SU726082A1 - Method of preparing nitrosophenols - Google Patents

Description

The invention relates to the synthesis of organic compounds, in particular to a method for producing nitrosophenols, which may find application as extractants for metals, reagents in analytical chemistry.

A known method of producing copper complexes of nitrosophenols, which can be converted into free nitrosophenols, by nitrosation of phenols with nitrogen oxides in an organic solvent in the presence of copper salts Ql].

The disadvantage of this method is—. The fact is that the final products are obtained in the form of complexes, which are difficult to convert to free nitrosophenols, while the purity of the product is low.

Closest to the invention according to. The technical essence and the result to be comprehended is a method for producing nitroeophilic nolg> r <by piclisapia of aliphatic chonntrozo -) ^ ~ face’1 |) bonyl1 >> first compounds with ketones under the influence of sodium ethyl acetate [2J and (3J.

However, the yield of nitrosophenols by this method is only 17% of the theoretical

A 3-fold excess of sodium ethylate was used in the synthesis, while the reaction time was 2 hours.

The aim of the invention is to increase the yield of the target product and reduce the reaction time.

The goal is achieved by the described method for producing ortho-nitrosophenols, which consists in the fact that aliphatic isonitroso-d-dicarbonyl compounds are condensed with ketones under the influence of sodium ethylene in 4-6-fold excess.

A distinctive feature of the method is the use of a 4-6-fold excess of sodium ethylate.

Example 1. Dissolve 0.05 g-at sodium in 20 ml of absolute alcohol; 0.01 mot, i.u. After 3 hours, the mixture was diluted with 100 ml of water and neutralized with 5% sulfuric acid under cooling. The precipitate formed is filtered, washed with water and dried. Exit'.

3,5-dimethyl-2-nitrosophenol is 73% of theoretical

Found,%: N9.53. Calculated,%: N9.27.

Example 2. In the conditions of experience. 1 from isonitrosopropionic acetone with acetone give 3,5,6 trimethyl-2nitrosophenol s. yield 67% of theoretical.

Found,%: '

Calculated,% * Example

N, 8.85. N 8.50.

3. In the experience

I from isonitrozoacetylacetone and methyl ethyl ketone 3,5,6-trimethyl-2-nitrosophenol are obtained in 36% yield.

Found,%: N8.75 Calculated,%: N8.50.

Example 4. Dissolve

0.05 g-at of sodium in 20 ml of absolute alcohol, 0.01 mol of 1-phenyl — butanetrion-1,2, 3 — oxime — 20,072 mol of acetone are introduced into the resulting solution.

II hours, the mixture is poured into 100 g of crushed ice and neutralized with dilute hydrochloric acid. The precipitated crystals of 3-methyl-5-phenyl-4-nitrosophenol are filtered, washed with water. Yield 59% of theory; t. pl.

Found,%: N6.58.

Calculated,%: N6.57.

Example 5. Under the conditions of experiment 1, 1 — p — chl orphenylbutantrion-1,2,3-ox im-2 and acetone were taken as starting compounds. Get 3-methyl — 5-p-chloro. * phenyl-4-nitrosophenol. Yield 83%;

t. pl. 110 ° C.

Found,%: Calculated,%: Example with water, su104 ° C.

N6.07.

N, 6.17.

7. The experimental conditions: ^{-butaitrion-1,2,3;}

j.

N5.72.

N, 6.66.

6. Under the conditions of experiment 1, 1-p-tolyl-butanetrione-1,2,3-ok-sim-2 and acetone were taken. Get 3-methyl • 5 — p — tolyl — 4-nitrosophenol. Yield 5 7%; t. pl. 114 ° C.

Found,%:

Calculated,%: An example is taken 1 — p — anisig-oxime-2 and acetone. Receive. 3-methyl — 5 — p — anisyl — 4-nitrosophenol, Yield 21% ^ mp. 121 ° C.

Found,%: N5.71.

Calculated,%: N5.76.

Example 8. In the conditions of experiment 1 take 1-chenylbutantrione-1,2,3-oxime-2

726082 4.

and methyl ethyl ketone. Obtain 2,3-dimethyl-5-phenyl-4-nitrosophenol. Yield 44%; t. pl. 159 ° C

Found,%: Calculated,%: Example 1-p-chlorophenyl-butanetrione-1,2,3-oxime-2 and methyl ethyl ketone are taken. Received 2,3-dimethyl-5-p-chlorophenyl-4-yi · trozophenol. Yield '62%; t. pl. 152 ° C.

Found,%: Calculated,%:

PRI me R take 1-p — holylbutanetrione-1,2,3—.-Oxime-2 and methyl ethyl ketone, Receive

2.3-cimethyl-5-π-tolyl-4-nitrosophenol. Yield 54%; t. pl. 141 ° C.

Found,% 1 N5.86. Calculated,%: N5.81.

Example 11. Under the conditions of experiment 1, 1-p-anisylbutanetrione-1,2,3-oxime-2 and methyl ethyl ketone are taken. Receive

2.3-cimethyl-5-p-anisyl-4-nitrosophenol. Yield 45%; t

Found,%: Calculated,%: Example 1 ~ 0 (thienyl-butanetrio-1,2,3-oxime-2 and acetone are taken. 3-methyl-5-cA is obtained. — Hyenyl-4-nitrosophenol, Yield 5 4% ;

mp 94 ° C.

Found,%: Calculated,%:

Example 13. Dissolve 0.01 m KOH in 10 ml of absolute alcohol, add 0.02 g mol of diethyl ether of acetone-carboxylic acid and O to the resulting solution; 01 g mol of 1-fendlbutantrione-1,2, 3 ~ oxime-2. After 48 hours, the mixture is diluted with diethyl ether until turbidity. The precipitated green crystals of potassium soda are dissolved in water, acidified once. diluted hydrochloric acid. The precipitate of 2,6-oicarbetoxy-methyl-5-phenyl-4- + strozophenol was filtered, washed with water, and dried. Yield 25%; t. pl. 105 ° C.

Found,%: Calculated,%:

Example

N, 6.48. N6.17,

9. In the experience 1

N, 5.34.

N, 5.36. .

10. In the conditions of experience pl. 143 ° C.

N, 5.34; N, 4.47.

12. In the experience

N, 6.17.

N, 6.39.

N, 3.95.

N 3.92.

14. Under the conditions of the experiment, 1 — p — chlorophenyl — butanetrione-1, 2,3-oxime-2 is taken. After 24 hours receive

3-methyl-5-π-chlorophenyl-2,6-dicarbetoxy-4-nitrosophenol. Yield 37%; t. pl. 128 ° C.

Found,%:

Calculated,%:

Example

Took 1 — P — GOLYL-butaNTrION-1,2,

N 3.58.

N 3.58.

15. In the experience

726082 6

3-oxime — 2. After 100 hours, 3-ME— TIL-5-P-TOLYL-2,6-dicarbetoxy-4-nitrosophenol is obtained. Yield 19%; t. pl. 115 ° C.

-Found,%: N 3.58.

Calculated,%: N 3.78. 5

UV spectra were recorded for all compounds, in which there was an absorption band in the range of 680–720 nm, which is characteristic of the nitro rosio group transition? 10

Feasibility study:. the use of such an excess of sodium ethylate gave a sharp increase in the yield of the target product (from 6% in the prototype to 59% in the proposed method), the reaction time ¹⁵ decreased from 93 to 11 hours. .

In the case when the ketone is activated by electron-withdrawing substituents, an alcohol solution of alkali can be used instead of gatrium ethylate (examples ^10–20 12).

In this case, spatially hindered nitrosophenols are formed, the preparation of which by existing methods was impossible.

Claims (3)

The invention relates to the synthesis of organic: combined, in particular, to a method for producing nitrosophenols, which can be used as extractants for metals, reagents in analytical chemistry. A known method for producing copper complexes of nitrosophenols, which can be converted into free nitrosophenols, by nitrosation of phenols with nitrogen oxides in an organic solvent solvent in the presence of salts of MICIOR1. The disadvantage of this method is that the final products are obtained in the form of complexes that difficult to convert to free nitrosophenols, while the purity of the product is low. f ai 6aaee close to the invention in terms of technical degree and achievable result is the method of obtaining neither pcd4 | enplog (by 1 hinge;) a11ii aliphatic and: k) h1p ti (i, io-JV-iiiKin6oiiM.4, fiHx combinations with ketone sodium t2j and 3, however, the yield of nitrosophenolop by this method is only 17% of Teope TH4ecKovo. In the synthesis, a 3-fold excess of sodium ethylate was used, the reaction time being 2 hours. the yield of the target product and the reduction of the reaction time. The goal is achieved as described by the method of obtaining 1 and ortho-nitro. zofenols, consisting in that aliphatic isonitroso-dicarbonyl compounds are condensed with ketones under the action of ethylene sodium in 4-fold excess. A distinctive feature of the method is the use of 4 "-Ci-KfinTHoro excess Sodium ethoxide. Example IL, Dissolve O, O5 g-at-sodium In 20 ml of absolute clotted solution, O, O1 may be added to the solution of citrono-nitrosoacetyl acetone and 0.06 mol of acetone. After 3 hours, the mixture was diluted with 100 Nm of water and neutralized while cooling with 5% sulfuric acid. The precipitate formed is filtered, washed with water and dried. The yield of 3,5-dimethyl-2-nitrosophenol was 73% of the theoretical. Found,%: H9.53, Calculated, 9 (: N9.27, Example 2. Under the experimental conditions, 1 of isonitro-propionyl acetone with acetone is obtained. 3,5,6 trimethyl-2 "itrozofe-NOL with a yield of 67% of the theoretical Found,%: - N8.85, Calculated,%: H8.5O, Example 3. In conditions of test 1, 3,5,6-trimethyl-2 "itrozphenol with a yield of 36% is found in isonitroacetylacetone and methyl ethyl ketone : 8.75 Calculated,%: N, 8.50 Example 4, Dissolved. 0.05 g of sodium at-sodium in 20 ml of absolute alcohol, introduced into the resulting solution of 0.01 mol of 1-phenyl-butanetrione-1,2, 3- oxime-2O, O72 mol addeton. After 1.1 hours, the mixture is poured into 1OO g crushed ice and neutralized with dilute hydrochloric acid. The precipitated crystals of 3-methyl-5-phenyl 4-nitrosophenol are filtered, washed with water, dried, Vykod 59% theory; t, mp, 1 O4 S. Nayeno,%: H6.58. ,%: L6.57 Example 5 1-p-chlorophenylbutanetrione - 1,2,3-oxime- and acetone were taken as starting compounds under starting conditions. 3-methyl-5-p-chlorophenyl-4 was obtained. -nitrosophenol. Vykod 83%; mp 110 ° C, Found,%: H 5.72. Calculated,%: W 6.66. Example 6. Under the conditions of the experiment, 1-p-chgolyl-butanetrione-1,2,3; -sux-2 and acetone were taken. 3-methyl 5-p-tolyl-4-nitrosophenol is obtained. Yield 57% m. Pl. Found%: .V16,07. Calculated,%: VI 6,17. Example 7. Under the conditions of the experiment, 1 p anisi is taken. -: - butantrione-1,2,3-oxime 2 and acetone. Get it. 3-methyl 5CH1-anis t-4-nitrosophenol. Output 2 t. Pl. . Found,%: N5.71. Calculated,%: N5.76, Example 8. Under the conditions of the experiment, 1-h}) enylbutantrione-1,2,3-oxime of methyl ethyl ketoi is taken. 2,3-Aimethyl-5-phenyl 4-nitrosophenol is obtained. Yield 44%; , pl. 159 ° С; Found,%: Ib, 48. Calculated,%: Nb, 17. P) and measure 9, Under the conditions of test 1, erute 1-p-chlorophenyl-but-tantrin, 2,3-oxy-2 and methyl ethyl ketone. Paragraphs of 2,3-dimethyl-5-p-chlorophenyl-4-nor rosophenol. Yield 62%; t, pl, 152 S. Nayeno,%: H 5.34. Calculated, N 5.36. . Example 10. Under the conditions of test 1, 1-p-tolylbutrionrion-1,2,3-yuxim-2 and methyl ethyl ketone are taken. 2,3-Cimethyl-5-p-tolyl-4-nitrosophenol is obtained. Yield 54%; m.p. 141 ° C. Found% 1 N5.86. Calculated,%: N5,81. Example 11 Under the conditions of experiment 1, take 1 "P1 anisylbutanetrione-1,2,3-oxime 2 and methyl ethyl ketone. 2,3-tsmethyl-5-p-a gizil-4-nitrosophenop is obtained. Yield 45%; mp, 143 ° C. Iadeno,%: U5.34 Calculated,%: U4.47. Example 12, Under the conditions of test 1, take (gthienylbutane trione-1,2,3-oxime .2 and acetone. 3-methyl-5-cA. Thienyl-4-h1 nitrosophenol is obtained. Yield 54%; mp. Naiceno,%: NbD7. Calculated,%: Nb, 39. Example 13. Dissolve 0.01 m KOC in 10 ml of absolute alcohol, add 0.02 g mole of acetone dicarboxylic acid diethyl ester and O; 01 g mole 1-Phenolbutantrione-1,2, 3 C1Xim-2. After 48 hours, the mixture is diluted with diethyl ether until cloudy. The infused green crystals of potassium soda are dissolved in water, acidified with dilute hydrochloric acid. The precipitated 2,6-dicarbetox and-methyl-5-phenyl-4 1 nitrosophenol is filtered, washed in, ode, dried. Yield 25%; mp, Found,%: VI 3.95, Calculated,%: H3.92. Example 14, Condition x experience 1O take 1 p-chlorophenyl-butanetrione 1, 2,3-oxime-2. After 24 h, 3 methyl 5-p-chlorophenyl-2,6-dicarbethoxy-4-nitrosophenol is obtained. Yield 37%; mp, Found,%: W3.58. Calcined,%:, 58. Example 15, Under the conditions of test 10, 1-p-olyl-butanetrione-1,2, 3-oxnm-2 was taken. After 10O h, 3 were obtained. -methyl-5 p-tolyl-2, b-cicarbethoxy-4-nor rosofeiol. Efeixon 19%; t, pl,. Found,%: 3.58. Calculated,%: N 3.78. For all the compounds, UV spectra were taken in which the absorption band was present in the region of 680–72 nm, which is characteristic of a nitro group transide. Technical and economic efficiency. the use of such an excess of sodium ethylate gave a sharp increase in the yield of the desired product (from 6% in the prototype to 59% in the proposed method), the reaction time was reduced from 93 to 11 hours. . In case the ketoi is activated by electron-accepting substituents, an alcoholic solution of alkali can be used instead of ethylate Guthrie (examples 10-12). This results in the formation of spatial obstructed nitrosophenols, the production of which by existing methods was not possible. Formula of the invention. characterized in that, in order to increase the yield of the target. VI products shorten the process time; sodium ethylate is taken in a 4-6-fold excess. Sources of information taken into account in the examination 1. US patent number 3964936, 260644, 1976. 2. Authors certificate of the USSR, C O7 C 8X / 05, 1974. 3. Belyev E. Yu., Et al. Reactions of the formation of nitroxyphenols. Journal of Organic Chemistry, No. 11, 1977 (prototype).