SU333166A1 - - Google Patents

Description

(54) METHOD FOR OBTAINING TRIGLICERIDES OF ALIPHATIC CARBON

ACID OR TRIACETATE

CH

/

E, C

H-SO.

li

NA

sn /

where RI and Rj are the same as above, in the presence of 30% hydrogen peroxide and cation exchanger KU-2 at 50-60 ° C and molar ratio of aliphatic carboxylic acid, hydrogen peroxide and the above-mentioned imide or allyl alcohol from 1 , 5: 0.3: 0.25 to 3.0: 0.3: 0.25.

Thus, using this method, it is possible to synthesize esters of N-substituted imides of D-cyclohexene-1,2-dicarboxylic acids in one stage, without replacing the epoxy derivatives of the corresponding compounds.

When olefin is oxidized in a mixture of carboxylic acid, hydrogen peroxide and catalyst, supracarboxylic acid is first formed, which oxidizes the olefin to epoxide. The formed epoxy cycle under the reaction conditions under the action of acetic acid and water, when crushed, forms a mixture of acetoxy and dioxy derivatives of olefin, which esterified to form esters of the corresponding carboxylic acids.

As a result of research, it was found that using this method, in one stage, both acetic esters and propionic, n-isobutyric, valeric and caproic esters can be synthesized from olefins. With an increase in the molecular weight of the starting carboxylic acid, the rate of formation of the corresponding percarboxylic acid decreases, as well as the oxidizing property of the latter at the moment of formation, and as a result of a decrease in the rate of double bond oxidation reaction.

The experiments were conducted in the following way.

The flask, equipped with a thermometer and a mechanical stirrer, is placed in a thermostat, where the temperature is maintained automatically with an accuracy of 0.1 ° C. At a given temperature, the calculated amount of carboxylic acid, hydrogen peroxide (in all cases, 30% hydrogen peroxide solution is used in all cases) is placed in a flask and the catalyst is stirred for 2 hours, then olefin is added dropwise. The reaction is carried out until complete consumption of hydrogen peroxide, and then, after adding benzene, water is separated by azeotropic distillation. Further filtering

the catalyzate is separated and the desired product is successively distilled by vacuum distillation.

In the preparation of the esters of glycerin by distillation, catalyzing the desired product, in an insignificant amount, an additional fraction, which, in all likelihood, consists of a mixture of the corresponding glycerol mono- and di-esters, is selected. Example 1.

180 (3.0 mol) 35 (0.3 mol) 14.5 (0,)

Total: 229.5

10 50

KU-2 Benzene according to the reaction:

Duration, hour

35 50 Temperature) F ° C The molar ratio of acetic acid.P2 Oj.

3.0: 0.3: 0.25 allyl alcohol, g:

CNAA + PaO

174.0 Katahshzat

52.5

45.5

triacetin

fraction boiling at

152-160 ° C / 2 mm Hg.

5.0 2.1

loss balance 3.0

Total: 229.5

The yield of triacetin on the allyl alcohol taken is 83%.

Example 2. In the reaction, g;

Propionic acid Hydrogen peroxide Allyl alcohol

KU-2 Benzene Reaction Conditions:

Duration, hour Temperature, C Molar ratio propionic acid: H2: allyl alcohol Received, g:

1.5 1.4

98.4

Total: al: tail

taken

264 (Z.Omol) 35 (0.3 mol) 14.5 (0.25 mol)

313.5

Total

15 Yu-2

50 Benzene according to the reaction:

45.

Lrodolzh taylyust, hour

Temperature, ° С 50 Molar ratio n-butyric acid: At 0-2:: a1 lilac alcohol 3.0: 0.3: 0.25

Received:

"- Isl on acid + H2O 240.0 Katylksat.70., O

n-tri6utirin61

Thracian. boiling at

160-18P C / 2 mmHg. 6

residue3

Loss3,5

Total: 313.5 V; -, 1. chots gribreyri.11a on the taken allyl

ii; pi80%.

G p ivi e p 4.

h then in reaction, g

from -Msl npy kispot264 (Z.Omol)

Hydrogen peroxide35 (0.3 mol)

.-Hlppyuy alcohol14,5 (0,25 mol)

Total: 313.5

.KU-215

Benzene50 according to the reaction:

Prolong: liveness, 45 hour

Temolar, ° С60 Molar ratio; o-butyric acid:

H7 allyl alcohol3.0: 0.3: 0.25%, g:

Jazo-Oil on acid + Н20239,5

Katali zat69,5

tri-isobut-irin 62.0 fraction boiling nri

176-180 ° C / 1 mmHg.

residue2.0

Example 5. In the reaction, g:

K-Valerianic acid Hydrogen peroxide 5Allyl alcohol

Total: 360.5

KU-2 20 60 Benzene Reaction Conditions:

Duration, hour

50 60 Temperature, С Molar ratio n-valeriac acid:: H2 02: allyl alcohol

3.0: 0.35: 0.25

Received, g:

.-Valerianic acid + H O 276.5

Catalyst

80.0 64.7

tri-n-valerin

fraction boiling at

150 ° C / mmHg

11.3

4.0

loss balance

4.0

Total: 360.5

Tri-n-Valerina Yield Allyl Yield

alcohol 75%.

Example 6

Take something in the reaction, g:

n-Kapron acid174 (1.5 mol)

Hydrogen peroxide29 (0.25 mol)

Allyl alcohol 10 (0.172 mol)

Total: 213

KU-210

Benzene 60 Reaction Conditions:

Duration, h50

Temerate) fa.C60 The molar ratio of k-caproic acid: H2O2:

: allyl alcohol 1.5 0.25: 0.172 Received, g:

and - Kapron acid + Ng O154

Catalysis56

tri-n-kapron46 fraction boiling up to

 mmr.rt.6

residue4

Loss3

Total - 213

The yield of tri-n-caproin on allyl alcohol taken is 70%.

55

cyclohexene-1 D-dicarboxylic acid

50

Total: 177

KU-28

Benzene50

tell me the reaction:

Duration, h50

Temperature, C50-60

The molar ratio of acetic acid is: Oz: imid 1,5: 0,3: 0,25

total, g:

Catalysis88,4

N- (3-hydroxyethyl) imip-cis-D cyclohexene-1,2-dicarboxylic acid triacetate76,9

balance8.9

losses2,6

SNSOOH + NgO84,6

Loss of 4.0

Total: 177

The yield on the catalyzed,% 86,4

Output on imid imid% 84,4

Example 8. then in the reaction, g:

Acetic acid86,

Hydrogen peroxide35

N- (| 3-hydroxyethyl) -imide-3-methyl-cis-d-cyclohexene-1,2-dicarboxylic acid50

Total: 171

KU-2V

Benzene50

tell me the reaction:

Temperature, C50-60

The molar ratio of acetic acid: Ng Og: imid1,5: 0,3: 0,25 Duration, 50 hours received, g:

Catalysis86,7

N- (jS-hydroxyethyl) -imide-3-methyl-cis-cyclohexane-1,2-dicarboxylic acid triacetate 75,1

balance8,8

losses2,8

United Nations Development Organization + NaO78.3

Loss6,0

Total

The yield on the taken catalysate, The yield on the taken imide,% Example 9. B into the reaction, g:

Hydrogen peroxide N- () 3-oxystil) - imide-4-methyl-cis-D - cyclohexene-1,2 - dicarboxylic acid50

Total: 171

KU-2 8 50 Benzene

Reaction Conditions: Temperature, C

50-60

The molar ratio of acetic acid: H20a: imid1,5: 0,3: 0,25

Duration, hours: 50

Received, g:

Catalysis86,3

N- () 3-hydroxyethyl) -imide -4-methyl-cis-D-cyclohexene-1,2-dicarboxylic acid triacetate72,7

balance 10.4

losses3,2

United Nations Development Organization + NaO77.2

Losses7,5

This is then: 171.0 Yield to catalyzate,% 84.2

Output on imid imid,% 82,3

Example 10. then in the reaction, g:

4,5 - Epoxy - N - (/ 3 - acetyl) ethyl - imide 3 - methyl cis - D cyclohexene-1, 2-dicarboxylic acid10

Acetic acid

Total: 20

KU-2

4 20

Benzene Reaction Conditions:

Temperature, C

75-80

Epoxide molar ratio:

1: 4

acetic acid

Duration, hour

15 Received, g:

N - (j3-hydroxyethyl) -imide triacetate - 4 methyl - cis - D - cyclohexane-1,2-dicarboxylic

4.6

acids CH2COOH + NaO 2.5

Balance 0.6

Loss of 0.3

Total: 8.0

but

s s s: y

H

§Ъч

l oe

cho oo

about t--;

about

cx (L

and u

1 / -V

cf 10

O sh

 00 OS

oo oo

oh oh oh

CN SL

G About t-G-. Cr

r- -o

Ox -i

fO

z; about about and about

r- i

what what

The method is better for triglycerides of aliphatic carboxylic acids or triacetate, for example, triacetin, triproggan. N - (| 3 hydroxyethyl) - imide - cis - L - cyclohexane - 1,2 dicarboxylic acid triacetate, which can be used as stabilizers-plasticizers, due to the presence of imkdnoy and acetate groups.

The known method will get t -figlycerides Pufa / C

sn,

СНССоо-нс / ен-со

however, esterified by Pikecher by carbolic acid in the presence of mineral acids.

In this method, it is necessary to have pure glycerin, which is associated with the additional cost of reagents, besides, a mixture of products of varying degrees of esterification of glycerin is obtained, which can be rubbed.

For the purpose of eliminating this, as well as for the purpose of producing alcohol triacetates of the general formula

P -NСНз

Ltd

i

V}

y-1

(

h 5

go

1 / -00o

YuchS

and 2 -,

-Dio

1st

G-1 MF of ON

one.-. Tjooo. / With

about

S2

g.,.

with-; go

Claims (1)

yy, 13 The claims The method of obtaining triglycerides of aliphatic carboxylic acids or triads of general formula 15. R, | USN. HjCOO-HC CH-CDv,, I, -0-CO-CH, u nnn-ur nu-nn / 22 H COO-HCCH-CDjQ g where RI and R2 are hydrogen, metal, the same or different, different that the corresponding aliphatic carboxylic acid is subjected to inter-. with allyl alcohol or substituted with 14 md of tetragadrophthalic acid, the general form | R.S. Chn-SOh,. 111, N, CH, -0-CDCH, HC, CH-CO / where RI and R2 are as defined above, in the presence of 30% hydrogen peroxide and cation exchanger KU-2 at 5 ° -60 ° C and molar ratio aliphatic carboxylic acid, hydrogen peroxide and the allyl alcohol indicated above and from 1.5: 0.3: 0.25 to 3.0: 0.3: 0.25, followed by isolation of the product by known methods.