngid | rata. After the addition, H | OI hydraz: in1 hydrate, the reaction mixture is mixed with inpn 20-30 ° C for 1 hour. After etuto, 75-80% of methanol is distilled off and replaced with a mixture of xylene. Solution: ar-xylene is cooled to C and twice npoiMbi with water to remove sodium chloride, methanol and unreacted sdrazine hydrate.

After the last wash with water in a nitrogen atmosphere, 2.20–5% of palladium 1 is added to the coal, and the reaction mixture is heated to boiling point (140-144 ° C) for 2 hours. A small amount of water is removed during jugrev and Zhsilol return | Shch. give IB p-factor. During the period of pressurization and extraction, RFA) and for 2 hours at the reverse flow the hydrogen is released (after hydrogenation. And 16.0 parts by weight of Dimethyl Ormamide are added and the isator is removed by filtration at three high temperatures ( .120 ° C). The catalyst is washed with xylene.

then it is treated with water vapor in order to remove the wrinkles from the water and return to the reaction. To the filtrate purified from the catalyst to; 63.1 wt. and. water, and the mixture is cooled to 10 ° C; 3,5-diphenylpyraz) Ol is filtered.

Get about 43.2 weight. including 3,5-diphenyl ra13ol (dry base). In recalculation of n. A. Shchetofenon the output makes

74%.

Example 2. Example 1 is repeated, because the platinum-on-carbon catalyst is replaced by a palladium-on-carbon catalyst. Get the same results. In another experiment, using the process of Example 1, palladium-carbon was replaced with copper pre-reconstituted xpOMiHTOiM. Odako apply tribdizitel about 0.5 weight. h. pre-reestablished

copper chromite 1 to 1 g mol of acetophenone, and hydrogenation is carried out in the presence of a aromatic solvent with a high point of 1K31peni 1P | at a temperature of about 200 ° C.

Likewise, the following pyrazoles of the general formula are obtained by Hp for MV corresponding to acetophenone and benzaldehyde with the corresponding ketone and aldehyde.

R

R

Mr N I

H

Phenyl

2-Chlorophenyl

| f, enil

3-Chlo rfen | IL

Phenyl

 phenyl

F en1il

2-M | e1; Ilfeiil

| f | en1il

4g / 7g-boot, ilfegail

Phenyl

2-Oxyphenyl

1f) enil

3 pMetokaifani l

| F) enil

4- | Methyl.iofbnil

F | 6N1IL

Z-Methylsulfonylfe1BIL

(.ilfeon, silt

2-Chlorfbyl.

12-ChlOrphenyl

2-Chlorophenyl,

5-Chlor: phen1IL

3-Chlorine fonil

2-.MetiLf | bN1Il

2n Methylphenyl

4-mmethoxyfvnil

4- (MetokOif, en1il

2-1Met.aCay1phenyl

2-Chl10 | rphenyl

3-Fluoro1IL.

Z-Fluorine

, 2,4 - Dich lorph en Il

2,4-Di (Chlorophenyl

4-; Cyanophenyl

4-Cyanophyl

Fekil

Z-Carbocoiphenyl

4-Chloromethyl 4-CL (arm etyl fbnil

Neil Phenyl

3- | Car | home6iS; Ifsnil

3; 4-Dimet And lFe3, 4-Dimethylfell Nile 2,4-Dimeto, xi0 2,4-Dimethoxyfbnyl

fynil

4-Chl0 | p-3-1methyl4 -: Chl about r -3-phenyl phenyl

fbnil

.3,6-Dibromfe3, 6-Di Bromfenyl

1NIL

P ip fl iM e ip 3. Obtaining o- (1-m-gtil-5f bn: and l - 3 -p razol l) - feio l a.

A suspension of 5% palladium coal (0.6 parts in 20 vol. Parts (cailol) IU | Dlenn10 is poured into a solution cooled to 5 ° C. 10.5 parts by weight of hours .- (1-meT | IL 5-PheN: IL -, 2-l: Yraz Ol: I1n - 3-yl) -phenol: At 50 ylb. Of xylene, the semi-nebulous suspension is heated to a TeiMineipaTypbi.

1Pe | p1i.od1ich1 take the samples of the taRiquid chromiumT | Graphic analysis.

WHEN the analysis indicated that all of the INSEC1; m.at & Rial was used, the reaction mixture was cooled and filtered, ruled, and after that, the mixture was vacuum dried to obtain an orange-colored color, which gradually disappeared.

Passed with thorough irosu-shivani, gain 8.1 weight. product with t. Kip. 90.5-93 ° C.

A yield of 78.2% in terms of "a o- (1-methyl-5phen | IL-2-P1I1razoli. N-3-yl) -fanyLa.

Calculated,%: C 76.78; H 5.64; N 11.19.

CieHi NzO.

Found,%: € 76, .60; H 5.72; N 10.63.

Example 4. Preparation of 1-methyl-3,5DI phenyllir az ol a.

The process is carried out ino 1, except for the fact that it is in the dipydrogenation stage; D1m.methylformamide is not introduced and the catalyst is not removed. The pea, cyo1 H1 mixture is cooled to approximately 50 ° C and 2.42 wt.% Is added. including methyl alcohol and 11.3 wt. including sherda anhydrous tidrook Si Natri. The reaction mixture was reduced to 95-100 ° C, after which 29.8 wt. including dimethyl sulfate. Re1Cz 0 (H1nuyu sm-gs is heated (At reflux10, more than 60 minutes, then cooled to 80 ° C and & 2 weight. Part of water is added. For the purpose of ipH up to 10 -11 water, add 50% -1% | VO (one sodium hydroxide. In order to restore the oTipaiSoTaHiHoro iKa catalyst, the reaction mixture was screened. | pI1M in xylene. The catalyst is washed with coilol: m and water, after which it is recycled to the subsequent α-stage of the dehydro-O2G1 (i.A. The second layer is removed, the organic layer is washed with 82 parts by weight of water, and the aqueous layer is removed. The Qalgal layer is removed from the skin (LAB | IT 82 parts by weight of 1-methyl-3,5-difelen; ilpyrazole. Yield 89, 5% and ooHOse 3,5-diphenyl1P | Irazole.

Example 5. Preparation of 1-methyl-3, 5D | And phenylp1p1azole a.

5 wt. Part 3, b-diphenylpyrazole. a is dissolved in 25 parts (by volume of adyl zobutyl ketan). Add 1.1 wt. including anhydrous sodium hydroxide, and the mixture is heated to 90 ° C. Add 3.43 wt. of dimethyl sulfate, and the 1-1G mixture is heated to 112-115 ° C. Through 1.5 × H a b r t samples of the reaction mixture and set up or less of 3.5–1.5 double diphenyl 1P.I1 razole. Reactionary

the mixture is cooled to a temperature of 50 ° C and 30 weight% is added. h of water. By adding an aqueous solution of sodium hydrate, the pH is adjusted. The organic layer is washed twice with 30 wt. h of water. In order to determine the yield of the target product, the methyl isobutyl ketone is removed under vacuum and 4.95 wt. including (93% crude yield) of an oil that crystallizes

at the cooling point (mp. 52-53 ° C). Analysis of the product indicates that the product is 85.5% pure 1-methyl 3, 5-diphenylpyrazole.

Example 6. Obtaining 1-methyl-3,5-diphenylpyrazole.

20 wt. including 3,5-diphenylpyrazole is dissolved in IB by 100 wt. including xylene containing 7.26 weight. including solid anhydrous hydroxide. Rea1Qsiannu | Yu mixture is etatreut to 120 ° C

and 13.8 wt. including dimethyl sulfate. The reflux temperature drops to 95 ° C, and after 15 minutes at 95 ° C, unreacted 3,5-Diphenylpyrazole does not appear in the reactionary Omesi. Through

The reaction mixture is cooled to 80 ° C for 30 minutes and 50 parts of water are added. In order to bring the pH to 10 and 11, a 50% aqueous solution of hydroxide n / atri is added. Org.neeky layer twice rumble 50 wt. h of water.

For the release of the product, the xylene is removed in vacuo to give 19.7 wt. including oil which crystallizes on the seed.

Analysis of the product shows that the product has a 98.5% purity.

Formula and 3 about b e e e (H and

Method for obtaining 3,5-dis-displaced. Pyrazoles of the formula

45

where Y, Y, Z and Z are hydrogen, halogen, methylTIO-, 1methylsulfo1-nyl-, cyano-, carboxyl-, Ci- € 4 - carbalkoxy- or oxitropyl, GI- | C4-alkyl, Ci-C4-haloalkyl, containing from 1 to 4 halogen atoms, d- € 4 alkoxy1gru1pp1a,

- about ti ich1a yu, just the fact that, in order to increase the yield of the target product and improve the technological process, the connection (formula

CO-CH60

where Z and Y have the indicated values, taken in an equimolar amount, are subjected to 65 1 v11 simulation at the compound-formula, where Z and Y have the values indicated, taken akaimo rio.m number, in Ored alcohol from 10 ° C to 70 ° C, the resulting reaction mixture. SILICATE with unorganized acid, such as 1sol 1 na1, sulfuric or phosphoric acid, to ipH 5-7 and treated with 1–2 mol-aquival antamid hydrazine to form disubstituted n; And, p1-azoline formulas

645567 where Y, Y, Z, and Z are index values, are dehydrated in the presence of a catalyst selected from the group consisting of lladium 1 on the coal, coal on the coal or just chromite, and the mixture is heated to the temperature of the boiling. 2. Method 1 of Section 1, characterized by the fact that the process of catalytic dehydrogenation is carried out in the presence of an inert taaa, the choice of 1H (but from 1 group, including nitrogen, argon, helium, or carbon dioxide. 3. Method; , characterized in that the process of the interaction of the compound "and formula II with the connection of formula III is carried out in an environment of aqueous paiCTBopa caustic soda or caustic calium at a temperature of 20 to 30 ° C