CN1266841A

CN1266841A - Synthesis of 5(6)-caproleic acid

Info

Publication number: CN1266841A
Application number: CN 99101497
Authority: CN
Inventors: 朱昌朋
Original assignee: YONGQUAN GROUP CO XIAMEN CITY
Current assignee: Xiamen Yongquan Science & Technology Development Co., Ltd.
Priority date: 1999-03-11
Filing date: 1999-03-11
Publication date: 2000-09-20

Abstract

A process for synthesizing 5(6)-caproleic acid using cyclohexanone and butanaldehyde as raw materials includes such steps as alkaline condensation, selective hydrogenation, ring enlargement with hydrogen peroxide to become lactone and dewatering in acidic condition.

Description

5 (6)--synthesizing of decylenic acid

The present invention relates to a kind of is raw material synthetic 5 (6)--the technology of decylenic acid with cyclohexanone and butyraldehyde.

Decylenic acid is widely used in the food spice additive, is usually used in milk preparation, soft drink baking, ice goods etc.Its synthetic method is not appeared in the newspapers.

The objective of the invention is to design a kind of synthesis route of decylenic acid.

The synthesis route of decylenic acid of the present invention is to be raw material with cyclohexanone and butyraldehyde, and through parlkaline condensation, selective hydrogenation, the hydrogen peroxide ring expansion is a lactone, and dehydration obtains 5 (6) under acidic conditions at last--decylenic acid.The present invention synthetic 5 (6)--decylenic acid, and the purity height, cost is low.

Embodiment is as follows:

Be equipped with in the there-necked flask of agitator, thermometer, dropping funnel one, add 1%NaOH149.3g (H ₂O147.7g NaOH1.6g), adds cyclohexanone 100.1g down in 25 ℃ of stirrings, and then drips butyraldehyde-n 42g at 35 ℃, adds in about 1 hour, stirs 1Hr in this temperature again.After the cooling, neutralize (about 21.6ml) to PH=7 with acetate.Divide oil-yielding stratum, water layer extracts with toluene, and toluene solution and oil reservoir merge back adding one and be equipped with in the there-necked flask of water-and-oil separator, add 5mlH ₃PO ₄, reflux is also told moisture content.When no longer including moisture content, cooling.Reactant is used saturated aqueous common salt, 5%Na successively ₂CO and washing, slough toluene after, 102--104 ℃/5mmHg, fraction 41.5g are collected in the residuum underpressure distillation.(product is

And

Mixture)

In having the autoclave of stirring rod, add 83g

And 0.243 (3%) Pd/c catalyzer, in 110C, the 10atm hydrogenation is to not inhaling till the hydrogen.Filtration catalizer gets product 81g.

(1) urea/H ₂O ₂, adducts synthetic:

450g30%H ₂O ₂, add 180g urea, low-grade fever is cooled to 0C and separates out adducts to the 30C stirring and dissolving, filter 264g.

(2) 810ml formic acid (86%) adds the 162g adducts, after the stirring and dissolving, adds 81g

, be warming up to 30C stirring reaction (needing cooling) 1Hr.Add 486mlH ₂O uses the toluene extracting, is washed to neutrality, and 126--130C/4mmHg fraction 51.7g (99% purity) is collected in underpressure distillation behind the piptonychia benzene.

54g Add 49.5gNaOH in the 87g aqueous solution, saponification 3Hr under 110C.The cooling back adds 60gH ₂SO ₄And 60gH ₂The mixed solution acidifying of O, branch vibration layer.Add 50gH again ₂SO ₄And 50%H ₂The mixed solution of O, back flow reaction 2Hr.Add the 100ml cyclohexane, branch vibration layer, oil-reservoir water are washed till the mixture that water layer PH=6. adds 0.5g carclazyte and 0.5g gac, reflux and stir the 15min decolouring, filter, and the decylization hexane gets product 48g.

Claims

1, a kind of synthesis technique of decylenic acid is characterized in that with cyclohexanone and butyraldehyde be raw material, and through parlkaline condensation, selective hydrogenation, the hydrogen peroxide ring expansion is a lactone, and dehydration obtains 5 (6) under acidic conditions at last--decylenic acid.

2, according to the decylenic acid synthesis technique of claim 1, it is characterized in that

(1) in reactor, add 1%NaOH149.3g, add cyclohexanone 100.1g down and then drip butyraldehyde-n 42g in 25 ℃ of stirrings at 35 ℃, added in about 1 hour, stir 1Hr in this temperature again; After the cooling, be neutralized to PH=7 with acetate; Divide oil-yielding stratum, water layer extracts with toluene, and toluene solution and oil reservoir merge back adding one and be equipped with in the there-necked flask of water-and-oil separator, add 5mlH ₃PO ₄, reflux is also told moisture content; When no longer including moisture content, cooling; Reactant is used saturated aqueous common salt, 5%Na successively ₂CO and washing, slough toluene after, fraction under the 102--104 ℃/5mmHg is collected in the residuum underpressure distillation;

(2) in having the autoclave of stirring rod, add 83g

And 0.243 (3%) Pd/c catalyzer, in 110 ℃, the 10atm hydrogenation is to not inhaling till the hydrogen;

(3) a: urea/H ₂O ₂, adducts synthetic:

450g30%H ₂O ₂, adding 180g urea, low-grade fever to 30 ℃ stirring and dissolving is cooled to 0C and separates out adducts;

B:810ml formic acid (86%) adds above-mentioned 162g adducts, after the stirring and dissolving, adds 81g

, be warming up to 30 ℃ of stirring reactions (needing cooling) 1Hr; Add 486mlH ₂O uses the toluene extracting, is washed to neutrality, and 126--130 ℃/4mmHg fraction is collected in underpressure distillation behind the piptonychia benzene;

(4) 54g

, add 49.5gNaOH in the 87g aqueous solution, at 110 ℃ of following saponification 3Hr; The cooling back adds 60gH ₂SO ₄And 60gH ₂The mixed solution acidifying of O, branch vibration layer.Add 50gH again ₂SO ₄And 50%H ₂The mixed solution of O, back flow reaction 2Hr; Add the 100ml cyclohexane, branch vibration layer, oil-reservoir water are washed till the mixture that water layer PH=6. adds 0.5g carclazyte and 0.5g gac, reflux and stir the 15min decolouring, filter, and the decylization hexane promptly gets product.