JPS5867662A - Glucosylurea-urea compound and its preparation - Google Patents

Abstract

NEW MATERIAL:A glucosylurea-urea compound of formulaI. USE:Useful as a nonproteinic nitrogenous feed for animals, e.g. ruminants or pigs, and usable as a good feed with a carbohydrate or cellulosic material without causing the ammonia posisening due to the large amount of ammonia formed by the rapid decomposition by the action of an enzyme urease in the first stomach of a ruminant as opposed to the well-known urea, etc. and assuming the protein deficiency due to the delay of the decomposition in the initial period of the feeding as opposed to the slow-acting feed. PROCESS:D-glucose of formula II is reacted with urea in the presence of an acidic catalyst at 40-100 deg.C to give the compound of formulaI.

Description

[Detailed description of the invention] The present invention is based on the formula Regarding the SoO manufacturing method.

This compound is useful as a non-protein supplementary feed for animals such as ruminants or pigs, and is useful as a non-protein supplementary feed for animals such as ruminants or pigs. It does not rapidly decompose due to its action and produce a large amount of ammonia, causing ammonia poisoning, and its decomposition is delayed during the initial stage of feeding, as is the case with slow-release feeds such as those containing 9-aldehyde and urea compounds. The situation of protein deficiency due to
It can be used with carbohydrates and cellulose material as an excellent non-salting feed.

This dalcosyl urea-urea compound can be produced by reacting D-glucose and urea in the presence of an acid catalyst, and the theoretical reaction formula is as follows. As shown in the formula, the theoretical reaction amount of D-glucose and urea is 1
:2, but during the reaction at the end of the day, D-glucose is 1
The reaction is carried out in a molar amount, generally in the range of 1.5 to 5.0 moles of urea. However, the single-stream yield improves when urea is used in a medium or excessive amount compared to the theoretical amount, and even when urea is used in excess, the contribution to yield improvement is small and it is disadvantageous from a cost perspective. , the use of 2.0 to 3.04 l of urea is preferred.

Even if D-glucose and urea are added to the reactor all at once or in portions, there is no effect on the reaction or yield. It is preferable to add it in portions. This is because the above reaction is an equilibrium reaction, so it is desirable that the amount of water be as small as possible, but it is preferable to maintain the reactor components in a dissolved state.
There is no particular limit to the amount of water in the reactor mixture, but as mentioned above, it is preferable that the amount of water be as small as possible within the range that can keep the reaction mixture in a dissolved state. It is desirable that the water content in the water is 1591 or less.

The above reaction is carried out in the presence of an acid catalyst, and examples of acid catalysts that can be used in this reaction include hydrochloric acid, sulfuric acid, and phosphoric acid, and there are no particular restrictions on the amount of these acid catalysts used. Generally speaking, it is 0 per mole of glucose.
．． It is used in a range of 0.05 to 0.3 mol, preferably 0.08 to 0.15 mol.

- After addition of the catalyst, the reaction mixture is generally heated to allow the reaction to proceed. The reaction temperature is generally 40 to 100°C, preferably 50 to 70°C, and the reaction is usually completed in about 3 to 6 hours.

After completion of the reaction, since it is difficult to directly isolate crystals of the glucosyl urea-urea compound produced from the reaction solution (filtration properties are extremely poor), water and then alcohol are added. This is because the crystallinity and yield of the target compound cannot be improved with water alone.Usually, approximately 0.1 to 0.3 times the total weight of the reaction mixture is mixed with water and 0.5 to 3 times the total weight of the reaction mixture. , use about 0 times the amount of alcohol.

As the alcohol, for example, methanol, ethanol, inglobil alcohol, etc. can be suitably used.

After adding water and alcohol, the reaction mixture is cooled to completely precipitate the target compound (there is no particular limit to the cooling temperature, but it is usually cooled to 0 to 5 degrees Celsius), and the precipitated crystals are The crystals are then washed with alcohol to remove acids, urea, glucosyl urea, etc. attached to the crystals. The amount of alcohol used is preferably about 0.1 to 1.0 times the total amount of the reaction vessel. If the amount of cleaning alcohol used is too large, the desired glucosylurine mono-urea compound will be decomposed into glucosylurea, resulting in a decrease in the isolated glycol; siluric volume - crystalline content of the urinary bulk compound, which is undesirable.

What must be noted here is that the filtered crystals must not be washed with water.According to the knowledge of the present inventors, as shown in the following table, glucosyl urea-urea The solubility of the compound in water is extremely high, and therefore most of the target glucosyl urea-urea compound is dissolved in water during water washing.

Compound Temperature (6) Solubility Glucofluorurea - Urea Compound 1 Approx. 50 Jl/100114 (
,0120 approx. 1001A 0oll HzO#
20 #0.81/10(Hd)f
i Minomyl glucosyl urea 25 Approximately 90j'/100
m100m1j# 25
0.215%/yil'/il urea 25 approx. 1
00N/100alH,0251,'ll/1001d
XI/- 11 Examples of the present invention below! I will clarify.

Example 1 D-glucose-hydrate 19811 (1 mol), urea 144j (
2.4 mol) and 5.8 d of water were charged and dissolved in a water bath at 160°C to obtain a colorless and transparent syrupy liquid. The time required for dissolution was about 2 hours. An aqueous solution prepared by dissolving 11.8 I of concentrated hydrochloric acid in 5.8 I of water was added to this horny liquid mixture, and the mixture was reacted with stirring at a temperature of 60°C. Approximately 3
After a period of time, crystals began to precipitate, and the reaction was continued for an additional 3 hours, and then heating was stopped.

The nine reaction mixture thus obtained was stirred with 70 g of water.
m and methanol 350 #i were added successively, the mixture was cooled to QC and filtered, then methanol 100 #i
After washing with II and drying, 231.5 ft of white crystals were obtained (yield 52-).

The xIm diffraction parable turn of the obtained crystal is #! The excess amount shown in Figure 1 is an equimolar mixture of glucosyl urea and urea OX.
It was unique to the glucosyl urea-urea compound, which is different from Figure 2, which shows @diffraction parable turns.・On the other hand, 1 of the obtained crystals (according to PLO analysis, this crystal is composed of glucosyl urea and urea in a molar ratio of 10-θ to 97)
Therefore, the yield in terms of glucose is about 83-6), the melting point is 168.5 to 170.0°C (9) [Melting point of glucosyl urea: 208°C (decomposition)], and a part of the obtained crystals When recrystallized from water and flJlllled, the melting point was 171
The temperature rose to ~172°C, and the elemental analysis values were as follows.

Theoretical value (C6H18N407): C: 56.44, H: 10.66, N: 3λ91 Actual value C: 56.86. H:10.79. N: 32.35 liters of D-glucose hydrate, 71.5 yu of urea and 5.8 yu of water were put into a reaction box and mixed in a hot water bath.
Heat to ~64°C to dissolve, add #t little by little to D-glucose hydrate 100 hours and urea 71.5 in equal proportions, and dissolve well (some parts are not good, but rarely). It wasn't really a problem).

Next, 4! Water 5.8! #Ki
N-dissolved water f#Il was added and reacted at a temperature of 62±2° C. for 5 hours. Approximately 3 hours after adding hydrochloric acid, crystals of glucosyl urea = urea compound began to precipitate, and a temperature rise of approximately 7°C was observed9.

After the reaction was completed, the hot water was removed and 40kII of water was added, followed by 99-
Inject 380 kft of methanol, freeze water and braai/
The furnace slag was cooled to O″C and passed through V. The furnace slag was brought to room temperature (099%
) It was washed with 1000 ml of tanol and dried for 2 days in a tray dryer at a temperature of 50° C. or less under normal pressure. In this way, 230 glucosyl urea-urea compound was obtained. The melting point of this crystal was 168.5 to 170.0°C, and the yield based on glucose was 81.0.
It was confirmed by IR and Xa diffraction that the crystals were a glucosyl urea-urea compound.

[Brief explanation of the drawing]

Figure 1 is the fDXm diffraction tree/of the glucofluorurea-urea compound synthesized in Example 1, and Figure 2 is the x11 diffraction/meter of an equimolar mixture of glucosyl urea and urea.

Claims (1)

[Claims] 1. A glucosyl urea-urea compound represented by the formula %. 2. A method for producing a dalcosyl urea-urea compound of the formula characterized by reacting 0-glucose and urea in the presence of an acid catalyst.